iupac-nist solubility data series. 74. actinide carbon compounds

IUPAC-NIST Solubility Data Series. 74. Actinide Carbon Compounds

Editor

Jiri Ha laa…

Department of Inorganic Chemistry, Masaryk University, Brno, Czech Republic

Contributors~*Evaluator!

Jiri Ha la*Masaryk University, Czech Republic

James D. NavratilClemson University, USA

~Received 15 August 2000; accepted 2 December 2000!

This volume presents solubility data of the carbonates, salts of carboxylic acids, andother carbon containing compounds of actinides. Covered are compounds of thorium,uranium, neptunium, plutonium, americium, and one system for curium. No solubilitydata on carbonates or other carbon containing compounds have been found for otheractinide elements. The literature has been covered up to the end of 1999, and there wasa great effort to have the literature survey as complete as possible. Only those publishedresults that report meaningful data were considered for the volume. Papers that reportedqualitative results with statements like ‘‘sparingly soluble’’ or ‘‘insoluble,’’ etc. were notconsidered. In addition to papers that published numerical data, some papers that pre-sented data in graphical form only were considered as well. They were considered for thevolume either if no other data were available for the system, if the data were published indifficult to obtain older literature, or if the data were considered to be of importance forother reasons. For many compounds it was not possible to provide theChemical Ab-stractsRegistry Numbers since these have not yet been assigned. For this reason, theRegistry Number index is incomplete. ©2001 American Institute of Physics.

Key words: actinides; actinide carbon compounds; aqueous solutions; nonaqueous solutions; solubility.

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Contents

1. Preface. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 532. Introduction to the Solubility Data Series:

Solubility of Solids in Liquids. . . . . . . . . . . . . . . . . 5342.1. The Nature of the Project. . . . . . . . . . . . . . . . 5342.2. Compilations and Evaluations. . . . . . . . . . . . 534

2.2.1. Compilations. . . . . . . . . . . . . . . . . . . 5342.2.2. Evaluations. . . . . . . . . . . . . . . . . . . . 535

2.3. Quantities and Units Used in Compilationand Evaluation of Solubility Data. . . . . . . . . 5352.3.1. Mixtures, Solutions, and

Solubilities. . . . . . . . . . . . . . . . . . . . . 5352.3.2. Physicochemical Quantities and

Units. . . . . . . . . . . . . . . . . . . . . . . . . 5362.4. References for the Introduction. . . . . . . . . . . 537

3. The Solubility of Actinium Compounds. . . . . . . . . 5393.1. Actinium Oxalate. . . . . . . . . . . . . . . . . . . . . . 539

4. The Solubility of Thorium Compounds. . . . . . . . . 541

a!Electronic mail: [email protected]© 2001 American Institute of Physics.

0047-2689Õ2001Õ30„2…Õ531Õ168Õ$35.00 531

4.1. Thorium Oxocarbonate. . . . . . . . . . . . . . . . . . 5414.2. Salts of Pentakis~carbonato! Thorate~6-!. . . 542

4.2.1 Evaluation of theNa6Th~CO3!51Na2CO31H2OSystem. . . . . . . . . . . . . . . . . . . . . . . . 542

4.3. Guanidinium Trisfluorotris~carbonato!Thorate~6-!. . . . . . . . . . . . . . . . . . . . . . . . . . . 544

4.4. Hexamminecobalt~III !Pentakis~carbonato!Aqua Thorate~6-!. . . . . . 545

4.5. Thorium Formate. . . . . . . . . . . . . . . . . . . . . . 5454.5.1. Thorium Formate Trihydrate. . . . . . 54

4.6. Thorium Acetate. . . . . . . . . . . . . . . . . . . . . . . 5464.7. Thorium Carboxylates. . . . . . . . . . . . . . . . . . 5474.8. Thorium O-Alkylcarbonodithioates. .. . . . . . 5484.9. Thorium Oxalate. . . . . . . . . . . . . . . . . . . . . . . 548

4.9.1. Evaluation of the Th~C2O4!21H2OSystem. . . . . . . . . . . . . . . . . . . . . . . . 548

4.9.2. Thorium Oxalate Dihydrate. . .. . . . 5494.9.3. Evaluation of the

Th~C2O4!21HNO31H2O System... 5514.9.4. Evaluation of the

Th~C2O4!21H2SO41H2O System. . 553

J. Phys. Chem. Ref. Data, Vol. 30, No. 2, 2001

532532 JIRI HALA

4.9.5. Evaluation of theTh~C2O4!21~NH4!2C2O41H2OSystem. . . . . . . . . . . . . . . . . . . . . . . . 557

4.9.6. Evaluation of theTh~C2O4!21C2H2O41HNO31H2OSystem. . . . . . . . . . . . . . . . . . . . . . . . 564

4.9.7. Th~C2O4!21Th~CO3!21Na2C2O4

1Na2CO31H2O System. . . . . . . . . . 5684.10. Ammonium Tetrakis~oxalato!thorate. .. . . . . 5694.11. Thorium Oxobis~o-hydroxybenzoate!. . . . . . 5694.12. Thorium~5-nitro!Barbiturate. . . . . . . . . . . . . 5704.13. Thorium 8-Hydroxyquinolinate. .. . . . . . . . . 5714.14. Thorium Phthalocyaninate. . . . . . . . . . . . . . . 571

5. The Solubility of Uranium Compounds. . . . . . . . . 5725.1. Uranium Dioxo Carbonate. . . . . . . . . . . . . . . 572

5.1.1. Evaluation of theUO2CO3–CO3

2–Na2CO3–H2OSystem. . . . . . . . . . . . . . . . . . . . . . . . 572

5.2. Sodium Dicarbonatodioxouranate~VI !~2-!. . . 5815.3. Salts of Tris~carbonato!Dioxouranante~4-!. . 5825.4. Sodium Pentakis~carbonato!

Bis$dioxouranate~VI !%~6-!. . . . . . . . . . . . . . . . 5875.5. Uranium~VI ! Dioxo Bis~carboxylates!. . . . . . 5885.6. Uranium~VI ! Dioxobis~acetate! Dihydrate... 5915.7. Sodium Tris~acetato! Dioxouranate~VI !. . . . . 5915.8. Sodium Zinc Tris~dioxouranium~VI !!

Nonakis~acetate!. . . . . . . . . . . . . . . . . . . . . . . 5935.9. Uranium~VI ! Dioxo

Bis~carboxylates!1Organic Solvent1WaterTernary Systems. .. . . . . . . . . . . . . . . . . . . . . 593

5.10. Uranium~VI ! DioxoBis~benzenesulfonate!1Phosphoric AcidTri-n-Butyl Ester1Water System. . . . . . . . . 600

5.11. Uranium~IV ! Oxalate. . . . . . . . . . . . . . . . . . . 6015.11.1 Evaluation of the U~C2O4!21H2O

System. . . . . . . . . . . . . . . . . . . . . . . . 6015.11.2 Evaluation of the

U~C2O4!21HCl1H2O System. . . . . 6035.11.3. Potassium Tetrakis~Oxalato!

Uranate~IV !. . . . . . . . . . . . . . . . . . . . 6095.11.4. Uranium~VI ! Dioxo~oxalate!. . . . . . 6095.11.5. Evaluation of the UO2C2O41H2O

System. . . . . . . . . . . . . . . . . . . . . . . . 6095.11.6. Evaluation of the

UO2C2O41HNO31H2O System.... 6115.11.7. Uranium~VI ! Dioxo~oxalate!

N,N8-Dimethyl FormamideMonosolvate. .. . . . . . . . . . . . . . . . . 624

5.12. Ammonium Tris~o-hydroxybenzoato!Dioxouranate~VI !. . . . . . . . . . . . . . . . . . . . . . 625

5.13. Uranium~VI ! Dioxo~8-hydroxyquino-linate!. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 626

5.14. Uranium~VI !Dioxo~ethylenediaminetetraacetate!. . . . . . . . 629

5.15. Uranium~VI ! Dioxo@4,4,4-trifluoro-1-~2-thienyl!-1,3-butanedionate#. . . . . . . . . . . . . . . . . . . . . . . . . 629


5.16. Uranium~IV ! Phthalocyaninate. . . . . . . . . . . . 6306. The Solubility of Neptunium Compounds.. . . . . . 630

6.1. Neptunium~VI ! Dioxocarbonate. . . . . . . . . . . 6306.2. Salts of Dioxocarbonato Neptunate~V!~-1!. . 631

6.2.1. Evaluation of theNaNpO2CO31CO21NaClO41H2OSystem. . . . . . . . . . . . . . . . . . . . . . . . 631

6.3. Salts of Dioxo Bis~carbonato!Neptunate~V!~-3!. . . . . . . . . . . . . . . . . . . . . . . 632

6.4. Salts of Dioxo Tris~carbonato!Neptunate~V!~-5!. . . . . . . . . . . . . . . . . . . . . . . 643

6.5. Hexamminecobalt~III ! Salts ofDioxo~carbonate! Neptunates.. . . . . . . . . . . . 645

6.6. Neptunium~IV ! Oxalate. . . . . . . . . . . . . . . . . 6456.7. Neptunium~VI ! Dioxo~oxalate!. . . . . . . . . . . 647

7. The Solubility of Plutonium Compounds. . . . . . . . 6487.1. Plutonium~VI ! Dioxocarbonate. . . . . . . . . . . 648

7.1.1. Evaluation of thePuO2CO31CO21NaClO41H2OSystem. . . . . . . . . . . . . . . . . . . . . . . . 648

7.2. Ammonium Tris~carbonato!Dioxoplutonate~VI !~-4!. . . . . . . . . . . . . . . . . . 652

7.3. Ammonium HydroxocarbonatoDioxoplutonate~VI !~-1!. . . . . . . . . . . . . . . . . . 654

7.4. Hexamminecobalt~III ! Salt ofPentakis~carbonato!Aquaplutonate~IV !~-6!. . 654

7.5. Plutonium~III ! Formate. . . . . . .. . . . . . . . . . . 6557.6. Plutonium~III ! Oxalate. . . . . . . . . . . . . . . . . . 656

7.6.1. Evaluation of thePu2~C2O4!31C2H2O41HNO31AscorbicAcid or Hydrazine1H2O System... 657

7.7. Plutonium~IV ! Oxalate. . . . . . . . . . . . . . . . . . 6617.7.1. Evaluation of the Pu~C2O4!21H2O

System. . . . . . . . . . . . . . . . . . . . . . . . 6617.7.2. Evaluation of the

Pu~C2O4!21HNO31H2O System. . . 6627.8. Plutonium~VI ! Dioxo~oxalate!. . . . . . . . . . . . 6667.9. Plutonium~III ! o-hydroxybenzoate. . . . . . . . . 6687.10. Plutonium~IV ! oxo~o-hydroxybenzoates!. . . . 6697.11. Plutonium~IV ! 8-Hydroxyquinolinates. . . . . . 6717.12. Plutonium~IV !

N-Hydroxy-N-Nitrosobenzeneaminate. . . . . . 6728. The Solubility of Americium Compounds. . . . . . . 673

8.1. Americium~III ! Carbonate andAmericium~III ! Hydrogencarbonate. . . . . . . . 6738.1.1. Evaluation of the Am~OH!CO3 or

Am2~CO3!31CO3221NaClO41H2O

System. . . . . . . . . . . . . . . . . . . . . . . . 6738.2. Salts of Carbonatodioxoamericiate~V!~-1!... 6778.3. Americium~III ! Formate. .. . . . . . . . . . . . . . . 6788.4. Americium~III ! Oxalate. . . . . . . . . . . . . . . . . 679

9. The Solubility of Curium Compounds. . . . . . . . . . 6849.1. Curium~III ! Oxalate. .. . . . . . . . . . . . . . . . . . 684

10. System Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68611. Registry Number Index. . . . . . . . . . . . . . . . . . . . . . 69112. Author Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 694

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533533IUPAC-NIST SOLUBILITY DATA SERIES

List of Tables1. Interconversions between quantities used as

measures of solubilities. . . . . . . . . . . . . . . . . . . . . . 538

List of Figures1. Thorium tetrakis~formate!–formic acid–water

system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 542. Thorium bis~oxalate!–nitric acid–water system.. . 553. Thorium bis~oxalate!–ammonium oxalate–water

system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 564. Uranium~VI ! dioxobis~acetate!–tri-n-butyl

phosphate–water system. . . . . . . . . . . . . . . . . . . . . 5905. Uranium~VI ! dioxo bis~trifluoroacetate!–diethyl

ether–water system. . . . . . . . . . . . . . . . . . . . . . . . . 5946. Uranium~VI ! dioxo bis~trifluoroacetate!–

tri-n-butyl phosphate–water system. . . . . . . . . . . . 5957. Uranium~VI ! dioxo bis~monochloroacetate!–

diethyl ether–water system. . . . . . . . . . . . . . . . . . . 5958. Uranium~VI ! dioxo bis~monochloroacetate!–

tri-n-butyl phosphate–water system. . . . . . . . . . . . 5979. Uranium~VI ! dioxo bis~trichloroacetate!–diethyl

ether–water system. . . . . . . . . . . . . . . . . . . . . . . . . 59810. Uranium~VI ! dioxo bis~trichloroacetate!–

tri-n-butyl phosphate–water system. . . . . . . . . . . . 59911. Uranium~VI ! dioxo bis~benzenesulfonate!–

tri-n-butyl phosphate–water system. . . . . . . . . . . . 60012. Uranium~VI ! dioxooxalate–sodium oxalate–

water system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60113. Uranium~VI ! dioxooxalate–ammonium oxalate–

water system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61714. Uranium~VI ! dioxooxalate–potassium oxalate–

water system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61815. Sodium carbonato dioxoneptunate~V!–sodium

perchlorate–carbon dioxide–water system. . . . . . . 61816. Sodium carbonato dioxoneptunate~V!–sodium



chloride–carbon dioxide–water system. . . . . . . . . . 63719. Sodium bis~carbonato! dioxoneptunate~V!–

sodium carbonate–sodium nitrate–carbondioxide–water system. . . . . . . . . . . . . . . . . . . . . . . 639

20. Plutonium~VI ! dioxocarbonate–sodiumhydrogen carbonate–sodium perchlorate–carbondioxide–water system. . . . . . . . . . . . . . . . . . . . . . . 649

21. Diplutonium~III !–tris~oxalate!–oxalic acid–nitric acid–water system. . . . . . . . . . . . . . . . . . . . . 658

22. Plutonium~IV ! bis~oxalate!–nitric acid–watersystem. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

23. Diamericium tris~carbonate!–sodiumperchlorate–carbon dioxide–water system. . . . . . . 674

24. Diamericium~III !–tris~oxalate!–oxalic acid–nitric acid–water system. . . . . . . . . . . . . . . . . . . . . 682

25. Dicurium~III !–tris~oxalate!–oxalic acid–nitricacid–water system. . . . . . . . . . . . . . . . . . . . . . . . . . 684

1. Preface

This volume presents solubility data of the carbonatsalts of carboxylic acids, and other carbon containing copounds of actinides. Covered are compounds of thoriuuranium, neptunium, plutonium, americium, and one systfor curium. No solubility data on carbonates or other carbcontaining compounds have been found for other actinelements. The literature has been covered up to the en1999, and there was a great effort to have the literaturevey as complete as possible.

Only those published results that report meaningful dwere considered for the volume. Papers that reported qutative results with statements like ‘‘sparingly soluble’’ o‘‘insoluble,’’ etc. were not considered. In addition to papethat published numerical data some papers that presedata in graphical form only were considered as well. Thwere considered for the volume either if no other data wavailable for the system, if the data were published in dicult to obtain older literature, or if the data were considerto be of importance for other reasons. The first two criteled the compiler to include sometimes papers in whichauthors failed to specify conditions such as temperatuequilibrium time, or methods of analysis. The last criterihas particularly been applied to many of the recent paperthe solubility of actinide carbonates where high precisiontitration technique was used to obtain the solubility dawhich were, however, reported in graphical form, or occsionally as solubility products, without reporting numericsolubility data. Another reason for including these data wtheir importance from the point of view of environmentscience since carbonates of actinides are substances relto the chemical behavior of actinides in radioactive warepositories. Phase diagrams were included for some ofmulticomponent systems. Of the many systems coveredthe volume relatively few were studied by more than olaboratory. Thus the opportunity to carry out evaluations hbeen limited, and only 17 systems have been evaluatedsome of these systems, however, there has been so muncertainty that even tentative solubility values could notrecommended.

Of all published papers only two remained unavailablethe compiler, and could not be included. These are thelowing two reports from the Institute of RadiochemistrTechnical University, Munich, Germany: M. F. Bernkopf,I. Kim, Report RCM-02884, 1984, reporting the solubility oAm~OH!CO3 in 0.1 mol dm23 NaClO4, and W. Runde, J. I.Kim, Report RCM-01094, 1994, reporting the solubility oNaAm~V!O2CO3 in 3 and 5 mol dm23 NaCl. For many com-pounds it was not possible to show theChemical AbstractsRegistry Numbers since these have not been assignedthis reason, the Registry Number index is incomplete.


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534534 JIRI HALA

2. Introduction to the Solubility DataSeries: Solubility of Solids in Liquids

2.1. The Nature of the Project

The Solubility Data project~SDP! has as its aim a comprehensive review of published data for solubilities of gasliquids, and solids in liquids or solids. Data of suitable pcision are compiled for each publication on data sheetsuniform format. The data for each system are evaluatedwhere data from independent sources agree sufficiently,ommended values are proposed. The evaluation sheetsommended values, and compiled data sheets are publion consecutive pages.

2.2. Compilations and Evaluations

The formats for the compilations and critical evaluatiohave been standardized for all volumes. A descriptionthese formats follows.

2.2.1. Compilations

The format used for the compilations is, for the most paself-explanatory. Normally, a compilation sheet is dividinto boxes, with detailed contents described below.

Components Each component is listed accordingIUPAC name, formula, and Chemical Abstracts~CA! Regis-try Number. The Chemical Abstracts name is also includethis differs from the IUPAC name, as are trivial namesappropriate. IUPAC and common names are croreferenced to Chemical Abstracts names in the Systemdex.

The formula is given either in terms of the IUPAC oHill 1 system and the choice of formula is governed by wis usual for most current users; i.e., IUPAC for inorgancompounds, and Hill system for organic compounds. Coponents are ordered on a given compilation sheet accorto:

~a! saturating components,~b! nonsaturating components, and~c! solvents.

In each of~a!, ~b! or ~c!, the components are arrangedorder according to the IUPAC 18-column periodic table wtwo additional rows:

Columns 1 and 2: H, alkali elements, ammonium, alkalearth elements

Columns 3–12: transition elementsColumns 13–17: boron, carbon, nitrogen groups; cha

genides, halogensColumn 18: noble gasesRow 1: Ce to LuRow 2: Th to the end of the known elements, in order

atomic number.The same order is followed in arranging the compilati

sheets within a given volume.


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Original MeasurementsReferences are abbreviated in thforms given by Chemical Abstracts Service Source Ind~CASSI!. Names originally in other than Roman alphabeare given as transliterated by Chemical Abstracts. In the cof multiple entries~for example, translations! an asterisk in-dicates the publication used for compilation of the data.

Variables Ranges of temperature, pressure, etc., are incated here.

Prepared by The names of all compilers are given herExperimental Data Components are described as~1!, ~2!,

etc., as defined in the ‘‘Components’’ box. Data are reporin the units used in the original publication, with the excetion that modern names for units and quantities are use.g., mass percent for weight percent; mol dm23 for molar;etc. Usually, only one type of value~e.g., mass percent! isfound in the original paper, and the compiler has addedother type of value~e.g., mole percent! from computer cal-culations based on 1989 atomic weights.2 Temperatures areexpressed ast/°C, t/°F or T/K as in the original; if neces-sary, conversions toT/K are made, sometimes in the complations and always in the critical evaluation. However, tauthor’s units are expressed according to IUPArecommendations3 as far as possible.

Errors in calculations, fitting equations, etc., are noted, awhere possible corrected. Material inserted by the compis identified by the word ‘‘compiler’’ or by the compiler’sname in parentheses or in a footnote. In addition, compicalculated values of mole or mass fractions are includethe original data do not use these units. If densities areported in the original paper, conversions from concentratito mole fractions are included, but otherwise this is donethe evaluation, with the values and sources of the densbeing quoted and referenced.

Details of smoothing equations~with limits! are includedif they are present in the original publication and if the teperature or pressure ranges are wide enough to justifyprocedure and if the compiler finds that the equationsconsistent with the data.

The precision of the original data is preserved whenrived quantities are calculated, if necessary by the inclusof one additional significant figure. In some cases, compinote that numerical data have been obtained from publisgraphs using digitizing techniques. In these cases, the psion of the data can be determined by the quality oforiginal graph and the limitations of the digitizing techniquIn some cases graphs have been included, either to illusdata more clearly, or if this is the only information in thoriginal. Full grids are not usually inserted all it is not intended that users should read data from the graphs.

Method The apparatus and procedure are mentionbriefly. Abbreviations used in Chemical Abstracts are oftused here to save space, reference being made to sourcfurther detail if these are cited in the original paper.

Source and Purity of MaterialsFor each component, referred to as~1!, ~2!, etc., the following information~in thisorder and in abbreviated form! is provided if available in the

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original paper: source and specified method of preparatproperties; degree of purity.

Estimated Error If estimated errors were omitted by thoriginal authors, and if relevant information is available, tcompilers have attempted to estimate errors~identified by‘‘compiler’’ or the compiler’s name in parentheses or infootnote! from the internal consistency of data and typeapparatus used. Methods used by the compilers for estiing and reporting errors are based on Ku and Eisenhart.4

Comments and/or Additional DataMany compilationsinclude this section which provides short comments relevto the general nature of the work or additional experimenand thermodynamic data which are judged by the compilebe of value to the reader.

References The format for these follows the format fothe Original Measurements box, except that final page nbers are omitted. References~usually cited in the originalpaper! are given where relevant to interpretation of the copile data, or where cross reference can be made to ocompilations.

2.2.2. Evaluations

The evaluator’s task is to assess the reliability and quaof the data, to estimate errors where necessary, and toommend ‘‘best’’ values. The evaluation takes the form osummary in which all the data supplied by the compiler habeen critically reviewed. There are only three boxes otypical evaluation sheet, and these are described below.

Components The format is the same as on the Compition sheets.

Evaluator The name and affiliation of the evaluator~s!and date up to which the literature was checked.

Critical Evaluation ~a! Critical text. The evaluatorchecks that the compiled data are correct, assesses theiability and quality, estimates errors where necessary,recommends numerical values based on all the publisdata ~including theses, patents and reports! for each givensystem. Thus, the evaluator reviews the merits or shortcings of the various data. Only published data are consideDocumented rejection of some published data may occuthis stage, and the corresponding compilations may bemoved.

The solubility of comparatively few systems is knowwith sufficient accuracy to enable a set of recommendedues to be presented. Although many systems have beenied by at least two workers, the range of temperatureoften sufficiently different to make meaningful comparisimpossible.

Occasionally, it is not clear why two groups of workeobtained very different but internally consistent sets ofsults at the same temperature, although both sets of rewere obtained by reliable methods. In such cases, a definassessment may not be possible. In some cases, two orsets of data have been classified as tentative even thougsets are mutually inconsistent.

~b! Fitting equations. If the use of a smoothing equation

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justifiable the evaluator may provide an equation represing the solubility as a function of the variables reportedall the compilation sheets, stating the limits within whichshould be used.

~c! Graphical summary. In addition to~b! above, graphicalsummaries are often given.

~d! Recommended values. Data are recommended ifresults of at least two independent groups are availablethey are in good agreement, and if the evaluator has no das to the adequacy and reliability of the applied experimeand computational procedures. Data are reported as tentif only one set of measurements is available, or if the evaator considers some aspect of the computational or expmental method as mildly undesirable but estimates thashould cause only minor error. Data are considered as doful if the evaluator considers some aspect of the computional or experimental method as undesirable but still consers the data to have some value where the order of magniof the solubility is needed. Data determined by an inadequmethod or under ill-defined conditions are rejected. Hoever, references to these data are included in the evaluatogether with a comment by the evaluator as to the reasontheir rejection.

~e! References. All pertinent references are given heincluding all those publications appearing in the accompaing compilation sheets and those which, by virtue of thpoor precision, have been rejected and not compiled.

~f! Units. While the original data may be reported in thunits used by the investigators, the final recommended vaare reported in SI units3 when the data can be accurateconverted.

2.3. Quantities and Units Used in Compilation andEvaluation of Solubility Data

2.3.1. Mixtures, Solutions, and Solubilities

A mixture5 describes a gaseous, liquid or solid phase ctaining more than one substance, where the substances atreated in the same way.

A solution5 describes a liquid or solid phase containinmore than one substance, when for convenience one osubstances, which is called thesolvent, and may itself be amixture, is treated differently than the other substancwhich are calledsolutes. If the sum of the mole fractions othe solutes is small compared to unity, the solution is cala dilute solution.

The solubility of a solute 1~solid, liquid, or gas! is theanalytical composition of a saturated solution, expressedterms of the proportion of the designated solute in a denated solvent.6

‘‘Saturated’’ implies equilibrium with respect to the processes of dissolution and precipitation; the equilibrium mbe stable or metastable. The solubility of a substancemetastable equilibrium is usually greater than that ofsame substance in stable equilibrium.~Strictly speaking, it isthe activity of the substance in metastable equilibrium tha


lit

in-

tiv

oi

hyo

foaemtinu

eth

eit

-

asi

ys-con-

and

.

se

re.

he

isolu-

536536 JIRI HALA

greater.! Care must be taken to distinguish true metastabifrom supersaturation, where equilibrium does not exist.

Either point of view, mixture or solution, may be takendescribing solubility. The two points of view find their expression in the reference states used for definition of acties, activity coefficients, and osmotic coefficients.

Note that the composition of a saturated mixture~or solu-tion! can be described in terms of any suitable set of thermdynamic components. Thus, the solubility of a salt hydratewater is usually given as the relative proportions of androus salt in solution, rather then the relative proportionshydrated salt and water.

2.3.2. Physicochemical Quantities and Units

Solubilities of solids have been the subject of researcha long time, and have been expressed in a great many was described below. In each case, specification of the tperature and either partial or total pressure of the saturagaseous component is necessary. The nomenclature andfollow, where possible, IUPAC Green Book.3 A few quanti-ties follow the ISO standards7 or the German standard;8 see areview by Cvitasˇ9 for details.

A Note on Nomenclature The nomenclature of theIUPAC Green Book3 calls the solute component B and thsolvent component A. In compilations and evaluations,first-named component~component 1! is the solute, and thesecond~component 2 for a two-component system! is thesolvent. The reader should bear these distinctions in nomclature in mind when comparing equations given here wthose in theGreen Book.

1. Mole fraction of substance 1,x1 or x(1) ~condensedphases!, y1 ~gases!:

xl5n1Y (s51

c

ns , ~1!

wherens is the amount of substance ofs, andc is the numberof distinct substances present~often the number of thermodynamic components in the system!. Mole percentof sub-stance 1 is 100x1 .

2. Ionic mole fractionsof salt i, xi 1 ,xi 2 : For mixture ofsbinary saltsi, each of which ionizes completely intoni 1

cations andy i 2 anions, withy i5v i 11y i 2 and a mixture ofp nonelectrolytesk, of which some may be consideredsolvent components, a generalization of the definitionRobinson and Stokes gives:10

x1 i5y1 ix1 i

11( j 51s ~y j21!xj

, x2 i5y2 ix1 i

y1 ii 51...s,

~2!

x0k5xj

11( j 51s ~y j21!xj

, k5~s11!...c. ~3!

The sum of these mole fractions is unity, so that, withc5s1p


y

i-

-n-f

rys,

-g

nits

e

n-h

n

(i 51

s

~x1 i1x2 i !1 (i 5s11

c

xoi51. ~4!

General conversions to other units in multicomponent stems are complicated. For a three-component systemtaining nonelectrolyte 1, electrolyte 2, and solvent 3,

x15y12xo1

y122~y221!x12x25

x12

y122~y221!x12. ~5!

These relations are used in solubility equations for salts,for tabulation of salt effects of solubilities of gases.

3. Mass fractionof substance 1,w1 or w(1):

w15g1Y (s51

c

gs ~6!

wheregs is the mass of substances. Mass percentof sub-stance 1 is 100w1 . The equivalent termsweight fraction,weight percent, andg(1)/100 gsolutionare no longer used

4. Solute mole fractionof substance 1,xy,1 :

xs,15m1Y (s51

c8

ms5x1Y (s51

c8

xs , ~7!

where c8 is the number of solutes in the mixture. Thequantities are sometimes called Ja¨necke mole ~mass!fractions.11,12 Solute mass fractionof substance 1,ws,1 , isdefined analogously.

5. Solvent mole fractionof substance 1,xy,1 :

xy,15x1Y (s51

p

xs . ~8!

Here,p is the number of solvent components in the mixtuSolvent mass fractionof substance 1,wy,1 , is defined analo-gously.

6. Molality of solute 1 in a solvent 2,m1 :

m15n1 /n2M2 ~9!

SI base units: mol kg21. Here,M2 is the molar mass of thesolvent.

7. Aquamolality, Solvomolalityof substance 1 in a mixedsolvent with components 2, 3,13 m1

(3) :

m1~3!5m1M /M3 ~10!

SI base units: mol kg21. Here, the average molar mass of tsolvent is

M5xy,2M21~12yy,2!M3 ~11!

and xy , is the solvent mole fraction of component 2. Thterm is used most frequently in discussing comparative sbilities in water~component 2! and heavy water~component3! and in their mixtures.

8. Amount concentrationof solute 1 in a solution of vol-umeV, c1 :

c15@ formula of solute#5n1 /V ~12!

do

eerlyrrhihe.tiss

Atrl

ngth

.

, 1

on-usmic

culticalbe

ulddi-forods.

de-

ure

try

-


SI base units: mol cm23. The symbolc1 is preferred to@for-mula of solute#, but both are used. The old termsmolarity,molar andmoles per unit volumeare no longer used.

9. Mass concentrationof solute 1 in a solution of volumeV, r1 :

r15g1 /V5c1M1 /V ~13!

SI base units: kg m23.10. Mole ratio, r A,B ~dimensionless!:9

r n,125n1 /n2 . ~14!

Mass ratio, symbolzA,B , may be defined analogously.9

11. Ionic strength, I m ~molality basis!, or I c ~concentrationbasis!:

I m51

2 (i

mizi2, I c5

1

2 (i

ciziz, ~15!

wherezi is the charge number of ioni. While these quantitiesare not used generally to express solubilities, they are useexpress the compositions of nonsaturating components. Fsingle salti with ions of charge numbersz1 andz2 ,

I m5uz1z2uymi , I c5uz1z2uyci . ~16!

Mole and mass fractions and mole ratios are appropriateither the mixture of the solution point of view. The othquantities are appropriate to the solution point of view onConversions between pairs of these quantities can be caout using the equation given in Table 1 at the end of tIntroduction. Other useful quantities will be defined in tprefaces to individual volumes or on specific data sheets

Salt hydrates are generally not considered to be saturacomponents since most solubilities are expressed in termthe anhydrous salt. The existence of hydrates or solvatenoted carefully in the critical evaluation.

Mineralogical names are also quoted, along with their CRegistry Numbers, again usually in the text and CA RegisNumbers~where available! are given usually in the criticaevaluation.

In addition to the quantities defined above, the followiare useful in conversions between concentrations and oquantities.

12. Density, r:

r5g/V5(sÞ1

c

rs ~17!

SI base units: kg m23. Hereg is the total mass of the system13. Relative density, d5r/r0: the ratio of the density of a

mixture at temperaturet, pressurep to the density of a ref-

tor a

to

.ieds

ngofis

y

er

erence substance at temperaturet8, pressurep8. For liquidsolutions, the reference substance is often water at 4 °Cbar.~In some cases 1 atm is used instead of 1 bar.! The termspecific gravityis no longer used.

Thermodynamics of SolubilityThermodynamic analysisof solubility phenomena provides a rational basis for the cstruction of functions to represent solubility data, and thaids in evaluation, and sometimes enables thermodynaquantities to be extracted. Both these aims are often diffito achieve because of a lack of experimental or theoretactivity coefficients. Where thermodynamic quantities canfound, they are not evaluated critically, since this task woinvolve examination of a large body of data that is notrectly relevant to solubility. Where possible, proceduresevaluation are based on established thermodynamic methSpecific procedures used in a particular volume will bescribed in the Preface to this volume.

2.4. References for the Introduction

1E. A. Hill, J. Am. Chem. Soc.22, 473 ~1900!.2IUPAC Commission on Atomic Weights and Isotopic Abundances, PAppl. Chem.63, 975 ~1989!.

3L. Mills et al., eds.,Quantities, Units and Symbols in Physical Chemis~The Green Book! ~Blackwell Scientific Publications, Oxford, UK, 1993!.

4H. H. Ku, p. 73; C. Eisenhart, p. 69; in H. H. Ku, ed.,Precision Measure-ment and CalibrationNBS Special Publication 300, Vol. 1~NBS, Wash-ington, 1969!.

5V. Gold et al., eds.,Compendium of Analytical Nomenclature~The GoldBook! ~Blackwell Scientific Publications, Oxford, UK, 1987!.

6H. Freiser and G. H. Nancollas, eds.,Compendium of Analytical Nomenclature ~The Orange Book! ~Blackwell Scientific Publications, Oxford,UK, 1987!, Sect. 9.1.8.

7ISO Standards Handbook,Quantities and Units~International StandardsOrganization, Geneva, 1993!.

8German Standard, DIN 1310,Zusammensetzung von Mischphasen~BeuthVerlag, Berlin, 1984!.

9T. Cvitas, Chem. Int17, 123 ~1995!.10R. A. Robinson and R. H. Stokes,Electrolyte Solutions, 2nd ed.~Butter-

worths, London, 1959!.11E. Z. Janecke, Anorg. Chem.51, 132 ~1906!.12H. L. Priedman, J. Chem. Phys.32, 1351~1960!.13J. W. Lorimer, R. Cohen-Adad, and J. W. Lorimer,Alkali Metal and

Ammonium Chlorides in Water and Heavy Water (Binary Systems), IU-PAC Solubility Data Series, Vol. 47~Pergamon, Oxford, UK, 1991!, p.495.

This section was written by:R. Cohen-Adad Villeurbeanne, FranceJ. W. Lorimer London, Ont, CanadaM. Salomon Sea Bright, NJ, USAM.-T. Saugier-Cohen Adad Villeurbenne, France

December 1995


538538 JIRI HALA

TABLE 1. Interconversions between quantities used as measures of solubilitiesc-component systems containingc21 solutesi and single solventc ~r—densityof solution:M1—molar masses ofi. For relations for two-component systems, set summations to 0!.

xi wi mi ci

xi5 xi

1

11Mi

McH 1

wi211(

jÞ1

c21 SMc

Mi21D wj

wiJ

1

111

miMc1(

jÞi

c21

mj

mi

1

111

McSr

ci2MiD1(

jÞ1

c21cj

ciS12

Mj

McD

wi5

1

11Mc

MiH1

xi211(

jÞ1

c21 SMj

Mc21D xj

xiJ wi

1

111

miM1S11(

jÞ1

c21

mjMjD ciMi

r

mi5

1

Mc S1

xi212(

jÞ1

c21xj

xiD

1

Mi S 1

wi212(

jÞ1

c21wj

wiD mi

1

1

ciSr2(

jÞ1

c21

cjMjD2Mi

ci5

r

Mi1McH1

xi211(

jÞ1

c21 SMj

Mc21D xj

xiJ rwi

Mi

r

1

miS11(

jÞ1

c21

mjMjD2Mj

ci


.24

h,th

eso

lutio

nw

asej

ecte

dfr

omth

eco

neby

gase

ous

radi

olyt

icpr

oduc

ts!.

Sam

ples

from

satu

rate

dso

lutio

ns(;

102

4m

l)w

ere

take

nin

toca

libra

ted

capi

llarie

san

dpl

aced

into

akn

own

volu

me

of1

mol

dm2

3H

NO

3.F

rom

this

solu

tion

sam

ples

for

coun

ting

of227 A

cw

ere

take

n.F

orm

icro

scal

em

easu

rem

ents

,th

ew

ork

was

done

in0.

5–

2m

lvo

lum

es.

Ac 2~

C2O

4!3

was

prec

ipita

ted

from

HN

O 3so

lutio

nw

itha

satu

rate

dso

lutio

nof~

NH

4!2C

2O4.

The

prec

ipita

tew

asce

ntrif

uged

and

repe

ated

lyw

ashe

dan

dco

vere

dw

ithw

ater

.T

opr

epar

esa

mpl

esfo

rco

untin

g,th

esa

mpl

esw

ere

take

nth

roug

ha

capi

llary

fille

dw

ithfin

egl

ass

fiber

byus

ing

am

icro

pum

p,in

to1

mL

1m

oldm

23

HN

O3

afte

rw

hich

the

pipe

ttew

asw

ashe

dse

vera

ltim

esw

ithth

isso

lutio

n.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Dia

ctin

ium

tris~

oxal

ate!;

Ac 2

~C2O

4!3;

@726

4-35

-9#O

xalic

acid

;C 2

H2O

4;

@144

-62-

7#W

ater

;H 2

O;

@773

2-18

-5#

D.

M.

Ziv

and

I.A

.S

hest

akov

a,R

adio

khim

iya7,

166

–75

~196

5!.

riabl

es:

Pre

pare

dby

:

K:2

94/m

oldm

23:5

310

25–

0.5

J.H

alaan

dJ.

D.

Nav

ratil

Exp

erim

enta

lDat

a

Com

posi

tion

ofox

alic

acid

solu

tions

satu

rate

dat

21°C

with

Ac

2~C

2O4!

3a

C2H

2O4

2/m

oldm

23 )

pHA

c31

~mg

dm2

3 !A

c31

(106

mol

dm2

3 !A

c 2~C

2O4!

3

(106

c 1/m

oldm

23 !

C2O

422

b

(105

mol

dm2

3 !

53

102

53.

42.

511

5.5

0.69

53

102

43.

01.

25.

32.

62.

96

53

102

32.

30.

964.

22.

15.

85

53

102

10.

97.

85c

34.6

c17

.3c

8.0

heco

mpo

sitio

nof

the

equi

libriu

mso

lidph

ases

was

not

repo

rted

.al

cula

ted

byau

thor

sfr

omto

tal

oxal

icac

idco

ncen

trat

ion,

pH,

and

diss

ocia

tion

cons

tant

sof

oxal

icac

id,

Ka1

55.

9310

22

mol

dm2

3 ,

a25

6.43

102

5m

oldm

23 .

his

incr

ease

inso

lubi

lity

ofA

c 2~C

2O4!

3w

asex

plai

ned

byth

eau

thor

sby

ash

arpe

rin

crea

sein

the

H1

ion

conc

entr

atio

nin

com

paris

onith

that

ofC 2

O422

ion,

and

part

lyby

com

plex

form

atio

n.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

onm

icro

scal

ew

asus

ed.

Ac

2~C

2O4!

3w

asec

ipita

ted

from

HN

O 3so

lutio

nw

ithsa

tura

ted

solu

tion

ofH

4!2C

2O4.

The

prec

ipita

tew

asce

ntrif

uged

and

repe

ated

lysh

edan

dco

vere

dw

ithox

alic

acid

solu

tion

inw

hich

the

lubi

lity

was

tobe

dete

rmin

ed,

and

stirr

edfo

r10

–15

h.T

his

rrin

gtim

ew

asta

ken

assu

ffici

ent

tore

ach

equi

libriu

m,

byal

ogy

toa

sim

ilar

stud

yof

La~III

!ox

alat

e.1T

opr

epar

em

ples

for22

7 Ac

coun

ting

~em

anat

ion

met

hod!,

cent

rifug

ing

elf

was

not

suffi

cien

tsi

nce

afil

mof

Ac

2~C

2O4!

3re

mai

ned

the

supe

rnat

ant

surf

ace.

The

sam

ples

wer

eta

ken

thro

ugh

api

llary

fille

dw

ithfin

egl

ass

fiber

byus

ing

am

icro

pum

p,in

to1

ml1

mol

dm2

3H

NO

3af

ter

whi

chth

epi

pette

was

was

hed

seve

ralt

imes

with

this

solu

tion.

Sou

rce

and

purit

yof

227 A

cpr

epar

atio

nan

dof

chem

ical

sus

edno

tsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!S

olub

ility

:In

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e

Ref

eren

ces:

1 R.V

.Bry

zgal

ova

and

N.V

.Che

rnits

kaya

,Rad

iokh

imiy

a3,

478

~196

1!.


. Phys. Chem. Ref. Data, Vol. 30, No. 2, 2001

3.T

heS

olub

ility

ofA

ctin

ium

Com

poun

ds

3.1.

Act

iniu

mO

xala

te

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Dia

ctin

ium

tris~

oxal

ate!;

Ac 2

~C2O

4!3;

@726

4-35

-9#~2

!W

ater

,H 2

O;

@773

2-18

-5#D

.M

.Z

ivan

dI.

A.

She

stak

ova,

Rad

iokh

imiy

a7,16

6–

75~1

965!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:294

J.H

alaan

dJ.

D.

Nav

ratil

Exp

erim

enta

lDat

a

Sol

ubili

tyat

21°C

ofA

c 2~C

2O4!

3in

wat

era

Met

hod

Ac31

a

~mg

dm2

3 !A

c31b

106

mol

dm2

3A

c 2~C

2O4!

3

(106

c 1/m

oldm

23 !

1027

Ksp0

c

~mol

5dm

215

!10

27K

sp0d

~mol

5dm

215

!

Mic

ro0.

863.

861.

902.

702.

67

Ultr

amic

ro1.

56.

63.

342

.04.

22

Ultr

amic

ro1.

77.

53.

780

.07.

69

a The

com

posi

tion

ofth

eeq

uilib

rium

solid

phas

esw

asno

tre

port

ed.

b The

auth

ors

did

not

com

men

ton

the

diffe

renc

esin

resu

ltsob

tain

edby

the

two

met

hods

used

.c C

alcu

late

dby

the

auth

ors

asKsp0

5@A

c31#2 @

C2O

422#3 .

Inso

lutio

nsof

Ac 2~

C2O

4!3

inw

ater

the

auth

ors

assu

med

the

C2O

422co

ncen

trat

ion

tobe

equa

lto

thre

etim

esth

eex

perim

enta

llyfo

und

conc

entr

atio

nof

Ac

2~C

2O4!

3,an

dg

65

1.0.

d Cal

cula

ted

byco

mpi

ler

acco

rdin

gto

the

proc

edur

eou

tline

din

foot

note

,c.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Tw

ova

riatio

nsof

the

isot

herm

alm

etho

dw

ere

used

.F

orul

tram

icro

scal

em

easu

rem

ents

,30mg

~;2

mC

i!of

227 A

cw

asdi

ssol

ved

in0.

01m

l1.5

mol

dm23

HN

O3

and

prec

ipita

ted

with

0.25

mol

dm2

3~N

H4!

2C2O

4in

aw

orki

ngco

ne~v

olum

eof

10–

30m

l!un

der

am

icro

scop

e.A

fter1

hof

stand

ing

the

prec

ipita

tew

asce

ntrif

uged

,m

othe

rliq

uor

rem

oved

,re

peat

edly

was

hed,

cove

red

with

H 2O,

and

stirr

edfo

r10

–15

hin

ave

ssel

fille

dw

ithw

ater

orgl

ycer

ine

into

whi

chan

ultr

athe

rmoc

oupl

ew

aslo

wer

edto

mon

itor

the

tem

pera

ture

.T

his

stirr

ing

time

was

assu

med

tobe

suffi

cien

tto

reac

heq

uilib

rium

,by

anal

ogy

toa

sim

ilar

stud

yof

La~I

II!

oxal

ate,1

and

also

was

suita

ble

from

the

poin

tof

view

ofra

diol

ysis

effe

cts~for

equi

libra

tion

times

Sou

rce

and

purit

yof

227 A

cpr

epar

atio

nan

dof

chem

ical

sus

edno

tsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e

Ref

eren

ces:

1 R.V

.Bry

zgal

ova

and

N.V

.Che

rnits

kaya

,Rad

iokh

imiy

a3,

478

~196

1!.

Co

~1!

~2!

~3!

Va

T/

c 2 (c a T b C K c T w Me

Iso

pr ~N wa

so sti

an sa its on ca

J

onth

esu

pern

atan

tsu

rfac

e.T

hesa

mpl

esw

ere

take

nth

roug

ha

capi

llary

fille

dw

ithfin

egl

ass

fiber

byus

ing

am

icro

pum

p,in

to1

ml1

mol

dm2

3 HN

O3

afte

rw

hich

the

pipe

ttew

asw

ashe

dse

vera

ltim

esw

ithth

isso

lutio

n.

~196

1!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Dia

ctin

ium

tris~

oxal

ate!;

Ac 2

~C2O

4!3;

@726

4-35

-9#O

xalic

acid

;C 2

H2O

4;@1

44-6

2-7#

Nitr

icac

id;

HN

O3;

@769

7-37

-2#W

ater

;H 2

O;

@773

2-18

-5#

M.

L.S

alut

sky

and

H.

W.

Kirb

y,A

nal.

Che

m.28

,17

80–

2~1

956!

.

riabl

es:

Pre

pare

dby

:

/mol

dm2

3 :0.2

5/m

oldm

23 :0

.1J.

Hala

and

J.D

.N

avra

til

Exp

erim

enta

lDat

ao

mea

sure

men

tsw

ere

mad

eat

anun

spec

ified

room

tem

pera

ture

.T

hetw

ova

lues

ofac

tiniu

mco

ncen

trat

ion

inso

lutio

nof

0.25

ldm

23

oxal

icac

idan

dap

prox

imat

ely

0.1

mol

dm23

HN

O3

(pH

51.

2)sa

tura

ted

with

actin

ium

oxal

ate

wer

e0.

0149

and

0.01

58m

g/m

l.T

hese

wer

ere

calc

ulat

edby

the

com

pile

rsto

the

solu

bilit

yof

Ac

2~C

2O4!

3as

0.01

79an

d0.

0190

mg

Ac

2~C

2O4!

3/m

lor

3.28

102

5an

d3.

483

102

5m

oldm

23 .

The

aver

age

solu

bilit

yis

thenc

15

3.43

102

5m

oldm

23 .

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

eso

lubi

lity

data

wer

eob

tain

edfr

omth

em

ass

bala

nce

ring

the

prep

arat

ive

wor

kon

carr

ier

free

prec

ipita

tion

ofcr

ocon

cent

ratio

ns~7

mg

or0.

5m

Ci/m

L!of

227 A

c.A

fter

opr

ecip

itatio

nsw

ithdi

met

hylo

xala

te,

actin

ium

oxal

ate

was

rred

at60

–70

°Cfo

r30

min

,th

enfo

ran

addi

tiona

l90

min

anun

spec

ified

room

tem

pera

ture

,an

dfil

tere

d.T

hefil

trat

esre

anal

yzed

radi

oche

mic

ally

for

227 A

c.1

227 T

hw

asre

mov

eddo

uble

thor

ium

ioda

tepr

ecip

itatio

n,th

en223 R

aw

asm

oved

bydo

uble

prec

ipita

tion

ofB

a~N

O3!

2in

80%

HN

O 3.

iquo

tsof

the

solu

tion

cont

aini

ngth

efr

eshl

ypu

rified

tiniu

mw

ere

mou

nted

onst

ainl

ess

stee

ldis

ksan

da

-cou

nted

1da

yor

mor

eaf

ter

purifi

catio

n.T

heco

unts

wer

eco

rrec

ted

the

grow

thof

the

actin

ium

deca

ypr

oduc

ts.

Mac

roco

ncen

trat

ions

of22

7 Ac

wer

epr

epar

edby

neut

ron

irrad

iatio

nof

radi

um.F

rom

the

actin

ium

frac

tion

obta

ined

byio

nex

chan

geon

Dow

ex50

resi

n,ac

tiniu

mox

alat

ew

aspr

epar

edby

doub

leho

mog

eneo

uspr

ecip

itatio

nw

ithdi

met

hylo

xala

teat

60–

70°C

.D

imet

hylo

xala

tew

asre

crys

talli

zed

from

met

hano

l.

Est

imat

edE

rror

:S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 H.

W.

Kirb

y,U

.S.A

.E.C

.R

epor

tM

LM-7

73,

1952

.

540540 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Dia

ctin

ium

tris~

oxal

ate!;

Ac 2

~C2O

4!3;

@726

4-35

-9#~2

!N

itric

acid

;H

NO

3;

@769

7-37

-2#~3

!W

ater

;H 2

O;

@773

2-18

-5#

D.

M.

Ziv

and

I.A

.S

hest

akov

a,R

adio

khim

iya7,

166

–75

~196

5!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:294

J.H

alaan

dJ.

D.

Nav

ratil

Exp

erim

enta

lDat

a

Fou

rm

easu

rem

ents

for

the

solu

bilit

yof

Ac

2~C

2O4!

3in

0.01

mol

dm2

3H

NO

3at

21°C

a

Ac31

~mg

dm2

3 !A

c31

(104

mol

dm2

3 !A

c 2~C

2O4!

3

(105

c 1/m

oldm

23 )

Ksp

d

(1026

mol

5dm

215

!C

2O422

(106

mol

dm2

3 )K

sp0e

(1027

mol

5dm

215

!

41.0

b1.

89.

014

.81.

667.

5

40.0

c1.

768.

813

.21.

626.

7

34.0

c1.

507.

54.

21.

232.

1

30.0

c1.

36.

52.

961.

21.

5

a The

com

posi

tion

ofth

eeq

uilib

rium

solid

phas

esw

asno

tre

port

ed.

b pH5

1.85

.c pH

52.

00.

d Cal

cula

ted

byau

thor

sasK

sp5

@Ac3

1#2

@C2O

422#3

.T

otal

oxal

ate

conc

entr

atio

nin

the

satu

rate

dso

lutio

nsw

asas

sum

edto

beeq

ualt

oth

ree

times

the

expe

rimen

tally

foun

dco

ncen

trat

ion

ofA

c2~

C2O

4!3.

The

equi

libriu

mco

ncen

trat

ion

ofC 2O

422w

asth

enca

lcul

ated

byus

ing

the

diss

ocia

tion

cons

tant

sof

oxal

icac

id,

Ka1

55.

9310

22

mol

dm2

3an

dK

a25

6.43

102

5m

oldm

23

~sou

rce

not

repo

rted!,

and

the

expe

ri-m

enta

llyde

term

ined

pH.

e Cal

cula

ted

byth

eau

thor

sby

taki

ngg6

50.

55as

the

mea

nio

nic

activ

ityco

effic

ient

ofA

c2~

C2O

4!3.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

don

mic

rosc

ale

was

used

.A

c2~

C2O

4!3

was

prec

ipita

ted

from

HN

O 3so

lutio

nw

ithsa

tura

ted

solu

tion

of~N

H4!

2C2O

4.T

hepr

ecip

itate

was

cent

rifug

edan

dre

peat

edly

was

hed

and

cove

red

with

oxal

icac

idso

lutio

nin

whi

chth

eso

lubi

lity

was

tobe

dete

rmin

ed,

and

stirr

edfo

r10

–15

h.T

his

stirr

ing

time

was

take

nas

suffi

cien

tto

reac

heq

uilib

rium

,by

anal

ogy

toa

sim

ilar

stud

yof

La~III

!ox

alat

e.1T

opr

epar

esa

mpl

esfo

r227 A

cco

untin

g~e

man

atio

nm

etho

d!,ce

ntrif

ugin

gits

elf

was

not

suffi

cien

tsi

nce

afil

mof

Ac

2~C

2O4!

3re

mai

ned

Sou

rce

and

purit

yof22

7 Ac

prep

arat

ion

and

ofch

emic

als

used

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 R.V

.Bry

zgal

ova

and

N.V

.Che

rnits

kaya

,Rad

iokh

imiy

a3,

478

Co

~1!

~2!

~3!

~4!

Va

c 2 c 3 Tw

mo

Ac

3 Me

Th

du ma

tw sti

at we

by re Al

ac for

for


purit

yw

asch

ecke

dby

mea

surin

gits

half-

life

and

max

imum

beta

ener

gy.

Th~N

O3!

4w

aspu

rified

from

beta

activ

ede

cay

prod

ucts

ofT

hBby

copr

ecip

itatio

nw

ithle

adsu

lfide

.S

ourc

eof

mat

eria

lsus

edno

tsp

ecifi

ed.

NaC

lO 4w

asa

chem

ical

lypu

repr

oduc

t,an

dw

asre

crys

talli

zed

from

wat

er.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

05K

~aut

hors!

Sol

ubili

ty:

prec

isio

nof

the

radi

omet

ricm

etho

d6~2

–3%

!~a

utho

rs!.

Ref

eren

ces:

1 G.

T.

Sea

borg

,E

dito

r,Th

eA

ctin

ide

s~R

ussi

antr

ansl

atio

n!~I

nizd

at,

Mos

cow

,19

95!,

p.45

4.2 T

.S

ollm

ann

and

E.

D.

Bro

wn,

Am

.J.

Phy

s.18,

427

~190

7!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

oxoc

arbo

nate

;T

hOC

O 3;@

#S

odiu

mca

rbon

ate;

Na

2CO

3;@4

97-1

9-8#

Sod

ium

perc

hlor

ate;

NaC

lO 4;@7

601-

89-0#

Wat

er;

H 2O

;@7

732-

18-5#

O.

I.Z

akha

rov

and

G.

G.

Mik

hailo

v,Iz

v.V

UZ

Khi

m.

Khi

m.

Tek

hnol

.3,

No.

1,45

–8~

1960

!.

riabl

es:

Pre

pare

dby

:

K:

293

/mol

dm2

3 :0–

0.97

atco

nsta

ntio

nic

stre

ngth

of3.

00ld

m2

3

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofT

hOC

O 3in

Na 2

CO

3–

NaC

lO4

solu

tions

a

Na 2

CO

3

2/m

oldm

23 )

Th

~Mg

L2

1 !T

hOC

O 3(1

02m

oldm

23 )b

Sol

idph

asec

025

.30.

0109

ThO

CO 3•

8H2O

,@

#

0.00

760

.20.

0259

-

0.01

424

20.

1043

Th:

CO 25

1.0:

1.5

0.02

358

50.

252

Th:

CO 25

1.0:

1.8

0.03

110

000.

431

Th:

CO 25

1.0:

1.99

0.04

415

600.

672

Th:

CO 25

1.0:

2.16

0.07

725

601.

10-

0.09

128

101.

21-

0.14

638

001.

64d

0.16

147

302.

04d

0.19

151

502.

22d

0.20

957

702.

49d

0.27

266

602.

87d

0.37

583

703.

61d

0.41

591

203.

93d

0.54

1055

04.

55d

0.74

1120

04.

83d

0.97

1317

05.

68d

nic

stre

ngth

kept

cons

tant

at3.

00m

oldm2

3by

usin

gN

aClO 4

.al

cula

ted

byco

mpi

ler.

c Res

ults

base

don

two

orth

ree

anal

yses

inea

chm

easu

rem

ent.

d The

solid

phas

esh

owed

the

Na:

Th:

CO

3:H

2Ora

tioof

6:1:

5:12

.T

heau

thor

ssu

gges

ted

thre

epo

ssib

lefo

rmul

asfo

rit,

i.e.,

Na 6

Th~

CO

3!5•

12H

2O,

Na 4

Th~

CO

3!4•

Na 2

CO

3•12

H2O

,an

dN

a 2Th~

CO

3!3•

2Na 2

CO

3•12

H2O

.O

fth

ese

they

pref

erre

dth

ela

ston

ew

ithco

ordi

natio

nnu

mbe

rof

6fo

rth

oriu

m~IV

!.S

ince

the

Th~C

O3!

562io

nis

aw

elle

stab

lishe

dsp

ecie

s,3

the

com

pile

rte

ntat

ivel

ysu

gges

tsth

eN

a 6T

h~C

O3!

5•12

H2O

@123

86-4

7-9#

asa

mor

epr

obab

leso

lidph

ase.



4.T

heS

olub

ility

ofT

horiu

mC

ompo

unds

4.1.

Tho

rium

Oxo

carb

onat

e

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

oxoc

arbo

nate

;T

hOC

O 3;

@#

~2!

Sod

ium

perc

hlor

ate;

NaC

lO 4;

@760

1-89

-0#~3

!W

ater

;H 2

O;

@773

2-18

-5#

O.

I.Z

akha

rov

and

G.

G.

Mik

hailo

v,Iz

v.V

UZ

Khi

m.

Khi

m.

Tek

hnol

.3,

No.

1,45

–8~

1960

!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

3c 2

/mol

dm2

3 :0

and

3J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofT

hOC

O 3in

wat

eran

d3.

0m

oldm

23

NaC

lO4

NaC

lO4

(c2

/mol

dm2

3 )T

hOC

O 3~m

gL2

1 !T

hOC

O 3(1

05c 1

/mol

dm2

3 )N

aClO

4

(c2

/mol

dm2

3 )T

hOC

O 3~m

gL2

1 !T

hOC

O 3(1

05c 1

/mol

dm2

3 )

022

.13.

000

25.9

23.0

23.6

21.2

25.3

22.1

61.

1a7.

17b

24.9

61.

2a8.

08

a Ave

rage

valu

e~au

thor

s!.b C

alcu

late

dby

com

pile

rfo

rth

eav

erag

eva

lue.

Add

ition

alin

form

atio

n:S

olub

ility

prod

uct

ofT

hOC

O 3w

asca

lcul

ated

byth

eau

thor

sasK

sp05

@ThO

21#@

CO

322#5

93

102

9m

ol2

dm2

6as

sum

ing

unit

activ

ityco

effic

ient

s.S

olid

phas

esw

ere

not

inve

stig

ated

but

base

don

mea

sure

men

tsin

the

ThO

CO

3–

Na 2

CO

3–

NaC

lO4–

H2O

syst

emin

the

sam

edo

cum

ent,

com

pile

ras

sum

esth

isto

beT

hOC

O3•

8H2O

,@

#.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

solid

was

equi

libra

ted

for

3–

10h

ina

ther

mos

tat.

Fre

shly

prep

ared

solid

was

used

sinc

eth

eso

lubi

lity

ofT

hOC

O 3w

asfo

und

tobe

som

ewha

tde

pend

ent

onth

eag

eof

the

prod

uct.

Sat

urat

edso

lutio

nsw

ere

anal

yzed

radi

omet

rical

lyfo

rth

oriu

m.

ThO

CO 3•8H

2Ow

aspr

epar

edby

prec

ipita

tion

ofT

h~N

O3!

4

solu

tion

labe

led

with

UX 1

~234 T

h!,

with

aneq

uiva

lent

amou

ntof

Na 2

CO

3so

lutio

n.1

The

prec

ipita

tew

asw

ashe

dw

ithw

ater

and

air

drie

d.A

naly

sis

~mas

s%!

:fo

und

57.5

ThO

2,10

.4C

O 2,

32.4

H 2O

,ca

lcul

ated

for

octa

hydr

ate~c

ompi

ler!

58.3

9T

hO2,

9.73

CO 2

,31

.87

H 2O

.U

X1

was

prep

ared

from

aged

uran

ium

salts

acco

rdin

gto

Sol

lman

nan

dB

row

n,2

and

itsra

dioc

hem

ical

Co

~1!

~2!

~3!

~4!

Va

T/

c 2 mo

(c a Io b C

J

4.2.

Sal

tsof

Pen

taki

s„ca

rbon

ato…

Tho

rate

„6-…

Eva

luat

ion

ofth

eN

a 6T

h„C

O3…

5¿N

a 2C

O3¿

H2O

Sys

tem

mpo

nent

s:E

valu

ator

:

Hex

asod

ium

pent

akis~c

arbo

nato!

thor

ate;

Na 6T

h~C

O3!

5;96

10-6

2-9#

Sod

ium

carb

onat

e;N

a2C

O3;

@497

-19-

8#W

ater

;H 2

O;

@773

2-18

-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try

Mas

aryk

Uni

vers

ity,

611

37B

rno,

Cze

chR

epub

lic,

Feb

ruar

y20

00

Crit

ical

Eva

luat

ion

The

solu

bilit

yin

this

syst

emw

asre

port

edin

two

docu

men

ts.

1,2

Con

side

rabl

edi

scre

panc

ies

betw

een

the

two

sets

ofda

ta,

exce

edin

gse

whi

chco

uld

bedu

eto

diffe

rent

cond

ition

s~i.

e.,

ioni

cst

reng

th,

rang

eof

Na

2CO

3co

ncen

trat

ion!

used

,ar

eob

viou

s.Lu

zhna

yaan

dva

leva

1re

port

edth

eso

lubi

lity

at29

8.15

Kof

Na

6Th~

CO

3!5

asa

func

tion

ofso

dium

carb

onat

eco

ncen

trat

ion

abov

e0.

78m

oldm

23

2CO

3.In

this

conc

entr

atio

nra

nge,

the

solu

bilit

yof

the

salt

was

repo

rted

tode

crea

sew

ithin

crea

sing

Na

2CO

3co

ncen

trat

ion~

the

auth

ors

reun

able

tom

easu

reth

eso

lubi

lity

atlo

wer

Na

2CO

3co

ncen

trat

ions

beca

use

ofhy

drol

ysis

ofN

a6T

h~C

O3!

5!.

On

the

cont

rary

,D

ervi

nd

Fau

cher

re2re

port

edth

eso

lubi

lity

ofN

a 6Th~

CO

3!5

toin

crea

sew

ithin

crea

sing

Na

2CO

3co

ncen

trat

ion

abov

e0.

4m

oldm2

3N

a 2C

O3

dex

plai

ned

the

data

byth

efo

rmat

ion

ofth

eT

h~C

O3!

682io

nin

solu

tion.

At

Na 2C

O3

conc

entr

atio

nbe

low

0.4

mol

dm23

and

atio

nic

engt

hof

2.0

mol

dm2

3 ,th

eso

lubi

lity

ofN

a 6Th~

CO

3!5

was

repo

rted

tobe

inde

pend

ent

onN

a2C

O3

conc

entr

atio

n.S

ince

ther

edo

esno

tem

tobe

any

obvi

ous

reas

onfo

rgi

ving

pref

eren

ceto

one

set

ofda

taov

erth

eot

her,

rein

vest

igat

ion

ofth

issy

stem

wou

ldbe

need

edfo

rea

final

conc

lusi

onab

out

the

solu

bilit

yof

Na

6Th~

CO

3!5

inaq

ueou

sN

a 2CO

3so

lutio

nsco

uld

bem

ade.

fere

nces

:

.P

.Lu

zhna

yaan

dI.

S.

Kov

alev

a,Z

h.N

eorg

.K

him

.6,

1440

~196

1!.

.D

ervi

nan

dJ.

Fau

cher

re,

Bul

l.S

oc.

Chi

m.

Fra

nce,

2930

~197

3!.

542542 JIRI HALA

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

solid

was

equi

libra

ted

for

3–

10h

ina

ther

mos

tat.

Fre

shly

prep

ared

solid

was

used

sinc

eth

eso

lubi

lity

ofT

hOC

O 3w

asfo

und

tobe

som

ewha

tde

pend

ent

onth

eag

eof

the

prod

uct.

The

solid

was

equi

libra

ted

with

NaC

lO 4/N

a 2C

O3

solu

tions

atco

nsta

ntio

nic

stre

ngth

of3.

0m

oldm

23 .

Sat

urat

edso

lutio

nsw

ere

anal

yzed

for

thor

ium

eith

erra

diom

etric

ally

orgr

avim

etric

ally

,de

pend

ing

onth

oriu

mco

ncen

trat

ion,

and

for

carb

onat

etit

rimet

rical

lyus

ing

ast

anda

rdH

Cls

olut

ion.

Sol

idph

ases

wer

ean

alyz

edfo

rw

ater

and

carb

ondi

oxid

egr

avim

etric

ally

durin

gth

erm

alde

com

posi

tion,

and

inth

ere

sidu

eN

a2C

O3

was

dete

rmin

edtit

rimet

rical

lyan

dth

oriu

mgr

avim

etric

ally

.

ThO

CO 3•8H

2Ow

aspr

epar

edby

prec

ipita

tion

ofT

h~N

O3!

4

solu

tion

labe

led

with

UX 1

~234 T

h!,

with

aneq

uiva

lent

amou

ntof

Na 2

CO

3so

lutio

n.1

The

prec

ipita

tew

asw

ashe

dw

ithw

ater

and

air

drie

d.A

naly

sis

~mas

s%!

:fo

und

57.5

ThO

2,10

.4C

O 2,

32.4

H 2O

,ca

lcul

ated

for

octa

hydr

ate~c

ompi

ler!

58.3

9T

hO2,

9.73

CO 2

,31

.87

H 2O

.U

X1

was

prep

ared

from

aged

uran

ium

salts

acco

rdin

gto

Sol

lman

nan

dB

row

n,2

and

itsra

dioc

hem

ical

purit

yw

asch

ecke

dby

mea

surin

gha

lf-lif

ean

dm

axim

umbe

taen

ergy

.T

h~NO

3!4

was

purifi

edfr

ombe

taac

tive

deca

ypr

oduc

tsof

ThB

byco

prec

ipita

tion

with

lead

sulfi

de.

Sou

rce

ofm

ater

ials

used

not

spec

ified

.S

odiu

msa

ltsus

edw

ere

chem

ical

lypu

repr

oduc

ts,

and

wer

ere

crys

talli

zed

from

wat

er.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

05K

~aut

hors!

.R

adio

met

ricm

etho

d:pr

ecis

ion6

~2–

3!%

~aut

hors!

.

Ref

eren

ces:

1 G.

T.

Sea

borg

,E

dito

r,Th

eA

ctin

ide

s~R

ussi

antr

ansl

atio

n!~I

nizd

at,

Mos

cow

,19

95!,

p.45

4.2 T

.S

ollm

ann

and

E.

D.

Bro

wn,

Am

.J.

Phy

s.18,

427

~190

7!.

3 J.D

ervi

nan

dJ.

Fau

cher

re,

Bul

l.S

oc.

Chi

m.

Fra

nce,

2930

~197

3!.

Co

~1!

@1 ~2!

~3!

tho

Ko

Na

we

an an str

se be Re

1 N 2 J


Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Mix

ture

sw

ere

equi

libra

ted

ina

ther

mos

tate

dba

thfo

r2

days

whi

chw

assu

ffici

ent

tore

ach

equi

libriu

m.

Sam

ples

ofth

esa

tura

ted

solu

tions

and

the

solid

phas

esw

ere

anal

yzed

grav

imet

rical

lyfo

rth

oriu

m,

sodi

uman

dca

rbon

ate.

Tho

rium

was

dete

rmin

edas

ThO

2an

dso

dium

asN

a 2S

O4.

To

dete

rmin

eca

rbon

ate,

the

sam

ple

was

reac

ted

with

dilu

teH

Cla

ndth

eca

rbon

diox

ide

evol

ved

was

abso

rbed

ina

wei

ghed

Utu

befil

led

with

asca

rite.

Sol

idph

ases

wer

eal

soch

arac

teriz

edby

the

met

hod

ofw

etre

sidu

es,

x-ra

ydi

ffrac

tion

and

ther

mal

anal

ysis

.

Sou

rce,

purit

y,or

met

hod

ofpr

epar

atio

nof

Na

6Th~

CO

3!5

was

not

spec

ified

.N

a 2CO

3w

aspr

epar

edfr

omre

agen

tgr

ade

deca

hydr

ate~s

ourc

eno

tsp

ecifi

ed!by

heat

ing

itin

asi

lver

dish

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

wer

egi

ven

toal

low

for

erro

res

timat

e.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Hex

asod

ium

pent

akis~c

arbo

nato!

thor

ate;

Na 6T

h~C

O3!

5;96

10-6

2-9#

Sod

ium

carb

onat

e;N

a2C

O3;

@497

-19-

8#or

Sod

ium

drog

enca

rbon

ate;

NaH

CO

3;@1

44-5

5-8#

Wat

er;

H 2O

;@7

732-

18-5#

J.D

ervi

nan

dJ.

Fau

cher

re,B

ull.

Soc

.Chi

m.F

ranc

ept

.1,2

930

–3

~197

3!.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

dm2

3 :0.

15–

1.0~

Na 2

CO

3or

NaH

CO 3

!J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

ties

at25

°Cof

Na 6T

h~C

O3!

5in

aque

ous

solu

tions

ofN

a2C

O3

orN

aHC

O 3

CO

322or

HC

O32

(c2

/mol

dm2

3 )N

a 6T

h~C

O3!

5

~mol

dm2

3 !K

spd

~mol

7dm

221

!S

olid

phas

e

O322

#,0,

4a,b,

e0.

0215

1.37

Na 6T

h~C

O3!

5•12

H2O

CO

32#5

0.15

–1.

0a,c

0.02

08f

1.34

not

repo

rted

olut

ions

cont

aine

dco

nsta

ntco

ncen

trat

ion

ofN

a1

ions

of2.

0m

oldm

23 .

olut

ions

ofN

a 2CO

3.ol

utio

nsof

NaH

CO 3

.

sp5

@Th~

CO

3!562

#@N

a1#6 .

thig

her

carb

onat

eio

nco

ncen

trat

ion

the

solu

bilit

yof

Na

6Th~

CO

3!5

incr

ease

d~re

sults

wer

epr

esen

ted

ingr

aphi

calf

orm

only

!w

hich

was

terp

rete

dby

the

auth

ors

asbe

ing

due

toth

efo

rmat

ion

ofth

eT

h~C

O3!

682io

nin

the

satu

rate

dso

lutio

n.bt

aine

dby

auth

ors

asth

eav

erag

eof

eigh

tm

easu

rem

ents

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

xces

sso

lidw

aseq

uilib

rate

dfo

r48

with

Na 2

CO

3or

NaH

CO 3

solu

tions

ofco

nsta

ntN

a1io

nnc

entr

atio

nin

poly

ethy

lene

bottl

es.

The

salt

used

toin

tain

Na1

conc

entr

atio

nat

the

cons

tant

valu

ew

asno

tec

ified

.A

fter

equi

libra

tion,

thor

ium

was

dete

rmin

edin

the

tura

ted

solu

tions

titrim

etric

ally

with

ED

TA

.T

heeq

uilib

rium

lidph

ases

wer

ean

alyz

edto

asce

rtai

nth

atth

eir

com

posi

tion

not

chan

gedu

ring

equi

libra

tion.

Na 6

Th~

CO

3!5

was

prep

ared

bycr

ysta

lliza

tion

from

1m

oldm2

3T

h~N

O3!

4on

addi

tion

ofN

a 2CO

3so

lutio

nac

cord

ing

toD

ervi

ne

ta

l.1C

ompi

ler

assu

mes

that

Na

6Th~

CO

3!5•

12H

2Ow

aspr

epar

ed.S

ourc

ean

dpu

rity

ofm

ater

ials

used

wer

eno

tspe

cifie

d.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 J.D

ervi

n,J.

Fau

cher

re,

P.

Her

pin,

and

S.

Vol

itois

,B

ull.

Soc

.C

him

.F

ranc

e26

34~1

973!

.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Hex

asod

ium

pent

akis~c

arbo

nato!

thor

ate;

Na 6T

h~C

O3!

5;@1

9610

-62-

9#~2

!S

odiu

mca

rbon

ate;

Na

2CO

3;@4

97-1

9-8#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

N.P

.Luz

hnay

aan

dI.

S.K

oval

eva,

Zh.

Neo

rg.K

him

.6,

1440

–2

~196

1!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

810

2w

2/m

ass

%:7

.60

–22

.97

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

ty25

°Cof

Na 6

Th~

CO

3!5

inN

a 2C

O3

solu

tions

Na 2

CO

3

~mas

s%!

Na 2

CO

3

~mol

kg2

1 !aN

a 2C

O3

~mol

dm2

3 !aT

h~C

O3!

2

~mas

s%!

Th~

CO

3!2

~mol

kg2

1 !aT

h~C

O3!

2

~mol

dm2

3 !aD

ensi

ty~g

cm2

3 !S

olid

phas

eb

7.60

0.78

020.

7887

2.20

0.06

928

0.07

412

1.09

60A

8.59

0.89

020.

8984

2.05

0.06

517

0.07

047

1.10

62A

10.8

81.

152

1.15

71.

640.

0532

50.

0590

31.

1293

A

14.5

71.

604

1.59

51.

340.

0452

70.

0519

91.

1668

A

18.6

72.

155

2.11

41.

090.

0385

90.

0460

31.

2090

A

20.0

22.

347

2.31

01.

010.

0363

30.

0442

51.

2336

A

22.8

12.

767

2.67

60.

860.

0320

00.

0397

51.

2562

A1

B

22.9

72.

796

2.69

80.

960.

0358

50.

0444

71.

2561

A1

B

22.7

02.

750

2.66

40.

860.

0319

60.

0397

01.

2562

A1

B

22.6

02.

723

2.63

10.

530.

0195

90.

0243

31.

2503

A

22.5

52.

709

2.61

70.

380.

0140

10.

0174

11.

2488

B

22.7

72.

730

2.62

1—

——

1.24

33B

a Cal

cula

ted

byco

mpi

ler.

b A:N

a 6T

h~C

O3!

5•12

H2O

;@1

2386

-47-

9#B

:Na 2

CO

3•10

H2O

@613

2-02

-1#.

Add

ition

alin

form

atio

n:T

heso

lubi

lity

bran

chco

rres

pond

ing

toth

ecr

ysta

lliza

tion

ofN

a6T

h~C

O3!

5•12

H2O

was

stud

ied

only

upto

2.20

mas

s%

Th

~CO

3!2

~i.e.

,at

Na 2

CO

3co

ncen

trat

ions

.7.

60m

ass

%!si

nce

the

salt

hydr

olyz

edat

high

erth

oriu

mco

ncen

trat

ions

.T

heph

ase

diag

ram

show

edon

etr

iple

poin

tat

22.8

3m

ass

%N

a2C

O31

0.86

mas

s%

Th~C

O3!

2w

ithA

and

Bas

the

coex

istin

gso

lidph

ases

.

Aux

iliar

yIn

form

atio

n

Co

~1!

@1 ~2!

hy ~3!

Va

T/

c 2 @C @H a S b S c S d K e A in f O Me

Iso

h co ma

sp sa so did

J

did

not

chan

gedu

ring

equi

libra

tion.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 J.D

ervi

n,J.

Fau

cher

re,

P.

Her

pin,

and

S.

Vol

itois

,B

ull.

Soc

.C

him

.F

ranc

e26

34~1

973!

.

4.3.

Gua

nidi

nium

Tris

fluor

otris

„ca

rbon

ato…

Tho

rate

„6-…

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pen

tagu

anid

iniu

mtr

is~fluo

ro!-

tris

~car

bona

to!th

orat

e;H

6N3!

5ThF

3~C

O3!

3;@5

5328

-36-

4#G

uani

dini

umca

rbon

ate;

(CH 6N

3!2C

O3;

@593

-85-

1#G

uani

dini

umflu

orid

e;C

H 6N3F

;@3

8078

-70-

5#W

ater

;H 2

O;

@773

2-18

-5#

J.D

ervi

nan

dF

.F

rom

age,

Bul

l.S

oc.

Chi

m.

Fra

nce

pt.

1,13

3–

7~1

975!

.

riabl

es:

Pre

pare

dby

:

K:

293

/mol

dm2

3 :0.

05–

0.30

/mol

dm2

3 :0.

03–

0.30

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

of(C

H 6N

3!5T

hF3~

CO

3!3

inaq

ueou

sso

lutio

nsof

guan

idin

ium

carb

onat

ean

dgu

anid

iniu

mflu

orid

ea

CO

322

~mol

dm2

3 !F2

~mol

dm2

3 !(C

H6N

3!3T

hF3~

CO

3!3

~mol

dm2

3 !

0.30

b0.

25–

0.30

b0.

0032

d

0.05

–0.

30c

0.30

c0.

032d

olid

phas

ew

as(C

H 6N3!

6Th~

CO

3!5

@553

28-3

6-4#.

olut

ions

cont

aini

ngva

ryin

gflu

orid

eio

nco

ncen

trat

ion

and

cons

tant

guan

idin

ium

ion

conc

entr

atio

nof

1.0

mol

dm2

3at

cons

tant

ioni

ctr

engt

hof

1.3

mol

dm2

3 .ol

utio

nsco

ntai

ning

vary

ing

carb

onat

eio

nco

ncen

trat

ion

and

cons

tant

guan

idin

ium

ion

conc

entr

atio

nof

1.0

mol

dm2

3 .Io

nic

stre

ngth

ried

from

1.0

to1.

3m

oldm

23 .

heeq

uilib

rium

solid

phas

ew

asno

tst

ated

expl

icitl

y.T

heco

mpi

ler

assu

mes

this

tobe

(CH

6N3!

3ThF

3~C

O3!

3.A

tth

eco

ncen

trat

ions

ofO

322an

dF2

ions

used

,th

eso

lidph

ase

was

ineq

uilib

rium

with

the

ThF

3~C

O3!

352io

n.A

tflu

orid

eio

nco

ncen

trat

ions,

0.20

mol

dm2

3 ,e

solu

bilit

yof

(CH 6

N3!

3ThF

3~C

O3!

3de

crea

sed

toth

atof

(CH 6N

3!6T

h~C

O3!

5~D

ervi

nan

dF

auch

erre1 !

due

toth

etr

ansf

orm

atio

nof

the

hF3~

CO

3!352

ion

toT

h~C

O3!

562.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

xces

sso

lidw

aseq

uilib

rate

dfo

r36

with

solu

tions

cont

aini

ngde

sire

dco

ncen

trat

ions

ofan

idin

ium

carb

onat

ean

dflu

orid

e.T

hesu

spen

sion

was

ntrif

uged

and

filte

red,

and

the

solid

resi

due

was

anal

yzed

toce

rtai

nth

atits

com

posi

tion

did

not

chan

gedu

ring

uilib

ratio

n.In

the

satu

rate

dso

lutio

nsth

oriu

mw

asde

term

ined

grav

imet

rical

lyas

ThO 2

afte

rev

apor

atio

nof

the

solu

tion

and

igni

tion

the

resi

due

to80

0°C

.

(CH

6N3!

5ThF

3~C

O3!

3w

aspr

epar

edby

prec

ipita

tion

at50

to60

°Cfr

omso

lutio

nsco

ntai

ning

1m

oldm2

3gu

anid

iniu

mio

nw

ithF2

/CO

322ra

tiova

ryin

gfr

om1

to6,

byad

ding

aco

ncen

trat

edso

lutio

nof

Th~N

O3!

4.A

naly

sis

~mas

s%!

:fo

und

30.4

Th,

7.45

F,

12.2

C,

27.5

N,

3.91

H,

17.3

CO

2;ca

lcul

ated

30.2

Th,

7.41

F,

12.5

C,

27.3

N,

3.90

H,

17.2

CO

2.S

ourc

ean

dpu

rity

ofm

ater

ials

used

was

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 J.D

ervi

nan

dJ.

Fau

cher

re,

Bul

l.S

oc.

Chi

m.

Fra

nce

2930

~197

3!.

544544 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Hex

agua

nidi

nium

pent

akis~c

arbo

nato!

thor

ate;

(CH

6N3!

6Th~

CO

3!5;

@514

07-0

2-4#

~2!

Gua

nidi

nium

carb

onat

e;(C

H 6N3!

2CO

3;@5

93-8

5-1#;

orG

uani

dini

umhy

drog

enca

rbon

ate;

(CH

6N3!

HC

O3;

@124

-46-

9#~3

!G

uani

dini

umni

trat

e;(C

H 6N3!

NO

3;@5

06-9

3-4#

~4!

Wat

er;

H 2O

;@7

732-

18-5#

J.D

ervi

nan

dJ.

Fau

cher

re,B

ull.

Soc

.Chi

m.F

ranc

ept

.1,2

930

–3

~197

3!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8c 2

/mol

dm2

3 :0.

25–

1.0~~

CH

6N3!

2CO

3);

0.20

–0.

60(C

H 6N

3!H

CO

3)

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

ties

at25

°Cof

(CH 6N

3!6T

h~C

O3!

5in

aque

ous

solu

tions

ofgu

anid

iniu

mca

rbon

ate

orgu

anid

iniu

mhy

drog

enca

rbon

ate

CO

322or

HC

O32

(c2

/mol

dm2

3 )(C

H6N

3!6T

h~C

O3!

5

~mol

dm2

3 !K

spd

~mol

7dm

221

!S

olid

phas

e

0.25

–0.

35(C

O 322)a,

b0.

0017

c0.

109

(CH 6

N3!

6Th~

CO

3!5•

4H2O

0.2

–0.

60(H

CO 32

)e0.

0015

7f0.

10no

tre

port

ed

a Gua

nidi

nium

carb

onat

eso

lutio

ns;g

uani

dini

umio

nco

ncen

trat

ion

kept

at2.

0m

oldm

23 ,i

onic

stre

ngth

varie

dfr

om2.

25to

3.0

mol

dm23 .

b At

high

erca

rbon

ate

ion

conc

entr

atio

ns,

the

solu

bilit

yof

the

salt

incr

ease

dw

ithin

crea

sing

carb

onat

eio

nco

ncen

trat

ion

~res

ults

pres

ente

din

grap

hica

lfor

mon

ly!.

The

incr

easi

ngso

lubi

lity

was

expl

aine

dB

yth

eau

thor

sas

bein

gdu

eto

the

form

atio

nof

the

Th

~CO

3!682

ion

inth

esa

tura

ted

solu

tions

.c A

vera

geva

lue

offo

urm

easu

rem

ents~aut

hors!

.d K

sp5

@Th~

CO

3!562

#@C

H6N

31#6 .

e Gua

nidi

nium

hydr

ogen

carb

onat

eso

lutio

ns;

guan

idin

ium

ion

conc

entr

atio

nan

dio

nic

stre

ngth

kept

at2.

0m

oldm

23 .

f Obt

aine

dby

auth

ors

asth

eav

erag

eof

seve

nm

easu

rem

ents

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

solid

was

equi

libra

ted

for

48h

with

guan

idin

ium

carb

onat

eor

guan

idin

ium

hydr

ogen

carb

onat

eso

lutio

nsin

poly

ethy

lene

bottl

es.

Ioni

cst

reng

thw

aske

ptat

the

desi

red

valu

eby

usin

ggu

anid

iniu

mni

trat

e.A

fter

equi

libra

tion,

thor

ium

was

dete

rmin

edin

the

satu

rate

dso

lutio

nstit

rimet

rical

lyw

ithE

DT

A.

The

equi

libriu

mso

lidph

ases

wer

ean

alyz

edto

asce

rtai

nth

atth

eir

com

posi

tion

(CH

6N3!

6Th~

CO

3!5•

4H2O

was

prep

ared

bypr

ecip

itatio

nw

ithgu

anid

iniu

mca

rbon

ate

ofa

1m

oldm

23

Th~

NO

3!4

solu

tion

acco

rdin

gto

Der

vine

ta

l.1S

ourc

ean

dpu

rity

ofm

ater

ials

used

wer

eno

tsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Co

~1!

(C ~2!

~3!

~4!

Va

T/

c 2 c 3 a S b S s c S va d T C th T Me

Iso

h gu ce as eq


4.5.

Tho

rium

For

mat

e

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

tetr

akis~

form

ate!

;T

h~H

CO

2!4;

@562

-99-

2#F

orm

icac

id;

H 2C

O2;

@64-

18-6

#W

ater

;H 2

O;@

7732

-18-

5#

B.

Cla

udel

and

B.

Men

tzen

,B

ull.

Soc

.C

him

.F

ranc

e15

47–

50~1

966!

.

riabl

es:

Pre

pare

dby

:

K:

298

J.H

ala

Exp

erim

enta

lDat

aP

hase

diag

ram

ofth

eT

h~HC

O2!

4–

H2C

O2–

H2O

~com

posi

tion

inm

ass

%!at

25°C

was

repo

rted

ingr

aphi

calf

orm~s

eeF

ig.

1!.T

hely

num

eric

alva

lue

repo

rted

was

that

ofth

eso

lubi

lity

ofT

h~H

CO

2!4

inw

ater

,i.e

.,80

.7g

Th~H

CO

2!4.

3H2O

in1

dm2

3w

ater

.T

his

was

calc

ulat

edby

the

com

pile

rtom

15

0.17

2m

olkg

21 .

FIG

.1.

Tho

rium

tetr

akis~f

orm

ate!

–fo

rmic

acid

–w

ater

syst

em.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Not

hing

spec

ified

.T

h~HC

O2!

4•3H

2Ow

aspr

epar

edby

actio

nof

hot

40%

form

icac

idon

fres

hly

prec

ipita

ted

Th~O

H! 4

.T

hesa

ltcr

ysta

llize

dup

onev

apor

atio

nor

cool

ing.

Ana

lysi

s,fo

und/

calc

ulat

ed,

for

Th~

HC

O2!

4•3H

2O~m

ass

%):

Th

49.8

2/49

.78,

HC

O 2238

.65/

38.6

3,H 2

O12

.45/

11.5

9.



4.4.

Hex

amm

inec

obal

t„III…

Pen

taki

s„ca

rbon

ato…A

qua

Tho

rate

„6-…

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Bis

~hex

amm

inec

obal

t~III

!!pe

ntac

arbo

nato

-aqu

atho

rate

;@C

o~N

H3!

6#2@

Th~

CO

3!5H

2O#;

@#

~2!

Wat

er;

H 2O

;@7

732-

18-5#

orA

ceto

ne;

C 3H

6O;

@67-

64-1

#

K.

Uen

oan

dM

.H

oshi

,J.

Inor

g.N

ucl.

Che

m.32,

3817

–22

~197

0!

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

3J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

of@C

o~N

H3!

6#2@

Th~

CO

3!5H

2O#

inw

ater

and

acet

onea

Sol

vent

Th

~mg/

100

g!so

lven

t@C

o~N

H3!

6#2@

Th~

CO

3!5H

2O#

(105

m1

/mol

kg2

1 )b

Wat

er0.

52.

15

Ace

tone

0.1

0.43

1

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.b C

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

ofdr

yth

oriu

mco

mpo

und

was

allo

wed

tost

and

inth

eso

lven

tfo

r24

h.T

heam

ount

of60

Co~

NH

3!631

inth

esa

tura

ted

solu

tion

was

dete

rmin

edra

diom

etric

ally

.

@Co~

NH

3!6#

2@T

h~C

O3!

5H2O

#w

aspr

epar

edby

prec

ipita

tion

with

60C

o~N

H3!

6Cl 3

ofth

oriu

m~I

V!

from

2m

oldm

23

(NH

4!2C

O3.

The

prec

ipita

tew

asw

ashe

dw

ithw

ater

,an

dva

cuum

drie

d.A

naly

sis

~mas

s%!

:fo

und

Th

25.0

3,C

o~NH

3!6

34.8

9,C

O3

32.4

2;ca

lcul

ated

for @

Co~

NH

3!6#

2@T

h~C

O3!

5H2O

#•3H

2O,

Th

25.0

5,C

o~NH

3!6

34.7

8,C

O 332

.39.

Tho

rium

solu

tion

used

was

purifi

edby

ion

exch

ange

and

solv

ent

extr

actio

nm

etho

ds.

Sou

rce

and

purit

yof

thor

ium

salt

used

not

spec

ified

.C

o~N

H3!

6Cl 3

was

prep

ared

acco

rdin

gto

Bilt

z.1D

istil

led

wat

eran

dre

agen

tgr

ade

acet

one

~sou

rce

not

spec

ified!

wer

eus

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

5K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 W.

Bilt

z,Z

.A

norg

.A

llgem

.C

hem

.83,

177

~191

4!

Co

~1!

~2!

~3!

Va

T/

on re

J

Th~

HC

O2!

4–

HC

O2–

H2O

syst

emre

port

edin

the

sam

edo

cum

ent

the

auth

ors

stat

edpr

ecis

ion

of60.

05K

for

tem

pera

ture

and

6~2

–3!

%fo

rth

era

diom

etric

met

hod

used

for

thor

ium

dete

rmin

atio

n.

4.6.

Tho

rium

Ace

tate

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

tetr

akis~

acet

ate!;

Th~

C2H

3O2!

4;@1

3075

-28-

0#W

ater

;H 2

O;

@773

2-18

-5#K

.N.K

oval

enko

,D.V

.Kaz

ache

nko,

and

O.N

.Sam

sono

va,Z

h.N

eorg

.K

him

8,22

22–

5~19

63!.

riabl

es:

Pre

pare

dby

:

K:

298

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofT

h~C

2H3O

2!4

at25

°Cis

repo

rted

tobe

1.5

gT

h~C

2H3O

2!4

in10

0g

wat

er~c

ompi

ler

calc

ulat

edm

1

0.03

20m

olkg

21 !

.A

dditi

onal

info

rmat

ion:

The

pHof

0.00

025

–0.

008

mol

dm23

solu

tions

ofT

h~C2H

3O2!

4va

ried

from

4.22

to3.

95.

Und

erth

eas

sum

ptio

nth

atth

ehy

drol

ysis

the

salt

proc

eede

dto

Th~O

H! 4

the

auth

ors

calc

ulat

edth

esa

ltto

behy

drol

yzed

to84

.2%

.In

am

ore

rece

ntst

udy,

1th

epr

oduc

tsof

drol

ysis

wer

eid

entifi

edto

bea

mix

ture

ofba

sic

thor

ium

acet

ates

whi

chfo

rmed

collo

idso

lutio

ns,a

ndth

eso

lubi

lity

ofT

h~C

2H3O

2!4

was

port

edto

vary

with

inth

era

nge

of1.

5–

1.9

g/10

0g

wat

er.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

thin

gsp

ecifi

ed.

Anh

ydro

usth

oriu

mac

etat

ew

asob

tain

edby

reac

ting

Th~

NO

3!4•

5H2O

with

exce

ssac

etic

anhy

drid

e.T

hepr

oduc

t,in

solu

ble

inac

etic

anhy

drid

e,w

asfil

tere

d,w

ashe

dw

ithac

etic

anhy

drid

ean

dva

cuum

drie

dov

erN

aOH

.A

naly

sis,

foun

d/ca

lcul

ated

for

Th~C

2H3O

2!4

~mas

s%!

:T

h49

.24/

49.5

6,C

20.2

5/20

.50,

H2.

52/2

.56.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 A.

K.

Mol

odki

n,O

.M

.Iv

anov

a,an

dG

.A

.S

kotn

ikov

a,Z

h.N

eorg

.K

him

.12,

116

~196

7!.

546546 JIRI HALA

4.5.

1.T

horiu

mF

orm

ate

Trih

ydra

te

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

tetr

akis~

form

ate!

trih

ydra

te;

Th~H

CO

2!4•

3H2O

;@1

3266

-86-

9#~2

!V

ario

usso

lven

ts

B.

Cla

udel

and

B.

Men

tzen

,B

ull.

Soc

.C

him

.F

ranc

e15

47–

50~1

966!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Th~

HC

O2!

4•3H

2Oat

25°C

inva

rious

solv

entsa

Sol

vent

Th~

HC

O2!

4.3H

2O~m

gL2

1 !T

h~H

CO

2!4.

3H2O

(c1/1

05m

oldm

23 !

b

oxira

ne~e

thyl

ene

oxid

e!;C

2H4O

;@9

5-21

-8#

10.7

2.30

acet

one;

C 3H6O

;@6

7-64

-1#

17.2

3.69

tric

hlor

oeth

ylen

e;C 2H

Cl 3

;@7

9-01

-6#

17.2

3.69

etha

nol;

C 2H

6O;

@64-

17-5

#23

.65.

06

benz

ene;

C 6H6;

@71-

43-2

#36

.57.

83

carb

onte

trac

hlor

ide;

CC

l4;

@56-

23-5

#47

.210

.1

2-pr

opan

ol;

C 3H

8O;

@67-

63-0

#57

.912

.4

met

hano

l;C

H 4O

;@6

7-56

-1#

137.

329

.5

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.b C

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dw

asus

ed.

The

solv

ents

wer

eeq

uilib

rate

dw

ithex

cess

Th~H

CO

2!4•

3H2O

labe

led

with

228 T

h~1

0m

Cig

21 ;

3.73

105

Bq

g21 !

until

equi

libriu

mw

asre

ache

d.A

sam

ple

of1

cm3 of

the

satu

rate

dso

lutio

nw

asan

alyz

edfo

rT

hco

nten

tby

mea

surin

ggac

tivity

inth

era

nge

of0

–4

MeV

.A

ctiv

ities

ofth

esa

tura

ted

solu

tions

wer

eco

mpa

red

agai

nst

that

ofa

stan

dard

solu

tion

cont

aini

ng1

gT

h~H

CO

2!4•

3H2O

/dm

3w

ithsp

ecifi

cac

tivity

of0.

01m

Cic

m2

3~3

70B

qcm

23 !.

228 T

h-la

bele

dT

h~HC

O2!

4•3H

2Ow

aspr

epar

edby

actio

nof

hot

40%

form

icac

idon

fres

hly

prec

ipita

ted22

8 Th~

OH

! 4,

prep

ared

from

228 T

h~N

O3!

4.T

hesa

ltcr

ysta

llize

dup

onev

apor

atio

nor

cool

ing.

For

anal

ysis

,se

eth

eda

tash

eet

for

the

Th~

HC

O2!

4–

HC

O2–

H2O

syst

emof

the

sam

eor

igin

aldo

cum

ent.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

prec

isio

nno

tsp

ecifi

edsp

ecifi

ed;

for

the

Co

~1!

~2!

Va

T/

5 of hy re Me

No


Ref

eren

ces:

1D

.Pat

naik

and

S.P

anda

,J.I

ndia

n.C

hem

.Soc

.12

,877

~195

6!.

4.7.

Tho

rium

Car

boxy

late

s

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

tetr

akis

~car

boxy

late

s!;~O

2C~C

H2!

nC

H3!

4

Pot

assi

umni

trat

e;K

NO 3;

@775

7-79

-1#W

ater

;H 2

O;

@773

2-18

-5#

L.D

.S

kryl

ev,

O.

V.

Per

lova

,V

.F

.S

azon

ova,

and

C.

V.

Fel

dman

,Iz

v.V

UZ

Tsv

et.

Met

alN

o.4,

23–

8~199

0!.

riabl

es:

Pre

pare

dby

:

K:

293

/mol

dm2

3 :0.0

18J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyin

wat

erof

thor

ium

carb

oxyl

ates

at20

°Ca

Sal

tT

h~O

2C~C

H2!

nC

H3!

4

(c1/1

06m

oldm

23 !

oriu

mte

trak

is~de

cano

ate!;

Th~

O2C

~CH

2!8C

H3!

4;@

#1.

25

oriu

mte

trak

is~un

deca

noat

e!;T

h~O

2C~C

H2!

9CH

3!4;

@134

893-

75-7#

0.91

oriu

mte

trak

is~do

deca

noat

e!;T

h~O

2C~C

H2!

10C

H3!

4;@1

0730

5-72

-6#0.

67

oriu

mte

trak

is~tr

idec

anoa

te!;T

h~O

2C~C

H2!

11C

H3!

4;@1

3489

3-76

-8#0.

51

oriu

mte

trak

is~te

trad

ecan

oate!;

Th~

O2C

~CH

2!12

CH

3) 4

;@10

7176

-04-

5#0.

37

oriu

mte

trak

is~pe

ntad

ecan

oate!;

Th~

O2C

~CH

2!13

CH

3!4;

@#

0.27

oriu

mte

trak

is~he

xade

cano

ate!;T

h~O

2C~C

H2!

14C

H3!

4;@

#0.

19

llsa

tura

ted

solu

tions

show

edpH

of6.

0,co

ntai

ned

0.01

08m

oldm

23

KN

O3,

and

wer

eof

collo

idal

natu

re.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

tass

ium

salts

ofth

eco

rres

pond

ing

carb

oxyl

icac

ids,

inth

em

of0.

01m

oldm

23

solu

tions

,w

ere

adde

dto

aT

h~N

O3!

4

lutio

nin

stoi

chio

met

ricam

ount

sre

quire

dfo

rth

efo

rmat

ion

the

corr

espo

ndin

gth

oriu

msa

lts.

Sat

urat

edso

lutio

nsw

ere

alyz

edfo

rth

eth

oriu

mco

nten

tne

phel

omet

rical

ly.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

tetr

akis~

acet

ate!;

Th~

C2H

3O2!

4;@1

3075

-28-

0#~2

!S

olve

nts

T.M

uniy

appa

nan

dB

.Anj

aney

alu,

Pro

c.In

dian

Aca

d.S

ci.

A45

,41

2–

7~1

957!

,C

urr.

Sci

.26,

319

–20

~195

7!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:30

3J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

30°C

ofT

h~C2H

3O2!

4in

thre

eso

lven

tsa

Sol

vent

Th~

C2H

3O2!

4

~g/1

00cm

3so

lutio

n!T

h~C

2H3O

2!4

~mol

dm2

3 !T

h~C

2H3O

2!4

~g/1

00g

solv

ent!

Th~

C2H

3O2!

4

~m1

/mol

kg2

1 !b

1,2-

etha

nedi

amin

e;C 2H

8N2;

@107

-15-

3#3.

730.

084.

300.

0884

2-am

inoe

than

ol;

C 2H7N

O;

@141

-43-

5#

cc

70.8

11.

456

1,2-

etha

nedi

ol;

C 2H6O

2;@1

07-2

1-1#

cc

0.41

0.00

843

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

c Not

repo

rted

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

d.A

nhyd

rous

mat

eria

lsw

ere

hand

led

and

solu

tions

prep

ared

inm

oist

ure-

and

CO

2-fr

eeai

rin

agl

ove

box.

Sol

ubili

tym

easu

rem

ents

wer

eca

rrie

dou

tin

test

tube

sfit

ted

with

grou

ndgl

ass

stop

pers

seal

edw

ithD

ow-C

orni

ngsi

licon

ehi

gh-v

acuu

mgr

ease

.T

heso

lven

tsw

ere

equi

libra

ted

with

exce

ssso

lidsa

ltin

ath

erm

osta

ted

bath

for

5da

ysw

ithfr

eque

ntag

itatio

n.T

hetu

bes

wer

eth

ence

ntrif

uged

for

20m

inan

dop

ened

inth

edr

ybo

x.T

heth

oriu

mco

nten

tw

asde

term

ined

bypr

ecip

itatin

ghy

drou

sox

ide

upon

addi

tion

ofw

ater

,an

dw

eigh

ing

the

igni

ted

oxid

e.

Anh

ydro

usT

h~IV

!ac

etat

ew

asob

tain

edby

the

reac

tion

ofT

hni

trat

ew

ithac

etic

anhy

drid

e.1T

heco

mpo

sitio

nof

the

prod

uct

was

esta

blis

hed

byig

nitio

nto

ThO 2

.1,

2-et

hane

diam

ine

mon

ohyd

rate

~B.D•H

.!w

asde

hydr

ated

and

purifi

edbe

fore

use.

The

purifi

edpr

oduc

tha

da

spec

ific

cond

ucta

nce

of1.

353

102

6V

21

cm2

1at

30°C

,an

dw

asst

ored

ingl

ass

stop

pere

dfla

sks

whi

chw

ere

kept

ina

desi

ccat

orov

erso

dalim

e,M

gpe

rchl

orat

ean

dP 2O

5.A

nhyd

rous

2-am

inoe

than

olan

d1,

2-et

hane

diol

wer

eus

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

05K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Co

~1!

Th

~2!

~3!

Va

T/

c 2 Th

Th

Th

Th

Th

Th

Th

a A Me

Po

for

so of an

J

4.9.

Tho

rium

Oxa

late

4.9.

1.E

valu

atio

nof

the

Th

„C

2O4…

2¿H

2OS

yste

m

mpo

nent

s:E

valu

ator

:

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#W

ater

;H 2

O;

@773

2-18

-5#J.

Hala

,D

epar

tmen

tof

Inor

gani

cC

hem

istr

y,M

asar

ykU

nive

rsity

,61

137

Brn

o,C

zech

Rep

ublic

,F

ebru

ary

2000

Crit

ical

Eva

luat

ion:

The

rear

efiv

eva

lues

avai

labl

efo

rth

eso

lubi

lity

ofth

oriu

mox

alat

ein

wat

erof

whi

chth

ree

have

been

extr

acte

dfr

omdo

cum

ents

alin

gw

ithte

rnar

ysy

stem

s.2,3,

5A

t298

.15

K,t

heso

lubi

lity

ofT

h~C2O

4!2

has

been

repo

rted

tobe

(4.1

–4.

8)3

102

5~G

rinbe

rg,P

etrz

hak,

dE

vtee

v1 !,1.

843

102

6~L

uzhn

aya

and

Kov

alev

a2 !,an

d4.

743

102

5~K

urna

kova

and

Shu

boch

kin

3 !,al

lin

mol

kg2

1 ,an

d2.

710

27

mol

dm2

3 .4T

hese

valu

esdi

ffer

from

one

anot

her

by2

orde

rsof

mag

nitu

dean

dw

ere

obta

ined

unde

rdi

ffere

nteq

uilib

ratio

nnd

ition

s.It

seem

sth

atth

eva

lue

of2.

73

102

7m

oldm

23

~Spi

tsyn

4 !co

uld

have

resu

lted

from

rath

ersh

ort

equi

libra

tion

time

appl

ied

~6on

ly!

sinc

ein

othe

rdo

cum

ents

cons

ider

ably

long

ereq

uilib

ratio

nto

okpl

ace.

The

reas

onfo

rth

edi

scre

panc

ybe

twee

nth

eda

tain

Ref

s.nd

3,w

here

roug

hly

the

sam

eeq

uilib

ratio

ntim

eof

5–

6da

ysw

asus

ed,i

sno

tcle

ar.T

heva

lue

ofC

olan

i,5

alth

ough

obta

ined

atdi

ffere

ntpe

ratu

res,

seem

sag

ain

tobe

poin

ting

toth

eim

port

ance

ofeq

uilib

ratio

nco

nditi

ons.

Inth

isdo

cum

ent

equi

libra

tion

took

plac

efo

r3

nths

,and

the

obta

ined

solu

bilit

yis

ingo

odag

reem

entw

ithth

eda

taof

Grin

berg

and

Pet

rzha

k1

and

Kur

nako

vaan

dS

hubo

chki

n.3

Sin

cein

berg

and

Pet

rzha

k1

repo

rted

ara

nge

for

the

solu

bilit

yra

ther

than

asi

ngle

valu

eth

eev

alua

tor

reco

mm

ends

the

solu

bilit

yva

lue

ofrn

akov

aan

dS

hubo

chki

n3

beus

edas

ate

ntat

ive

valu

eat

298.

15K

.

fere

nces

:.

A.

Grin

berg

,G

.I.

Pet

rzha

k,an

dL.

I.E

vtee

v,Z

h.N

eorg

.K

him3,

204

~195

8!.

.P

.Lu

zhna

yaan

dI.

S.

Kov

alev

a,Z

h.N

eorg

.K

him

.6,

1436

~196

1!.

.S

.K

urna

kova

and

L.K

.S

hubo

chki

n,Z

h.N

eorg

.K

him

.8,

1249

~196

3!.

.I.

Spi

tsyn

,Z

h.R

uss.

Fiz

.K

him

.O

bsh.4

9,35

7~1

917!

..

Col

ani,

Com

pt.

Ren

d.156

,10

75~1

913!

;15

6,19

07~1

913!

.

548548 JIRI HALA

4.8.

Tho

rium

O-A

lkyl

carb

onod

ithio

ates

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

tetr

akis~

O-a

lkyl

carb

onod

ithio

ates!;

~xan

thog

enat

es!;T

h~O

S 2C

~CH

2!nC

H3!

4

~2!

Pot

assi

umni

trat

e;K

NO 3;

@775

7-79

-1#~3

!W

ater

;H 2

O;

@773

2-18

-5#

L.D

.S

kryl

ev,

O.

V.

Per

lova

,V

.F

.S

azon

ova,

and

C.

V.

Fel

dman

,Iz

v.V

UZ

Tsv

et.

Met

alN

o.4,

23–

8~199

0!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

3c 2

/mol

dm2

3 :0.0

18J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyin

wat

erof

thor

ium

xant

hoge

nate

sat

20°C

a

Sal

tT

h~O

S 2C

~CH

2!nC

H3!

4

(c1/1

06m

oldm

23 !

Th~

OS 2

C~C

H2!

CH

3!4;

@134

902-

18-4#

36.6

0

Th~

OS 2

C~C

H2!

3CH

3!4;

@134

902-

19-5#

20.6

0

Th~

OS 2

C~C

H2!

5CH

3!4;

@134

902-

20-8#

12.0

0

Th~

O2C

~CH

2!9C

H3!

4;@1

3490

2-21

-9#4.

33

a All

satu

rate

dso

lutio

nssh

owed

pHof

6.0,

cont

aine

d0.

0108

mol

dm2

3K

NO

3,an

dw

ere

ofco

lloid

alna

ture

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Pot

assi

umsa

ltsof

the

corr

espo

ndin

gxa

ntho

geni

cac

ids,

inth

efo

rmof

0.01

mol

dm2

3so

lutio

ns,

wer

ead

ded

toa

Th

~NO

3!4

solu

tion

inst

oich

iom

etric

amou

nts

requ

ired

for

the

form

atio

nof

the

corr

espo

ndin

gth

oriu

msa

lts.

Sat

urat

edso

lutio

nsw

ere

anal

yzed

for

the

thor

ium

cont

ent

neph

elom

etric

ally

.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

de an 3 co h 2a

tem

mo

Gr

Ku

Re

1A

2N

3A

4V

5M


4.9.

2.T

horiu

mO

xala

teD

ihyd

rate

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

bis~o

xala

te!di

hydr

ate;

Th~C

2O4!

2•2H

2O;

4041

-32-

8#A

mm

onia

;N

H 3;

@766

4-41

-7#

G.W

.Wat

t,W

.A.J

enki

ns,a

ndJ.

M.M

cCui

ston

,J.A

m.C

hem

.S

oc.7

2,22

60–

2~19

50!.

riabl

es:

Pre

pare

dby

:

K:

298

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofT

h~C

2O4!

2•2H

2Oat

25°C

was

repo

rted

tobe

0.51

gT

h~C

2O4!

2•2H

2O/1

00g

NH 3

.m

pile

rca

lcul

ated

the

solu

bilit

yto

bem15

0.01

15m

olkg

21 .

The

equi

libriu

mso

lidph

ase

was

Th

~C2O

4!2•

2H2O

;@1

4041

-32-

8#.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used.

2g

ofT

h~C

2O4!

2.2H

2Ow

ere

trea

ted

thliq

uid

NH

3fo

r3

hin

asp

ecia

lrea

ctor1

at25

°C.

The

thod

for

Th

dete

rmin

atio

nin

the

satu

rate

dso

lutio

nw

asno

tec

ified

.T

heco

mpo

sitio

nof

the

equi

libriu

mso

lidph

ase

was

nfirm

edby

chem

ical

anal

ysis

.E

xces

sN

H3

from

the

tura

ted

solu

tion

was

evap

orat

ed,

the

solid

was

was

hed

and

cuum

drie

d.T

here

was

novi

sual

evid

ence

ofa

reac

tion

ofso

lidw

ithN

H 3,

and

Th~

C2O

4!2•

2H2O

was

reco

vere

dch

ange

dex

cept

for

asm

allr

eten

tion

ofN

H3.

Dih

ydra

teof

the

salt

was

obta

ined

byde

hydr

atio

nof

Th~

C2O

4!2•

6H2O

at11

0°C

.T

hela

tter

was

prep

ared

from

Th~

NO

3!4•

4H2O

~A.D

.M

acK

ayC

o.!an

dre

agen

tgr

ade

oxal

icac

id.

The

dihy

drat

ew

asan

alyz

edfo

rT

hco

nten

t:fo

und

52.3

%,

calc

ulat

edfo

rT

h~C2O

4!2•

2H2O

,52.

3%

.

Est

imat

edE

rror

:T

empe

ratu

re:

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1G

.W

.W

atan

dT

.E

.M

oore

,J.

Am

.C

hem

.S

oc.

70,

1197

~194

8!.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#~2

!W

ater

;H 2

O;

@773

2-18

-5#A

.A

.G

rinbe

rg,

G.

I.P

etrz

hak,

and

L.I.

Evt

eev,

Zh.

Neo

rg.

Khi

m.

3,20

4–

11~1

958!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofT

h~C

2O4!

2•6H

2Oat

25°C

inw

ater

was

repo

rted

tobe

(2.1

–2.

5)3

102

2g

salt/

kgw

ater

or(4

.1–

4.8)

310

25

mol

kg2

1 .

Add

ition

alin

form

atio

n:pH

and

mol

arco

nduc

tivity

ofth

esa

tura

ted

solu

tions

wer

e5.

9an

dap

prox

imat

ely

200

Scm

2m

ol2

1on

aver

age,

resp

ectiv

ely.

Fro

mth

isth

eau

thor

sco

nclu

ded

that

inth

esa

tura

ted

solu

tions

Th

~IV

!ox

alat

ew

asdi

ssoc

iate

dm

ainl

yto

Th

~C2O

4!21

and

C 2O

422io

ns.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Not

hing

spec

ified

.N

othi

ngsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Co

~1!

@1 ~2!

Va

T/

Co

Me

Iso

wi

me

sp co sa va the

un

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#H

ydro

gen

chlo

ride;

HC

l;@76

47-0

1-0#

Wat

er;

H 2O

;@7

732-

18-5#

M.

Col

ani,

Com

pt.

Ren

d.15

6,10

75–

6~1

913!

;15

6,19

07–

9~1

913!

.

riabl

es:

Pre

pare

dby

:

K:

285

–32

30w

2/m

ass%

:0

–35

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Th~

C2O

4!2

inaq

ueou

sH

Cls

olut

ions

mpe

ratu

re~°

C!

HC

l(1

00w

2/m

ass

%)

HC

l(m

2/m

olkg

21 )a

Th

~mas

s%!

Th~

C2O

4!2

(103

m1

/mol

kg2

1 )aS

olid

phas

eb

123.

20.

907

0.00

270.

1202

A

23.0

8.20

00.

072

4.03

B

29.9

11.7

30.

169.

86B

33.1

13.6

30.

3120

.1B

1526

.39.

800.

105.

86B

32.5

13.1

60.

2818

.0B

35.0

14.9

10.

6040

.2B

170

00.

001

0.04

31A

1.2

0.33

30.

002

0.08

72A

3.6

1.02

40.

0035

0.15

6A

4.6

1.32

20.

0054

0.24

4A

8.4

2.51

50.

010

0.47

1A

13.1

4.13

60.

016

0.79

9A

16.2

5.30

30.

022

1.13

A

19.8

6.77

50.

037

1.99

A

500

00.

0010

0.04

31A

4.1

1.13

70.

0058

0.26

1A

8.4

2.51

50.

016

0.75

3A

12.4

3.88

40.

033

1.62

A

16.1

5.28

60.

059

3.03

A

18.0

6.02

60.

077

4.05

A

19.9

6.82

20.

097

5.26

A

21.6

7.56

90.

133

7.32

A

21.2

7.58

80.

179.

56B

23.0

8.23

50.

2011

.3B

26.8

10.0

80.

2716

.0B

29.8

11.7

20.

4427

.2B

32.3

13.2

60.

8856

.8B

34.6

14.8

51.

5110

2B

a Cal

cula

ted

byco

mpi

ler.

b ~A!

Th~

C2O

4!2•

6H2O

,@1

6788

-62-

8#;~B

!T

h 4~C

2O4!

6Cl 4•20

H2O

,@

#.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dw

asus

ed.

No

deta

ilsw

ere

give

nex

cept

that

at17

°C3

mon

ths

wer

ene

cess

ary

tobr

ing

the

solu

tion

into

equi

libriu

mw

ithso

lidT

h~C2O

4!2•

6H2O

.E

xper

imen

tsat

.21

mas

s%

wer

eca

rrie

dou

tus

ing

Th

4~C

2O4!

6Cl 4•20

H2O

asth

est

artin

gso

lidph

ase.

The

com

posi

tion

ofth

ela

tter

asth

eeq

uilib

rium

solid

phas

ew

asco

nfirm

edby

chem

ical

anal

ysis

.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

550550 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#~2

!H

ydro

gen

chlo

ride;

HC

l;@76

47-0

1-0#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

G.

Hau

ser

and

F.

Wirt

h,Z

.A

norg

.C

hem

.78

,75

–94

~191

2!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

810

0w2

/mas

s%:

24.8

–37

.6J.

Hala

Exp

erim

enta

lDat

a

Com

posi

tion

ofH

Cls

olut

ions

satu

rate

dw

ithT

h~C

2O4!

2at

25°C

a

HC

l(1

00w

2/m

ass%

)T

hO2

~gkg

21

solu

tion!

Th~

C2O

4!2

~mol

kg2

1so

lutio

n!b

24.8

0.10

03.

79310

24

37.0

3.45

00.

0131

37.6

3.49

20.

0133

a Equ

ilibr

ium

solid

phas

ew

asre

port

edto

be3T

h~C

2O4!

2•T

hCl 4•

20H

2O,

@#.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

d1us

ed.

Exc

ess

Th~C

2O4!

2•6H

2Ow

aseq

uilib

rate

din

ath

erm

osta

ted

bath

with

solu

tions

ofth

ede

sire

dco

mpo

sitio

nfo

rat

leas

t24

h.T

heso

lidph

ase

was

allo

wed

tose

ttle

inth

eba

th,

and

som

e60

–10

0g

ofth

esa

tura

ted

solu

tion

was

with

draw

nth

roug

ha

filte

rla

yer.

The

aliq

uot

was

evap

orat

edan

dig

nite

dto

ThO 2.

Asm

all

corr

ectio

nw

asap

plie

dfo

rth

em

ass

ofsi

licat

esdi

ssol

ved

from

glas

swar

e.T

heeq

uilib

rium

solid

phas

ew

asch

arac

teriz

edby

chem

ical

anal

ysis

:ca

lcul

ated

/foun

d~mas

s%!

for

3Th~

C2O

4!2•T

hCl 4•

20H

2O:T

hO2

47.3

7/47

.11,

Cl7

.24/

7.00

.

Th~

C2O

4!2•

6H2O

was

prep

ared

bypr

ecip

itatin

git

with

conc

entr

ated

HC

lfr

omth

eso

lutio

nof

the

salt

inam

mon

ium

oxal

ate.

The

proc

edur

ew

asre

peat

edse

vera

ltim

esto

purif

yth

eth

oriu

mox

alat

efr

omla

ntha

nide

s.A

fter

air

dryi

ngth

epr

oduc

tco

ntai

ned,

inm

ass

%,5

0.68

ThO 2,

27.4

7C 2

O3,

and

21.6

7H 2

O.

Cal

cula

ted

for

the

hexa

hydr

ate~res

pect

ive

valu

es!:51

.21,

27.8

8,an

d20

.91.

Oxa

licac

idus

eddi

dno

tsh

owan

yre

sidu

eon

igni

tion.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~Hau

ser

and

Wirt

h1 !.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 O.

Hau

ser

and

F.

Wirt

h,Z

.A

nal.

Che

m.

47,

389

~190

8!.

Co

~1!

~2!

~3!

Va

T/

10 Te


activ

ityw

ithth

atof

akn

own

amou

ntof

labe

led

Th~

C2O

4!2•

6H2O

.E

stim

ated

Err

or:

Tem

pera

ture

:no

tre

port

ed.

Tho

rium

conc

entr

atio

n:pr

ecis

ion6

~1–

2!%

~aut

hor!.

Ref

eren

ces:

1 M.

Col

ani,

Com

pt.

Ren

d.156

,10

75~1

913!

;15

6,19

07~1

913!

.

4.9.

3.E

valu

atio

nof

the

Th

„C

2O4…

2¿H

NO

3¿H

2OS

yste

m

mpo

nent

s:E

valu

ator

:

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#N

itric

acid

;H

NO

3;@7

697-

37-2#

Wat

er;

H 2O

;@7

732-

18-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

611

37B

rno,

Cze

chR

epub

lic,

Feb

ruar

y20

00

Crit

ical

Eva

luat

ion:

Fou

rse

tsof

data

are

avai

labl

efo

rth

eso

lubi

lity

ofT

h~C

2O4!

2in

aque

ous

HN

O 3so

lutio

ns1

–4

ofw

hich

the

data

ofP

azuk

hinet

al.4

vebe

enex

trac

ted

from

the

stud

yof

the

quar

tern

ary

syst

emT

h~C

2O4!

2–

oxal

icac

id–

HN

O 3–

H2O

.W

hile

the

data

from

docu

men

ts1,

3,4

emto

agre

ew

ithon

ean

othe

rw

ithin

expe

rimen

tale

rror

,the

data

ofK

urna

kova

and

Shu

boch

kin

2ar

ehi

gher

bya

fact

orra

ngin

gfr

om1.

53.

5.T

oill

ustr

ate

the

situ

atio

n,th

eda

tafo

rm

2,

4m

olH

NO

3/k

gfr

omR

efs.

1–

4ha

vebe

ensu

mm

ariz

edin

agr

aphi

calf

orm

~see

Fig

.T

his

diffe

renc

ein

solu

bilit

ies

seem

sto

coin

cide

wel

lwith

the

diffe

rent

equi

libra

tion

times

used

.W

hile

Kur

nako

vaan

dS

hubo

chki

n2

edeq

uilib

ratio

ntim

eof

5–

6da

ys,

the

auth

ors

ofot

her

stud

ies

equi

libra

ted

the

syst

ems

for

afe

who

urs

only

.It

seem

sth

uslik

ely

that

eeq

uilib

rium

was

not

reac

hed

inR

efs.

1,3,

4.It

isno

tew

orth

yth

atth

esa

me

prob

lem

appe

ars

inth

ebi

nary

syst

emT

h~C

2O4!

2–

H2O

eC

ritic

alE

valu

atio

n!in

this

sect

ion.

Mor

eove

r,K

urna

kova

and

Shu

boch

kin

2us

eda

mor

ese

nsiti

vera

diom

etric

met

hod

for

the

term

inat

ion

ofth

oriu

m,

and

Bry

zgal

ovaet

al.3

repo

rted

rath

erlo

wpr

ecis

ion

for

thei

rco

lorim

etric

met

hod.

The

very

good

agre

emen

tso

me

ofth

eda

tafr

omR

ef.

3an

d4~e

.g.,

for

0.5,

1.6,

and

2.7

mol

HN

O 3/k

g!ca

nth

usbe

fort

ituou

s.T

heev

alua

tor

ther

efor

eco

mm

ends

the

data

ofK

urna

kova

and

Shu

boch

kin

2be

used

aste

ntat

ive

ones

.

FIG

.2.

Tho

rium

bix~o

xala

te!–

nitr

icac

id–

wat

ersy

stem

Ref

eren

ces:

1 V.

I.S

pits

yn,

Zh.

Rus

s.F

iz.

Khi

m.

Obs

h.49,

357

~191

7!.

2 A.

G.

Kur

nako

vaan

dL.

K.

Shu

boch

kin,

Zh.

Neo

rg.

Khi

m.

8,12

49~1

963!

.3 R

.V

.B

ryzg

alov

a,Y

u.M

.R

ogoz

in,

and

I.V

.C

hern

itska

ya,

Rad

iokh

imiy

a12

,28

6~1

970!

.4 E

.M

.P

azuk

hin,

E.

A.

Sm

irnov

a,A

.S

.K

rivok

hats

kii,

and

Yu.

L.P

azuk

hina

,R

adio

khim

iya

27,

606

~198

5!.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#~2

!H

ydro

gen

chlo

ride;

HC

l;@76

47-0

1-0#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

V.

I.S

pits

yn,

Zh.

Rus

s.F

iz.

Khi

m.

Obs

h.~J.

Rus

s.P

hys.

Che

m.

Soc

.!49

,35

7–

70~1

917!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8c 2

/mol

dm2

3 :0.

04–

1.0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofT

h~C2O

4!2

inH

Cls

olut

ions

a

HC

l(c

2/m

oldm

23 !

ThO

2

~mg

dm2

3 !T

h~C

2O4!

2b

(105

c 1/m

oldm

23 )

0.04

0.6

0.23

0.09

1.7

0.65

0.23

4.7

1.81

0.38

72.

69

0.48

8.5

3.29

0.50

124.

61

0.64

166.

15

0.82

218.

08

1.0

249.

23

a Sol

idph

ases

not

inve

stig

ated

.B

ased

onth

eda

tape

rtai

ning

toth

era

nge

ofH

Clc

once

ntra

tion

used

~Col

ani1 !,

com

pile

ras

sum

esth

isto

beT

h~C

2O4!

2•6H

2O,

@167

88-6

2-8#.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

Th

~C2O

4!2•

6H2O

labe

led

with

234 T

hw

aseq

uilib

rate

dw

ithth

eso

lutio

nof

the

desi

red

com

posi

tion

for6

hw

hich

was

foun

dsu

ffici

ent

for

satu

ratio

nto

bere

ache

d.A

fter

equi

libra

tion,

100

–20

0m

Lof

the

satu

rate

dso

lutio

nw

asev

apor

ated

ona

porc

elai

nedi

shan

db

activ

ityof

the

resi

due

was

mea

sure

din

anel

ectr

osco

pe.

The

amou

ntof

thor

ium

was

obta

ined

byco

mpa

ring

the

mea

sure

d

Labe

led

Th~C

2O4!

2•6H

2Ow

aspr

epar

edby

prec

ipita

tion.

An

aliq

uot

ofU

X 1(23

4 Th)

prep

arat

ion

was

adde

dto

aso

lutio

nof

Th~

NO

3!4,

and

Th~

C2O

4!2•

6H2O

was

prec

ipita

ted

byad

ding

hot

solu

tion

ofox

alic

acid

.The

prec

ipita

tew

asw

ashe

dse

vera

ltim

esw

ithho

tw

ater

.A

fter

seve

ral

deca

ntat

ions

with

cold

wat

erth

epr

ecip

itate

turn

edin

tocr

ysta

lline

form

.

Co

~1!

~2!

~3!

ha se to 2!.

us tru

~se

de of re

J

24

22

2!%

~aut

hor!.

Ref

eren

ces:

1 A.

G.

Kur

nako

vaan

dL.

K.

Shu

boch

kin,

Zh.

Neo

rg.

Khi

m.

8,12

49~1

963!

.2 P

hys

ico

-Ch

em

ica

lT

ab

les,P

ubl.

Hou

seT

ech.

Lit.,

Pra

gue,

~195

3!,

Vol

.1,

p.21

3.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#N

itric

acid

;H

NO

3;@7

697-

37-2#

Wat

er;

H 2O

;@7

732-

18-5#

A.

G.

Kur

nako

vaan

dL.

K.

Shu

boch

kin,

Zh.

Neo

rg.

Khi

m.

8,12

49–

54~1

963!

;R

uss.

J.In

org.

Che

m.8,

647

–50

~196

3!.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

kg2

1 :0

–23

.74

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofT

h~C2O

4!2

inH

NO

3so

lutio

nsa

HN

O3

2/m

ass

%)

HN

O3

~mol

kg2

1 !bH

NO

3

(m2

/mol

kg2

1 )cT

h~m

ass

%!T

h(1

04m

olkg

21 )b

Th

(104

m1

/mol

kg2

1 )

00

00.

0011

0.47

0.47

4

1.45

0.23

0.23

40.

0029

1.25

1.27

3.45

0.55

0.56

70.

0050

2.15

2.23

4.74

0.75

0.79

00.

0052

2.24

2.35

7.40

1.17

1.27

0.00

863.

694.

00

14.3

42.

282.

660.

0154

6.63

7.75

16.0

72.

553.

040.

0182

7.84

9.35

18.6

32.

963.

630.

0221

9.52

11.7

1

20.8

53.

314.

180.

0304

13.1

016

.56

27.5

24.

376.

030.

0481

20.7

228

.62

31.3

44.

977.

250.

0685

29.5

143

.04

36.8

05.

849.

250.

0981

42.2

667

.00

46.9

27.

4514

.09

0.23

8d10

2.53

194.

1

53.0

68.

4218

.13

0.48

5d20

8.9

450.

0

59.2

89.

4123

.74

1.09

3d46

7.0

1188

heeq

uilib

rium

solid

phas

ew

asT

h~C

2O4!

2•6H

2O,

@167

88-6

2-8#,

inal

lsol

utio

ns.

olso

lute

per

kgso

lutio

n.al

cula

ted

byco

mpi

ler

usin

gde

nsiti

esof

HN

O3

solu

tions

from

Ref

.1.

hesh

arp

incr

ease

ofT

h~C2O

4!2

solu

bilit

yat

high

HN

O 3co

ncen

trat

ions

was

ascr

ibed

byth

eau

thor

sto

the

form

atio

nof

nitr

ato

and/

oritr

ato

–ox

alat

oco

mpl

exes

ofth

oriu

min

thes

eso

lutio

ns.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Sol

utio

nsw

ithex

cess

solid

wer

eag

itate

dfo

r5

–6

days

.T

heco

ncen

trat

ion

ofH

NO

3in

the

satu

rate

dso

lutio

nsw

asde

term

ined

bytit

ratio

nw

ith0.

1N

NaO

H.

Tho

rium

conc

entr

atio

nw

asde

term

ined

radi

omet

rical

ly.

Afte

rce

ntrif

ugat

ion,

five

toei

ght

drop

sof

the

satu

rate

dso

lutio

nw

ere

wei

ghed

out

onto

anas

hles

sfil

ter

for

b-c

ount

ing.

Fro

mso

lutio

nsof

dilu

teH

NO 3w

here

the

solu

bilit

yof

Th~

C2O

4!2

islo

w,

0.3

–5

gof

the

solu

tion

wer

ew

ithdr

awn

in15

sepa

rate

port

ions

with

dryi

ngaf

ter

each

addi

tion,

and

coun

ted.

Theb

activ

ityof

the

satu

rate

dso

lutio

nsw

asco

mpa

red

with

that

ofth

est

anda

rds

prep

ared

from

labe

led

Th~

C2O

4!2•

6H2O

.A

thi

ghT

h~C

2O4!

2co

ncen

trat

ions

,th

oriu

min

the

satu

rate

dso

lutio

nsw

asde

term

ined

grav

imet

rical

ly~m

etho

dno

tsp

ecifi

ed!.

The

com

posi

tion

ofth

eeq

uilib

rium

solid

phas

esw

asde

term

ined

byop

tical

mic

rosc

opy,

inso

lutio

nsco

ntai

ning

high

HN

O 3co

ncen

trat

ions

bych

emic

alan

alys

isan

dth

em

etho

dof

wet

resi

dues

.

Th~

C2O

4!2•

6H2O

was

prep

ared

from

thor

ium

nitr

ate

ofun

spec

ified

sour

cean

dpu

rity.

To

incr

ease bac

tivity

ofth

oriu

mfo

rits

subs

eque

ntra

diom

etric

dete

rmin

atio

n,ag

edU

O2~

NO

3!2

inra

dioa

ctiv

eeq

uilib

rium

with

the

thor

ium

isot

ope

UX

1~23

4 Th!

was

adde

dto

Th~N

O3!

4,an

dT

h~C

2O4!

2•6H

2Ow

aspr

ecip

itate

dfr

omho

tso

lutio

nw

itha

stoi

chio

met

ricam

ount

ofox

alic

acid

.T

hela

bele

dT

h~C2O

4!2•

6H2O

was

filte

red,

was

hed

ten

times

with

boili

ngw

ater

,an

dai

rdr

ied

for

4–

5da

ys.

Fre

shly

dist

illed

60.4

%H

NO 3

was

used

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 Ph

ysic

o-C

he

mic

al

Ta

ble

s,~P

ubl.

Hou

seT

ech.

Lite

r.,

Pra

gue,

1953

!,V

ol.

1,p.

213.

552552 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#~2

!N

itric

acid

;H

NO

3;@7

697-

37-2#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

V.

I.S

pits

yn,

Zh.

Rus

s.F

iz.

Khi

m.

Obs

h.~J.

Rus

s.P

hys.

Che

m.

Soc

.!49

,35

7–

70~1

917!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8c 2

/mol

dm2

35

0.01

6–

1.0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofT

h~C2O

4!2

inH

NO

3so

lutio

nsa

HN

O3

(c2

/mol

dm2

3 )H

NO

3

(m2

/mol

kg2

1 )b,c

ThO

2

~mg

dm2

3 !T

h~C

2O4!

2b

(105

c 1/m

oldm

23 )

0.01

60.

016

0.3

0.12

0.06

0.06

1.3

0.50

0.24

0.24

4.5

1.73

0.47

0.48

10.1

3.88

0.50

0.50

911

4.23

0.78

0.80

514

.45.

54

1.0

1.03

433

12.7

a Sol

idph

ases

noti

nves

tigat

ed.W

ithre

fere

nce

toan

othe

rst

udy

ofth

eso

lubi

lity

inth

eT

h~C

2O4!

2–

HN

O3–

H2O

syst

em,1co

mpi

ler

assu

mes

this

tobe

Th~C

2O4!

2•6H

2O,

@167

88-6

2-8#.

b Cal

cula

ted

byco

mpi

ler.

c Cal

cula

ted

byus

ing

dens

ities

ofH

NO

3so

lutio

nsfr

omR

ef.

2.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

Th

~C2O

4!2•

6H2O

labe

led

with

234 T

hw

aseq

uilib

rate

dw

ithth

eso

lutio

nof

the

desi

red

com

posi

tion

for6

hw

hich

was

foun

dsu

ffici

ent

for

satu

ratio

nto

bere

ache

d.A

fter

equi

libra

tion,

100

–20

0m

Lof

the

satu

rate

dso

lutio

nw

asev

apor

ated

ona

porc

elai

nedi

shan

db

activ

ityof

the

resi

due

was

mea

sure

din

anel

ectr

osco

pe.

The

amou

ntof

thor

ium

was

obta

ined

byco

mpa

ring

the

mea

sure

dac

tivity

with

that

ofa

know

nam

ount

ofla

bele

dT

h~C

O!•6H

O.

Labe

led

Th~C

2O4!

2•6H

2Ow

aspr

epar

edby

prec

ipita

tion.

An

aliq

uot

ofU

X 1(23

4 Th)

prep

arat

ion

was

adde

dto

aso

lutio

nof

Th~

NO

3!4,

and

Th~

C2O

4!2•

6H2O

was

prec

ipita

ted

byad

ding

hot

solu

tion

ofox

alic

acid

.The

prec

ipita

tew

asw

ashe

dse

vera

ltim

esw

ithho

tw

ater

.A

fter

seve

ral

deca

ntat

ions

with

cold

wat

erth

epr

ecip

itate

turn

edin

tocr

ysta

lline

form

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

prec

isio

n6

~1–

Co

~1!

~2!

~3!

Va

T/

m2

(w a T b M c C d T n


te,

Tho

rium

inth

efil

trat

ew

asde

term

ined

colo

rimet

rical

lyw

ithar

sena

zoIII

.3D

ata

repo

rted

are

aver

age

valu

esof

3–

4de

term

inat

ions

.

was

hing

was

repe

ated

until

the

was

hso

lutio

nco

ntai

ned

equi

vale

ntco

ncen

trat

ions

ofth

oriu

man

dox

alic

acid

.T

hepr

ecip

itate

was

then

filte

red,

was

hed

with

wat

er,

etha

nol

and

ethe

r,an

dai

rdr

ied

atro

omte

mpe

ratu

re.T

heco

mpo

sitio

nof

the

prod

uct

asfo

und

byan

alys

isw

asT

h:ox

alat

e:H

2O5

1:1

.98:

6.3.

Est

imat

edE

rror

:T

empe

ratu

re:p

reci

sion6

0.2

K~a

utho

rs!.

Tho

rium

conc

entr

atio

n:pr

ecis

ion

610

%fo

rC

Th.

1.2

310

26

mol

dm2

3an

d6

~20

–30

!%fo

rC

Th,

1.2

310

26

mol

dm2

3~a

utho

rs!.

Ref

eren

ces:

1 A.

G.

Kur

nako

vaan

dL.

K.

Sch

uboc

hkin

,Z

h.N

eorg

.K

him8,

1249

~196

3!.

2 Ph

ysic

o-c

he

mic

alT

ab

les~P

ubl.

Hou

seof

Tec

hnic

alLi

tera

ture

,P

ragu

e,19

53!,

Vol

.1,

p.21

3.3 A

.A

.N

emod

ruk

and

N.

E.

Koc

hetk

ova,

Zh.

Ana

lit.

Khi

m.

17,

330

~196

2!.

4.9.

4.E

valu

atio

nof

the

Th

„C

2O4…

2¿H

2SO

4¿H

2OS

yste

m

mpo

nent

s:E

valu

ator

:

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#S

ulfu

ricac

id;

H 2S

O4;

@766

4-93

-9#W

ater

;H 2

O;

@773

2-18

-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,

June

2000

Crit

ical

Eva

luat

ion:

The

solu

bilit

yof

Th~

C2O

4!2

inaq

ueou

sH 2S

O4

solu

tions

has

been

repo

rted

inth

ree

docu

men

ts.

1–

3In

all

docu

men

tsm

easu

rem

ents

vebe

enpe

rfor

med

at29

8.1

K.

Ast

rict

com

paris

onis

not

poss

ible

due

todi

ffere

ntun

itsus

edfo

rth

oriu

mco

ncen

trat

ion,

i.e.,

mg

ThO

2

rkg

satu

rate

dso

lutio

n1,

2or

mg

ThO

2pe

rdm

3sa

tura

ted

solu

tion.3

Ifth

isdi

ffere

nce

isdi

sreg

arde

d,ap

prox

imat

eco

mpa

rison

can

bede

for

two

conc

entr

atio

nsof

H 2SO

4on

ly,

i.e.,

0.25

and

0.50

mol

dm23 .

For

thes

etw

oH 2S

O4

conc

entr

atio

nsth

eso

lubi

lity

of~C

2O4!

2re

port

edby

Wirt

han

dH

ause

r1,

2is

high

erth

anth

atof

Spi

tsyn2

bya

fact

orof

appr

oxim

atel

y2.

5.It

may

beof

rele

vanc

eth

atirt

han

dH

ause

r1,2

used

24h

equi

libra

tion

time

whi

leS

pits

yn3eq

uilib

rate

dth

esy

stem

sfor6

hon

ly.S

ince

deta

ilsof

actu

aleq

uilib

ratio

nhn

ique

sus

edar

eno

tava

ilabl

eit

isno

tcer

tain

tow

hate

xten

twhe

ther

the

diffe

rent

equi

libriu

mtim

esus

edco

ntrib

uted

toth

edi

ffere

nces

the

solu

bilit

ies.

How

ever

,the

data

ofW

irth

and

Hau

ser

1,2

seem

mor

elik

ely

tore

pres

entt

hetr

ueeq

uilib

rium

valu

esan

d,as

such

,sho

uld

give

npr

efer

ence

.

fere

nces

:

.W

irth,

Z.

Ano

rg.

Che

m.7

6,17

4~1

912!

.

.H

ause

ran

dF

.W

irth,

Z.

Ano

rg.

Che

m78,

75~1

912!

.

.I.

Spi

tsyn

,Z

h.R

uss.

Fiz

.K

him

.O

bsh.4

9,35

7~1

917!

.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#~2

!N

itric

acid

;H

NO

3;@7

697-

37-2#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

R.

V.

Bry

zgal

ova,

Yu.

M.

Rog

ozin

,an

dI.

V.

Che

rnits

kaya

,R

adio

khim

iya1

2,28

6–

91~1

970!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8c 2

/mol

dm2

3 50.

5–

2.5

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofT

h~C2O

4!2

inH

NO

3so

lutio

nsa

HN

O3

(c2

/mol

dm2

3 )bH

NO

3

(m2

/mol

kg2

1 )cT

h~C

2O4!

2

(104

c 1/m

oldm

23 )

Ksp

d

(1021

mol

3dm

29 )

0.5

0.50

90.

61.

2

0.86

50.

890

1.4

1.9

1.0

1.03

41.

62.

0

1.5

1.57

63.

21.

2

2.0

2.14

04.

21.

4

2.5

2.71

56.

01.

1

a The

natu

reof

the

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.W

ithre

fere

nce

toR

ef.

1co

mpi

ler

assu

mes

this

tobe

the

hexa

hydr

aT

h~C

2O4!

2•6H

2O,

@167

88-6

2-8#.

b The

met

hod

for

the

dete

rmin

atio

nof

HN

O3

conc

entr

atio

nin

the

satu

rate

dso

lutio

nsw

asno

tsp

ecifi

ed.

Com

pile

ras

sum

edth

atth

eda

tare

port

edre

fer

toin

itial

acid

conc

entr

atio

n.c C

alcu

late

dby

com

pile

rus

ing

dens

ities

ofH

NO

3so

lutio

nsfr

omR

ef.

2.d T

heK

spva

lues

wer

eob

tain

edin

atw

o-st

epap

prox

imat

ion.

Firs

t,fu

lldi

ssoc

iatio

nof

Th

~C2O

4!2

was

assu

med

.B

yus

ing

theK

spso

obta

ined

(1.53

102

21m

ol3

dm2

9 )th

ein

stab

ility

cons

tant

sof

Th~C

2O4!

21an

dT

h~C

2O4!

2co

mpl

exes

wer

eca

lcul

ated

asK15

9.5

310

29

mol

dm2

3an

dK

25

2.53

102

5m

ol2

dm2

6 ,re

spec

tivel

y,an

d,in

turn

,use

dto

calc

ulat

eth

ere

fined

Ksp

valu

es.T

heav

erag

eva

lue

reco

mm

ende

dby

auth

ors

is1.

23

102

21m

ol3

dm2

9 .T

heef

fect

ofio

nic

stre

ngth

and

com

plex

ing

ofth

oriu

m~I

V!

with

nitr

ate

ion

wer

eno

tta

ken

into

acco

unt.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

20–

100

mg

ofT

h~C

2O4!

2•6H

2Ow

ere

stirr

edw

itha

rota

ryst

irrer

at20

0–

600

rpm

with

10m

Lso

lutio

nun

tileq

uilib

rium

was

reac

hed~a

few

hour

s!.E

xces

sso

lidw

asfil

tere

dof

fin

ath

erm

osta

ted

spac

eat

25°C

.

Th~

C2O

4!2•

6H2O

was

prep

ared

bypr

ecip

itatio

nfr

om0.

1m

oldm

23

solu

tions

ofT

h~NO

3!4

and

oxal

icac

id.T

hepr

ecip

itate

was

allo

wed

tost

and

for

1da

y,th

em

othe

rliq

uor

deca

nted

,an

dth

epr

ecip

itate

stirr

edw

ith0.

1m

oldm2

3H

NO

3fo

r5

–6

h.T

he

Co

~1!

~2!

~4!

ha pe ma

Th

W tec

in be Re

1 F 2 O 3 V

J

Exc

ess

Th~C

2O4!

2•6H

2Ow

aseq

uilib

rate

din

ath

erm

osta

ted

bath

with

solu

tions

ofth

ede

sire

dco

mpo

sitio

nfo

rat

leas

t24

h.T

heso

lidph

ase

was

allo

wed

tose

ttle

inth

eba

th,

and

som

e60

–10

0g

ofth

esa

tura

ted

solu

tion

was

with

draw

nth

roug

ha

filte

rla

yer.

The

aliq

uot

was

evap

orat

edan

dig

nite

dto

ThO

2.A

smal

lcor

rect

ion

was

appl

ied

for

the

mas

sof

silic

ates

diss

olve

dfr

omgl

assw

are.

24

22

conc

entr

ated

HC

lfro

mth

eso

lutio

nof

the

salt

inth

eso

lutio

nof

NH

41ox

alat

e.T

hepr

oced

ure

was

repe

ated

seve

ralt

imes

topu

rify

Th

oxal

ate

from

lant

hani

des.

Afte

rai

rdr

ying

the

prod

uct

cont

aine

d~in

mas

s%!

50.6

8T

hO2,

27.4

7C 2

O3,

and

21.6

7H 2

O.

The

resp

ectiv

eca

lcul

ated

for

Th

~C2O

4!2•

6H2O

are

51.2

1,27

.88,

and

20.9

1.O

xalic

acid

used

did

noty

ield

any

resi

due

onig

nitio

n.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~Hau

ser

and

Wirt

h1 !.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 O.

Hau

ser

and

F.

Wirt

h,Z

.A

nal.

Che

m47,

389

~190

8!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#S

ulfu

ricac

id;

H 2S

O4;

@766

4-93

-9#W

ater

;H 2

O;

@773

2-18

-5#

V.

I.S

pits

yn,

Zh.

Rus

s.F

iz.

Khi

m.

Obs

h.~J.

Rus

s.P

hys.

Che

m.

Soc

.!49

,35

7–

70~1

917!

.

riabl

es:

Pre

pare

dby

:

KK

:29

8/m

oldm

23 5

0.00

35–

0.59

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofT

h~C2O

4!2

inH

2SO

4so

lutio

nsa

H2S

O4

2/m

oldm

23 )b

ThO

2

~mg

dm2

3 !T

h~C

2O4!

2c

(104

c 1/m

oldm

23 )

H2S

O4

(c2

/mol

dm2

3 )bT

hO2

~mg

dm2

3 !T

h~C

2O4!

2c

(104

c 1/m

oldm

23 )

0.00

350.

80.

031

0.24

461.

74

0.01

20.

076

0.24

553

2.01

0.01

53

0.11

40.

2555

2.08

0.03

6.9

0.26

20.

2960

2.27

0.05

120.

454

0.45

903.

41

0.10

180.

682

0.49

108

4.09

0.20

431.

630.

5912

04.

54

atur

eof

the

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.W

ithre

fere

nce

toW

irth

1th

eco

mpi

ler

assu

mes

this

tobe

the

hexa

hydr

ate,

h~C

2O4!

2•6H

2O,

@167

88-6

2-8#.

once

ntra

tion

give

nin

norm

ality

inth

eor

igin

aldo

cum

ent.

Rec

alcu

late

dto

mol

dm2

3by

com

pile

r.al

cula

ted

byco

mpi

ler.

ditio

nali

nfor

mat

ion:

sore

port

edw

asth

eso

lubi

lity

ofT

h~C2O

4!2

insu

lfuric

acid

solu

tions

satu

rate

dw

ithC

e2~

C2O

4!3.

The

conc

entr

atio

nof

the

latte

rw

asno

tpo

rted

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

was

used

.E

xces

sT

h~C

2O4!

2•6H

2Ola

bele

dth

234 T

hw

aseq

uilib

rate

dw

ithth

eso

lutio

nof

the

desi

red

mpo

sitio

nfor

6h

whi

chw

asfo

und

suffi

cien

tfo

rsa

tura

tion

bere

ache

d.A

fter

equi

libra

tion,

100

–20

0m

Lof

the

tura

ted

solu

tion

was

evap

orat

edon

apo

rcel

aine

dish

and

bac

tivity

ofth

ere

sidu

ew

asm

easu

red

inan

elec

tros

cope

.T

heam

ount

ofth

oriu

mw

asob

tain

edby

com

parin

gth

em

easu

red

activ

ityw

ithth

atof

akn

own

amou

ntof

labe

led

Th~

C2O

4!2•

6H2O

.

Labe

led

Th~C

2O4!

2•6H

2Ow

aspr

epar

edby

prec

ipita

tion.

An

aliq

uot

ofU

X 1(23

4 Th)

prep

arat

ion

was

adde

dto

aso

lutio

nof

Th~

NO

3!O

4,an

dT

h~C

2O4!

2•6H

2Ow

aspr

ecip

itate

dby

addi

ngho

tso

lutio

nof

oxal

icac

id.

The

prec

ipita

tew

asw

ashe

dse

vera

ltim

esw

ithho

tw

ater

.A

fter

seve

rald

ecan

tatio

nsw

ithco

ldw

ater

the

prec

ipita

tetu

rned

into

crys

talli

nefo

rm.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

prec

isio

n6~1

–2!

%~a

utho

r!.

Ref

eren

ces:

1 F.

Wirt

h,Z

.A

norg

.C

hem

.76,

174

~191

2!.

554554 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#~2

!S

ulfu

ricac

id;

H 2S

O4;

@766

4-93

-9#~3

!W

ater

;H 2

O;

@773

2-18

-5#

1 F.

Wirt

h,Z

.A

norg

.C

hem

.76,

174

–20

0~19

12!.

2 O.

Hau

ser

and

F.

Wirt

h,Z

.A

norg

.C

hem

.78

,75

–94

~191

2!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8c 2

/mol

dm2

3 50.

125

–4.

225

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofT

h~C2O

4!2

inH

2SO

4so

lutio

nsa

H2S

O4

(c2

/mol

dm2

3 )bT

hO2

~g/k

gso

lutio

n!T

h~C

2O4!

2

~103

mol

/kg

solu

tion!

0.12

5c0.

070.

264

0.25

c0.

140.

529

0.50

c0.

260.

983

0.50

d0.

258

0.97

7e

1.00

d0.

391.

48e

1.05

c0.

418

1.58

1.60

c0.

712.

68

2.16

d1.

14.

17e

2.45

c1.

324.

99

3.09

d1.

513

5.73

e

3.34

d1.

794

6.79

e

4.22

5d2.

473

9.37

e

a Equ

ilibr

ium

solid

phas

eT

h~C2O

4!2•

6H2O

,@1

6788

-62-

8#,in

alls

atur

ated

solu

tions

.b C

once

ntra

tion

ofH 2S

O4

repo

rted

inno

rmal

ityin

the

orig

inal

docu

men

ts.

Rec

alcu

late

dto

mol

dm2

3by

com

pile

r.T

heda

tare

fer

toth

ein

itial

acid

conc

entr

atio

n.c D

ata

from

orig

inal

docu

men

t.2

d Dat

afr

omor

igin

aldo

cum

ent.1

e Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dac

cord

ing

toH

ause

ran

dW

irth

1w

asus

ed.

Th~

CO

!•6H

Ow

aspr

epar

edby

prec

ipita

ting

itw

ith

Co

~1!

~2!

~3!

Va

T/

c 2 (c a N T b C c C Ad

Al

re Me

Iso

wi

co to sa


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

bis~o

xala

te!;

Th~

C2O

4)2

;@2

040-

52-0#

Oxa

licac

id;

C 2H

2O4;

@144

-62-

7#W

ater

;H 2

O;

@773

2-18

-5#

A.

G.

Kur

nako

vaan

dL.

K.

Shu

boch

kin,

Zh.

Neo

rg.

Khi

m.

8,12

49–

54;

Rus

s.J.

Inor

g.C

hem

.8,

647

–50

~196

3!.

riabl

es:

Pre

pare

dby

:

K:

298

mol

kg2

15

0–

1.29

6J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofT

h~C2O

4)2

inC

2H2O

4so

lutio

ns

C2H

2O4

00w

2/m

ass

%)

C2H

2O4

~mol

kg2

1 !aC

2H2O

4

(m2

/mol

kg2

1 )bT

h~m

gkg

21 !c

Th

(104

mol

kg2

1 )aT

h(m

1/1

04m

olkg

21 )

00

011

0.47

4e0.

474f

0.35

0.03

90.

039

12d0.

517

0.51

9f

2.39

0.26

50.

272

150.

646

0.66

2f

3.50

0.38

90.

403

170.

732

0.75

9f

4.85

0.53

90.

566

180.

775

0.81

5f

10.4

51.

161

1.29

618

0.77

50.

866

g

olpe

rkg

solu

tion.

alcu

late

dby

com

pile

r.ili

gram

spe

rkg

solu

tion.

heva

lue

of22

mg

kg21

solu

tion

give

nin

the

orig

inal

docu

men

tis

obvi

ousl

ya

mis

prin

t,as

follo

ws

from

the

auth

ors’

corr

espo

ndin

gol

kg2

1so

lutio

nva

lue.

ecal

cula

ted

byco

mpi

ler;

the

auth

ors

repo

rted

0.45

43

102

4m

olkg

21

solu

tion.

quili

briu

mso

lidph

ase

was

Th~C

2O4!

2•6H

2O,

@167

88-6

2-8#.

quili

briu

mso

lidph

ases

wer

eT

h~C2O

4!2•

6H2O

,@1

6788

-62-

8#an

dC 2

H2O

4•2H

2O,

@615

3-56

-6#.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.S

olut

ions

with

exce

ssso

lidw

ere

itate

dfo

r7

days

.T

heco

ncen

trat

ion

ofC

2H2O

4in

the

tura

ted

solu

tions

was

dete

rmin

edby

titra

tion

with

0.05

NnO

4.T

horiu

mco

ncen

trat

ion

was

dete

rmin

eddi

omet

rical

lyby

bco

untin

g.A

fter

cent

rifug

atio

n,4

–5

gof

satu

rate

dso

lutio

nw

ere

wei

ghed

out

inse

vera

ladd

ition

son

toan

ashl

ess

filte

rw

ithdr

ying

afte

rea

chad

ditio

n.T

hebac

tivity

ofth

esa

tura

ted

solu

tions

was

com

pare

dw

ithth

ose

ofth

est

anda

rds

prep

ared

from

labe

led

Th

~C2O

4!2•

6H2O

.T

heco

mpo

sitio

nof

the

equi

libriu

mso

lidph

ases

was

dete

rmin

edby

optic

alm

icro

scop

y.

Th~

C2O

4!2•

6H2O

was

prep

ared

from

thor

ium

nitr

ate

ofun

spec

ified

sour

cean

dpu

rity.

To

incr

ease bac

tivity

ofth

oriu

mfo

rits

subs

eque

ntra

diom

etric

dete

rmin

atio

n,ag

edU

O2~

NO

3!2

inra

dioa

ctiv

eeq

uilib

rium

with

the

thor

ium

isot

ope

UX

1~23

4 Th)

was

adde

dto

Th~N

O3!

4,an

dT

h~C

2O4!

2•6H

2Ow

aspr

ecip

itate

dfr

omho

tso

lutio

nw

itha

stoi

chio

met

ricam

ount

ofox

alic

acid

.T

hela

bele

dT

h~C2O

4!2•

6H2O

was

filte

red,

was

hed

ten

times

with

boili

ngw

ater

and

air

drie

dfo

r4

–5

days

.O

xalic

acid~c.p

.!w

asre

crys

talli

zed

and

air

drie

d.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4)2

;@2

040-

52-0#

~2!

Oxa

licac

id;

C 2H

2O4;

@144

-62-

7#~3

!W

ater

;H 2

O;

@773

2-18

-5#

M.

Col

ani,

Com

pt.

Ren

d.,15

6,10

75–

6~19

13!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:32

310

0w2

/mas

s%5

1.7

–23

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

50°C

ofT

h~C2O

4!2

inox

alic

acid

solu

tionsa

C2H

2O4

(100

w2

/mas

s%

)C

2H2O

4

(m2

/mol

kg2

1 )aT

h~m

ass

%!T

h~C

2O4!

2

(105

m1

/mol

kg2

1 )b

1.7

0.19

20.

0002

0.87

6

6.5

0.77

20.

0007

3.23

9.3

1.14

0.00

14.

75

23.0

3.32

0.00

316

.8

a Equ

ilibr

ium

solid

phas

ew

asT

h~C2O

4!2•

6H2O

,@1

6788

-62-

8#,in

alls

olut

ions

.b C

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Not

hing

spec

ified

.N

othi

ngsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Co

~1!

~2!

~3!

Va

T/

m2

(1 a M b C c M d T m e R f E g E Me

Iso

ag sa KM

ra the

J

filte

rpa

pers

,an

dai

rdr

ied.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

bis~o

xala

te!;

Th~

C2O

4)2

;@2

040-

52-0#

Pot

assi

umox

alat

e;K 2C

2O4;

@583

-52-

8#W

ater

;H 2

O;

@773

2-18

-5#

N.P

.Luz

hnay

aan

dI.

S.K

oval

eva,

Zh.

Neo

rg,K

him

.6,

1436

–9

~196

1!;

Rus

s.J.

Inor

g.C

hem

.6,73

6–

8~1

961!

.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

kg2

1 :0

–2.

69J.

Hala

Exp

erim

enta

lDat

a

Com

posi

tion

ofK 2

C2O

4so

lutio

nssa

tura

ted

with

Th~C

2O4)

2at

25°C

K2C

2O4

2/m

ass

%)

K2C

2O4

(m2

/mol

kg2

1 )aT

h~C

2O4)

2

(w1

/mas

s%

)T

h~C

2O4)

2

(m1

/mol

kg2

3 )D

ensi

ty~g

cm2

3 !S

olid

phas

eb

00

7.53

102

51.

843

102

6—

A

0.96

0.05

860.

560.

0139

1.00

88A

0.98

0.60

00.

720.

0179

1.01

07A

1.85

0.15

51.

530.

0388

1.01

5A

2.90

0.18

31.

710.

0439

1.03

7A1B

3.19

0.20

21.

700.

0438

1.03

6A1B

3.19

0.20

21.

850.

0477

1.03

7A1B

6.58

0.43

11.

650.

0441

1.05

9B

9.32

0.63

21.

970.

0544

1.08

5B

14.2

21.

028

2.58

0.07

601.

132

B

28.2

22.

555.

100.

187

1.28

4B

29.3

72.

695.

060.

189

1.28

8B1C

29.3

22.

695.

110.

191

1.28

8B1C

27.9

02.

463.

730.

137

1.24

6C

27.4

12.

311.

160.

0398

1.23

2C

27.2

32.

25—

—1.

214

C

alcu

late

dby

com

pile

r.!T

h~C

2O4!

2•6H

2O,

@167

88-6

2-8#;

~B!

K4T

h~C

2O4!

4•4H

2O,

@#;

~C!

K2C

2O4•

H2O

,@6

487-

48-5#

.

ditio

nalI

nfor

mat

ion:

eso

lubi

lity

isot

herm

ofth

eK 2C

2O4–

Th~

C2O

4!2–

H2O

syst

emsh

owed

thre

ebr

anch

esco

rres

pond

ing

toth

ecr

ysta

lliza

tion

of~C

2O4!

2•6H

2O,

K4T

h~C

2O4!

4•4H

2O,

and

K 2C

2O4•

H2O

.T

here

wer

etw

ote

rnar

ypo

ints

onth

eis

othe

rm:

the

euto

nic

poin

tat

29.3

5ss

%K 2

C2O

4an

d5.

08m

ass

%T

h~C2O

4!2,

and

the

tran

sitio

npo

int

at3.

09m

ass

%K

2C2O

4an

d1.

75m

ass

%T

h~C2O

4!2.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Sol

utio

nsw

ithex

cess

solid

wer

est

irred

ina

ther

mos

tate

dve

ssel

at25

°Cfo

r2

days

whi

chw

asfo

und

suffi

cien

tto

reac

heq

uilib

rium

.S

ampl

esfo

ran

alys

isw

ere

take

naf

ter

3da

ys.

Inth

esa

tura

ted

solu

tions

and

solid

phas

es,

pota

ssiu

mw

asde

term

ined

grav

imet

rical

lyas

K2S

O4

orK

3Co~

NO

2!6,

thor

ium

grav

imet

rical

lyas

ThO 2

,an

dox

alat

etit

rimet

rical

lyw

ithst

anda

rdK

MnO

4so

lutio

n.T

heco

mpo

sitio

nof

the

equi

libriu

mso

lidph

ases

was

also

dete

rmin

edby

the

met

hod

ofw

etre

sidu

es,

and

the

phas

esw

ere

also

char

acte

rized

byx-

ray

diffr

actio

nan

dth

erm

alan

alys

is.

Tw

ice

recr

ysta

llize

dpo

tass

ium

and

thor

ium

oxal

ates

wer

eus

ed.

No

othe

rde

tails

wer

ere

port

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

556556 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#~2

!S

odiu

mox

alat

e;N

a 2C2O

4;@6

2-76

-0#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

H.

T.

S.

Brit

ton

and

M.

E.

D.

Jarr

ett,

J.C

hem

.S

oc.,

1494

–5

~193

6!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8c 2

/mol

dm2

3 :0.

01–

0.27

J.H

ala

Exp

erim

enta

lDat

a

Com

posi

tion

ofN

a 2C2O

4so

lutio

nssa

tura

ted

with

Th~C

2O4!

2at

25°C

Na 2

C2O

4

(c2

/mol

dm2

3 )T

h~C

2O4!

2

(c1

/mol

dm2

3 )S

olid

phas

eaN

a 2C

2O4

(c2

/mol

dm2

3 )T

h~C

2O4!

2

(c1

/mol

dm2

3 )S

olid

phas

ea

0.01

002

0.00

0901

A0.

2281

0.03

920

B

0.02

005

0.00

2762

A0.

2879

0.03

852

B

0.03

844

0.00

9055

A0.

3257

0.04

543

B

0.04

839

0.01

338

A0.

3184

0.03

900

B1

C

0.05

520

0.01

550

A0.

3110

0.03

490

C

0.07

554

0.02

398

A0.

3022

0.03

036

C

0.09

158

0.03

051

A0.

2793

0.01

166

C

0.14

080.

0463

4A

0.26

720.

0036

1C

0.16

790.

0512

8A1

B0.

2676

0C

0.19

450.

0442

0B

a ~A!

Th~

C2O

4!2•

6H2O

,@1

6788

-62-

8#;~B

!N

a 4T

h~C

2O4!

4•6H

2O,

@#;

~C!

Na 2

C2O

4@6

2-76

-0#.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dw

asus

ed.

Sui

tabl

em

ixtu

res

ofso

lutio

nsof

each

oxal

ate

wer

eal

low

edto

com

eto

equi

libriu

min

ath

erm

osta

ted

bath

whi

chto

okab

out

3w

eeks

.T

heco

nten

tof

oxal

ate

inth

esa

tura

ted

solu

tions

was

dete

rmin

edby

titra

tion

with

KM

nO4

solu

tion,

the

cont

ent

ofth

oriu

mw

asde

term

ined

grav

imet

rical

lyas

thor

ium

oxal

ate

prec

ipita

ted

from

1to

2m

oldm

23

HC

lsol

utio

ns.

The

solid

phas

esw

ere

anal

yzed

afte

rbe

ing

filte

red,

free

dfr

omad

herin

gliq

uid

bypr

essu

rebe

twee

n

Th~

C2O

4!2•

6H2O

was

obta

ined

bypr

ecip

itatin

gth

oriu

mch

lorid

eso

lutio

nw

ithox

alic

acid

.Ana

lysi

s~mas

s%!

:ThO

2fo

und

51.2

0,ca

lcul

ated

51.1

6.N

a 2C2O

4w

asof

antir

eflec

tion~

A.

R.!

qual

ity.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Co

~1!

~2!

~3!

Va

T/

m2

(w a C b ~A Ad

Th

Th

ma


Th~

C2O

4!2

was

foun

dto

fitth

eeq

uatio

n:

log

CT

h50.

893

log @

C2O

422#2

0.85

2.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

Th

~C2O

4!2•

6H2O

was

equi

libra

ted

inth

erm

osta

ted

vess

els

for

6h

whi

chw

asfo

und

suffi

cien

tto

reac

heq

uilib

rium

.T

heeq

uilib

rium

conc

entr

atio

nof

oxal

ate

ion

inth

eso

lutio

nsw

asva

ried

byva

ryin

gei

ther

acid

ityat

cons

tant

oxal

ate

conc

entr

atio

n,or

tota

loxa

late

conc

entr

atio

nat

afix

edac

idity

.A

fter

equi

libra

tion

the

satu

rate

dso

lutio

nsw

ere

cent

rifug

edan

dth

eco

ncen

trat

ion

ofth

oriu

mw

asde

term

ined

colo

rimet

rical

lyw

ithar

sena

zoIII

.2

The

met

hods

ofpH

mea

sure

men

tan

dof

the

dete

rmin

atio

nof

tota

lequ

ilibr

ium

oxal

ate

conc

entr

atio

nw

ere

not

spec

ified

.

Th~

C2O

4!2•

6H2O

was

prep

ared

bypr

ecip

itatio

nac

cord

ing

toR

abch

ikov

and

Gol

brai

kh.

3

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

2K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.V

.Ste

pano

van

dE

.M.P

azuk

hin,

Zh.

Neo

rg.K

him

.15

,148

3~1

970!

.2 S

.B

.S

avvi

n,A

rse

na

zoII

I~A

tom

izda

t,M

osco

w,

1966!

~inR

ussi

an!,

p.10

7.3 D

.I.

Rab

chik

ovan

dE

.K

.G

olbr

aikh

,An

aly

tica

lC

he

mis

try

of

Th

oriu

m,

~Pub

l.H

ouse

Aca

d.S

ci.

US

SR

,M

osco

w,

1960

!~in

Rus

sian

!,p.

33.

4.9.

5.E

valu

atio

nof

the

Th

„C

2O4…

2¿„N

H4…

2C2O

4¿H

2OS

yste

m

mpo

nent

s:E

valu

ator

:

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#A

mm

oniu

mox

alat

e;~N

H4!

2C2O

4;@1

113-

38-8#

Wat

er;

H 2O

;@7

732-

18-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

611

37B

rno,

Cze

chR

epub

lic,

Feb

ruar

y20

00

Crit

ical

Eva

luat

ion:

Alth

ough

this

syst

emha

sbe

enst

udie

din

five

docu

men

tsth

ere

seem

sto

bem

uch

unce

rtai

nty

inbo

thth

eso

lubi

lity

ofT

h~C

2O4!

2in

mon

ium

oxal

ate

solu

tions

and

inth

ena

ture

ofth

eeq

uilib

rium

solid

phas

es.

Intw

ost

udie

s1,

2w

here

the

resu

ltsw

ere

repo

rted

inld

m2

3un

its,

the~

NH

4!2C

2O4

conc

entr

atio

nra

nge

cove

red

was

63

102

4–

5310

22,1

and

0.02

5–

0.1

mol

dm23 .2

Ifth

edi

ffere

nce

inpe

ratu

re,

i.e.,

298.

1K

inR

ef.

1an

d29

3.1

Kin

Ref

.2,

isne

glec

ted

then

the

solu

bilit

yof

Th

~C2O

4!2

can

beco

mpa

red

only

attw

oH

4!2C

2O4

conc

entr

atio

ns:

for

0.05

mol

dm23

~NH

4!2C

2O4

the

solu

bilit

yof

Th~

C2O

4!2

was

repo

rted

tobe

0.01

22

and

0.03

85ld

m2

3 ,1w

hile

for

0.02

5m

oldm

23

~NH

4!2C

2O4

the

solu

bilit

ies

wer

e0.

05–

0.08

32

and

0.01

71m

oldm

3 .Apa

rtfr

omth

edi

scre

panc

yin

lubi

litie

s,th

ew

ork

ofP

azuk

hine

ta

l.2in

dica

tes

that

the

solu

bilit

yof

Th~C

2O4!

2in

~NH

4!2C

2O4

solu

tions

ispH

depe

nden

tsi

nce

ange

sin

pHaf

fect

the

equi

libriu

mox

alat

eio

nco

ncen

trat

ion.

InR

efs.

1an

d2

equi

libra

tion

time

of6

was

used

.In

Ref

s.3

and

4th

ere

sults

wer

ere

port

edin

mas

s%

orm

olpe

rkg

satu

rate

dso

lutio

nso

that

the

data

coul

dbe

reca

lcul

ated

tola

litie

s.T

hese

two

stud

ies

agre

ein

that

equi

libriu

min

the

Th

~C2O

4!2–

~NH

4!2C

2O4–

H2O

syst

emis

atta

ined

very

slow

lyso

that

uilib

rium

times

ofse

vera

lwee

ksw

ere

need

ed.J

ames

et

al.3

repo

rted

that

,in

orde

rto

avoi

dm

etas

tabl

esy

stem

s,eq

uilib

ratio

nof

seve

ral

nths

was

nece

ssar

yin

the

vici

nity

oftr

ansi

tion

poin

ts.

Mea

ning

ful

com

paris

onw

hich

wou

ldre

veal

serio

usdi

scre

panc

ies

can

berf

orm

edfo

r~NH

4!2C

2O4

conc

entr

atio

nsof

the

orde

rof

1022

mol

kg2

1 .F

or0.

039

–0.

064

mol

kg21

~NH

4!2C

2O4,

Jam

ese

ta

l.3re

port

edso

lubi

lity

ofT

h~C

2O4!

2to

rang

efr

om0.

0049

to0.

0086

mol

kg21

whi

chne

glec

ting

diffe

rent

conc

entr

atio

nun

its,i

sco

nsid

erab

lylo

wer

nar

eth

ere

spec

tive

data

inR

efs.

1an

d2.

On

the

cont

rary

,H

ause

ran

dW

irth

4re

port

edth

eso

lubi

lity

ofT

h~C2O

4!2

tobe

0.01

22an

d21

4m

olkg

21

at0.

04an

d0.

09m

olkg2

1~N

H4!

2C2O

4w

hich

iscl

oser

toth

eda

tain

Ref

s.1

and

2.C

ontr

over

syse

ems

toex

ist

also

asas

the

natu

reof

the

solid

phas

esis

conc

erne

d.W

hile

Paz

ukhi

ne

ta

l.2re

port

edth

eso

lidph

ase

tobe

Th

~C2O

4!2•

6H2O

,H

ause

ran

dirt

h4

repo

rted

~NH

4!2T

h 2~C

2O4!

5•7H

2Oto

exis

tin

this

syst

em.

The

rese

ems

tobe

are

lativ

ely

good

agre

emen

tof

solu

bilit

yda

taat

H4!

2C2O

4co

ncen

trat

ions

abov

e0.

4m

olkg2

1 .3,4

How

ever

,di

ffere

ntso

lidph

ases

wer

eid

entifi

edin

this

regi

on.

Whi

leH

ause

ran

dirt

h4re

port

ed~N

H4!

2Th~

C2O

4!3•

3H2O

,Ja

mes

et

al.3

repo

rted

thor

ium

oxal

ate

ofun

spec

ified

com

posi

tion

and

H4!

2Th 2

~C2O

4!5•

2H2O

.P

hase

diag

ram

ofth

eT

h~C

2O4!

2–

~NH

4!2C

2O4–

H2O

syst

emw

asst

udie

dby

Cla

udelet

al.5

who

,ho

wev

er,

port

edth

eir

data

ingr

aphi

calf

orm

only

.T

hus,

due

todi

scre

panc

ies

inth

ere

quire

men

tsfo

req

uilib

ratio

ntim

ene

cess

ary

tore

ach

true

equi

libriu

m,

toth

eim

port

ance

ofpH

ofui

libriu

mso

lutio

ns,

and

todi

scre

panc

ies

inth

ena

ture

ofeq

uilib

rium

solid

phas

es,

none

ofth

ere

port

edse

tsof

data

can

begi

ven

efer

ence

and

itse

ems

that

the

syst

emw

ould

need

ath

orou

ghre

inve

stig

atio

n.

fere

nces

:

.I.

Spi

tsyn

,Z

h.R

uss.

Fiz

.K

him

.O

bsh.4

9,35

7~1

917!

.

.M

.P

azuk

hin,

E.

A.

Sm

irnov

a,A

.S

.K

rivok

hats

kii,

Yu.

L.P

azuk

hina

,an

dS

.M

.K

oche

rgin

,R

adio

khim

iya

27,

606

~198

5!.

.Ja

mes

,C

.F

.W

hitte

mor

e,an

dH

.C

.H

olde

n,J.

Am

.C

hem

.S

oc.

36,

1853

~191

4!.

.H

ause

ran

dF

.W

irth,

Z.

Ano

rg.

Che

m.

78,

75~1

912!

.5 B

.C

laud

el,

G.

Lang

,an

dA

.N

avar

ro,

Bul

l.S

oc.

Chi

m.

Fra

nce

2094

~196

6!.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4)2

;@2

040-

52-0#

~2!

Pot

assi

umox

alat

e;K 2C

2O4;

@583

-52-

8#~3

!W

ater

;H 2

O;

@773

2-18

-5#

E.

M.

Paz

ukhi

n,E

.A

.S

mirn

ova,

A.

S.

Kriv

okha

tski

i,Y

u.L.

Paz

ukhi

na,

and

S.

M.

Koc

herg

in,

Rad

iokh

imiy

a,27,

606

–11

~198

5!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

3E

quili

briu

mox

alat

eio

nco

ncen

trat

ion/

mol

dm23 :

0.11

4–

0.29

8J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofT

h~C2O

4!2

inK

2C2O

4so

lutio

nsa

K2C

2O4b

(c2

/mol

dm2

3 )C

2O

422

c

~mol

dm2

3 !pH

@C2O

422#d

~mol

dm2

3 !T

h~C

2O4!

2

~mol

dm2

3 !

0.20

0.21

36.

120.

212

0.02

89

0.20

0.21

56.

060.

214

0.03

23

0.39

40.

298

6.25

0.29

80.

0463

0.09

30.

134

4.54

0.11

60.

0212

0.09

30.

129

4.61

0.11

40.

0191

0.2

0.21

36.

120.

212

0.02

89

0.2

0.21

56.

060.

214

0.03

23

0.4

0.27

66.

150.

275

0.03

27

0.4

0.29

86.

250.

298

0.04

63

0.1

0.13

14.

540.

116

0.02

12

0.1

0.12

95.

610.

114

0.01

91

0.1

0.11

85.

960.

117

0.02

80

0.1

0.12

25.

680.

121

0.03

12

0.1

0.12

255.

840.

122

0.02

67

0.1

0.11

76.

140.

117

0.02

62

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

Itw

asm

entio

ned,

how

ever

,th

atT

h~C

2O4!

2•6H

2Odi

dno

tun

derg

oan

ych

ange

durin

geq

uilib

ratio

n.b In

itial

conc

entr

atio

n.c E

quili

briu

mto

talo

xala

teio

nco

ncen

trat

ion.

d Equ

ilibr

ium

conc

entr

atio

nof

the

C 2O422

ion

calc

ulat

edby

auth

ors

from

tota

lox

alat

eco

ncen

trat

ion

and

the

mea

sure

dpH

byus

ing

diss

ocia

tion

cons

tant

sof

oxal

icac

id,

Ka1

51.

053

102

1an

dK

a25

1.88

310

25.1

Add

ition

alIn

form

atio

n:In

the

rang

eof

equi

libriu

mox

alat

eio

nco

ncen

trat

ion

cove

red

inth

isst

udy

ofth

eT

h~C

2O4!

2–

K2C

2O4–

H2O

syst

em,

the

solu

bilit

yof

Co

~1!

~2!

~3!

am mo

tem

~N mo

so ch mo

eq mo

pe the

tha

0.0

far

W ~N W ~N re eq pr Re

1 V 2 E 3 C 4 O

J

1.47

12.

5014

8.1

0.56

00.

951

C

1.48

02.

5214

8.9

0.56

30.

960

C

a Mol

per

kgso

lutio

n.b C

alcu

late

dby

com

pile

r.c A

:T

h~C

2O4!

2•6H

2O,

@167

88-6

2-8#;

B:

~NH

4!2T

h 2~C

2O4!

5•7H

2O,

@#;

C:~

NH

4!2T

h~C

2O4!

3•3H

2O,

@#.

d Not

repo

rted

.e T

hese

two

mea

sure

men

tsw

ere

repo

rted

tosh

owth

atbo

thw

ays

ofap

proa

chin

geq

uilib

rium

yiel

ded

iden

tical

resu

lts.

f Dat

aob

tain

edby

prol

onge

deq

uilib

ratio

nof

Th

~C2O

4!2•

6H2O

insu

cha

way

that

the

supe

rnat

ant

solu

tion

was

repe

ated

lyre

plac

edby

fres

hpo

rtio

nsin

orde

rto

elim

inat

eth

ein

fluen

ceof

the

decr

ease

of~N

H4!

2C2O

4co

ncen

trat

ion

inth

eso

lutio

ndu

eto

the

form

atio

nof

the

com

plex

solid

phas

e.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.S

ince

the

diss

olut

ion

ofth

oriu

mal

ate

indi

lute

solu

tions

ofam

mon

ium

oxal

ate

isa

very

slow

oces

s,th

esy

stem

sin

the

first

thre

ese

ries

ofm

easu

rem

ents

eab

ove!w

ere

prep

ared

bydi

lutin

gso

lutio

nsof

the

4–

Th

–ox

alat

eco

mpl

exw

ithth

ere

quire

dam

ount

ofw

ater

.lu

tions

with

the

prec

ipita

ted

solid

phas

ew

ere

allo

wed

tond

for

3w

eeks

with

freq

uent

shak

ing.

Inth

efo

urth

serie

s,ce

ssT

h~C2O

4!2•

6H2O

was

equi

libra

ted

for

seve

rald

ays

with

mon

ium

oxal

ate

solu

tions

pres

atur

ated

with

~C2O

4!2•

6H2O

,an

din

the

pres

ence

ofso

lid~NH

4!2C

2O4

rodu

ced

toth

esy

stem

ina

silk

bag

imm

erse

din

toth

elu

tion.

As

inH

ause

ran

dW

irth,1

som

e60

–10

0g

ofth

etu

rate

dso

lutio

nw

asw

ithdr

awn

thro

ugh

afil

ter

laye

r,ig

hed,

evap

orat

edan

dig

nite

d.A

smal

lcor

rect

ion

for

icat

esdi

ssol

ved

from

glas

swar

ew

asap

plie

d.S

olid

phas

esre

iden

tified

bych

emic

alan

alys

isan

dop

tical

mic

rosc

opy.

Th~

C2O

4!2•

6H2O

was

prep

ared

bypr

ecip

itatio

nfr

oma

solu

tion

ofth

oriu

mox

alat

ein

conc

entr

ated~

NH

4!2C

2O4

solu

tion

byac

tion

ofco

ncen

trat

edH

Cl.

The

prec

ipita

tion

proc

edur

ew

asre

peat

edse

vera

ltim

esto

purif

yth

oriu

mox

alat

efr

omla

ntha

nide

s.A

fter

air

dryi

ngth

epr

oduc

tco

ntai

ned

~inm

ass

%!50

.86

ThO

2,27

.47

C 2O

3,an

d21

.67

H 2O

.T

here

spec

tive

calc

ulat

edva

lues

for

Th~C

2O4!

2•6H

2Oar

e51

.21,

27.8

8an

d20

.91.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~aut

hors

inR

ef.

1!.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 O.

Hau

ser

and

F.

Wirt

h,Z

.A

nal.

Che

m.

47,

389

~190

8!.

558558 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#~2

!A

mm

oniu

mox

alat

e;~N

H4!

2C2O

4;@1

113-

38-8#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

O.

Hau

ser

and

F.

Wirt

h,Z

.A

norg

.C

hem

.78

,75

–94

~191

2!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:298

m2

/mol

kg2

1:0

.000

33–

2.52

J.H

ala

Exp

erim

enta

lDat

a

Com

posi

tion

of~N

H4!

2C2O

4so

lutio

nssa

tura

ted

with

Th~C

2O4!

2at

25°C

~NH

4!2C

2O4

~mol

kg2

1 !a~N

H4!

2C2O

4

(m2

/mol

kg2

1 )bT

hO2

~gkg

21 !a

Th~

C2O

4!2

~mol

kg2

1 !aT

h~C

2O4!

2

(m1

/mol

kg2

1 !b

Sol

idph

asec

0.00

033

0.00

033

d0.

000

050

0.00

005

0A

0.00

044

0.00

044

d0.

000

081

0.00

008

1A

0.00

072

0.00

072

0.03

20.

000

120

0.00

012

0A

0.00

109

0.00

109

0.05

30.

000

200

0.00

020

0A

0.00

120

0.00

120

0.05

50.

000

208

0.00

020

8A

0.00

130

0.00

130

0.05

70.

000

220

0.00

022

0A

0.00

148

0.00

148

0.06

60.

000

250

0.00

025

0A

0.00

153

0.00

153

d0.

000

260

0.00

026

0A

0.00

230.

0023

0.1

0.00

038

0.00

038

B

0.04

10.

0414

3.2

0.01

210.

0122

B

0.09

00.

0918

5.55

40.

0210

0.02

14B

0.14

50.

150

10.1

040.

0382

0.03

95B

0.22

50.

237

15.8

440.

0599

0.06

32B

0.25

f0.

265

17.6

00.

0665

0.07

06B

0.25

f0.

265

17.7

50.

0670

0.07

12B

0.30

120.

326

25.1

280.

0950

0.10

3C

0.37

000.

409

31.8

200.

1203

0.13

3C

0.60

12e

0.71

151

.577

0.19

500.

231

C

0.60

1e0.

711

51.5

70.

195

0.23

1C

0.88

01.

142

78.1

70.

295

0.38

3C

1.18

11.

739

112.

90.

427

0.62

9C

1.42

02.

3514

2.8

0.54

00.

895

C

Me

Iso

ox pr ~se

NH

So

sta

ex am Th

int

so sa we

sil

we


Cal

cula

ted

byco

mpi

ler.

b A:

auth

ors

desc

ribed

this

solid

phas

eas

thor

ium

oxal

ate

with

out

repo

rtin

gon

the

num

ber

ofm

olec

ules

ofw

ater

ofcr

ysta

lliza

tion;

B:

2Th~

C2O

4!2.~

NH

4!2C

2O4•

2H2O

,@

#.c T

heau

thor

sre

port

thes

epo

ints

tobe

tran

sitio

npo

ints

,an

das

sum

edth

atw

ithin

the

rang

eof

thes

eco

mpo

sitio

nsth

eeq

uilib

rium

solid

phas

ew

as2T

h~C2O

4!2•

~NH

4!2C

2O4•

7H2O

repo

rted

inB

raun

er.

1

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Mix

ture

sco

ntai

ning

wat

eran

dde

sire

dam

ount

sof

thor

ium

and

amm

oniu

mox

alat

esw

ere

rota

ted

inbo

ttles

for

seve

ralw

eeks

ina

ther

mos

tate

dba

than

dal

low

edto

settl

eat

the

sam

ete

mpe

ratu

re.

Inth

evi

cini

tyof

tran

sitio

npo

ints

itw

asne

cess

ary

toeq

uilib

rate

the

mix

ture

sfo

rse

vera

lmon

ths

toav

oid

met

asta

ble

syst

ems.

Inth

ecl

ear

satu

rate

dso

lutio

ns,

thor

ium

was

dete

rmin

edgr

avim

etric

ally

byev

apor

atin

ga

wei

ghed

aliq

uot

ina

plat

inum

dish

and

igni

ting

the

resi

due

toT

hO2.

Oxa

late

cont

ent

was

dete

rmin

edtit

rimet

rical

lyag

ains

tst

anda

rdK

MnO 4

solu

tion.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 J.B

raun

er,

J.C

hem

.S

oc.

73,

951

~189

8!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#A

mm

oniu

mox

alat

e;~N

H4!

2C2O

4;@1

113-

38-8#

Wat

er;

H 2O

;@7

732-

18-5#

V.

I.S

pits

yn,

Zh.

Rus

s.F

iz.

Khi

m.

Obs

h.~J.

Rus

s.P

hys.

Che

m.

Soc

.!49

,35

7–

70~1

917!

.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

dm2

3 :0.

0006

–0.

05J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofT

h~C2O

4!2

in~N

H4!

2C2O

4so

lutio

nsa

~NH

4!2C

2O4

c 2/m

oldm

23 !

ThO

2

~mg

dm2

3 !T

hb

(104

mol

dm2

3 )

0.00

062.

30.

088

0.00

104

0.15

4

0.00

2510

0.38

5

0.00

540

1.54

0.00

7570

2.69

0.01

010

03.

85

0.01

518

06.

92

0.02

034

013

.1

0.02

545

017

.3

0.03

060

023

.1

0.05

010

0038

.5

quili

briu

mso

lidph

ases

wer

eno

tin

vest

igat

ed.

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

was

used

.E

xces

sT

h~C

2O4!

2•6H

2Ola

bele

dth

234 T

hw

aseq

uilib

rate

dw

ithth

eso

lutio

nof

the

desi

red

mpo

sitio

nfor

6h

whi

chw

asfo

und

suffi

cien

tfo

rsa

tura

tion

bere

ache

d.A

fter

equi

libra

tion,

100

–20

0m

Lof

the

tura

ted

solu

tion

was

evap

orat

edon

apo

rcel

aine

dish

and

btiv

ityof

the

resi

due

was

mea

sure

din

anel

ectr

osco

pe.

The

amou

ntof

thor

ium

was

obta

ined

byco

mpa

ring

the

mea

sure

dac

tivity

with

that

ofa

know

nam

ount

ofla

bele

dT

h~C

2O4!

2•6H

2O.

Labe

led

Th~C

2O4!

2•6H

2Ow

aspr

epar

edby

prec

ipita

tion.

An

aliq

uot

ofU

X 1(23

4 Th)

prep

arat

ion

was

adde

dto

aso

lutio

nof

Th~

NO

3!4,

and

Th~

C2O

4!2•

6H2O

was

prec

ipita

ted

byad

ding

hot

solu

tion

ofox

alic

acid

.The

prec

ipita

tew

asw

ashe

dse

vera

ltim

esw

ithho

tw

ater

.A

fter

seve

ral

deca

ntat

ions

with

cold

wat

erth

epr

ecip

itate

turn

edin

tocr

ysta

lline

form

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Tho

rium

conc

entr

atio

n:pr

ecis

ion6

~1–

2!%

~aut

hor!.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#~2

!A

mm

oniu

mox

alat

e;~N

H4!

2C2O

4;@1

113-

38-8#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

C.

Jam

es,

C.

F.

Whi

ttem

ore,

and

H.

C.

Hol

den,

J.A

m.

Che

m.

Soc

.36,

1853

–6~

1914

!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:298

100w

2/m

ass%

50.

03–

17.4

9J.

Hala

Exp

erim

enta

lDat

a

Com

posi

tion

of~N

H4!

2C2O

4so

lutio

nssa

tura

ted

with

Th~C

2O4!

2at

20°C

~NH

4!2C

2O4

(100

w2

/mas

s%)

~NH

4!2C

2O4

(m2

/mol

kg2

1 )aT

h~C

2O4!

2

(100

w1

/mas

s%)

Th~

C2O

4!2

(m1

/mol

kg2

1 )aS

olid

phas

eb

0.03

0.00

242

0.03

0.00

0735

A

0.48

0.03

890.

200.

0049

0A

0.52

0.04

260.

360.

0088

2A

0.79

0.06

440.

350.

0085

8A

0.89

0.07

280.

570.

0142

B

1.50

0.12

41.

310.

0331

B

1.65

0.13

71.

380.

0348

B

4.83

0.43

25.

060.

138

B

6.93

0.65

57.

790.

224

B

10.2

71.

069

12.3

50.

391

B

12.2

01.

357

15.3

50.

519

B

15.0

71.

857

19.5

40.

732

B

17.4

9c2.

375

23.1

90.

958

B

5.62

0.48

71.

430.

0377

A

6.93

0.62

84.

070.

112

A

8.70

0.83

67.

400.

216

A

11.6

81.

246

12.7

60.

414

A

11.6

81.

246

12.7

70.

414

A

14.5

21.

730

17.8

40.

646

A

17.1

1c2.

270

22.1

80.

895

A

17.1

3c2.

274

22.1

60.

894

A

a

Co

~1!

~2!

~3!

Va

T/

c 2

(

a E b C Me

Iso

wi

co to sa ac

J

FIG

.3.

Tho

rium

bis~o

xala

te!–

amm

oniu

mox

alat

e–

wat

ersy

stem

.~I

!ho

mog

eneo

usso

lutio

ns;~II–

VIII

!he

tero

gene

ous

regi

ons,

satu

rate

d

lutio

nsin

equi

libriu

mw

ith:~

II!:

Th~

C2O

4!2•

6H2O

,@1

6788

-62-

8#,~I

II!

2Th~

C2O

4!2•

~NH

4!2C

2O4•

7H2O

,@

#,~I

V!

Th~

C2O

4!2•

H4!

2C2O

4•3H

2O,@

#,~V

!~N

H4!

2C2O

4•H

2O,

@600

0-70

-7#,

~VI!

Th~

C2O

4!2•

~NH

4!2C

2O4•

3H2O

1~N

H4!

2O4•

H2O

,~V

II!

Th~

C2O

4!2•

H4!

2C2O

4•3H

2O1

2Th~

C2O

4!2,

~NH

4!2C

2O4•

7H2O

,~V

III!

Th~

C2O

4!2•

6H2O

12T

h~C

2O4!

2•~N

H4!

2C2O

4•7H

2O

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

thin

gsp

ecifi

ed.

Not

hing

spec

ified

.

Est

imat

edE

rror

:N

othi

ngsp

ecifi

ed.

560560 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#~2

!A

mm

oniu

mox

alat

e;(N

H 4!2C

2O4;

@111

3-38

-8#~3

!W

ater

;H 2

O;

@773

2-18

-5#

B.

Cla

udel

,G

.La

ng,

and

A.

Nav

arro

,B

ull.

Soc

.C

him

.F

ranc

e20

94–

9~19

66!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8co

mpo

sitio

nJ.

Hala

Exp

erim

enta

lDat

a

Pha

sedi

agra

m~F

ig.

3!of

the

Th~

C2O

4!2–

~NH

4!2C

2O4–

H2O

syst

emat

25°C

.

so ~N ~N Me

No


0.1

0.13

14.

6211

.623

6

0.1

0.14

14.

6812

.722

4

0.1

0.13

66.

1313

.623

1

0.1

0.13

46.

2113

.422

8

0.1

0.13

14.

6211

.623

6

0.1

0.14

14.

6812

.722

4

0.1

0.13

66.

1313

.66

231

0.1

0.13

46.

2113

.422

8

0.05

0.08

304.

747.

5912

0

0.05

0.07

404.

806.

7612

0

0.02

50.

0375

4.90

3.55

530

0.02

50.

0355

4.98

3.39

500

0.1

0.11

73.

412.

8271

.1

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.T

heco

mpi

ler

assu

mes

this

tobe

Th

~C2O

4!2•

6H2O

,@1

6788

-62-

8#si

nce

the

auth

ors

repo

rted

that

the

initi

also

lidph

ase

did

not

unde

rgo

any

chan

gedu

ring

equi

libra

tion.

b Initi

alco

ncen

trat

ion.

c Equ

ilibr

ium

tota

loxa

late

ion

conc

entr

atio

n.d S

olut

ions

with

pH,

3w

ere

brou

ght

toth

ede

sire

dac

idity

byad

ding

HN

O3.

e Equ

ilibr

ium

conc

entr

atio

nof

the

C 2O422

ion

calc

ulat

edby

usin

gdi

ssoc

iatio

nco

nsta

nts

ofox

alic

acid

,K

a15

1.05

310

21

and

Ka2

51.

88

102

5~R

ef.

1!fr

omto

tal

oxal

ate

conc

entr

atio

nan

dH

1io

nco

ncen

trat

ion.

Inso

lutio

nsof~N

H4!

2C2O

4no

tac

idifi

edw

ithH

NO 3

,th

enc

entr

atio

nof

H1io

nw

asob

tain

edas

log@H

1#5

2pH

2lo

gg~H

1!,

whe

re2

log

g~H

1!5

0.50

63AI/

(11

1.51

AI)

20.

2395

I~I

isio

nic

reng

th!.

Inac

idifi

ed~N

H4!

2C2O

4so

lutio

ns,

the

conc

entr

atio

nof

H1

ion

was

obta

ined

from

the

equa

tion

1#5

CH

NO

32@H

C2O

42#2

2@H

2C2O

4#an

ddi

ssoc

iatio

nco

nsta

nts

ofox

alic

acid

.

ditio

nali

nfor

mat

ion:

eso

lubi

lity

ofT

h~C

2O4!

2in

the

Th~

C2O

4!2–

~NH

4!2C

2O4–

H2O

syst

emat

equi

libriu

mox

alat

eio

nco

ncen

trat

ions<0.

01m

oldm

23

was

own

byth

eau

thor

sto

fitth

esa

me

equa

tion

asin

the

Th

~C2O

4!2–

C2H

2O4–

H2O

syst

em,

i.e.,

log

CT

h50.

2683

~log

@C2O

422#!

21

2.94

7lo

g @C

2O422

#12.

330.

high

erox

alat

eco

ncen

trat

ions

the

solu

bilit

yco

uld

beex

pres

sed

as

log

CT

h50.

893

log @

C2O

422#2

0.85

2.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

xces

sT

h~C

2O4!

2•6H

2Ow

asui

libra

ted

inth

erm

osta

ted

vess

els

for

6h

whi

chw

asfo

und

ffici

ent

tore

ach

equi

libriu

m.

The

equi

libriu

mco

ncen

trat

ion

oxal

ate

ion

inth

eso

lutio

nsw

asva

ried

byva

ryin

gei

ther

idity

atco

nsta

ntox

alat

eco

ncen

trat

ion,

orto

talo

xala

tenc

entr

atio

nat

afix

edac

idity

.A

fter

equi

libra

tion

the

tura

ted

solu

tions

wer

ece

ntrif

uged

and

the

conc

entr

atio

nof

rium

was

dete

rmin

edco

lorim

etric

ally

with

arse

nazo

III.

2

em

etho

dsof

pHm

easu

rem

ent

and

ofth

ede

term

inat

ion

ofal

equi

libriu

mox

alat

eco

ncen

trat

ion

wer

eno

tsp

ecifi

ed.

Th~

C2O

4!2•

6H2O

was

prep

ared

bypr

ecip

itatio

nac

cord

ing

toR

ef.

3.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

2K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.V

.Ste

pano

van

dE

.M.P

azuk

hin,

Zh.

Neo

rg.K

him

.15

,148

3~1

970!

.2 S

.B

.S

avvi

n,A

rse

na

zoII

I~A

tom

izda

t,M

osco

w,

1966!

~inR

ussi

an!,

p.10

7.3 D

.I.

Rya

bchi

kov

and

E.

K.

Gol

brai

kh,An

aly

tica

lCh

em

istr

yo

fT

ho

riu

m~P

ubl.

Hou

seA

cad.

Sci

.U

SS

R,

Mos

cow

,19

60!

~inR

ussi

an!,

p.33

.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#~2

!A

mm

oniu

mox

alat

e;~N

H4!

2C2O

4;@1

113-

38-8#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

E.

M.

Paz

ukhi

n,E

.A

.S

mirn

ova,

A.

S.

Kriv

okha

tski

i,Y

u.L.

Paz

ukhi

na,

and

S.

M.

Koc

herg

in,

Rad

iokh

imiy

a27,

606

–11

~198

5!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

3c 2

/mol

dm2

3 :0.

025

–0.

1J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofT

h~C2O

4!in

~NH

4!2C

2O4

solu

tions

a

(NH

4!2C

2O4b

(c2

/mol

dm2

3 !C

2O422

c

~mol

dm2

3 !pH

d@C

2O422

#e

(102

mol

dm2

3 )T

h~C

2O4!

(104

c 1/m

oldm

23 )

0.1

0.09

812.

660.

634

14.9

0.1

0.09

812.

640.

613

14.9

0.1

0.09

62.

420.

364

7.20

0.1

0.09

62.

390.

344

7.20

0.1

0.09

881.

840.

0890

0.75

4

0.1

0.10

01.

590.

0452

0.16

4

0.1

0.09

701.

150.

0109

0.06

80

0.1

0.09

701.

120.

0109

0.03

96

0.09

950.

0997

1.27

0.01

780.

101

0.09

950.

0994

1.64

0.05

340.

221

0.09

950.

0994

1.62

0.05

237

0.22

1

0.1

0.1

1.96

0.12

40.

668

0.1

0.1

2.17

0.20

93.

55

0.09

950.

106

2.84

1.01

32.3

0.1

0.10

72.

660.

832

230

0.1

0.15

95.

7715

.73

297

0.1

0.13

86.

2613

.821

8

0.1

0.11

73.

463.

0271

.1

0.1

0.20

06.

1820

.040

9

0.1

0.14

16.

5214

.128

4

0.05

0.08

304.

747.

5912

0

0.05

0.07

44.

806.

7612

0

3 co st @H Ad

Th

sh At

Me

Iso

eq su of ac co sa tho

Th

tot

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#H

ydro

gen

chlo

ride;

HC

l;@76

47-0

1-0#

Sod

ium

chlo

ride;

NaC

l;@764

7-14

-5#W

ater

;H 2

O;

@773

2-18

-5#

I.M

.K

oren

man

and

V.

V.

Kor

olik

hin,

Tru

dyK

him

.K

him

.T

ekhn

ol.3

,10

6–

9~1

960!

.

riabl

es:

Pre

pare

dby

:

K:

293

/mol

dm2

3 :0.

01–

2.0

icst

reng

th/m

oldm

23 :

0.5,

1.0,

and

2.0

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

at20

°of

CT

h~C2O

4!2

inH

Cl–

NaC

lsol

utio

nsa

HC

l

2/m

oldm

23 )

Ioni

cst

reng

th~m

oldm

23 !

Tot

alox

alat

e(1

04m

oldm

23 )

Ksp

b

(1022

mol

3dm

29 )

Ksp

c

(1022

mol

3dm

29 )

0.01

0.5

0.2

440

0.85

30.

025

0.5

0.3

830

1.21

50.

10.

50.

549

1.43

50.

250.

50.

910

1.43

50.

50.

51.

32.

40.

797

0.01

1.0

0.1

200

0.40

40.

025

1.0

0.3

690

1.21

50.

11.

00.

654

1.84

30.

251.

01.

013

1.73

10.

51.

01.

42.

30.

940

0.75

1.0

2.0

1.5

0.77

21.

01.

02.

51.

00.

588

0.5

2.0

1.7

4.6

1.43

60.

752.

02.

754.

01.

629

1.0

2.0

3.1

3.0

1.00

81.

52.

04.

41.

00.

723

2.0

2.0

60.

90.

648

quili

briu

mso

lidph

ases

wer

eno

tin

vest

igat

ed.

alcu

late

dby

auth

ors

asKsp

5@T

h41

#@C

2O

422

#2as

the

first

appr

oxim

atio

nun

der

the

assu

mpt

ion

that

noco

mpl

exfo

rmat

ion

ofT

h41

with

xala

teio

nta

kes

plac

ein

the

satu

rate

dso

lutio

ns.

The

conc

entr

atio

nsof

C2O

422an

dT

h41w

ere

obta

ined

as @C

2O422

#5@o

xal # t

otZ

21

and

h41

#5@o

xal # t

ot/2

,w

here

@oxa

l # tot

isth

eex

perim

enta

llyde

term

ined

oxal

ate

conc

entr

atio

nin

the

satu

rate

dso

lutio

nan

dZ

5(1

@H1

#/K

a21

@H1

#2/K

a1K

a2).

The

auth

ors

used

Ka1

55.

9310

22

mol

dm2

3an

dK

a25

6.43

102

5m

oldm

23

for

the

diss

ocia

tion

con-

tant

sof

oxal

icac

id.T

hede

finite

tren

din

the

Ksp

valu

esso

obta

ined

led

the

auth

ors

toas

sum

eth

efo

rmat

ion

ofth

eT

h~C

2O4!

21co

mpl

exin

the

satu

rate

dso

lutio

nsfo

rw

hich

they

obta

ined

from

thei

rso

lubi

lity

data

the

inst

abili

tyco

nsta

ntas

K5

@Th4

1#@

C2O

422#

3@T

h~C

2O4!

21#2

1 5~1

.56

0.5!

310

29

mol

dm2

3 .T

hen

the

conc

entr

atio

nof

the

oxal

ate

anio

nbe

cam

e@C

2O422

#5@o

xal # t

ot/(

Z1

@oxa

l # tot/2

K!

and

Ks0

52

K2 @o

xal # t

ot3/(

2KZ

1@o

xal # t

ot)2 .

The

auth

ors

repo

rted

only

one

refin

edva

lue

obta

ined

from

this

equa

tion

asK

s05

(16

0.1)

310

222

mol

3dm

29

with

nosp

ecifi

catio

nof

the

mea

ning

ofth

ede

viat

ion

and

with

noin

dica

tion

asto

whe

ther

the

refin

edK

s0va

lue

was

the

mea

nof

allv

alue

sob

tain

edat

vario

usio

nic

stre

ngth

s.c C

alcu

late

dby

com

pile

rby

usin

gth

eau

thor

s’re

fined

form

ula

for

Ksp

.N

om

ean

valu

ew

asca

lcul

ated

beca

use

ofth

ede

finite

tren

din

Ksp

valu

esin

each

serie

sof

mea

sure

men

tsfo

rdi

ffere

ntio

nic

stre

ngth

s.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

solid

was

shak

enw

ith~H

/Na!

Cls

olut

ions

atco

nsta

ntio

nic

stre

ngth

for

4–

6h

whi

chw

asfo

und

suffi

cien

tto

reac

heq

uilib

rium

.T

heox

alat

eco

ncen

trat

ion

in20

mL

aliq

uots

ofth

esa

tura

ted

solu

tion

was

dete

rmin

edby

titra

tion

with

0.05

NK

MnO 4

.S

ever

alpa

ralle

lex

perim

ents

wer

eru

nfo

rea

chH

Clc

once

ntra

tion,

and

two

orth

ree

aliq

uots

for

oxal

ate

dete

rmin

atio

nw

ere

take

nfr

omea

chsa

tura

ted

solu

tion.

Th~

C2O

4!2•

6H2O

was

prep

ared

bypr

ecip

itatio

n,w

ashe

dw

ithw

ater

and

air

drie

dat

room

tem

pera

ture

.S

ourc

ean

dpu

rity

ofch

emic

als

used

wer

eno

tsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Oxa

late

conc

entr

atio

n:th

eau

thor

sst

ated

the

erro

rof

titra

tion

as<

60.

015

mL

0.05

NK

Mn

O4.

Con

side

ring

the

volu

mes

of0.

05N

KM

nO4

solu

tion

need

edfo

rtit

ratio

ns~0.

015

–0.

48m

L!th

eco

mpi

ler

estim

ates

aner

ror

of6~3

–10

0!%

.

562562 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#~2

!S

alts

~3!

Wat

er;

H 2O

;@7

732-

18-5#

V.

I.S

pits

yn,

Zh.

Rus

s.F

iz.

Khi

m.

Obs

h.~J.

Rus

s.P

hys.

Che

m.

Soc

.!49

,35

7–

70~1

917!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofT

h~C2O

4!2

inso

lutio

nsof

vario

ussa

ltsa

Sal

tS

alt

(c2

/mol

dm2

3 )T

hO2

~mg

dm2

3 !T

h~C

2O4!

2

(105

c 1/m

oldm

23 !

b

Non

e—

0.07

0.02

7

Sod

ium

chlo

ride;

NaC

l;@764

7-14

-5#0.

10.

20.

077

Sod

ium

sulfa

te;

Na 2S

O4;

@775

7-82

-6#0.

050.

60.

231

Pot

assi

umhy

drog

ensu

lfate

;K

HS

O4

;@7

646-

93-7#

0.5

3011

.5

1.0

7729

.6

Am

mon

ium

chlo

ride;

NH 4

Cl;

@121

25-0

2-9#

0.1

0.3

0.11

5

Am

mon

ium

sulfa

te;~N

H4!

2SO

4;@7

783-

20-2#

0.05

1.0

0.38

5

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.b C

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dw

asus

ed.

Exc

ess

Th

~C2O

4!2•

6H2O

labe

led

with

234 T

hw

aseq

uilib

rate

dw

ithth

eso

lutio

nof

the

desi

red

com

posi

tion

for6

hw

hich

was

foun

dsu

ffici

ent

for

satu

ratio

nto

bere

ache

d.A

fter

equi

libra

tion,

100

–20

0m

Lof

the

satu

rate

dso

lutio

nw

asev

apor

ated

ona

porc

elai

nedi

shan

db

activ

ityof

the

resi

due

was

mea

sure

din

anel

ectr

osco

pe.

The

amou

ntof

thor

ium

was

obta

ined

byco

mpa

ring

the

mea

sure

dac

tivity

with

that

ofa

know

nam

ount

ofla

bele

dT

h~C

2O4!

2•6H

2O.

Labe

led

Th~C

2O4!

2•6H

2Ow

aspr

epar

edby

prec

ipita

tion.

An

aliq

uot

ofU

X 1~23

4 Th!

prep

arat

ion

was

adde

dto

aso

lutio

nof

Th~

NO

3!4,

and

Th~

C2O

4!2•

6H2O

was

prec

ipita

ted

byad

ding

hot

solu

tion

ofox

alic

acid

.The

prec

ipita

tew

asw

ashe

dse

vera

ltim

esw

ithho

tw

ater

.A

fter

seve

ral

deca

ntat

ions

with

cold

wat

erth

epr

ecip

itate

turn

edin

tocr

ysta

lline

form

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

prec

isio

n6~1

–2!

%~a

utho

r!.

Co

~1!

~2!

~3!

~4!

Va

T/

c 2 ion

(c a E b C o @T 1 s


24

22

stirr

edw

ith~H

1N

H4!

ClO

4so

lutio

nsfo

r4

hin

ath

erm

osta

ted

appa

ratu

s.T

heox

alat

eco

ncen

trat

ion

inth

esa

tura

ted

solu

tions

was

dete

rmin

edby

titra

tion

agai

nst

0.01

NK

MnO 4so

lutio

n.

24

22

purit

yof

chem

ical

sw

ere

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

3K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 C.

W.

Dav

ies,

J.C

hem

.S

oc20

93~193

8!.

2 A.

A.

Grin

berg

and

G.

I.P

ertz

hak,

Tru

dyR

adie

v.In

st.

Aka

d.N

auk

SS

SR7

,50

~195

6!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2

;@2

040-

52-0#

Oxa

licac

id;

C 2H

2O4

;@1

44-6

2-7#

Hyd

roge

nch

lorid

e;H

Cl;@

7647

-01-

0#W

ater

;H 2

O;

@773

2-18

-5#

M.

Col

ani,

Com

pt.

Ren

d.15

6,10

75–

6~1

913!

;15

6,19

07–

9~1

913!

.

riabl

es:

Pre

pare

dby

:

K:

276,

280,

and

323

0w2

/mas

s%

:0.

02–

10.9

0w3

/mas

s%

:1.

2–

35.0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

thre

edi

ffere

ntte

mpe

ratu

res

ofT

h~C

2O4!

2in

C2H

2O4–

HC

lsol

utio

ns

mpe

ratu

re~°

C!

HC

l(1

00w

2/m

ass

%)

C2H

2O4

(100

w3

/mas

s%

)T

h~m

ass

%!S

olid

phas

ea

1334

.80.

310.

30B

34.9

0.56

0.18

B

35.0

0.79

0.11

B

34.9

1.52

0.05

B

35.0

1.81

0.04

B

171.

20.

710.

0013

A

40.

710.

0020

A

8.5

0.71

0.00

18A

13.2

0.71

0.00

22A

13.2

1.44

0.00

14A

13.3

2.63

0.00

13A

5012

.40.

024

0.03

3A

12.3

0.14

0.01

2A

12.4

0.28

0.00

54A

12.4

0.43

0.00

48A

12.4

1.37

0.00

33A

12.4

2.06

0.00

25A

12.3

2.76

0.00

26A

12.4

5.49

0.00

26A

12.3

10.9

0.00

17A

32.6

0.43

0.63

B

32.8

0.82

0.37

B

32.6

1.34

0.26

B

32.9

2.30

0.14

B

32.5

4.46

0.08

6B

32.0

6.64

0.07

0B

a ~A!

Th~

C2O

4!2•

6H2O

,@1

6788

-62-

8#;~B

!T

h 4~C

2O4!

6Cl 4•20

H2O

,@

#.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

No

deta

ilsgi

ven

exce

ptth

atat

17°C

3m

onth

sw

ere

nece

ssar

yto

brin

gth

eso

lutio

nin

toeq

uilib

rium

with

the

solid

phas

eA

.E

xper

imen

tsat.

30m

ass

%H

Clw

ere

carr

ied

out

usin

gB

asth

est

artin

gso

lidph

ase.

The

com

posi

tion

ofB

asth

eeq

uilib

rium

solid

phas

ew

asco

nfirm

edby

chem

ical

anal

ysis

.

Sou

rce

and

purit

yof

chem

ical

sus

edw

ere

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2

;@2

040-

52-0#

~2!

Per

chlo

ricac

id;

HC

lO 4;

@760

1-90

-3#~3

!A

mm

oniu

mpe

rchl

orat

e;N

H 4ClO

4;

@779

0-98

-9#~4

!W

ater

;H 2

O;

@773

2-18

-5#

A.

I.M

oskv

inan

dL.

N.

Ess

en,

Zh.

Neo

rg.

Khi

m.,12

,68

8–

93~1

967!

;R

uss.

J.In

org.

Che

m.12

,35

9–

62~1

967!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8c 2

/mol

dm2

3 :0.

01–

1.0

c 3/m

oldm

23 :

0.25

–1.

0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofT

h~C2O

4!in

~H1

NH

4!C

lO4

solu

tions

ofco

nsta

ntio

nic

stre

ngth

of1.

0m

oldm2

3a

HC

lO4

(c2

/mol

dm2

3 )N

H4C

lO4

(c3

/mol

dm2

3 )T

h~C

2O4!

2

(105

c 1/m

oldm

23 )

—1.

01.

20

0.01

1.0

1.25

0.1

0.9

2.46

0.25

0.75

4.07

0.50

0.50

7.17

0.75

0.25

8.14

1.0

—9.

01

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.

Add

ition

alin

form

atio

n:In

the

satu

rate

dso

lutio

ns,

Th

~C2O

4!2,

Th~

C2O

4!21

and

Th41

spec

ies

wer

eco

nsid

ered

toex

ist.

Fro

mth

eso

lubi

lity

data

the

equi

libriu

mco

nsta

ntfo

rth

ere

actio

nT

h~C2O

4!21

4H1�

Th41

12C

2H2O

4w

asob

tain

edas

K5

(2.7

61.

2)3

102

12m

ol2

2dm

6 ,an

dfr

omth

isth

eso

lubi

lity

prod

uct

ofT

h~C2O

4!2

was

obta

ined

asK

sp5

(Ka1

Ka2

)2K

54.

3310

222

mol

3dm

29 .

The

diss

ocia

tion

cons

tant

sof

oxal

icac

id,

Ka1

50.

118

mol

dm2

3an

dK

a25

1.06

310

24

mol

dm2

3 ,fo

rio

nic

stre

ngth

of1.

0m

oldm

23 ,

wer

eob

tain

edfr

omun

spec

ified

ther

mod

y-na

mic

cons

tant

sby

usin

gD

avie

s’eq

uatio

n.1

Als

oca

lcul

ated

wer

eov

eral

lsta

bilit

yco

nsta

nts

ofth

eT

h~C

2O4!

21an

dT

h~C

2O4!

2co

mpl

exes

asb

15

1.73

108

mol

21

dm3

and

b25

2.83

1016

mol

22

dm6 ,

resp

ectiv

ely.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dw

asus

ed.

Exc

ess

Th

~CO

!•6H

Ow

asT

h~C

O!•6H

Ow

aspr

epar

edac

cord

ing

toR

ef.

2.S

ourc

ean

d

Co

~1!

~2!

~3!

~4!

Va

T/

10 10 Te

J

In ries

ed ne.

um

R.

V.

Bry

zgal

ova,

Yu.

M.

Rog

ozin

,an

dI.

V.

Che

rnits

kaya

,R

adio

khim

iya

12,

286

~197

0!.

3 P.

R.

Mon

son

and

R.

Hal

l,U

SD

OE

Rep

ort

DP

-157

6,19

81.

4 E.

M.

Paz

ukhi

n,E

.A

.S

mirn

ova,

A.

S.

Kriv

ocha

tski

i,Y

u.L.

Paz

ukhi

na,

and

S.

M.

Koc

herg

in,

Rad

iokh

imiy

a27

,60

6~1

985!

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

bis~o

xala

te!;

Th~

C2O

4) 2

;@2

040-

52-0#

Oxa

licac

id;

C 2H

2O4

;@1

44-6

2-7#

Nitr

icac

id;

HN

O3

;@7

697-

37-2#

Wat

er;

H 2O

;@7

732-

18-5#

A.

G.

Kur

nako

vaan

dL.

K.

Shu

boch

kin,

Zh.

Neo

rg.

Khi

m.

8,12

49–

54~1

963!

;R

uss.

J.In

org.

Che

m.8,

647

–50

~196

3!.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

kg2

1:

0.63

–1.

35/m

olkg

21:

0–

22.9

6

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofT

h~C2O

4!2

inC

2H2O

4–

HN

O3a

NO

3

00w

3/

ass

%)

HN

O3

~mol

kg2

1 !bH

NO

3

(m3

/mol

kg2

1 )c

C2H

2O4

(100

w2

/m

ass

%)

C2H

2O4

~mol

kg2

1 !bC

2H2O

4

(m2

/mol

kg2

1 )cT

h~m

gkg

21 !b

Th

(104

mol

kg2

1 )bT

h(m

2/

mol

kg2

1 )c

00

010

.45

1.16

1.30

180.

780.

87

4.36

0.69

0.78

7.39

0.82

0.93

180.

780.

88

1.78

1.87

2.29

6.60

0.73

0.90

170.

730.

90

5.88

2.52

3.22

5.76

0.64

0.82

170.

730.

93

1.69

3.44

4.70

5.14

0.57

0.78

150.

650.

88

8.03

4.45

6.58

4.40

0.49

0.72

230.

991.

47

5.42

5.62

9.25

3.83

0.43

0.70

261.

121.

84

7.0

5.89

9.85

3.40

0.38

0.63

411.

772.

96

6.89

7.44

14.8

73.

070.

340.

6877

3.32

6.63

6.34

8.94

22.9

64.

720.

521.

3545

619

.65

50.5

heeq

uilib

rium

solid

phas

esw

ere

mix

ture

sof

Th

~C2O

4!2•

6H2O

,@1

6788

-62-

8#,an

dC 2

H2O

4•2H

2O,

@615

3-56

-6#in

all

satu

rate

dso

lu-

ns.

olpe

rkg

solu

tion.

alcu

late

dby

com

pile

r

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.O

xalic

acid

was

adde

dto

satu

rate

dlu

tions

ofT

h~C2O

4!2•

6H2O

inH

NO

3so

lutio

nsof

vario

usco

ncen

trat

ions

,an

dth

em

ixtu

res

wer

eag

itate

dfo

r6

–7

days

.T

hesa

tura

ted

solu

tions

wer

ean

alyz

edfo

rox

alat

eco

nten

tan

dto

tala

cidi

tyby

titra

tion

with

0.05

NK

MnO

4an

d0.

1N

NaO

H,

resp

ectiv

ely,

and

the

HN

O 3co

ncen

trat

ion

was

obta

ined

bydi

ffere

nce.

The

conc

entr

atio

nof

thor

ium

inth

esa

tura

ted

solu

tions

was

dete

rmin

edra

diom

etric

ally

.S

ampl

esof

the

satu

rate

dso

lutio

nsw

ere

with

draw

non

toas

hles

sfil

ter,

drie

d,an

dbco

unte

d.T

heb

activ

ityof

the

satu

rate

dso

lutio

nsw

asco

mpa

red

with

thos

eof

stan

dard

spr

epar

edfr

omla

bele

dT

h~C

2O4!

2•6H

2O.

The

com

posi

tion

ofth

eeq

uilib

rium

solid

phas

esw

asco

nfirm

edby

optic

alm

icro

scop

yan

dch

emic

alan

alys

is.

Th~

C2O

4!2•

6H2O

was

prep

ared

from

thor

ium

nitr

ate

ofun

spec

ified

sour

cean

dpu

rity.

To

incr

ease

the

bac

tivity

ofth

oriu

mfo

rits

subs

eque

ntra

diom

etric

dete

rmin

atio

n,ag

edU

O2~

NO

3!2

inra

dioa

ctiv

eeq

uilib

rium

with

thor

ium

isot

ope

UX

1(23

4 Th)

was

adde

dto

thor

ium

nitr

ate,

and

Th

~C2O

4!2•

6H2O

was

prec

ipita

ted

from

hot

solu

tion

with

ast

oich

iom

etric

amou

ntof

oxal

icac

id.

The

labe

led

Th~C

2O4!

2•6H

2Ow

asfil

tere

d,w

ashe

dte

ntim

esw

ithbo

iling

wat

er,

and

air

drie

d.F

resh

lydi

still

ed60

.4%

HN

O 3w

asus

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

564564 JIRI HALA

4.9.

6.E

valu

atio

nof

the

Th

„C

2O4…

2¿C

2H2O

4¿H

NO

3¿H

2OS

yste

m

Com

pone

nts:

Eva

luat

or:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2

;@2

040-

52-0#

~2!

Oxa

licac

id;

C 2H

2O4

;@1

44-6

2-7#

~3!

Nitr

icac

id;

HN

O3

;@7

697-

37-2#

~4!

Wat

er;

H 2O

;@7

732-

18-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

611

37B

rno,

Cze

chR

epub

lic,

Feb

ruar

y20

00

Crit

ical

Eva

luat

ion:

Thi

ssy

stem

has

been

stud

ied

info

urre

fere

nces

.1

–4

Alth

ough

quite

anu

mbe

rof

expe

rimen

talr

esul

tsar

eav

aila

ble

thei

rco

mpa

rison

isdi

fficu

ltsi

nce

the

solu

bilit

ies

have

been

repo

rted

inva

rious

units

,an

dth

eau

thor

sus

edva

rious

appr

oach

esto

stud

ying

this

syst

em.

spite

ofal

lthi

s,ev

ena

roug

h,co

mpa

rison

reve

als

cons

ider

able

inco

nsis

tenc

yam

ong

the

publ

ishe

dda

ta.T

hus

inR

efs.

1an

d3,

one

seof

expe

rimen

tsw

asru

nw

ithbo

thH

NO 3an

dC 2

H2O

4co

ncen

trat

ions

bein

gva

ried

atth

esa

me

time.

Neg

lect

ing

vario

usun

itsus

edan

dte

mpe

ratu

reof

the

mea

sure

men

ts~m

olkg

21

solu

tion

at29

8.15

Kin

Ref

.1

and

mol

dm23

at29

6.15

inR

ef.

3!,on

eca

nfin

dex

perim

ents

with

sim

ilar

HN

O3

and

C 2H

2O4

conc

entr

atio

nsbu

tw

idel

ydi

fferin

gin

Th~C

2O4!

2so

lubi

litie

sin

both

serie

s,e.

g.,

8.94

mol

HN

O 3kg

21

solu

tion/

0.52

mol

C 2H2O

4kg

21

solu

tion/

1.96

5310

23

mol

Th

kg2

1so

lutio

n1

8.2

mol

dm2

3H

NO

3/0

.50

mol

dm2

3C

2H2O

4/3

.233

102

5m

oldm

23

Th,

3or

3.44

mol

HN

O 3kg

21

solu

tion/

0.57

mol

C 2H2O

4kg

21

solu

tion/

6.53

102

5m

olT

hkg

21

solu

tion1

3.2

mol

dm2

3H

NO

3/0

.54

mol

dm2

3C

2H2O

4/9

.913

102

6m

oldm

23

Th.

3

Suc

hdi

ffere

nces

are

muc

hgr

eate

rth

anco

uld

resu

ltfr

omth

edi

ffere

nces

inco

ncen

trat

ions

.S

mal

ler

diffe

renc

esca

nbe

obse

rvbe

twee

nth

ere

sults

inR

efs.

2an

d4

whe

real

way

sth

eco

ncen

trat

ion

ofon

eco

mpo

nent

was

kept

cons

tant

whi

leva

ryin

gth

eot

her

oH

ere

com

paris

onca

nbe

done

mor

eea

sily

sinc

eid

entic

alco

ncen

trat

ion

unit,

mol

dm2

3 ,w

asus

ed.

Neg

lect

ing

the

diffe

renc

esin

tem

pera

ture

,i.e

.,29

8.15

Kin

Ref

.2

and

293.

15K

inR

ef.

4,on

eca

nfin

dth

efo

llow

ing

data

:1.

0m

oldm

23

HN

O3/0

.5m

oldm

23

C2H

2O4/5

310

27

mol

dm2

3T

h~C

2O4!

22

1.0

mol

dm2

3H

NO

3/0

.5m

oldm

23

C2H

2O4/1

.93

102

6m

oldm

23

Th~

C2O

4!24

1.48

mol

dm2

3H

NO

3/0

.05

mol

dm2

3C

2H2O

4/2

.43

102

6m

oldm

23

Th~

C2O

4!22

1.5

mol

dm2

3H

NO

3/0

.05

mol

dm2

3C

2H2O

4/4

.313

102

6m

oldm

23

Th~

C2O

4!24

2.49

mol

dm2

3H

NO

3/0

.05

mol

dm2

3C

2H2O

4/7

.23

102

6m

oldm

23

Th~

C2O

4!22

2.5

mol

dm2

3H

NO

3/0

.05

mol

dm2

3C

2H2O

4/6

.473

102

6m

oldm

23

Th~

C2O

4!24

Inad

ditio

n,th

epa

per

byB

ryzg

alov

aeta

l.2sh

ows

disc

repa

ncie

sev

enbe

twee

ntw

ose

ries

ofex

perim

ents

ofth

atsa

me

docu

men

tw

here

two

data

for

the

solu

bilit

yof

Th~C

2O4!

2in

the

syst

em1.

0m

oldm2

3H

NO

3/0

.05

mol

dm2

3C

2H2O

4di

ffer

bya

fact

orof

4.T

hesa

me

isfo

und

inth

esy

stem

1.0

mol

dm23

HN

O3/0

.01

mol

dm2

3C

2H2O

4.It

can

thus

beco

nclu

ded

that

alth

ough

the

solu

bilit

yda

tapu

blis

hed

for

Th

~C2O

4!2

inth

eC 2

H2O

4–

HN

O3–

H2O

syst

emof

fer

good

appr

oxim

atio

n,no

neof

them

can

bere

com

men

ded

aspr

efer

red

valu

es.

The

disc

repa

nces

may

part

lybe

due

todi

ffere

nces

ineq

uilib

ritim

e~6

–7

days

inR

efs.

1,3

and

seve

ralh

ours

inR

efs.

2,4

!,pa

rtly

todi

ffere

ntpr

ecis

ion

ofth

em

etho

dsus

edfo

rth

oriu

mde

term

inat

ion

~col

orim

etry

and

radi

omet

ry!.

Ref

eren

ces:

1 A.

G.

Kur

nako

vaan

dL.

K.

Shu

boch

kin,

Zh.

Neo

rg.

Khi

m.

8,12

49~1

963!

.2

Co

~1!

~2!

~3!

~4!

Va

T/

m2

m3 H

(1 m

1 1 2 2 3 3 4 5

a T tio b M c C Me

Iso

so


Tw

om

odifi

catio

nsof

isot

herm

alm

etho

dw

ere

used

.In

the

first

one,

thor

ium

oxal

ate

was

equi

libra

ted

with

C2H

2O4–

HN

O3

solu

tions

ofth

ede

sire

dco

mpo

sitio

nfo

r6

–7

days

,w

hich

was

know

nto

besu

ffici

ent

tore

ach

the

equi

libriu

m.

2In

the

seco

ndm

etho

d,th

oriu

mox

alat

ew

aspr

ecip

itate

ddi

rect

lyby

addi

tion

ofC

2H2O

4in

a20

%–

40%

exce

ssto

aT

h~N

O3!

4so

lutio

nin

0.5

–8.

0m

oldm

23

HN

O3

solu

tions

.T

hese

solu

tions

wer

eeq

uilib

rate

dfo

r10

–14

h.It

has

not

been

men

tione

dif

the

solu

tions

wer

eth

erm

osta

ted

durin

geq

uilib

ratio

n,or

whi

chre

sults

wer

eob

tain

edby

whi

chof

the

two

met

hods

used

.T

horiu

mw

asde

term

ined

inth

esa

tura

ted

solu

tions

spec

trop

hoto

met

rical

lyby

the

arse

nazo

~III

!m

etho

dm

odifi

edfo

rH

NO

3so

lutio

ns3

~sul

fam

icac

idw

asus

edto

rem

ove

HN

O2

whi

chde

stro

ysth

ere

agen

tan

dits

thor

ium

com

plex

!.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 A.

I.M

oskv

inan

dL.

N.

Ess

en,

Rus

s.J.

Inor

g.C

hem

.12

,35

9~1

967!

.2 A

.G

.K

urna

kova

and

L.K

.S

hubo

chki

n,R

uss.

J.In

org.

Che

m8,

647

~196

3!.

3 E.

W.

Bau

man

n,U

SD

OE

Rep

ort

DP

-156

0,19

80.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#O

xalic

acid

;C 2

H2O

4;@1

44-6

2-7#

Nitr

icac

id;

HN

O3;

@769

7-37

-2#W

ater

;H 2

O;

@773

2-18

-5#

R.

V.

Bry

zgal

ova,

Yu.

M.

Rog

ozin

,an

dI.

V.

Che

rnits

kaya

,R

adio

khim

iya1

2,28

6–

91~1

970!

.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

dm2

3 :0

–0.

5/m

oldm

23 :

0.99

5–

2.49

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofT

h~C2O

4!2

inC

2H2O

4/H

NO

3so

lutio

nsa

HN

O3

3/m

oldm

23 )

C2H

2O4

(c2

/mol

dm2

3 )C

2O422

b

(107

mol

dm2

3 )T

h~C

2O4!

2

(106

c 1/m

oldm

23 )

1.0

——

160

1.0

0.00

100.

133

16

1.0

0.00

250.

330

4.2

1.0

0.00

500.

665

2.5

1.0

0.01

01.

331.

1

1.0

0.02

53.

300.

75

1.0

0.05

06.

650.

5

1.0

0.10

13.3

0.5

1.0

0.35

46.5

0.4

1.0

0.50

66.5

0.5

0.99

50.

011.

354.

0

1.43

0.01

0.50

8.1

2.0

0.01

0.24

21

2.49

0.01

0.15

653

0.99

50.

056.

71.

9

1.48

0.05

2.5

2.4

2.0

0.05

1.2

3.8

2.49

0.05

0.78

7.2

quili

briu

mso

lidph

ases

wer

eno

tinv

estig

ated

.The

com

pile

ras

sum

esth

isto

beth

ehe

xahy

drat

e,T

h~C

2O4!

2•6H

2O,@

1678

8-62

-8#,w

hich

asbe

enre

port

edto

best

able

inac

idic

solu

tions

.1

b Dis

soci

atio

nco

nsta

nts

ofox

alic

acid

used

inca

lcul

atin

gth

eox

alat

eio

nco

ncen

trat

ion

wer

eno

tre

port

ed.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#~2

!O

xalic

acid

;C 2

H2O

4;@1

44-6

2-7#

~3!

Nitr

icac

id;

HN

O3;

@769

7-37

-2#~4

!W

ater

;H 2

O;

@773

2-18

-5#

P.

R.

Mon

son

and

R.

Hal

l,U

SD

OE

Rep

ort

DP

-157

6,E

.I.

Du

Pon

tde

Nem

ours

and

Co.

,S

avan

nah

Riv

erLa

bora

tory

,19

81.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

6c 2

/mol

dm2

3 :0.

18–

0.81

c 3/m

oldm

23 :

0.28

–10

.9

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

23°C

ofT

h~C2O

4!2

inC

2H2O

4–

HN

O3

solu

tions

a

C2H

2O4b

(c2

/mol

dm2

3 )H

NO

3b

(c3

/mol

dm2

3 )T

h41

~mg

dm2

3 !T

h~C

2O4!

2

(106

c 1/m

oldm

23 )c

0.41

10.9

320

1380

0.50

8.2

7.5

32.3

0.42

5.1

3.7

15.9

0.37

4.1

1.9

8.19

0.54

3.2

2.3

9.91

0.57

1.7

0.7

3.02

0.18

0.58

1.6

6.90

0.81

0.28

1.8

7.76

a Equ

ilibr

ium

solid

phas

esno

tin

vest

igat

edb In

itial

~tot

al!

conc

entr

atio

n.c C

alcu

late

dby

com

pile

r.

Add

ition

alIn

form

atio

n:W

hen

plot

ted

agai

nst

the

ratio @

C2H

2O4#

/ @H

NO

3#2

~pro

port

iona

lto

@C2O

422#/

Ka1

Ka2

,w

here

Ka1

and

Ka2

are

diss

ocia

tion

cons

tant

sof

oxal

icac

id!,

the

solu

bilit

yof

Th~

C2O

4!2

pass

edth

roug

ha

shal

low

min

imum

at @C2H

2O4#

/ @H

NO

3#2

ofap

prox

imat

ely

0.2

–0.

4.T

hem

inim

umso

lubi

lity

was

expl

aine

dby

the

auth

ors

asco

rres

pond

ing

toth

esi

tuat

ion

whe

reth

esp

arin

gly

solu

ble

Th

~C2O

4!2

com

plex

pred

omin

ated

inth

eso

lutio

n.T

hein

crea

sein

solu

bilit

yat

low

eror

high

er@C

2H2O

4#/ @

HN

O3#

2va

lues

then

corr

espo

nded

toth

efo

rmat

ion

inth

eso

lutio

nof

the

catio

nic

Th~C

2O4!

21or

anio

nic

Th~C

2O4!

322an

dT

h~C

2O4!

442co

mpl

exes

,1re

spec

tivel

y.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Co

~1!

~2!

~3!

~4!

Va

T/

c 2 c 3 (c a E h

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#O

xalic

acid

;C 2

H2O

4;@1

44-6

2-7#

Nitr

icac

id;

HN

O3;

@769

7-37

-2#W

ater

;H 2

O;

@773

2-18

-5#

E.

M.

Paz

ukhi

n,E.

A.

Sm

irnov

a,A

.S

.K

rivok

hats

kii,

Yu.

L.P

azuk

hina

,an

dS

.M

.K

oche

rgin

,R

adio

khim

iya27

,60

6–

11~1

985!

.

riabl

es:

Pre

pare

dby

:

K:

293

/mol

dm2

3 :0.

001

–0.

5/m

oldm

23 :

0.5

–3.

0

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

at20

°Cof

Th~C

2O4!

2in

C2H

2O4–

HN

O3

solu

tions

a

HN

O3b

3/m

oldm

23 )

C2H

2O4b

(c2

/mol

dm2

3 )T

otal

oxal

atec

~mol

dm2

3 !@C

2O422

#d

(107

mol

dm2

3 )T

h~C

2O4!

2

(106

c 1/m

oldm

23 )

HN

O3e

(m2

/m

olkg

21 )

0.5

—0.

000

135

0.08

8467

.70.

523

1.0

—0.

000

432

0.07

7221

61.

05

1.5

—0.

000

604

0.04

9530

21.

56

2.0

—0.

000

984

0.04

6149

22.

10

2.5

—0.

001

180.

0358

590

2.70

3.0

—0.

001

500.

0318

750

3.29

3.0

0.05

1.06

6.90

3.0

0.02

50.

503

9.91

2.0

0.2

9.38

2.93

2.0

0.1

4.69

2.37

2.0

0.02

51.

177.

11

2.5

0.1

3.03

2.72

2.5

0.05

1.52

6.47

2.5

0.02

50.

758

7.24

1.5

0.2

16.4

2.59

1.5

0.1

8.20

2.37

1.5

0.02

52.

54.

96

1.5

0.05

4.10

4.31

1.35

0.15

916

.02.

07

1.35

0.1

10.1

1.8

1.35

0.1

10.1

2.2

1.32

50.

0026

0.27

07.

89

1.30

70.

0016

50.

176

11.4

1.28

80.

0010

50.

116

22.5

1.27

0.10

511

.92.

20

1.25

0.17

520

.42.

07

1.24

0.41

549

.11.

81

1.00

0.50

89.3

2.16

0.50

0.10

65.2

1.98

0.50

0.05

32.6

1.90

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.It

can

beas

sum

edth

isto

beth

ehe

xahy

drat

e,T

h~C

2O4!

2•6H

2O,

@167

88-6

2-8#,

inal

l

solu

tions

sinc

eth

eau

thor

sre

port

edth

atth

ein

itial

solid

phas

edi

dno

tun

derg

oan

ych

ange

durin

geq

uilib

ratio

n.b In

itial

conc

entr

atio

n.c In

solu

tions

with

initi

ally

noox

alic

acid

adde

d,th

ese

valu

esar

egi

ven

byth

eso

lubi

lity

ofT

h~C

2O4!

2.d E

quili

briu

mco

ncen

trat

ion

ofth

eC 2O

422io

nca

lcul

ated

from

tota

loxa

late

conc

entr

atio

nan

dH

1io

nco

ncen

trat

ion

byus

ing

diss

ocia

tion

cons

tant

sof

oxal

icac

id,K

a15

1.05

310

21

and

Ka2

51.

883

102

5ta

ken

from

Ref

.1.

e Cal

cula

ted

byco

mpi

ler

from

dens

ities

ofH

NO

3so

lutio

nta

ken

from

Ref

.2.

Add

ition

alIn

form

atio

n:

The

solu

bilit

yof

Th~

C2O

4!2

inth

eT

h~C

2O4!

2–

C2H

2O4–

HN

O3–

H2O

syst

emw

assh

own

byth

eau

thor

sto

fitth

esa

me

equa

tion

asin

the

Th~

C2O

4!2–

C2H

2O4–

H2O

syst

em,

i.e.,

logC

Th5

0.26

83(l

og@C

2O422

#)21

2.94

7lo

g @C

2O422

#12.

330.

566566 JIRI HALA

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

20–

100

mg

ofT

h~C

2O4!

2•6H

2Ow

ere

stirr

edw

itha

rota

ryst

irrer

at20

0–

600

rpm

with

10m

Lso

lutio

nun

tileq

uilib

rium

was

reac

hed~a

few

hour

s!.E

xces

sso

lidw

asfil

tere

dof

fin

ath

erm

osta

ted

spac

eat

25°C

.T

horiu

min

the

filtr

ate

was

dete

rmin

edco

lorim

etric

ally

with

arse

nazo

III.2D

ata

repo

rted

are

aver

age

valu

esof

3–

4de

term

inat

ions

.

The

Th~

C2O

4!2•

6H2O

was

prep

ared

bypr

ecip

itatio

nfr

om0.

1m

oldm

23

solu

tions

ofT

h~NO

3!4

and

oxal

icac

id.T

hepr

ecip

itate

was

allo

wed

tost

and

for

1da

y,th

em

othe

rliq

uor

deca

nted

,an

dth

epr

ecip

itate

stirr

edw

ith0.

1m

oldm2

3H

NO

3fo

r5

–6

h.T

hew

ashi

ngw

asre

peat

edun

tilth

ew

ash

solu

tion

cont

aine

deq

uiva

lent

conc

entr

atio

nsof

thor

ium

and

oxal

icac

id.

The

prec

ipita

tew

asth

enfil

tere

d,w

ashe

dw

ithw

ater

,et

hano

l,an

det

her,

and

air

drie

dat

room

tem

pera

ture

.The

com

posi

tion

ofth

epr

oduc

tas

foun

dby

anal

ysis

was

Th:

oxal

ate:

H2O

51

:1.9

8:6.

3.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

2K

~aut

hors!

.T

horiu

mco

ncen

trat

ion:

prec

isio

n6

10%

for

CT

h.1.

23

102

6m

oldm

23

and

6~2

0–

30!

%fo

rC

Th,

1.2

310

26

mol

dm2

3~a

utho

rs!.

Com

paris

onof

the

solu

bilit

ies

ofT

h~C

2O4!

2ob

tain

edfo

r1.

0m

oldm

23

HN

O3

at0.

01an

d0.

05m

oldm

23

oxal

icac

idw

ithth

eco

rres

pond

ing

valu

esfo

r0.

995

mol

dm2

3H

NO

3in

the

seco

ndan

dth

irdse

ries

ofm

easu

rem

ents

show

sde

viat

ions

muc

hla

rger

than

wou

ldfo

llow

from

the

stat

edpr

ecis

ion.

Ref

eren

ces:

1 E.

M.

Paz

ukhi

n,E

.A

.S

mirn

ova,

A.

S.

Kriv

okha

tski

i,Y

u.L.

Paz

ukhi

na,

and

S.

M.

Koc

herg

in,

Rad

iokh

imiy

a27

,60

6~1

985!

.2 A

.A

.N

emod

ruk

and

N.

E.

Koc

hetk

ova,

Zh.

Ana

lit.

Khi

m.

17,

330

~196

2!.

Co

~1!

~2!

~3!

~4!

Va

T/

c 2 c 3 (c


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

bis~o

xala

te!;

Th~

C2O

4!2;

@204

0-52

-0#O

xalic

acid

;C 2

H2O

4;@1

44-6

2-7#

Per

chlo

ricac

id;

HC

lO 4;

@760

1-90

-3#W

ater

;H 2

O;

@773

2-18

-5#

A.

I.M

oskv

inan

dL.

N.

Ess

en,

Zh.

Neo

rg.

Khi

m.12,

688

–93

;~1

967!

Rus

s.J.

Inor

g.C

hem

.,12,

359

–62

~196

7!.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

dm2

3 :0.

08–

0.55

5/m

oldm

23 :

1.0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofT

h~C2O

4!2

inC

2H2O

4–

HC

lO4

solu

tions

a

C2H

2O4

(c2

/mol

dm2

3 !T

h~C

2O4!

2

(104

c 1/m

oldm

23 !

0.08

00.

060

0.15

80.

940

0.23

81.

00

0.31

71.

30

0.39

71.

60

0.47

61.

70

0.55

51.

86

llso

lutio

nsco

ntai

ned

1.0

mol

dm23

HC

lO4.

Sol

idph

ases

wer

eno

tin

vest

igat

ed.

The

com

pile

ras

sum

esth

isto

beth

ehe

xahy

drat

e,h~

C2O

4!•6H

2O,

@167

88-6

2-8#,

whi

chpr

ecip

itate

sfr

omac

idic

solu

tions

cont

aini

ngox

alic

acid

.1

ditio

nali

nfor

mat

ion:

eso

lubi

lity

data

wer

eus

edto

obta

inth

eso

lubi

lity

prod

uct

ofT

h~C

2O4!

2in

two

diffe

rent

way

s.G

raph

ical

trea

tmen

tac

cord

ing

toR

efs.

and

3of

the

data

yiel

ded

the

valu

eofK

sp5

13

1022

mol

3dm

29 .

Ano

ther

appr

oach

cons

ider

edth

ein

crea

sing

solu

bilit

yof

Th

~C2O

4!2

inH

2O4–

HC

lO4

solu

tions

.A

ssum

ing

that

Th~C

2O4!

2an

dT

h~C

2O4!

322on

lyco

ntrib

uted

toth

eso

lubi

lity

ofT

h~C2O

4!2

inth

ese

solu

tions

,so

lubi

lity

was

expr

esse

das

@Th~

C2O

4!2#

1@T

h~C

2O4!

322#5

b2@T

h41#@

C2O

422#2

1b

3@T

h41#@

C2O

422#3

5b

2K

s01

b3K

s0@C

2O422

#

ere

b2

and

b3

are

over

alls

tabi

lity

cons

tant

sof

the

corr

espo

ndin

gco

mpl

exes

.T

heso

lubi

lity

prod

uct

was

then

obta

ined

bygr

aphi

cal

trap

olat

ion

ofS

toze

roox

alic

acid

conc

entr

atio

nas

4.1

310

222

mol

3dm

29 .

Tak

ing

then

into

cons

ider

atio

nth

eva

lueKsp

obta

ined

inT

h~C

2O4!

2–

HC

lO4–

NH

4ClO

4–

H2O

syst

em,

anav

erag

eva

lue

ofKsp

5(4

.26

0.1)

310

222

mol

3dm

29

was

give

nw

hich

was

reca

lcu-

edto

Ksp0

51.

1310

225

mol

3dm

29

byus

ing

the

Dav

ies’

equa

tion.4

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dw

asus

ed.

Exc

ess

Th

~C2O

4!2•

6H2O

was

stirr

edw

ith1.

0m

oldm

23

solu

tions

ofH

ClO

4co

ntai

ning

vario

usam

ount

sof

oxal

icac

idfor4

hin

ath

ermos

tate

dap

para

tus.

The

conc

entr

atio

nof

thor

ium

inth

esa

tura

ted

solu

tions

was

dete

rmin

edby

anun

spec

ified

grav

imet

ricm

etho

d.

Th~

C2O

4!2•

6H2O

was

prep

ared

acco

rdin

gto

Ref

.5.

Sou

rce

and

purit

yof

chem

ical

sw

ere

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

3K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 R.

V.

Bry

zgal

ova,

Yu.

M.

Rog

ozin

,an

dI.

V.

Che

rnits

kaya

,R

adio

khim

iya1

2,28

6~1

970!

.2 A

.I.

Mos

kvin

and

A.

D.

Gel

man

,Z

h.N

eorg

.K

him

.3,95

6~1

958!

.3 F

.A

.Z

akha

rova

and

A.

I.M

oskv

in,

Zh.

Neo

rg.

Khi

m.

5,12

28~1

960!

.4 C

.W

.D

avie

s,J.

Che

m.

Soc

.20

93~193

8!.

5 A.

A.

Grin

berg

and

G.

I.P

ertz

hak,

Tru

dyR

adie

v.In

st.

Aka

d.N

auk

SS

SR7

,50

~195

6!.



Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

Th

~C2O

4!2•

6H2O

was

equi

libra

ted

inth

erm

osta

ted

vess

els

for

6h

whi

chw

asfo

und

suffi

cien

tto

reac

heq

uilib

rium

.T

heeq

uilib

rium

conc

entr

atio

nof

oxal

ate

ion

inth

eso

lutio

nsw

asva

ried

byva

ryin

gei

ther

acid

ityat

cons

tant

oxal

ate

conc

entr

atio

n,or

tota

loxa

late

conc

entr

atio

nat

afix

edac

idity

.A

fter

equi

libra

tion

the

satu

rate

dso

lutio

nsw

ere

cent

rifug

edan

dth

eco

ncen

trat

ion

ofth

oriu

mw

asde

term

ined

colo

rimet

rical

lyw

ithar

sena

zoIII

.3

The

met

hod

for

the

dete

rmin

atio

nof

oxal

ate

was

not

spec

ified

.T

heau

thor

sre

port

edth

atth

ein

itial

solid

phas

edi

dno

tun

derg

oan

ych

ange

durin

geq

uilib

ratio

n.

Th~

C2O

4!2•

6H2O

was

prep

ared

bypr

ecip

itatio

nac

cord

ing

toR

ef.

4.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

2K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.V

.Ste

pano

van

dE

.M.P

azuk

hin,

Zh.

Neo

rg.K

him

.15

,148

3~1

970!

.2 P

hys

ico

-Ch

em

ica

lT

ab

les~

Pub

l.H

ouse

Tec

h.Li

tera

ture

,P

ragu

e,19

53!,

Vol

.1,

p.21

2.3 S

.B

.S

avvi

n,A

rse

na

zoII

I~A

tom

izda

t,M

osco

w,

1966!

~inR

ussi

an!,

p.10

7.4 D

.I.

Rya

bchi

kov

and

E.

K.

Gol

brai

kh,An

aly

tica

lCh

em

istr

yo

fT

ho

riu

m~P

ubl.

Hou

seA

cad.

Sci

.U

SS

R,

Mos

cow

,19

60!

~inR

ussi

an!,

p.33

.

Co

~1!

~2!

~3!

~4!

Va

T/

c 2 c 3 a A T Ad

Th

2 C2

the

S5

wh

ex the

lat

J

1.47

3.83

11.

341.

320

——

3.16

2.50

8B

1X

3.22

8.66

01.

481.

504

——

4.18

3.42

3B

1X

2.65

7.08

90.

890.

8996

——

4.85

3.95

1B

1D

2.86

7.65

41.

291.

305

——

4.29

3.49

7X

1X

1.22

3.15

80.

340.

3326

——

3.78

2.98

0D

1X

1.02

2.63

50.

490.

4783

——

3.62

2.84

8D

1X

1.14

2.91

30.

280.

2704

——

2.68

2.08

6D

1X

0.86

2.18

10.

040.

0383

——

2.44

1.88

4D

1E

1.63

4.14

4tr

aces

trac

es—

—2.

011.

557

D1

E5.

9616

.96

3.84

4.12

9—

—4.

073.

527

X0.

822.

142.

502.

448

——

2.09

1.64

9B

0.04

10.

1017

0.25

0.24

02—

—3.

322.

570

B—

—22

.70

27.5

00.

863.

196

——

A1C

——

22.9

327

.63

——

0.21

0.20

39A1B

1.59

4.13

9—

——

—4.

273.

385

B1D

2.09

5.35

4—

——

—2.

251.

755

C1E

0.73

2.33

822

.30

26.9

90.

451.

670

——

A1

B1

C

a ~A!

Na 2

CO

3•10

H2O

,@6

132-

02-1#

;~B

!N

a 2C

2O4,

@62-

76-0

#;~C

!N

a 6T

h~C

O3!

5•12

H2O

,@1

2386

-47-

9#;~D

!N

a 4T

h~C

2O4!

4•6H

2O,

@#;

~E!

Th~

C2O

4!2•

6H2O

,@1

6788

-62-

8#;~X

!un

iden

tified

solid

phas

e.b C

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.T

hem

easu

rem

ents

wer

eca

rrie

dou

tst

irred

vess

els

equi

pped

with

anoi

lsea

ling.

Sta

rtin

gfr

omlu

tions

corr

espo

ndin

gto

inva

riant

poin

ts,

incr

easi

ngam

ount

sth

eth

irdco

mpo

nent

wer

ead

ded.

Equ

ilibr

ium

was

atta

ined

one

day

for

syst

ems

rich

inN

a2C

O3

or4

days

for

syst

ems

hin

sodi

umor

thor

ium

oxal

ates

.S

ampl

esof

the

satu

rate

dlu

tions

wer

ean

alyz

edfo

rox

alat

eco

nten

tw

ithK

MnO 4

atio

n,an

dgr

avim

etric

ally

for

CO 2

and

thor

ium

~as

ThO

2!.

dium

was

dete

rmin

edby

diffe

renc

e,in

som

eca

ses

also

avim

etric

ally

asN

a 2SO

4.C

ompo

sitio

nof

the

solid

phas

ess

inve

stig

ated

byth

em

etho

dof

wet

resi

dues

and

chec

ked

optic

alm

icro

scop

yan

dx-

ray

diffr

actio

n.

Th~

C2O

4!26

H2O

was

obta

ined

from

Th~N

O3!

4,its

sour

cean

dpu

rity

not

spec

ified

.F

orm

easu

rem

ents

with

thor

ium

carb

onat

eso

lidph

ases

,th

eso

lidus

edw

asN

a6T

h~C

O3!

5•12

H2O

,pr

epar

edac

cord

ing

toR

ef.

1.O

ther

chem

ical

sus

edw

ere

reag

ent

grad

epr

oduc

ts.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 I.I.

Che

rnya

ev,

V.

A.

Gol

ovni

a,an

dA

.K

.M

olod

kin,

Pro

ceed

ings

2nd

Inte

rnat

iona

lC

onfe

renc

eP

eace

ful

Use

sA

t.E

nerg

y,G

enev

a,19

58,

pp.

28,

203.

568568 JIRI HALA

4.9.

7.T

h„C

2O4…

2¿T

h„C

O3…

2¿N

a 2C

2O4¿

Na 2

CO

3¿H

2OS

yste

m

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

Th41

,Na1

i CO

322,C

2O422

2H

2O~1

!T

horiu

mbi

s~oxa

late!

;T

h~C

2O4!

2;@2

040-

52-0#

~2!

Tho

rium

carb

onat

e;T

h~CO

3!2;

@190

24-6

2-5#

~3!

Sod

ium

oxal

ate;

Na 2C

2O4;

@62-

76-0

#~4

!S

odiu

mca

rbon

ate;

Na

2CO

3;@4

97-1

9-8#

~1!

Wat

er;

H 2O

;@7

732-

18-5#

I.S

.Kov

alev

aan

dN

.P.L

uzhn

aya,

Zh.

Neo

rg.K

him

.7,

1693

–8

~196

2!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:298

com

posi

tion

J.H

ala

Exp

erim

enta

lDat

aC

ompo

sitio

nof

solu

tions

satu

rate

dat

25°C

Th~

C2O

4!2

(100

w1

/m

ass

%)

Th~

C2O

4!2

(m1/1

03

mol

kg2

1 !b

Na 2

CO

3

(100

w4

/m

ass

%)

Na 2

CO

3

~m4/

102

mol

kg2

1 !b

Th~

CO

3!2

(100

w2

/m

ass

%)

Th~

CO

3!2

(m2

/mol

kg2

1 !b

Na 2

C2O

4

~100

w3

/m

ass

%)

Na 2

C2O

4

(m3/1

02

mol

kg2

1 !b

Sol

idph

asea

0.28

0.89

4122

.68

27.3

7—

——

—A1B

0.45

1.39

519

.86

23.2

60.

632.

263

——

B1

C0.

451.

394

19.8

223

.19

0.60

2.15

4—

—B

1C

1.06

3.08

614

.25

15.6

80.

531.

789

——

B1

C0.

982.

822

13.2

514

.42

0.67

2.23

6—

—B

1C

1.06

3.03

712

.70

13.7

50.

704

2.33

8—

—B

1C

1.10

3.12

912

.04

12.9

40.

704

2.32

1—

—B

1C

1.43

4.01

710

.52

11.1

70.

812.

637

——

B1

C1.

965.

466

9.96

10.5

00.

210.

6788

——

B1

C2.

988.

163

7.21

7.46

30.

351.

111

——

B1

C0.

982.

660

6.06

6.21

62.

688.

432

——

C6.

2818

.13

8.64

9.23

10.

391.

305

——

C1

X5.

9217

.08

8.44

9.20

20.

704

2.35

4—

—C

1X

4.53

12.8

17.

407.

907

1.41

4.62

2—

—C

1X

5.63

16.6

99.

4610

.60

2.25

7.73

2—

—C

1X

5.92

16.9

27.

828.

448

——

0.54

0.47

01B

1X

3.84

10.4

65.

305.

455

——

0.88

0.72

99B

1X

2.08

5.50

03.

053.

048

——

2.20

1.77

2B

1X

1.92

5.05

72.

692.

678

——

2.36

1.89

3B

1X

Me

Iso

in so of in ric so titr

So

gr wa

by


4.11

.T

horiu

mO

xobi

s„o

-hyd

roxy

benz

oate

…

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

oxob

is~hy

drox

yben

zoat

e!;T

hO~C

7H5O

3!2;

@#

Am

mon

ium

hydr

oxyb

enzo

ate~s

alic

ylat

e!;N

H4~

C7H

5O3!

;# W

ater

;H 2

O;

@773

2-18

-5#

O.

E.

Zvy

agin

tsev

and

B.

N.

Sud

arik

ov,

Zh.

Neo

rg.

Khi

m.

2,12

8–

37~1

957!

.

riabl

es:

Pre

pare

dby

:

K:

293

–36

9/m

oldm

23 :

0–

1.76

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofT

hO~C

7H5O

3!2

inw

ater

and

inso

lutio

nsof

NH 4~

C7H

5O3!

atdi

ffere

ntte

mpe

ratu

res

a

mpe

ratu

re~

°C!

Th

~mg

dm2

3 !T

hO~C

7H5O

3!2

(106

c 1/m

oldm

23 !

bT

empe

ratu

re~

°C!

Th

~mg

dm2

3 !T

hO~C

7H5O

3!2

(106

c 1/m

oldm

23 !

b

Sol

ubili

tyof

ThO

~C7H

5O3!

2in

wat

eras

afu

nctio

nof

tem

pera

ture

200.

30.

415

701.

11.

5230

0.4

0.55

480

1.4

1.94

400.

50.

692

901.

72.

3550

0.7

0.96

996

2.6

3.60

600.

91.

25

pHT

h~m

gdm

23 !

ThO

~C7H

5O3!

2

(106

c 1/m

oldm

23 !

bpH

Th

~mg

dm2

3 !T

hO~C

7H5O

3!2

(106

c 1/m

oldm

23 !

b

Sol

ubili

tyof

ThO

~C7H

5O3!

2in

wat

eras

afu

nctio

nof

pHc

1.2

20.0

27.7

5.6

0.3

0.41

52.

23.

75.

126.

81.

11.

523.

01.

21.

667.

91.

31.

804.

20.

50.

692

8.5

1.2

1.66

4~C

7H5O

3!~g

dm2

3 !N

H4~

C7H

5O3!

(c2

/mol

dm2

3 !b

Th

~mg

dm2

3 !T

hO~C

7H5O

3!2

(106

c 1/m

oldm

23 !

NH

4~C

7H5O

3!~g

dm2

3 !N

H4~

C7H

5O3!

(c2

/mol

dm2

3 !b

Th

~mg

dm2

3 !

ThO

~C7H

5O3!

2

(106

c 1/

mol

dm2

3 !

Sol

ubili

tyat

30°C

ofT

hO~C

7H5O

3!2

inN

H4~

C7H

5O3!

solu

tions

d

00

1.4

1.94

500.

196

0.1

0.13

810

0.03

920.

10.

138

100

0.39

21.

41.

9420

0.07

840.

10.

138

200

0.78

41.

72.

3530

0.11

80.

10.

138

450

1.76

330

.241

.8

NH

4~C

7H5O

3!~g

dm2

3 !N

H4~

C7H

5O3!

(c2

/mol

dm2

3 !b

Th

~mg

dm2

3 !T

hO~C

7H5O

3!2

(106

c 1/m

oldm

23 !

NH

4~C

7H5O

3!~g

dm2

3 !N

H4~

C7H

5O3!

(c2

/mol

dm2

3 !b

Th

~mg

dm2

3 !

ThO

~C7H

5O3!

2

(106

c 1/

mol

dm2

3 !

Sol

ubili

tyat

96°C

ofT

hO~C

7H5O

3!2

inN

H4~

C7H

5O3!

solu

tions

d

00

2.6

3.60

600.

235

0.5

0.69

210

0.03

920.

20.

277

100

0.39

21.

82.

4920

0.07

840.

10.

138

150

0.58

83.

64.

9830

0.11

80.

10.

138

200

0.78

45.

47.

4840

0.15

70.

10.

138

250

0.98

07.

29.

9750

0.19

60.

20.

277

300

1.17

69.

012

.5

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.b C

alcu

late

dby

com

pile

r.c pH

adju

sted

byad

ditio

nsof

HC

lor

NH 3so

lutio

ns.

d pH5

5;4

hst

irrin

g.



4.10

.A

mm

oniu

mT

etra

kis

„ox

alat

o…th

orat

e

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

tetr

akis~o

xala

to!th

orat

e;~N

H4!

4Th~

C2O

4!4;

@#

~2!

Am

mon

ium

oxal

ate;

(NH 4!

2C2O

4;@1

113-

38-8#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

B.

Bra

uner

,J.

Che

m.

Soc

.73,

951

–85

~189

8!.

Var

iabl

es:

Pre

pare

dby

:

m2

/mol

kg2

1 :0.7

33J.

Ha´ la

Exp

erim

enta

lDat

aT

heso

lubi

lity

of(N

H 4! 4

Th~

C2O

4!4,

atun

spec

ified

room

tem

pera

ture

,was

dete

rmin

edto

be90

.3g

~NH

4!4T

h~C

2O4!

4•4H

2Oin

100

gw

ater

.T

heso

lutio

nal

soco

ntai

ned

9.3

g~N

H4!

2C2O

4pe

r10

0g

wat

ersi

nce

the

com

plex

salt

isun

stab

leto

war

dshy

drol

ysis

inpu

rew

ater

.T

heso

lubi

lity

was

calc

ulat

edby

the

auth

orfr

oman

alys

isof

one

sam

ple

~2.8

235

g!of

the

satu

rate

dso

lutio

nw

hich

prod

uced

are

sidu

eof

1.37

40g

ondr

ying

at10

5°C

,w

hich

furt

her

prod

uced

0.48

22g

ThO

2on

igni

tion.

Fro

mth

ese

data

the

com

pile

rca

lcul

ated

the

solu

bilit

yof

(NH

4!4T

h~C

2O4!

4to

be80

.464

g/10

0g

wat

er~1.2

26m

olkg

21 !

inth

epr

esen

ceof

90.9

7g~N

H4!

2C2O

4/k

gw

ater

~0.7

33m

olkg

21 !.

The

figur

e90

.3g

salt/

100

gw

ater

give

nby

the

auth

orob

viou

sly

refe

rsto

the

tetr

ahyd

rate

~89.

29g/

100

gw

ater

,co

mpi

ler

!.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

yw

asde

term

ined

byan

alyz

ing

the

satu

rate

dm

othe

rliq

uor

obta

ined

inth

eco

urse

ofth

epr

epar

atio

nof

(NH

4!4T

h~C

2O4!

4•4H

2O.

Tho

rium

was

dete

rmin

edgr

avim

etric

ally

asT

hO2.

Pur

eth

oriu

mox

alat

e,pr

epar

edfr

oma

thor

ium

prep

arat

ion

purifi

edfr

omla

ntha

nide

sby

prec

ipita

tion

ofth

eN

a/T

hsu

lfate

,w

ashe

ated

with

wat

erto

boili

ng,

and

amm

oniu

mox

alat

ew

asad

ded

until

half

ofth

eth

oriu

mox

alat

edi

ssol

ved.

Afte

rco

olin

g,th

eso

lutio

nw

asfil

tere

dan

dth

efil

tere

dco

ncen

trat

edun

til,w

hen

allo

wed

toco

ol,n

eedl

e-sh

aped

crys

tals

ofth

ete

trah

ydra

tebe

gan

tofo

rm.

Co

~1!

~2!

@ ~3!

Va

T/

c 2 Te

NH

J

4.12

.T

horiu

m„5-

nitr

o…B

arbi

tura

te

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tho

rium

tetr

akis

$~5-

nitr

o!ba

rbitu

rate%

;T

h~C

4H2N

3O5!

4or

6H8N

12O

20T

h;@

#W

ater

;H 2

O;

@773

2-18

-5#

M.

W.

Goh

een

and

R.

J.R

obin

son,

Ana

lyt.

Chi

m.

Act

a31

,17

5–

9~1

964!

.

riabl

es:

Pre

pare

dby

:

K:

297

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

inw

ater

ofth

oriu

mte

trak

is$~5-

nitr

o!ba

rbitu

rate%

isre

port

edto

be1.

4310

24

mol

dm2

3at

24°C

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

xces

ssa

ltw

asst

irred

with

wat

erfo

rve

ralh

ours

,an

dth

enal

low

edto

stan

dfo

rse

vera

lday

sin

satu

rate

dso

lutio

n.A

nal

iquo

tof

the

satu

rate

dso

lutio

nw

asn

evap

orat

edby

wat

erpu

mp

desi

ccat

ion,

and

the

resi

due

sw

eigh

ed.

Th~

C4H

2N3O

5!4•

20H

2Ow

aspr

epar

edby

trea

ting

anaq

ueou

s0.

1m

oldm

23

Th~

NO

3!4

solu

tion

~rea

gent

grad

e,B

aker

and

Ada

mso

n!w

itha

stoi

chio

met

ricam

ount

of5-

nitr

obar

bitu

ricac

idin

the

form

of0.

05m

oldm

23

solu

tion

in50

%et

hano

l.T

hepr

ecip

itate

was

allo

wed

tost

and

for

1da

y,th

enit

was

filte

red

and

was

hed

with

wat

eran

d95

%et

hano

l.

ditio

nalI

nfor

mat

ion:

Exc

ept

for

the

wat

erof

crys

talli

zatio

n,co

mpo

sitio

nof

the

salt

was

not

repo

rted

inth

eor

igin

aldo

cum

ent.

Itw

asde

duce

dby

the

mpi

ler

from

the

repo

rted

ther

mog

ravi

met

riccu

rve

whi

chsh

owed

that

igni

tion

ofth

eai

r-dr

ied

hydr

ated

salt

toT

hO2

yiel

ded

are

sidu

e20

%of

the

initi

alsa

mpl

em

ass.

570570 JIRI HALA

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

of234 T

h-la

bele

dT

hO~C

7H5O

3!2

was

stirr

edfo

r1

–4

hw

ithth

eso

lutio

nsun

der

the

desi

red

cond

ition

s.In

mos

tca

ses,

1–

2h

stirr

ing

was

suffi

cien

tfo

req

uilib

rium

tobe

reac

hed.

The

nan

aliq

uot

ofth

esa

tura

ted

solu

tion

was

with

draw

n,ev

apor

ated

,an

dth

eco

ncen

trat

ion

ofth

oriu

mw

asde

term

ined

bybco

untin

gof

234 T

hus

ing

aG

eige

rco

unte

r.

ThO

~C7H

5O3!

2la

bele

dw

ith23

4 Th

was

prep

ared

bypr

ecip

itatio

nof

ara

dioc

hem

ical

lypu

re,

boili

ngT

h~NO

3!4

solu

tion

with

salic

ylic

acid

atpH

4–

51in

the

pres

ence

ofU

O 2~N

O3!

2.T

hepr

ecip

itate

ofT

hO~C

7H5O

3!2

was

thor

ough

lyw

ashe

dw

ithw

ater

from

U~V

I!sa

licyl

ate,

and

repr

ecip

itate

d.T

heT

h/sa

licyl

ate

ratio

inth

epr

oduc

tw

as1:

2.S

peci

ficac

tivity

ofth

epr

oduc

tw

as10

4–

105

coun

tsm

g21

min

21 .

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 O.

E.

Zvy

agin

tsev

and

B.

N.

Sud

arik

ov,

Zh.

Neo

rg.

Khi

m.

1,24

1~1

956!

.

Co

~1!

C1

~2!

Va

T/

Me

Iso

se the

the

wa

Ad

co of


r

Equ

ilibr

atio

ntim

ew

as36

hal

thou

gha

perio

dof

4–

6h

was

foun

das

suffi

cien

tfo

req

uilib

rium

tobe

reac

hed.

The

satu

rate

dso

lutio

nsw

ere

filte

red,

and

the

cont

ent

of8-

hydr

oxoq

uino

linol

was

dete

rmin

edtit

rimet

rical

lyw

ithK

BrO 3

solu

tion.

For

each

HC

lcon

cent

ratio

n,5

–7

para

llele

xper

imen

tsw

ere

perf

orm

ed.

toav

oid

cont

amin

atio

nw

ith8-

hydr

oxoq

uino

line.

The

prod

uct

was

char

acte

rized

byel

emen

tal

anal

ysis

.C

alcu

late

d/fo

und

for

the

dihy

drat

e:T

h27

.49/

27.5

,8-

hydr

oxoq

uino

line

60.2

4/68

.0,

H2O

4.27

/4.5

,in

mas

s%

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~aut

hors!

.S

olub

ility

:th

ere

port

edra

nge

of8-

hydr

oxoq

uino

linat

eco

ncen

trat

ion

sugg

ests

prec

isio

nof,

5%fo

rth

etit

rimet

ricm

etho

d.

Ref

eren

ces:

1 A.

E.

Kly

gina

and

N.

S.

Kol

yada

,Z

h.N

eorg

.K

him

.3,27

67~1

958!

.2 F

.J.

Wel

cher

,Org

an

icA

na

lytic

alR

ea

ge

nts~N

J,19

48!,

Vol

.1,

p.26

5.

4.14

.T

horiu

mP

htha

locy

anin

ate

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Bis

~pht

halo

cyan

inat

o!tho

rium

;C 6

4H32

N16

Th

or~C

32H

16N

8!2;

@125

81-7

8-1#

Sol

vent

s

P.N

.Mos

kale

v,G

.N.S

hapk

in,a

ndY

u.S

.Mis

ko,R

adio

khim

iya

20,

343

–4

~197

8!.

riabl

es:

Pre

pare

dby

:

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Th~

C32

H16

N8!

2in

two

solv

entsa

Sol

vent

Th~

C32

H16

N8!

2

~gdm

23 !

Th~

C32

H16

N8!

2

(104

c 1/m

oldm

23 )b

chlo

rona

phth

alen

e;C 10H

7Cl;

@90-

13-1

#0.

567.

52

nzen

e;C 6H

6;@7

1-43

-2#

0.03

90.

524

empe

ratu

reno

tsp

ecifi

ed.

The

solu

bilit

ies

wer

ere

port

edto

bein

depe

nden

tof

tem

pera

ture

over

the

rang

efr

om13

to50

°C.

alcu

late

dby

com

pile

r.

ditio

nalI

nfor

mat

ion:

eso

lubi

lity

ofT

h~C

32H

16N

8!2

indi

met

hylfo

rmam

ide~

C3H

7NO

,@6

8-12

-2#!

was

repo

rted

tobe

less

than

0.00

1g

dm2

3 .T

heco

mpo

und

sfo

und

topr

actic

ally

inso

lubl

ein

met

hano

l~C

H4O

,@6

7-56

-1#!

and

etha

nol~C

2H6O

,@6

4-17

-5#!

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.T

heso

lidw

aseq

uilib

rate

dw

ithth

esi

red

solv

ent

ingr

ound

glas

sst

oppe

red

cylin

ders

ina

rmos

tate

dba

thun

tileq

uilib

rium

was

atta

ined

.T

hesa

tura

ted

lutio

nsw

ere

filte

red

thro

ugh

agl

ass

filte

r,an

aliq

uot

was

uted

to;

102

5m

oldm

23

with

dim

ethy

lform

amid

ent

aini

ng1%

N 2H

4•H

2O,

and

the

conc

entr

atio

nof

thal

ocya

nine

was

dete

rmin

edsp

ectr

opho

tom

etric

ally

.

Th~

C32

H16

N8!

2w

aspr

epar

edac

cord

ing

toR

ef.

1.Its

chem

ical

com

posi

tion

and

purit

yw

asch

ecke

dby

chem

ical

anal

ysis

and

x-ra

ydi

ffrac

tion.

Rea

gent

grad

eso

lven

tsw

ere

used

with

out

furt

her

purifi

catio

n.

Est

imat

edE

rror

:S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 F.L

ux,D

.Dem

pf,a

ndD

.Gro

w,A

ngew

.Che

m.

80,7

92~1

968!

.



4.13

.T

horiu

m8-

Hyd

roxy

quin

olin

ate

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Tho

rium

tetr

akis~

8-hy

drox

oqui

nolin

ate!;

C24

H36

N4O

4Th

orT

h~C

6H9N

O! 4

;@1

8153

-67-

8#~2

!H

ydro

gen

chlo

ride;

HC

l;@76

47-0

1-0#

~3!

Sod

ium

chlo

ride;

NaC

l;@764

7-14

-5#~4

!W

ater

;H 2

O;

@773

2-18

-5#

I.M

.K

oren

man

and

V.

V.

Kor

olik

hin,

Tru

dy.

Khi

m.

Khi

m.

Tek

hnol

.4,

304

–6

~196

1!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8c 2

/mol

dm2

3 :0.

001

–0.

025

(c21

c 3)/

mol

dm2

3 :0.

5

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

typr

oduc

tof

Th~C

6H9N

O! 4

in~H

1N

a!C

lsol

utio

nsat

ioni

cst

reng

thof

0.5

mol

dm23

and

25°C

a

HC

lb

(c2

/mol

dm2

3 )pH

c@R

# tot

d

(103

mol

dm2

3 )K

spe,

f

(1045

mol

5dm

215

)

0.00

104.

00.

57–

0.63

4.9

–8.

0

0.00

253.

81.

14–

1.25

6.6

–8.

6

0.00

53.

553.

0–

3.2

6.3

–8.

7

0.01

03.

45.

8–

5.9

11.4

–12

.5

0.02

53.

114

.0–

14.1

3.8

–3.

9

a Itw

asno

tst

ated

expl

icitl

yw

heth

erth

eeq

uilib

rium

solid

phas

ew

asth

ean

hydr

ous

salt

orth

edi

hydr

ate.

b Initi

alco

ncen

trat

ion.

c pHof

the

satu

rate

dso

lutio

ns.

d Tot

al8-

hydr

oxoq

uino

line

conc

entr

atio

nin

the

satu

rate

dso

lutio

n.U

sing

thes

eda

ta,

conc

entr

atio

nof

free

8-hy

drox

oqui

nolin

ate

anio

n,o

R2

,w

asca

lcul

ated

usin

gdi

ssoc

iatio

nco

nsta

nts

of8-

hydr

oxoq

uino

line,

K15

@H1

#@R

2#@

HR

#215

1.54

310

210

and

K25

@HR

#@H

1#

3@H

2R1

#215

9.61

310

26.1

e The

aver

age

valu

eofK

sp5

@Th41

#@R

2#4

was

repo

rted

tobe

(762

)310

245

mol

5dm

215

.In

divi

dual

Ksp

valu

esw

ere

obta

ined

assu

min

gth

eT

h41co

ncen

trat

ion

inth

esa

tura

ted

solu

tions

was

equa

lto

@R# t

ot/4

.f T

hera

nge

cove

rsth

ere

sults

ofpa

ralle

lmea

sure

men

ts.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

Th

~C6H

9NO

! 4•2H

2Ow

assh

aken

with

the

solu

tions

ofth

ede

sire

dco

mpo

sitio

n.T

h~C

6H9N

O! 4•2H

2Ow

aspr

epar

edby

prec

ipita

tion

acco

rdin

gto

Ref

.2.T

hepr

ecip

itate

was

boile

dw

ithth

em

othe

rliq

uor

for

1h

Co

~1!

Th

~2!

Va

1- Be

a T b C Ad

Th

wa

Me

Iso

de the

so dil

co ph

J

f

3.0

13.9

460.

063

2976

210

00.

113

.896

0.11

4

2986

0.1

100

0.1

14.1

860.

035

298

100

0.1

13.2

960.

116

2956

110

00.

113

.356

0.14

7

014

.216

0.14

d7

2986

28

0.1

14.0

560.

098

014

.916

0.10

d8

2986

110

00.

114

.106

0.14

10

a Est

imat

edby

eval

uato

r.b O

verp

ress

ure

ofC

O 2of

0.1

–0.

2at

m.

c Con

cent

ratio

nun

itfo

rKsp

ism

oldm

26 .

d Ksp0

;ca

lcul

ated

byth

eau

thor

sfr

omth

eir

Ksp

valu

es.

The

data

obta

ined

for

ioni

cst

reng

thof

0.1

mol

dm23

are

gene

rally

ingo

odag

reem

ent

but

som

eun

cert

aint

yst

illpe

rsis

tsev

enth

ough

high

prec

isio

nso

lubi

lity

mea

sure

men

ts,

cond

ucte

das

pHtit

ratio

ns,

have

been

used

inth

em

ore

rece

ntst

udie

s.3

–8

Inth

ese

mea

sure

men

ts,

equi

libra

tion

time

ofse

vera

lwee

ksup

to6

mon

ths

was

used

toen

sure

atta

inm

ent

ofst

eady

stat

eat

pH,

6.5

whe

reth

eeq

uilib

rium

solid

phas

eis

UO 2

CO

3,th

eso

lidph

ases

wer

ech

arac

teriz

edco

ntin

uous

lydu

ring

the

expe

rimen

ts,

and

high

-pre

cisi

onpr

oced

ures

for

pHm

easu

rem

entw

ere

used

.In

som

eca

ses

the

mea

sure

men

tsw

ere

perf

orm

edst

artin

gfr

ombo

thun

ders

atur

ated

and

supe

rsat

urat

edso

lutio

ns.

Neg

lect

ing

min

ordi

ffere

nces

inte

mpe

ratu

reat

whi

chm

easu

rem

ents

wer

epe

rfor

med

,th

eva

lues

ofth

eso

lubi

lity

prod

uct

ofU

O2C

O3

repo

rted

for

0.1

mol

dm2

3N

aClO

4in

Ref

s.6,

7ag

ree

exce

llent

lybu

tar

eap

prox

imat

ely

five

times

high

erth

anth

etw

ova

lues

repo

rted

Ref

s.4,

5,8.

The

latte

rau

thor

sre

peat

edth

eir

mea

sure

men

tsre

port

edin

Ref

s.4,

5af

ter

seve

raly

ears

8w

ithex

celle

ntre

prod

ucib

ility

.e

reas

onfo

rth

isdi

ffere

nce

amon

gKsp

valu

esob

tain

edby

diffe

rent

auth

ors

isno

tcl

ear

sinc

ene

arly

iden

tical

expe

rimen

talc

ondi

tions

dpr

oced

ures

atpH,

6.5

wer

eus

edin

alls

tudi

es.

Itse

ems

likel

yth

atth

esc

atte

rin

the

solu

bilit

yda

tare

port

edin

indi

vidu

alst

udie

sis

eto

syst

emat

icer

rors

inhe

rent

toex

perim

enta

lpro

cedu

res

used

,an

dth

edi

ffere

nce

inK

spva

lues

then

,at

leas

tpa

rtly

,al

soto

the

choi

ceth

eaq

ueou

sU~V

I!sp

ecie

s~se

ebe

low!

cons

ider

edin

com

pute

rtr

eatm

ent

ofso

lubi

lity

data

.It

has

been

sugg

este

dre

cent

ly11

that

the

fere

nces

inth

eso

lubi

lity

enco

unte

red

inth

issy

stem

are

prob

ably

not

due

toth

esi

zeof

UO

2CO

3cr

ysta

lsor

todi

ffere

nces

inU

O 2CO

3

stal

linity

.N

eith

erar

eth

edi

ffere

nces

inso

lubi

lity

caus

edby

the

proc

edur

eus

edto

calc

ulat

eth

eeq

uilib

rium

carb

onat

eio

nco

ncen

tra-

n.T

hela

tter

isob

tain

edfr

omth

em

easu

red

pHan

da

set

ofC

O2

solu

tion

equi

libria

CO

2~g!

KH

�C

O2~

aq!

K*�

H2C

O3

Ka1

�H

CO

32

Ka2

�C

O322

log @

CO

322#5

log

K1

log

p~C

O2!

12

pH,

with

log

K5

log(

KHK

* Ka1

Ka2

).T

heco

nsta

ntK,

eith

erde

term

ined

byso

me

auth

ors

orta

ken

mlit

erat

ure

sour

ces,

show

sa

very

smal

lsca

tter

~2lo

gK

:17

.65,7

17.6

4,1217

.62,13

17.6

8,1417

.65;

15al

lin

0.1

mol

dm2

3N

aClO

4!.

Logi

cally

,si

mila

rsi

tuat

ion

isob

serv

edw

ithth

eKsp0

valu

es.

The

sew

ere

obta

ined

eith

erex

perim

enta

llyat

very

low

ioni

cst

reng

th,

1,2

calc

ulat

edfr

omth

eva

lues

obta

ined

athi

gher

ioni

cst

reng

ths

byap

plyi

ngsp

ecifi

cio

nin

tera

ctio

nth

eory

.3,

7,8

The

aver

age

valu

efr

omse

repo

rted

inR

efs.

1,2,

3,7

is102(1

4.26

0.2)

mol

2dm

26

with

som

ewha

thi

gher

valu

eob

tain

edin

Ref

.8.

Bas

edon

thes

eK

sp0va

lues

itn

beco

nclu

ded

that

the

valu

e10

210

.73m

ol2

dm2

6ob

tain

edea

rlier16

from

the

solu

bilit

yof

UO 2

~OH

! 2in

Na 2

CO

3so

lutio

nsis

erro

neou

s.T

here

isle

ssag

reem

ent

asto

the

equi

libriu

mU

~VI!

solu

tion

spec

ies

exis

ting

inth

eU

O2C

O3–

CO

2–

NaC

lO4–

H2O

and/

or

2CO

3–

CO

2–

H2O

syst

ems.

Whi

leai

min

gat

obta

inin

gth

ebe

stfit

ofth

eir

expe

rimen

tald

ata

with

am

odel

,th

eau

thor

sha

veco

nsid

ered

varie

tyof

spec

ies

and

thei

rco

mbi

natio

ns:

UO

221an

dU

O 2C

O3;

1U

O221

,U

O2O

H1

,U

O2~

OH

! 2,

and

U 2O

521;2

UO

221,

UO

2CO

3,

2~C

O3!

222,

UO

2~C

O3!

342,

and

~UO

2!3~

CO

3!662

;3U

O221

,U

O2C

O3,

UO

2~C

O3!

222,

and

UO 2

~CO

3!342

;9U

O2C

O3,

2~C

O3!

222,U

O2~

CO

3!32

4 ,~U

O2!

2~O

H! 221

,an

d~U

O2!

3~O

H! 61

;5U

O2C

O3,

UO

2~C

O3!

222an

dU

O 2~C

O3!

342.6

The

sesp

ecie

sco

ntrib

ute

toto

talU

~VI!

conc

entr

atio

nin

the

satu

rate

dso

lutio

nsth

atar

ein

equi

libriu

mw

ithU

O2C

O3,

and

thei

rre

lativ

eim

port

ance

isde

pend

ent

pHan

d/or

@CO

322#.

Whi

leth

ere

isge

nera

lagr

eem

ent

inth

atth

een

hanc

edso

lubi

lity

ofU

O2C

O3

athi

gher

pHan

d/or @

CO

322#

valu

esca

used

byth

efo

rmat

ion

ofan

ioni

cca

rbon

atoc

ompl

exes

ofU

O221

,th

eim

port

ance

ofva

rious

hydr

olyz

edhy

drox

osp

ecie

sha

sno

tbe

enlv

edun

ambi

guou

sly.

Inth

isre

spec

tso

me

mor

ere

cent

stud

ies

8,10

have

brou

ght

abe

tter

insi

ght

into

the

prob

lem

byex

perim

enta

llyrif

ying

the

exis

tenc

eof

som

eof

the

solu

tion

spec

ies.

~The

UO 221

–C

O322

–O

H2

solu

tion

equi

libria

have

been

the

subj

ect

ofst

udy

inve

ral

mor

edo

cum

ents

whe

re,

how

ever

,so

lubi

lity

ofU

O2C

O3

has

not

been

stud

ied.

Con

sequ

ently

,su

chdo

cum

ents

have

not

been

lude

din

this

eval

uatio

n.!

fere

nces

:

.I.

Ser

geev

a,A

.A

.N

ikiti

n,I.

L.K

hoda

kovs

kii,

and

G.

B.

Nau

mov

,G

eokh

imiy

a13

40~1

972!

;G

eoch

em.

Inte

rnat9

,90

0~1

972!

.

.V

.P

irozh

kov

and

N.

M.

Nik

olae

va,

Izv.

Sib

irsk.

Otd

el.

Aka

d.N

auk

SS

SR

,S

er.

Khi

m.

5,55

~197

6!;

6,30

~197

6!.

Gre

nthe

,D

.F

erri,

F.

Sal

vato

re,

and

G.

Ric

cio,

J.C

hem

.S

oc.

Dal

ton

Tra

ns.

2439

~198

4!.

.M

einr

ath

and

T.

Kim

ura,

Inor

g.C

him

.A

cta20

4,79

~199

3!.

.M

einr

ath

and

T.

Kim

ura,

J.A

lloys

Com

pds20

2,89

~199

3!.

.K

ram

er-S

chna

bel,

H.

Bis

chof

f,R

.H

.X

i,an

dG

.M

arx,

Rad

ioch

im.

Act

a56

,18

3~1

992!

.

Pas

halid

is,

W.

Run

de,

and

J.I.

Kim

,R

adio

chim

.A

cta

61,

141

~199

3!.

.M

einr

ath,

Y.

Kat

o,T

.K

imur

a,an

dZ

.Y

oshi

da,

Rad

ioch

im.

Act

a75

,15

9~1

996!

.

Pas

halid

is,

K.

R.

Cze

rwin

ski,

F.

Fan

ghan

el,

and

J.I.

Kim

,R

adio

chim

.A

cta

76,

55~1

997!

.

.K

ato,

T.

Kim

ura,

Z.

Yos

hida

,an

dN

.N

itani

,R

adio

chim

.A

cta74,

21~1

996!

.

G.

Mei

nrat

h,Y

.K

ato,

T.

Kim

ura,

and

Z.

Yos

hida

,R

adio

chim

.A

cta

84,

21~1

999!

.12

R.

M.

Sm

ithan

dA

.E

.M

arte

ll,Critic

alS

tab

ility

Co

nst

an

ts~P

lenu

m,

New

Yor

k,19

76!,

Vol

.4.

13G

.M

einr

ath

and

J.I.

Kim

,R

adio

chim

Act

a52Õ5

3,29

~199

1!.

14L.

May

a,In

org.

Che

m.21

,28

95~1

982!

.15

W.

Run

de,

G.

Mei

nrat

h,an

dJ.

I.K

im,

Rad

ioch

im.

Act

a58

Õ59,

93~1

992!

.16

A.

K.

Bab

koan

dV

.S

.K

aden

skay

a,Z

h.N

eorg

.K

him

.5,

2568

~196

0!.

572572 JIRI HALA

5.T

heS

olub

ility

ofU

rani

umC

ompo

unds

5.1.

Ura

nium

Dio

xoC

arbo

nate

5.1.

1.E

valu

atio

nof

the

UO

2CO

3–

CO

32–

Na 2

CO

3–

H2O

Sys

tem

Com

pone

nts:

Eva

luat

or:

~1!

Ura

nium

~VI!

diox

oca

rbon

ate;

UO 2C

O3;

@122

74-9

5-2#

~2!

Car

bon

diox

ide;

CO 2;

@124

-38-

9#~3

!S

odiu

mpe

rchl

orat

e;N

aClO 4;

@760

1-89

-0#~4

!W

ater

;H 2

O;

@773

2-18

-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,

June

2000

Crit

ical

Eva

luat

ion:

Gre

atat

tent

ion

has

been

paid

toth

eso

lubi

lity

ofU

O2C

O3,

and

also

ofU

O 3•xH

2O,

due

toth

eim

port

ance

ofso

lid/li

quid

equi

libria

ofth

ese

com

poun

dsin

rela

tion

toec

olog

ical

risk

pote

ntia

lst

emm

ing

from

uran

ium

min

es,

mill

taili

ngs,

and

rock

pile

s,an

dto

tran

sfer

our

aniu

mfr

omth

ese

faci

litie

sin

toth

ebi

osph

ere.

Sol

ubili

tyof

UO

2CO

3in

wat

eror

inaq

ueou

sso

lutio

nsis

not

acce

ssib

leto

expe

rimen

tal

mea

sure

men

tsat

norm

alat

mos

pher

icco

nditi

ons,

i.e.,

atpa

rtia

lpr

essu

reof

CO

2of

0.03

%,

sinc

eU

O 2CO

3is

ther

mod

ynam

ical

lyst

able

only

athi

gher

part

ialp

ress

ures

ofC

O2.

~At

part

ialp

ress

ure

ofC

O 2,1

%,U

O3•

xH2O

isth

eth

erm

odyn

amic

ally

stab

leph

ase.

8 !T

here

fore

the

solu

bilit

yof

UO 2

CO

3ha

sbe

enm

easu

red

inth

eU

O2C

O3–

CO

2–

H2O

and

UO 2

CO

3–

CO

2–

NaC

lO4–

H2O

syst

ems

unde

rhi

gher

part

ial

pres

sure

sof

CO 2

orin

the

atm

osph

ere

ofpu

reC

O2.

Sev

eral

sets

ofda

taar

eav

aila

ble

for

the

solu

bilit

yof

UO

2CO

3in

thes

esy

stem

s.S

ome

auth

ors1

–3,

5–

7,9re

port

ednu

mer

ical

data

whi

leot

hers

8,10

publ

ishe

dth

eir

data

ingr

aphi

cal

form

orre

port

edth

eso

lubi

lity

prod

uct

ofU

O2C

O3

only

.4T

here

isge

nera

lagr

eem

ent

amon

gth

epu

blis

hed

data

inth

atth

eso

lubi

lity

ofU

O2C

O3

isat

itsm

inim

um,

and

cons

tant

,at

appr

oxim

atel

y102

8.3 –

102

7.0

mol

dm2

3eq

uilib

rium

carb

onat

eio

nco

ncen

trat

ion.

5,6,

9W

ithin

this

@CO

322#

inte

rval

,th

eso

lubi

lity

ofU

O2C

O3

has

been

repo

rted

tobe

betw

een

102

4.2

102

4.6~R

efs.

6,9!

orap

prox

imat

ely

1025.

0~R

ef.5

!m

oldm

23 ,w

ithra

ther

ala

rge

scat

ter

ofso

lubi

lity

data

inso

me

stud

ies.

At

low

eror

high

er @CO

322#

valu

esth

eso

lubi

lity

ofU

O 2CO

3in

crea

ses.

At

low

erC

O 322co

ncen

trat

ions

,pa

rtic

ular

lyin

acid

icso

lutio

ns,

the

enha

nced

solu

bilit

yis

caus

edby

the

actio

nof

H3O

1io

non

UO 2

CO

3w

hile

the

form

atio

nof

anio

nic

carb

onat

ocom

plex

esof

U~VI!

inth

esa

tura

ted

solu

tions

isre

spon

sibl

eat

high

erC

O322

conc

entr

atio

ns.

Inne

arly

all

stud

ies

the

auth

ors

com

pute

rfit

ted

thei

rex

perim

enta

ldat

aw

ithm

odel

sco

nsid

erin

gU

O2C

O3

asth

eso

lidph

ase

and

vario

usU

~VI!

solu

tion

spec

ies,

with

the

aim

atca

lcul

atin

gth

eso

lubi

lity

prod

uct

ofU

O 2CO

3an

deq

uilib

rium

orst

abili

tyco

nsta

nts

ofva

rious

aque

ous

U~V

I!sp

ecie

s.T

heta

ble

sum

mar

izes

the

avai

labl

eva

lues

for

the

solu

bilit

ypr

oduc

tof

UO

2CO

3at

orcl

ose

to29

8.1

K.

T/K

p2/%

NaC

lO4

(c3

/mol

dm2

3 )2

log

Ksp

cR

efer

ence

2986

0.5

100

,0.

02a

14.2

51

2986

0.1

110

–12

0b0

14.0

560.

082

2986

0.02

9–

980

14.46

0.1d

3

0.5

13.2

160.

063

in Th

an du of dif

cry

tio as fro

or tho

ca UO

a UO

UO

the

on is so ve se inc

Re

1 E 2 A 3 I. 4 G 5 G 6 U 7 I. 8 G 9 I. 10Y

11


atpH

4.4

–5.

3:U

O 2C

O3~

s!�

UO

2CO

3~aq

!,w

itheq

uilib

rium

cons

tant

of(4

.16

0.7)

310

25,

(4.3

60.

3)3

102

5,

4.53

102

5,

4.63

102

5,

and

6.13

102

5at

25,

50,

100,

150,

and

200

°C,

resp

ectiv

ely,

atpH

.5.

3:U

O2C

O3~

s!1

CO

2~g!

1H

2O�

UO

2~C

O3!

2~aq

!22

12H

~aq!

1,

with

equi

libriu

mco

nsta

ntof

(2.2

60.

7)3

102

16an

d(1

.060.

5)3

102

16at

25an

d50

°C,

resp

ectiv

ely.

All

equi

libriu

mco

nsta

nts

refe

rto

zero

ioni

cst

reng

th.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

ither

UO

2CO

3or

UO

2~O

H! 2

wer

eed

asth

est

artin

gso

lid.

To

atta

inth

efin

alde

sire

dui

libriu

mpH

,sm

alla

liquo

tsof

dilu

teH

ClO 4

orN

aHC

O 3lu

tion

wer

ead

ded

toth

est

artin

gsl

urry

ofth

eso

lid.

Inpe

rimen

tsat

25an

d50

°Cth

eso

lutio

nsco

ntai

ning

exce

sslid

wer

eeq

uilib

rate

din

vess

els

equi

pped

with

elec

trod

esan

dgl

ass

filte

r,1by

pass

ing

thro

ugh

them

ast

ream

ofpu

rified

2at

CO 2

pres

sure

of1

atm

.T

hega

sw

aspr

esat

urat

edw

ithte

rva

por.

The

equi

libra

tion

time

rang

edfr

om17

to79

days

25°C

orfr

om9

to31

days

at50

°C.

The

atta

inm

ent

ofui

libriu

mw

asch

ecke

dby

uran

ium

and

pHde

term

inat

ion.

esa

tura

ted

solu

tions

wer

eal

low

edto

stan

dfo

r2

–14

days

fore

taki

ngsa

mpl

esfo

ran

alys

is.

Exp

erim

ents

athi

gher

pera

ture

sw

ere

carr

ied

out

ina

stee

laut

ocla

ve1

elec

tric

ally

ated

inan

alum

inum

bloc

k.T

hete

mpe

ratu

rew

asch

ecke

dth

ther

moc

oupl

es.

Afte

req

uilib

ratio

n,th

eau

tocl

ave

was

pidl

yco

oled

with

wat

er,

sam

ples

wer

ew

ithdr

awn

with

arin

gean

dul

trac

entr

ifuge

d.pH

was

mea

sure

dw

itha

glas

sct

rode

unde

rco

ntin

uous

stre

amof

CO

2.T

heco

ncen

trat

ion

uran

ium

inth

esa

tura

ted

solu

tions

was

dete

rmin

edlo

rimet

rical

lyw

ithar

sena

zoIII

.T

heco

mpo

sitio

nof

the

uilib

rium

solid

phas

esw

asch

ecke

dby

x-ra

ydi

ffrac

tion.

UO

2CO

3w

aspr

epar

edby

pass

ing

CO

2ga

sth

roug

ha

slur

ryof

UO

2~O

H! 2

.2T

hela

tter

was

prep

ared

from

UO

2~N

O3!

2by

eith

erca

rbon

ate3

orpe

roxi

dem

etho

d.D

oubl

ydi

still

edw

ater

was

used

.N

aHC

O 3an

dH

ClO

4w

ere

reag

ent

grad

epr

oduc

ts.

Est

imat

edE

rror

:T

empe

ratu

re:p

reci

sion6

0.5

Kat

298

and

323

K;6

2.5

Kat

373

Kan

dab

ove~

auth

ors!.

pH:

prec

isio

n60.

04pH

unit

at29

8K

;60.

3pH

unit

at32

3K

~aut

hors!

.

Ref

eren

ces:

1 A.

A.

Nik

itin,

E.

I.S

erge

eva,

I.L.

Kho

dako

vski

i,an

dG

.B

.N

aum

ov,

Geo

khim

iya

297~1

972!

.2 I.

I.C

hern

yaye

v,V

.A

.G

olov

nya,

and

G.

V.

Elle

rt,

Zh.

Neo

rg.

Khi

m.

127

26~1

956!

.3 R

.W

ey,

I.La

uffe

nbur

ger,

and

D.

Sae

hr,

Bul

l.S

oc.

Chi

m.

Fra

nce

1874

~196

8!.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

ocar

bona

te;

UO 2C

O3;

@122

74-9

5-2#

~2!

Car

bon

diox

ide;

CO 2;

@124

-38-

9#~3

!W

ater

;H 2

O;

@773

2-18

-5#

E.

I.S

erge

eva,

A.

A.

Nik

itin,

I.L.

Kho

dako

vski

i,an

dG

.B

.N

aum

ov,

Geo

khim

iya

1340

–50~

1972

!;G

eoch

em.

Inte

rnat

.9,90

0~1

972!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:298

–47

3p

2~p

ress

ure

ofC

O 2!/a

tmos

pher

e51

(9.8

1310

4P

a)at

25an

d50

°CpH

:3.

2–

6.2

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

UO

2CO

3in

wat

erat

part

ialp

ress

ure

ofC

O2

of1

atm

asa

func

tion

ofte

mpe

ratu

rea

Tem

pera

ture

~°C

!pH

UO

2CO

3

(105

m1

/mol

kg2

1 )T

empe

ratu

re~°

C!

pHU

O2C

O3

(105

m1

/mol

kg2

1 )

253.

2225

3.0

503.

4712

0.0

4.09

17.1

4.88

4.20

4.33

6.30

5.04

4.50

4.44

4.31

5.20

4.22

4.66

4.83

5.28

5.32

4.87

5.71

6.02

13.0

5.07

5.36

6.16

70.0

5.22

4.29

5.31

5.17

100b

4.10

4.47

5.55

9.9

150b

4.05

4.58

5.83

14.4

200b

3.95

6.09

6.23

100.

0

a Equ

ilibr

ium

solid

phas

ew

asU

O 2CO

3,@1

2274

-95-

2#,in

alls

olut

ions

.b P

ress

ure

ofC

O 2no

tsp

ecifi

ed.

Add

ition

alIn

form

atio

n:T

hede

pend

ence

ofth

eU

O2C

O3

solu

bilit

yon

pH,

ata

cons

tant

tem

pera

ture

,w

asin

terp

rete

dby

the

auth

ors

byas

sum

ing

the

follo

win

geq

uilib

ria:

atpH

,4.

4:U

O2C

O3~

s!1

2H~a

q!1�

UO

2~aq

!21

1C

O2~

g!1

H2O

,w

itheq

uilib

rium

cons

tant

of(8

.06

4.0)

310

3at

25°C

and

4.453

103

at50

°C,

Me

Iso

us eq so ex so a CO

wa

at eq Th

be tem

he wi

ra sy ele

of co eq

J

re.

and

the

stab

ility

cons

tant

ofth

eU

O2C

O3

com

plex

inth

eso

lutio

nw

ere

calc

ulat

edby

the

auth

ors

asa

func

tion

ofte

mpe

ratu

re.

The

leas

tsq

uare

str

eatm

ent

ofth

eda

tayi

elde

dfo

rth

eth

erm

odyn

amic

stab

ility

cons

tant

~act

ivity

ofio

nsco

nsid

ered

tobe

equa

lto

conc

entr

atio

nssi

nce

the

satu

rate

dso

lutio

nsw

ere

extr

emel

ydi

lute

d,io

nic

stre

ngth

was

<3

310

24

mol

dm2

3 !b

5@U

O2C

O3#

@UO

221#2

1 @C

O322

#21 ,

the

equa

tion

log

b5

28.

9881

0.04

053T

162

1959

.1/T

2

and

for

the

ther

mod

ynam

icso

lubi

lity

prod

uct

ofU

O2C

O3

2lo

gK

s005

15.0

4–

0.01

756T

15.

0269

310

25T

2

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.T

hem

easu

rem

ents

wer

eco

nduc

ted

inte

flon

auto

clav

e.1S

lurr

yof

UO

2CO

3in

wat

erw

asfir

stui

libra

ted

bypa

ssin

gth

roug

hit

ast

ream

ofC

O2

gas

for

2h

room

tem

pera

ture

atat

mos

pher

icpr

essu

re.

The

nan

erpr

essu

reof

CO 2

of0.

1–

0.2

atm

was

appl

ied,

and

the

xtur

ew

ashe

ated

atth

ede

sire

dte

mpe

ratu

reun

der

ntin

uous

mix

ing

for

seve

rald

ays.

Atta

inm

ent

ofeq

uilib

rium

sch

ecke

dby

mea

surin

gpH

and

CO

2pr

essu

reun

tilco

nsta

ntlu

esw

ere

obta

ined

.T

hen

two

sam

ples

ofth

esa

tura

ted

lutio

nw

ere

with

draw

nby

mea

nsof

teflo

nfil

ters

plac

edid

eth

eau

tocl

ave

tode

term

ine

uran

ium

ectr

opho

tom

etric

ally

with

arse

nazo

I2

and

CO 2

avim

etric

ally

.S

olid

phas

esw

ere

not

inve

stig

ated

.T

hepH

ofsa

tura

ted

solu

tions

was

mea

sure

dat

the

desi

red

pera

ture

inth

epr

esen

ceof

solid

UO

2CO

3w

itha

high

pera

ture

glas

sel

ectr

ode.

UO

2CO

3w

aspr

epar

edby

prol

onge

dpa

ssin

gth

roug

ha

slur

ryof

UO

3~r

eage

ntgr

ade!

indo

ubly

dist

illed

wat

era

stre

amof

purifi

edC

O 2ga

s.3A

naly

sis

ofth

epr

oduc

tyi

elde

dre

sults

whi

chag

reed

with

in6

0.1%

with

the

form

ula

UO 2C

O3.

Pur

ified

CO 2

and

doub

lydi

still

edw

ater

wer

eus

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~aut

hors!

.pH

:pr

ecis

ion6

0.02

pHun

it~au

thor

s!.U

rani

umco

ncen

trat

ion:

prec

isio

n63%

~aut

hors!

.C

O2

conc

entr

atio

n:pr

ecis

ion6

0.1%

~aut

hors!

.

Ref

eren

ces:

1 A.

V.

Piro

zhko

v,Iz

v.S

ibirs

k.O

tdel

.A

kad.

Nau

kS

SS

R,

Ser

.K

him

.4,

153

~197

6!.

2 An

aly

tica

lC

he

mis

try

of

Ura

niu

m~in

Rus

sian

!,ed

ited

byD

.I.

Rya

bchi

kov

and

M.

M.

Sen

yavi

n~Nau

ka,

Mos

cow

,19

62!,

p.13

2.3 I.

I.C

hern

yaye

v,V

.A

.G

olov

nya,

and

G.

V.

Elle

rt,

Zh.

Neo

rg.

Khi

m.

1,27

26~1

956!

.

574574 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

ocar

bona

te;

UO 2C

O3;

@122

74-9

5-2#

~2!

Car

bon

diox

ide;

CO 2;

@124

-38-

9#~3

!W

ater

;H 2

O;

@773

2-18

-5#

A.V

.Piro

zhko

van

dN

.M.N

ikol

aeva

,Izv

.Sib

irsk.

Otd

el.A

kad.

Nau

kS

SS

R,

Ser

.K

him

.5,55

–9

~197

6!N

.M

.N

ikol

aeva

,ibid

.6,

30–

1~1

976!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:298

–42

3J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofU

O2C

O3

inw

ater

inth

epr

esen

ceof

CO 2as

afu

nctio

nof

tem

pera

turea,b

Tem

pera

ture

~°C

!C

O2c

(102

mol

dm2

3 )pH

U(1

05m

oldm

23 )

UO

2CO

3d

(c1/1

05m

oldm

23 )

2lo

gK

s0e

2lo

gK

s0f

254.

322

4.06

17.2

210

.238

14.0

314

.30

14.0

56

0.08

14.1

214

.15

502.

925

3.95

3.23

1.48

4014

.74

14.8

114

.84

60.

06

14.8

414

.95

752.

384.

003.

421.

4930

14.9

915

.02

15.0

46

0.04

15.1

0

100

2.52

4.07

6.75

2.47

5015

.30

15.1

715

.22

60.

05

15.2

0

125

1.98

4.18

4.89

1.08

8016

.22

16.0

916

.14

60.

04

16.1

116

.15

150

0.29

44.

694.

640.

0674

817

.05

17.8

3g

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

Sin

ceth

em

easu

rem

ents

wer

epe

rfor

med

inan

atm

osph

ere

unde

rC

O2

over

pres

sure

the

com

pile

ras

sum

es,

base

don

othe

rpu

blis

hed

data

,th

atth

eeq

uilib

rium

solid

phas

ew

asU

O2C

O3,

@122

74-9

5-2#,

inal

lsol

utio

ns.

b The

auth

ors

repo

rted

only

one

mea

sure

men

tar

bitr

arily

chos

enou

tof

thre

eto

four

mea

sure

men

tsca

rrie

dou

tat

each

tem

pera

tuH

owev

er,

allt

heca

lcul

ated

valu

esof

solu

bilit

ypr

oduc

tw

ere

repo

rted

.c T

otal

CO 2

conc

entr

atio

n,i.e

.th

esu

mof

the

conc

entr

atio

nsof

CO

2,H

2CO

3,H

CO

32,

and

CO 322

,D

eter

min

edgr

avim

etric

ally

.d @U

O2C

O3#

5to

talc

once

ntra

tion

ofur

aniu

m2~@

UO

2211

@UO

2~O

H!1

#1@U

O2~

OH

! 2#1

2@U

2O521

#!.

e Cal

cula

ted

byth

eau

thor

sfr

omin

divi

dual

mea

sure

men

ts.

f Ave

rage

valu

e.g N

otca

lcul

ated

beca

use

at15

0°C

UO

2CO

3hy

drol

yzed

alm

ost

com

plet

ely

toU

O 2~O

H! 2

whi

chre

sulte

din

inco

nsis

tentK

s0va

lues

.

Add

ition

alIn

form

atio

n:U

sing

liter

atur

eda

tafo

rth

eeq

uilib

rium

cons

tant

sof

hydr

olyt

iceq

uilib

riaof

the

UO

221io

nan

ddi

ssoc

iatio

nco

nsta

nts

ofH

2CO

3,th

eco

ncen

trat

ion

ofth

eU

O 221,

UO

2~O

H!1

,U

O2~

OH

! 2,

and

U 2O

521sp

ecie

sw

ere

calc

ulat

ed,a

ndfr

omth

ese

the

solu

bilit

ypr

oduc

tofU

O2C

O3

Me

Iso

a eq at ov mi

co wa

va so ins

sp gr the

tem

tem


Con

cent

ratio

nof

uran

ium

inm

oldm

.d C

once

ntra

tion

ofN

aClO 4

50.

5m

oldm

23 .

e Con

cent

ratio

nof

NaC

lO 45

3.0

mol

dm2

3 .

Add

ition

alIn

form

atio

n:T

heva

riatio

nof

UO 2

CO

3so

lubi

lity

with

hydr

ogen

ion

conc

entr

atio

nan

dC

O2

pres

sure

was

inte

rpre

ted

byth

eau

thor

sas

bein

gdu

eto

the

form

atio

nof

(UO 2

) p~C

O3!

t2(p

2t)

com

plex

spec

ies

inth

esa

tura

ted

solu

tions

.B

yco

mbi

ning

the

solu

bilit

ym

easu

rem

ents

with

addi

tiona

lch

emic

alin

form

atio

nfr

omth

est

udie

sof

hom

ogen

eous

equi

libria

inth

eU

~VI!

–C

O2–

H2O

syst

em1,

2th

eso

lubi

lity

prod

uct

ofU

O 2C

O3

and

the

over

alls

tabi

lity

cons

tant

sof

the

com

plex

esfo

rmed

at25

°Cw

ere

obta

ined

:

3.0

mol

dm2

3N

aClO

40.

5m

oldm

23

NaC

lO4

Wat

er

CO

2~g!

1H

2O�

CO

3221

2H1

;lo

gK

a2:

217

.616

0.03

217

.156

0.03

218

.106

0.05

UO

2CO

3~s!�

UO

2211

CO

322;

log

Ksp

:2

13.9

460.

062

13.2

160.

062

14.4

60.

1

UO

2211

CO

322�

UO

2CO

3~aq

!;lo

gb

1,1:

8.36

0.1

8.36

0.1

9.56

0.2

UO

2211

2CO

322�

UO

2~C

O3!

222;

log

b2,

1:

16.2

060.

1515

.366

0.15

16.66

0.2

UO

2211

3CO

322�

UO

2~C

O3!

342;

log

b3,

1:

22.6

160.

1521

.466

0.15

21.36

0.2

3UO

2211

6CO

322�

~UO

2!3~

CO

3!662

;lo

gb

6,3:

56.2

60.

353

.760.

353

.460.

8

The

cons

tant

sgi

ven

for

wat

erw

ere

obta

ined

byth

eau

thor

sby

usin

gsp

ecifi

cio

n–

inte

ract

ion

theo

ry.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.T

heso

lubi

lity

ofU

O2C

O3

was

asur

edas

afu

nctio

nof

the

part

ialp

ress

ure

ofC

O2

and

H1

conc

entr

atio

n.T

hrou

ghin

itial~

Na1

H!C

lO4

solu

tions

ofns

tant

ioni

cst

reng

tha

stre

amof

CO

2/N

2ga

sm

ixtu

rew

asss

edan

dth

ede

sire

dco

ncen

trat

ion

ofH

1io

nw

asac

hiev

edco

ulom

etric

gene

ratio

nof

OH2

orH

1io

ns.

The

nex

cess

2CO

3w

asad

ded,

the

mix

ture

was

cont

inuo

usly

stirr

edun

tilui

libriu

mw

asat

tain

edw

hich

was

indi

cate

dw

hen

the

tent

ialo

fth

egl

ass

elec

trod

ere

mai

ned

cons

tant

with

in0.

2du

ring

seve

rald

ays.

The

nth

eto

talc

once

ntra

tion

ofan

ium

inth

esa

tura

ted

solu

tion

was

dete

rmin

edec

trop

hoto

met

rical

lyus

ing

the

thio

cyan

ate

met

hod.

3T

hert

ialp

ress

ure

ofC

O 2w

asca

lcul

ated

from

the

know

nm

posi

tion

ofth

ega

sm

ixtu

re,

the

mea

sure

dat

mos

pher

ices

sure

and

the

vapo

rpr

essu

reof

wat

erov

era

solu

tion

ntai

ning

the

resp

ectiv

eco

ncen

trat

ion

ofN

aClO

4.T

hefr

eeio

nco

ncen

trat

ion

was

dete

rmin

edby

the

auth

ors’

met

hod

1

ing

agl

ass

elec

trod

e.A

llm

easu

rem

ents

wer

eca

rrie

dou

tin

ther

mos

tate

dap

para

tus.

4T

hepr

essu

rew

asm

easu

red

with

azo

resi

stiv

etr

ansd

ucer

.T

heco

mpo

sitio

nof

the

solid

phas

eseq

uilib

rium

with

the

solu

tions

was

chec

ked

byx-

ray

pow

der

otog

raph

y.N

och

ange

sof

the

initi

also

lidw

ere

obse

rved

oneq

uilib

ratio

n.

UO

2CO

3w

aspr

ecip

itate

dfr

omU

O 2~N

O3!

2so

lutio

nsa

tura

ted

with

CO

2ga

s,by

drop

wis

ead

ding

aso

lutio

nof

NaH

CO

3.T

heso

lidw

asst

irred

unde

rth

em

othe

rliq

uor

ina

CO

2at

mos

pher

ein

orde

rto

avoi

dlo

sses

ofC

O 2,ce

ntrif

uged

,an

dw

ashe

dw

ithN

aClO

4so

lutio

nof

the

resp

ectiv

eco

ncen

trat

ion

satu

rate

dw

ithC

O2.

The

com

posi

tion

ofU

O 2CO

3w

asco

nfirm

edby

elem

enta

lan

alys

isan

dx-

ray

diffr

actio

n.C

omm

erci

ally

avai

labl

eC

O2

/N2

mix

ture

sw

ere

used

.T

hega

ses

wer

epu

rified

bypa

ssin

gth

emth

roug

ha

H 2S

O4

/NaC

lO4

solu

tion

and

aG

4gl

ass

filte

r.P

erch

loric

acid

~Mer

ck!

was

are

agen

tgr

ade

prod

uct.

NaC

lO4

was

prep

ared

acco

rdin

gto

Ref

.5.

The

solu

tion

was

mad

eto

cont

ain

abou

t102

3m

oldm

23

H1

.

Est

imat

edE

rror

:P

ress

ure:

prec

isio

n65.

102

4at

m~a

utho

rs!.

Tem

pera

ture

:pr

ecis

ion6

0.02

K~a

utho

rs!.

H1

conc

entr

atio

n:pr

ecis

ion6

0.02

mV

~aut

hors!

.

Ref

eren

ces:

1 L.C

iava

tta,D

.Fer

ri,I.

Gre

nthe

,and

F.S

alva

tore

,Ino

rg.C

hem

.20

,46

3~1

981!

.2 D

.F

erri,

I.G

rent

he,

and

F.

Sal

vato

re,

Act

aC

hem

.S

cand

.35

A,

165

~198

1!.

3 S.

Ahr

land

,S

vens

k.K

em.

Tid

skr.72

,75

7~1

960!

.4 L.

Cia

vatta

,D

.F

erri,

I.G

rent

he,

F.

Sal

vato

rean

dK

.S

pahi

u,In

org.

Che

m.2

2,20

88~1

983!

.5 G

.B

iede

rman

n,A

rk.

Kem

i9,27

7~1

956!

.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

ocar

bona

te;

UO 2C

O3;

@122

74-9

5-2#

~2!

Car

bon

diox

ide;

CO 2

;@1

24-3

8-9#

~3!

Per

chlo

ricac

id;

HC

lO 4;

@760

1-90

-3#~4

!S

odiu

mpe

rchl

orat

e;N

aClO 4;

@760

1-89

-0#~5

!W

ater

;H 2

O;

@773

2-18

-5#

I.G

rent

he,

D.

Fer

ri,F

.S

alva

tore

,an

dG

.R

icci

o,J.

Che

m.

Soc

.D

alto

nT

rans

.24

39–

43~1

984!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:298

p2

/atm

osph

ere5

0.04

77–

0.97

97H

1io

nco

ncen

trat

ion/

mol

dm2

35

53

102

7–

3.23

102

4

c 4/m

oldm

23 5

0.5

and

3.0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofU

O 2C

O3

inN

aClO

4so

lutio

nsa

2lo

g @H

1#b

CO

2

~p2/

atm

!2

log

Cuc,

d2

log @

H1

#bC

O2

~p2/

atm

!2

log

Cuc,

e

3.98

00.

0983

2.93

83.

841

0.09

752.

976

4.62

90.

0974

4.18

14.

066

0.09

843.

458

5.24

60.

0982

4.72

46.

215

0.09

703.

234

5.91

80.

0981

3.80

76.

303

0.09

782.

921

6.17

50.

0987

2.67

63.

621

0.29

092.

987

3.75

30.

2900

2.97

64.

406

0.28

634.

427

4.34

90.

2844

4.04

24.

981

0.29

104.

928

4.82

60.

2932

4.65

35.

916

0.28

873.

554

5.50

10.

2932

4.22

46.

014

0.29

173.

122

5.88

50.

2917

2.93

76.

210

0.47

73.

887

3.49

10.

9797

3.01

53.

568

0.97

684.

084

5.00

80.

9666

4.63

83.

621

0.97

133.

570

5.49

60.

9742

3.56

04.

113

0.96

584.

372

4.62

50.

9577

4.89

3

5.18

00.

9599

4.07

3

5.65

20.

9758

3.50

5

a Equ

ilibr

ium

solid

phas

ew

asU

O 2CO

3,@1

2274

-95-

2#,in

alls

olut

ions

.b F

ree

hydr

ogen

ion

conc

entr

atio

n.c

23

Me

Iso

me

ion

co pa by UO

eq po mV

ur sp pa co pr co H1

us a pie

in ph up

J

y

know

nco

ncen

trat

ions

.S

ampl

esof

satu

rate

dso

lutio

nsw

ere

sepa

rate

dfr

omth

eso

lidby

ultr

afiltr

atio

nw

ithfil

ters

of0.

45an

d0.

2mm

pore

size

.S

olid

phas

esw

ere

char

acte

rized

byD

TA

/TG

A,

phot

oaco

ustic

FT

IRsp

ectr

osco

py,

UV

-VIS

phot

oaco

ustic

spec

tros

copy

and

x-ra

ydi

ffrac

tion.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

ocar

bona

te;

UO 2C

O3

;@1

2274

-95-

2#C

arbo

ndi

oxid

e;C

O 2;

@124

-38-

9#S

odiu

mpe

rchl

orat

e;N

aClO 4

;@7

601-

89-0#

Wat

er;

H 2O

;@7

732-

18-5#

G.

Mei

nrat

h,Y

.K

ato,

T.

Kim

ura,

and

Z.

Yos

hida

,R

adio

chim

.A

cta,

75,

159

–67

~199

6!.

riabl

es:

Pre

pare

dby

:

K:

298

~par

tialp

ress

ure

ofC

O 2!/%

:8/m

oldm

23 :

0.1

J.H

ala

Exp

erim

enta

lDat

ae

solu

bilit

yof

UO 2

CO

3as

afu

nctio

nof

pHor

CO 32

2io

nco

ncen

trat

ion

was

repo

rted

ingr

aphi

cal

form

only

.S

olub

ility

prod

uct

of

2CO

3,K

sp5

@UO

221

#@C

O32

2#,

was

repo

rted

tobe

102(1

4.05

60.

09)

at25

°Can

dat

ioni

cst

reng

thof

0.1

mol

dm23

NaC

lO4.

Fro

mth

islu

e,us

ing

sing

leio

nac

tivity

coef

ficie

nts

oflo

gg(U

O22

1)5

20.

40,

log

g(C

O32

2)5

20.

46,

and

logg

(H1

)52

0.09

,th

erm

odyn

amic

lubi

lity

prod

uct

was

obta

ined

asKspo

510

2(1

4.91

60.

10) .

At

part

ialp

ress

ure

ofC

O 2of

8%,

and

atpH

2.8

–4.

6th

eeq

uilib

rium

solid

phas

es

mic

rocr

ysta

lline

UO 2C

O3,

@122

74-9

5-2#.

ditio

nalI

nfor

mat

ion:

~1!

The

follo

win

geq

uatio

nsw

ere

deriv

edto

expr

ess

the

conc

entr

atio

nof

UO

2~aq

!2

1as

afu

nctio

nof

pHor

conc

entr

atio

nof

CO

322

ion,

spec

tivel

y,at

ioni

cst

reng

thof

0.1

mol

dm23

NaC

lO4,

log @

UO

221

#5lo

gK

sp~U

O2C

O3)2

Slo

gK

2lo

gp(

CO

2)2

2pH

,an

dlo

g @UO

221

#

log

Ksp

~UO

2CO

3)2

Slo

g @C

O32

2#.

Equ

ilibr

ium

carb

onat

eio

nco

ncen

trat

ion

was

calc

ulat

edby

the

auth

ors

usin

g,as

inR

efs.

1–

3,H

enry

cons

tant

ofC

O2

inw

ater

(KH)

ddi

ssoc

iatio

nco

nsta

nts

ofca

rbon

icac

id,

K1

and

K2

,in

0.1

mol

dm2

3N

aClO

4,as

log @

CO

322

#5S

log

K1

log

p~C

O2!

12p

H,

whe

relo

gK

5lo

gK

H1

log

K11

log

K2

~Slo

gK

52

17.6

7,R

ef.

4!.~2

!A

tpa

rtia

lpr

essu

res

ofC

O 2of

0.3%

,an

d0.

03%

,an

dpH

2.8

–4.

6,th

eeq

uilib

rium

solid

phas

ew

asid

entifi

edas

UO

3•2H

2O.

At

50.

03%

and

pH.

7,th

eso

lidph

ase

was

anam

orph

ous

sodi

umpo

lyur

anat

e.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

lubi

lity

expe

rimen

tsw

ere

cond

ucte

das

pHtit

ratio

nsin

the

rang

efr

om2.

8to

4.6

unde

r8%

part

ialp

ress

ure

ofC

O2.

stof

expe

rimen

talp

roce

dure

was

iden

tical

with

that

inth

eth

ors’

prev

ious

wor

k.1–

3S

olut

ions

for

the

titra

tion

cont

aine

d5

mol

dm2

3U

~VI!

~dep

lete

dur

aniu

m!an

d0.

1m

oldm

23

ClO

4to

mai

ntai

nco

nsta

ntio

nic

stre

ngth

,an

dw

ere

flush

ednt

inuo

usly

with

ace

rtifi

edN 2

/CO

2ga

sm

ixtu

rem

oist

ened

was

hing

flask

s.T

hepH

titra

tions

wer

epe

rfor

med

forw

ard

dba

ckw

ard

byad

ditio

nof

eith

er0.

1m

oldm2

3H

ClO

4or

0.05

mol

dm2

3N

a 2C

O3.

Com

bina

tion

glas

sel

ectr

odes

~RO

SS

-typ

e,O

rion!

used

for

pHm

easu

rem

ent

wer

eca

libra

ted

agai

nst

five

stan

dard

buffe

rso

lutio

nsin

the

pHra

nge

of1.

7–

10.

Pha

sese

para

tion

was

achi

eved

byul

trafi

ltrat

ion

at0.

45or

0.2m

mpo

resi

ze.

The

conc

entr

atio

nof

U~V

I!w

asde

term

ined

spec

trop

hoto

met

rical

ly.

Sol

idph

ases

wer

ech

arac

teriz

edco

ntin

uous

lydu

ring

solu

bilit

yst

udie

sby

DT

A/T

GA

,ph

otoa

cous

ticF

ourie

rtr

ansf

orm

infr

ared~F

TIR

!,an

dul

trav

iole

t-vi

sibl

e~U

V-V

IS!

spec

tros

copy

,an

dx-

ray

diffr

actio

n.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Sol

ubili

typr

oduc

t:st

anda

rdde

viat

ion

see

abov

e.

Ref

eren

ces:

1 G.

Mei

nrat

han

dT

.K

imur

a,In

org.

Chi

m.

Act

a204,

79~1

993!

.2 Y

.K

ato,

T.

Kim

ura,

Z.

Yos

hida

,an

dN

.N

itani

,R

adio

chim

.A

cta

74,

21~1

996!

.3 G

.M

einr

ath

and

T.

Kim

ura,

J.A

lloys

Com

pd.20

2,89

~199

3!.

4 G.

Mei

nrat

h,Y

.K

ato,

T.

Kim

ura,

and

Z.

Yos

hida

,R

adio

chim

.A

cta

84,

21~1

999!

.

576576 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

ocar

bona

te;

UO 2C

O3;

@122

74-9

5-2#

~2!

Car

bon

diox

ide;

CO 2;

@124

-38-

9#~3

!S

odiu

mpe

rchl

orat

e;N

aClO 4;

@760

1-89

-0#~4

!W

ater

;H 2

O;

@773

2-18

-5#

G.

Mei

nrat

han

dT

.K

imur

a,In

org.

Chi

m.

Act

a204,

79–

85~1

993!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

7p

2(p

artia

lpre

ssur

eof

CO 2)

/%:1

00c 3

/mol

dm2

3 :0.1

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

prod

uct

ofU

O 2C

O3,

Ks0

5@U

O221

#@C

O322

#,w

asre

port

edto

be102

(13.

896

0.11

)at

24°C

and

atio

nic

stre

ngth

of0.

1m

oldm

23

NaC

lO4.

Fro

mth

isva

lue,

usin

gsi

ngle

ion

activ

ityco

effic

ient

sof

log

g(U

O221

)52

0.40

,lo

gg

(CO

322)5

20.

46,

and

log

g(H

1)5

20.

09,

ther

mod

ynam

icso

lubi

lity

prod

uct,

was

late

rob

tain

edas

Ksp0

510

2(1

4.75

60.

10) .

Add

ition

alIn

form

atio

n:S

olub

ility

data

wer

ere

port

edin

grap

hica

lfor

mon

ly.E

quili

briu

mca

rbon

ate

ion

conc

entr

atio

nin

the

satu

rate

dso

lutio

nsw

asca

lcul

ated

bth

eau

thor

sfr

omth

em

easu

red

pHby

usin

gth

eH

enry

cons

tant

and

the

diss

ocia

tion

cons

tant

sof

H2C

O3

in0.

1m

oldm

23

NaC

lO4.

At

100%

part

ial

pres

sure

ofC

O 2,th

eeq

uilib

rium

solid

phas

ew

asU

O2C

O3,

@122

74-9

5-2#

~rut

herf

ordi

ne!.

At

part

ial

pres

sure

sof

CO 2

of0.

98%

~mix

ture

sof

CO 2

and

N 2!

or0.

03%

,th

eso

lidph

ase

was

UO

3•2H

2O,

@205

93-3

9-9#.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Sol

ubili

tyex

perim

ents

wer

eco

nduc

ted

aspH

titra

tions

ina

glas

sve

ssel

inth

epH

rang

efr

om2.

8to

4.6

inC

O2

atm

osph

ere~1

00%

part

ialp

ress

ure

ofC

O 2!.

The

gas

was

bubb

led

thro

ugh

the

solu

tion

cont

inuo

usly

afte

rbe

ing

moi

sten

edin

was

hing

flask

s.T

heso

lidw

aspr

ecip

itate

dfr

om;

23

102

3m

oldm

23

U~V

I!so

lutio

nby

addi

tion

of0.

05m

oldm

23

Na 2

CO

3.T

hesy

stem

was

allo

wed

toeq

uilib

rate

for

3w

eeks

and

then

pHtit

ratio

nw

asca

rrie

dou

tby

step

wis

ead

ding

eith

er0.

05m

oldm2

3N

a 2C

O3

or0.

1m

oldm

23

HC

lO4

solu

tion.

Afte

rea

chad

ditio

n,st

eady

pHva

lue

was

reac

hed

with

in2

or3

days

.T

hepH

was

mea

sure

dsi

mul

tane

ousl

yw

ithtw

ogl

ass

elec

trod

es~RO

SS

-typ

e,O

rion!

calib

rate

dw

ithst

anda

rdbu

ffer

solu

tions

.T

heco

ncen

trat

ion

ofU

~VI!

was

dete

rmin

edsp

ectr

opho

tom

etric

ally

.T

hesp

ectr

opho

tom

eter

was

calib

rate

dby

usin

gU

O221

solu

tions

of

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Ref

eren

ces:

1 G.

Mei

nrat

h,Y

.K

ato,

T.

Kim

ura,

and

Z.

Yos

hida

,R

adio

chim

.A

cta

75,

159

~199

9!.

Co

~1!

~2!

~3!

~4!

Va

T/

p2

c 3 Th

UO

va so wa

Ad

re 5 an S p2

Me

So

pH Mo

au 0.0

Na

co in an


c Con

cent

ratio

nsin

mol

dm23 .

Add

ition

alin

form

atio

n:F

rom

the

solu

bilit

yda

tare

port

edin

this

docu

men

tan

din

the

auth

ors’

prev

ious

wor

k,1

and

the

solu

bilit

ypr

oduc

tof

UO 2C

O3

take

nfr

omR

ef.

1,th

eov

eral

lsta

bilit

yco

nsta

nts

for

the

com

plex

atio

nof

the

UO

221

ion

with

CO

322

,w

ere

calc

ulat

ed.

Dep

endi

ngon

the

equi

libriu

mco

ncen

trat

ion

ofth

eC

O 322

ion

the

solu

tion

spec

ies

wer

eU

O22

1,

UO

2CO

3,U

O2~

CO

3) 22

2,

and

UO 2

~CO

3) 34

2.

Als

oev

alua

ted

wer

eac

tivity

coef

ficie

nts

ofal

lspe

cies

appl

ying

the

Pitz

erap

proa

ch.T

hen,

base

don

the

Pitz

erin

tera

ctio

npa

ram

eter

s,th

eso

lubi

lity

ofU

O2C

O3

in0.

1m

oldm

23

NaC

lO4

was

calc

ulat

ed.

The

calc

ulat

edva

lues

show

eda

fairl

ygo

odag

reem

ent

with

the

expe

rimen

talr

esul

ts.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

lubi

lity

expe

rimen

tsw

ere

cond

ucte

das

pHtit

ratio

nsin

mol

dm2

3N

aClO

4un

der

100%

part

ialp

ress

ure

ofC

O2

incl

osed

glas

sve

ssel

.S

olut

ions

for

the

titra

tion

cont

aine

dso

lid

2CO

3.T

hepH

was

mea

sure

dby

usin

gco

mbi

natio

ngl

ass

ctro

des~

RO

SS

-typ

e,O

rion!

whi

chw

ere

calib

rate

dag

ains

tst

anda

rdbu

ffer

solu

tions

inth

epH

rang

eof

2–

8.T

henc

entr

atio

nof

U~VI!

was

dete

rmin

edsp

ectr

opho

tom

etric

ally

ing

arse

nazo

IIIre

agen

t.2

The

solid

phas

esw

ere

arac

teriz

edby

infr

ared~

IR!

spec

tros

copy

,an

dx-

ray

frac

tion.

To

prep

are

UO 2

CO

3,ab

out

1g

UO 2

~NO

3!2

was

diss

olve

din

50m

L0.

1m

oldm

23

NaC

lO4,

adju

sted

topH

3.5,

and

CO 2ga

sw

assl

owly

bubb

led

thro

ugh

the

solu

tion

for

1w

eek.

The

yello

wis

hpr

ecip

itate

was

colle

cted

,w

ashe

dw

ithw

ater

,an

dpl

aced

in30

mL

0.1

mol

dm2

3N

aClO

4un

der

CO 2

atm

osph

ere

for

the

pHtit

ratio

nm

easu

rem

ent.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Err

orof

log @

UO

221

#:6

0.01

to6

0.06

log

units

~rep

orte

dse

para

tely

for

ever

ym

easu

rem

ent

!.

Ref

eren

ces:

1 I.P

asha

lidis

,W.R

unde

,and

J.I.

Kim

,Rad

ioch

im.A

cta

61,1

41~1

993!

.2 J.

Bor

ak,

Z.

Slo

vak,

and

J.F

isch

er,

Tal

anta17,

215

~197

0!.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

oca

rbon

ate;

UO 2C

O3

;@1

2274

-95-

2#~2

!C

arbo

ndi

oxid

e;C

O 2;

@124

-38-

9#~3

!S

odiu

mpe

rchl

orat

e;N

aClO 4

;@7

601-

89-0#

~4!

Wat

er;

H 2O

;@7

732-

18-5#

I.P

asha

lidis

,K

.R

.C

zerw

insk

i,T

.F

angh

anel

,an

dJ.

I.K

im,

Rad

ioch

im.

Act

a76,

55–

62~1

997!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

5p

2~p

artia

lpre

ssur

eof

CO 2!

/%:

100

c 3/m

oldm

23 :

0.1

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

UO

2CO

3as

afu

nctio

nof

carb

onat

eio

nco

ncen

trat

ion

in0.

1m

oldm

23

NaC

lO4

at22

°Ca

pH2

log @

CO

322

#b,c

2lo

g @U

O22

1#c

pH2

log @

CO

322

#a,b

2lo

g @U

O22

1#c

3.89

9.77

3.43

5.31

6.93

4.46

3.91

9.73

3.47

5.33

6.89

4.37

3.98

9.59

3.62

5.37

6.81

4.46

4.18

9.19

3.84

5.38

6.79

4.08

4.64

8.27

4.38

5.42

6.71

4.37

4.66

8.23

4.46

5.52

6.51

4.39

4.68

8.19

4.29

5.53

6.49

4.10

4.70

8.15

4.21

5.55

6.45

4.02

4.83

7.89

4.24

5.57

6.41

4.09

4.86

7.83

4.52

5.60

6.35

4.01

4.91

7.73

4.52

5.63

6.29

4.01

5.02

7.51

4.21

5.79

5.97

3.70

5.04

7.47

4.59

5.80

5.95

3.77

5.10

7.35

4.47

5.82

5.91

3.74

5.21

7.13

4.19

5.92

5.71

3.46

5.22

7.11

4.33

5.93

5.69

3.35

5.26

7.03

4.18

5.95

5.65

3.36

5.28

6.99

4.22

a Equ

ilibr

ium

solid

phas

ew

asU

O 2CO

3,@1

2274

-95-

2#,in

alls

olut

ions

.b E

quili

briu

mco

ncen

trat

ion

ofth

eca

rbon

ate

ion;

itw

asca

lcul

ated

byth

eau

thor

sfr

omth

eeq

uatio

nlo

g@C

O32

2#5

Slo

gK

1lo

gp~

CO

2!1

2pH

,w

here

Slo

gK

52

17.5

5(6

0.09

)in

clud

esH

enry

cons

tant

for

CO

2,an

ddi

ssoc

iatio

nco

nsta

nts

ofca

rbon

icac

id.

Me

So

0.1

a UO

ele

six

co us ch dif

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

ocar

bona

te;

UO 2C

O3

;@1

2274

-95-

2#C

arbo

ndi

oxid

e;C

O 2;

@124

-38-

9#S

odiu

mpe

rchl

orat

e;N

aClO 4

;@7

601-

89-0#

Wat

er;

H 2O

;@7

732-

18-5#

G.

Mei

nrat

han

dT

.K

imur

a,J.

Allo

ysC

ompd

.202,

89–

93~1

993!

.

riabl

es:

Pre

pare

dby

:

K:

298

~par

tialp

ress

ure

ofC

O 2!/%

:10

0/m

oldm

23 :

0.1

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

UO

2CO

3in

0.1

mol

dm2

3N

aClO

4so

lutio

nssa

tura

ted

at25

°Cun

der

CO

2at

mos

pher

ea

pH2

log

Cub

2lo

gC

(CO 32

2)c

bpH

2lo

gC

ub2

log

C(C

O 322

)c

3.08

2.71

11.4

64.

504.

868.

62

3.11

2.66

11.4

04.

754.

898.

12

3.15

2.94

11.3

25.

164.

897.

30

3.17

2.93

11.2

85.

284.

887.

06

3.28

3.12

11.0

65.

334.

866.

96

3.41

3.32

10.8

05.

554.

726.

52

3.77

3.95

10.0

85.

614.

626.

40

4.10

4.50

9.42

5.75

4.29

6.12

4.15

4.60

9.32

5.77

4.19

6.08

4.15

4.61

9.32

5.97

3.52

5.68

4.22

4.63

9.18

5.98

3.58

5.66

4.31

4.71

9.00

6.13

3.04

5.36

4.33

4.76

8.96

6.16

2.88

5.30

4.40

4.79

8.82

6.17

2.92

5.28

4.47

4.84

8.68

6.19

2.68

5.24

heso

lidph

ase

ateq

uilib

rium

was

UO

2CO

3,@1

2274

-95-

2#,in

alls

olut

ions

.ot

alur

aniu

m~V

I!co

ncen

trat

ion

inth

esa

tura

ted

solu

tion.

quili

briu

mC

O 322

conc

entr

atio

nca

lcul

ated

byth

eau

thor

sfr

omth

eso

lutio

neq

uilib

riaof

CO

2an

ddi

ssoc

iatio

nco

nsta

nts

ofH

2CO

3~1

!.

ditio

nalI

nfor

mat

ion:

eso

lubi

lity

Sof

UO

2CO

3w

asin

terp

rete

dby

the

auth

ors

asS5

Ksp

@CO

322

#21(1

1S

bn@C

O32

2#n

),w

here

Ksp

5@U

O22

1#@

CO

322

#

102

(14.

186

0.03

) ,an

db

n5

@UO

2~C

O3) n2

22

n] @

UO

221

#21@C

O32

2#2

n,

with

b15

10(9

.236

0.04

) ,b

25

10(1

5.38

60.

17) ,

and

b35

10(2

1.86

60.

05) ,

all

atio

nic

stre

ngth

of0.

1m

oldm2

3N

aClO

4.N

osi

gnifi

cant

cont

ribut

ion

toth

eso

lubi

lity

from

UO 2~O

H!1

was

obse

rved

.T

heco

ntrib

utio

nfr

om(U

O2) 3

~OH

! 51an

d(U

O 2) 2

~OH

! 221

spec

ies

was

less

than

0.8%

.B

yus

ing

sing

leio

nac

tivity

coef

ficie

nts

oflo

gg

(UO

221

)52

0.40

,lo

gg

(CO

322

)52

0.46

,an

dlo

gg~H

1)5

20.

09,

ther

mod

ynam

icso

lubi

lity

prod

uct

ofU

O2C

O3

was

late

rob

tain

edas

Ksp0

510

2(1

5.04

60.

04) .

578578 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

ocar

bona

te;

UO 2C

O3

;@1

2274

-95-

2#~2

!C

arbo

ndi

oxid

e;C

O 2;

@124

-38-

9#~3

!S

odiu

mpe

rchl

orat

e;N

aClO 4

;@7

601-

89-0#

~4!

Wat

er;

H 2O

;@7

732-

18-5#

Y.K

ato,

T.K

imur

a,Z

.Yos

hida

,and

N.N

itani

,Rad

ioch

im.A

cta

74,

21–

5~1

996!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8p

2~p

artia

lpre

ssur

eof

CO 2!

/%:

0.03

;10

0c 3

/mol

dm2

3 :0.

1

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

prod

uct

ofU

O 2C

O3,

Ksp

5@U

O22

1#@

CO

322

#,w

asre

port

edto

be102

(14.

106

0.14

)m

ol2

dm2

6at

25°C

and

atio

nic

stre

ngth

of0.

1m

oldm

23

NaC

lO4.

Thi

sva

lue

was

obta

ined

from

the

solu

bilit

ym

easu

rem

ents

unde

rpa

rtia

lpr

essu

reof

CO

2of

100%

.U

nder

such

cond

ition

sth

eeq

uilib

rium

solid

phas

ew

asU

O2C

O3,

@122

74-9

5-2#.

The

solu

bilit

yda

taw

ere

pres

ente

din

grap

hica

lfo

rmon

ly,

and

calc

ulat

ion

ofK

spw

aspe

rfor

med

usin

gth

esa

me

proc

edur

eas

inth

eau

thor

s’pr

evio

usw

ork.

1,2

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Sol

ubili

tyex

perim

ents

wer

eco

nduc

ted

aspH

titra

tions

ina

ther

mos

tate

dgl

ass

vess

elin

the

pHra

nge

from

2.9

to4.

9in

anat

mos

pher

eof

air

(0.0

3%C

O 2!or

pure

CO 2

.T

heso

lidph

ase

was

prec

ipita

ted

from

0.02

mol

dm23

solu

tion

ofU~

VI!

byad

ditio

nof

0.1

mol

dm2

3N

aHC

O 3,

or0.

1m

oldm

23

HC

lO4.

The

pHw

asm

easu

red

byus

ing

com

bina

tion

glas

sel

ectr

odes

~Hor

iba!

whi

chw

ere

calib

rate

dag

ains

tbu

ffer

solu

tions

with

pHof

4.01

and

6.86

~bot

h6

0.01

!.P

hase

sepa

ratio

nw

asac

hiev

edby

cent

rifug

atio

nat

3000

rpm

and

ultr

afiltr

atio

nw

itha

filte

rof

0.22

mm

pore

size

.T

heco

ncen

trat

ion

ofU

~VI!

was

dete

rmin

edby

fluor

esce

nce

spec

trop

hoto

met

ry~H

itach

iF

-450

0!in

solu

tions

acid

ified

to1

mol

dm23

HC

lO4.

Sol

idph

ases

wer

ech

arac

teriz

edby

phot

oaco

ustic

UV

-VIS

and

FT

IRsp

ectr

osco

py,

and

x-ra

ycr

ysta

llogr

aphy~R

igak

uR

AD

-3C!

.F

orph

otoa

cous

ticsp

ectr

osco

py,

abou

t5

–10

mg

ofai

r-dr

ied

solid

phas

ew

asus

ed.

Not

hing

spec

ified

exce

ptth

atU

O 221

stoc

kso

lutio

nw

aspr

epar

edfr

omre

agen

tgr

ade

U 3O8.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~aut

hors!

.

Ref

eren

ces:

1 G.

Mei

nrat

han

dT

.K

imur

a,In

org.

Chi

m.

Act

a204,

79~1

993!

.2 G

.M

einr

ath

and

T.

Kim

ura,

J.A

lloys

Com

pd.20

2,89

~199

3!.

Co

~1!

~2!

~3!

~4!

Va

T/

p2

c 3 a T b T c E Ad

Th

5


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

ocar

bona

te;

UO 2C

O3;

@122

74-9

5-2#

Car

bon

diox

ide;

CO 2;

@124

-38-

9#S

odiu

mpe

rchl

orat

e;N

aClO 4;

@760

1-89

-0#W

ater

;H 2

O;

@773

2-18

-5#

U.

Kra

mer

-Sch

nabe

l,H

.B

isch

off,

and

R.

H.

Xi,

Rad

ioch

im.

Act

a56

,18

3–

8~1

992!

.

riabl

es:

Pre

pare

dby

:

K:

295

~par

tialp

ress

ure!/%

:10

0/m

oldm

23 :

0.1

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

UO

2CO

3in

0.1

mol

dm2

3so

lutio

nof

NaC

lO4

at25

°Can

d10

0%pa

rtia

lpre

ssur

eof

CO

2

pHa

2lo

g @C

O322

#b2

log

CU

cpH

a2

log @

CO

322#b

2lo

gC

Uc

3.63

10.3

82.

984.

398.

864.

23

3.90

9.84

2.91

4.46

8.72

4.31

3.94

9.76

3.48

4.55

8.54

4.42

4.18

9.28

3.96

4.79

8.06

4.35

4.19

9.26

3.94

4.81

8.02

4.29

4.19

9.25

3.98

4.83

7.98

4.28

4.24

9.15

3.40

4.90

7.84

4.24

4.27

9.10

4.00

5.04

7.56

3.95

4.28

9.08

4.00

5.05

7.54

4.14

4.33

8.99

4.07

5.41

6.82

2.61

4.34

8.96

4.04

5.47

6.70

2.78

4.34

8.96

4.10

heso

lubi

lity

ofU

O 2C

O3

was

stud

ied

inth

epH

rang

efr

om3

to6

sinc

eun

der

thes

eco

nditi

ons

UO

2CO

3,@1

2274

-95-

2#,w

asth

equ

ilibr

ium

solid

phas

e.T

heso

lidch

ange

dto

am

ixed

uran

ylhy

drox

ocar

bona

teat

pH.

6.5,

and

toU

O 2~O

H! 2

and

Na 2

U2O

7at

pH8. qu

ilibr

ium

conc

entr

atio

nof

free

carb

onat

eio

n;it

was

calc

ulat

edfr

omth

em

easu

red

pH,

part

ialp

ress

ure

ofC

O2,

and

the

diss

ocia

tion

onst

ants

ofca

rbon

icac

id.

otal

uran

ium

conc

entr

atio

nin

the

satu

rate

dso

lutio

n.

ditio

nalI

nfor

mat

ion:

eso

lubi

lity

data

wer

efit

ted

tova

rious

mod

els

whi

chto

okin

toco

nsid

erat

ion

diffe

rent

U~V

I!sp

ecie

s.T

hebe

stfit

was

foun

dfo

ra

mod

elns

ider

ing

UO 2

CO

3as

the

solid

phas

e,an

dso

lutio

nco

mpl

exes

UO

2~C

O3)

n22

2n

(n5

1–

3)

with

stab

ility

cons

tant

sbn

5@U

O2~

CO

3)n2

22

n] @

UO

221#2

1@C

O322

#2n.

The

follo

win

gco

nsta

nts

wer

eob

tain

ed:Ksp

5@U

O221

#@C

O322

#510

213

.29 ,

b15

108.

70,

b2

510

16.3

3 ,an

db

35

1023

.92 .

The

solu

bilit

yof

UO 2

CO

3w

asal

sost

udie

dis

othe

rmal

lyby

diss

olvi

ngit

inN

aHC

O3

solu

tions

.T

heda

taob

tain

edag

reed

basi

cally

with

thos

efr

omth

etit

ratio

nte

chni

que

but

wer

eno

tco

nsid

ered

for

the

subs

eque

ntca

lcul

atio

nssi

nce

they

show

edra

ther

larg

esc

atte

r.



Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Mea

sure

men

tsw

ere

carr

ied

out

inC

O2

atm

osph

ere

in0.

1m

oldm2

3N

aClO

4so

lutio

nsin

ath

erm

osta

ted

titra

tion

vess

el.

A0.

01m

oldm2

3so

lutio

nof

U~V

I!la

bele

dw

ith23

3 Uw

aspr

ecip

itate

dat

pH;

6by

addi

ng0.

05m

oldm

23

Na 2

CO

3.M

oist

ened

CO 2

was

bubb

led

thro

ugh

the

solu

tion

cont

inuo

usly

.T

heso

lutio

nw

ithth

epr

ecip

itate

was

allo

wed

tost

and

unde

rC

O2

atm

osph

ere

for

3w

eeks

.D

urin

gth

ispe

riod,

pHan

dU~V

I!co

ncen

trat

ion

wer

ech

ecke

dre

peat

edly

and

whe

nth

eyre

mai

ned

unch

ange

d,th

epH

ofth

eso

lutio

nw

asva

ried

step

wis

ein

the

pHra

nge

from

3.0

to6.

2by

addi

ngsm

allp

ortio

nsof

eith

er0.

1m

oldm2

3H

ClO

4or

0.05

mol

dm2

3N

a 2C

O3.

Ast

eady

stat

ew

ithst

abili

zed

pHva

lue

was

usua

llyat

tain

edw

ithin

1–

3da

ys,

from

both

supe

rsat

urat

ion

and

unde

rsat

urat

ion.

Pha

sese

para

tion

was

then

achi

eved

byul

trafi

ltrat

ion

thou

gha

220

nmpo

resi

zefil

ter,

and

the

conc

entr

atio

nof

U~VI!

inth

eso

lutio

nw

asm

easu

red

byliq

uid

scin

tilla

tion

coun

ting

of23

3 Uus

ing

Tric

arb

300

~Pac

kard!

spec

trom

eter

.T

hea

coun

ting

effic

ienc

yw

asde

term

ined

tobe

99.6

4%,

byca

libra

tion

with

an241 A

mst

anda

rd.

Com

bina

tion

glas

sel

ectr

odes~O

rion!

wer

eus

edfo

rpH

mea

sure

men

taf

ter

calib

ratio

nag

ains

tfo

urst

anda

rdbu

ffer

solu

tions

.S

olid

phas

esw

ere

char

acte

rized

usin

gD

TA

/TG

Aan

dx-

ray

pow

der

diffr

actio

n.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~aut

hors!

.pH

:pr

ecis

ion6

0.02

pHun

its~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 W.

Run

de,

G.

Mei

nrat

h,an

dJ.

I.K

im,

Rad

ioch

im.

Act

a58

Õ59,

93~1

992!

.2 G

.M

einr

ath,

Y.

Kat

o,T

.K

imur

a,an

dZ

.Y

oshi

da,

Rad

ioch

im.

Act

a75

,15

9~1

999!

.

Co

~1!

~2!

~3!

~4!

Va

T/

p2

c 3 a T e . b E c c T Ad

Th

co

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

ocar

bona

te;

UO 2C

O3;

@122

74-9

5-2#

Car

bon

diox

ide;

CO 2;

@124

-38-

9#S

odiu

mpe

rchl

orat

e;N

aClO 4;

@760

1-89

-0#W

ater

;H 2

O;

@773

2-18

-5#

I.P

asha

lidis

,W

.R

unde

,an

dJ.

I.K

im,

Rad

ioch

im.

Act

a61

,14

1–

6~1

993!

.

riabl

es:

Pre

pare

dby

:

K:

295

~par

tialp

ress

ure!/%

:10

0/m

oldm

23 :

0.1

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofU

O2C

O3

in0.

1m

oldm

23

solu

tion

ofN

aClO

4at

25°C

and

100%

part

ialp

ress

ure

ofC

O2a

pH2

log @

CO

322#b

2lo

g @U

O221

#2

log

Ksp

c

3.11

11.4

01.

81d13

.21

3.11

11.4

01.

73e13

.14

3.26

11.4

02.

33d13

.43

3.45

10.7

32.

61d13

.34

3.45

10.7

32.

68e13

.41

3.45

10.6

92.

78e13

.47

3.46

10.6

92.

76d13

.45

3.56

10.5

12.

89d13

.39

3.69

10.2

33.

03d13

.27

3.69

10.2

33.

19e13

.43

3.78

10.0

63.

15d13

.21

3.78

10.0

63.

55e13

.61

3.84

9.94

3.23d

13.1

74.

009.

613.

58d13

.19

4.00

9.61

3.91e

13.5

2

quili

briu

mso

lidph

ase

was

UO 2C

O3,

@122

74-9

5-2#,

inal

lsol

utio

ns.

heco

ncen

trat

ion

offr

eeca

rbon

ate

ion.

Itw

asca

lcul

ated

from

the

mea

sure

dpH

,pa

rtia

lpr

essu

reof

CO

2,H

enry

cons

tant

,an

dis

soci

atio

nco

nsta

nts

ofca

rbon

icac

id.

sp5

@UO

221#@

CO

322#.

eter

min

edby

UV

spec

tros

copy

.et

erm

ined

byIC

P-A

ES

.

ditio

nalI

nfor

mat

ion:

eav

erag

eva

lue

ofKsp

was

repo

rted

tobe

102(1

3.35

60.

14)

mol

2dm

26 .

By

usin

gth

esp

ecifi

cio

nin

tera

ctio

nth

eory

proc

edur

e,th

isw

asre

calc

ulat

edby

the

auth

ors

toze

roio

nic

stre

ngth

toob

tain

Ksp0

510

2(1

4.21

60.

14)

mol

2dm

26 .

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Apo

rtio

nof

UO

221st

ock

solu

tion

was

dilu

ted

with

0.1

mol

dm2

3N

aClO

4,ne

utra

lized

topH

7w

ithN

aOH

,an

dC

O 2ga

sw

asbu

bble

dth

roug

hth

epr

ecip

itate

ofU

O2C

O3.

The

prec

ipita

tion

proc

edur

ean

dsu

bseq

uent

solu

bilit

ym

easu

rem

ents

wer

epe

rfor

med

ina

clos

edgl

ass

vess

el.

The

pHof

the

solu

tion

inco

ntac

tw

ithU

O2C

O3

was

adju

sted

step

wis

eby

addi

tion

of0.

1m

oldm2

3H

ClO

4or

NaO

H.

The

gas

was

bubb

led

thro

ugh

the

vess

elco

ntin

uous

ly.

The

pHw

asm

easu

red

with

aR

OS

S-t

ype

com

bina

tion

elec

trod

eco

ntai

ning

3m

oldm2

3N

aClO

4as

afil

ling

solu

tion.

The

elec

trod

ew

asca

libra

ted

agai

nst

six

diffe

rent

buffe

rso

lutio

ns.

The

time

ofeq

uilib

ratio

naf

ter

each

adju

stm

ent

ofpH

was

not

repo

rted

.T

heeq

uilib

rium

uran

ium

conc

entr

atio

nin

the

satu

rate

dso

lutio

nw

asde

term

ined

byIC

P-A

ES

toob

tain

the

tota

lura

nium

conc

entr

atio

n,an

dby

UV

spec

tros

copy

toob

tain

the

UO 221

conc

entr

atio

n.T

heso

lidph

ases

wer

ech

arac

teriz

edby

x-ra

ypo

wde

rdi

ffrac

tion,

and

IRan

dU

Vsp

ectr

osco

py.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

580580 JIRI HALA

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

The

solid

was

diss

olve

din

solu

tions

ofva

ryin

gin

itial

pHun

der

CO 2

atm

osph

ere.

The

gas

was

purifi

edan

deq

uilib

rate

dby

pass

ing

itth

roug

h1

mol

dm23

H2S

O4,

dist

illed

wat

er,

and

0.1

mol

dm23

NaC

lO4

befo

reit

ente

red

the

reac

tion

vess

el.

Con

stan

tpH~w

ithin

60.

02pH

unit!

was

reac

hed

with

in3

–14

days

.T

hen

sam

ples

ofth

esa

tura

ted

solu

tions

wer

ew

ithdr

awn

and

filte

red

thro

ugh

450

nmpo

resi

zefil

ter.

Gre

atca

rew

asta

ken

toen

sure

that

durin

gsa

mpl

ing

and

filtr

atio

nth

eco

ntac

tof

the

sam

ple

with

air

was

assh

ort

aspo

ssib

leto

avoi

dC

O2

cont

amin

atio

nor

loss

.T

hesa

mpl

esw

ere

anal

yzed

for

U~VI!

byliq

uid

scin

tilla

tion

coun

ting

usin

ga

Bec

kman

LS28

00co

unte

rca

libra

ted

with

U~V

I!so

lutio

nsco

ntai

ning

1310

25–

3310

23

mol

dm2

3

U~V

I!,

orsp

ectr

opho

tom

etric

ally~H

itach

i330

spec

trop

hoto

met

er!by

usin

ga

mod

ified

arse

nazo

IIIm

etho

d.1

The

uran

ium

conc

entr

atio

nsob

tain

edby

thes

etw

om

etho

dsag

reed

with

in3%

.T

heco

mpo

sitio

nof

the

equi

libriu

mso

lidph

ases

was

inve

stig

ated

bym

eans

ofx-

ray

diffr

actio

nan

d14

C-la

bele

dU

O 2C

O3.

Sol

utio

nsof

UO 221

wer

epr

epar

edfr

omU

O 2~N

O3!

2•6H

2O~M

erck

p.a.!

.T

hede

cay

prod

ucts

wer

ere

mov

edon

the

day

the

expe

rimen

tst

arte

dby

pass

ing

the

UO

221so

lutio

nin

9m

oldm

23

HC

lth

roug

hD

owex

134

ion

exch

ange

resi

n,an

del

utin

g~VI!

with

1m

oldm

23

HC

l.T

heso

lutio

nw

asev

apor

ated

todr

ynes

s,an

dU

O 2C

O3

was

prep

ared

byad

ding

satu

rate

dN

aHC

O3

solu

tion

toth

edr

yre

sidu

eat

room

tem

pera

ture

.~T

here

sidu

ew

asre

diss

olve

dfo

rth

esa

keof

stan

dard

izin

git

with

ED

TA

titra

tion.

!T

here

sidu

edi

ssol

ved

with

the

evol

utio

nof

CO

2un

tila

pale

yello

wpr

ecip

itate

form

ed.

The

nth

ere

actio

nve

ssel

was

stop

pere

dan

dal

low

edto

stan

dov

erni

ght,

the

prec

ipita

tew

asce

ntrif

uged

,w

ashe

dw

ithw

ater

seve

ralt

imes

,an

dch

arac

teriz

edby

x-ra

ydi

ffrac

tion.

Itw

asid

entifi

edas

UO 2C

O3

byco

mpa

ring

the

diffr

actio

npa

ttern

with

liter

atur

eda

ta.

2,3

The

prec

ipita

te,

drie

dov

ersi

lica

gel,

was

also

anal

yzed

for

uran

ium

cont

ent:

for

UO

2CO

3,ca

lcul

ated

3.6%

,fo

und

3.1%

.O

ther

chem

ical

sw

ere

Mer

ckre

agen

tgr

ade

prod

ucts

.D

oubl

ydi

still

edde

ioni

zed

wat

erw

asus

edfo

rth

epr

epar

atio

nof

the

solu

tions

.It

was

boile

dbe

fore

use

tore

mov

eal

ltra

ces

ofC

O2.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 S.

B.

Sav

vin,

Tal

anta8

,67

3~1

961!

.2 J.

R.

Cla

rkan

dC

.L.

Chr

ist,

Am

.M

iner

.41

,84

4~1

956!

.3 P

owde

rD

iffra

ctio

nF

ile,

Inor

gani

cph

ases

.In

t.C

ente

rfo

rD

iffra

ctio

nD

ata,

U.S

.A.

Co

~1!

~2!

~3!

~4!

Va

T/

p2

c 3 a E b T d c K d D e D Ad

Th


tem

pera

ture

room

.T

heco

nten

tsof

the

bottl

ew

asth

ence

ntrif

uged

,an

dbo

thth

eso

lidan

dliq

uid

phas

esw

ere

anal

yzed

for

uran

ium

,so

dium

,an

dca

rbon

ate.

Dep

endi

ngon

uran

ium

conc

entr

atio

nin

the

satu

rate

dso

lutio

ns,

uran

ium

was

dete

rmin

edei

ther

bypo

tent

iom

etric

titra

tion

with

FeS

O4

afte

rre

duct

ion

ofur

aniu

m,

orco

lorim

etric

ally

with

asco

rbic

acid

.S

odiu

mw

asde

term

ined

byfla

me

phot

omet

ry,

and

carb

onat

eby

abso

rptio

n-gr

avim

etric

met

hod.

3

obta

ined

.U

O 3us

edw

aspr

epar

edby

prec

ipita

ting

the

pero

xide

UO

4•xH

2Ofr

oma

solu

tion

ofU

O 2~N

O3!

2at

pH2.

5w

ithsu

bseq

uent

deco

mpo

sitio

nof

the

prec

ipita

teat

325

°C.

Sou

rce

and

purit

yof

UO 2

~NO

3!2

not

spec

ified

.R

eage

ntgr

ade

Na

2CO

3

was

used

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

2K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

5.2.

Sod

ium

Dic

arbo

nato

diox

oura

nate

„V

I…„2-…

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

dica

rbon

atod

ioxo

uran

ate;

Na

2UO

2~C

O3!

2;@

#W

ater

;H 2

O;

@773

2-18

-5#M

.Bac

hele

t,E

.Che

ylan

,M.D

uis,

and

J.C

.Gou

lette

,Bul

l.S

oc.

Chi

m.

Fra

nce

173

–9~1

954!

.

riabl

es:

Pre

pare

dby

:

K:

291

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

at18

°Cof

Na 2U

O2~

CO

3!2

inw

ater

was

repo

rted

tobe

1415

gsa

lt/L

solu

tion

~3.2

6m

oldm

23 ,

com

pile

r!.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

thin

gsp

ecifi

ed.

Na 2U

O2~

CO

3!2

was

prep

ared

bydi

ssol

utio

nof

UO

3•1/

2H2O

in1

Lof

aso

lutio

nco

ntai

ning

stoi

chio

met

ricam

ount

ofN

aHC

O3

bypa

ssin

ga

stre

amof

CO 2

thro

ugh

the

slur

ry.

The

resu

lting

solu

tion

was

evap

orat

edat

40°C

.A

naly

sis

~fou

nd/c

alcu

late

d,in

mas

s%!

:U

O3

64.7

/65.

6,N

a 2O14

.6/1

4.22

,C

O 220

.7/2

0.18

.S

ourc

ean

dpu

rity

ofm

ater

ials

used

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

ocar

bona

te;

UO 2C

O3;

@122

74-9

5-2#

~2!

Sod

ium

carb

onat

e;N

a2C

O3;

@593

-85-

1#~3

!W

ater

;H 2

O;

@773

2-18

-5#

C.

A.

Bla

ke,

C.

F.

Col

eman

,K

.B

.B

row

n,D

.G

.H

ill,

R.

S.

Low

rie,

and

J.M

.S

chm

itt,

J.A

m.

Che

m.

Soc

.78

,59

78–

83~1

956!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

9c 2

/mol

dm2

3 :0.

094

–1.

41J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

UO

2CO

3in

Na 2

CO

3so

lutio

nsat

26°Ca

Na 2

CO

3

(c2

/mol

dm2

3 )N

a 2C

O3

(m2

/mol

kg2

1 )cU

O2C

O3

(c1

/mol

dm2

3 )U

O2C

O3

(m1

/mol

kg2

1 )cD

ensi

tyb

~gcm

23 !

0.09

40.

0949

0.08

70.

0879

1.02

9

0.18

90.

192

0.17

40.

177

1.06

1

0.33

70.

389

0.33

80.

349

1.12

1

0.56

60.

593

0.52

10.

546

1.18

8

0.75

50.

811

0.74

20.

797

1.25

7

0.94

31.

025

0.88

60.

963

1.31

4

1.13

1.26

81.

091.

223

1.37

3

1.41

1.76

31.

351.

640

1.42

3

a Com

posi

tion

ofeq

uilib

rium

solid

phas

esno

tre

port

ed.

b At

25°C

.c C

alcu

late

dby

com

pile

r.

Add

ition

alIn

form

atio

n:T

heau

thor

sre

port

edth

atso

lubi

litie

sup

to32

mas

s%

UO

3w

ere

also

mea

sure

d.N

oda

taw

ere

repo

rted

,ho

wev

er,

sinc

eth

eso

lutio

nsin

this

regi

onw

ere

very

visc

ous,

diffi

cult

toce

ntrif

uge,

and

ineq

uilib

rium

with

appr

ecia

ble

CO

2pr

essu

re~2

0m

m!.

Equ

ilibr

ium

conc

en-

trat

ions

inth

ese

solu

tions

coul

dno

tbe

mea

sure

dbe

caus

eof

supe

rsat

urat

ion.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Sol

utio

nsco

ntai

ning

exce

ssU

O2C

O3

wer

eeq

uilib

rate

din

Pyr

exor

poly

fluor

oeth

ylen

ebo

ttles

for

atle

ast

10da

ysbu

tus

ually

for

3or

mor

ew

eeks

toen

sure

equi

libriu

m.

The

agita

tion

was

carr

ied

out

ina

cons

tant

UO

2CO

3w

aspr

epar

edby

agita

ting

am

ixtu

reof

UO

3,w

ater

and

exce

ssof

solid

CO 2

ina

stee

lbo

mb

for5

hat

90–

105

°Can

dpr

essu

res

of25

00to

3000

ppsi~1

7.2

–20

.7M

Pa!.

Apa

leye

llow

prod

uctw

ithco

nsis

tent

lyco

nsta

ntU

/COra

tioof

1.01

–1.

03w

as

Co

~1!

~2!

Va

T/

Me

No

J

31.0

0,C

O 222

.48/

21.8

0;R

bsa

lt—U

O 335

.04/

36.1

0,R

b 2O47

.95/

47.2

0,C

O 217

.01/

16.7

0;C

ssa

lt—U

O 329

.30/

29.1

0,C

s 2O56

.70/

57.4

5,C

O 214

.00/

13.4

6.A

naly

sis

ofth

eN

asa

ltw

asno

tre

port

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

tric

arbo

nato

diox

oura

nate~VI!

;N

a 4U

O2~

CO

3!3;

2076

-52-

7#S

odiu

mca

rbon

ate;

Na

2CO

3;

@497

-19-

8#W

ater

;H 2

O;

@773

2-18

-5#

C.

A.

Bla

ke,

C.

F.

Col

eman

,K

.B

.B

row

n,D

.G

.H

ill,

R.

S.

Low

rie,

and

J.M

.S

chm

itt,

J.A

m.

Che

m.

Soc

.78

,59

78–

83~1

956!

.

riabl

es:

Pre

pare

dby

:

K:

299

/mol

dm2

3 :0

–0.

5J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Na 4

UO

2~C

O3!

3in

Na 2

CO

3so

lutio

nsat

26°Ca

Na 2

CO

3

(c2

/mol

dm2

3 )N

a 4U

O2~

CO

3!3

(c1

/mol

dm2

3 )

00.

286

0.3

0.17

3

0.5

0.13

0

ompo

sitio

nof

equi

libriu

mso

lidph

ases

was

not

repo

rted

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.S

olut

ions

cont

aini

ngex

cess

solid

reeq

uilib

rate

din

Pyr

exor

poly

fluor

oeth

ylen

ebo

ttles

for

atst

10da

ys,

but

usua

llyfo

r3

orm

ore

wee

ksto

ensu

reui

libriu

m.

The

agita

tion

was

carr

ied

out

ina

nsta

nt-t

empe

ratu

rero

om.

The

cont

ents

ofth

ebo

ttle

wer

en

cent

rifug

ed,

and

both

the

solid

and

liqui

dw

ere

anal

yzed

uran

ium

,so

dium

,an

dca

rbon

ate.

Dep

endi

ngon

uran

ium

ncen

trat

ion

inth

esa

tura

ted

solu

tion,

uran

ium

was

term

ined

eith

erby

pote

ntio

met

rictit

ratio

nw

ithF

eSO

4af

ter

duct

ion

ofur

aniu

m,

orco

lorim

etric

ally

with

asco

rbic

acid

.di

umw

asde

term

ined

byfla

me

phot

omet

ry,

and

carb

onat

eab

sorp

tion-

grav

imet

ricm

etho

d.

Na 4

UO

2~C

O3!

3w

aspr

epar

edac

cord

ing

toR

ef.

1.F

irst,

sodi

umur

anat

ew

aspr

ecip

itate

dfr

omU

O2~

NO

3!2

solu

tion

with

NaO

H,

was

hed

and

diss

olve

din

aso

lutio

nof

NaH

CO

3.T

hesa

ltw

asth

enob

tain

edby

evap

orat

ing

the

solu

tion

toa

low

volu

me

whi

lepa

ssin

gC

O 2th

roug

hth

eso

lutio

n.T

hesa

ltw

asre

crys

talli

zed

from

wat

erto

yiel

da

brig

htye

llow

prod

uct

with

the

CO

3/U

ratio

of3:

3.2.

Sou

rce

and

purit

yof

mat

eria

lsus

edw

ere

not

spec

ified

.N

a 2CO

3w

asa

reag

ent

grad

epr

oduc

t.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 W.E

.Bun

ce,N

.H.F

urna

m,a

ndR

.T.M

undy

,Rep

ortM

-423

8,19

47.

582582 JIRI HALA

5.3.

Sal

tsof

Tris

„ca

rbon

ato…D

ioxo

uran

ante

„4-…

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Alk

alim

etal

tric

arbo

nato

diox

oura

nate

s~V

I!~2

!W

ater

;H 2

O;

@773

2-18

-5#~1

!M

.B

ache

let,

E.

Che

ylan

,K

.D

uis,

and

J.C

.G

oule

tte,

Bul

l.S

oc.

Chi

m.

Fra

nce

55–

60~19

52!.

~2!

M.

Bac

hele

t,E

.C

heyl

an,

K.

Dui

s,an

dJ.

C.

Gou

lette

,B

ull.

Soc

.C

him

.F

ranc

e17

3–

9~195

4!.

Var

iabl

es:

Pre

pare

dby

:

Tem

pera

ture

J.H

a´ l

a

Exp

erim

enta

lDat

a

Sol

ubili

tyof

alka

lim

etal

tric

arbo

nato

diox

oura

nate

s~V

I!in

wat

era

Sal

tT

empe

ratu

re~°

C!

Sal

tin

the

satu

rate

dso

lutio

n~g

dm2

3 !

Sal

tin

the

satu

rate

dso

lutio

n~m

oldm

23 !e

Na 4

UO

2~C

O3!

3b20

204d

0.71

3

K4U

O2~

CO

3!3c

047

0.07

75

1871

0.11

7

Rb 4

UO

2~C

O3!

3c20

550

0.69

5

Cs 4

UO

2~C

O3!

3c20

1300

1.32

5

a Equ

ilibr

ium

solid

phas

esno

tin

vest

igat

ed.

b @120

76-5

2-7#;

orig

inal

mea

sure

men

tin

Ref

.1.

c Orig

inal

mea

sure

men

tsin

Ref

.2.

d gU

O3

dm2

3 .e C

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Not

hing

spec

ified

.T

hesa

ltsw

ere

prep

ared

bydi

ssol

ving

UO

3•1/

2H2O

ina

solu

tion

ofth

eco

rres

pond

ing

alka

lim

etal

hydr

ogen

carb

onat

eat

room

tem

pera

ture

.T

hem

ole

ratio

ofre

acta

nts

was

1:4.

Fro

mth

ere

sulti

ngso

lutio

nsth

eso

dium

salt

was

prec

ipita

ted

at50

°C,a

ndth

eot

her

salts

wer

eob

tain

edaf

ter

evap

orat

ion

ofth

eso

lutio

nsat

room

tem

pera

ture

and

recr

ysta

lliza

tion

from

wat

er.

Sou

rce

and

purit

yof

mat

eria

lsus

edw

ere

not

spec

ified

.A

naly

sis

~fou

nd/

calc

ulat

ed,

mas

s%!:

Ksa

lt—U

O3

47.1

4/47

.20,

K 2O30

.38/

Co

~1!

@1 ~2!

~3!

Va

T/

c 2 a C Me

Iso

we

lea

eq co the

for

co de re So

by


byab

sorp

tion-

grav

imet

ricm

etho

d.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 W.E

.Bun

ce,N

.H.F

urna

m,a

ndR

.T.M

undy

,Rep

ortM

-423

8,19

47.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

tric

arbo

nato

diox

oura

nate~VI!

;N

a 4U

O2~

CO

3) 3

;20

76-5

2-7#

Sod

ium

sulfa

te;

Na 2S

O4

;@7

757-

82-6#

Wat

er;

H 2O

;@7

732-

18-5#

C.

A.

Bla

ke,

C.

F.

Col

eman

,K

.B

.B

row

n,D

.G

.H

ill,

R.

S.

Low

rie,

and

J.M

.S

chm

itt,

J.A

m.

Che

m.

Soc

.78

,59

78–

83~1

956!

.

riabl

es:

Pre

pare

dby

:

K:

299

/mol

dm2

3 :0.

3–

3.0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Na 4

UO

2~C

O3!

3in

Na 2

SO

4so

lutio

nsat

26°Ca

Na 2

SO

4

(c2

/mol

dm2

3 )N

a 4U

O2~

CO

3!3

(c1

/mol

dm2

3 )

0.3

0.16

8

0.5

0.13

5

1.5

0.04

5

2.0

0.03

5

3.0

0.01

1

ompo

sitio

nof

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.S

olut

ions

cont

aini

ngex

cess

solid

reeq

uilib

rate

din

Pyr

exor

poly

fluor

oeth

ylen

ebo

ttles

for

atst

10da

ys,

but

usua

llyfo

r3

orm

ore

wee

ksto

ensu

reui

libriu

m.

The

agita

tion

was

carr

ied

out

ina

nsta

nt-t

empe

ratu

rero

om.

The

cont

ents

ofth

ebo

ttle

wer

en

cent

rifug

ed,

and

both

the

solid

and

liqui

dw

ere

anal

yzed

uran

ium

,so

dium

,an

dca

rbon

ate.

Dep

endi

ngon

uran

ium

ncen

trat

ion

inth

esa

tura

ted

solu

tion,

uran

ium

was

term

ined

eith

erby

pote

ntio

met

rictit

ratio

nw

ithF

eSO

4af

ter

duct

ion

ofur

aniu

m,

orco

lorim

etric

ally

with

asco

rbic

acid

.di

umw

asde

term

ined

byfla

me

phot

omet

ry,

and

carb

onat

eab

sorp

tion-

grav

imet

ricm

etho

d.

Na 4

UO

2~C

O3!

3w

aspr

epar

edac

cord

ing

toR

ef.

1.F

irst,

sodi

umur

anat

ew

aspr

ecip

itate

dfr

omU

O2~

NO

3!2

solu

tion

with

NaO

H,

was

hed

and

diss

olve

din

aso

lutio

nof

NaH

CO

3.T

hesa

ltw

asob

tain

edby

evap

orat

ing

the

solu

tion

toa

low

volu

me

whi

lepa

ssin

gC

O 2th

roug

hth

eso

lutio

n.T

hesa

ltw

asth

enre

crys

talli

zed

from

wat

erto

yiel

da

brig

htye

llow

prod

uct

with

the

CO 3

/Ura

tioof

3:3.

2.S

ourc

ean

dpu

rity

ofm

ater

ials

used

wer

eno

tsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 W.E

.Bun

ce,N

.H.F

urna

m,a

ndR

.T.M

undy

,Rep

ortM

-423

8,19

47.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

tric

arbo

nato

diox

oura

nate~VI!

;N

a 4U

O2~

CO

3!3;

@120

76-5

2-7#

~2!

Sod

ium

chlo

ride;

NaC

l;@764

7-14

-5#~3

!W

ater

;H 2

O;

@773

2-18

-5#

C.

A.

Bla

ke,

C.

F.

Col

eman

,K

.B

.B

row

n,D

.G

.H

ill,

R.

S.

Low

rie,

and

J.M

.S

chm

itt,

J.A

m.

Che

m.

Soc

.78

,59

78–

83~1

956!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

9c 2

/mol

dm2

3 :1.

0–

4.0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Na 4

UO

2~C

O3!

3in

NaC

lsol

utio

nsat

26°Ca

NaC

l(c

2/m

oldm

23 )

Na 4

UO

2~C

O3!

3

c 1/m

oldm

23

1.0

0.07

5

1.5

0.03

4

2.0

0.02

0

2.5

0.01

2

3.0

0.00

6

3.5

0.00

3

4.0

0.00

25

a Com

posi

tion

ofeq

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Sol

utio

nsco

ntai

ning

exce

ssso

lidw

ere

equi

libra

ted

inP

yrex

orpo

lyflu

oroe

thyl

ene

bottl

esfo

rat

leas

t10

days

,bu

tus

ually

for

3or

mor

ew

eeks

toen

sure

equi

libriu

m.

The

agita

tion

was

carr

ied

out

ina

cons

tant

-tem

pera

ture

room

.T

heco

nten

tsof

the

bottl

ew

ere

then

cent

rifug

ed,

and

both

the

solid

and

liqui

dw

ere

anal

yzed

for

uran

ium

,so

dium

,an

dca

rbon

ate.

Dep

endi

ngon

uran

ium

conc

entr

atio

nin

the

satu

rate

dso

lutio

n,ur

aniu

mw

asde

term

ined

eith

erby

pote

ntio

met

rictit

ratio

nw

ithF

eSO

4af

ter

redu

ctio

nof

uran

ium

,or

colo

rimet

rical

lyw

ithas

corb

icac

id.

Sod

ium

was

dete

rmin

edby

flam

eph

otom

etry

,an

dca

rbon

ate

Na 4

UO

2~C

O3!

3w

aspr

epar

edac

cord

ing

toR

ef.

1.F

irst,

sodi

umur

anat

ew

aspr

ecip

itate

dfr

omU

O2~

NO

3!2

solu

tion

with

NaO

H,

was

hed

and

diss

olve

din

aso

lutio

nof

NaH

CO

3.T

hesa

ltw

asth

enob

tain

edby

evap

orat

ing

the

solu

tion

toa

low

volu

me

whi

lepa

ssin

gC

O 2th

roug

hth

eso

lutio

n.T

hesa

ltw

asre

crys

talli

zed

from

wat

erto

yiel

da

brig

htye

llow

prod

uct

with

the

CO

3/U

ratio

of3:

3.2.

Sou

rce

and

purit

yof

mat

eria

lsus

edw

ere

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Co

~1!

@1 ~2!

~3!

Va

T/

c 2 a C Me

Iso

we

lea

eq co the

for

co de re So

by

J

conc

entr

atio

nin

the

satu

rate

dso

lutio

n,ur

aniu

mw

asde

term

ined

eith

erby

pote

ntio

met

rictit

ratio

nw

ithF

eSO

4af

ter

redu

ctio

nof

uran

ium

,or

colo

rimet

rical

lyw

ithas

corb

icac

id.

Sod

ium

was

dete

rmin

edby

flam

eph

otom

etry

,an

dca

rbon

ate

byab

sorp

tion-

grav

imet

ricm

etho

d.

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 H.

S.

Har

ned

and

B.

B.

Ow

en,Th

eP

hys

ica

lC

he

mis

try

of

Ele

ctro

lytic

So

lutio

ns~

Rei

nhol

d,N

ewY

ork,

1950!

,p.

476.

2 W.E

.Bun

ce,N

.H.F

urna

m,a

ndR

.T.M

undy

,Rep

ortM

-423

8,19

47.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

tric

arbo

nato

diox

oura

nate~VI!

;N

a 4U

O2~

CO

3) 3

;20

76-5

2-7#

Sod

ium

carb

onat

e;N

a2C

O3

;@4

97-1

9-8#

Sod

ium

chlo

ride;

NaC

l;@764

7-14

-5#W

ater

;H 2

O;

@773

2-18

-5#

C.

A.

Bla

ke,

C.

F.

Col

eman

,K

.B

.B

row

n,D

.G

.H

ill,

R.

S.

Low

rie,

and

J.M

.S

chm

itt,

J.A

m.

Che

m.

Soc7

8,59

78–

83~1

956!

.

riabl

es:

Pre

pare

dby

:

K:

299

/mol

dm2

35

0.22

–1.

72/m

oldm

23 :

0.28

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

26°C

ofN

a 4UO

2~C

O3!

3in

Na 2

CO

3–

NaC

lsol

utio

nsa

Na 2

CO

3a

(c2

/mol

dm2

3 )N

a 4U

O2~

CO

3!3

(c1

/mol

dm2

3 )

0.22

0.12

6

0.72

0.06

3

1.22

0.03

4

1.72

0.02

0

ompo

sitio

nof

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.A

llso

lutio

nsco

ntai

ned

also

0.28

mol

dm2

3N

aCl.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.S

olut

ions

cont

aini

ngex

cess

solid

reeq

uilib

rate

din

Pyr

exor

poly

fluor

oeth

ylen

ebo

ttles

for

atst

10da

ys,

but

usua

llyfo

r3

orm

ore

wee

ksto

ensu

reui

libriu

m.

The

agita

tion

was

carr

ied

out

ina

nsta

nt-t

empe

ratu

rero

om.

The

cont

ents

ofth

ebo

ttle

wer

en

cent

rifug

ed,

and

both

the

solid

and

liqui

dw

ere

anal

yzed

uran

ium

,so

dium

,an

dca

rbon

ate.

Dep

endi

ngon

uran

ium

ncen

trat

ion

inth

esa

tura

ted

solu

tion,

uran

ium

was

term

ined

eith

erby

pote

ntio

met

rictit

ratio

nw

ithF

eSO

4af

ter

duct

ion

ofur

aniu

m,

orco

lorim

etric

ally

with

asco

rbic

acid

.di

umw

asde

term

ined

byfla

me

phot

omet

ry,

and

carb

onat

eab

sorp

tion-

grav

imet

ricm

etho

d.

Na 4

UO

2~C

O3!

3w

aspr

epar

edac

cord

ing

toR

ef.

1.F

irst,

sodi

umur

anat

ew

aspr

ecip

itate

dfr

omU

O2~

NO

3!2

solu

tion

with

NaO

H,

was

hed

and

diss

olve

din

aso

lutio

nof

NaH

CO

3.T

hesa

ltw

asth

enob

tain

edby

evap

orat

ing

the

solu

tion

toa

low

volu

me

whi

lepa

ssin

gC

O 2th

roug

hth

eso

lutio

n.T

hesa

ltw

asre

crys

talli

zed

from

wat

erto

yiel

da

brig

htye

llow

prod

uct

with

the

CO

3/U

ratio

of3:

3.2.

Sou

rce

and

purit

yof

mat

eria

lsus

edw

ere

not

spec

ified

.N

a 2C

O3

was

are

gent

grad

epr

oduc

t.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 W.E

.Bun

ce,N

.H.F

urna

m,a

ndR

.T.M

undy

,Rep

ortM

-423

8,19

47.

584584 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

tric

arbo

nato

diox

oura

nate~VI!

;N

a 4U

O2~

CO

3) 3

;@1

2076

-52-

7#~2

!S

odiu

mpe

rchl

orat

e;N

aClO 4

;@7

601-

89-0#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

C.

A.

Bla

ke,

C.

F.

Col

eman

,K

.B

.B

row

n,D

.G

.H

ill,

R.

S.

Low

rie,

and

J.M

.S

chm

itt,

J.A

m.

Che

m.

Soc

.78

,59

78–

83~1

956!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

9c 2

/mol

dm2

3 :0.

5–

3.5

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Na 4

UO

2~C

O3!

3in

NaC

lO4

solu

tions

at26

°Ca

NaC

lO4

(c2

/mol

dm2

3 )N

a 4U

O2~

CO

3!3

(c1

/mol

dm2

3 )

0.5

0.13

4

1.0

0.05

6

1.5

0.02

8

2.0

0.01

5

2.5

0.00

8

3.0

0.00

5

3.5

0.00

2

a Com

posi

tion

ofeq

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

Add

ition

alin

form

atio

n:A

ctiv

ityso

lubi

lity

prod

uct

ofN

a 4U

O2~

CO

3!3

was

calc

ulat

edby

the

auth

ors

from

the

solu

bilit

yda

taus

ing

the

met

hod

ofH

arne

dan

dO

wen

1fo

rhi

ghly

solu

ble

salts

,an

dre

port

edto

beKsp0

5@N

a1#4

@UO

2~C

O3) 34

2]5

0.01

mol5

dm2

15.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Sol

utio

nsco

ntai

ning

exce

ssso

lidw

ere

equi

libra

ted

inP

yrex

orpo

lyflu

oroe

thyl

ene

bottl

esfo

rat

leas

t10

days

,bu

tus

ually

for

3or

mor

ew

eeks

toen

sure

equi

libriu

m.

The

agita

tion

was

carr

ied

out

ina

cons

tant

-tem

pera

ture

room

.T

heco

nten

tsof

the

bottl

ew

ere

then

cent

rifug

ed,

and

both

the

solid

and

liqui

dw

ere

anal

yzed

for

uran

ium

,so

dium

,an

dca

rbon

ate.

Dep

endi

ngon

uran

ium

Na 4

UO

2~C

O3!

3w

aspr

epar

edac

cord

ing

toR

ef.

2.F

irst,

sodi

umur

anat

ew

aspr

ecip

itate

dfr

omU

O2~

NO

3!2

solu

tion

with

NaO

H,

was

hed

and

diss

olve

din

aso

lutio

nof

NaH

CO

3.T

hesa

ltw

asth

enob

tain

edby

evap

orat

ing

the

solu

tion

toa

low

volu

me

whi

lepa

ssin

gC

O 2th

roug

hth

eso

lutio

n.T

hesa

ltw

asre

crys

talli

zed

from

wat

erto

yiel

da

brig

htye

llow

prod

uct

with

the

CO

3/U

ratio

of3:

3.2.

Sou

rce

and

purit

yof

mat

eria

lsus

edw

ere

not

Co

~1!

@1 ~2!

~3!

~4!

Va

T/

c 2 c 3 a C Me

Iso

we

lea

eq co the

for

co de re So

by


d 0

Tem

pera

ture

:pr

ecis

ion

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

tric

arbo

nato

diox

oura

nate~V

I!;

H4!

4UO

2~C

O3!

3;@1

8077

-77-

5#S

odiu

mtr

icar

bona

todi

oxou

rana

te~VI!

;N

a 4U

O2~

CO

3!3;

2076

-52-

7#W

ater

;H 2

O;

@773

2-18

-5#

N.

N.

Elo

vski

khan

dA

.I.

Sta

brov

skii,

Zh.

Neo

rg.

Khi

m.6,

1300

–1~

1961

!.

riabl

es:

Pre

pare

dby

:

K:

296

lera

tioof

com

pone

nts~1

!an

d~2

!J.

Hala

Exp

erim

enta

lDat

a

Con

cent

ratio

nof

uran

ium

in(N

H 4!4U

O2~

CO

3!3

/Na 4

UO

2~C

O3!

3so

lutio

nssa

tura

ted

at23

°C

NH

4!4U

O2~

CO

3!3

~g!a

Na 4

UO

2~C

O3!

3

~g!a

Mol

era

tiob

U~g

dm2

3 !cU

~mol

dm2

3 !c,d

3.97

1.95

1:0.

512

6.40

0.53

1

2.91

3.01

1:1

169.

750.

713

1.93

4.00

1:2

154.

710.

650

1.44

4.49

1:3

142.

000.

597

1.16

4.77

1:4

132.

100.

555

0.96

4.97

1:5

117.

230.

493

ass

ofth

esa

lteq

uilib

rate

dw

ith10

mL

wat

er.

ole

ratio

ofsa

ltsin

the

initi

alsy

stem

.on

cent

ratio

nof

uran

ium

inth

esa

tura

ted

solu

tions

.al

cula

ted

byco

mpi

ler.

ditio

nali

nfor

mat

ion:

hen

mix

ture

sof

(NH 4

! 4U

O2~

CO

3!3

and

Na 4

UO

2~C

O3!

3w

ere

diss

olve

dst

able

solu

tions

wer

eob

tain

edw

ithur

aniu

mco

ncen

trat

ion

her

than

that

corr

espo

ndin

gto

the

bina

rysa

lt/w

ater

syst

ems,

i.e.,

;66

gdm

23

or0.

28m

oldm

23

uran

ium

for

Na 4U

O2~

CO

3!3,

and

;30

dm2

3or

0.13

mol

dm2

3ur

aniu

mfo

r(N

H 4! 4

UO

2~C

O3!

3.1

The

effe

ctw

asas

crib

edto

the

form

atio

nof

am

ixed

sodi

um/a

mm

oniu

mar

bona

todi

oxou

rana

te.

Fro

ma

solu

tion

initi

ally

cont

aini

ngbo

thsa

ltsin

a1:

1m

ole

ratio

the

mix

edsa

ltN

a2~

NH

4!2U

O2~

CO

3!3•

H2O

uld

bepr

ecip

itate

dw

ithet

hano

l.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.M

ixtu

res

ofbo

thsa

ltsin

vario

usm

ole

ratio

sw

ere

equi

libra

ted

with

10m

Lw

ater

for

16h.

Met

hod

ofur

aniu

mde

term

inat

ion

inth

esa

tura

ted

solu

tions

was

not

repo

rted

.S

olid

phas

esw

ere

not

inve

stig

ated

.

No

deta

ilsre

port

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

tric

arbo

nato

diox

oura

nate~V

I!;

(NH

4!4U

O2~

CO

3!3;

@180

77-7

7-5#

~2!

Wat

er;

H 2O

;@7

732-

18-5#

F.

Gio

litti

and

V.

Vec

chia

relli

,G

azz.

Chi

m.

Ital.3

5,17

0–

81~1

985!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

2–

360

J.H

a´ la

Exp

erim

enta

lDat

a

Com

posi

tion

ofso

lutio

nsof

(NH 4!

4UO

2~C

O3!

3sa

tura

ted

atva

rious

tem

pera

ture

s

Tem

pera

ture

~°C

!U

~g/1

00g!

aC

O2

~g/1

00g!

aN

H3

~g/1

00g!

aU

:CO

2:N

H3b

18.6

2.71

1.54

0.79

51:

3.08

:4.1

0

36.5

3.09

2.29

1.18

81:

4.01

:5.3

5

48.3

3.03

2.71

1.35

1:4.

95:6

.35

62.0

—3.

171.

62—

87.3

3.95

3.96

2.02

71:

5.52

:7.1

5

a g/10

0g

satu

rate

dso

lutio

n.b M

ole

ratio

inth

esa

tura

ted

solu

tions

.

Add

ition

alin

form

atio

n:T

heco

mpo

sitio

nof

the

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.A

t18

.6°C

the

com

posi

tion

ofth

esa

tura

ted

solu

tion

corr

espo

nde

toth

efo

rmul

ara

tioof

the

salt.

The

auth

ors

repo

rted

the

solu

bilit

yof

(NH

4!4U

O2~

CO

3!3

atth

iste

mpe

ratu

reas

6.04

gsa

lt/10

0g

satu

rate

dso

lutio

n.U

sing

the

auth

ors’

valu

eof

uran

ium

conc

entr

atio

nin

the

satu

rate

dso

lutio

n,co

mpi

ler

calc

ulat

edth

eso

lubi

lity

as5.

95g

salt/

10g

solu

tion

(m15

0.12

1m

olkg

21 ).

At

high

erte

mpe

ratu

res

the

salt

deco

mpo

sed

inth

eso

lutio

n.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Ala

rge

exce

ssof

the

solid

was

agita

ted

for

betw

een

4an

d24

hw

ithw

ater

ina

ther

mos

tate

dba

that

the

desi

red

tem

pera

ture

.T

hecl

ear

solu

tion

was

anal

yzed

for

uran

ium~

grav

imet

rical

lyas

U 3O

8!,

CO

2,an

dN

H3

~met

hods

not

spec

ified!.

(NH

4!4U

O2~

CO

3!3

was

prep

ared

byad

ditio

nto

aso

lutio

nof

UO

2~N

O3!

2he

ated

to50

°Cco

ncen

trat

edso

lutio

nof

(NH

4!2C

O3

ina

twof

old

exce

ssov

erth

eam

ount

nece

ssar

yto

obta

ina

clea

ral

kalin

eso

lutio

n,an

dth

enco

ncen

trat

edam

mon

iaso

lutio

n.C

ryst

als

of(N

H 4! 4

UO

2~C

O3!

3pr

ecip

itate

don

cool

ing.

Sou

rce

and

purit

yof

mat

eria

lsus

edw

ere

not

spec

ified

.

Est

imat

edE

rror

:

Co

~1!

(N ~2!

@1 ~3!

Va

T/

Mo (

a M b M c C d C Ad

W hig

g tric

co Me

Iso

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Cal

cium

tric

arbo

nato

diox

oura

nate~V

I!;

Ca 2

UO

2~C

O3!

3;#

Wat

er;

H 2O

;@7

732-

18-5#

M.

Bac

hele

t,E

.C

heyl

an,

M.

Dou

is,

and

J.C

.G

oule

tte,

Bul

l.S

oc.

Chi

m.

Fra

nce

565

–9~1

952!

.

riabl

es:

Pre

pare

dby

:

K:

273

–32

8J.

Ha´ la

Exp

erim

enta

lDat

a

Com

posi

tion

ofso

lutio

nsof

Ca 2U

O2~

CO

3!3

satu

rate

dat

vario

uste

mpe

ratu

res

a

Tem

pera

ture

~°C

!U

~gdm

23 !

Mg 2

UO

2~C

O3!

3

(c1

/mol

dm2

3 )b

00.

330.

0013

86

231.

340.

0056

30

403.

680.

0154

6

555.

020.

0210

8

ompo

sitio

nth

eth

eeq

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

alcu

late

dby

com

pile

r.

ditio

nali

nfor

mat

ion:

2UO

2~C

O3!

3hy

drol

yzed

abov

e60

°C.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

thin

gsp

ecifi

ed.

Ca 2U

O2~

CO

3!3•

10H

2Ow

asob

tain

edby

pass

ing

ast

ream

ofC

O2

thro

ugh

asl

urry

ofst

oich

iom

etric

amou

nts

ofU

O3•

1/2H

2Oan

dC

aCO 3

for

24h,

filte

ring

off

the

unre

acte

dm

ater

ial

and

evap

orat

ion.

Ana

lysi

s~fo

und/

calc

ulat

edfo

ran

hydr

ous

salt

obta

ined

byhe

atin

gth

ede

cahy

drat

eat

80°C

,m

ass

%!:

UO

3

54.4

0/54

.40,

CaO

20.8

/21.

1,C

O2

24.8

/24.

9.S

ourc

ean

dpu

rity

ofm

ater

ials

used

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

586586 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Mag

nesi

umtr

icar

bona

todi

oxou

rana

te~V

I!;

Mg 2

UO

2~C

O3!

3;@

#~2

!W

ater

;H 2

O;

@773

2-18

-5#

M.

Bac

hele

t,E

.C

heyl

an,

M.

Dou

is,

and

J.C

.G

oule

tte,

Bul

l.S

oc.

Chi

m.

Fra

nce

565

–9~1

952!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

6–

325

J.H

a´ la

Exp

erim

enta

lDat

a

Com

posi

tion

ofso

lutio

nsof

Mg 2U

O2~

CO

3!3

satu

rate

dat

vario

uste

mpe

ratu

res

a

Tem

pera

ture

~°C

!U

~gdm

23 !

Mg 2

UO

2~C

O3!

3

~gdm

23 !b

Mg 2

UO

2~C

O3!

3

(c1

/mol

dm2

3 )b

2339

.081

.71

0.16

38

3241

.586

.94

0.17

43

4257

.812

1.1

0.24

28

5281

.016

9.7

0.34

03

a Com

posi

tion

ofeq

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Add

ition

alin

form

atio

n:M

g 2U

O2~

CO

3!3

hydr

olyz

edab

ove

70°C

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Not

hing

spec

ified

.M

g 2UO

2~C

O3!

3•18

H2O

was

obta

ined

bypa

ssin

ga

stre

amof

CO

2th

roug

ha

slur

ryof

stoi

chio

met

ricam

ount

sof

UO

3•1/

2H2O

and

basi

cm

agne

sium

carb

onat

efo

r2

–3

days

unde

rag

itatio

n.T

here

acta

nts

diss

olve

dan

dth

esa

ltw

asob

tain

edei

ther

bycr

ysta

lliza

tion

orby

prec

ipita

tion

with

acet

one

asst

rong

lyef

flore

scen

tye

llow

crys

tals

.A

naly

sis~f

ound

/cal

cula

ted

for

anhy

drou

ssa

ltob

tain

edat

60°C

,m

ass

%!:

UO

357

.35/

57.0

0,M

gO16

.15/

16.2

0,C

O 226

.5/2

6.80

.S

ourc

ean

dpu

rity

ofm

ater

ials

used

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

@ ~2!

Va

T/

a C b C Ad

Ca

Me

No


5.4.

Sod

ium

Pen

taki

s„ca

rbon

ato…

Bisˆdi

oxou

rana

te„V

I…‰„6-…

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

pent

acar

bona

tobi

s$d

ioxo

uran

ate~V

I!%;

6~U

O2!

2~C

O3!

5;@

#W

ater

;H 2

O;

@773

2-18

-5#

M.B

ache

let,

E.C

heyl

an,M

.Dui

s,an

dJ.

C.G

oule

tte,B

ull.

Soc

.C

him

.F

ranc

e55

–60

~195

2!.

riabl

es:

Pre

pare

dby

:

K:

293

J.H

ala

Exp

erim

enta

lDat

aso

lutio

nin

wat

erof

Na 6~

UO

2!2~

CO

3!5

satu

rate

dat

20°C

was

repo

rted

toco

ntai

n19

0g

UO

3/d

m3

solu

tion.

Fro

mth

isva

lue

the

com

pile

rlc

ulat

edth

eco

ncen

trat

ion

ofur

aniu

mto

be0.

664

mol

dm2

3 .C

ompo

sitio

nof

the

equi

libriu

mso

lidph

ase

was

not

inve

stig

ated

.

ditio

nali

nfor

mat

ion:

Ref

.1,

Na 6

~UO

2!2~

CO

3!5

was

repo

rted

tobe

am

ixtu

reof

Na

4UO

2~C

O3!

3an

dN

a 2U

O2~

CO

3!2•

xH2O

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

thin

gsp

ecifi

ed.

Na 6~U

O2!

2~C

O3!

5w

aspr

epar

edby

prol

onge

dag

itatio

nof

asl

urry

ofU

O3•

1/2H

2Oan

dN

aHC

O 3~m

ole

ratio

1:3!

inw

ater

bypa

ssin

gth

roug

hit

ast

ream

ofC

O2

gas

atro

omte

mpe

ratu

re.

Fro

mth

ere

sulti

ngso

lutio

n,th

esa

ltw

aspr

ecip

itate

dat

50°C

.S

ourc

ean

dpu

rity

ofm

ater

ials

used

not

spec

ified

.1

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Ref

eren

ces:

1 L.A

.M

cCla

ine,

E.

P.

Bul

lwin

kel,

and

J.C

.H

uggi

ns,

Pro

ceed

ings

Pea

cefu

lUse

sA

tom

icE

nerg

y,G

enev

a,19

55,

Vol

.8,

p.26

.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Str

ontiu

mtr

icar

bona

todi

oxou

rana

te~VI!

;S

r 2U

O2~

CO

3!3;

@#

~2!

Wat

er;

H 2O

;@7

732-

18-5#

M.B

ache

let,

E.C

heyl

an,M

.Dui

s,an

dJ.

C.G

oule

tte,B

ull.

Soc

.C

him

.F

ranc

e56

5–

9~195

2!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

2J.

Hala

Exp

erim

enta

lDat

aT

heso

lubi

lity

at19

°Cof

Sr 2U

O2~

CO

3!3

inw

ater

was

repo

rted

tobe

1.7

gdm2

3sa

ltor

0.65

5g

uran

ium

/dm3

solu

tion

~usi

ngth

ela

tter

valu

eth

eco

mpi

ler

calc

ulat

edc15

2.75

310

23

mol

dm2

3 !.

The

com

posi

tion

ofth

eeq

uilib

rium

solid

phas

ew

asno

tin

vest

igat

ed.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Not

hing

spec

ified

.S

r 2UO

2~C

O3!

3•9H

2Ow

aspr

epar

edei

ther

bypr

olon

ged

pass

ing

ast

ream

ofC

O 2th

roug

ha

slur

ryof

UO 3•1/

2H2O

and

SrC

O 3un

der

agita

tion,

orby

doub

lede

com

posi

tion

reac

tion

betw

een

Na 2

UO

2~C

O3!

3an

dS

rCl 2.

Ana

lysi

s~f

ound

/cal

cula

ted

for

the

anhy

drou

ssa

lt,m

ass

%!:U

O3

46.7

5/45

.7,S

rO32

.70/

33.1

5,C

O2

20.5

5/21

.15.

Sou

rce

and

purit

yof

mat

eria

lsus

edno

tsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Co

~1!

Na

~2!

Va

T/

A ca Ad

In Me

No

J

he

othe

rwis

e~se

eab

ove!,

the

satu

rate

dso

lutio

nsw

ere

stab

lew

ithre

spec

tto

hydr

olys

isw

hen

expo

sed

tolig

ht.

eith

erin

solu

tion

orin

the

form

ofa

susp

ensi

onin

wat

er,

onU

O2~

OH

! 2.

The

salts

wer

ere

crys

talli

zed,

and

char

acte

rized

byel

emen

tala

naly

sis.

Est

imat

edE

rror

:P

reci

sion

ofte

mpe

ratu

reor

solu

bilit

yno

tre

port

ed.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

diox

obis~

form

ate!

;U

O2~

CH

O2!

2;@1

6984

-59-

1#F

orm

icac

id;

CH 2

O2;

@64-

18-6

#W

ater

;H 2

O;

@773

2-18

-5#

A.

Col

ani,

Bul

l.S

oc.

Chi

m.

Fra

nce45

,62

4–

6~1

929!

.

riabl

es:

Pre

pare

dby

:

K:2

980

w2

/mas

s%:0

.012

–93

.93

J.H

ala

Exp

erim

enta

lDat

a

Com

posi

tion

ofaq

ueou

sso

lutio

nsof

form

icac

idsa

tura

ted

with

UO

2~C

HO

2!2

at25

°C

CH

2O2

(100

w2

/mas

s%)

UO

3

~mas

s%!

UO

2~C

HO

2!2

(100

w1

/mas

s%)b

Sol

idph

asea

0.01

20.

076

A

0.28

50.

368

A

0.80

60.

759

A

1.33

1.07

A

4.88

3.06

A

8.23

4.87

A

10.8

76.

05c

A1

B

12.3

35.

717.

19B

20.1

64.

125.

19B

31.5

72.

523.

17B

44.8

51.

151.

45B

50.6

70.

765

0.96

3B

61.3

20.

325

0.40

9B

72.2

90.

116

0.14

6B

85.8

60.

058

0.07

3B

93.9

30.

057

0.07

2B

:U

O2~

CH

O2!

2•U

O3•

3H2O

,@

#;B

:U

O2~

CH

O2!

2•H

2O,

@#.

alcu

late

dby

com

pile

run

der

the

assu

mpt

ion

that

UO

2~C

HO

2!2

isth

esp

ecie

sex

istin

gin

thes

eso

lutio

ns.

orth

isso

lutio

nth

eau

thor

repo

rted

7.99

gU

O2~

CH

O2!

2•H

2Ope

r10

0g

solu

tion.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:E

stim

ated

Err

or:

Isot

herm

alm

etho

dus

ed.

The

solid

used

for

expe

rimen

tsw

asU

O2~

CH

O2!

2•H

2O.

No

furt

her

deta

ilsw

ere

repo

rted

exce

ptth

ateq

uilib

ratio

nw

asca

rrie

dou

tin

the

dark

.

Pre

cisi

onof

tem

pera

ture

mea

sure

men

tor

solu

bilit

yde

term

inat

ion

not

repo

rted

.

588588 JIRI HALA

5.5.

Ura

nium

„V

I…D

ioxo

Bis

„ca

rbox

ylat

es…

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

obis~

carb

oxyl

ates!

~2!

Wat

er;

H 2O

;@7

732-

18-5#

G.

Cou

rtoi

s,C

ompt

.R

end.1

58,

1511

–4~

1914

!;15

8,16

88–

91~1

914!

;B

ullS

oc.

Chi

m.

Fra

nce3

3,17

61–

73~1

923!

.

Var

iabl

es:

Pre

pare

dby

:

Con

stan

tte

mpe

ratu

reJ.

Ha

´ la

Exp

erim

enta

lDat

a

Sol

ubili

ties

ofur

aniu

m~V

I!di

oxob

is~ca

rbox

ylat

es!in

wat

er

Dic

arbo

xyla

te,

UO 2

Ry•

xH2O

aT

empe

ratu

re~°

C!

Sol

ubili

tyb

~gsa

lt/10

0g

satu

rate

dso

lutio

n!

UO

2~H

CO

2!2•

H2O

;~f

orm

ate!

;@

157.

20c

UO

2~C

2H3O

2!2•

2H2O

;~a

ceta

te!;

@615

9-44

-0#17

7.73

d

UO

2~C

3H5O

2!2•

2H2O

;~p

ropi

onat

e!;@

198.

48

UO

2~C

4H7O

2!2•

2H2O

;~b

utyr

ate!;

@17

10.5

3

UO

2~C

4H7O

2!2•

2H2O

;~is

o-bu

tyra

te!;

@20

4.25

UO

2~C

5H9O

2!2•

2H2O

;~v

aler

ate!;

@14

3.72

UO

2~C

H2~

OH

!CO

2!2;

~gly

cola

te!;

@19

15.6

0e

UO

2~C

H3C

H~O

H!C

O2!

2;~la

ctat

e!;@

182.

92f

UO

2C4H

4O6•

4H2O

;~t

artr

ate!;

@17

3.82

UO

2~C

7H5O

2!2;

~ben

zoat

e!;@

180.

32

UO

2~C

7H4~

OH

!O2!

2•2H

2O;

~sal

icyl

ate!;

@18

0.52

a Com

posi

tion

ofth

ein

itial

solid

salt.

Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.b F

orsa

ltspr

epar

edas

hydr

ates

itw

asno

tst

ated

whe

ther

the

repo

rted

solu

bilit

ies

refe

rto

the

hydr

ate

oran

hydr

ous

salt.

Onl

yfo

rt

salic

ylat

eth

eso

lubi

lity

was

expl

icitl

yre

port

edas

that

ofth

edi

hydr

ate.

c Sat

urat

edso

lutio

nsof

uran

ium

diox

ide

form

ate

wer

eun

stab

le;

even

inth

eda

rka

basi

csa

ltpr

ecip

itate

dou

taf

ter

24h.

d Sat

urat

edso

lutio

nw

asun

stab

lein

the

dark

.W

hen

expo

sed

todi

fuse

light

,a

basi

csa

lt,U

O2~

C2H

3O2!

2•U

O3•

4H2O

,pr

ecip

itate

dou

t.e S

atur

ated

solu

tions

wer

eun

stab

le,

and

aba

sic

salt,

UO

2~C

H2~

OH

!CO

2!2•

UO

3•4H

2O,

prec

ipita

ted

out

inth

eda

rk.

f Sat

urat

edso

lutio

nsst

able

inth

eda

rk.

Whe

nex

pose

dto

light

,a

gree

nhy

drol

ytic

prod

uct

prec

ipita

ted

out,

and

asm

allq

uant

ityof

CO

2

was

prod

uced

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed,

node

tails

repo

rted

.U

nles

sst

ated

The

salts

wer

epr

epar

edby

actio

nof

the

corr

espo

ndin

gac

id,

Co

~1!

~2!

~3!

Va

T/

10 a A b C c F


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

obis~

acet

ate!;

UO

2~C

2H3O

2!2;

@541

-09-

3#A

cetic

acid

;C 2

H4O

2;@6

4-19

-7#

Wat

er;

H 2O

;@7

732-

18-5#

A.

Col

ani,

Bul

l.S

oc.

Chi

m.

Fra

nce41

,12

91–

3~19

27!.

riabl

es:

Pre

pare

dby

:

K:2

980

w2

/mas

s%:

0.27

–97

.8J.

Hala

Exp

erim

enta

lDat

a

Com

posi

tion

ofaq

ueou

sso

lutio

nsof

acet

icac

idsa

tura

ted

with

UO

2~C

2H3O

2!2

at25

°C

C2H

4O2

00w

2/m

ass%

)U

O3

~mas

s%!

UO

2~C

2H3O

2!2

(100

w1

/mas

s%)b

Sol

idph

asea

C2H

4O2

(100

w2

/mas

s%)

UO

3

~mas

s%!

UO

2~C

2H3O

2!2

(100

w1

/mas

s%)b

Sol

idph

asea

0.27

00.

544

A30

.73.

114.

22C

0.49

90.

883

A36

.92.

883.

91C

0.61

81.

11A

41.1

2.65

3.60

C

0.74

71.

28A

46.4

2.36

3.20

C

1.20

2.07

A56

.71.

872.

54C

2.32

4.12

A1B

65.9

1.38

1.87

C

2.49

4.47

B77

.40.

831

1.13

C

2.64

4.89

B1C

79.9

0.85

81.

16C1

D

2.87

4.54

6.16

C81

.60.

645

0.87

5D

4.55

4.07

5.52

C88

.20.

405

0.55

0D

11.3

3.79

5.14

C97

.80.

306

0.41

5D

24.8

3.30

4.48

C

:U

O2~

C2H

3O2!

2•2U

O2~

OH

! 2,

@#;

B:

UO

2~C

2H3O

2!2•

UO

2~O

H! 2•3H

2O,

@#;

C:

UO

2~C

2H3O

2!2•

2H2O

,@6

159-

44-0#

;D

:O

2~C

2H3O

2!2•

C2H

4O2•

2H2O

,@

#.al

cula

ted

byco

mpi

ler

unde

rth

eas

sum

ptio

nth

atU

O2~

C2H

3O2!

2is

the

spec

ies

exis

ting

inth

ese

solu

tions

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

cess

UO 2

~C2H

3O2!

2•2H

2Oor

UO

2~C

2H3O

2!2•

2UO

2~O

H! 2

dth

eso

lutio

nof

acet

icac

idof

the

desi

red

conc

entr

atio

nre

kept

ata

tem

pera

ture

clos

eto

100

°Cfo

rse

vera

lhou

rsin

der

tosp

eed

uphy

drol

ytic

reac

tions

.T

hem

ixtu

rew

asth

enth

erm

osta

ted

at25

°Cun

der

freq

uent

stirr

ing

until

equi

libriu

mw

asre

ache

d.E

xper

imen

tsw

ere

cond

ucte

din

flask

spr

otec

ted

from

light

.E

quili

brat

ion

time

and

met

hods

used

toan

alyz

eth

esa

tura

ted

solu

tions

wer

eno

tre

port

ed.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

obis~

acet

ate!;

UO

2~C

2H3O

2!2;

@541

-09-

3#~2

!W

ater

;H 2

O;

@773

2-18

-5#J.

Zeh

ente

r,M

onat

sh.

Che

m.

21,

235

–55

~190

0!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:288

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofU

O 2~C

2H3O

2!2

was

repo

rted

tobe

7.69

4g

salt

in10

0g

wat

erat

15°C

.C

ompo

sitio

nof

the

equi

libriu

mso

lidph

ase

was

not

inve

stig

ated

.

Add

ition

alIn

form

atio

n:It

isno

tcl

ear

from

the

docu

men

tw

heth

erth

ere

port

edso

lubi

lity

refe

rsto

the

anhy

drou

ssa

ltor

toth

edi

hydr

ate,

UO

2~C

2H3O

2!2•

2H2O

,@6

159-

44-0#

.T

here

port

edso

lubi

lity

valu

eis

alm

ost

iden

tical

with

that

repo

rted

inR

ef.

1.It

was

repo

rted

that

solu

tions

ofU

O 2~C

2H3O

2!2

are

fully

stab

lew

hen

kept

inth

eda

rk.W

hen

expo

sed

tolig

ht,t

heso

lutio

nsbe

cam

etu

rbid

,an

da

spar

ingl

yso

lubl

ehy

drol

ytic

prod

uct

prec

ipita

ted.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed,

node

tails

spec

ified

.U

O2~

C2H

3O2!

2w

asa

prod

uct

ofM

erck

~pur

iss.!

.

Est

imat

edE

rror

:P

reci

sion

ofte

mpe

ratu

reor

solu

bilit

ym

easu

rem

entn

otre

port

ed.

Ref

eren

ces:

1 G.

Cou

rtoi

s,C

ompt

.R

end.1

58,

1511

~191

4!.

Co

~1!

~2!

~3!

Va

T/

10 (1 a A U b C Me

Ex

an we

or

J

.4.

Ura

nium

~VI!

diox

obis~

acet

ate!–

tri-n

-but

ylph

osph

ate

–w

ater

syst

em.L

egen

dto

the

phas

edi

agra

m:

~A!

two-

phas

ere

gion

;~B!

two

uid

phas

esin

equi

libriu

mw

ithU

O 2~C

2H3O

2!2•

2H2O

;~C

!sa

tura

ted

solu

tions

ineq

uilib

rium

with

UO 2~C

2H3O

2!2•

2H2O

;~D

!sa

tura

ted

lutio

nsin

equi

libriu

mw

ithU

O 2~C

2H3O

2!2•

2H2O

and

UO 2

~C2H

3O2!

2•H

2O;

~E!

satu

rate

dso

lutio

nsin

equi

libriu

mw

ith

2~C

2H3O

2!2•

H2O

;~F

!sa

tura

ted

solu

tions

ineq

uilib

rium

with

UO 2~C

2H3O

2!2•

H2O

and

UO 2

~C2H

3O2!

2;~G

!sa

tura

ted

solu

tions

inui

libriu

mw

ithU

O 2~C

2H3O

2!2;

~H!

unsa

tura

ted

aque

ous-

orga

nic

solu

tions

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.D

esire

dam

ount

sof

the

salt,

n-bu

tylp

hosp

hate

and

wat

erw

ere

equi

libra

ted

inse

aled

ssam

poul

espr

otec

ted

from

light

ina

ther

mos

tate

dba

th.

eco

ncen

trat

ion

ofur

aniu

man

dw

ater

inth

eeq

uilib

rium

ases

wer

ede

term

ined

grav

imet

rical

lyan

dby

Fis

cher

met

hod,

resp

ectiv

ely.

Com

posi

tion

ofth

eeq

uilib

rium

solid

phas

esw

asde

term

ined

byS

chre

inem

aker

sm

etho

d.D

etai

lsof

the

met

hods

used

wer

eid

entic

alw

ithth

ose

inR

ef.

1.

UO

2~C

2H3O

2!2•

2H2O

used

was

are

agen

tgr

ade

prod

uct,

sour

cew

asno

tsp

ecifi

ed.

Mon

ohyd

rate

and

anhy

drou

ssa

ltw

ere

obta

ined

byva

cuum

dehy

drat

ion.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

05K

~aut

hors!

.S

olub

ility

:pr

ecis

ion

not

repo

rted

.

Ref

eren

ces:

1 A.

V.

Bal

uev,

A.

A.

Lum

pov,

and

I.G

.S

uglu

bova

,R

adio

khim

iya2

6,19

6~1

984!

.

590590 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

obis~

acet

ate!;

UO

2~C

2H3O

2!2;

@541

-09-

3#~2

!P

hosp

horic

acid

tri-n-

buty

lest

er;

C 12H

27O

4P;

@126

-73-

8#~3

!W

ater

;H 2

O;

@773

2-18

-5#

A.

V.

Bal

uev,

A.

Yu.

Sili

n,I.

G.

Sug

lubo

va,

and

A.

P.

Tar

anov

,R

adio

khim

iya3

0,44

2–

7~1

988!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:298

100

w2

/mas

s%:5

0.8

–71

.610

0w

3/m

ass%

:0–

3.16

J.H

ala

Exp

erim

enta

lDat

a

Com

posi

tion

ofbi

nary

tri-n-

buty

lph

osph

ate

–w

ater

solu

tions

satu

rate

dw

ithU

O2~

C2H

3O2!

2,an

dph

ase

diag

ram

ofth

eU

O2~

C2H

3O2!

2–

C12

H27

O4P

–H 2

Osy

stem

at25

°C

C12

H27

O4P

(100

w2

/mas

s%)b

H2O

(100

w3

/mas

s%)

UO

2~C

2H3O

2!2

(100

w1

/mas

s%)

Sol

idph

ase

a

71.6

33.

1625

.21

A

64.3

52.

2033

.45

A

58.0

21.

6340

.35

B

53.8

61.

0845

.12

B1C

50.4

80.

3649

.16

C

50.8

049

.2cC

a ~A!

UO

2~C

2H3O

2!2•

2H2O

,@6

159-

44-0#

;~B

!U

O2~

C2H

3O2!

2•H

2O,

@#;

~C!

UO

2~C

2H3O

2!2,

@541

-09-

3#b C

alcu

late

dby

com

pile

rby

diffe

renc

e.c S

olub

ility

ofan

hydr

ous

UO 2~

C2H

3O2!

2in

dry

tri-n

-but

ylph

osph

ate;m

15

2.50

mol

kg2

1~a

utho

rs!.

Pha

sedi

agra

m~F

ig.

4!of

the

UO 2

~C2H

3O2!

2–

C12

H27

O4P

–H 2

Osy

stem

at25

°C:

FIG

liq so UO

eq Me

Iso

tri-

gla

Th

ph


5.7.

Sod

ium

Tris

„ac

etat

o…

Dio

xour

anat

e„V

I…

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

tris~

acet

ato!

diox

oura

nate~

VI!

;U

O2~

C2H

3O2) 3

;@1

4286

-13-

6#S

odiu

mac

etat

e;C 2H

3O2N

a;@1

27-0

9-3#

Ace

ticac

id;

C 2H

4O2;

@64-

19-7

#W

ater

;H 2

O;

@773

2-18

-5#

B.

P.

Nik

olsk

ii,V

.I.

Par

amon

ova,

L.A

.K

otch

evan

ova,

and

G.

G.

Pam

filov

a,K

him

iya

Tra

nsur

anov

ych

Osk

oloc

hnyc

hE

lem

ento

v~C

hem

istr

yof

Tra

nsur

aniu

mE

lem

ents

and

Fis

sion

Pro

duct

s!,A

NS

SS

R,

Otd

.O

bsh.

Tek

h.K

him

.,19

–26

,19

67.

riabl

es:

Pre

pare

dby

:

K:

293

/mol

dm2

3 :0.

18–

4.0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

typr

oduc

tof

NaU

O 2~C

2H3O

2!3

at20

°C

C2H

3O2N

a

2/m

oldm

23 )

Ksp

a

(103

mol

2dm

26 )

pHb

0.18

5.2

3.9

–4.

4

0.25

5.9

4.0

–4.

8

0.5

5.9

4.6

–5.

2

1.0

5.0

4.4

–6.

3

2.0

3.3

4.3

–6.

3

3.0

2.05

5.6

–6.

7

4.0

1.54

5.5

–6.

9

sp5

@Na1

#@U

O2~

C2H

3O2) 32

];it

was

obta

ined

byth

eau

thor

sas

the

prod

uct

ofex

perim

enta

llyde

term

ined

sodi

uman

dur

aniu

mco

n-nt

ratio

nsin

the

satu

rate

dso

lutio

ns.

The

auth

ors

assu

med

that

atac

etat

eco

ncen

trat

ions

used

all

U~V

I!w

aspr

esen

tas

the

O2~

C2H

3O2)

32io

n.T

heva

lues

Ksp

repo

rted

are

aver

age

valu

esof

seve

rald

eter

min

atio

nsca

rrie

dou

tin

the

pHra

nge

indi

cate

d.H

rang

ew

ithin

whi

chK

spre

mai

ned

cons

tant

.Con

cent

ratio

nof

acet

icac

idus

edto

adju

stpH

was

nots

peci

fied.

Atp

Hhi

gher

than

thos

eho

wn,

anin

crea

seofK

sw

asob

serv

edw

hich

was

ascr

ibed

byth

eau

thor

sto

hydr

olys

isof

U~V

I!.

The

seda

taw

ere

not

cons

ider

edw

hen

vera

geK

spw

asca

lcul

ated

.A

tpH

,4

ade

crea

seinK

spw

asob

serv

eddu

eto

the

pres

ence

ofhi

gher

acet

icac

idco

ncen

trat

ion.

Nei

ther

ese

data

wer

eco

nsid

ered

inth

eca

lcul

atio

nof

the

aver

age

Ksp

valu

es.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.T

oa

give

nvo

lum

eof

aso

lutio

nw

ithde

sire

dco

mpo

sitio

nN

aUO 2~C

2H3O

2!3

was

adde

din

anou

ntto

obta

ina

satu

rate

dso

lutio

nco

ntai

ning

exce

ssso

lid.

The

pHof

the

solu

tions

was

adju

sted

byad

ditio

nsof

acet

icac

id.

The

solu

tions

wer

eal

low

edto

stan

dfo

rse

vera

lday

sat

room

tem

pera

ture

,an

dth

ensh

aken

ina

ther

mos

tate

dba

thfo

r2

h.S

atur

ated

solu

tions

wer

ean

alyz

edfo

rur

aniu

mgr

avim

etric

ally

asU 3

O8

afte

rre

mov

alof

acet

ate

from

the

sam

ple

byre

peat

edev

apor

atio

nw

ithH

NO

3,an

dfo

rso

dium

grav

imet

rical

lyas

Na/

Zn/

UO 2

acet

ate

orN

a 2SO

4.T

hepH

was

dete

rmin

edw

itha

glas

sel

ectr

ode.

Atta

inin

geq

uilib

rium

was

confi

rmed

byus

ing

othe

req

uilib

ratio

npr

oced

ures

such

aspr

ecip

itatio

nof

NaU

O 2~C

2H3O

2!3

inth

ede

sire

dm

ediu

m,

orby

cool

ing

to20

°Ca

solu

tion

satu

rate

dpr

evio

usly

at85

°C.

Not

hing

spec

ified

.

Est

imat

edE

rror

:~a

utho

rs!.

Tem

pera

ture

:pr

ecis

ion6

0.2

K.

Con

cent

ratio

nof

uran

ium

orso

dium

:pr

ecis

ion

6~1

–3!

%.

pH:

prec

isio

n60.

05pH

units

.K

sp:

6~3

–5!

%.



5.6.

Ura

nium

„V

I…D

ioxo

bis„ac

etat

e…

Dih

ydra

te

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

obis~

acet

ate!

dihy

drat

e;U

O2~

C2H

3O2!

2•2H

2O;

@615

9-44

-0#~2

!S

olve

nts

M.

Szi

lagy

,A

t.K

ozle

m.2

,49

–52

~196

0!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:298

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

UO

2~C

2H3O

2!2•

2H2O

at25

°Cin

four

solv

ents

Sol

vent

UO

2~C

2H3O

2!2•

2H2O

a

(100

w1

/mas

s%)

Pht

halic

acid

di-n-

octy

lest

er;

C 24H

38O

4;@1

17-8

4-0#

~PO

E!0.

0008

7

Pht

halic

acid

di-n-

buty

lest

er;

C 16H

22O

4;@8

4-74

-2#

~PB

E!0.

0502

Pho

spho

ricac

idtr

i-n-bu

tyle

ster

;C 1

2H27

O4P

;@1

26-7

3-8#

~TB

P!3.

17

Pho

spho

ricac

iddi

-n-bu

tyle

ster

;C 8

H19

O4P

;@1

07-6

6-4#

~DB

P!30

.9

a Com

pile

ras

sum

edth

eso

lubi

lity

data

refe

rred

toth

edi

hydr

ate.

Thi

sw

asno

tst

ated

expl

icitl

yin

the

orig

inal

docu

men

tw

here

the

solu

bilit

yda

taw

ere

repo

rted

tore

fer

to‘‘u

rany

lace

tate

.’’

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dw

asus

ed.

Sol

vent

sw

ere

equi

libra

ted

with

exce

ssso

lidin

ath

erm

osta

ted

bath

ingr

ound

-gla

ssst

oppe

red

vess

els.

Equ

ilibr

atio

ntim

ew

as5,

26,

14,

and

70da

ysfo

rP

OE

,P

PE

,T

BP

,an

dD

BP

,re

spec

tivel

y.T

heco

ncen

trat

ion

ofur

aniu

min

the

satu

rate

dso

lutio

nsw

asde

term

ined

fluor

imet

rical

lyin

case

ofP

OE

and

PB

E,

orgr

avim

etric

ally

asU

3O8

inca

seof

TB

Pan

dD

BP

.S

atur

ated

solu

tions

did

not

show

any

prec

ipita

tion

ofa

solid

orco

lor

chan

geov

era

perio

dof

12m

onth

s.C

ompo

sitio

nof

the

equi

libriu

mso

lidph

ase

was

not

repo

rted

.

UO

2~C

2H3O

2!2•

2H2O

was

are

agen

tgr

ade

prod

uct,

sour

ceno

tsp

ecifi

ed.T

heso

lven

tsw

ere

com

mer

cial

prod

ucts

ofun

spec

ified

purit

yw

ithde

nsiti

es~g

cm2

3 !of

0.98

25~P

OE!

,1.

0478

~PB

E!,

1.05

51~T

BP!

,an

d0.

9732

~DB

P!.

Est

imat

edE

rror

:P

reci

sion

ofte

mpe

ratu

reor

solu

bilit

ym

easu

rem

entn

otre

port

ed.

Co

~1!

Na

~2!

~3!

~4!

Va

T/

c 2 (c a K ce U b p s a th Me

Iso

the

am

J

NaC

lO4;

@760

1-89

-0#2.

01.

03.

03.

9

NH

4NO

3;@6

484-

52-2#

2.0

1.0

3.0

3.2

C2H

3O2N

H4;

@631

-61-

8#2.

01.

03.

03.

3

a At

20°C

.A

vera

geva

lue

oftw

oor

thre

em

easu

rem

ents

inth

epH

rang

ew

here

Ksp

was

inde

pend

ent

ofpH

.S

olut

ions

cont

aine

dun

spec

ified

conc

entr

atio

nof

acet

icac

idus

edto

adju

stpH

.

mpe

ratu

re~°

C!

C2H

4O2

(c3

/mol

dm2

3 )pH

aK

spb

(103

mol

2dm

26 )

200.

095.

294.

2

0.34

5.01

4.0

1.04

4.43

4.1

4.16

0.1c

500.

15.

587.

6

0.5

4.87

7.5

1.0

4.59

7.9

7.76

0.1c

750.

15.

5115

.4

0.5

4.88

15.7

1.0

4.47

15.9

15.7

60.

2c

Hof

the

equi

libriu

mso

lutio

ns.

t20

°C.

All

solu

tions

cont

aine

d1.

00m

oldm2

3C

2H3O

2Na

and

2.00

mol

dm2

3N

aNO

3.ve

rage

valu

e.

ditio

nali

nfor

mat

ion:

eK

spva

lues

obta

ined

inC 2H

3O2N

a–

C 2H

4O2

and

C 2H

3O2N

a–

NaN

O 3~C

2H3O

2Na/

NaN

O 3ra

tio1:

1,io

nic

stre

ngth

2–

5m

oldm2

3 !

lutio

nsw

ere

used

toca

lcul

ate

theKsp0

valu

eas

Ksp0

5K

spg

625

(2.7

60.

2)3

102

3m

ol2

dm2

6 .T

hem

ean

activ

ityco

effic

ientg

6w

aslc

ulat

edac

cord

ing

toR

ef.

1us

ing

Åan

d3.

8Å

for

the

para

met

erof

clos

est

ion

appr

oach

inN

aUO

2~C

2H3O

2!3

inC

2H3O

2Na

–C 2

H4O

2

dC 2

H3O

2Na

–N

aNO 3

solu

tions

,re

spec

tivel

y.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.T

oa

give

nvo

lum

eof

aso

lutio

nw

ithde

sire

dco

mpo

sitio

nN

aUO 2~C

2H3O

2!3

was

adde

din

anou

ntto

obta

ina

satu

rate

dso

lutio

nco

ntai

ning

exce

ssso

lid.

epH

ofth

eso

lutio

nsw

asad

just

edby

addi

tions

ofac

etic

id.

The

solu

tions

wer

eal

low

edto

stan

dfo

rse

vera

lday

sat

omte

mpe

ratu

re,

and

then

shak

enin

ath

erm

osta

ted

bath

for

h.S

atur

ated

solu

tions

wer

ean

alyz

edfo

rur

aniu

mav

imet

rical

lyas

U 3O

8af

ter

rem

oval

ofac

etat

efr

omth

em

ple

byre

peat

edev

apor

atio

nw

ithH

NO

3,an

dfo

rso

dium

avim

etric

ally

asN

a/Z

n/U

O 2ac

etat

eor

Na 2S

O4.

The

pHw

aste

rmin

edw

itha

glas

sel

ectr

ode.

Atta

inin

geq

uilib

rium

was

nfirm

edby

usin

got

her

equi

libra

tion

proc

edur

essu

chas

prec

ipita

tion

ofN

aUO 2

~C2H

3O2!

3in

the

desi

red

med

ium

,or

byco

olin

gto

20°C

aso

lutio

nsa

tura

ted

prev

ious

lyat

85°C

.

Not

hing

spec

ified

.

Est

imat

edE

rror

:~a

utho

rs!.

Tem

pera

ture

:pr

ecis

ion6

0.2

Kin

the

first

two

serie

sof

mea

sure

men

ts,60.

1K

inth

eth

irdse

ries.

Con

cent

ratio

nof

uran

ium

orso

dium

:pr

ecis

ion

6~1

–3!

%.

pH:

prec

isio

n60.

05pH

units

.

Ref

eren

ces:

1 G.H

arne

dan

dB

.Ow

en,Th

eP

hys

ica

lCh

em

istr

yo

fE

lect

roly

teS

olu

tion

s~R

ussi

anT

rans

l.!~M

osco

w,

1952

!,p.

371.

592592 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

tris~

acet

ato!

diox

oura

nate~

VI!

;N

aUO

2~C

2H3O

2) 3

;@1

4286

-13-

6#~2

!S

odiu

mac

etat

e;C 2H

3O2N

a;@1

27-0

9-3#

~3!

Ace

ticac

id;

C 2H

4O2

;@6

4-19

-7#

~4!

Sal

ts~5

!W

ater

;H 2

O;

@773

2-18

-5#

B.

P.

Nik

olsk

ii,V

.I.

Par

amon

ova,

L.A

.K

otch

evan

ova,

and

G.

G.

Pam

filov

a,K

him

iya

Tra

nsur

anov

ych

Osk

oloc

hnyc

hE

lem

ento

v~C

hem

istr

yof

Tra

nsur

aniu

mE

lem

ents

and

Fis

sion

Pro

duct

s!,A

NS

SS

R,O

td.O

bsh.

Tek

h.K

him

.,19

67,p

p.19

–26

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

3;32

3;34

8c 2

/mol

dm2

3 :1

–3

c 3/m

oldm

23 :

0.06

–2

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

typr

oduc

tof

NaU

O 2~C

2H3O

2!3

atva

rious

ioni

cst

reng

ths

and

tem

pera

ture

s

Sal

tS

alt

(c4

/mol

dm2

3 )C

2H3O

2Na

(c2

/mol

dm2

3 )C

2H4O

2

(c3

/mol

dm2

3 )K

spa

(103

mol

2dm

26 )

——

2.99

0.06

–1.

32.

0560.

07

C2H

3O2N

H4;

@631

-61-

8#3.

00—

23.

346

0.03

2.00

1.00

13.

360.

1

NaC

lO4

;@7

601-

89-0#

2.00

1.00

13.

960.

1

NaN

O3

;@7

631-

99-4#

2.00

1.00

14.

160.

1

NH

4NO

3;

@648

4-52

-2#1.

002.

001

3.546

0.04

2.00

1.00

15.

260.

1

a At

20°C

.A

vera

geva

lue

oftw

oor

thre

em

easu

rem

ents

inth

epH

rang

ew

here

Ksp

was

inde

pend

ent

ofpH

.

Sal

tS

alt

(c4

/mol

dm2

3 )C

2H3O

2Na

(c2

/mol

dm2

3 )Io

nic

stre

ngth

~mol

dm2

3 !K

spa

(103

mol

2dm

26 )

NaN

O3;

@763

1-99

-4#1.

01.

02.

04.

5

1.5

1.5

3.0

3.5

2.0

2.0

4.0

2.8

2.5

2.5

5.0

2.4

2.0

1.0

3.0

4.1

3.0

1.0

4.0

3.4

4.0

1.0

5.0

2.6

Te

a p b A c A Ad

Th

so ca an Me

Iso

the

am Th

ac ro 2 gr sa gr de co


5.9.

Ura

nium

„V

I…D

ioxo

Bis

„ca

rbox

ylat

es…¿

Org

anic

Sol

vent

¿W

ater

Ter

nary

Sys

tem

s

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

obi

s~tr

ifluo

roac

etat

e!;U

O2~

C2F

3O2!

2;49

74-8

0-0#

Die

thyl

ethe

r;C 4

H10

O;

@60-

29-7

#W

ater

;H 2

O;

@773

2-18

-5#

V.

M.

Vdo

venk

o,A

.V

.B

alue

v,an

dI.

G.

Sug

lubo

va,

Rad

iokh

imiy

a,17

,62

–5

~197

5!.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

17.5

8–

92.0

30

w3

/mas

s%

:50.

20–

5.92

J.H

ala

Exp

erim

enta

lDat

a

mpo

sitio

nof

bina

rydi

ethy

let

her–

wat

erso

lutio

nssa

tura

ted

with

UO

2~C

2F3O

2!2,

and

phas

edi

agra

mof

the

UO

2~C

2F3O

2!2–

H10

O–

H2O

syst

emat

25°C

C4H

10O

(100

w2

/mas

s%

)bH

2O(1

00w

3/m

ass

%)

UO

2~C

2F3O

2!2a

(100

w1

/mas

s%

)

92.0

30.

207.

77

84.6

30.

7614

.61

60.8

72.

5136

.62

59.2

32.

6138

.16

17.5

85.

9276

.50c

heeq

uilib

rium

solid

phas

ew

asU

O2~

C2F

3O2!

2•2C

4H10

Oin

alls

olut

ions

.

alcu

late

dby

com

pile

rby

diffe

renc

e.

this

syst

emth

em

ole

ratio

H 2O/U

O2~

C2F

3O2!

2is

2:1,

and

the

syst

emca

n,ac

cord

ing

toth

eau

thor

s,be

cons

ider

edto

repr

esen

tm

olte

n

O2~

C2F

3O2!

2•2H

2O•1.

5C 4

H10

O.

Ats

altc

once

ntra

tions

high

erth

an77

mas

s%

itw

asno

tpos

sibl

eto

inve

stig

ate

the

solu

bilit

yis

othe

rm

ueto

high

visc

osity

ofth

esy

stem

whi

chpr

even

ted

the

solid

phas

eto

sepa

rate

.F

orth

esa

me

reas

onth

eso

lubi

lity

ofU

O2~

C2F

3O2!

2in

ater

coul

dno

tbe

dete

rmin

ed.

ase

diag

ram~

Fig

.5!

ofth

eU

O 2~C

2F3O

2!2–

C4H

10O

–H

2Osy

stem

at25

°C.



5.8.

Sod

ium

Zin

cT

ris„di

oxou

rani

um„V

I……

Non

akis„ac

etat

e…

Com

pone

nts:

Orig

inal

mea

sure

men

ts:

~1!

Sod

ium

zinc

tris$

uran

ium~

VI!

diox

o%no

naki

s~ace

tate!

;N

aZn~

UO

2!3~

C2H

3O2) 9

;@

#~2

!E

than

ol;

C 2H

6O;

@64-

17-5

#~3

!W

ater

;H 2

O;

@773

2-18

-5#

G.

W.

B.

van

der

Ling

en,

Ana

lyst5

7,37

6–

7~1

932!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8E

than

ol/v

olum

e%

:50

–10

0J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyin

etha

nol–

wat

erm

ixtu

res

ofN

aZn

~UO

2!3~

C2H

3O2!

9at

25°C

a

C2H

6O(w

2/v

ol.

%)

NaZ

n~U

O2!

3~C

2H3O

2!9

~g/1

00cm

3so

lutio

n!

500.

967

600.

316

700.

194

800.

119

900.

062

960.

042

100

0.13

2

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.F

rom

aque

ous

solu

tions

the

salt

crys

talli

zes

ashe

xahy

drat

e,1

and

itw

asno

tm

entio

ned

whe

ther

itre

tain

sth

ew

ater

ofcr

ysta

lliza

tion

whe

nin

equi

libriu

mw

ithet

hano

l–w

ater

mix

ture

sor

with

neat

etha

nol.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dw

asus

ed.

The

solu

bilit

yof

the

salt

was

dete

rmin

edby

evap

orat

ing

todr

ynes

sof

anal

iquo

tof

the

satu

rate

dso

lutio

n,an

dw

eigh

ing

the

resi

due.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 H.

H.

Bar

ber

and

I.M

.K

olth

off,

J.A

m.

Che

m.

Soc

.50

,16

25~1

928!

.

Co

~1!

@5 ~2!

~3!

Va

T/

10 10 Co

C4

a T b C c In U d w Ph

J

22

32

2

stro

ngly

hygr

osco

pic.

Tem

pera

ture

:pr

ecis

ion6

0.05

K~a

utho

rs!.

Sol

ubili

ty:

prec

isio

nno

tre

port

ed.

Ref

eren

ces:

1 V.

M.

Vdo

venk

o,A

.V

.B

alue

v,an

dI.

G.

Sug

lubo

va,

inC

om

ple

xF

orm

atio

na

nd

Ext

ract

ion

of

La

nth

an

ide

sa

nd

Act

inid

es~

inR

ussi

an!

~Nau

ka,

Leni

ngra

d,19

74!,p.

35.

2 A.

Wei

sber

ger,

E.

Pos

kaue

r,J.

Rid

dick

,an

dE

.T

ups,

Org

an

icS

olv

en

ts~R

ussi

anT

rans

l.!~I

L,M

osco

w,

1958

!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

obi

s~tr

ifluo

roac

etat

e!;U

O2~

C2F

3O2!

2;49

74-8

0-0#

Pho

spho

ricac

idtr

i-n-bu

tyle

ster

;C 1

2H27

O4P

;@1

26-7

3-8#

Wat

er;

H 2O

;@7

732-

18-5#

A.

V.

Bal

uev,

A.

A.

Lum

pov,

and

I.G

.S

uglu

bova

,R

adio

khim

iya2

7,27

4–

80~1

985!

.

riabl

es:

Pre

pare

dby

:

K:2

980

w2

/mas

s%

:3.9

5–

57.7

00

w3

/mas

s%

:0–

12.6

7

J.H

ala

Exp

erim

enta

lDat

a

mpo

sitio

nof

bina

rytr

i-n-bu

tylp

hosp

hate

–w

ater

solu

tions

satu

rate

dw

ithU

O2~

C2F

3O2!

2,an

dph

ase

diag

ram

ofth

eU

O2~

C2F

3O2!

2–

2H27

O4P

–H 2

Osy

stem

at25

°C

C12

H27

O4P

~100

w2

/mas

s%!

bH

2O~1

00w

3/m

ass

%!U

O2~

C2F

3O2!

2

~100

w1

/mas

s%!

Sol

idph

asea

57.7

00

42.3

0cA

55.6

80.

1044

.22

A

55.7

80.

3143

.91

A

52.9

41.

0146

.05

A1B

51.5

41.

4746

.99

B

51.0

31.

7447

.23

B

48.7

01.

5349

.77

B

47.8

01.

9750

.23

B

45.3

51.

8652

.79

B

44.7

31.

8653

.41

B

43.0

22.

6154

.37

B

41.4

72.

6555

.88

B

35.9

63.

5260

.52

B

35.7

33.

2661

.01

B

28.8

85.

2065

.92

B1C

27.9

95.

0067

.01

B1C

26.9

35.

4167

.66

B1C

7.62

10.5

081

.88

C

3.95

12.6

783

.38

C

a ~A!

UO

2~C

2F3O

2!2,

@549

74-8

0-0#;

~B!

UO

2~C

2F3O

2!2•

H2O

,@

#;~C

!un

spec

ified

hydr

olyz

edfo

rms

ofU

O 2~C

2F3O

2!2.

b Cal

cula

ted

byco

mpi

ler

bydi

ffere

nce.

c Sol

ubili

tyof

anhy

drou

sU

O 2~C

2F3O

2!2

indr

ytr

i-n-b

utyl

phos

phat

e;m15

1.48

mol

kg2

1~c

ompi

ler!.

Pha

sedi

agra

m~F

ig.

6!of

the

UO 2

~C2F

3O2!

2–

C12

H27

O4P

–H 2

Osy

stem

at25

°C:

594594 JIRI HALA

FIG

.5.

Ura

nium

~VI!

diox

obi

s~tr

ifluo

roac

etat

e!–di

ethy

let

her–

wat

ersy

stem

.Le

gend

toth

eph

ase

diag

ram

:~A

!tw

o-ph

ase

regi

on;~B

!

unsa

tura

ted

hom

ogen

eous

wat

er–

diet

hyle

ther

solu

tions

;~C

!sa

tura

ted

solu

tions

ineq

uilib

rium

with

UO 2~C

2F3O

2!2•

C4H

10O

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

The

phas

esw

ere

brou

ght

toeq

uilib

rium

bysh

akin

gth

emin

seal

edgl

ass

ampo

ules

.T

heco

ncen

trat

ion

ofur

aniu

man

dw

ater

inth

eeq

uilib

rium

phas

esw

asde

term

ined

grav

imet

rical

ly~met

hod

not

spec

ified!

and

byF

isch

erm

etho

d,re

spec

tivel

y.A

llw

ork

was

cond

ucte

din

atm

osph

ere

ofdr

yai

rsi

nce

the

solv

ate

ofU

O~CF

O!

was

Anh

ydro

usU

O 2~C

2F3O

2!2

and

itsso

lvat

ew

ere

prep

ared

acco

rdin

gto

Ref

.1.D

ieth

ylet

her

was

purifi

edac

cord

ing

toR

ef.

2,dr

ied

over

sodi

umm

etal

,an

ddi

still

edon

are

ctifi

catio

nco

lum

n.

Est

imat

edE

rror

:

Co

~1!

@5 ~2!

~3!

Va

T/

10 10 Co

C1


hydr

olyz

ein

syst

ems

cont

aini

ngm

ore

than

3%–

4%of

wat

er,

and

tohi

ghvi

scos

ityof

conc

entr

ated

solu

tions

.R

efer

ence

s:1 A

.V

.B

alue

v,S

.V

.Z

hdan

ovsk

ii,an

dI.

G.

Sug

lubo

va,

Rad

iokh

imiy

a20,

68~1

978!

.2 V

.M

.V

dove

nko,

A.

V.

Bal

uev,

and

I.G

.S

uglu

bova

,in

Co

mp

lex

Fo

rma

tion

an

dE

xtra

ctio

no

fL

an

tha

nid

es

an

dA

ctin

ide

s~in

Rus

sian

!~N

auka

,Le

ning

rad,

1974!,

p.35

.3 H

.Ir

ving

and

D.

N.

Edg

ingt

on,

J.In

org.

Nuc

l.C

hem

.10

,30

6~1

959!

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

obi

s~m

onoc

hlor

oace

tate!;

2~C

2H2O

2Cl! 2

;@1

5221

-09-

7#D

ieth

ylet

her;

C 4H

10O

;@6

0-29

-7#

Wat

er;

H 2O

;@7

732-

18-5#

V.

M.

Vdo

venk

o,A

.V

.B

alue

v,an

dI.

G.

Sug

lubo

va,

Rad

iokh

imiy

a17,

65–

8~1

975!

.

riabl

es:

Pre

pare

dby

:

K:2

980

w2

/mas

s%

:87.

97–

99.6

90

w3

/mas

s%

:0–

1.30

J.H

ala

Exp

erim

enta

lDat

a

mpo

sitio

nof

bina

rydi

ethy

let

her–

wat

erso

lutio

nssa

tura

ted

with

UO

2~C

2H2O

2Cl! 2

,an

dph

ase

diag

ram

ofth

e

2~C

2H2O

2Cl! 2

–C

4H10

O–

H2O

syst

emat

25°C

C4H

10O

~100

w2

/mas

s%!

bH

2O~1

00w

2/m

ass

%!U

O2~

C2H

2O2C

l! 2~1

00w

1/m

ass

%!S

olid

phas

ea

99.6

90

0.31

cA

98.4

70.

111.

42A1

B

98.4

70.

111.

42B

96.3

50.

253.

40B

96.5

70.

333.

10B

89.2

90.

6110

.10

B

87.9

71.

3010

.73

B

!U

O2~

C2H

2O2C

l! 2,

@152

21-0

9-7#;

~B!

UO

2~C

2H2O

2Cl! 2•H

2O,

@#.

alcu

late

dby

com

pile

rby

diffe

renc

e.ol

ubili

tyof

UO

2~C

2H2O

2Cl! 2

indr

ydi

ethy

leth

er;m

15

6.80

310

23

mol

kg2

1~c

ompi

ler!.

ditio

nali

nfor

mat

ion:

eto

hydr

olys

isin

mix

ture

sco

ntai

ning

high

eram

ount

ofw

ater

itw

aspo

ssib

leto

inve

stig

ate

syst

ems

with

mol

era

tios

H2O

/sal

t,3

only

.as

edi

agra

m~F

ig.

7!of

the

UO 2

~C2H

2O2C

l! 2–

C4H

10O

–H

2Osy

stem

at25

°C.

FIG

.7.

Ura

nium

~VI!

diox

obi

s~m

onoc

hlor

oace

tate!–

diet

hyle

ther

–w

ater

syst

em.L

egen

dto

the

phas

edi

agra

m:

~A!

two

liqui

dph

ases

;~B!

unsa

tura

ted

hom

ogen

eous

wat

er–

diet

hyle

ther

solu

tions

;~C

!sa

tura

ted

solu

tions

ineq

uilib

rium

with

UO 2~C

2H2O

2Cl! 2

H2O

;~D

!sa

tura

ted

solu

tions

ineq

uilib

rium

with

UO 2

~C2H

2O2C

l! 2;

~E!

satu

rate

dso

lutio

nsin

equi

libriu

mw

ithU

O 2~C

2H2O

2Cl! 2

and

UO 2

~C2H

2O2C

l! 2•H

2O.



FIG

.6.

Ura

nium

~VI!

diox

obi

s~tr

ifluo

roac

etat

e!–tr

i-n-b

utyl

phos

phat

e–

wat

ersy

stem

.Le

gend

toth

eph

ase

diag

ram

:~A

!tw

o-ph

ase

regi

on;~

b!un

satu

rate

daq

ueou

s-or

gani

cso

lutio

ns;

~C!

satu

rate

dso

lutio

nsin

equi

libriu

mw

ithU

O 2~C

2F3O

2!2

and

UO 2

~C2F

3O2!

2•H

2O;~

D!

satu

rate

dso

lutio

nsin

equi

libriu

mw

ithU

O 2~C

2F3O

2!2•

H2O

;~E

!sa

tura

ted

solu

tions

ineq

uilib

rium

with

UO 2~C

2F3O

2!2.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Cal

cula

ted

amou

nts

ofth

esa

lt,tr

i-n-

buty

lpho

spha

tean

dw

ater

wer

eeq

uilib

rate

din

seal

edgl

ass

ampo

ules

prot

ecte

dfr

omlig

htin

ath

erm

osta

ted

bath

for

4da

ysw

hich

was

foun

dsu

ffici

ent

for

equi

libriu

mto

bere

ache

d.T

heph

ases

wer

ese

para

ted

byce

ntrif

ugat

ion

and

anal

yzed

asin

Ref

.1.

Equ

ilibr

ium

solid

phas

esw

ere

iden

tified

byS

chre

inem

aker

sm

etho

d.It

was

not

poss

ible

toob

tain

the

who

leso

lubi

lity

curv

edu

eto

the

stro

ngte

nden

cyof

the

salt

to

UO

2~C

2F3O

2!2

and

itsm

onoh

ydra

tew

ere

prep

ared

acco

rdin

gto

Ref

.2.

Tri-

n-bu

tyl

phos

phat

ew

aspu

rified

acco

rdin

gto

Ref

.3,

and

then

dist

illed

at15

mm

Hg

pres

sure

.F

ract

ion

boili

ngat

172

–17

5°C

was

colle

cted

for

use.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

05K

~aut

hors!

.S

olub

ility

:pr

ecis

ion

not

repo

rted

.

Co

~1!

UO

~2!

~3!

Va

T/

10 10 Co

UO

a ~A b C c S Ad

Du

Ph

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

obi

s~m

onoc

hlor

oace

tate!;

2~C

2H2O

2Cl! 2

;@1

5221

-09-

7#P

hosp

horic

acid

tri-n-

buty

lest

er;

C 12H

27O

4P;

@126

-73-

8#W

ater

;H 2

O;

@773

2-18

-5#

A.

V.

Bal

uev,

A.

A.

Lum

pov,

and

I.G

.S

uglu

bova

,R

adio

khim

iya2

7,28

0–

8~1

985!

.

riabl

es:

Pre

pare

dby

:

K:2

980

w2

/mas

s%

:30.

97–

60.3

0w

3/m

ass

%:0

.09

–3.

50

J.H

ala

Exp

erim

enta

lDat

a

mpo

sitio

nof

bina

rytr

i-n-bu

tyl

phos

phat

e–

wat

erso

lutio

nssa

tura

ted

with

UO

2~C

2H2O

2Cl! 2

,an

dph

ase

diag

ram

ofth

e

2~C

2H2O

2Cl! 2

–C

12H

27O

4P–

H 2O

syst

emat

25°C

C12

H27

O4P

~100

w2

/mas

s%!

bH

2O~1

00w

3/m

ass

%!U

O2~

C2H

2O2C

l! 2~1

00w

1/m

ass

%!S

olid

phas

ea

30.9

73.

5065

.53

A

30.9

42.

8566

.21

A

35.2

92.

6862

.03

A

41.9

31.

1256

.95

A

43.2

51.

0655

.69

A

43.2

81.

0355

.69

A

44.9

71.

3053

.73

A

46.0

41.

0152

.95

A

48.0

30.

9251

.05

A

50.2

60.

9248

.82

A

55.1

60.

4844

.36

A1B

59.4

10.

1240

.47

B

60.3

00.

0939

.61

B

!U

O2~

C2H

2O2C

l! 2•H

2O,

@#;

~B!

UO

2~C

2H2O

2Cl! 2

@152

21-0

9-7#.

alcu

late

dby

com

pile

rby

diffe

renc

e.

ditio

nali

nfor

mat

ion:

mpo

sitio

nof

the

phas

esre

port

edar

eav

erag

eva

lues

oftw

oto

thre

em

easu

rem

ents

.E

xtra

pola

ted

valu

eof

the

solu

bilit

yof

2~C

2H2O

2Cl! 2

indr

ytr

i-n-b

utyl

phos

phat

ew

asre

port

edto

beap

prox

imat

ely

m15

1.45

mol

kg2

1 .In

am

ore

rece

ntdo

cum

ent,

1m

1

1.43

mol

kg2

1w

asre

port

ed.

Pha

sedi

agra

m~F

ig.

8!of

the

UO 2

~C2H

2O2C

l! 2–

C12

H27

O4P

–H 2

Osy

stem

at25

°C.

596596 JIRI HALA

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

The

phas

esw

ere

brou

ght

toeq

uilib

rium

bysh

akin

gth

emin

seal

edgl

ass

ampo

ules

.T

heco

ncen

trat

ion

ofur

aniu

man

dw

ater

inth

eeq

uilib

rium

phas

esw

asde

term

ined

grav

imet

rical

ly~met

hod

not

spec

ified!

and

byF

isch

erm

etho

d,re

spec

tivel

y.

Anh

ydro

usU

O 2~C

2H2O

2Cl! 2

and

itshy

drat

ew

ere

prep

ared

and

anal

yzed

acco

rdin

gto

Ref

.1.

Die

thyl

ethe

rw

aspu

rified

acco

rdin

gto

Ref

.2,

drie

dov

erso

dium

met

al,

and

dist

illed

ona

rect

ifica

tion

colu

mn.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

05K

~aut

hors!

.S

olub

ility

:pr

ecis

ion

not

repo

rted

.

Ref

eren

ces:

1 V.

M.

Vdo

venk

o,A

.V

.B

alue

v,an

dI.

G.

Sug

lubo

va,

Co

mp

lex

Fo

rma

tion

an

dE

xtra

ctio

no

fL

an

tha

nid

es

an

dA

ctin

ide

s~in

Rus

sian

!~N

auka

,Le

ning

rad,

1974!,

p.35

.2 A

.W

eisb

erge

r,E

.P

oska

uer,

J.R

iddi

ck,

and

E.

Tup

s,O

rga

nic

So

lve

nts

~Rus

sian

Tra

nsl.!~I

L,M

osco

w,

1958

!.

Co

~1!

UO

~2!

~3!

Va

T/

10 10 Co

UO

a ~A b C Ad

Co

UO

5


byS

chre

inem

aker

sm

etho

d.T

empe

ratu

re:

prec

isio

n60.

05K

~aut

hors!

.S

olub

ility

:pr

ecis

ion

not

repo

rted

.

Ref

eren

ces:

1 A.V

.Bal

uev,

A.Y

u,S

ilin,

I.G

.Sug

lubo

va,a

ndA

.P.T

aran

ov,

Rad

iokh

imiy

a30,

442

~198

8!.

2 A.

V.

Bal

uev,

S.

V.

Zhd

anov

skii,

and

I.G

.S

uglu

bova

,R

adio

khim

iya2

0,68

~197

8!.

3 V.

M.

Vdo

venk

o,A

.V

.B

alue

v,an

dI.

G.

Sug

lubo

va,

inC

om

ple

xF

orm

atio

na

nd

Ext

ract

ion

of

La

nth

an

ide

sa

nd

Act

inid

es~

inR

ussi

an!

~Nau

ka,

Leni

ngra

d,19

74!,p.

35.

4 H.

Irvi

ng,

and

D.

N.

Edg

ingt

on,

J.In

org.

Nuc

l.C

hem

.10

,30

6~1

959!

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

obi

s~tr

ichl

oroa

ceta

te!;U

O2~

C2O

2Cl 3

! 2;

1740

-41-

0#D

ieth

ylet

her;

C 4H

10O

;@6

0-29

-7#

Wat

er;

H 2O

;@7

732-

18-5#

V.

M.

Vdo

venk

o,A

.V

.B

alue

v,an

dI.

G.

Sug

lubo

va,

Rad

iokh

imiy

a17,

58–

62~1

975!

.

riabl

es:

Pre

pare

dby

:

K:2

980

w2

/mas

s%

:1.3

–98

.80

w3

/mas

s%

:0.2

–19

.4

J.H

ala

Exp

erim

enta

lDat

a

mpo

sitio

nof

bina

rydi

ethy

let

her–

wat

erso

lutio

nssa

tura

ted

with

UO

2~C

2O2C

l 3! 2

,an

dph

ase

diag

ram

ofth

e

2~C

2O2C

l 3! 2

–C

4H10

O–

H2O

syst

emat

25°C

C4H

10O

~100

w2

/mas

s%!

bH

2O~1

00w

3/m

ass

%!U

O2~

C2O

2Cl 3

! 2~1

00w

1/m

ass

%!S

olid

phas

ea

1.30

19.4

079

.30

A

2.85

17.0

080

.15

A

5.70

12.6

081

.70

A

5.95

13.1

580

.90

A1B

4.53

13.1

282

.35

A1B

8.70

12.8

078

.50

A1B

10.2

216

.43

73.3

5B

16.6

520

.00

63.3

5B1

C

19.1

816

.95

63.8

7B1

C

17.3

018

.30

64.4

0C

25.1

011

.70

63.2

0C

47.4

04.

8847

.72

C

50.9

84.

0544

.97

C

60.7

02.

5036

.80

C

59.7

71.

8538

.38

C1D

69.8

51.

6028

.55

D

81.2

00.

9017

.90

D

85.2

31.

2513

.25

D

86.8

30.

6012

.57

D1E

98.8

00.

201.

00E

a ~A!

UO

2~C

2O2C

l 3! 2•3H

2O,

@#;

~B!

UO

2~C

2O2C

l 3! 2•2H

2O•C

4H10

O,

@#;

~C!

UO

2~C

2O2C

l 3! 2•2H

2O•2C

4H10

O,

@#;

~D!

UO

2~C

2O2C

l 3! 2•H

2O•C

4H10

O,

@#;

~E!

UO

2~C

2O2C

l 3! 2•C

4H10

O,

@#.

b Cal

cula

ted

byco

mpi

ler

bydi

ffere

nce.

Pha

sedi

agra

m~F

ig.

9!of

the

UO 2

~C2O

2Cl 3

! 2–

C4H

10O

–H

2Osy

stem

at25

°C.



FIG

.8.

Ura

nium

~VI!

diox

obi

s~m

onoc

hlor

oace

tate!–

tri-n

-but

ylph

osph

ate

–w

ater

syst

em.

Lege

ndto

the

phas

edi

agra

m:

~A!

two-

phas

ere

gion

;~B

!un

satu

rate

daq

ueou

s–

orga

nic

solu

tions

;~C

!sa

tura

ted

solu

tions

ineq

uilib

rium

with

UO 2~C

2H2O

2Cl! 2

;~D

!sa

tura

ted

solu

tions

ineq

uilib

rium

with

UO 2

~C2H

2O2C

l! 2an

dU

O 2~C

2H2O

2Cl! 2•H

2O;~

E!

satu

rate

dso

lutio

nsin

equi

libriu

mw

ithU

O 2~C

2H2O

2Cl! 2•H

2O;

~F!

UO

2~C

2H2O

2Cl! 2•H

2Oin

equi

libriu

mw

ithsa

tura

ted

orga

nic

and

aque

ous

solu

tions

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Cal

cula

ted

amou

nts

ofth

esa

lt,tr

i-n-

buty

lpho

spha

te,

and

wat

erw

ere

equi

libra

ted

inse

aled

glas

sam

poul

espr

otec

ted

from

light

ina

ther

mos

tate

dba

thfo

r4

days

whi

chw

asfo

und

suffi

cien

tfo

req

uilib

rium

tobe

reac

hed.

The

phas

esw

ere

sepa

rate

dby

cent

rifug

atio

nan

dan

alyz

edas

inR

ef.

2.E

quili

briu

mso

lidph

ases

wer

eid

entifi

ed

UO

2~C

2H2O

2Cl! 2

and

itsm

onoh

ydra

tew

ere

prep

ared

acco

rdin

gto

Ref

.3.T

ri-n-

buty

lpho

spha

tew

aspu

rified

acco

rdin

gto

Ref

.4,

and

then

dist

illed

at15

mm

Hg

pres

sure

.F

ract

ion

boili

ngat

172

–17

5°C

was

colle

cted

for

use.

Est

imat

edE

rror

:

Co

~1!

@2 ~2!

~3!

Va

T/

10 10 Co

UO

J

Fis

cher

met

hod,

resp

ectiv

ely.

All

wor

kw

asco

nduc

ted

inth

eat

mos

pher

eof

dry

air

sinc

eth

ehy

drat

esan

dhy

drat

o-so

lvat

esof

UO

2~C

2O2C

l 3! 2

are

stro

ngly

hygr

osco

pic.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

05K

~aut

hors!

.S

olub

ility

:pr

ecis

ion

not

repo

rted

.

Ref

eren

ces:

1 V.

M.

Vdo

venk

o,A

.V

.B

alue

v,an

dI.

G.

Sug

lubo

va,

inC

om

ple

xF

orm

atio

na

nd

Ext

ract

ion

of

La

nth

an

ide

sa

nd

Act

inid

es~

inR

ussi

an!

~Nau

ka,

Leni

ngra

d,19

74!,p.

35.

2 A.

Wei

sber

ger,

E.

Pos

kaue

r,J.

Rid

dick

,an

dE

.T

ups,

Org

an

icS

olv

en

ts~R

ussi

anT

rans

l.!~I

L,M

osco

w,

1958

!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

obi

s~tr

ichl

oroa

ceta

te!;U

O2~

C2O

2Cl 3

! 2;

1740

-41-

0#P

hosp

horic

acid

tri-n-

buty

lest

er;

C 12H

27O

4P;

@126

-73-

8#W

ater

;H 2

O;

@773

2-18

-5#

A.

V.

Bal

uev,

A.

A.

Lum

pov,

and

I.G

.S

uglu

bova

,R

adio

khim

iya2

6,19

6–

206~

1984

!.

riabl

es:

Pre

pare

dby

:

K:2

980

w2

/mas

s%:6

.5–

48.1

0w

3/m

ass%

:0.0

1–

14.2

8

J.H

ala

Exp

erim

enta

lDat

a

mpo

sitio

nof

bina

rytr

i-n-bu

tyl

phos

phat

e–

wat

erso

lutio

nssa

tura

ted

with

UO

2~C

2O2C

l 3! 2

,an

dph

ase

diag

ram

ofth

e

2~C

2O2C

l 3! 2

–C

12H

27O

4P–

H 2O

syst

emat

25°C

C12

H27

O4P

~100

w2

/mas

s%!b

H2O

~100

ww

3/m

ass%

!U

O2~

C2O

2Cl 3

! 2~1

00w

1/m

ass%

!S

olid

phas

ea

48.0

90.

0151

.90

A

46.7

20.

7552

.53

A1B

45.7

60.

6653

.58

A1B

37.9

21.

1060

.98

B

33.6

61.

8164

.53

B

29.3

23.

6567

.03

B

30.4

02.

3567

.25

B

28.3

54.

1267

.53

B

26.2

35.

3368

.40

B1C

26.4

24.

2069

.38

B1C

24.3

65.

7469

.90

C

21.4

36.

8271

.75

C1D

17.2

58.

4074

.35

D

11.1

811

.20

77.6

2D

4.72

16.6

878

.60

D

6.51

14.2

879

.21

D

!U

O2~

C2O

2Cl 3

! 2,

@217

40-4

1-0#;

~B!

UO

2~C

2O2C

l 3! 2•H

2O,

@#;

~C!

UO

2~C

2O2C

l 3! 2•2H

2O,

@#;

~D!

UO

2~C

2O2C

l 3! 2•3H

2O,

#.al

cula

ted

byco

mpi

ler

bydi

ffere

nce.

Add

ition

alin

form

atio

n:In

am

ore

rece

ntre

fere

nce,1th

eso

lubi

lity

at25

°Cin

dry

tri-n-

buty

lpho

spha

teof

UO 2~

C2O

2Cl 3

! 2w

asre

port

edasm

15

1.81

mol

kg2

1 .

Pha

sedi

agra

m~F

ig.

10!

ofth

eU

O 2~C

2O2C

l 3) 2

–C

12H

27O

4P–

H 2O

syst

emat

25°C

.

598598 JIRI HALA

FIG

.9.

Ura

nium

~VI!

diox

obi

s~tr

ichl

oroa

ceta

te!–

diet

hyle

ther

–w

ater

syst

em.

Lege

ndto

the

phas

edi

agra

m~f

orno

tatio

nof

solid

phas

esse

eab

ove!:

~I!

two

liqui

dph

ases

;~II!

unsa

tura

ted

hom

ogen

eous

wat

er–

diet

hyl

ethe

rso

lutio

ns;

regi

on~I

II!–

~XI!

repr

esen

tfie

lds

ofsa

tura

ted

solu

tions

ineq

uilib

rium

with

the

follo

win

gso

lidph

ases

:~I

II!

C;~

IV!

C1

D;

~V!

D;

~VI!

D1

E;~

VII

!E

;~V

III!

B1

C;~

IX!

B;

~X!

A1

B;

~XI!

A.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

The

phas

esw

ere

brou

ght

toeq

uilib

rium

bysh

akin

gth

emin

seal

edgl

ass

ampo

ules

.T

heco

ncen

trat

ion

ofur

aniu

man

dw

ater

inth

eeq

uilib

rium

phas

esw

asde

term

ined

grav

imet

rical

ly~met

hod

not

spec

ified!

and

by

Anh

ydro

usU

O 2~C

2O2C

l 3! 2

and

itshy

drat

ew

ere

prep

ared

and

anal

yzed

acco

rdin

gto

Ref

.1.

Die

thyl

ethe

rw

aspu

rified

acco

rdin

gto

Ref

.2,

drie

dov

erso

dium

met

al,

and

dist

illed

ona

rect

ifica

tion

colu

mn.

Co

~1!

@2 ~2!

~3!

Va

T/

10 10 Co

UO

a ~A @ b C


reac

hed.

The

phas

esw

ere

sepa

rate

dby

cent

rifug

atio

nan

dan

alyz

edas

inR

ef.

2.C

ompo

sitio

nof

the

phas

esre

port

edar

eav

erag

ere

sults

oftw

oto

thre

em

easu

rem

ents

.E

quili

briu

mso

lidph

ases

wer

eid

entifi

edby

Sch

rein

emak

ers

met

hod.

All

wor

kw

asco

nduc

ted

inat

mos

pher

eof

dry

argo

nsi

nce

UO

2~C

2O2C

l 3! 2

tend

sto

hydr

olyz

ean

dis

stro

ngly

hygr

osco

pic.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

05K

~aut

hors!

.S

olub

ility

:pr

ecis

ion

not

repo

rted

.

Ref

eren

ces:

1 A.V

.Bal

uev,

A.Y

u.S

ilin,

I.G

.Sug

lubo

va,a

ndA

.P.T

aran

ov,

Rad

iokh

imiy

a30,

442

~198

8!.

2 A.

V.

Bal

uev,

S.

V.

Zhd

anov

skii,

and

I.G

.S

uglu

bova

,R

adio

khim

iya2

0,68

~197

8!.

3 V.

M.

Vdo

venk

o,A

.V

.B

alue

v,an

dI.

G.

Sug

lubo

ya,

inC

om

ple

xF

orm

atio

na

nd

Ext

ract

ion

of

La

nth

an

ide

sa

nd

Act

inid

es~

inR

ussi

an!

~Nau

ka,

Leni

ngra

d,19

74!,p.

35.

4 H.

Irvi

ngan

dD

.N

.E

dgin

gton

,J.

Inor

g.N

ucl.

Che

m.

10,

306

~195

9!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

obi

s~tr

ichl

oroa

ceta

te!;U

O2~

C2O

2Cl 3

! 2;

1740

-41-

0#4-

met

hyl-2

-pen

tano

ne~m

ethy

liso

buty

lket

one!;

C6H

12O

;08

-10-

1#W

ater

;H 2

O;

@773

2-18

-5#

A.V

.Bal

uev,

M.A

.Mya

gkov

a-R

oman

ova,

and

I.G

.Sug

lubo

va,

Rad

iokh

imiy

a34,

59–

68~1

992!

.

riabl

es:

Pre

pare

dby

:

K:2

980

w2

/mas

s%:0

.09

–85

.90

w3

/mas

s%:0

.02

–20

.70

J.H

ala

Exp

erim

enta

lDat

a

mpo

sitio

nof

bina

ry4-

met

hyl-2

-pen

tano

ne–

wat

erso

lutio

nssa

tura

ted

with

UO

2~C

2O2C

l 3! 2

,an

dph

ase

diag

ram

ofth

e

2~C

2O2C

l 3! 2

–C

6H12

O–

H2O

syst

emat

25°C

C6H

12O

~100

w2

/mas

s%!b

H2O

~100

w3

/mas

s%!

UO

2~C

2O2C

l 3! 2

~100

w1

/mas

s%!

Sol

idph

asea

85.8

80.

0214

.10

A

66.0

22.

1031

.88

A

56.2

23.

8539

.93

A

33.6

58.

3458

.01

A1B

32.4

68.

5059

.04

A1B

29.7

48.

9061

.36

B

19.7

210

.29

69.9

9B

7.79

13.5

578

.66

B

3.78

17.4

078

.82

B

0.09

20.7

079

.21

B

!U

O2~

C2O

2Cl 3

! 2•C

6H12

O,

@#;

~B!

UO

2~C

2O2C

l 3! 2•3H

2O,

@#

alcu

late

dby

com

pile

rby

diffe

renc

e.

ase

diag

ram~

Fig

.11

!of

the

UO 2

~C2O

2Cl 3

! 2–

C6H

12O

–H

2Osy

stem

at25

°C.



FIG

.10

.U

rani

um~V

I!di

oxo

bis~

tric

hlor

oace

tate!

–tr

i-n-b

utyl

phos

phat

e–

wat

ersy

stem

.Le

gend

toth

eph

ase

diag

ram

:~A

!tw

o-ph

ase

regi

on;~

B!

unsa

tura

ted

aque

ous-

orga

nic

solu

tions

;~C

!sa

tura

ted

solu

tions

ineq

uilib

rium

with

UO 2~C

2O2C

l 3! 2

;~D

!sa

tura

ted

solu

tions

ineq

uilib

rium

with

UO 2

~C2O

2Cl 3

! 2an

dU

O 2~C

2O2C

l 3! 2•H

2O;~

E!

satu

rate

dso

lutio

nsin

equi

libriu

mw

ithU

O 2~C

2O2C

l 3! 2•H

2O;~

F!sa

tura

ted

solu

tions

ineq

uilib

rium

with

UO 2

~C2O

2Cl 3

! 2•H

2Oan

dU

O 2~C

2O2C

l 3! 2•2H

2O;

~G!

satu

rate

dso

lutio

nsin

equi

libriu

mw

ithU

O2~

C2O

2Cl 3

! 2•2H

2Oan

dU

O 2~C

2O2C

l 3! 2•3H

2O;

~H!

satu

rate

dso

lutio

nsin

equi

libriu

mw

ithU

O 2~C

2O2C

l 3! 2•2H

2O;

~I!

satu

rate

dso

lu-

tions

ineq

uilib

rium

with

UO 2

~C2O

2Cl 3

! 2•3H

2O.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Cal

cula

ted

amou

nts

ofth

esa

lt,tr

i-n-

buty

lpho

spha

tean

dw

ater

wer

eeq

uilib

rate

din

seal

edgl

ass

ampo

ules

prot

ecte

dfr

omlig

htin

ath

erm

osta

ted

bath

for

4da

ysw

hich

was

foun

dsu

ffici

ent

for

equi

libriu

mto

be

UO

2~C

2O2C

l 3! 2

and

itshy

drat

esw

ere

prep

ared

acco

rdin

gto

Ref

.3.

Tri-

n-bu

tylp

hosp

hate

was

purifi

edac

cord

ing

toR

ef.

4,an

dth

endi

still

edat

15m

mH

gpr

essu

re.

Fra

ctio

nbo

iling

at17

2–

175

°Cw

asco

llect

edfo

rus

e.

Co

~1!

@2 ~2!

@1 ~3!

Va

T/

10 10 Co

UO

a ~A b C Ph

J

byS

chre

inem

aker

sm

etho

d.V

.M

.V

dove

nko

et

al.,

Rad

iokh

imiy

a17,

58~1

975!

.2 A

.V.B

alue

and

I.G

.Sug

lubo

va,i

nTh

eC

he

mis

try

ofU

ran

ium

~inR

ussi

an!,

edite

dby

B.

N.

Lask

orin~

Nau

ka,

Mos

cow

,19

89!,

p.18

8.3 V

.M

.V

dove

nko,

A.

V.

Bal

uev,

and

I.G

.S

uglu

bova

,in

Co

mp

lex

Fo

rma

tion

an

dE

xtra

ctio

no

fL

an

tha

nid

es

an

dA

ctin

ide

s~in

Rus

sian

!~N

auka

,Le

ning

rad,

1974!,

p.35

.

5.10

.U

rani

um„V

I…D

ioxo

Bis

„be

nzen

esul

fona

te…¿

Pho

spho

ricA

cid

Tri-

n-B

utyl

Est

er¿

Wat

erS

yste

m

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

obi

s~be

nzen

esul

fona

te!;

2~C

6H5O

3S! 2

;@9

4667

-45-

5#P

hosp

horic

acid

tri-n-

buty

lest

er;

C 12H

27O

4P;

@126

-73-

8#W

ater

;H 2

O;

@773

2-18

-5#

A.V

.Bal

uev,

I.G

.Sug

lubo

va,a

ndA

.P.T

aran

ov,R

adio

khim

iya

30,

349

–54

~198

8!.

riabl

es:

Pre

pare

dby

:

K:

298

0w

2/m

ass%

:0–

52.6

40

w3

/mas

s%:0

–26

.06

J.H

ala

Exp

erim

enta

lDat

a

mpo

sitio

nof

bina

rytr

i-n-bu

tyl

phos

phat

e–

wat

erso

lutio

nssa

tura

ted

with

UO

2~C

6H5O

3S! 2

,an

dph

ase

diag

ram

ofth

e

2~C

6H5O

3S! 2

–C

12H

27O

4P–

H 2O

syst

emat

25°C

C12

H27

O4P

~100

w2

/mas

s%!b

H2O

~100

w3

/mas

s%!

UO

2~C

6H5O

3S! 2

~100

w1

/mas

s%!

Sol

idph

asea

52.6

40

47.3

6cA

49.9

40.

8849

.18

A

45.9

82.

0152

.11

A1B

43.8

73.

0953

.04

B

34.4

56.

0259

.40

B

28.0

39.

4862

.49

B

14.7

119

.10

66.1

9B

2.97

25.7

671

.27

B

026

.06

73.9

3dB

!U

O2~

C6H

5O3S

! 2,

@946

67-4

5-5#;

~B!

UO

2~C

6H5O

3S! 2•H

2O,

@#.

alcu

late

dby

com

pile

rby

diffe

renc

e.ol

ubili

tyat

25°C

ofU

O 2~C

6H5O

3S! 2

indr

ytr

i-n-b

utyl

phos

phat

e;m15

1.54

mol

kg2

1~c

ompi

ler!.

olub

ility

at25

°Cof

UO 2

~C6H

5O3S

! 2in

wat

er;m

15

4.85

mol

kg2

1~c

ompi

ler!.

ase

diag

ram~

Fig

.12

!of

the

UO 2

~C6H

5O3S

! 2–

C12

H27

O4P

–H 2

Osy

stem

at25

°C.

ditio

nali

nfor

mat

ion:

eph

ase

diag

ram

ofth

eU

O2~

C6H

5O3S

! 2–

H2O

–C 1

2H27

O4P

syst

emat

25°C

was

stud

ied

byth

e1 H

the

nucl

ear

mag

netic

reso

nanc

eM

R!

met

hod1

with

fairl

ygo

odag

reem

entw

ithth

eda

tare

port

edin

the

com

pile

ddo

cum

ent,

exce

ptfo

rso

me

diffe

renc

esin

the

boun

dary

betw

een

regi

ons

Aan

dB

.

600600 JIRI HALA

FIG

.11

.U

rani

um~V

I!di

oxo

bis~

benz

enes

ulfo

nate!–

tri-n

-but

ylph

osph

ate

–w

ater

syst

em.

Lege

ndto

the

phas

edi

agra

m:

~A!

two-

phas

ere

gion

;~B

!un

satu

rate

daq

ueou

s–

orga

nic

solu

tions

;~C

!sa

tura

ted

solu

tions

ineq

uilib

rium

with

UO 2~C

2O2C

l 3! 2•C

6H12

O;

~D!

satu

rate

dso

lutio

nsin

equi

libriu

mw

ithU

O 2~C

2O2C

l 3! 2•C

6H12

Oan

dU

O 2~C

2O2C

l 3! 2•3H

2O;

~E!

satu

rate

dso

lutio

nsin

equi

libriu

mw

ithU

O2~

C2O

2Cl 3

! 2•3H

2O

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Cal

cula

ted

amou

nts

ofth

esa

lt,m

ethy

liso

buty

lket

one,

and

wat

erw

ere

equi

libra

ted

inse

aled

glas

sam

poul

espr

otec

ted

from

light

ina

ther

mos

tate

dba

th.

Equ

ilibr

atio

ntim

ew

asno

tre

port

ed.

The

phas

esw

ere

sepa

rate

dby

cent

rifug

atio

nan

dan

alyz

edfo

rth

eco

nten

tof

the

salt

and

wat

erac

cord

ing

toR

efs.

1an

d2.

Com

posi

tions

ofth

eph

ases

repo

rted

are

aver

age

resu

ltsof

two

toth

ree

mea

sure

men

ts.

By

anal

ogy

toot

her

auth

ors’

wor

k,th

eco

mpi

ler

assu

mes

that

equi

libriu

mso

lidph

ases

wer

eid

entifi

ed

UO

2~C

2O2C

l 3! 2

and

itshy

drat

esw

ere

prep

ared

acco

rdin

gto

Ref

.3.

Met

hyl

isob

utyl

keto

new

asa

reag

ent

grad

epr

oduc

t~s

ourc

eno

tsp

ecifi

ed!

and

was

used

with

out

furt

her

purifi

catio

n.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

05K

~aut

hors!

.S

olub

ility

:pr

ecis

ion

not

repo

rted

.

Ref

eren

ces:

1

Co

~1!

UO

~2!

~3!

Va

T/

10 10 Co

UO

a ~A b C c S d S Ph

Ad

Th

~N


Sch

rein

emak

ers’

met

hod.

Tem

pera

ture

:pr

ecis

ion6

0.05

K~a

utho

rs!.

Sol

ubili

ty:

prec

isio

nno

tre

port

ed.

Ref

eren

ces:

1 E.O

.Ash

evsk

aya,

L.L.

Sch

erba

kova

,and

V.A

.Sch

erba

kov,

J.R

adio

anal

.N

ucl.

Che

m.,

Art

icle

s143,

307

~199

0!.

2 A.V

.Bal

uev,

S.G

.Kry

lov,

I.G

.Sug

lubo

va,a

ndA

.P.T

aran

ov,

Ves

t.Le

ning

rad.

Gos

ud.

Uni

v.,

Phy

s.C

hem

.22

,36

~198

4!.

3 H.

Irvi

ng,

and

D.

N.

Edg

ingt

on,

J.In

org.

Nuc

l.C

hem

.10

,30

6~1

959!

.

5.11

.U

rani

um„IV…

Oxa

late

5.11

.1.

Eva

luat

ion

ofth

eU

„C

2O4…

2¿H

2OS

yste

m

mpo

nent

s:E

valu

ator

:

Ura

nium

~IV

!bi

s~ox

alat

e!;U

~C2O

4) 2

;@2

847-

15-6#

Wat

er;

H 2O

;@77

32-1

8-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

611

37B

rno,

Cze

chR

epub

lic,

May

2000

Crit

ical

Eva

luat

ion:

The

only

exte

nsiv

est

udy

onth

issy

stem

has

been

carr

ied

out

byG

rinbe

rgan

dP

etrz

hak

1w

hom

easu

red

the

solu

bilit

yof

C2O

4!2•

6H2O

inw

ater

at29

8K

asa

func

tion

ofsp

ecifi

cac

tivity

ofth

esa

ltan

deq

uilib

ratio

ntim

eby

two

diffe

rent

equi

libra

tion

hniq

ues,

and

used

thre

edi

ffere

ntm

etho

dsfo

rth

ede

term

inat

ion

ofur

aniu

min

the

satu

rate

dso

lutio

ns.

The

yob

serv

edra

ther

larg

eat

ter

ofre

sults

,an

das

crib

edit

tolo

wdi

ssol

utio

nra

teof

the

salt

and

cons

eque

ntly

tosl

owat

tain

men

tof

equi

libriu

m.

Mor

eove

r,th

esu

ltsob

tain

edw

hen

uran

ium

was

dete

rmin

edby

copr

ecip

itatio

nw

ithLa

F3

~whi

chen

able

dth

emto

elim

inat

eth

ein

fluen

ceof

UO

221

oduc

edby

oxid

atio

nof

U~IV

!!w

ere

cons

iste

ntly

muc

hlo

wer

than

thos

eba

sed

onto

talu

rani

umco

ncen

trat

ion

inth

esa

tura

ted

solu

tions

.is

indi

cate

dth

atth

eso

lubi

lity

ofU~C

2O4!

2w

asra

ther

sens

itive

toox

idat

ion

ofU~IV

!by

trac

esof

oxyg

enin

solu

tions

whi

chco

uld

not

elim

inat

edev

enth

ough

the

mea

sure

men

tsw

ere

perf

orm

edin

anin

ert

atm

osph

ere.

The

diss

olut

ion

proc

ess

was

furt

her

com

plic

ated

byfa

ctth

atdu

ring

oxid

atio

nof

U~C2O

4!2

toU

O2C

2O4,

oxal

icac

idw

asre

leas

ed,

and

caus

edth

eso

lubi

lity

ofU

~C2O

4!2

furt

her

tore

ase.

Bec

ause

ofth

ese

proc

esse

s,th

eau

thor

sco

nsid

ered

the

U~C

2O4) 2

–H

2Osy

stem

tobe

ano

nequ

ilibr

ium

one.

As

the

mos

tre

liabl

elu

bilit

yva

lue

they

prop

osed

that

obta

ined

byth

eLa

F3

met

hod,

i.e.,

20–

25m

gU~C

2O4!

2•6H

2Ope

rdm

3 .T

akin

gth

eav

erag

eof

the

two

lues

,th

eev

alua

tor

obta

ined

the

solu

bilit

yof

U~C

2O4!

2in

wat

erat

298

Kas

4.33

102

5m

olkg

21 ,

whi

chis

sugg

este

dto

beus

edas

ata

tive

valu

e.It

isal

mos

tide

ntic

alw

ithth

atof

Zak

haro

vaan

dM

oskv

in2

who

,in

thei

rst

udy

ofth

ete

rnar

yU~C

2O4) 2

–H

Cl–

H2O

syst

em,

tain

edth

eso

lubi

lity

tobe

4.273

102

5m

olkg

21 .

The

seau

thor

s,ho

wev

er,

did

not

spec

ifyth

ete

mpe

ratu

reof

the

mea

sure

men

t,or

mm

ent

onth

eef

fect

ofth

eox

idat

ion

ofU~IV

!in

this

syst

em.

Orig

inal

ly,

Grin

berg

and

Pet

rzha

kre

port

edth

eso

lubi

lity

ofU

~C2O

4!2

inte

rto

be9.

7310

25

mol

kg2

1 .3In

thei

rm

ore

rece

ntst

udy1th

eyre

ject

edth

isva

lue

aser

rone

ousl

yhi

ghdu

eto

the

inte

rfer

ence

from

idat

ion

ofU~

IV!.

fere

nces

:

.A

.G

rinbe

rgan

dG

.I.

Pet

rzha

k,R

adio

khim

iya5,

319

~196

3!.

.A

.Z

akha

rova

and

A.

I.M

oskv

in,

Zh.

Neo

rg.

Khi

m.5,12

28~1

960!

.

.A

.G

rinbe

rgan

dG

.I.

Pet

rzha

k,Z

h.N

eorg

.K

him

.3,

204

~195

8!.



FIG

.12

.U

rani

um~V

I!di

oxoo

xala

te–

sodi

umox

alat

e–

wat

ersy

stem

.Le

gend

toth

eph

ase

diag

ram

:~A

!tw

o-ph

ase

regi

on;~B

!un

satu

rate

daq

ueou

s–

orga

nic

solu

tions

;~C

!sa

tura

ted

solu

tions

ineq

uilib

rium

with

UO 2~C

6H5O

3S! 2

and

UO 2

~C6H

5O3S

! 2•H

2O;

~D!

satu

rate

dso

lu-

tions

ineq

uilib

rium

with

UO 2

~C6H

5O3S

! 2;

~E!

satu

rate

dso

lutio

nsin

equi

libriu

mw

ithU

O 2~C

6H5O

3S! 2•H

2O.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Cal

cula

ted

amou

nts

ofth

esa

lt,tr

i-n-

buty

lpho

spha

tean

dw

ater

wer

eeq

uilib

rate

din

seal

edgl

ass

ampo

ules

prot

ecte

dfr

omlig

htin

ath

erm

osta

ted

bath

for

4da

ysw

hich

was

foun

dsu

ffici

ent

for

equi

libriu

mto

bere

ache

d.T

heph

ases

wer

eal

low

edto

sepa

rate

onst

andi

ngor

byce

ntrif

ugat

ion,

and

anal

yzed

for

the

cont

ent

ofur

aniu

man

dw

ater

bygr

avim

etric

~uns

peci

fied!

and

Fis

cher

met

hods

,re

spec

tivel

y.B

yan

alog

yto

othe

rau

thor

s’w

ork

the

com

pile

ras

sum

esth

atth

eeq

uilib

rium

solid

phas

esw

ere

iden

tified

by

UO

2~C

6H5O

3S! 2•H

2Ow

aspr

epar

edby

diss

olvi

ngam

orph

ous

UO

3in

aque

ous

solu

tions

ofbe

nzen

esul

foni

cac

id,

and

crys

talli

zing

the

salt.

Anh

ydro

ussa

ltw

asob

tain

edby

vacu

umde

hydr

atio

nof

the

hydr

ate

acco

rdin

gto

Ref

.2.

Tri-

n-bu

tylp

hosp

hate

was

purifi

edac

cord

ing

toR

ef.

3,an

dth

endi

still

edat

15m

mH

gpr

essu

re.

Fra

ctio

nbo

iling

at17

2–

175

°Cw

asco

llect

edfo

rus

e.

Est

imat

edE

rror

:

Co

~1!

~2!

U~

tec

sc re pr Th

be the

inc

so va ten

ob co wa

ox Re

1 A 2 F 3 A

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~IV

!bi

s~ox

alat

e!;U

~C2O

4) 2

;@2

847-

15-6#

Wat

er;

H 2O

;@77

32-1

8-5#

A.

A.

Grin

berg

and

G.

I.P

etrz

hak,

Rad

iokh

imiy

a,5,31

9–

29~1

963!

.

riabl

es:

Pre

pare

dby

:

K:

298

ecifi

cac

tivity

ofU~

C2O

4!2

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofU~

C2O

4!2

inw

ater

Isot

herm

alm

etho

d-m

odifi

catio

nA~s

eeM

etho

dse

ctio

n!

C2O

4!2•

6H2O

~g!a

U~C

2O4!

2•6H

2O~c

ount

sm

in21

mg2

1 !bE

quili

brat

ion

time

~h!

U~C

2O4!

2•6H

2O~m

gdm

23 !c

U~C

2O4!

2•6H

2O~m

gdm

23 !d

0.25

8.75

310

39

4421

0.30

5.92

310

39.

546

15

13.5

—24

1.00

5.92

310

30.

545

17

23.5

5622

7.20

310

39.

540

18

23.5

9825

5.5e

7118

9.5e

100

28

0.10

7.20

310

64.

025

14

7.0

4016

0.20

4.64

310

66

248

1644

13

2375

14

3068

15

3783

19

5097

18

8610

019

0.20

4.64

310

67

239

1130

9

1845

10

2254

15

2670

17

1.07

4.64

310

65.

554

7

11.5

7710

2410

113

5214

020

8718

931

122

238

32

170

274

32

a Am

ount

ofU~

C2O

4!2•

6H2O

used

inth

eex

perim

ent.

b Spe

cific

activ

ityof

U~C

2O4!

2•6H

2O.

c Obt

aine

dby

dire

ctaco

untin

g.d O

btai

ned

byco

prec

ipita

tion

with

LaF

3.e In

the

pres

ence

ofai

r.

Add

ition

alin

form

atio

n:A

nav

erag

eso

lubi

lity

valu

eof;

20m

gU~

C2O

4!2•

6H2O

/dm

3~;

3.83

102

5m

oldm

23;

com

pile

r!w

asgi

ven

byth

eau

thor

sba

sed

onth

eLa

F 3m

etho

dof

uran

ium

dete

rmin

atio

n.

602602 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~IV

!bi

s~ox

alat

e!;U

~C2O

4!2;

@284

7-15

-6#~2

!W

ater

;H 2

O;@

7732

-18-

5#A

.A

.G

rinbe

rg,

G.

I.P

etrz

hak,

and

L.I.

Evt

eev,

Zh.

Neo

rg.

Khi

m.

3,20

4–

11~1

958!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aT

heso

lubi

lity

inw

ater

ofU~

C2O

4!2•

6H2O

was

repo

rted

tobe

0.05

1g

salt/

kgH

2Oor

9.73

102

5m

olkg

21

at25

°C

Add

ition

alin

form

atio

n:T

hepH

ofth

esa

tura

ted

solu

tions

was

4.3

onav

erag

e,an

dth

em

olar

elec

tric

alco

nduc

tivity

varie

dbe

twee

n45

1an

d49

5V

21

cm2

2 .Fro

mth

isth

eau

thor

sco

nclu

ded

that

inth

esa

tura

ted

solu

tions

U~C

2O4!

2is

fully

diss

ocia

ted

acco

rdin

gto

the

equa

tion

U~C

2O4!

2~H

2O! n

12

H2O�

U~C

2O4!

~H2O

) n1

22

11

C2O

422

whi

leth

eU~

C2O

4!~H

2O! n

12

21

ion

diss

ocia

ted

byab

out

70%

acco

rdin

gto

the

reac

tion

U~C

2O4!

~H2O

! n1

22

1�

U~C

2O4!

~H2O

! n1

1~O

H!1

1H

1

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Not

hing

spec

ified

inth

edo

cum

ent

com

pile

d.B

yan

alog

yto

am

ore

rece

ntau

thor

s’pa

per

1it

can

beas

sum

edth

atis

othe

rmal

met

hod

was

used

,th

atth

eso

lutio

nsw

ere

brou

ght

tosa

tura

tion

for

6–

8h

unde

rH 2

atm

osph

ere,

and

that

oxal

ate

conc

entr

atio

nin

the

satu

rate

dso

lutio

nsw

asde

term

ined

titrim

etric

ally

with

KM

nO4

solu

tion.

Not

hing

spec

ified

.

Est

imat

edE

rror

:P

reci

sion

ofte

mpe

ratu

reor

solu

bilit

ym

easu

rem

entn

otre

port

ed.

Ref

eren

ces:

1 A.A

.Grin

berg

and

G.I

.Pet

rzha

k,R

adio

khim

iya5,31

9~1

963!

.

Co

~1!

~2!

Va

T/

Sp

U~


of

Sou

rce

and

Pur

ityof

Mat

eria

ls:

Est

imat

edE

rror

:

U~C

2O4!

2•6H

2Ola

bele

dw

ith23

3 Uw

aspr

epar

edby

redu

ctio

nof

UO

221

with

rong

alite

inac

idic

solu

tions

.H

ydro

gen

gas

was

free

dfr

omox

ygen

bypa

ssin

git

over

palla

dium

-tre

ated

asbe

stos

.

Tem

pera

ture

:pr

ecis

ion6

0.1

Kfo

rm

etho

dA

,60.

3K

for

met

hod

B~a

utho

rs!.

Ref

eren

ces:

1 A.

A.

Grin

berg

,E

.I.

Pet

rzha

k,an

dL.

I.E

vtee

v,Z

h.N

eorg

.K

him

.3,

204

~195

8!.

2 A.

A.

Grin

berg

,L.

E.

Nik

olsk

aya,

G.

I.P

etrz

hak,

V.

I.S

pits

yn,

and

F.

M.

Fili

nov,

Zh.

Ana

l.K

him

.12,

92~1

957!

.

5.11

.2.

Eva

luat

ion

ofth

eU

„C

2O4…

2¿H

Cl¿

H2O

Sys

tem

mpo

nent

s:E

valu

ator

:

Ura

nium

~IV

!bi

s~ox

alat

e!;U

~C2O

4!2;

@284

7-15

-6#H

ydro

gen

chlo

ride;

HC

l;@76

47-0

1-0#

Wat

er;

H 2O

;@7

732-

18-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

611

37B

rno,

Cze

chR

epub

lic,

May

2000

Crit

ical

Eva

luat

ion:

The

solu

bilit

yof

U~C

2O4!

2in

aque

ous

HC

lsol

utio

nsw

asm

easu

red

asa

func

tion

ofH

Clc

once

ntra

tion

intw

odo

cum

ents

.1,

2In

the

rkof

Dor

ough

,1th

em

easu

rem

ents

wer

eca

rrie

dou

tat

298

K,

and

care

was

take

nto

prev

ent

uran

ium

~IV

!fr

omox

idat

ion

byox

ygen

solv

edin

the

solu

tions

mea

sure

d.N

osu

chpr

ecau

tions

wer

eta

ken

inth

ew

ork

ofZ

akha

rova

and

Mos

kvin

2w

here

,be

side

sth

is,

pera

ture

was

not

spec

ified

.In

spite

ofth

is,

both

sets

ofda

tafit

onon

ecu

rve

whe

npl

otte

dgr

aphi

cally

.O

win

gto

the

less

defin

ednd

ition

sin

Ref

.2,

how

ever

,th

eev

alua

tor

sugg

ests

the

data

ofD

orou

gh1

begi

ven

pref

eren

ce.

fere

nces

:

.D

.D

orou

gh,

U.

S.

At.

Ene

rgy

Com

m.

Rep

ort

TID

5290

,B

ook

2,19

58,

p.53

5.

.A

.Z

akha

rova

and

A.

I.M

oskv

in,

Zh.

Neo

rg.

Khi

m.5,12

28~1

960!

.



Isot

herm

alm

etho

d-m

odifi

catio

nB

U~C

2O4!

2•6H

2O~c

ount

sm

in21

mg2

1 !aE

quili

brat

ion

time

~h!

U~C

2O4!

2•6H

2O~m

gdm

23 !b

U~C

2O4!

2•6H

2O~m

gdm

23 !c

U~C

2O4!

2•6H

2O~m

gdm

23 !d

1.57

310

3e

686

94—

1.19

310

3e

3593

9725

1110

9—

—

2417

218

8—

3018

318

9—

100

182

179

32

2.89

310

3f

923

25—

2.55

310

3f

1474

71—

2069

65—

3472

7326

180

113

9222

200

109

100

24

200

111

103

27

4.64

310

3f

19—

9717

31—

100

16

157

—10

017

a Spe

cific

activ

ityof

U~C

2O4!

2•6H

2Ous

edin

the

expe

rimen

t.b O

btai

ned

byel

ectr

opla

ting.

c Obt

aine

dby

dire

ctaco

untin

g.d O

btai

ned

byco

prec

ipita

tion

onto

LaF

3.e M

easu

rem

ents

carr

ied

out

with

finel

ygr

ound

U~C

2O4!

2•6H

2O.

f Coa

rse

crys

talli

neU~C

2O4!

2•6H

2Opl

aced

inbo

iling

wat

eran

dco

oled

ina

stre

amof

nitr

ogen

gas.

Add

ition

alin

form

atio

n:A

nav

erag

eso

lubi

lity

valu

eof;

25m

gdm

23

U~C

2O4!

2•6H

2O~;

4.83

102

5m

oldm

23;

com

pile

r!w

asgi

ven

byth

eau

thor

sba

sed

onth

eLa

F 3m

etho

dof

uran

ium

dete

rmin

atio

n.T

heau

thor

sst

ate

that

the

grea

tsc

atte

rof

solu

bilit

yva

lues

obta

ined

byth

eth

ree

met

hods

was

due

toth

elo

wdi

ssol

utio

nra

teU

~C2O

4!2•

6H2O

,an

dco

nseq

uent

lyto

slow

atta

inm

ent

ofeq

uilib

rium

,an

d—as

indi

cate

dby

the

diffe

renc

ein

the

figur

esob

tain

edby

diffe

rent

anal

ytic

alm

etho

ds—

also

bypa

rtia

loxi

datio

nof

uran

ium

~IV

!.T

hela

tter

effe

ctw

asca

used

bytr

aces

ofO

2no

trem

oved

from

the

syst

em,

and

part

ially

byth

epr

oduc

tsof

radi

olys

isof

wat

er.

The

proc

ess

ofU

~C2O

4!2•

6H2O

diss

olut

ion

was

furt

her

com

plic

ated

byth

efa

ctth

atdu

ring

itsox

idat

ion

toU

O 2C2O

4,ox

alic

acid

was

rele

ased

whi

chin

crea

sed

the

solu

bilit

yof

U~C

2O4!

2an

dat

the

sam

etim

ehi

nder

edits

oxid

atio

n.B

ecau

seof

thes

epr

oces

ses,

the

auth

ors

char

acte

rized

the

U~C

2O4) 2

–H

2Osy

stem

asa

none

quili

briu

mon

e,an

dco

nclu

ded

the

solu

bilit

yof

U~C2O

4!2

inw

ater

give

nby

them

ina

prev

ious

pape

r1

tobe

erro

neou

s.

Aux

iliar

yIn

form

atio

n

Co

~1!

~2!

~3!

wo

dis

tem

co Re

1 G 2 F

J

ofox

alic

acid

,Ka1

55.

9310

22

and

Ka2

56.

4310

25

~sou

rce

not

give

n!.

Add

ition

alin

form

atio

n:B

ased

onth

eva

lue

ofth

eco

nsta

ntK,

the

auth

orco

nclu

ded

that

near

lyco

mpl

ete

hydr

olys

isof

U~I

V!

toU

~OH

!31to

okpl

ace

inH

Cl

solu

tions

satu

rate

dw

ithU~C

2O4!

2.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.G

reat

care

was

take

nto

prev

ent

idat

ion

ofU~

IV!

oxal

ate

sinc

eU

O 2C2O

4is

rela

tivel

yqu

itelu

ble.

Prio

rto

solu

bilit

yde

term

inat

ion,

the

solu

tions

wer

eile

dto

rem

ove

diss

olve

dO 2an

dth

enke

ptun

der

N 2os

pher

e.A

sam

ple

ofU

O 221-f

ree

U~IV

!ox

alat

ew

assh

eda

num

ber

oftim

esw

ithth

eso

lutio

nin

whi

chth

elu

bilit

yw

asto

bem

easu

red

and

shak

enw

ithth

esa

me

lutio

nin

agl

ass-

stop

pere

dfla

skun

der

N2

atm

osph

ere

ina

rmos

tate

dba

th.

Afte

r24

hth

esa

tura

ted

solu

tion

was

thdr

awn

thro

ugh

asu

ctio

nfil

ter

appa

ratu

s,an

dan

alyz

edfo

ran

ium

cont

ent

bya

coun

ting.

Tw

om

etho

dsw

ere

used

toep

are

the

sam

ples

for

coun

ting.

Inth

eel

ectr

opla

ting

met

hod,

sam

ples

ofth

esa

tura

ted

solu

tions

wer

eco

nver

ted

to

2SO

4by

fum

ing

with

conc

entr

ated

H 2SO

4,di

lute

dw

ithte

r,an

del

ectr

odep

osite

don

apl

atin

umca

thod

eas

UF

4fr

omdi

umflu

orid

eso

lutio

n.T

heca

thod

ew

asth

enig

nite

dan

da

unte

d.In

the

filte

rpa

per

met

hod,

the

sam

ples

ofth

etu

rate

dso

lutio

nsw

ere

conv

erte

dto

UO

2SO

4,an

aliq

uot

was

ced

ona

filte

rpa

per,

whi

chw

asth

enm

ount

edon

aco

pper

k,dr

ied,

and

coun

ted.

No

diffe

renc

esw

ere

note

insa

mpl

esep

ared

byap

proa

chin

geq

uilib

rium

from

abov

ean

dbe

low

equi

libriu

mte

mpe

ratu

re.

All

mea

sure

men

tsw

ere

mad

eon

C2O

4!2

sam

ples

3da

ysol

d,si

nce

fres

hly

prec

ipita

ted

C2O

4!2

was

repo

rted

toha

vea

cons

ider

ably

high

erlu

bilit

y.2

U~C

2O4!

2•6H

2Ow

aspr

epar

edfr

omU

O 3.T

hela

tter

was

diss

olve

din

HC

l~1:1

!,an

dth

ere

sulti

ngso

lutio

nof

UO 2C

l 2w

asre

duce

del

ectr

olyt

ical

lyto

U~IV

!,w

hich

was

prec

ipita

ted

with

oxal

icac

id.

The

prec

ipita

tew

asfil

tere

d,w

ashe

dw

ithbo

iled

3m

oldm

23

HC

l,an

dsh

aken

with

oxyg

en-f

ree

3m

oldm2

3H

Cl

vigo

rous

lyfo

r3

hin

N2

atm

osph

ere.

The

last

oper

atio

nw

asre

peat

edth

ree

times

.S

ourc

ean

dpu

rity

ofch

emic

als

used

not

spec

ified

.

Est

imat

edE

rror

:U

rani

umco

ncen

trat

ion:

stan

dard

devi

atio

nof

the

mea

n5

1.1%

–6

%~a

utho

r!.

Ref

eren

ces:

1 G.

N.

Lew

isan

dM

.R

anda

ll,Th

erm

od

yna

mic

s~McG

raw

–H

ill,

New

Yor

k,19

23!,

p.33

6.2 E

.L.

Wag

ner,

The

Sol

ubili

tyan

dS

olub

ility

Pro

duct

ofU

~IV

!O

xala

te,

Rep

ort

RL-

4.6.

321.

604604 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~IV

!bi

s~ox

alat

e!;U

~C2O

4!2;

@284

7-15

-6#~2

!H

ydro

gen

chlo

ride;

HC

l;@76

47-0

1-0#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

G.

D.

Dor

ough

,U

.S

.A

tE

nerg

yC

omm

.,T

ID52

90,

Boo

k2,

1958

,pp

.53

5–

42.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8c 2

/mol

dm2

3 :0.

118

–6.

18J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofU~

C2O

4!2•

6H2O

inH

Cls

olut

ions

a

HC

l(c

2/

mol

dm2

3 )U

~mg

dm2

3 !

U~C

2O4!

2f

(104

c 1/

mol

dm2

3 )

Kg

(1022

mol

4dm

212

)

HC

l(c

2/

mol

dm2

3 )U

~mg

dm2

3 !

U~C

2O4!

2f

(104

c 1/

mol

dm2

3 )

Kg

(1022

mol

4dm

212

)

0.11

85.

15c

3.62

142c

5.51

c14

2c

5.33

b0.

224

2.87

142b

5.97

0.57

5

1.04

928

.9c6.

0153

6c

28.3

c46

2c

28.6

b1.

201.

2352

3d

1.18

37.3c

465d

38.3

b51

8e

37.8

b1.

591.

6545

8e

3.09

99.3c

494b

20.8

0.68

107c

6.18

515d

112d

461d

101d

488b

20.5

0.50

8

105b

4.41

0.56

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.b A

vera

geva

lue~

auth

or!.

c Det

erm

ined

bypl

atin

g.d D

eter

min

edby

the

filte

rpa

per

met

hod.

e Det

erm

ined

byan

unsp

ecifi

edvo

lum

etric

met

hod.

f Cal

cula

ted

byco

mpi

ler.

g Equ

ilibr

ium

cons

tant

for

the

reac

tion

U~C2O

4!2~

H2O

! ~s!�

U~O

H!31

12C

2O422

1H

1,

calc

ulat

edby

the

auth

orasK

5@U

~OH

!31#

3@C

2O422

#2@H

1#

byus

ing

mea

nio

nic

activ

ityco

effic

ient

sof

HC

las

inte

rpol

ated

from

the

data

inR

ef.

1,an

dth

edi

ssoc

iatio

nco

nsta

ntsMe

Iso

ox so bo atm

wa

so so the

wi

ur pr the

UO

wa

so co sa pla

dis

pr the

U~

U~

so


Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Sol

utio

nsco

ntai

ning

exce

ssso

lidw

ere

equi

libra

ted

for

4–

6h

whi

chw

assu

ffici

ent

for

equi

libriu

mto

bere

ache

d.U

rani

umin

the

satu

rate

dso

lutio

nsw

asde

term

ined

bya

coun

ting.

U~C

2O4!

2•6H

2Ow

aspr

epar

edfr

om23

3 U-la

bele

dU

O 2~N

O3!

2

solu

tion

byre

duct

ion

with

rong

alite

.U~IV

!ox

alat

ew

asdi

ssol

ved

in~N

H4!

2C2O

4so

lutio

n,th

eso

lutio

nw

asce

ntrif

uged

,an

dth

eox

alat

oco

mpl

exde

com

pose

dw

ithH

Cl.

U~C

2O4!

2•6H

2Opr

ecip

itate

dw

asce

ntrif

uged

,w

ashe

dto

rem

ove

exce

ssox

alic

acid

,an

dai

rdr

ied.

Sou

rce

and

purit

yof

chem

ical

sno

tre

port

ed.

Est

imat

edE

rror

:a

coun

ting:

prec

isio

n65%

~aut

hors!

.

Ref

eren

ces:

1 L.E

.D

rabk

ina,

A.

I.M

oskv

in,

and

A.

D.

Gel

man

,Z

h.N

eorg

.K

him

.3,1

934~

1958

!.2 K

.A.K

raus

and

F.N

elso

n,J.

Am

.Che

m.

Soc

.72,

3901

~195

0!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~IV

!bi

s~ox

alat

e!;U

~C2O

4!2;

@284

7-15

-6#S

ulfu

ricac

id;

H 2S

O4;

@766

4-93

-9#W

ater

;H 2

O;

@773

2-18

-5#

G.

D.

Dor

ough

,U

.S

.A

tE

nerg

yC

omm

.,T

ID52

90,

Boo

k2,

1958

,pp

.53

5–

542.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

dm2

3 :0.

515

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofU~

C2O

4!2•

6H2O

in0.

515

mol

dm2

3H

2SO

4so

lutio

na

H2S

O4

(c2

/mol

dm2

3 )U

~mg

dm2

3 !U

~C2O

4!2c

(104

c 1/m

oldm

23 )

0.51

516

0

174

167b

7.02

quili

briu

mso

lidph

ases

wer

eno

tin

vest

igat

ed.

vera

geva

lue~

auth

or!.

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.G

reat

care

was

take

nto

prev

ent

idat

ion

ofU~

IV!

oxal

ate

sinc

eU

O 2C2O

4is

rela

tivel

yqu

itelu

ble.

Prio

rto

solu

bilit

yde

term

inat

ion,

the

solu

tions

wer

eile

dto

rem

ove

diss

olve

dO 2an

dth

enke

ptun

der

N 2os

pher

e.A

sam

ple

ofU

O 221-f

ree

U~IV

!ox

alat

ew

assh

eda

num

ber

oftim

esw

ithth

eso

lutio

nin

whi

chth

elu

bilit

yw

asto

bem

easu

red

and

shak

enw

ithth

esa

me

lutio

nin

agl

ass-

stop

pere

dfla

skun

der

N2

atm

osph

ere

ina

rmos

tate

dba

th.

Afte

r24

hth

esa

tura

ted

solu

tion

was

thdr

awn

thro

ugh

asu

ctio

nfil

ter

appa

ratu

s,an

dan

alyz

edfo

ran

ium

cont

ent

bya

coun

ting.

Sam

ples

ofth

esa

tura

ted

lutio

nsw

ere

conv

erte

dto

UO 2S

O4

byfu

min

gw

ithnc

entr

ated

H 2SO

4,di

lute

dw

ithw

ater

,an

del

ectr

odep

osite

da

plat

inum

cath

ode

asU

F4

from

sodi

umflu

orid

eso

lutio

n.T

heca

thod

ew

asth

enig

nite

dan

da

coun

ted.

All

mea

sure

men

tsw

ere

mad

eon

U~C

2O4!

2sa

mpl

es3

days

old,

sinc

efr

eshl

ypr

ecip

itate

dU~C

2O4!

2ha

sa

cons

ider

ably

high

erso

lubi

lity.

1

U~C

2O4!

2•6H

2Ow

aspr

epar

edfr

omU

O 3.T

hela

tter

was

diss

olve

din

HC

l~1:1

!,an

dth

ere

sulti

ngso

lutio

nof

UO 2C

l 2w

asre

duce

del

ectr

olyt

ical

lyto

U~IV

!,w

hich

was

prec

ipita

ted

with

oxal

icac

id.

The

prec

ipita

tew

asfil

tere

d,w

ashe

dw

ithbo

iled

3m

oldm

23

HC

l,an

dsh

aken

with

oxyg

en-f

ree

3m

oldm2

3H

Cl

vigo

rous

lyfo

r3

hin

N2

atm

osph

ere.

The

last

oper

atio

nw

asre

peat

edth

ree

times

.S

ourc

ean

dpu

rity

ofch

emic

als

used

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Ura

nium

conc

entr

atio

n:st

anda

rdde

viat

ion

ofth

em

ean

54

%~a

utho

r!.

Ref

eren

ces:

1 E.

L.W

agne

r,T

heS

olub

ility

and

Sol

ubili

tyP

rodu

ctof

U~I

V!

Oxa

late

,R

epor

tR

L-4.

6.32

1.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~IV

!bi

s~ox

alat

e!;U

~C2O

4!2;

@284

7-15

-6#~2

!H

ydro

gen

chlo

ride;

HC

l;@76

47-0

1-0#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

F.

A.

Zak

haro

vaan

dA

.I.

Mos

kvin

,Z

h.N

eorg

.K

him

.5,

1228

–33

;R

uss.

J.In

org.

Che

m.5,

592

–5

~196

0!.

Var

iabl

es:

Pre

pare

dby

:

c 2/m

oldm

23 :

0–

3.0

J.H

a´ la

Exp

erim

enta

lDat

a

Sol

ubili

tyat

°Cof

U~C

2O4!

2•6H

2Oin

HC

lsol

utio

nsa

HC

l(c

2/m

oldm

23 )

U~C

2O4!

2•6H

2O(1

02g

dm2

3 )bU

~C2O

4!2•

6H2O

(104

c 1/m

oldm

23 )c

Ksp

d

(1022

mol

3dm

29 )

Ksp

e

(1025

mol

3dm

29 )

02.

230.

427

——

0.1

1.26

0.24

1—

—

0.3

1.71

0.32

86.

62.

1

0.5

2.19

0.41

92.

80.

5

1.0

5.00

0.95

83.

20.

8

2.0

14.0

02.

86—

—

3.0

23.5

64.

51—

—

4.36

1.6f

1.16

0.7f

a Mea

sure

men

tsw

ere

cond

ucte

dat

unsp

ecifi

edte

mpe

ratu

re.

Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.b A

vera

geva

lue

ofth

ree

mea

sure

men

ts.

c Cal

cula

ted

byco

mpi

ler.

d Cal

cula

ted

byau

thor

sasK

sp5

@U41

#@C

2O422

#2by

usin

gth

eU41

and

C 2O

422co

ncen

trat

ions

obta

ined

from

equi

libriu

mco

nsta

nts

for

the

reac

tions

U~C

2O4!

212H

1�

U~C

2O4!

211

C2H

2O4,

and

U~C

2O4!

214H

1�

U41

12C

2H2O

4de

term

ined

from

the

solu

bilit

yda

ta,

and

the

diss

ocia

tion

cons

tant

sof

oxal

icac

idta

ken

from

Ref

.1.

Hyd

roly

sis

ofU

41an

dth

efo

rmat

ion

ofth

eU

Cl

31co

mpl

exw

ere

cons

ider

edus

ing

the

appr

opria

teda

tafr

omR

ef.

2.e S

ourc

eof

activ

ityco

effic

ient

sno

tre

port

ed.

f Ave

rage

valu

e~au

thor

s!.

Add

ition

alin

form

atio

n:In

anot

her

appr

oach

,th

eeq

uilib

rium

cons

tant

for

the

reac

tion

U~C

2O4!

214H

1�

U41

12C

2H2O

4w

asob

tain

edas

K5

1.5

310

211

mol

22

dm6 ,

and

from

this

the

solu

bilit

ypr

oduc

tof

U~C2O

4!2

was

obta

ined

asK

s05

K(K

a1K

a2)2

57.

0310

22m

ol3

dm2

9w

ithdi

ssoc

iatio

nco

nsta

nts

ofox

alic

acid

take

nfr

omR

ef.

1.

Aux

iliar

yIn

form

atio

n

Co

~1!

~2!

~3!

Va

T/

c 2 a E b A c C Me

Iso

ox so bo atm

wa

so so the

wi

ur so co on

J

for

uran

ium

cont

ent

eith

erph

otom

etric

ally

with

arse

nazo

IIIin

4m

oldm

231

or,

athi

gher

uran

ium

conc

entr

atio

ns,

titrim

etric

ally

with

stan

dard

KM

nO4

solu

tion.

anal

yzed

grav

imet

rical

lyfo

rur

aniu

m~a

sU 3

O8!

,an

dtit

rimet

rical

lyfo

rox

alat

eco

nten

t.It

cont

aine

d2%

free

oxal

icac

id.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~aut

hor!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 D.

I.R

yabc

hiko

van

dM

.M

.S

enya

vina

,E

ds.,An

aly

tica

lC

he

mis

try

of

Ura

niu

m~in

Rus

sian

!~A

cad.

Sci

.U

SS

R,

1962!

,p.

134.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~IV

!bi

s~ox

alat

e!;U

~C2O

4) 2

;@2

847-

15-6#

Sod

ium

oxal

ate;

C 2O4N

a 2;

@62-

76-0

#W

ater

;H 2

O;@

7732

-18-

5#

N.

M.

Nik

olae

va,

Izv.

Sib

irsk.

Otd

el.

Aka

d.N

auk

SS

SR

,S

er.

Khi

m.

Nau

k.6,

64–

9~1

979!

.

riabl

es:

Pre

pare

dby

:

K:2

98–

363

/mol

dm2

3 :0.0

1J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyin

0.01

mol

dm2

3C

2O4N

a 2so

lutio

nsof

U~C

2O4!

2•6H

2Oas

afu

nctio

nof

tem

pera

turea

Tem

pera

ture

~°C

!U

~C2O

4!2

(103

c 1/m

oldm

23 )

255.

52

405.

95

506.

21

606.

51

706.

68

807.

25

907.

71

quili

briu

mso

lidph

ases

wer

eno

tin

vest

igat

ed.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

xces

sU

~C2O

4!2•

6H2O

was

uilib

rate

dw

ith50

ml0

.01

mol

dm23

C2O

4Na 2

solu

tion

ina

rmos

tate

dte

flon

vess

el.

Agi

tatio

nof

the

mix

ture

was

rrie

dou

tby

mea

nsof

ast

ream

ofar

gon

gas.

Equ

ilibr

ium

sre

ache

dw

ithin

4–

5h.

Sat

urat

edso

lutio

nsw

ere

anal

yzed

uran

ium

cont

ent

eith

erph

otom

etric

ally

with

arse

nazo

IIIin

mol

dm2

31or

,at

high

erur

aniu

mco

ncen

trat

ions

,im

etric

ally

with

stan

dard

KM

nO4

solu

tion.

U~C

2O4!

2•6H

2Ow

aspr

epar

edby

addi

ngho

t~9

0°C

!so

lutio

nof

oxal

icac

idsa

tura

ted

atro

omte

mpe

ratu

reto

abo

iling

solu

tion

ofU

~IV

!ob

tain

edby

elec

trol

ytic

redu

ctio

nof

UO 2C

l 2.

Pal

egr

een

hexa

hydr

ate

was

kept

onw

ater

bath

for

30m

in,

filte

red,

and

was

hed

thre

eor

four

times

with

hot

wat

er.

The

prod

uct

was

anal

yzed

grav

imet

rical

lyfo

rur

aniu

m~a

sU 3

O8!

,an

dtit

rimet

rical

lyfo

rox

alat

eco

nten

t.It

cont

aine

d2%

free

oxal

icac

id.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~aut

hor!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 D.

I.R

yabc

hiko

van

dM

.M

.S

enya

vina

,E

ds.,An

aly

tica

lC

he

mis

try

of

Ura

niu

m~in

Rus

sian

!~A

cad.

Sci

.U

SS

R,

1962!

,p.

134.

606606 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~IV

!bi

s~ox

alat

e!;U

~C2O

4!2;

@284

7-15

-6#~2

!P

erch

loric

acid

;H

ClO 4

;@7

601-

90-3#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

N.

M.

Nik

olae

va,

Izv.

Sib

irsk.

Otd

el.

Aka

d.N

auk

SS

SR

,S

er.

Khi

m.

Nau

k.6,

64–

9~1

979!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8–

363

c 2/m

oldm

23 :

0.1

and

0.73

5J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyin

HC

lsol

utio

nsof

U~C

2O4!

2•6H

2Oas

afu

nctio

nof

tem

pera

turea

HC

lO4

(c2

/mol

dm2

3 )T

empe

ratu

re~°

C!

U(1

05c 1

/mol

dm2

3 )H

ClO

4

(c2

/mol

dm2

3 )T

empe

ratu

re~°

C!

U(1

05c 1

/mol

dm2

3 )

0.10

0525

1.5

0.73

525

3.75

401.

840

6.35

502.

050

9.20

603.

460

15.2

704.

670

21.6

806.

880

30.8

9010

.790

40.6

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.

Add

ition

alIn

form

atio

n:T

heau

thor

desc

ribed

the

solu

bilit

yof

U~C2O

4!2•

6H2O

in0.

1m

oldm

23

HC

lby

the

reac

tion

U~C

2O4!

2•6H

2O~s

!�U

~C2O

4!2~

aq!

In0.

735

mol

dm2

3H

Clt

hefo

llow

ing

reac

tion

was

repo

rted

tota

kepl

ace

inth

eso

lutio

n:

U~C

2O4!

2~aq

!12H

1�

U~C

2O4!

211

H2C

2O4

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

U~C

2O4!

2•6H

2Ow

aseq

uilib

rate

dw

ith50

mL

solu

tion

ofth

ede

sire

dco

mpo

sitio

nin

ath

erm

osta

ted

teflo

nve

ssel

.A

gita

tion

ofth

em

ixtu

rew

asca

rrie

dou

tby

mea

nsof

ast

ream

ofar

gon

gas.

Equ

ilibr

ium

was

reac

hed

with

in4

–5

h.S

atur

ated

solu

tions

wer

ean

alyz

ed

U~C

2O4!

2•6H

2Ow

aspr

epar

edby

addi

ngho

t~9

0°C

!so

lutio

nof

oxal

icac

idsa

tura

ted

atro

omte

mpe

ratu

reto

abo

iling

solu

tion

ofU

~IV

!ob

tain

edby

elec

trol

ytic

redu

ctio

nof

UO 2C

l 2.

Pal

egr

een

hexa

hydr

ate

was

kept

onw

ater

bath

for

30m

in,

filte

red,

and

was

hed

thre

eor

four

times

with

hot

wat

er.

The

prod

uct

was

Co

~1!

~2!

~3!

Va

T/

c 2 a E Me

Iso

eq the

ca wa

for

4 titr


189

190

E

194

190

P

0.75

202

214

216

221

218

215

218

225

201

204

D4.

09

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.b ~D

!di

rect

aco

untin

g;~E

!a

coun

ting

ofel

ectr

odep

osite

dur

aniu

m;

~P!

prec

ipita

tion

ofU~

IV!

with

La~I

II!.

c Cal

cula

ted

byco

mpi

ler

byus

ing

the

aver

age

valu

eof

auth

ors’

data

ofur

aniu

mco

ncen

trat

ion

inth

esa

tura

ted

solu

tions

.d T

his

valu

ew

asno

tco

nsid

ered

whe

nta

king

the

aver

age

valu

e.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

was

used

.F

irst,

the

usua

lapp

roac

hw

asd

inw

hich

exce

ssU~C

2O4!

2•6H

2Ow

asst

irred

with

lutio

nsof

oxal

icac

idin

ath

erm

osta

ted

vess

elfo

r8

–10

htil

equi

libriu

mw

asre

ache

d.T

opr

even

tox

idat

ion

ofan

ium~

IV!

byO

2du

ring

the

satu

ratio

npr

oces

s,ct

roly

tical

lypr

oduc

edH 2

was

bubb

led

thro

ugh

the

solu

tion.

mpl

esof

the

satu

rate

dso

lutio

nsw

ere

take

nw

itha

pipe

tteth

aco

tton

wad

anda

coun

ted

ona

plat

inum

targ

et.

Whe

nh

oxal

icac

idco

ncen

trat

ion

was

pres

ent,

the

sam

ples

wer

et

evap

orat

edan

dig

nite

din

apo

rcel

ain

cruc

ible

tore

mov

eal

icac

id,

the

dry

resi

due

was

then

diss

olve

din

mol

dm2

3H

NO

3,an

dm

ount

edon

toa

plat

inum

targ

et.

lubi

lity

data

soob

tain

edw

ere

illre

prod

ucib

le,

fluct

uatin

gth

inup

to30

%–

50%

beca

use

oftu

rbid

ityin

som

esa

tura

ted

lutio

ns,

whi

chco

uld

not

bere

mov

edby

filtr

atio

n.T

helo

win

gm

odifi

catio

nof

the

met

hod

yiel

ded

good

resu

lts.

–40

mg

ofU~

C2O

4!2•

6H2O

and

aso

lutio

nof

oxal

icac

idre

plac

edin

ate

sttu

be,

and

ast

ream

ofN

2w

aspa

ssed

ough

for

5–

10m

in.

With

out

inte

rrup

ting

the

flow

ofga

sth

et

tube

was

seal

ed,

and

then

agita

ted

for

30–

360

hin

an-t

herm

osta

ted

appa

ratu

s.T

hree

sam

ples

for

uran

ium

term

inat

ion

wer

eta

ken

from

each

test

tube

,an

dur

aniu

ms

dete

rmin

edby

diffe

rent

met

hods

inea

chon

e:~i

!by

dire

ctco

untin

gon

apl

atin

umta

rget

eith

erw

ithor

with

out

oxal

icid

rem

oval

,~ii!

aco

untin

gof

uran

ium

depo

site

dct

roly

tical

lyon

plat

inum

from

HN

O 3so

lutio

nsat

pH3

with

rren

tde

nsity

of0.

5A

cm2

2 ,~ii

i!by

copr

ecip

itatio

nof

aniu

m~IV

!w

ithLa

F 3~0

.5m

gLa

~III

!us

ed!.

The

last

met

hod

deit

poss

ible

toju

dge

the

chan

gein

vale

ncy

ofur

aniu

mrin

gth

epr

oces

sof

satu

ratio

n.S

ince

ityi

elde

dso

lubi

lity

taco

nsis

tent

with

the

othe

rtw

om

etho

ds,

the

auth

ors

nclu

ded

that

oxid

atio

nof

U~C2O

4!2

did

not

take

plac

ein

alic

acid

solu

tions

.

U~C

2O4!

2•6H

2Ola

bele

dw

ith23

3 Uw

aspr

epar

edby

redu

ctio

nof

UO

221w

ithro

ngal

ite1

inac

idic

solu

tions

.H 2

and

N 2ga

ses

wer

efr

eed

from

oxyg

enby

pass

ing

them

over

palla

dium

-tre

ated

asbe

stos

orth

roug

hal

kalin

eso

lutio

nof

pyro

gallo

l,re

spec

tivel

y.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

3K

for

mea

sure

men

tsin

seal

edte

sttu

bes

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.

A.

Grin

berg

,L.

E.

Nik

olsk

aya,

G.

I.P

etrz

hak,

V.

I.S

pits

yn,

and

F.

M.

Fili

nov,

Zh.

Ana

l.K

him

.12,

92~1

957!

.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~IV

!bi

s~ox

alat

e!;U

~C2O

4!2;

@284

7-15

-6#~2

!O

xalic

acid

;C 2

O4H

2;@1

44-6

2-7#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

A.

A.

Grin

berg

and

G.

I.P

etrz

hak,

Rad

iokh

imiy

a5,31

9–

29~1

963!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:298

c 2/m

oldm

23 :0

.000

4–

0.75

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofU~

C2O

4!2

inox

alic

acid

solu

tionsa

C2O

4H2

(c2

/mol

dm2

3 )aU

~C2O

4!2•

6H2O

~mg

dm2

3 !M

etho

dof

U~IV

!de

term

inat

ionb

U~C

2O4!

2

(104

c 1/m

oldm

23 )c

0.00

0429

39D

0.66

1

3935

E

3332

P

0.00

0538

4136

3543

4443

4346

4245

39D

0.77

9

40E

35P

0.00

553

4952

5458

5660

5761

60E

1.07

0.04

267

7266

D1.

36

7171

71E

6977

73P

0.05

8480

8181

8891

8789

8583

7476

D1.

60

8591

E

7678

P

0.12

511

611

411

811

611

411

511

7D

2.22

0.21

140

D2.

76

141

E

152

P

0.25

154

151

149

145

151

154

142

D2.

95

156

171

161

E

156

156

154

P

0.33

516

716

216

6D

3.16

0.50

201

190

122d

187

176

181

172

181

183

D3.

57

Me

Iso

trie

so un ur ele

Sa

wi

hig

firs

ox 1.5

So

wi

so fol

20 we

thr

tes

air

de wa

a ac ele

cu ur ma

du da co ox

J

was

hed

anu

mbe

rof

times

with

the

solu

tion

inw

hich

the

solu

bilit

yw

asto

bem

easu

red

and

shak

enw

ithth

esa

me

solu

tion

ina

glas

s-st

oppe

red

flask

unde

rN

2at

mos

pher

ein

ath

erm

osta

ted

bath

.A

fter

24h

the

satu

rate

dso

lutio

nw

asw

ithdr

awn

thro

ugh

asu

ctio

nfil

ter

appa

ratu

s,an

dan

alyz

edfo

rur

aniu

mco

nten

t.S

ampl

esof

the

satu

rate

dso

lutio

nsw

ere

conv

erte

dto

UO 2

SO

4by

fum

ing

with

conc

entr

ated

H 2SO

4,di

lute

dw

ithw

ater

,an

del

ectr

odep

osite

don

apl

atin

umca

thod

eas

UF 4

from

sodi

umflu

orid

eso

lutio

n.T

heca

thod

ew

asth

enig

nite

dan

d aco

unte

d.A

llm

easu

rem

ents

wer

em

ade

onU

~C2O

4!2

sam

ples

3da

ysol

d,si

nce

fres

hly

prec

ipita

ted

U~C

2O4!

2w

asre

port

edto

have

aco

nsid

erab

lyhi

gher

solu

bilit

y.1

vigo

rous

lyfo

r3

hin

N 2at

mos

pher

e.T

hela

stop

erat

ion

was

repe

ated

thre

etim

es.

Sou

rce

and

purit

yof

chem

ical

sus

edno

tsp

ecifi

ed.

Est

imat

edE

rror

:U

rani

umco

ncen

trat

ion:

stan

dard

devi

atio

nof

the

mea

n5

(6–

9)%

~aut

hor!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 E.

L.W

agne

r,T

heS

olub

ility

and

Sol

ubili

tyP

rodu

ctof

U~I

V!

Oxa

late

,R

epor

tR

L-4.

6.32

1.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~IV

!bi

s~ox

alat

e!;U

~C2O

4!2;

@284

7-15

-6#A

mm

oniu

mox

alat

e;~N

H4!

2C2O

4;@1

113-

38-8#

Hyd

roge

nch

lorid

e;H

Cl;@

7647

-01-

0#W

ater

;H 2

O;

@773

2-18

-5#

F.

A.

Zak

haro

vaan

dA

.I.

Mos

kvin

,Z

h.N

eorg

.K

him

.5,

1228

–33

~196

0!;

Rus

s.J.

Inor

g.C

hem

.5,59

2–

5~1

960!

.

riabl

es:

Pre

pare

dby

:

/mol

dm2

3 :0.0

7–

0.24

/mol

dm2

3 :0.5

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

U~C

2O4!

2•6H

2Oin

~NH

4!2C

2O4

solu

tions

cont

aini

ng0.

5m

oldm2

3H

Cla

~NH

4!2C

2O4

(c2

/mol

dm2

3 )U

~C2O

4!2

(104

c 1/m

oldm

23 )

0.07

02.

15

0.10

52.

30

0.14

02.

66

0.15

82.

90

0.17

63.

10

0.19

34.

30

0.21

16.

28

0.22

810

.8

0.24

115

.9

easu

rem

ents

wer

eco

nduc

ted

atun

spec

ified

tem

pera

ture

.C

ompo

sitio

nof

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.

ditio

nali

nfor

mat

ion:

ein

crea

sing

solu

bilit

yof

U~C2O

4!2

with

incr

easi

ng~N

H4!

2C2O

4co

ncen

trat

ion

was

ascr

ibed

byth

eau

thor

sto

the

form

atio

nof

U~I

V!

alat

oco

mpl

exes

inth

esa

tura

ted

solu

tions

.F

rom

thei

rso

lubi

lity

data

the

auth

ors

obta

ined

over

all

inst

abili

tyco

nsta

nts

ofth

eC

2O4)

x42

2x

(x5

1–

4)

com

plex

es.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.S

olut

ions

cont

aini

ngex

cess

solid

reeq

uilib

rate

dfo

r4

–6

hw

hich

was

suffi

cien

tfo

rui

libriu

mto

bere

ache

d.U

rani

umin

the

satu

rate

dso

lutio

nsw

asde

term

ined

bya

coun

ting.

U~C

2O4!

2•6H

2Ow

aspr

epar

edfr

om23

3 U-la

bele

dU

O 2~N

O3!

2

solu

tion

byre

duct

ion

with

sodi

umsu

lfoxy

late

,an

dsu

bseq

uent

prec

ipita

tion.

U~IV

!ox

alat

ew

asdi

ssol

ved

in~N

H4!

2C2O

4

solu

tion,

the

solu

tion

was

cent

rifug

ed,

and

the

oxal

ato

com

plex

deco

mpo

sed

with

HC

l.U~C

2O4!

2•6H

2Opr

ecip

itate

dw

asce

ntrif

uged

,w

ashe

dto

rem

ove

exce

ssox

alic

acid

,an

dai

rdr

ied.

Sou

rce

and

purit

yof

chem

ical

sno

tre

port

ed.

Est

imat

edE

rror

:a

coun

ting:

prec

isio

n65%

~aut

hors!

.

608608 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~IV

!bi

s~ox

alat

e!;U

~C2O

4!2;

@284

7-15

-6#~2

!O

xalic

acid

;C 2

H2O

4;@1

44-6

2-7#

~3!

Hyd

roge

nch

lorid

e;H

Cl;@

7647

-01-

1#~4

!W

ater

;H 2

O;

@773

2-18

-5#

G.

D.

Dor

ough

,U

.S

.A

t.E

nerg

yC

omm

.,T

ID52

90,

Boo

k2,

1958

,pp

.53

5–

42.

Var

iabl

es:

Pre

pare

dby

:

T/K

:298

100w

2/m

ass%

:0.2

6c 3

/mol

dm2

3 :3.0

8an

d6.

05

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofU~

C2O

4!2•

6H2O

inC

2H2O

4–

HC

lsol

utio

nsa

HC

l(c

3/m

oldm

23 )

C2H

2O4

(100

w2

/mas

s%)

U~m

gdm

23 !

U~C

2O4!

2c

(106

c 1/m

oldm

23 )

3.08

40.

261.

4

1.64

1.52

b6.

39

6.05

0.26

813

.6

15.4

14.5

b60

.9

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.b A

vera

geva

lue~

auth

or!.

c Cal

cula

ted

byco

mpi

ler.

Add

ition

alin

form

atio

n:A

ttem

pts

mad

eby

the

auth

orto

calc

ulat

eth

eso

lubi

lity

prod

uct

ofU

~C2O

4!2

wer

eun

succ

essf

ulbe

caus

eof

unkn

own

exte

ntof

hydr

olys

isan

dco

mpl

exat

ion

ofU~I

V!.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Gre

atca

rew

asta

ken

topr

even

tox

idat

ion

ofU~

IV!

oxal

ate

sinc

eU

O 2C2O

4is

rela

tivel

yqu

iteso

lubl

e.P

rior

toso

lubi

lity

dete

rmin

atio

n,th

eso

lutio

nsw

ere

boile

dto

rem

ove

diss

olve

dO 2an

dth

enke

ptun

der

N 2at

mos

pher

e.A

sam

ple

ofU

O 221-f

ree

U~IV

!ox

alat

ew

as

U~C

2O4!

2•6H

2Ow

aspr

epar

edfr

omU

O 3.T

hela

tter

was

diss

olve

din

HC

l~1:

1!,

the

resu

lting

solu

tion

ofU

O 2Cl 2

was

redu

ced

elec

trol

ytic

ally

toU~I

V!,

whi

chw

asth

enpr

ecip

itate

dw

ithox

alic

acid

.The

prec

ipita

tew

asfil

tere

d,w

ashe

dw

ithbo

iled

3m

oldm

23

HC

l,an

dsh

aken

with

oxyg

en-f

ree

3m

oldm2

3H

Cl

Co

~1!

~2!

~3!

~4!

Va

c 2 c 3 a M Ad

Th

ox U~

Me

Iso

we

eq


d.

5.11

.4.

Ura

nium

„V

I…D

ioxo

„ox

alat

e…

5.11

.5.

Eva

luat

ion

ofth

eU

O2C

2O4¿

H2O

Sys

tem

mpo

nent

s:E

valu

ator

:

Ura

nium

~VI!

diox

o~ox

alat

e!;U

O2C

2O4;

@203

1-89

-2#W

ater

;H 2

O;

@773

2-18

-5#J.

Hala

,D

epar

tmen

tof

Inor

gani

cC

hem

istr

y,M

asar

ykU

nive

rsity

,61

137

Brn

o,C

zech

Rep

ublic

,M

ay20

00

Crit

ical

Eva

luat

ion:

The

mos

tex

tens

ive

stud

yof

the

solu

bilit

yof

UO

2C2O

4in

wat

eris

that

ofC

olan

i1w

hore

port

edso

lubi

litie

sov

erth

ete

mpe

ratu

reer

valf

rom

284.

1to

373.

1K

.O

ther

data

have

been

publ

ishe

dby

Bol

shak

ove

ta

l.2–

4in

thei

rst

udie

sof

vario

uste

rnar

ysy

stem

s.W

hile

irva

lue

at29

8.1

K~10

0w

15

0.58

mas

s%

;m15

0.01

63m

olkg

21 !

2,3

isin

exce

llent

agre

emen

tw

ithth

atof

Col

ani,

1th

eir

valu

eat

3.1

K~1

00w

15

0.21

mas

s%

;m15

0.00

588

mol

kg2

1 !4

falls

belo

wth

eC

olan

i’sso

lubi

lity/

tem

pera

ture

curv

e.It

is,

ther

efor

e,re

com

-nd

edto

use

the

data

ofC

olan

ias

tent

ativ

eva

lues

.T

hetw

om

easu

rem

ents

at28

7.1

and

373.

1K

repo

rted

byE

belm

en5

are

som

ewha

tbi

ous

sinc

eit

isno

tcle

arw

heth

erth

eyre

fer

toth

ean

hydr

ous

salt

orto

the

trih

ydra

te,U

O2C

2O4•

3H2O

.A

ssum

ing

the

orig

inal

data

refe

rth

etr

ihyd

rate

whi

chw

asre

port

edto

beth

eeq

uilib

rium

phas

ein

aque

ous

HN

O3

solu

tions

cont

aini

ngle

ssth

an31

mas

s%

HN

O3,

1,2

the

lubi

lity

ofth

ean

hydr

ous

salt

at37

3.1

Kis

foun

dto

be10

0w

15

3.06

mas

s%

orm15

0.08

8m

olkg

21 ,

whi

chis

inex

celle

ntag

reem

ent

thC

olan

i’sm

easu

rem

ents

.T

heE

belm

en’s

valu

eat

287.

1K

seem

sto

beer

rone

ousl

yhi

gh.

fere

nces

:

.C

olan

i,B

ull.

Soc

.C

him

.F

ranc

e37,

856

~192

5!.

.A

.B

olsh

akov

and

S.

S.

Kor

ovin

,T

rudy

Mos

k.In

st.

Ton

koiK

him

.T

ekhn

ol.

7,16

5~1

958!

.

.A

.B

olsh

akov

and

S.

S.

Kor

ovin

,Z

h.N

eorg

.K

him

.2,

1940

~195

7!.

.A

.B

olsh

akov

,V

.E

.P

lyus

hche

v,an

dT

.A

.E

rmak

ova,

Zh.

Neo

rg.

Khi

m.

2,22

2~1

957!

.

.E

belm

en,

Ann

.C

him

.P

hys.5

,18

9~1

842!

.



5.11

.3.

Pot

assi

umT

etra

kis

„O

xala

to…

Ura

nate„IV…

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umte

trak

is~oxa

lato!

uran

ate~I

V!;

K4U

~C2O

4) 4

;@

#~2

!W

ater

;H 2

O;

@773

2-18

-5#

N.

A.

Orlo

v,Z

h.R

uss.

Fiz

.K

him

.O

bsh.~J

.R

uss.

Phy

s.C

hem

.S

oc.!

34,

375

–80

~190

2!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

0J.

Hala

Exp

erim

enta

lDat

aT

heso

lubi

lity

inw

ater

ofK 4

U~C

2O4!

4w

asre

port

edto

be21

.73

gsa

ltin

100

gH

2Oat

17°C

.Thi

sva

lue

was

obta

ined

from

anex

perim

ent

whe

re4.

9878

gsa

tura

ted

solu

tion

yiel

ded

0.89

03g

dry

resi

due

afte

rev

apor

atio

n.T

heco

mpo

sitio

nof

the

resi

due

was

not

spec

ifie

Ass

umin

gth

ere

sidu

eto

beth

ehe

xahy

drat

e,K

4U~C

2O4!

4•6H

2O,

the

com

pile

rca

lcul

ated

the

solu

bilit

yof

K4U

~C2O

4!4

tobe

m1

50.

247

mol

kg2

1 .

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

d,no

deta

ilsre

port

ed.

K4U

~C2O

4!4•

6H2O

was

prep

ared

asgr

een

crys

tals

bydi

ssol

ving

U~C

2O4!

2•6H

2Oin

conc

entr

ated

solu

tion

ofK 2C

2O4,

and

allo

win

gth

eso

lutio

nto

crys

talli

ze.

The

com

posi

tion

ofth

epr

oduc

twas

confi

rmed

bych

emic

alan

alys

is:t

hepr

oduc

tyie

lded

63.1

7%K 2

U2O

71K

2CO

3up

onig

nitio

n,an

d83

.91%

UO

2SO

41K

2SO

4up

onfu

min

gw

ithco

ncen

trat

edH 2S

O4.

Cal

cula

ted

for

the

hexa

hydr

ate:

63.2

7%an

d83

.63%

,re

spec

tivel

y.

Co

~1!

~2!

int

the

27 me

du to so wi

Re

1 M 2 K 3 K 4 K 5 M

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4;

@203

1-89

-2#W

ater

;H 2

O;

@773

2-18

-5#M

.C

olan

i,B

ull.

Soc

.C

him

.F

ranc

e37,

856

–61

~192

5!.

riabl

es:

Pre

pare

dby

:

K:

284

–37

3J.

Ha´ la

Exp

erim

enta

lDat

a

Sol

ubili

tyof

UO

2C2O

4in

wat

eras

afu

nctio

nof

tem

pera

ture

a

Tem

pera

ture

~°C

!U

O2C

2O4

(100

w1

/mas

s%

)U

O2C

2O4

~mol

kg2

1 !b

110.

450.

0126

150.

470.

0132

200.

500.

0140

501.

000.

0282

751.

650.

0469

100

3.06

0.08

82

heeq

uilib

rium

solid

phas

ew

asU

O2C

2O4•

3H2O

,@1

8860

-43-

0#in

alls

olut

ions

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

thin

gsp

ecifi

ed.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

610610 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4;

@203

1-89

-2#~2

!W

ater

;H 2

O;

@773

2-18

-5#M

.E

belm

en,

Ann

.C

him

.P

hys.5

,18

9–

223~

1842

!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:28

7;37

3J.

Ha´ la

Exp

erim

enta

lDat

aT

heso

lubi

lity

inw

ater

ofU

O 2C

2O4

was

repo

rted

tobe

0.8

and

3.4

gsa

ltin

100

gH

2Oat

14an

d10

0°C

,re

spec

tivel

y.N

ote

:It

itno

tcl

ear

whe

ther

thes

efig

ures

refe

rto

the

trih

ydra

te,

UO

2C2O

4•3H

2O,

@188

60-4

3-0#,

orto

the

anhy

drou

ssa

lt.A

ssum

ing

that

they

refe

rto

the

trih

ydra

te,

the

com

pile

rca

lcul

ated

the

solu

bilit

yof

the

anhy

drou

ssa

ltas

w15

0.69

and

3.06

mas

s%

,re

spec

tivel

y.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Not

hing

spec

ified

.U

O 2C2O

4•3H

2Ow

aspr

epar

edby

prec

ipita

tion

from

aco

ncen

trat

edso

lutio

nof

UO 2~N

O3!

2w

itha

hot

conc

entr

ated

solu

tion

ofox

alic

acid

.A

visc

ous

prod

uct

was

obta

ined

whi

chtu

rned

into

aye

llow

crys

talli

nepo

wde

raf

ter

som

etim

e.It

was

purifi

edby

recr

ysta

lliza

tion.

Co

~1!

~2!

Va

T/

a T b C Me

No


used

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4;

@203

1-89

-2#N

itric

acid

;H

NO

3;@7

697-

37-2#

Wat

er;

H 2O

;@7

732-

18-5#

C.

B.

Am

phle

ttan

dO

.T

.D

avid

ge,

J.C

hem

.S

oc.

2938

–9

~195

2!.

riabl

es:

Pre

pare

dby

:

K:

293

0w

2/m

ass

%:

15.1

–69

.5J.

Hala

Exp

erim

enta

lDat

a

Com

posi

tion

ofH

NO 3

solu

tions

satu

rate

dw

ithU

O 2C2O

4at

20°C

a

HN

O3

00w

2/m

ass

%)

HN

O3

~mol

kg2

1of

the

HN

O3

/H2O

solv

ent!b

UO

2C2O

4

~g/1

00g

ofth

eH

NO

3/H

2Oso

lven

t!U

O2C

2O4

(100

w1

/mas

s%

)b

UO

2C2O

4

~mol

kg2

1of

the

HN

O3

/H2O

solv

ent!b

15.1

2.40

1.63

1.60

0.04

55

26.8

4.25

1.88

1.85

0.05

25

27.9

4.43

1.87

1.84

0.05

22

35.8

5.68

2.19

2.14

0.06

12

41.5

6.59

2.68

2.61

0.07

49

42.0

6.67

2.84

2.76

0.07

93

46.5

7.38

3.48

3.36

0.09

72

58.9

9.35

4.04b

3.88

0.11

3

69.5

11.0

33.

993.

840.

111

quili

briu

mso

lidph

ase

atth

isH

NO 3co

ncen

trat

ion

isth

ean

hydr

ous

salt,

UO

2C2O

4,@2

031-

89-2#

;at

low

erH

NO 3

conc

entr

atio

nsit

was

etr

ihyd

rate

,U

O 2C

2O4•

3H2O

,@1

8860

-43-

0#.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

xces

sso

lidw

assh

aken

with

HN

O3

lutio

nsfo

rse

vera

lday

sin

flask

sw

ithse

cure

lyw

axed

pper

s.2

days

suffi

ced

toen

sure

satu

ratio

n.T

hera

teof

alic

acid

deco

mpo

sitio

nw

asfo

und

tobe

too

low

toca

use

ydi

spla

cem

ent

ofeq

uilib

rium

.T

hesa

tura

ted

solu

tions

wer

eal

yzed

for

uran

ium

and,

afte

rre

mov

alof

uran

ium

aspe

roxi

de,

for

free

acid

cont

ent.

Met

hods

ofan

alys

isw

ere

not

spec

ified

.A

ttem

pts

tode

term

ine

the

com

posi

tion

ofth

eso

lidph

ase

bydi

rect

anal

ysis

wer

eon

lypa

rtly

succ

essf

ul,

owin

gto

the

diffi

culti

esen

coun

tere

din

rem

ovin

gad

sorb

edliq

uid

from

the

solid

with

out

was

hing

.O

nego

oddu

plic

ated

dete

rmin

atio

nw

asob

tain

edfo

r58

.9%

HN

O 3sy

stem

.

UO

2C2O

4•3H

2Ow

aspr

epar

edby

prec

ipita

tion

from

aque

ous

UO

2~N

O3!

2so

lutio

nw

ithso

dium

oxal

ate.

The

prec

ipita

tew

asfil

tere

d,w

ashe

dfr

eefr

omN

O 32,

and

drie

dat

60°C

.Ana

lysi

sfo

rur

aniu

man

dox

alat

eco

nten

tco

rres

pond

edto

the

trih

ydra

te.

Sou

rce

and

purit

yof

mat

eria

lsus

edno

tsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.



5.11

.6.

Eva

luat

ion

ofth

eU

O2C

2O4¿

HN

O3¿

H2O

Sys

tem

Com

pone

nts:

Eva

luat

or:

~1!

Ura

nium

~VI!

diox

o~ox

alat

e!;U

O2C

2O4;

@203

1-89

-2#~2

!N

itric

acid

;H

NO

3;@7

697-

37-2#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

611

37B

rno,

Cze

chR

epub

lic,

May

2000

Crit

ical

Eva

luat

ion:

The

solu

bilit

yof

UO 2

C2O

4in

aque

ous

HN

O 3so

lutio

nsw

asst

udie

din

four

docu

men

ts.

InR

efs.

1–

3th

eso

lubi

lity

ofU

O2C

2O4

was

mea

sure

das

afu

nctio

nof

HN

O3

conc

entr

atio

n,in

mas

s%

,at

293.

1K

,1,

2or

298.

1an

d32

3.1

K,

3w

hile

Mos

kvin

and

Zak

haro

va4

mea

sure

dth

eso

lubi

lity

asa

func

tion

ofco

ncen

trat

ion

ofH

NO

3in

mol

dm2

3at

293.

1K

.T

hetw

ose

ries

ofm

easu

rem

ents

perf

orm

edat

293.

1K1,

2do

not

coin

cide

.T

heda

taof

Am

phle

ttan

dD

avid

ge2

are

low

erth

anth

ose

ofC

olan

i,1

the

diffe

renc

ebe

ing

mor

epr

onou

nced

with

incr

easi

ngH

NO 3

conc

entr

atio

n.T

here

ason

for

this

disc

repa

ncy

isno

tcle

arsi

nce

Col

ani

1di

dno

trep

orta

nyde

tails

ofth

epr

oced

ure

used

.A

noth

erdi

scre

panc

yex

ists

betw

een

the

data

ofC

olan

i1

and

thos

eof

Bol

shak

ovan

dK

orov

in.

3W

hile

inth

ela

tter

docu

men

tth

eso

lubi

lity

ofU

O2C

2O4

was

repo

rted

toin

crea

sew

ithin

crea

sing

tem

pera

ture

,th

eda

taob

tain

edat

298.

1K

3se

emto

beso

mew

hat

low

erth

anth

ose

ofC

olan

i1

take

nat

293.

1K

.T

heda

taof

Mos

kvin

and

Zak

haro

va4

cann

otbe

com

pare

dw

ithth

ose

inR

efs.

1–

3be

caus

eof

diffe

rent

conc

entr

atio

nun

itsus

ed.

For

thes

ere

ason

sno

neof

the

publ

ishe

dda

taca

nbe

give

npr

efer

ence

,an

dea

chse

tof

data

can

beas

tent

ativ

eon

efo

rth

esp

ecifi

cco

nditi

ons

for

whi

chth

eyw

ere

obta

ined

.A

sfo

rth

eeq

uilib

rium

solid

phas

es,C

olan

i1

and

Bol

shak

ovan

dK

orov

in3ag

ree

inth

atth

etr

ihyd

rate

,UO 2C

2O4•

3H2O

,@18

860-

43-0#

,ex

ists

inso

lutio

nsco

ntai

ning

less

than

31m

ass

%H

NO

3.H

owev

er,a

t.48

.5m

ass

%H

NO 3,

Bol

shak

ovan

dK

orov

in3re

port

edth

eso

lidph

ase

tobe

the

mon

ohyd

rate

,U

O2C

2O4•

H2O

,@

#,w

hile

Am

phle

ttan

dD

avid

ge2re

port

edth

ean

hydr

ous

salt,

UO

2C2O

4,@2

031-

89-2#

tobe

ineq

uilib

rium

with

58.9

mas

s%

HN

O 3.

Ref

eren

ces:

1 M.

Col

ani,

Bul

l.S

oc.

Chi

m.

Fra

nce37

,85

6~1

925!

.2 C

.B

.A

mph

lett

and

O.

T.

Dav

idge

,J.

Che

m.

Soc

.29

38~195

2!.

3 K.

A.

Bol

shak

ovan

dS

.S

.K

orov

in,

Tru

dyM

osk.

Inst

.T

onko

iKhi

m.

Tek

hnol

.7,

165

~195

8!.

4 A.

I.M

oskv

inan

dE

.A

.Z

akha

rova

,Z

h.N

eorg

.K

him

.4,21

51~1

959!

.

Co

~1!

~2!

~3!

Va

T/

10 (1 a E th b C Me

Iso

so sto

ox an an

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4

;@2

031-

89-2#

Nitr

icac

id;

HN

O3

;@7

697-

37-2#

Wat

er;

H 2O

;@77

32-1

8-5#

K.

A.

Bol

shak

ovan

dS

.S

.K

orov

in,

Tru

dyM

osk.

Inst

.T

onko

iK

him

.T

ekhn

ol.7

,16

5–

70~1

958!

.

riabl

es:

Pre

pare

dby

:

K:

298;

323

0w2

/mas

s%

:0

–77

J.H

ala

Exp

erim

enta

lDat

a

Com

posi

tion

ofH

NO 3

solu

tions

satu

rate

dw

ithU

O 2C2O

4at

25an

d50

°C

HN

O3a

00w

2/m

ass

%)

UO

2C2O

4a

(100

w1

/mas

s%

)S

olid

phas

ec

HN

O3b

(100

w2

/mas

s%

)U

O2C

2O4b

(100

w1

/mas

s%

)S

olid

phas

ec

00.

58A

01.

00A

3.98

0.85

A4.

381.

49A

5.70

1.12

A6.

481.

73A

6.68

1.11

A11

.49

2.34

A

9.50

1.16

A20

.36

2.81

A

10.2

01.

20A

30.3

73.

85A

13.1

91.

59A

34.9

04.

68A

16.5

01.

71A

43.2

46.

91A

19.7

51.

73A

47.2

010

.35

e

20.7

01.

95A

61.0

8.42

e

30.7

02.

08A

65.1

07.

26e

39.1

22.

83A

73.8

37.

55e

48.5

04.

76A1

B

51.2

04.

32B

53.8

63.

90B

60.1

33.

70B

62.7

23.

80B

67.1

04.

10B1

Cd

75.9

62.

39B1

Cd

77.1

02.

12B1

Cd

t25

°C.

t50

°C.

c A:

UO

2C2O

4•3H

2O,

@188

60-4

3-0#;

B:U

O2C

2O4•

H2O

,@#;

C:

UO

2~N

O3!

2,@1

0102

-06-

4#.d T

heau

thor

sex

plai

ned

the

pres

ence

ofU

O2~

NO

3!2

inth

eso

lidph

ase

byth

ere

actio

nU

O2C

2O41

2HN

O3�

UO

2~N

O3!

21C

2H2O

4,si

nce

the

equi

libriu

msa

tura

ted

solu

tions

cont

aine

dm

ore

oxal

ate

than

wou

ldco

rres

pond

toth

est

oich

iom

etry

ofU

O2C

2O4.

e The

solid

phas

eco

ntai

ned

less

than

3m

ole

H2O

/mol

eU

O 2C

2O4

;th

eex

act

com

posi

tion

ofth

ehy

drat

eco

uld

not

bede

term

ined

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:E

stim

ated

Err

or:

Isot

herm

alm

etho

dus

ed.

Exc

ess

UO

2C2O

4•3H

2Ow

aseq

uilib

rate

dw

ithH

NO 3

solu

tions

ofth

ede

sire

dco

mpo

sitio

nin

ther

mos

tate

dve

ssel

seq

uipp

edw

itha

stirr

eran

da

hydr

aulic

mer

cury

seal

.E

quili

briu

mtim

ew

asno

tre

port

ed.

Sam

ples

ofth

esa

tura

ted

solu

tions

wer

ew

ithdr

awn

usin

ga

pipe

tteeq

uipp

edw

itha

glas

sw

oolfi

lter,

and

wei

ghed

.In

the

sam

ples

,ur

aniu

mw

asde

term

ined

bypo

tent

iom

etric

titra

tion

with

KM

nO4,

and

NO 32

byth

eK

jeld

ahlm

etho

d.E

quili

briu

mso

lidph

ases

wer

eid

entifi

edby

the

met

hod

ofin

ert

com

pone

nt(N

O32

)an

dby

chem

ical

anal

ysis

.

Tem

pera

ture

:pr

ecis

ion6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

612612 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4;

@203

1-89

-2#~2

!N

itric

acid

;H

NO

3;@7

697-

37-2#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

M.

Col

ani,

Bul

l.S

oc.

Chi

m.

Fra

nce37

,85

6–

61~1

925!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

310

0w

2/m

ass%

:1.

84–

31.0

J.H

ala

Exp

erim

enta

lDat

a

Com

posi

tion

ofH

NO 3

solu

tions

satu

rate

dw

ithU

O 2C2O

4at

20°C

a

HN

O3

(100

w2

/mas

s%

)U

O2C

2O4

(100

w1

/mas

s%

)

UO

2C2O

4

~mol

kg2

1of

the

HN

O3

/H2O

solv

ent!b

1.84

0.79

0.02

22

5.34

1.19

0.03

36

12.1

41.

560.

0443

17.6

01.

760.

0500

21.4

71.

880.

0535

31.0

02.

280.

0652

a The

equi

libriu

mso

lidph

ase

was

UO

2C2O

4•3H

2O,

@188

60-4

3-0#,

inal

lsol

utio

ns.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Not

hing

spec

ified

.N

othi

ngsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va

T/

10 (1 a A b A


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4

;@2

031-

89-2#

Per

chlo

ricac

id;

HC

lO 4;

@760

1-90

-3#W

ater

;H2O

;@77

32-1

8-5#

A.I

.Mos

kvin

and

E.A

.Zak

haro

va,Z

h.N

eorg

.Khi

m.

4,21

51–

60~1

959!

.

riabl

es:

Pre

pare

dby

:

K:2

93/m

oldm

23 :

0.5

–3.

0J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofU

O 2C

2O4

inH

ClO

4so

lutio

nsa

HC

lO4

2/m

oldm

23 !

UO

2C2O

4

(c1/1

02m

oldm

23 !

Ksb

(109

mol

2dm

26 !

0.5

2.31

2.8

1.0

2.77

1.55

1.5

3.12

2.8

2.0

3.44

2.0

2.5

3.66

1.4

3.0

3.69

1.0

2.06

0.9c

quili

briu

mso

lidph

ases

wer

eno

tin

vest

igat

ed.

olub

ility

prod

uctK

s5@U

O22

1#@

C2O

422

#.It

was

obta

ined

byth

eau

thor

sfr

omth

eso

lubi

lity

ofU

O2C

2O4,

and

the

equi

libriu

mco

ncen

-at

ion

ofth

eox

alat

eio

n.T

hela

tter

was

calc

ulat

edby

usin

gdi

ssoc

iatio

nco

nsta

nts

ofox

alic

acid

~Ka1

50.

108,

Ka2

56.

4310

25;

sour

ceot

repo

rted

!,an

das

sum

ing

the

equi

libriu

mco

ncen

trat

ion

ofH

1io

nw

aseq

ualt

oth

eH

ClO 4

conc

entr

atio

nus

ed.

vera

geva

lue~

auth

ors!.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

xces

sU

O2C

2O4•

3H2O

was

stirr

edth

the

solu

tions

ofth

ede

sire

dco

mpo

sitio

nfo

r6

h.el

imin

ary

expe

rimen

tssh

owed

that

this

was

suffi

cien

tto

ach

equi

libriu

m.

Con

cent

ratio

nof

uran

ium

inth

esa

tura

ted

lutio

nsw

asde

term

ined

grav

imet

rical

lyas

U3O

8af

ter

apor

atin

gan

dig

nitin

gan

aliq

uot

ofth

esa

tura

ted

solu

tion.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

Ura

nium

conc

entr

atio

n:pr

ecis

ion6

2.5%

~aut

hors!

.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

ooxa

late

,U

O 2C

2O4

;@2

031-

89-2#

~2!

Nitr

icac

id;

HN

O3

;@7

697-

37-2#

~3!

Wat

er;

H 2O

;@77

32-1

8-5#

A.I

.Mos

kvin

and

E.A

.Zak

haro

va,Z

h.N

eorg

.Khi

m.

4,21

51–

60~1

959!

.

Var

iabl

es;

Pre

pare

dby

:

T/K

:29

3c 2

/mol

dm2

3 :0.5

–3.

0J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofU

O 2C

2O4

inH

NO

3so

lutio

nsa

HN

O3

(c2

/mol

dm2

3 !U

O2C

2O4

(c1/1

02m

oldm

23 !

Ksb

(109

mol

2dm

26 !

0.5

2.67

4.9

1.0

3.54

3.4

1.5

4.17

2.5

2.0

4.53

3.4

2.5

5.22

2.9

3.0

5.61

2.3

3.26

1.3c

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.b S

olub

ility

prod

uctK

s5@U

O221

#@C

2O422

#.It

was

obta

ined

byth

eau

thor

sfr

omth

eso

lubi

lity

ofU

O2C

2O4,

and

the

equi

libriu

mco

ncen

-tr

atio

nof

oxal

ate

ion.

The

latte

rw

asca

lcul

ated

byus

ing

diss

ocia

tion

cons

tant

sof

oxal

icac

id~K

a15

0.10

8,K

a25

6.43

102

5;

sour

ceno

tre

port

ed!,

and

assu

min

geq

uilib

rium

conc

entr

atio

nof

H1

ion

was

equa

lto

the

HC

lO 4co

ncen

trat

ion

used

.C

ompl

exat

ion

ofU

O22

1w

ithN

O32

was

not

take

nin

toac

coun

tw

hich

,ac

cord

ing

toth

eau

thor

s,w

asth

ere

ason

for

Ks

bein

ghi

gher

inH

NO 3

solu

tions

than

inH

ClO 4

solu

tions

.c A

vera

geva

lue~

auth

ors!.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

UO

2C2O

4•3H

2Ow

asst

irred

with

the

solu

tions

ofth

ede

sire

dco

mpo

sitio

nfo

r6

h.P

relim

inar

yex

perim

ents

show

edth

atth

isw

assu

ffici

ent

tore

ach

equi

libriu

m.

Con

cent

ratio

nof

uran

ium

inth

esa

tura

ted

solu

tions

was

dete

rmin

edgr

avim

etric

ally

asU

3O8

afte

rev

apor

atin

gan

dig

nitin

gan

aliq

uot

ofth

esa

tura

ted

solu

tion.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

Ura

nium

conc

entr

atio

n:pr

ecis

ion6

2.5%

~aut

hors!

.

Co

~1!

~2!

~3!

Va

T/

c 2 (c a E b S tr n c A Me

Iso

wi

Pr

re so ev

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4

;@2

031-

89-2#

Hyd

roge

nch

lorid

e;H

Cl;@

7647

-01-

0#W

ater

;H 2

O;@

7732

-18-

5#

M.

Col

ani,

Bul

l.S

oc.

Chi

m.

Fra

nce37

,85

6–

61~1

925!

.

riabl

es:

Pre

pare

dby

:

K:2

840

w2

/mas

s%

:3.

6–

17.6

5J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

11°C

ofU

O 2C

2O4

inH

Cls

olut

ions

a

HC

l(1

00w

2/m

ass

%)

UO

2C2O

4

(100

w1

/mas

s%

)

3.60

1.14

8.20

2.00

11.4

92.

91

14.9

94.

90

17.6

58.

82

heeq

uilib

rium

solid

phas

ew

asU

O2C

2O4•

3H2O

,@1

8860

-43-

0#,in

alls

olut

ions

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

thin

gsp

ecifi

ed.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tsp

ecifi

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

614614 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4

;@2

031-

89-2#

~2!

Pho

spho

ricac

id;

H 3PO

4;

@766

4-38

-2#~3

!W

ater

;H 2

O;@

7732

-18-

5#

M.

Col

ani,

Bul

l.S

oc.

Chi

m.

Fra

nce37

,85

6–

61~1

925!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:293

100w

2/m

ass

%:

0.77

–15

.76

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofU

O 2C

2O4

inH

3PO

4so

lutio

nsa

H3P

O4

(100

w2

/mas

s%

)U

O2C

2O4

(100

w1

/mas

s%

)

0.77

2.10

1.51

3.56

2.67

5.66

4.94

9.25

8.75

15.1

4

15.7

625

.74

a The

equi

libriu

mso

lidph

ase

was

UO

2C2O

4•3H

2O,

@188

60-4

3-9

0#,in

alls

olut

ions

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Not

hing

spec

ified

.N

othi

ngsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va

T/

10 a T Me

No


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

oox

alat

e;U

O 2C

2O4

;@2

031-

89-2#

Oxa

licac

id;

C 2H

2O4

;@1

44-6

2-7#

Wat

er;

H 2O

;@7

732-

18-5#

K.

A.

Bol

shak

ov,

S.

S.

Kor

ovin

,V

.E

.P

lyus

hche

v,an

dT

.A

.E

rmak

ova,

Zh.

Neo

rg.

Khi

m2,

222

–8

~195

7!.

riabl

es:

Pre

pare

dby

:

K:

273

–34

30

w2

/mas

s%

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

UO

2C2O

4in

oxal

icac

idso

lutio

nsas

afu

nctio

nof

tem

pera

ture

mpe

ratu

re~°

C!

C2H

2O4

(100

w2

/mas

s%

)C

2H2O

4

(m2

/mol

kg2

1 )aU

O2C

2O4

(100

w1

/mas

s%

)U

O2C

2O4

(m1

/mol

kg2

1 !a

00

00.

210.

0058

8

0.74

0.08

371.

030.

0293

1.51

0.17

21.

250.

0359

2.89

0.33

51.

380.

0403

3.45

0.40

31.

400.

0411b

3.42

0.39

70.

910.

0266

3.41

0.39

40.

450.

0131

3.41

0.39

20

0

250

00.

580.

0162

0.66

0.07

481.

370.

0376

1.73

0.19

91.

800.

0521

2.58

0.30

02.

020.

0591

4.01

0.47

42.

100.

0625

7.80

0.96

42.

340.

0727

8.70

1.08

62.

340.

0735

9.70

1.12

32.

400.

0763

9.90

1.25

42.

440.

0777b

10.0

01.

267

2.33

0.07

42

10.1

21.

267

1.17

0.03

68

10.2

01.

267

0.40

0.01

25

10.1

71.

257

00

400

00.

830.

0234

0.99

0.11

31.

800.

0517

2.23

0.25

92.

220.

0649

3.91

0.46

42.

530.

0755

9.02

1.13

72.

840.

0900

12.4

01.

626

2.91

0.09

60

15.6

42.

129

2.75

0.09

41

17.2

22.

387

2.64

0.09

20b

17.4

22.

399

1.93

0.06

68

17.6

42.

412

1.14

0.03

92

17.8

02.

420

0.51

0.01

74

17.7

12.

390

00

500

01.

000.

0282

1.34

0.15

52.

350.

0681

1.90

0.22

02.

500.

0730

4.64

0.55

72.

810.

0848

6.37

0.78

13.

070.

0947

7.90

0.98

63.

100.

0973

9.72

1.24

3.14

0.10

1

10.5

61.

363.

190.

103



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4

;@2

031-

89-2#

~2!

Sul

furic

acid

;H 2

SO

4;

@766

4-93

-9#~3

!W

ater

;H 2

O;@

7732

-18-

5#

M.

Col

ani,

Bul

l.S

oc.

Chi

m.

Fra

nce37

,85

6–

61~1

925!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:293

100

w2

/mas

s%

:0.

82–

29.6

7J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofU

O 2C

2O4

inH

2SO

4so

lutio

nsa

H2S

O4

(100

w2

/mas

s%

)U

O2C

2O4

(100

w1

/mas

s%

)

0.82

0.85

2.59

1.34

3.05

1.61

5.53

2.04

15.0

73.

85

19.8

84.

93

25.5

85.

98

27.3

16.

46

29.6

77.

49

a The

equi

libriu

mso

lidph

ase

was

UO

2C2O

4•3H

2O,

@188

60-4

3-0#,

inal

lsol

utio

ns.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Not

hing

spec

ified

.N

othi

ngsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va

T/

10 Te

J

Isot

herm

alm

etho

dus

ed.

Mix

ture

sw

ere

stirr

edin

ath

erm

osta

ted

vess

eleq

uipp

edw

itha

hydr

aulic

seal

.T

heve

ssel

was

prot

ecte

dag

ains

tsu

nlig

htto

avoi

dre

duct

ion

ofU

O22

1to

U~I

V!.

Equ

ilibr

ium

was

reac

hed

in4

–5

days

at25

°C,

and

in10

–11

hat

70°C

.A

tte

mpe

ratu

res

abov

e25

°Csa

mpl

esof

the

satu

rate

dso

lutio

nsw

ere

with

draw

nby

usin

gpr

ehea

ted

pipe

ts.

Sat

urat

edso

lutio

nsan

dth

eso

lidph

ases

wer

ean

alyz

edfo

rox

alat

eby

dire

cttit

ratio

nw

ithst

anda

rdK

MnO 4

solu

tion,

and

for

uran

ium

~the

sam

ple

was

evap

orat

ed,

igni

ted

at60

0–

700

°Cto

deco

mpo

seth

eox

alat

e,U

3O8

was

conv

erte

dto

UO

2SO

4,an

dU

O 221

was

redu

ced

with

Cd

met

alto

U~IV

!w

hich

was

titra

ted

with

0.02

–0.

04N

KM

nO 4w

ithpo

tent

iom

etric

,en

d-po

int

dete

ctio

n!.

Com

posi

tion

ofth

eso

lidph

ases

was

also

dete

rmin

edby

Sch

rein

emak

ers

met

hod.

UO

2C2O

4w

asob

tain

edas

trih

ydra

teby

prec

ipita

tion

ofa

conc

entr

ated

UO 2~

NO

3!2

solu

tion

with

asa

tura

ted

solu

tion

ofox

alic

acid

.T

hege

latin

ous

prec

ipita

tew

asth

orou

ghly

was

hed

with

wat

eran

dai

rdr

ied

toob

tain

trih

ydra

tepo

wde

r.S

ourc

ean

dpu

rity

ofm

ater

ials

used

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

05K

at0

and

25°C

,60.

1K

athi

gher

tem

pera

ture

s~aut

hors!

.U

rani

umco

ncen

trat

ion:,

60.

5%~a

utho

rs!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4

;@2

031-

89-2#

Sod

ium

oxal

ate;

Na 2C

2O4

;@6

2-76

-0#

Wat

er;

H 2O

;@7

732-

18-5#

A.

Col

ani,

Com

pt.

Ren

d.A

cad.

Sci

.165,

111

–3

~191

7!.

riabl

es:

Pre

pare

dby

:

K:

288;

323

0w

2/m

ass

%:

0–

4.9

and

0–

9,re

spec

tivel

yJ.

Hala

Exp

erim

enta

lDat

a

ase

diag

ram

ofth

eU

O 2C2O

4–

Na 2

C2O

4–

H2O

syst

emat

15an

d50

°C,

and

com

posi

tions

ofth

esa

tura

ted

solu

tions

atsi

gnifi

cant

ints

empe

ratu

re~°

C!

Sig

nific

ant

poin

taN

a 2C

2O4

(100

w2

/mas

s%

)N

a 2C

2O4

(m2

/mol

kg2

1 !b

UO

2C2O

4

(100

w1

/mas

s%

)U

O2C

2O4

(m1

/mol

kg2

1 !b

Sol

idph

asec

15a

00

0.47

0.01

32I

b0.

800.

0460

2.65

0.07

67I

1II

c1.

800.

107

5.01

0.15

0II1III

d4.

930.

298

3.14

0.09

54III1

IV

e3.

090.

177

00

IV

50A

00

1.00

0.02

82I

B1.

010.

0588

3.58

0.10

5I

1II

C3.

600.

231

9.84

0.31

7II1V

D4.

620.

309

12.3

30.

414

V1III

E9.

030.

649

13.6

90.

495

III1IV

F4.

280.

248

00

IV

eeF

ig.

13al

cula

ted

byco

mpi

ler.

!U

O2C

2O4•

3H2O

,@1

8860

-43-

0#;~I

I!N

a 2~U

O2!

4~C

2O4!

5•11

H2O

,@

#;~I

II!

Na 2

UO

2~C

2O4!

2•5H

2O,

@#;

~IV

!N

a 2C

2O4

;@6

2-76

-;

~V!

Na 2

~UO

2!2~

C2O

4!3•

5H2O

,@

#.

ase

diag

ram~

Fig

.13

!of

the

UO 2

C2O

4–

Na 2

C2O

4–

H2O

syst

emat

15an

d50

°C.

616616 JIRI HALA

11.5

01.

503.

220.

105

13.4

51.

793.

070.

103

15.2

92.

082.

870.

0979

18.5

32.

622.

790.

0990

23.4

03.

512.

510.

0946

23.7

03.

567

2.50

0.09

46b

23.7

23.

566

2.40

0.09

07

23.8

53.

581

2.18

0.08

23

24.0

3.56

31.

190.

0444

23.9

53.

500

0

70c

00

1.60

0.04

54

1.03

0.11

92.

670.

0774

1.82

0.21

22.

930.

0859

2.63

0.31

13.

400.

101

2.92

0.34

83.

760.

113

5.23

0.63

93.

840.

118

7.52

0.94

33.

960.

125

10.7

21.

404.

120.

135

11.9

41.

584.

130.

137

13.5

11.

824.

020.

136

14.6

21.

993.

980.

137

16.9

12.

373.

930.

131

22.1

93.

313.

300.

124

27.7

84.

442.

680.

108

29.9

64.

922.

360.

0974

36.6

86.

611.

640.

0743

37.8

66.

951.

660.

0766

37.9

26.

941.

400.

0644

38.2

46.

980.

880.

0404

37.9

26.

780

0

a Cal

cula

ted

byco

mpi

ler.

b Tw

oso

lidph

ases

,i.e

.,U

O 2C2O

4•3H

2O,

@188

60-4

3-0#

~A!

and

C 2H

2O4•

2H2O

,@6

153-

56-6#

~B!,

wer

ein

equi

libriu

mw

ithth

isso

lutio

n.In

solu

tions

cont

aini

nglo

wer

and

high

erox

alic

acid

conc

entr

atio

ns,

the

equi

libriu

mso

lidph

ases

wer

eA

and

B,

resp

ectiv

ely.

c For

mea

sure

men

tsat

this

tem

pera

ture

the

solid

phas

esw

ere

not

repo

rted

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Co

~1!

~2!

~3!

Va

T/

10 Ph

po T a S b C c ~I 0# Ph


Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

No

deta

ilsre

port

ed.

No

deta

ilsre

port

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4

;@2

031-

89-2#

Am

mon

ium

oxal

ate;

(NH 4!

2C2O

4;

@111

3-38

-8#W

ater

;H 2

O;

@773

2-18

-5#

A.

Col

ani,

Com

pt.

Ren

d.A

cad.

Sci

.165,

234

–6

~191

7!.

riabl

es:

Pre

pare

dby

:

K:

288;

323

0w

2/m

ass

%:

0–

6.4

and

0–

15.9

,re

spec

tivel

yJ.

Hala

Exp

erim

enta

lDat

a

ase

diag

ram

ofth

eU

O 2C2O

4–

~NH

4!2C

2O4–

H2O

syst

emat

15an

d50

°C,

and

com

posi

tions

ofth

esa

tura

ted

solu

tions

atsi

gnifi

cant

ints

empe

ratu

re~°

C!

Sig

nific

ant

poin

ta~N

H4!

2C2O

4

(100

w2

/mas

s%

)~N

H4!

2C2O

4

(m2

/mol

kg2

1 )bU

O2C

2O4

(100

w1

/mas

s%

)U

O2C

2O4

(m1

/mol

kg2

1 )bS

olid

phas

ec

15a

00

0.47

0.01

32I

b2.

140.

190

7.19

0.22

1I

1II

c2.

990.

273

8.78

0.22

8II1III

d6.

430.

618

9.66

0.32

2III1

IV

e3.

690.

309

00

IV

50A

00

1.00

0.02

82I

B1.

360.

110

5.11

0.15

3I

1V

C8.

520.

959

19.8

90.

776

V1V

I

D15

.90

2.16

23.8

21.

10V

I1

IV

E9.

360.

832

00

IV

eeF

ig.

14al

cula

ted

byco

mpi

ler.

!U

O2C

2O4•

3H2O

,@1

8860

-43-

0#;~I

I!~N

H4!

2~U

O2!

2~C

2O4!

3•3H

2O,

@#;

~III

!~N

H4!

2UO

2~C

2O4!

2•2H

2O,

@#;

~IV

!H

4!2C

2O4•

H2O

,@

#;~V

!~N

H4!

2~U

O2!

2~C

2O4!

3,@

#;~V

I!~N

H4!

2UO

2~C

2O4!

2,@

#.

ditio

nali

nfor

mat

ion:

75°C

,~N

H4!

4UO

2~C

2O4!

3,@

#,w

asid

entifi

edas

the

solid

phas

ein

solu

tions

cont

aini

ng18

.70

and

21.1

7m

ass

%~N

H4!

2C2O

4.

ase

diag

ram~

Fig

.14

!of

the

UO 2

C2O

4–

~NH

4!2C

2O4–

H2O

syst

emat

15an

d50

°C.



FIG

.13

.U

rani

um~V

I!di

oxoo

xala

te–

amm

oniu

mox

alat

e–

wat

ersy

stem

.

Aux

iliar

yIn

form

atio

n

Co

~1!

~2!

~3!

Va

T/

10 Ph

po T a S b C c ~I ~N Ad

At

Ph

J

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

No

deta

ilsre

port

ed.

No

deta

ilsre

port

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4

;@2

031-

89-2#

Pot

assi

umox

alat

e;K 2C

2O4

;@5

83-5

2-8#

Wat

er;

H 2O

;@7

732-

18-5#

A.

Col

ani,

Com

pt.

Ren

d.A

cad.

Sci

.163,

123

–5

~191

6!.

riabl

es:

Pre

pare

dby

:

K:

288;

323

0w

2/m

ass

%:

0–

24.3

and

0–

32.7

5,re

spec

tivel

yJ.

Hala

Exp

erim

enta

lDat

a

ase

diag

ram

ofth

eU

O 2C2O

4–

K2C

2O4–

H2O

syst

emat

15an

d50

°C,

and

com

posi

tions

ofth

esa

tura

ted

solu

tions

atsi

gnifi

cant

ints

mpe

ratu

re~°

C!

Sig

nific

ant

poin

taK

2C2O

4

(100

w2

/mas

s%

)K

2C2O

4

(m2

/mol

kg2

1 !b

UO

2C2O

4

(100

w1

/mas

s%

)U

O2C

2O4

(m1

/mol

kg2

1 !b

Sol

idph

asec

15a

00

0.47

0.01

32I

b0.

420.

0257

1.34

0.03

81I

1II

c1.

830.

117

3.89

0.11

5II1III

d1.

850.

118

3.76

0.11

1III1

IV

e24

.30

1.94

0.10

0.00

368

IV1V

f24

.09

1.91

00

V

50A

00

1.00

0.02

82I

B1.

110.

0700

3.45

0.10

1I

1II

C4.

830.

340

9.82

0.32

1II1III

D5.

610.

398

9.52

0.31

4III1

IV

E32

.65

2.97

1.22

0.05

15IV1

V

F32

.75

2.93

00

V

eeF

ig.

15.

alcu

late

dby

com

pile

r.!

UO

2C2O

4•3H

2O,@

1886

0-43

-0#;~

II!

K2~

UO

2!2~

C2O

4!3•

4H2O

,@#;

~III

!K

2UO

2~C

2O4!

2•3.

5H2O

,@#;

~IV

!K

6~U

O2!

2~C

2O4!

5•10

H2O

,@#;

!K

2C2O

4•H

2O,

@648

7-48

-5#.

ase

diag

ram~

Fig

.15

!of

the

UO 2

C2O

4–

K2C

2O4–

H2O

syst

emat

15an

d50

°C.

FIG

.15

.S

odiu

mca

rbon

ato

diox

onep

tuna

te~V!–

sodi

umpe

rchl

orat

e–

carb

ondi

oxid

e–

wat

ersy

stem

.

618618 JIRI HALA

FIG

.14

.U

rani

um~V

I!di

oxoo

xala

te–

pota

ssiu

mox

alat

e–

wat

ersy

stem

.

Co

~1!

~2!

~3!

Va

T/

10 Ph

po Te

a S b C c ~I ~V Ph


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4

;@2

031-

89-2#

Cal

cium

oxal

ate;

CaC 2

O4

;@5

63-7

2-4#

Wat

er;

H 2O

;@7

732-

18-5#

A.

Col

ani,

Bul

l.S

oc.

Chi

m.

Fra

nce1,

1376

–9

~193

4!;

Com

pt.

Ren

d.A

cad.

Sci

.198,

1510

–2~

1934

!.

riabl

es:

Pre

pare

dby

:

K:

288;

323

0w2

/mas

s%

:0

–0.

079

and

0–

0.04

4,re

spec

tivel

yJ.

Hala

Exp

erim

enta

lDat

a

Com

posi

tion

ofth

esa

tura

ted

solu

tions

inth

eU

O2C

2O4–

CaC

2O4–

H2O

syst

emat

15an

d50

°C

mpe

ratu

re~°

C!

CaC

2O4

(100

w2

/mas

s%

)C

aC2O

4

(103

m2

/mol

kg2

1 !a

UO

2C2O

4

(100

w1

/mas

s%

)U

O2C

2O4

(m1

/mol

kg2

1 !a

Sol

idph

aseb

150

00.

470

0.01

32A

0.01

20.

941

0.46

90.

0132

A1B

0.01

10.

861

0.26

00.

0072

8B

0.07

96.

180.

137

0.00

383

B

0.07

55.

860.

088

0.00

246

B

500

01.

000.

0282

A

0.02

21.

740.

996

0.02

81A

0.04

43.

471.

070.

0302

A1B

0.03

83.

001.

040.

0294

B

0.03

72.

920.

924

0.02

61B

0.01

71.

330.

239

0.00

669

B

alcu

late

dby

com

pile

r.!

UO

2C2O

4•3H

2O,

@188

60-4

3-0#;

~B!

CaC

2O4•

H2O

,@5

794-

28-5#

.

ditio

nali

nfor

mat

ion:

roug

hsk

etch

only

was

give

nfo

rth

eph

ase

diag

ram

ofth

eU

O2C

2O4–

CaC

2O4–

H2O

syst

em.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.T

oa

give

nvo

lum

eof

wat

er,

the

sire

dqu

antit

ies

ofU

O 2C2O

4an

dC

aC2O

4w

ere

adde

d.T

hext

ures

wer

eag

itate

dun

tileq

uilib

rium

was

reac

hed.

Thi

sto

oka

long

,th

ough

unsp

ecifi

edpe

riod

oftim

e.T

hen

the

clea

rsu

pern

atan

tso

lutio

nw

asan

alyz

edgr

avim

etric

ally

~met

hods

not

spec

ified

!.

No

deta

ilsre

port

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.



Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

No

deta

ilsre

port

ed.

No

deta

ilsre

port

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Co

~1!

~2!

~3!

Va

T/

10 Te

a C b ~A Ad

A Me

Iso

de mi

J

Cal

cula

ted

byco

mpi

ler.

b ~A!

UO

2C2O

4•3H

2O,

@188

60-4

3-0#;

~B!

SrU

O2~

C2O

4!2•

4H2O

,@

#;~C

!S

rC2O

4•4H

2O,

@#,

inor

igin

alre

fere

nce,1

orS

rC2O

4•2.

5H2O

,@

#,in

orig

inal

refe

renc

es.2

Add

ition

alin

form

atio

n:A

roug

hsk

etch

ofth

eph

ase

diag

ram

ofth

eU

O2C

2O4–

SrC

2O4–

H2O

syst

emw

asre

port

ed.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

To

agi

ven

volu

me

ofw

ater

,th

ede

sire

dqu

antit

ies

ofU

O 2C2O

4an

dS

rC2O

4w

ere

adde

d.T

hem

ixtu

res

wer

eag

itate

dun

tileq

uilib

rium

was

reac

hed.

Thi

sto

oka

long

,th

ough

unsp

ecifi

edpe

riod

oftim

e.T

hen

the

clea

rsu

pern

atan

tso

lutio

nw

asan

alyz

edgr

avim

etric

ally

~met

hods

not

spec

ified

!.

No

deta

ilsre

port

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4

;@2

031-

89-2#

Bar

ium

oxal

ate;

BaC

2O4

;@5

16-0

2-9#

Wat

er;

H 2O

;@7

732-

18-5#

A.

Col

ani,

Bul

l.S

oc.

Chi

m.

Fra

nce1,

1376

–9~

1934

!.

riabl

es:

Pre

pare

dby

:

K:

288;

323

0w

2/m

ass

%:

0–

0.07

7an

d0

–0.

37,

resp

ectiv

ely

J.H

ala

Exp

erim

enta

lDat

aC

ompo

sitio

nof

the

satu

rate

dso

lutio

nsin

the

UO

2C2O

4–

BaC

2O4–

H2O

syst

emat

15an

d50

°C

mpe

ratu

re~°

C!

BaC

2O4

(100

w2

/mas

s%

)B

aC2O

4

(104

m2

/mol

kg2

1 !a

UO

2C2O

4

(100

w1

/mas

s%

)U

O2C

2O4

(m1

/mol

kg2

1 !a

Sol

idph

aseb

150

00.

470

0.01

32A

0.01

376.

110.

453

0.01

27A

0.02

5211

.20.

460

0.01

29A

0.07

7234

.50.

563

0.01

58B

0.07

0631

.50.

525

0.01

48B

0.06

4028

.50.

422

0.01

18B

0.06

0026

.70.

166

0.00

465

B0.

0592

c26

.30.

140

0.00

392

B0.

0479

21.3

0.07

770.

0021

7C

0.03

5315

.70.

0548

0.00

153

C0.

0306

13.6

0.04

490.

0012

6C

0.03

1514

.00.

0432

0.00

122

D0.

0209

9.28

0.02

210.

0006

17D

500

01.

000.

0282

A0.

193

86.9

1.30

0.03

66A

0.34

315

51.

580.

0450

A0.

370

167

1.62

0.04

62A1

B0.

354

160

1.54

0.04

38B

0.31

514

20.

911

0.02

58B

0.25

111

20.

648

0.01

93B

0.21

194

.30.

443

0.01

25B1C

0.18

683

.00.

368

0.01

03C

0.13

057

.80.

239

0.00

669

C1E

0.10

245

.40.

166

0.00

465

E0.

0366

16.3

0.04

610.

0012

9E

a Cal

cula

ted

byco

mpi

ler.

b ~A!

UO

2C2O

4•3H

2O,@

1886

0-43

-0#;~

B!

BaU

O2~

C2O

4!2•

5H2O

,@#;

~C!

Ba 2

UO

2~C

2O4!

3•7H

2O,@

#,~D

!B

aC2O

4•2H

2O,@

1858

1-91

-4#;~

E!

BaC

2O4•

0.5H

2O,

@185

81-8

9-0#.

c InR

ef.

1,th

isco

mpo

sitio

nis

repo

rted

tobe

that

ofth

eeu

toni

cpo

int

with

solid

phas

esB

and

Cat

equi

libriu

m.

Als

o,co

mpo

sitio

nof

two

mor

eeu

toni

cpo

ints

isre

port

edw

hich

dono

tag

ree

with

the

data

repo

rted

inth

isco

mpi

led

docu

men

t.

Add

ition

alin

form

atio

n:A

roug

hsk

etch

ofth

eph

ase

diag

ram

ofth

eU

O2C

2O4–

BaC

2O4–

H2O

syst

emw

asre

port

ed.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

To

agi

ven

volu

me

ofw

ater

,th

ede

sire

dqu

antit

ies

ofU

O 2C2O

4an

dB

aC2O

4w

ere

adde

d.T

hem

ixtu

res

wer

eag

itate

dun

tileq

uilib

rium

was

reac

hed.

Thi

sto

oka

long

,th

ough

unsp

ecifi

edpe

riod

oftim

e.T

hen

the

clea

rsu

pern

atan

tso

lutio

nw

asan

alyz

edgr

avim

etric

ally

~met

hods

not

spec

ified

!.

No

deta

ilsre

port

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tsp

ecifi

ed.

Sol

ubili

tyda

ta:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 A.

Col

ani,

Com

pt.

Ren

d.198

,15

10~1

934!

.

620620 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4

;@2

031-

89-2#

~2!

Str

ontiu

mox

alat

e;S

rC 2O

4;

@814

-95-

9#~3

!W

ater

;H 2

O;

@773

2-18

-5#

1 A.

Col

ani,

Bul

l.S

oc.

Chi

m.

Fra

nce1,

1376

–9~

1934

!;2 A

Col

ani,

Com

pt.

Ren

d.A

cad.

Sci

.198,

1510

–2~

1934

!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:28

8;32

310

0w

2/m

ass

%:

0–

0.16

and

0–

0.52

,re

spec

tivel

yJ.

Hala

Exp

erim

enta

lDat

a

Com

posi

tion

ofth

esa

tura

ted

solu

tions

inth

eU

O2C

2O4–

SrC

2O4–

H2O

syst

emat

15an

d50

°C

Tem

pera

ture

~°C

!S

rC2O

4

(100

w2

/mas

s%

)S

rC2O

4

(103

m2

/mol

kg2

1 !a

UO

2C2O

4

(100

w1

/mas

s%

)U

O2C

2O4

(m1

/mol

kg2

1 !a

Sol

idph

aseb

150

00.

470

0.01

32A

0.09

35.

330.

616

0.01

73A

0.16

49.

420.

711

0.02

00A1B

0.15

89.

070.

742

0.02

09B

0.16

09.

190.

701

0.01

97B

0.16

39.

350.

549

0.01

54B1C

0.14

78.

420.

481

0.01

35C

0.08

64.

910.

266

0.00

746

C

0.03

31.

880.

087

0.00

243

C

500

01.

000.

0282

A

0.12

16.

981.

230.

0348

A

0.34

319

.91.

750.

0499

A

0.41

224

.01.

920.

0549

A

0.52

130

.52.

100.

0602

A1B

0.50

829

.71.

990.

0570

B

0.50

029

.11.

820.

0520

B

0.47

727

.71.

450.

0413

B1C

0.43

525

.11.

320.

0373

C

0.18

910

.80.

524

0.01

47C

0.12

87.

320.

349

0.00

979

C

0.07

44.

220.

176

0.00

493

C

a

Co

~1!

~2!

~3!

Va

T/

10 Te


Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

UO

2C2O

4•3H

2Ow

asst

irred

with

solu

tions

ofth

ede

sire

dco

mpo

sitio

nfo

r6

h.P

relim

inar

yex

perim

ents

show

edth

atth

isw

assu

ffici

ent

for

equi

libriu

mto

bere

ache

d.C

once

ntra

tion

ofur

aniu

min

the

satu

rate

dso

lutio

nsw

asde

term

ined

grav

imet

rical

lyas

U3O

8af

ter

evap

orat

ing

and

igni

ting

anal

iquo

tof

the

solu

tion.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

Con

cent

ratio

nof

uran

ium

:62.

5%~a

utho

rs!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4

;@2

031-

89-2#

Oxa

licac

id;

C 2H

2O4

;@1

44-6

2-7#

Nitr

icac

id;

HN

O3

;@7

697-

37-2#

Wat

er;

H 2O

;@7

732-

18-5#

A.I

.Mos

kvin

and

E.A

.Zak

haro

va,Z

h.N

eorg

.Khi

m.

4,21

51–

60~1

959!

.

riabl

es:

Pre

pare

dby

:

K:

293

/mol

dm2

3 :0.

08–

0.63

for

0.5

and

2.0

mol

dm23

HN

O3

;8

–0.

47fo

r3.

0m

oldm

23

HN

O3

/mol

dm2

3 :0.

5;2.

0;3.

0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

ty20

°Cof

UO 2

C2O

4in

C2H

2O4–

HN

O3

solu

tions

a

HN

O3

3/m

oldm

23 )

C2H

2O4

(c2

/mol

dm2

3 )U

O2C

2O4

(102

c 1/m

oldm

23 )

HN

O3

(c3

/mol

dm2

3 )C

2H2O

4

(c2

/mol

dm2

3 )U

O2C

2O4

(102

c 1/m

oldm

23 )

0.5

0.08

01.

833.

00.

080

2.91

0.15

82.

070.

158

2.08

0.23

82.

280.

237

1.50

0.31

82.

430.

318

1.29

0.47

62.

680.

394

1.12

0.63

62.

980.

476

1.07

2.0

0.08

02.

48

0.15

81.

92

0.23

71.

66

0.31

61.

50

0.47

61.

30

0.63

61.

32

quili

briu

mso

lidph

ases

wer

eno

tin

vest

igat

ed.

ditio

nali

nfor

mat

ion:

omth

ein

crea

sing

solu

bilit

yof

UO 2C

2O4

with

incr

easi

ngox

alic

acid

conc

entr

atio

nin

0.5

mol

dm23

HC

lO4,

the

auth

ors

calc

ulat

edbi

lity

cons

tant

sof

the

UO 2C

2O4

and

UO 2

~C2O

4!22

2co

mpl

exes

.In

2.0

and

3.0

mol

dm23

HC

lO4,

the

decr

easi

ngso

lubi

lity

ofU

O 2C2O

4

thin

crea

sing

oxal

icac

idco

ncen

trat

ion

was

take

nas

anev

iden

cefo

rth

eab

senc

eof

com

plex

form

atio

nbe

twee

nU

O221

and

C 2O

422io

nsth

ese

solu

tions

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

UO

2C2O

4•3H

2Ow

asst

irred

with

solu

tions

ofth

ede

sire

dco

mpo

sitio

nfo

r6

h.P

relim

inar

yex

perim

ents

show

edth

atth

isw

assu

ffici

ent

for

equi

libriu

mto

bere

ache

d.C

once

ntra

tion

ofur

aniu

min

the

satu

rate

dso

lutio

nsw

asde

term

ined

grav

imet

rical

lyas

U3O

8af

ter

evap

orat

ing

and

igni

ting

anal

iquo

tof

the

solu

tion.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

Con

cent

ratio

nof

uran

ium

:62.

5%~a

utho

rs!.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4

;@2

031-

89-2#

~2!

Oxa

licac

id;

C 2H

2O4

;@1

44-6

2-7#

~3!

Per

chlo

ricac

id;

HC

lO 4;

@760

1-90

-3#~4

!W

ater

;H 2

O;

@773

2-18

-5#

A.I

.Mos

kvin

and

E.A

.Zak

haro

va,Z

h.N

eorg

.Khi

m.

4,21

51–

60~1

959!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

3c 2

/mol

dm2

3 :0.

08–

0.63

7c 3

/mol

dm2

3 :0.

5an

d1.

0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofU

O 2C

2O4

inC

2H2O

4–

HC

lO4

solu

tions

a

HC

lO4

(c3

/mol

dm2

3 )C

2H2O

4

(c2

/mol

dm2

3 )U

O2C

2O4

(102

c 1/m

oldm

23 )

0.5

0.08

01.

63

0.15

91.

71

0.23

81.

88

0.31

82.

14

0.47

62.

32

0.63

62.

56

1.0

0.08

01.

65

0.15

81.

59

0.31

61.

35

0.47

61.

29

0.63

61.

16

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.

Add

ition

alin

form

atio

n:F

rom

the

incr

easi

ngso

lubi

lity

ofU

O 2C2O

4w

ithin

crea

sing

oxal

icac

idco

ncen

trat

ion

in0.

5m

oldm23

HC

lO4,

the

auth

ors

calc

ulat

edst

abili

tyco

nsta

nts

ofth

eU

O 2C2O

4an

dU

O 2~C

2O4!

222

com

plex

es.

In1.

0m

oldm2

3H

ClO

4,th

ede

crea

sing

solu

bilit

yof

UO 2C

2O4

with

incr

easi

ngox

alic

acid

conc

entr

atio

nw

asta

ken

asan

evid

ence

for

the

abse

nce

ofco

mpl

exfo

rmat

ion

betw

een

UO

221an

dC 2

O422

ion

inth

ese

solu

tions

.S

olid

phas

esw

ere

not

inve

stig

ated

. Aux

iliar

yIn

form

atio

n

Co

~1!

~2!

~3!

~4!

Va

T/

c 2 0.0

c 3 (c a E Ad

Fr

sta

wi

in

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4

;@2

031-

89-2#

Am

mon

ium

oxal

ate;

~NH

4!2C

2O4

;@1

113-

38-8#

Per

chlo

ricac

id;

HC

lO 4;

@760

1-90

-3#W

ater

;H 2

O;

@773

2-18

-5#

A.I

.Mos

kvin

and

E.A

.Zak

haro

va,Z

h.N

eorg

.Khi

m.

4,21

51–

60~1

959!

.

riabl

es:

Pre

pare

dby

:

K:

293

/mol

dm2

3 :0.

07–

0.28

/mol

dm2

3 :0.

5,1.

0,an

d3.

0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofU

O 2C

2O4

in~N

H4!

2C2O

4–

HC

lO4

solu

tions

a

HC

lO4

3/m

oldm

23 )

~NH

4!2C

2O4

(c2

/mol

dm2

3 )U

O2C

2O4

(102

c 1/m

oldm

23 )

HC

lO4

(c3

/mol

dm2

3 )~N

H4!

2C2O

4

(c2

/mol

dm2

3 )U

O2C

2O4

(102

c 1/m

oldm

23 )

0.5

0.07

01.

963.

00.

070

1.16

0.10

52.

430.

140

1.13

0.14

03.

210.

175

0.96

0

0.17

04.

260.

210

0.87

8

0.21

05.

910.

245

0.78

0

0.24

57.

500.

280

0.75

9

0.28

09.

09

1.0

0.07

01.

54

0.10

51.

56

0.14

01.

60

0.17

01.

70

0.21

02.

00

0.24

52.

36

0.28

02.

65

quili

briu

mso

lidph

ases

wer

eno

tin

vest

igat

ed.

ditio

nali

nfor

mat

ion:

crea

sing

solu

bilit

yof

UO 2C

2O4

with

incr

easi

ngam

mon

ium

oxal

ate

in3.

0m

oldm2

3H

ClO

4so

lutio

nsco

ncen

trat

ion

was

take

nas

anid

ence

for

the

abse

nce

ofco

mpl

exfo

rmat

ion

betw

een

UO

221an

dC 2

O422

ions

inth

ese

solu

tions

.S

olid

phas

esw

ere

not

inve

stig

ated

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

UO

2C2O

4•3H

2Ow

asst

irred

with

solu

tions

ofth

ede

sire

dco

mpo

sitio

nfo

r6

h.P

relim

inar

yex

perim

ents

show

edth

atth

isw

assu

ffici

ent

for

equi

libriu

mto

bere

ache

d.C

once

ntra

tion

ofur

aniu

min

the

satu

rate

dso

lutio

nsw

asde

term

ined

grav

imet

rical

lyas

U3O

8af

ter

evap

orat

ing

and

igni

ting

anal

iquo

tof

the

solu

tion.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

Con

cent

ratio

nof

uran

ium

:62.

5%~a

utho

rs!.

622622 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4

;@2

031-

89-2#

~2!

Am

mon

ium

oxal

ate;

~NH

4!2C

2O4

;@1

113-

38-8#

~3!

Nitr

icac

id;

HN

O3

;@7

697-

37-2#

~4!

Wat

er;

H 2O

;@7

732-

18-5#

A.I

.Mos

kvin

and

E.A

.Zak

haro

va,Z

h.N

eorg

.Khi

m.

4,21

51–

60~1

959!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

3c 2

/mol

dm2

3 :0.

07–

0.28

c 3/m

oldm

23 :

0.5

and

1.0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofU

O 2C

2O4

in~N

H4!

2C2O

4–

HN

O3

solu

tions

a

HN

O3

(c3

/mol

dm2

3 )~N

H4!

2C2O

4

(c2

/mol

dm2

3 )U

O2C

2O4

(102

c 1/m

oldm

23 )

HN

O3

(c3

/mol

dm2

3 )~N

H4!

2C2O

4

(c2

/mol

dm2

3 )U

O2C

2O4

(102

c 1/m

oldm

23 )

0.5

0.07

02.

121.

00.

070

2.09

0.10

52.

610.

105

2.13

0.14

03.

480.

140

2.18

0.17

04.

440.

170

2.37

0.21

06.

120.

210

2.70

0.24

57.

870.

245

2.78

0.28

09.

710.

280

3.18

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

UO

2C2O

4•3H

2Ow

asst

irred

with

solu

tions

ofth

ede

sire

dco

mpo

sitio

nfo

r6

h.P

relim

inar

yex

perim

ents

show

edth

atth

isw

assu

ffici

ent

for

equi

libriu

mto

bere

ache

d.C

once

ntra

tion

ofur

aniu

min

the

satu

rate

dso

lutio

nsw

asde

term

ined

grav

imet

rical

lyas

U3O

8af

ter

evap

orat

ing

and

igni

ting

anal

iquo

tof

the

solu

tion.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

Con

cent

ratio

nof

uran

ium

:62.

5%~a

utho

rs!.

Co

~1!

~2!

~3!

~4!

Va

T/

c 2 c 3 (c a E Ad

De

ev


wer

eeq

uilib

rate

dfo

r3

–6

days

.T

hetim

ene

cess

ary

for

reac

hing

equi

libriu

min

crea

sed

with

incr

easi

ngco

ncen

trat

ion

ofU

O2~

NO

3!.

The

vess

els

used

wer

epr

otec

ted

from

light

topr

even

tth

efo

rmat

ion

ofba

sic

oxal

ates

ofU

~IV

!.S

atur

ated

solu

tions

wer

ean

alyz

edfo

rur

aniu

m,

oxal

ate,

and

nitr

ate.

Ura

nium

and

oxal

ate

wer

ede

term

ined

bytit

ratio

nw

ithK

MnO

4so

lutio

n,ni

trat

ew

asde

term

ined

byth

eK

jeld

ahl

met

hod

afte

rre

duci

ngN

O 32w

ithD

ewar

dal

loy.

Com

posi

tion

ofth

eeq

uilib

rium

solid

phas

esw

asde

term

ined

byth

em

etho

dof

indi

ffere

ntco

mpo

nent

(NO 32

),in

som

eca

ses

also

bych

emic

alan

alys

isan

dop

tical

mic

rosc

opy.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

oox

alat

e;U

O 2C

2O4;

@203

1-89

-2#U

rani

um~V

I!di

oxo

dini

trat

e;U

O 2~N

O3!

2;@1

0102

-06-

04#

Oxa

licac

id;

C 2H

2O4;

@144

-62-

7#N

itric

acid

;H

NO

3;

@769

7-37

-2#W

ater

;H 2

O;

@773

2-18

-5#

K.

A.

Bol

shak

ovan

dS

.S

.K

orov

in,

Zh.

Neo

rg.

Khi

m.

2,19

40–

50~1

957!

.

riabl

es:

Pre

pare

dby

:

K:

298

mpo

sitio

nJ.

Hala

Exp

erim

enta

lDat

a

ompo

sitio

nof

solu

tions

satu

rate

dat

25°C

,an

dco

rres

pond

ing

tose

lect

edse

ctio

nsof

the

quar

tern

ary

syst

emU

O221

,H1

i C2O

422,N

O32

UO

2~N

O3!

2

(100

w2

mas

s%

)

HN

O3

(100

w4

mas

s%

)

UO

2C2O

4

(100

w1

mas

s%

)S

olid

phas

ef

HN

O3

(100

w4

mas

s%

)

UO

2~N

O3!

2

(100

w2

mas

s%

)

UO

2C2O

4

(100

w1

mas

s%

)S

olid

phas

ef

47.5

0a6.

060

A22

.22c

26.5

20.

47B

47.1

06.

000.

43A1

B22

.31

23.3

80.

42B

39.9

05.

110.

38B

23.5

618

.73

0.40

B

28.3

13.

550.

46B

22.4

216

.01

0.41

B

21.2

1—

0.54

B22

.37

10.2

30.

48B

14.4

2—

0.57

B22

.60

5.46

0.70

B

7.58

—0.

53B

22.5

11.

811.

26B

42.9

3a11

.16

0A

41.0

610

.66

0.46

A1B

C2H

2O4

HN

O3

UO

2C2O

4S

olid

phas

ef

40.1

310

.35

0.44

B~1

00w

3~1

00w

4~1

00w

1

35.2

89.

150.

37B

mas

s%!

mas

s%!

mas

s%!

31.9

7—

0.43

B

22.8

0—

0.47

B1.

73d0

1.80

B

14.9

0—

0.55

B1.

742.

170.

94B

8.83

—0.

57B

1.72

9.00

0.64

B

8.83

—0.

57B

1.73

11.8

70.

62B

8.83

—0.

57B

1.69

27.1

60.

97B

1.68

31.0

11.

29B

31.9

6a23

.08

0A

1.68

35.5

01.

45B

31.4

422

.66

0.83

A1B

1.52

39.8

61.

82B

31.0

621

.05

0.55

B1.

5145

.30

2.28

B

27.0

617

.70

0.38

B1.

7546

.12

2.58

B

22.3

113

.93

0.37

B1.

7447

.02

2.93

B1

D

17.4

4—

0.42

B1.

5050

.55

2.60

D

16.6

310

.94

0.44

B1.

5164

.57

1.36

D

10.6

2—

0.47

B

6.27

—0.

55B



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

ooxa

late

;U

O 2C

2O4;

@203

1-89

-2#~2

!U

rani

um~V

I!di

oxo

dini

trat

e;U

O 2~N

O3!

2;@1

0102

-06-

4#~3

!W

ater

;H 2

O;

@773

2-18

-5#

K.

A.

Bol

shak

ovan

dS

.S

.K

orov

in,

Zh.

Neo

rg.

Khi

m.

2,19

40–

50~1

957!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

810

0w

2/m

ass

%:

0–

56.2

3J.

Hala

Exp

erim

enta

lDat

a

Com

posi

tion

ofso

lutio

nssa

tura

ted

at25

°C

UO

2~N

O3!

2

(100

w2

/mas

s%

)U

O2~

NO

3!(m

2/m

olkg

21 !

aU

O2C

2O4

(100

w1

/mas

s%

)U

O2C

2O4

(m1

/mol

kg2

1 !a

Sol

idph

aseb

00

0.58

0.01

63A

1.26

0.03

260.

580.

0165

A

5.18

0.14

00.

600.

0178

A

9.55

0.27

00.

630.

0196

A

12.6

60.

371

0.63

0.02

03A

18.7

60.

591

0.62

0.02

15A

20.4

00.

655

0.60

0.02

12A

23.6

40.

792

0.58

0.02

14A

31.0

31.

150.

540.

0220

A

43.3

91.

960.

440.

0219

A

51.7

82.

750.

350.

0204

A

55.5

03.

190.

310.

0196

A1B

55.8

53.

230.

260.

0166

B

56.0

03.

240.

120.

0076

4B

56.2

33.

260

0B

a Cal

cula

ted

byco

mpi

ler.

b ~A!

UO

2C2O

4•3H

2O,

@188

60-4

3-0#;

~B!

UO

2~N

O3!

2•6H

2O,

@135

20-8

3-7#.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Mix

ture

sof

the

desi

red

com

posi

tions

Not

hing

spec

ified

.

Co

~1!

~2!

~3!

~4!

~5!

Va

T/

co C

J

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Mix

ture

sof

the

desi

red

com

posi

tion

wer

eeq

uilib

rate

dfo

r3

–6

days

.T

hetim

ene

cess

ary

for

reac

hing

equi

libriu

min

crea

sed

with

incr

easi

ngco

ncen

trat

ion

ofU

O2~

NO

3!2.

The

vess

els

used

wer

epr

otec

ted

from

light

topr

even

tth

efo

rmat

ion

ofba

sic

U~IV

!ox

alat

es.

Sat

urat

edso

lutio

nsw

ere

anal

yzed

for

uran

ium

,ox

alat

e,an

dni

trat

e.U

rani

uman

dox

alat

ew

ere

dete

rmin

edby

titra

tion

with

KM

nO4

solu

tion,

nitr

ate

was

dete

rmin

edby

the

Kje

ldah

lm

etho

daf

ter

redu

cing

NO 32

with

Dew

ard

allo

y.C

ompo

sitio

nof

the

equi

libriu

mso

lidph

ases

was

dete

rmin

edby

the

met

hod

ofin

diffe

rent

com

pone

nt(N

O 32),

inso

me

case

sal

soby

chem

ical

anal

ysis

and

optic

alm

icro

scop

y.

No

deta

ilsre

port

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

5.11

.7.

Ura

nium

„V

I…D

ioxo

„ox

alat

e…

N,N

8-D

imet

hylF

orm

amid

eM

onos

olva

te

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

oox

alat

eN

,N 8

-dim

ethy

lfor

mam

ide

noso

lvat

e;U

O 2C2O

4•C

3H7N

O;

@838

35-4

9-8#

N,

N8-

dim

ethy

lfor

mam

ide;

C 3H7N

O;

@68-

12-2

#N

itric

acid

;H

NO

3;

@769

7-37

-2#O

xalic

acid

;C 2

H2O

4;

@144

-62-

7#W

ater

;H 2

O;

@773

2-18

-5#

D.

N.

Byk

hovs

kii,

M.

A.

Kuz

min

a,an

dG

.I.

Pet

rzha

k,R

adio

khim

iya2

5,45

–7

~198

3!.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

dm2

3 :0

–5.

0/m

oldm

23 :

1.0

/mol

dm2

3 :0.

15

J.H

ala

Exp

erim

enta

lDat

a

lubi

lity

ofU

O2C

2O4•

C3H

7NO

at25

°Cin

solu

tions

cont

aini

ng1.

0m

oldm2

3H

NO

3an

d0.

15m

oldm

23

oxal

icac

idas

afu

nctio

nof

H7N

Oco

ncen

trat

iona

C3H

7NO

(c2

/mol

dm2

3 )U

O2C

2O4•

C3H

7NO

(103

c 1/m

oldm

23 )

C3H

7NO

(c2

/mol

dm2

3 )U

O2C

2O4•

C3H

7NO

(103

c 1/m

oldm

23 )

015

.76

0.7

1.5

0.30

60.

01

0.10

2.35

60.

212.

00.

306

0.01

0.25

1.15

60.

073.

00.

306

0.02

0.50

0.58

60.

014.

00.

336

0.01

0.75

0.45

60.

025.

00.

416

0.02

1.0

0.37

60.

02

quili

briu

mso

lidph

ases

wer

eno

tin

vest

igat

ed.

ditio

nali

nfor

mat

ion:

sore

port

edw

as,

ingr

aphi

cal

form

,so

lubi

lity

ofU

O2C

2O4•

C3H

7NO

asa

func

tion

ofox

alic

acid

conc

entr

atio

n,in

mol

dm2

3H

NO

3/0

.5m

oldm

23

C3H

7NO

or1.

0m

oldm

23

HN

O3/2

.0m

oldm

23

C3H

7NO

solu

tions

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

xces

sso

lidw

aseq

uilib

rate

dw

ithlu

tions

ofth

ede

sire

dco

mpo

sitio

nfo

r30

hw

hile

equi

libriu

mw

asat

tain

edaf

ter

6h.

Con

cent

ratio

nof

uran

ium

inth

esa

tura

ted

solu

tions

was

dete

rmin

edsp

ectr

opho

tom

etric

ally

with

arse

nazo

III.

1

The

UO 2

C2O

4•C

3H7N

Oco

mpl

exw

aspr

epar

edby

prec

ipita

tion

with

0.8

mol

dm2

3ox

alic

acid

ofa

solu

tion

whi

chw

as0.

1m

oldm

23

inur

aniu

man

d0.

6m

oldm

23

inC

3H7N

O.2

The

crys

talli

neso

lidw

asw

ashe

dw

ithw

ater

,et

hano

land

ethe

r,an

dw

asch

arac

teriz

edby

chem

ical

anal

ysis

and

x-ra

ydi

ffrac

tion.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

2K

~aut

hors!

.S

olub

ility

:se

eau

thor

s’da

taab

ove.

Ref

eren

ces:

1 S.

A.

Nik

itina

,A

.A

.Li

povs

kii,

and

T.

A.

Dem

yano

va,

Rad

iokh

imiy

a20,

900

~197

8!.

2 D.

N.

Byk

hovs

kii,

M.

A.

Kuz

min

a,L.

V.

Sol

ncev

,an

dA

.G

.T

utov

,R

adio

khim

iya2

4,46

8~1

982!

.

624624 JIRI HALA

C2H

2O4

(100

w3

mas

s%!

HN

O3

(100

w4

mas

s%!

UO

2C2O

4

(100

w1

mas

s%!

Sol

idph

asef

C2H

2O4

(100

w3

mas

s%!

HN

O3

(100

w4

mas

s%!

UO

2C2O

4

(100

w1

mas

s%!

Sol

idph

asef

9.30

b2.

170

C9.

90e

02.

44B1

C

8.98

2.17

1.31

C1B

8.98

2.17

1.51

B1C

8.33

—1.

68B

7.81

5.10

0.78

B1C

7.05

1.33

1.80

B7.

326.

470.

61B

1C

6.14

1.25

1.67

B6.

659.

090.

49B

1C

4.45

—1.

98B

6.58

10.5

20.

40B1C

1.06

—1.

35B

5.99

13.8

90.

38B1C

4.63

21.5

40.

35B1

C

8.34

b5.

320

C4.

1326

.25

0.41

B1C

7.81

5.10

0.78

C1B

3.43

35.5

30.

66B1

C

6.97

4.62

1.31

B3.

4739

.15

0.89

B1

C

4.22

2.67

1.22

B3.

3445

.74

1.94

B1

C

2.04

—1.

32B

3.28

47.0

42.

14B1C

1D

1.19

—1.

24B

3.22

51.4

71.

86B1D

0.73

—1.

21B

4.26

62.3

01.

30B1D

7.02

b9.

520

C

6.65

9.09

0.49

C1B

6.48

8.60

0.73

B

4.59

5.68

0.72

B

2.30

—0.

80B

1.74

2.17

0.94

B

1.08

—0.

90B

a Sec

tion

with

cons

tant

ratio

ofU

O 2~N

O3!

2an

dH

NO 3

conc

entr

atio

ns.

b Sec

tion

with

cons

tant

ratio

ofC 2H

2O4

and

HN

O 3co

ncen

trat

ions

.c S

ectio

nw

ithco

nsta

ntH

NO 3

conc

entr

atio

n.d S

ectio

nw

ithco

nsta

ntC 2H

2O4

conc

entr

atio

n.e E

uton

icpo

ints

for

UO 2

C2O

4an

dC 2

H2O

4.f ~A

!U

O2~

NO

3!2•

6H2O

,@1

3520

-83-

7#;~B

!U

O2C

2O4•

3H2O

,@1

8860

-43-

0#;~C

!C

2H2O

4•2H

2O,

@615

3-56

-6#;

~D!

UO

2C2O

4•H

2O,

@#.

Add

ition

alin

form

atio

n:In

solu

tions

cont

aini

ng.

25m

ass

%U

O 2~N

O3!

2an

d.

30m

ass

%H

NO 3

,U

O2C

2O4

show

eda

tend

ency

tow

ard

form

atio

nof

supe

rsat

u-ra

ted

solu

tions

.Thu

sfo

r28

.95

mas

s%

UO

2~N

O3!

2an

d38

.45

mas

s%

HN

O 3,th

eco

ncen

trat

ion

ofU

O 2C2O

4re

ache

d8.

23m

ass

%,w

hile

the

corr

espo

ndin

geq

uilib

rium

solu

bilit

yw

ason

ly2.

72m

ass

%:

Met

asta

ble

solu

tions

wer

efo

rmed

only

whe

ndr

yU

O2C

2O4•

3H2O

was

adde

dto

aso

lutio

nof

UO 2~

NO

3!2

inH

NO

3.

Aux

iliar

yIn

form

atio

n

Co

~1!

mo

~2!

~3!

~4!

~5!

Va

T/

c 2 c 3 c 4 So

C3

a E Ad

Al

1.0

Me

Iso

so


not

inve

stig

ated

.E

stim

ated

Err

or:

Tem

pera

ture

:pr

ecis

ion6

0.2

K~a

utho

rs!.

Sol

ubili

ty:

see

auth

ors’

data

abov

e.

Ref

eren

ces:

1 S.

A.

Nik

itina

,A

.A

.Li

povs

kii,

and

T.

A.

Dem

yano

va,

Rad

iokh

imiy

a20,

900

~197

8!.

2 D.

N.

Byk

hovs

kii,

M.

A.

Kuz

min

a,L.

V.

Sol

ncev

,an

dA

.G

.T

utov

,R

adio

khim

iya2

4,46

8~1

982!

.

5.12

.Am

mon

ium

Tris

„o

-hyd

roxy

benz

oato

…D

ioxo

uran

ate

„V

I…

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

tris~

hydr

oxyb

enzo

ato!di

oxou

rana

te~V

I!;

4@U

O2~

C7H

5O3)

3];

@#

Am

mon

ium

hydr

oxyb

enzo

ate~s

alic

ylat

e!;N

H4~

C7H

5O3)

;#

Wat

er;

H 2O

;@7

732-

18-5#

O.

E.

Zvy

agin

tsev

and

B.

N.

Sud

arik

ov,

Zh.

Neo

rg.

Khi

m.

2,12

8–

37~1

957!

.

riabl

es:

Pre

pare

dby

:

K:

291

–36

9

4~C

7H5O

3!/g

kg2

1sa

tura

ted

solu

tion:

0–

230

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4@

UO

2~C

7H5O

3)3]

inw

ater

and

inso

lutio

nsof

NH 4~

C7H

5O3)

atdi

ffere

ntte

mpe

ratu

res

a

Sol

ubili

tyof

NH

4@U

O2~

C7H

5O3)

3]

inw

ater

asa

func

tion

ofte

mpe

ratu

re

Tem

pera

ture

~°C

!U

~gkg

21 !b

NH

4@U

O2~

C7H

5O3)

3]

(102

m1

/mol

kg2

1 )c

181.

400.

590

503.

731.

58

755.

722.

44

967.

963.

42

Sol

ubili

tyat

18°C

ofN

H 4@U

O2~

C7H

5O3)

3]

asa

func

tion

ofN

H 4~C

7H5O

3)co

ncen

trat

iond

Sol

ubili

tyat

40°C

ofN

H 4@U

O2~

C7H

5O3)

3]

asa

func

tion

ofN

H 4~C

7H5O

3)co

ncen

trat

iond

4~C

7H5O

3)~g

kg2

1 !bU

~gkg

21 !b

NH

4@U

O2~

C7H

5O3)

3]

(103

mol

kg2

1 )b,c

NH

4~C

7H5O

3)~g

kg2

1 !bU

~gkg

21 !b

NH

4@U

O2~

C7H

5O3)

3]

(103

mol

kg2

1 )b,c

01.

405.

880

3.09

13.0

200.

291.

2210

01.

245.

21

500.

110.

462

230

0.56

2.35

100

0.08

0.33

6

230

0.12

0.50

4

Sol

ubili

tyof

NH

4@U

O2~

C7H

5O3)

3]

inso

lutio

nsco

ntai

ning

230

gkg2

1N

H4~

C7H

5O3)

Tem

pera

ture

~°C

!U

~gkg

21 !b

NH

4@U

O2~

C7H

5O3)

3]

(103

mol

kg2

1 )b,c

180.

120.

504

400.

562.

35

701.

054.

41

Sol

ubili

tyat

18°C

ofN

H 4@U

O2~

C7H

5O3)

3]

inso

lutio

nsco

ntai

ning

100

gkg2

1N

H4~

C7H

5O3)

asa

func

tion

ofpH

Sol

ubili

tyat

18°C

ofN

H 4@U

O2~

C7H

5O3)

3]

inso

lutio

nsco

ntai

ning

200

gkg2

1N

H4~

C7H

5O3)

asa

func

tion

ofpH

pHU

~gkg

21 !b

NH

4@U

O2~

C7H

5O3)

3]

(103

mol

kg2

1 )b,c

pHU

~gkg

21 !b

NH

4@U

O2~

C7H

5O3)

3]

(103

mol

kg2

1 )b,c

5.10

0.08

0.33

65.

250.

120.

504

5.43

0.12

0.50

46.

463.

0913

.0

6.02

2.80

11.8

6.91

11.6

448

.9

6.25

3.09

13.0

8.64

12.9

454

.4

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.b G

ram

spe

rkg

satu

rate

dso

lutio

n.c C

alcu

late

dby

com

pile

r.d pH

55.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

oox

alat

eN

,N 8

-dim

ethy

lfor

mam

ide

mon

osol

vate

;U

O 2C2O

4•C

3H7N

O;

@838

35-4

9-8#

~2!

N,N

8-di

met

hylf

orm

amid

e;C 3H

7NO

;@6

8-12

-2#

~3!

Sod

ium

perc

hlor

ate;

NaC

lO 4;

@760

1-89

-0#~4

!W

ater

;H 2

O;

@773

2-18

-5#

D.

N.

Byk

hovs

kii,

M.

A.

Kuz

min

a,an

dG

.I.

Pet

rzha

k,R

adio

khim

iya2

5,45

–7

~198

3!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8c 2

/mol

dm2

3 :0.

05–

5.0

c 3/m

oldm

23 :

0.1

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

UO

2C2O

4•C

3H7N

Oin

0.1

mol

dm2

3N

aClO

4so

lutio

nsat

25°C

asa

func

tion

ofC

3H7N

Oco

ncen

trat

iona

C3H

7NO

(c2

/mol

dm2

3 !U

O2C

2O4•

C3H

7NO

(103

c 1/m

oldm

23 !

C3H

7NO

(c2

/mol

dm2

3 )U

O2C

2O4•

C3H

7NO

(103

c 1/m

oldm

23 !

0.05

03.

116

0.07

1.0

0.31

60.

01

0.10

1.68

60.

101.

50.

276

0.02

0.15

1.18

60.

042.

00.

256

0.01

0.20

0.99

60.

122.

50.

246

0.01

0.25

0.70

60.

083.

00.

256

0.01

0.35

0.60

60.

014.

00.

266

0.02

0.50

0.46

60.

025.

00.

316

0.02

0.75

0.32

60.

01

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.

Add

ition

alin

form

atio

n:T

heau

thor

sas

sum

edof

the

exis

tenc

eof

UO

2C2O

4~C

3H7N

O!

and

UO 2

C2O

4~C

3H7N

O! 2

spec

ies

inth

esa

tura

ted

solu

tions

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

solid

was

equi

libra

ted

with

solu

tions

ofth

ede

sire

dco

mpo

sitio

nfo

r30

hw

hile

equi

libriu

mw

asat

tain

edaf

ter

6h.

Con

cent

ratio

nof

uran

ium

inth

esa

tura

ted

solu

tions

was

dete

rmin

edsp

ectr

opho

tom

etric

ally

with

arse

nazo

III.

1S

olid

phas

esw

ere

The

UO 2

C2O

4•C

3H7N

Oco

mpl

exw

aspr

epar

edby

prec

ipita

tion

with

0.8

mol

dm2

3ox

alic

acid

ofa

solu

tion

whi

chw

as0.

1m

oldm

23

inur

aniu

man

d0.

6m

oldm

23

inC

3H7N

O.2

The

crys

talli

neso

lidw

asw

ashe

dw

ithw

ater

,et

hano

l,an

det

her,

and

was

char

acte

rized

bych

emic

alan

alys

isan

dx-

ray

diffr

actio

n.

Co

~1!

NH

~2!

@ ~3!

Va

T/

NH

NH

J

5.13

.U

rani

um„V

I…D

ioxo

„8-

hydr

oxyq

uino

-lina

te…

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

obi

s~8-

hydr

oxy-

quin

olin

ate!~

8-dr

oxyq

uino

line!;

UO

2~C

9H6N

O! 2•C

9H7N

O;

or

7H19

N3O

5U;

@178

55-7

5-3#

1,4-

diox

ane;

C 4H8O

2;@1

23-9

1-1#

R.

G.

Cha

rles

and

H.

Fre

iser

,J.

Am

.C

hem

.S

oc.

73,

5223

–4

~195

1!.

riabl

es:

Pre

pare

dby

:

K:

298

J.H

ala

Exp

erim

enta

lDat

ae

solu

bilit

yof

UO 2

~C9H

6NO

! 2•C

9H7N

Oin

1,4-

diox

ane

at25

°Cis

repo

rted

tobex 1

50.

000

51.

Fro

mth

isth

eco

mpi

ler

calc

ulat

ed5

2.76

310

25

mol

kg2

1 .

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

eso

lubi

lity

was

dete

rmin

edby

wei

ghin

gth

ere

sidu

eta

ined

byev

apor

atio

nof

aw

eigh

edpo

rtio

nof

the

satu

rate

dlu

tion.

The

latte

rw

aspr

epar

edby

extr

actin

gth

eso

lid

2~C

9H6N

O! 2•C

9H7N

Oin

aS

oxhl

etex

trac

tor,

and

allo

win

gsa

tura

ted

solu

tion

toco

olto

room

tem

pera

ture

.

UO

2~C

9H6N

O! 2•C

9H7N

Ow

aspr

epar

edby

prec

ipita

tion

with

8-hy

drox

yqui

nolin

eof

anaq

ueou

sso

lutio

nof

aU

O221

salt

acco

rdin

gto

Ref

.1.

The

prod

uct

was

drie

dat

the

reco

mm

ende

dte

mpe

ratu

rein

aco

nsta

ntte

mpe

ratu

reov

en.

8-hy

drox

yqui

nolin

eus

ed~L

emke

Co.!

was

recr

ysta

llize

dfr

omal

coho

lan

dw

ater

.1,

4-di

oxan

e~C

arbi

dean

dC

arbo

nC

o.!w

aspu

rified

byth

epr

oced

ure

give

nin

Ref

.2,

and

dist

illed

from

sodi

umbe

fore

use.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 F.

J.W

elch

er,O

rga

nic

An

aly

tica

lR

ea

ge

nts~

Van

Nos

tran

d,N

ewY

ork,

1947

!,V

ol.

1,p.

265.

2 A.

Wei

ssbe

rger

and

E.

Pos

kaue

r,O

rga

nic

So

lve

nts~

Cla

rend

on,

Oxf

ord,

1935

!.

626626 JIRI HALA

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

NH

4@U

O2~

C7H

5O3)

3]•

4H2O

was

stirr

edfo

r24

hw

ithth

eso

lutio

nsun

der

the

desi

red

cond

ition

s.In

the

satu

rate

dso

lutio

ns,

uran

ium

was

dete

rmin

edgr

avim

etric

ally

;a

wei

ghed

aliq

uot

ofth

esa

tura

ted

solu

tion

was

evap

orat

edto

dryn

ess,

and

the

resi

due

was

igni

ted

toU

3O8.

NH

4@U

O2~

C7H

5O3)

3]•

4H2O

was

obta

ined

bypr

ecip

itatio

nw

ithsa

licyl

icac

idof

aU

O 221so

lutio

nat

pH3

–6

inth

epr

esen

ceof

NH

41io

ns.

The

salt

was

obta

ined

asor

ange

crys

tals

.It

was

recr

ysta

llize

dfr

omho

tso

lutio

n,an

ddr

ied

at70

–75

°C.

Ana

lysi

s,fo

und/

calc

ulat

edfo

rth

ete

trah

ydra

te~mas

s%!

:U

O221

34.9

6/35

.02;

C 7H5O

3253

.28/

53.3

1;N

H41

2.41

/2.3

3;H 2

O9.

75/9

.34.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

hy C2

~2!

Va

T/

Th

m1

Me

Th

ob so UO

the


Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

ypr

oduc

tof

UO 2

~C9H

6NO

! 2•~C

9H7N

O)

was

dete

rmin

edby

two

proc

edur

es.

Inon

e,

1g

ofso

lidco

mpl

exw

aseq

uilib

rate

dfo

r4

days

with

100

mL

solu

tion

initi

ally

cont

aini

ng0.

005

35–

0.05

35m

oldm2

3H

Cl.

Inth

eot

her

one,

the

com

plex

was

prec

ipita

ted

in10

0m

Lvo

lum

etric

flask

sfr

om10

mL

0.1

mol

dm2

3U

O2~

NO

3!2

and

25m

L0.

1m

oldm

23

C9H

7NO

in0.

107

mol

dm2

3H

Cl,

and

pHof

the

solu

tion

was

adju

sted

byad

ding

vary

ing

volu

mes

ofam

mon

iaso

lutio

n.T

hevo

lum

esw

ere

fille

dup

toth

em

ark

with

dist

illed

wat

er,

and

the

flask

sw

ere

equi

libra

ted

for

4da

ys.

Equ

ilibr

atio

nin

both

serie

sof

mea

sure

men

tsw

asca

rrie

dou

tin

anai

r-he

ated

ther

mos

tat.

The

satu

rate

dso

lutio

nsw

ere

anal

yzed

for

uran

ium~

8-hy

drox

yqui

nolin

ew

asde

stro

yed

byig

nitio

nan

dur

aniu

mde

term

ined

titrim

etric

ally

byth

eH

SO

32/P

O432

met

hod3

or,

atlo

wur

aniu

mco

ncen

trat

ions

,co

lorim

etric

ally

with

arse

nazo

,4

and

8-hy

drox

yqui

nolin

e~t

itrim

etric

ally

with

brom

ate!.

The

pHw

asm

easu

red

pote

ntio

met

rical

lyw

itha

glas

sel

ectr

ode.

UO

2~C

9H6N

O! 2•C

9H7N

Ow

aspr

epar

edac

cord

ing

toR

ef.5

from

8-hy

drox

yqui

nolin

epu

rified

bysu

blim

atio

n.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

2K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 N.

P.

Kom

aran

dZ

.A

.T

rety

ak,

Zh.

Ana

l.K

him

.10,

236

~195

5!.

2 E.S

.Tin

ovsk

aya,

Nau

ch.Z

ap.K

ievs

k.U

niv.

,Chi

m.S

born

ik5,

220

~194

9!.

3 N.

P.

Kom

ar,

Zh.

Ana

l.K

him

.7,32

5~1

952!

.4 V

.I.

Kuz

nets

ov,

Dok

l.A

kad.

Nau

kS

SR5

0,22

7~1

945!

.5 R

.B

erg,

Th

eU

seo

fQ

uin

olin

ol

inA

na

lytic

al

Ch

em

istr

y~R

ussi

antr

ansl

atio

nof

Ger

man

editi

on!,~O

NT

I,M

osco

w,

1937

!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

o~8

-hyd

roxy

-qui

nolin

ate!~

8-hy

drox

yqui

nolin

e!;

2~C

9H6N

O! 2•C

9H7N

O;

orC 2

7H19

N3O

5U;

@178

55-7

5-3#

Am

mon

ium

carb

onat

e;(N

H 4!2C

O3;

@506

-87-

6#A

mm

oniu

mch

lorid

e;N

H 4C

l;@1

2125

-01-

8#W

ater

;H 2

O;

@773

2-18

-5#

A.

E.

Kly

gin

and

I.D

.S

mirn

ova,

Zh.

Neo

rg.

Khi

m.4,

42–

5~1

959!

.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

dm2

3 :0.

013

–0.

32J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

UO

2~C

9H6N

O! 2•C

9H7N

Oat

25°C

in(N

H 4! 2

CO

3so

lutio

nsa,

b

(NH

4!2C

O3

2/m

oldm

23 )

C9H

7NO

c

(103

mol

dm2

3 )U

d

(103

mol

dm2

3 )@H

1#e

(109

mol

dm2

3 )

0.01

299

0.23

50.

312

19.9

5

0.02

598

0.48

50.

231

8.71

0.03

897

0.41

50.

347

5.89

0.06

495

1.18

0.56

33.

89

0.12

992.

200.

9997

2.13

8

0.19

493.

071.

351.

349

0.25

983.

801.

590.

1514

0.29

884.

601.

780.

7763

0.32

474.

325

1.83

0.14

8

nic

stre

ngth

kept

at1.

0m

oldm2

3by

usin

gN

H 4C

l.he

auth

ors

did

not

repo

rtab

out

the

com

posi

tion

ofth

eeq

uilib

rium

solid

phas

e.T

heco

mpi

ler

assu

med

this

tobe

O2~

C9H

6NO

! 2•C

9H7N

O,

@178

55-7

5-3#.

otal

conc

entr

atio

nof

8-hy

drox

yqui

nolin

ein

the

satu

rate

dso

lutio

ns.

once

ntra

tion

ofur

aniu

min

the

satu

rate

dso

lutio

ns.

Hof

the

equi

libriu

msa

tura

ted

solu

tions

.

ditio

nalI

nfor

mat

ion:

Fro

mth

ein

crea

seof

the

solu

bilit

yof

UO 2~C

9H6N

O! 2•C

9H7N

Oin

the

pres

ence

of(N

H 4!2C

O3,

and

from

the

solu

bilit

yof

the

form

er,

1

auth

ors

calc

ulat

edth

ein

stab

ility

cons

tant

ofth

eU

O2~

CO

3!342

com

plex

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

solid

com

plex

UO

2~C

9H6N

O! 2•C

9H7N

Ow

aseq

uilib

rate

din

volu

met

ricfla

sks

with

solu

tions

cont

aini

ngth

ede

sire

dco

ncen

trat

ion

of(N

H4!

2CO

3at

ioni

cst

reng

thof

1.0

mol

dm23 .

the

flask

sw

ere

shak

enin

ath

erm

osta

tfo

r24

hw

hich

was

foun

dsu

ffici

ent

tore

ach

equi

libriu

m.

The

satu

rate

dso

lutio

nsw

ere

filte

red

thro

ugh

aN

o.4

sint

ered

glas

sfil

ter,

and

anal

yzed

for

uran

ium

~8-h

ydro

xyqu

inol

ine

was

dest

roye

dby

igni

tion

and

uran

ium

dete

rmin

edtit

rimet

rical

lyor

,at

low

conc

entr

atio

ns,

colo

rimet

rical

lyw

ithar

sena

zo!,an

d8-

hydr

oxyq

uino

line

~titr

imet

rical

lyw

ithbr

omat

e!.T

hepH

was

mea

sure

dpo

tent

iom

etric

ally

with

agl

ass

elec

trod

e.T

heco

ncen

trat

ion

ofth

e(N

H 4! 2

!CO

3st

ock

solu

tion

was

dete

rmin

edvo

lum

etric

ally

base

don

the

volu

me

ofC

O 2ga

sev

olve

d.

UO

2~C

9H6N

O! 2

.~C

9H7N

O!

was

prep

ared

acco

rdin

gto

Ref

.2

from

8-hy

drox

yqui

nolin

epu

rified

bysu

blim

atio

n.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.

E.

Kly

gin

and

N.

S.

Kol

yaga

,Z

h.N

eorg

.K

him3

,27

67~1

958!

.2 R

.B

erg,

Th

eU

seo

fQ

uin

olin

ol

inA

na

lytic

al

Ch

em

istr

y~R

ussi

antr

ansl

atio

nof

Ger

man

editi

on!~O

NT

I,M

osco

w,1

937!.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

obi

s~8-

hydr

oxy-

quin

olin

ate!~

8-hy

drox

yqui

nolin

e!;U

O2~

C9H

6NO

! 2•C

9H7N

O;

orC

27H

19N

3O5U

;@1

7855

-75-

3#~2

!W

ater

;H 2

O;

@773

2-18

-5#

A.

E.

Kly

gin

and

N.

S.

Kol

yaga

,Z

h.N

eorg

.K

him

.3,27

67–

70~1

958!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofU

O2~

C9H

6NO

! 2•C

9H7N

Oat

25°C

inw

atera

C9H

7NO

b

(103

mol

dm2

3 )U

e

(103

mol

dm2

3 )pH

fK

spg

(1029

mol

2dm

26 )

0.60

1c0.

218

3.90

1.63

2.40

c0.

797

3.40

1.79

2.95

c0.

983

3.26

0.87

5.75

c1.

913.

071.

4718

.7c

6.19

2.72

3.10

2.24

d1.

783.

382.

608.

95d

5.51

2.84

1.18

16.9

d7.

312.

651.

211.

960.

5h

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.b T

otal

conc

entr

atio

nof

8-hy

drox

yqui

nolin

ein

the

satu

rate

dso

lutio

n.c O

btai

ned

byis

othe

rmal

proc

edur

e.S

atur

ated

solu

tions

cont

aine

dva

ryin

gco

ncen

trat

ion

ofH

Cl,

from

0.00

535

to0.

0535

mol

dm2

3 .d O

btai

ned

bypr

ecip

itatio

npr

oced

ure.

Sat

urat

edso

lutio

nsco

ntai

ned

0.02

mol

dm2

3N

O32

,0.

027

mol

dm2

3C

l2,

and

0.04

3–

0.07

2m

oldm

23

NH

41.

e Tot

alco

ncen

trat

ion

ofur

aniu

min

the

satu

rate

dso

lutio

n.f pH

ofth

esa

tura

ted

solu

tion.

g Ksp

5@U

O221

#@R

2#2 @

HR

#~H

Rst

ands

for

C 9H7N

O!;

calc

ulat

edby

the

auth

ors

from

pHan

dco

ncen

trat

ions

ofur

aniu

man

dC

9H7N

Oby

usin

gau

thor

s’va

lues

ofdi

ssoc

iatio

nco

nsta

nts

of8-

hydr

oxyq

uino

line,K15

@H1

#@H

R#@

H2R

1#2

15

8.66

310

26

and

K2

5@H

1#@

R2

#@H

R#2

15

1.76

310

210

,an

dth

eeq

uilib

rium

cons

tant

for

the

hydr

olys

isof

UO

221,

Kh5

@UO

2OH

1#@

H1

#@U

O221

#21,

take

nfr

omR

ef.

1.h A

vera

geva

lue~

auth

ors!.

Add

ition

alin

form

atio

n:T

heau

thor

squ

ote

Ref

.2,

not

avai

labl

eto

the

com

pile

r,w

here

Ksp

ofU

O2~

C9H

6NO

! 2•C

9H7N

Ow

asre

port

edto

be3.

483

102

24m

ol2

dm2

6 .K

lygi

nan

dK

olya

gaco

nsid

ered

this

valu

eto

beer

rone

ous

sinc

ein

itsde

term

inat

ion

seve

ral

equi

libria

such

aspr

oton

atio

nof

C 9H

7NO

,co

mpl

exat

ion

ofU

O 221w

ithac

etat

eio

n,an

dhy

drol

ysis

ofU

O 221w

ere

not

take

nin

toco

nsid

erat

ion.

Co

~1!

bis

UO

~2!

~3!

~4!

Va

T/

c 2 (c a Io b T U c T d C e p Ad

the

J

Sol

ubili

ty:

see

abov

e.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

obi

s~8-

hydr

oxy-

quin

olin

ate!;

2~C

9H6N

O! 2

;or

UO

2C18

H12

N2O

4U;

@#

Tric

hlor

omet

hane

;C

HC

l3;

@67-

66-3

#

S.

Oki

,A

nal.

Chi

m.

Act

a44,

315

–22

~196

9!.

riabl

es:

Pre

pare

dby

:

J.H

ala

Exp

erim

enta

lDat

ae

solu

bilit

yof

UO 2

~C9H

6NO

! 2,

atan

unsp

ecifi

edro

omte

mpe

ratu

re,

inch

loro

form

isre

port

edto

bec 1

53.

993

102

4m

oldm

23 .

The

mpl

exdi

dno

tch

ange

inco

mpo

sitio

non

diss

olut

ion.

ditio

nali

nfor

mat

ion:

the

pres

ence

ofet

hano

lor

inch

loro

form

satu

rate

dw

ithw

ater

,th

eco

mpl

exde

com

pose

dup

ondi

ssol

utio

nac

cord

ing

toth

eeq

uatio

ns

3U

O2~

C9H

6NO

! 2~s

!1C

2H5O

H�

UO

2~C

9H6N

O! 2•C

9H7N

O1

UO

2~C

9H6N

O! 2•C

2H5O

H~s

!,

or

2U

O2~

C9H

6NO

! 2~s

!1H

2O�

UO

2~C

9H6N

O! 2•C

9H7N

O1

UO

2~C

9H6N

O!~

OH

! ~s!

,

spec

tivel

y~C

9H7N

Ois

8-hy

drox

yqui

nolin

e!.D

isso

lutio

nof

UO 2

~C9H

6NO

! 2in

etha

nolc

onta

inin

gch

loro

form

resu

lted

inth

efo

rmat

ion

ada

rkre

dso

lutio

nan

da

brow

nso

lidre

sidu

e.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

quili

briu

mw

asat

tain

edin

1–

2ys

.U

rani

umin

the

satu

rate

dso

lutio

nsw

asde

term

ined

lorim

etric

ally

with

arse

nazo

III1af

ter

rem

oval

ofC

HC

l 3an

dhy

drox

yqui

nolin

eby

heat

ing

the

sam

ple

at18

0°C

.

UO

2~C

9H6N

O! 2

was

prep

ared

acco

rdin

gto

Ref

.2by

heat

ing

the

UO

2~C

9H6N

O! 2•C

9H7N

Oco

mpl

exat

260

°Cfo

r1

h.T

hela

tter

was

prep

ared

acco

rdin

gto

the

proc

edur

egi

ven

inth

eco

mpi

latio

nfo

rth

eU

O 2~C

9H6N

O! 2•C

9H7N

O/e

than

ol/C

HC

l 3sy

stem

repo

rted

inth

esa

me

orig

inal

docu

men

t.T

heco

mpo

sitio

nof

UO

2~C

9H6N

O! 2

was

verifi

edby

chem

ical

anal

ysis

.C

hlor

ofor

m~G

.R

.gr

ade!

cont

aini

ng0.

5%et

hano

lw

asfir

stpu

rified

from

the

latte

rby

was

hing

with

dist

illed

wat

ertw

ice.

Itw

asth

ende

hydr

ated

,fir

stw

ithan

hydr

ous

Na

2SO

4,an

dth

enby

pass

ing

itth

roug

ha

colu

mn

ofsi

lica

gel.

Ref

eren

ces:

1 H.

Oni

shia

ndY

.H

iguc

hi,

Bun

seki

Kag

aku14

,11

41~1

965!

.2 W

.W

.W

endl

andt

,A

naly

t.C

hem

.28,

499

~195

6!.

628628 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

obi

s~8-

hydr

oxy-

quin

olin

ate!~

8-hy

drox

yqui

nolin

e!;U

O2~

C9H

6NO

! 2•C

9H7N

O;

orC 2

7H19

N3O

5U;

@178

55-7

5-3#

~2!

Eth

anol

;C 2

H6O

;@6

4-17

-5#

~3!

Tric

hlor

omet

hane

;C

HC

l3;

@67-

66-3

#

S.

Oki

,A

nal.

Chi

m.

Act

a44,

315

–22

~196

9!.

Var

iabl

es:

Pre

pare

dby

:

100

w2

/mas

s%:0

.5J.

Ha

´ la

Exp

erim

enta

lDat

a

Sol

ubili

tyof

UO

2~C

9H6N

O! 2•C

9H7N

Oin

chlo

rofo

rmco

ntai

ning

0.5%

etha

nol

a

Sol

vent

UO

2~C

9H6N

O! 2•C

9H7N

O(1

04c 1

/mol

dm2

3 !

CH

Cl 3

8.74

8.74

8.16

8.21

7.89

8.356

0.40

b

CH

Cl 31

0.5%

C 2H

6O9.

4810

.12

9.66

9.48

10.5

89.

8660.

48b

a At

unsp

ecifi

edro

omte

mpe

ratu

re.

Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.b A

vera

geva

lue

and

stan

dard

devi

atio

n~c

ompi

ler!.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Ura

nium

inth

esa

tura

ted

solu

tions

was

dete

rmin

ed,

afte

rre

mov

alof

CH

Cl

3an

d8-

hydr

oxyq

uino

line

byhe

atin

gth

esa

mpl

eto

180

°C,

colo

rimet

rical

lyw

ithar

sena

zoIII

.1

UO

2~C

9H6N

O! 2•~C

9H7N

O!

was

prep

ared

bypr

ecip

itatin

gur

aniu

mfr

om20

0m

Lso

lutio

nco

ntai

ning1

gU

O 2~N

O3!

2•6H

2Ow

itha

solu

tion

of1

g8-

hydr

oxyq

uino

line

in10

0m

L1

mol

dm2

3H

Cl.

The

solu

tion

was

heat

edto

70°C

and

2m

oldm

23

NH

4OH

solu

tion

was

adde

ddr

opw

ise

whi

lest

irrin

gun

tilno

furt

her

prec

ipita

teap

pear

ed.

Afte

rdi

gest

ion

for

1h,

the

prec

ipita

tew

asfil

tere

d,w

ashe

dw

ithho

tw

ater

,an

ddr

ied

over

P 2O

5.8-

hydr

oxyq

uino

line,

G.R

.gra

de,w

asus

edw

ithou

tfur

ther

purifi

catio

n.T

heco

mpo

sitio

nof

the

com

plex

was

verifi

edby

chem

ical

anal

ysis

.C

HC

l3,

G.

R.

grad

e,co

ntai

ning

0.5%

etha

nol

was

first

purifi

edfr

omet

hano

lby

was

hing

itw

ithdi

still

edw

ater

twic

e.It

was

then

dehy

drat

ed,

first

with

anhy

drou

sN

a2S

O4,

and

then

bypa

ssin

git

thro

ugh

aco

lum

nof

silic

age

l.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Co

~1!

UO

~2!

Va

Th

co Ad

In re of Me

Iso

da co 8-


The

solu

bilit

ypr

oduc

tof

UO 2

H2R

was

dete

rmin

edis

othe

rmal

lyat

pH3

to4.

5si

nce

atpH,

3so

lidH 4

Rco

ntam

inat

edU

O 2H2R

inth

eeq

uilib

rium

solid

phas

ew

hile

atpH

.4.

5th

eso

lubi

lity

ofU

O 2H

2Rin

crea

sed

cons

ider

ably

due

toco

mpl

exfo

rmat

ion

inth

eso

lutio

n.M

easu

rem

ents

wer

eca

rrie

dou

tin

volu

met

ricfla

sks,

each

cont

aini

ng25

mL

0.1

mol

dm2

3U

O2~

NO

3!2

and

50m

L0.

09m

oldm

23

~NH

4!2H

2R.

The

pHof

the

solu

tions

was

adju

sted

byad

ding

vary

ing

volu

mes

of0.

12m

oldm2

3am

mon

iaso

lutio

n.E

quili

briu

mw

asre

ache

din

9da

ys.

Inth

esa

tura

ted

solu

tions

,ur

aniu

mw

asde

term

ined

phot

omet

rical

lyw

ithH

2O2

inal

kalin

em

ediu

m,2

H4R

bytit

ratio

nw

ithT

h~N

O3!

4so

lutio

n,3

and

pHw

asde

term

ined

pote

ntio

met

rical

lyus

ing

quin

hydr

one

elec

trod

e.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

typr

oduc

t:se

eab

ove.

Ref

eren

ces:

1 N.

P.

Kom

aran

dZ

.A

.T

rety

ak,

Zh.

Ana

lit.

Khi

m.10

,23

6~1

955!

.2 J.

Rod

den,

inA

na

lytic

al

Ch

em

istr

yo

fth

eM

an

ha

tta

nP

roje

ct~R

ussi

antr

ansl

atio

n!~I

L,M

osco

w,

1956

!,p.

124.

3 J.J.

Frit

zan

dJ.

J.F

ord,

Ana

lyt.

Che

m.

25,

1640

~195

3!.

5.15

.U

rani

um„V

I…D

ioxo

†4,

4,4-

trifl

uoro

-1-„2-

thie

nyl…

-1,3

-but

aned

iona

te‡

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ura

nium

~VI!

diox

o@4

,4,4

-trifl

uoro

-1-~2

-thi

enyl!

-1,3

-but

aned

iona

te#;

6H10

F 6O

6S2U

orU

O2~

C8H

5F3O

2S! 2

;@1

8444

4-18

-3#S

olve

nts

K.A

kiba

,N.S

uzuk

i,an

dT

.Kan

no,K

akur

iken

Ken

kyu

Hok

oku

2,15

0–

2~1

969!

.

riabl

es:

Pre

pare

dby

:

K:2

98T

.T

omin

aga

Exp

erim

enta

lDat

a

Sol

ubili

tyof

C16

H10

F 6O

6S2U

at25

°Cin

vario

usso

lven

tsa

Sol

vent

C16

H10

F 6O

6S2U

(104

c 1/m

oldm

23 )

exan

e,C 6H

14,

@110

-54-

3#0.

10

epta

ne,

C 7H16

,@1

42-8

2-5#

0.12

cloh

exan

e,C 6H

12,

@110

-82-

7#0.

14

nzen

e,C 6H

6,@7

1-43

-2#

200

uene

,C 7

H8,

@108

-88-

3#15

0

prop

ylbe

nzen

e,C 9H

12,

@98-

82-8

#29

.0

loro

benz

ene,

C 6H5C

l,@1

08-9

0-7#

200

ichl

orob

enze

ne,

C 6H4C

l 2,

@95-

50-1

#10

0

hlor

omet

hane

,C

H 2Cl 2

,@7

5-09

-2#

700

loro

form

,C

HC

l 3,@6

7-66

-3#

270

rach

loro

met

hane

,C

Cl

4,@5

6-23

-5#

7.8

hlor

oben

zene

C 6H3C

l 3b

32.0

quili

briu

mso

lidph

ases

not

inve

stig

ated

.om

erno

tsp

ecifi

ed.

ditio

nali

nfor

mat

ion:

asu

bseq

uent

docu

men

t,1

the

auth

ors

repo

rted

,in

grap

hica

lfor

m,

the

solu

bilit

yof

C16

H10

F 6O

6S2U

inn-

hept

ane

and

CC

l4

asa

func

tion

the

conc

entr

atio

nof

4,4,

4-tr

ifluo

ro-1

-~2

-thi

enyl!

-1,3

-but

aned

ione

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

solu

tew

assh

aken

with

the

desi

red

solv

ent

for

abou

t10

0h

inan

air

ther

mos

tat.

Afte

rce

ntrif

ugat

ion,

gac

tivity

ofth

esu

pern

atan

tso

lutio

nw

asm

easu

red.

The

solu

bilit

ies

wer

eca

lcul

ated

usin

ga

calib

ratio

ncu

rve

prep

ared

bym

eans

ofso

lutio

nsco

ntai

ning

know

nam

ount

sof

237 U

O221

.

The

ofC 1

6H10

F 6O

6S2U

com

plex

was

prep

ared

byad

ding

stoi

chio

met

ricam

ount

ofth

elig

and

toa

war

mso

lutio

nof

uran

ium~

VI!

diox

ide

diac

etat

ela

bele

dw

ith237 U

.T

here

sulta

ntye

llow

prec

ipita

tew

asfil

tere

d,w

ashe

dw

ithw

ater

and

hexa

ne,

and

drie

dov

erP 2O

5un

der

redu

ced

pres

sure

.D

ryso

lven

tsw

ere

used

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 K.

Aki

baan

dN

.S

uzuk

i,K

akur

iken

Ken

kyu

Kok

oku3,

144

~197

0!.



5.14

.U

rani

um„V

I…D

ioxo

„et

hyle

nedi

amin

etet

raac

etat

e…

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~VI!

diox

oet

hyle

nedi

amin

ete

traa

ceta

te;

C10

H14

N2O

10U

;~2

!W

ater

;H 2

O;

@773

2-18

-5#

A.

E.

Kly

gin,

I.D

.S

mirn

ova,

and

N.

A.

Nik

olsk

ii,Z

h.N

eorg

.K

him

.4,

2623

–9~

1959

!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:298

J.H

ala

Exp

erim

enta

lDat

a

Com

posi

tion

ofso

lutio

nssa

tura

ted

with

C10

H14

N2O

10U

at25

°Ca

@H1

#(1

04m

oldm

23 )

Ub

(104

mol

dm2

3 )H

4Rc

(102

mol

dm2

3 )K

spd

(106

mol

2dm

26 )

8.51

1.72

2.00

2.04

7.94

1.61

2.01

1.96

6.46

1.65

1.99

2.11

5.89

1.71

1.63

1.82

5.29

1.64

1.99

2.18

3.98

1.71

2.04

2.41

1.35

2.44

1.97

3.02

0.25

73.

552.

012.

01

2.25

60.

18e

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.b T

otal

conc

entr

atio

nof

uran

ium

inth

esa

tura

ted

solu

tion.

c Tot

alco

ncen

trat

ion

ofet

hyle

nedi

amin

ete

traa

cetic

acid

(H4R

)in

the

satu

rate

dso

lutio

n.d K

sp5

@UO

221

#@H

2R22

#~H

4Rst

ands

for

ethy

lene

diam

ine

tetr

aace

tic!;

calc

ulat

edby

the

auth

ors

from

pH,

and

tota

lco

ncen

trat

ions

ofur

aniu

man

dH 4

Rby

usin

gau

thor

s’va

lues

ofth

efir

stan

dse

cond

diss

ocia

tion

cons

tant

ofH

4R,

and

the

equi

libriu

mco

nsta

ntfo

rth

ehy

drol

ysis

ofU

O 221,

Kh5

@UO

2OH

1#@

H1

#@U

O22

1#2

1,

take

nfr

omR

ef.

1.e A

vera

geva

lue~

auth

ors!.

Add

ition

alin

form

atio

n:F

rom

the

initi

alco

ncen

trat

ions

ofU

O 2~N

O3!

2an

dH 4

R,

and

from

the

stoi

chio

met

ryof

the

prec

ipita

tion

reac

tion,

the

com

pile

res

timat

edio

nic

stre

ngth

ofth

esa

tura

ted

solu

tions

tobe

appr

oxim

atel

y0.

11m

oldm

23 .

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Co

~1!

bis

C1

~2!

Va

T/

n-h

n-h

cy be tol

iso

ch o-d

dic

ch tet

tric

a E b Is Ad

In of Me

J

6.T

heS

olub

ility

ofN

eptu

nium

Com

poun

ds

6.1.

Nep

tuni

um„V

I…D

ioxo

carb

onat

e

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Nep

tuni

um~V

I!di

oxoc

arbo

nate

;N

pO 2C

O3

;@

#C

arbo

ndi

oxid

e;C

O 2;@1

24-3

8-9#

Sod

ium

perc

hlor

ate;

NaC

lO 4;@7

601-

89-0#

Wat

er;

H 2O

;@7

732-

18-5#

Y.K

ato,

T.K

imur

a,Z

.Yos

hida

,and

N.N

itani

,Rad

ioch

im.A

cta

82,

63–

8~1

998!

.

riabl

es:

Pre

pare

dB

y:

K:

298

~par

tialp

ress

ure

ofC

O 2!/%

:80

/mol

dm2

3 50.

1

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

NpO

2CO

3at

25°C

asa

func

tion

ofca

rbon

ate

ion

conc

entr

atio

nin

0.1

mol

dm2

3N

aClO

4so

lutio

nsa

2lo

g @C

O322

#2

log

Np@

~VI!

#pH

2lo

g @C

O322

#2

log

Np@

~VI!

#pH

2lo

g @C

O322

#2

log

Np@

~VI!

#

912

.27

2.37

3.24

11.3

72.

712.

8712

.11

2.01

812

.09

2.06

3.25

11.3

52.

763.

1411

.57

2.66

212

.01

2.46

3.64

10.5

73.

283.

1511

.55

2.04

511

.75

2.36

3.64

10.5

73.

103.

4211

.01

3.03

411

.57

2.80

5.81

6.23

5.11

3.81

10.2

33.

47

511

.55

2.52

5.90

6.05

4.86

6.29

5.27

4.36

511

.55

2.49

5.91

6.03

4.94

6.34

5.17

4.33

711

.11

2.51

5.93

5.99

5.06

6.35

5.15

4.42

310

.39

3.80

5.99

5.87

5.03

6.36

5.13

4.34

110

.23

3.74

6.03

5.79

4.71

6.43

4.99

3.66

49.

773.

896.

045.

774.

936.

444.

973.

71

59.

774.

026.

145.

574.

806.

464.

934.

04

89.

494.

266.

175.

514.

766.

474.

913.

65

89.

294.

226.

205.

454.

256.

504.

853.

41

99.

074.

816.

265.

334.

106.

534.

793.

56

28.

614.

866.

285.

293.

976.

544.

773.

22

88.

494.

886.

285.

293.

816.

664.

532.

88

88.

095.

136.

305.

253.

756.

714.

432.

51

5.05

7.75

4.96

6.42

5.01

3.47

6.72

4.41

2.50

5.19

7.47

5.10

6.47

4.91

2.90

6.75

4.35

2.47

5.20

7.45

5.18

6.50

4.85

2.78

6.76

4.33

2.42

5.94

5.97

4.73

6.52

4.81

2.71

6.77

4.31

2.48

5.97

5.91

4.62

6.54

4.77

2.63

6.82

4.21

2.42

6.63

4.59

2.52

a Sol

idph

ase

was

NpO 2

CO

3,@

#,in

alls

olut

ions

.

Add

ition

alin

form

atio

n:F

ree

carb

onat

eio

nco

ncen

trat

ion

was

calc

ulat

edby

the

sam

epr

oced

ure

asin

the

auth

ors’

prev

ious

wor

k.1,

2U

sing

leas

t-sq

uare

san

alys

is,

the

follo

win

gco

nsta

nts

wer

eob

tain

ed:

solu

bilit

ypr

oduc

tof

NpO

2CO

3,K

sp5

@NpO

221#@

CO

322#5

102

(14.

046

0.07

) ;st

abili

tyco

nsta

nts

ofN

p~V

I!ca

rbon

atoc

ompl

exes

,bn5

@NpO

2~C

O3!

n22

2n#@

NpO

221#2

1@C

O322

#2n,

b15

109.

206

0.10

,an

db

35

1020

.416

0.09

.F

orth

edi

carb

onat

o-co

mpl

ex,

the

uppe

rlim

iton

lyw

asob

tain

edasb

2,

1014

.2.

Inan

earli

erpa

per,3

the

auth

ors

repo

rted

Ksp

510

2(1

4.62

60.

12)

unde

rth

esa

me

cond

ition

s.In

this

pape

r,K

spw

asob

tain

edfr

omsi

xm

easu

rem

ents

perf

orm

edat

pH,4,

and

solu

bilit

yda

taw

ere

pres

ente

din

grap

hica

lfor

mon

ly.

630630 JIRI HALA

5.16

.U

rani

um„IV…

Pht

halo

cyan

inat

e

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ura

nium

~IV

!bi

s~ph

thal

ocya

nina

te!;C

64H

32H

16U

orU

~C32

H16

N8!

2;@

#~2

!S

olve

nts

P.N

.Mos

kale

v,G

.N.S

hapk

in,a

ndY

u.S

.Mis

ko,R

adio

khim

iya

20,

343

–4

~197

8!.

Var

iabl

es:

Pre

pare

dB

y:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

C64

H32

N16

Uin

two

solv

entsa

Sol

vent

C64

H32

N16

U~g

dm2

3 !C

64H

32N

16U

(104

c 1/m

oldm

23 )b

benz

ene,

C 6H6,

@71-

43-2

#0.

031

0.41

3

1-ch

loro

naph

thal

ene,

C 8H10

Cl,

@90-

13-1

#0.

314.

13

a The

solu

bilit

yw

asin

depe

nden

tof

tem

pera

ture

over

the

rang

eof

13–

50°C

.E

quili

briu

mso

lidph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

The

solid

was

equi

libra

ted

with

the

desi

red

solv

ent

ingr

ound

glas

sst

oppe

red

cylin

ders

ina

them

osta

ted

bath

until

equi

libriu

mw

asat

tain

ed.

The

satu

rate

dso

lutio

nsw

ere

filte

red

thro

ugh

agl

ass

filte

r,an

aliq

uot

was

dilu

ted

to;

102

5m

oldm

23

with

dim

ethy

lform

amid

eco

ntai

ning

1%hy

draz

ine

hydr

ate,

and

the

conc

entr

atio

nof

phth

aloc

ynai

new

asde

term

ined

spec

trop

hoto

met

rical

ly.

C64

H32

N16

Uw

aspr

epar

edac

cord

ing

toR

ef.

1.C

hem

ical

com

posi

tion

and

purit

yof

the

solu

tew

ere

chec

ked

bych

emic

alan

alys

isan

dx-

ray

diffr

actio

n.R

eage

ntgr

ade

solv

ents

wer

eus

edw

ithou

tfu

rthe

rpu

rifica

tion.

Est

imat

edE

rror

:S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 I.S

.K

irin,

A.

B.

Kol

yadi

n,an

dP

.N

.M

oska

lev,

Zh.

Neo

rg.

Khi

m.

16,

2731

~197

1!.

Co

~1!

~2!

~3!

~4!

Va

T/

p2

c 3 pH 2.7

2.8

2.9

3.0

3.1

3.1

3.1

3.3

3.7

3.8

4.0

4.0

4.1

4.2

4.3

4.6

4.6

4.8


6.2.

Sal

tsof

Dio

xoca

rbon

ato

Nep

tuna

te„V…„-1…

6.2.

1.E

valu

atio

nof

the

NaN

pO2C

O3¿

CO

2¿N

aClO

4¿H

2OS

yste

m

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

diox

ocar

bona

tone

ptun

ate

~V!;

NaN

pO2~

CO

3!;

7127

-86-

3#C

arbo

ndi

oxid

e;C

O 2;@1

24-3

8-9#

Sod

ium

perc

hlor

ate;

NaC

lO 4;@7

601-

89-0#

Wat

er;

H 2O

;@7

732-

18-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,

June

2000

Crit

ical

Eva

luat

ion:

The

NaN

pO2C

O3

isth

em

osti

mpo

rtan

tnep

tuni

umco

mpo

und

from

the

poin

tofv

iew

ofpo

ssib

lele

achi

ngne

ptun

ium

from

radi

oact

ive

ste

repo

sito

ries.

Itsso

lubi

lity

inca

rbon

ate

cont

aini

ngso

lutio

nsha

sbe

enin

vest

igat

edin

seve

rald

ocum

ents

.U

eno

and

Sai

to1

mea

sure

dso

lubi

lity

asa

func

tion

ofN

a 2CO

3co

ncen

trat

ion

at29

3.1

Kin

solu

tions

with

varia

ble

ioni

cst

reng

th.

May

a2

mea

sure

dth

eso

lubi

lity

298.

1K

inN

a 2CO

3so

lutio

nsco

ntai

ning

0.1

mol

dm23

NaC

lO4.

Lem

iree

ta

l.3us

edN

a 2CO

3/N

aClO

4so

lutio

nsof

cons

tant

ioni

cen

gth

of1.

0m

oldm

23

atth

ree

tem

pera

ture

s.M

einr

ath

4ca

rrie

dou

thi

sm

easu

rem

ents

atio

nic

stre

ngth

ofap

prox

imat

ely

0.1

mol

dm2

3

ClO

4in

anat

mos

pher

eof

nitr

ogen

gas

cont

aini

ng1%

CO

2.G

rent

hee

ta

l.5us

ed3.

0m

oldm

23

ioni

cst

reng

that

293.

1K

,an

dN

eck

al.6

perf

orm

edth

eir

mea

sure

men

tsat

seve

rali

onic

stre

ngth

san

dat

298.

1K

.In

Ref

s.2

–6,

the

solu

bilit

yof

NaN

pO2C

O3

was

repo

rted

afu

nctio

nof

equi

libriu

mca

rbon

ate

ion

conc

entr

atio

n.T

hela

tter

was

calc

ulat

edfr

omth

em

easu

red

pHof

the

satu

rate

dso

lutio

ns,

and

set

ofaq

ueou

seq

uilib

riaof

CO

2,H

CO

32,

and

CO 322

~see

Crit

ical

Eva

luat

ion

for

the

UO 2C

O3–

CO

2–

NaC

lO4–

H2O

syst

em!.

Due

toth

edi

ffere

ntco

nditi

ons

used

inth

ese

docu

men

ts,

and

also

beca

use

Ref

s.2

–5

pres

ente

dth

eso

lubi

lity

data

ingr

aphi

calf

orm

ly,

the

poss

ibili

ties

for

deta

iled

com

paris

onar

era

ther

limite

d.N

ever

thel

ess,

som

ege

nera

lfe

atur

esof

this

syst

emha

veem

erge

d.fe

renc

es2

–6

agre

ein

that

the

solu

bilit

yof

NaN

pO2C

O3,

whe

npl

otte

dag

ains

teq

uilib

rium

CO 322

conc

entr

atio

n,pa

sses

thro

ugh

ani

mum

.In

the

rang

eof

min

imum

solu

bilit

yof

NaN

pO 2CO

3,th

ela

tter

isde

term

ined

pred

omin

antly

byth

eso

lubi

lity

prod

uct.

The

tabl

em

mar

izes

the

appr

oxim

ate

min

imum

solu

bilit

yda

tafo

rN

aNpO

2CO

3,as

estim

ated

byth

eev

alua

tor

from

the

grap

hica

lrep

rese

ntat

ion

the

auth

ors’

data

:

nim

umN

aNpO

2CO

3so

lubi

lity

~mol

dm2

3 !C

orre

spon

ding

@CO

322#

rang

e~m

oldm

23 !

Ioni

cst

reng

th~m

oldm

23 !

Ref

eren

ce

33

102

63

310

24–

9310

24

1.0

2

13

102

61

310

24–

2.53

102

41.

03

23

102

52.

5310

24–

6.33

102

30.

14

1.33

102

61

310

24

3.0

5

23

102

51.

5310

24–

2310

23

0.1

6

3.23

102

61.

5310

24–

1310

23

1.0

6

13

102

61.

5310

24

3.0

6

23

102

71

310

24

5.0

6

Fro

mth

em

oste

xten

sive

stud

yof

Nec

ke

ta

l.6it

follo

ws

that

the

mag

nitu

deof

the

min

imum

solu

bilit

yof

NaN

pO 2CO

3,as

wel

las

the

carb

onat

eio

nco

ncen

trat

ion

rang

ew

here

itap

pear

s,ar

ede

pend

ent

onio

nic

stre

ngth

(NaC

lO4)

.T

akin

gth

isin

toac

coun

tth

ere

appe

ars

tobe

ago

odag

reem

ent

amon

gth

epu

blis

hed

data

.T

here

isal

soan

agre

emen

tin

Ref

s.2

–6

inth

atat

@CO

322#

conc

entr

atio

nshi

gher

than

102

3–

102

2m

oldm

23

the

solu

bilit

yof

NaN

pO2C

O3

incr

ease

sw

ithin

crea

sing

carb

onat

eio

nco

ncen

trat

ion.

Thi

sef

fect

ispa

rtic

ular

lypr

onou

nced

athi

ghca

rbon

ate

ion

conc

entr

atio

ns,

1an

dha

sbe

enex

plai

ned

2–

6in

term

sof

the

form

atio

nof

carb

onat

ocom

plex

esN

pO2~

CO

3!n1

22

nin

the

satu

rate

dso

lutio

ns.

The

num

ber

ofco

mpl

exes

exis

ting

depe

nds

onth

e@C

O322

#ra

nge

used

.T

hus,

whi

leM

einr

ath

4

repo

rted

the

com

plex

esw

ithn5

1an

d2

at@C

O322

#,10

22

mol

dm2

3 ,th

eex

iste

nce

ofth

eth

irdco

mpl

ex(

n5

3)

has

been

confi

rmed

athi

gher

carb

onat

eio

nco

ncen

trat

ions

.5,

6

Aco

nsis

tent

set

ofso

lubi

lity

prod

uct

valu

esof

NaN

pO 2CO

3ha

sbe

enre

port

edw

ithpa

rtic

ular

lyex

celle

ntag

reem

ent

for

Ksp

valu

esob

tain

edat

298.

1K

and

0.1

and

1.0

mol

dm23

NaC

lO4

inR

efs.

4,6

and

2,6,

resp

ectiv

ely.

The

avai

labl

eK

spva

lues

are

sum

mar

ized

inth

efo

llow

ing

tabl

e:



Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Sol

ubili

tyex

perim

ents

wer

eco

nduc

ted

aspH

titra

tions

ina

ther

mos

tate

dgl

ass

vess

elin

the

pHra

nge

from

2.8

to6.

8in

anat

mos

pher

eof

80%

CO 2/O

2.T

hega

sw

asfir

stpa

ssed

thro

ugh

anoz

one

gene

rato

rto

prod

uce

ozon

ein

the

gas

and

thus

stab

ilize

the

hexa

vela

ntst

ate

ofN

p.T

hega

sw

asth

enm

oist

ened

inw

ashi

ngfla

sks,

and

pass

edco

ntin

uous

lyth

roug

hth

eso

lutio

n.O

zone

was

show

nto

have

noef

fect

onth

eso

lid/li

quid

equi

libriu

m.

The

hexa

vela

ntst

ate

ofN

pw

asch

ecke

dby

mea

surin

gth

ere

dox

pote

ntia

lof

wor

king

solu

tions

usin

ga

Pt–

Ag/

AgC

lcom

bina

tion

elec

trod

e.T

heso

lidph

ase

was

prec

ipita

ted

from

0.02

mol

dm23

solu

tion

ofN

p~V

I!by

addi

tion

of0.

1m

oldm

23

NaH

CO 3

or0.

1m

oldm

23

NaO

H,

and

was

left

toeq

uilib

rate

with

the

solu

tion

for

2w

eeks

orm

ore.

The

npH

titra

tions

wer

epe

rfor

med

byad

ditio

nof

smal

lal

iquo

tsof

0.1

mol

dm2

3N

aOH

,0.

1m

oldm

23

NaH

CO 3

or0.

1m

oldm

23

HC

lO4.

The

pHw

asm

easu

red

byus

ing

com

bina

tion

glas

sel

ectr

odes~H

orib

a!w

hich

wer

eca

libra

ted

agai

nst

buffe

rso

lutio

nsw

ithpH

of4.

01an

d6.

86~bot

h6

0.01

!.T

hepH

and

nept

uniu

mco

ncen

trat

ion

wer

em

easu

red

once

per

wee

k,an

dth

eso

lubi

lity

data

wer

ead

opte

dw

hen

the

valu

esre

mai

ned

unch

ange

dfo

r2

wee

ksw

ithin

expe

rimen

tal

erro

r.P

hase

sepa

ratio

nw

asac

hiev

edby

cent

rifug

atio

nat

3000

rpm

and

ultr

afiltr

atio

nw

itha

filte

rof

220

nmpo

resi

ze.

The

conc

entr

atio

nof

Np~V

I!w

asde

term

ined

byliq

uid

scin

tilla

tion

coun

ting.

The

oxid

atio

nst

ate

ofN

p~V

I!w

asch

ecke

dby

spec

trop

hoto

met

ry~S

him

adzu

,U

V-3

100S!

.D

urin

gso

lubi

lity

expe

rimen

ts,

Np~V

!co

ncen

trat

ion

was

alw

ays,

2%of

the

tota

lnep

tuni

umco

ncen

trat

ion.

Sol

idph

ases

wer

ech

arac

teriz

edby

x-ra

ycr

ysta

llogr

aphy

~Rig

aku

RA

D-3

C!an

dph

otoa

cous

ticU

V-V

ISan

dF

TIR

spec

tros

copy

.F

orth

ela

tter

met

hod,

abou

t5

–10

mg

ofai

r-dr

ied

solid

phas

ew

asus

ed.

Sto

ckso

lutio

nof

NpO

221w

aspr

epar

edfr

omhi

ghly

pure

237 N

pO2

pow

der~

CE

A,

Fra

nce!.

The

latte

rw

asdi

ssol

ved

inco

ncen

trat

edH

NO 3,

the

resu

ltant

solu

tion

was

fum

edto

dryn

ess

afte

rad

ditio

nof

conc

entr

ated

HC

lO 4,an

dth

ere

sidu

ew

asdi

ssol

ved

in0.

1m

oldm

23

HC

lO4.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~aut

hors!

.S

olub

ility

prod

uct:

see

abov

e.

Ref

eren

ces:

1 G.

Mei

nrat

han

dT

.K

imur

a,In

org.

Chi

m.

Act

a204,

79~1

993!

.2 G

.M

einr

ath

and

T.

Kim

ura,

J.A

lloy

Com

pd.20

2,89

~199

3!.

3 Y.

Kat

o,T

.K

imur

a,Z

.Y

oshi

da,

and

N.

Nita

ni,

Rad

ioch

im.

Act

a74

,21

~199

6!.

Co

~1!

@5 ~2!

~3!

~4!

wa

the

at str

Na

et as a on Re

mi

su of Mi

J

, ter t

10C

.F

.N

ovak

and

K.

E.

Rob

erts

,M

ater

.R

es.

Soc

.S

ymp.

Pro

c.35

3,11

19~1

995!

.11

D.

B.

Tuc

ker,

E.

M.

Sta

ndife

r,H

.N

itsch

e,an

dR

.J.

Silv

a,La

ntha

nide

Act

inid

eR

es.

2,27

9~1

988!

.

6.3.

Sal

tsof

Dio

xoB

is„ca

rbon

ato…

Nep

tuna

te„V…„-3…

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

carb

onat

odi

oxon

eptu

nate

~V!;

NaN

pO2C

O3;

7127

-86-

3#S

odiu

mca

rbon

ate;

Na

2CO

3;@4

97-1

9-8#

Wat

er;

H 2O

;@7

732-

18-5#

K.

Uen

oan

dA

.S

aito

,R

adio

chem

.R

adio

anal

.Le

tt.22

,12

7–

33~1

995!

.

riabl

es:

Pre

pare

dB

y:

K:

293

/mol

dm2

3 :0.

05–

1.6

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

NaN

pO2C

O3

at20

°Cin

Na 2C

O3

solu

tions

a

Na 2

CO

3

(c2

/mol

dm2

3 )N

aNpO

2CO

3

(104

c 1/m

oldm

23 )

0.05

0.68

8

0.07

0.79

5

0.1

1.18

0.15

2.44

0.2

8.53

0.3

20.4

0.4

32.3

0.6

97.0

1.2

160.

0

1.6

161.

0

quili

briu

mso

lidph

ase

was

NaN

pO 2C

O3,

@571

27-8

6-3#,

inal

lsol

utio

ns.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.P

ortio

nsof

asl

ight

lyac

idic

solu

tion

ntai

ning

5–

30m

gN

p~V!

wer

ead

ded

to5

–10

mL

Na

2CO

3

lutio

nof

the

desi

red

conc

entr

atio

n.T

hene

ptun

ium

ncen

trat

ion

was

smal

leno

ugh

not

toch

ange

the

carb

onat

enc

entr

atio

n.A

whi

tepr

ecip

itate

ofN

aNpO 2C

O3

was

tain

edan

dal

low

edto

stan

dfo

r1

–2

days

with

occa

sion

alm

ixin

gto

atta

ineq

uilib

rium

.T

hesa

tura

ted

solu

tions

wer

ece

ntrif

uged

,an

dth

ene

ptun

ium

conc

entr

atio

nde

term

ined

radi

omet

rical

ly.

The

solid

phas

esw

ere

anal

yzed

for

Np,

Na,

and

carb

onat

e.S

atur

ated

solu

tions

and

the

solid

phas

esco

ntai

ned

pent

aval

ent

nept

uniu

maf

ter

equi

libra

tion.

AH

NO

3so

lutio

nof

237 N

ppu

rified

byan

ion

exch

ange

was

heat

edfo

rse

vera

lhou

rsto

oxid

ize

Np

~IV

!to

Np~

V!/

Np~

VI!

,and

then

evap

orat

edto

dryn

ess.

The

resi

due

was

diss

olve

din

NH

2OH•H

Cl

solu

tion

toen

sure

the

pent

aval

ent

stat

eof

nept

uniu

m,

whi

chw

asch

ecke

dsp

ectr

opho

tom

etric

ally

.T

heso

dium

carb

onat

eus

edw

asa

reag

ent

grad

epr

oduc

t.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

632632 JIRI HALA

2lo

gK

sp

Tem

pera

ture

~K!

Ioni

cst

reng

th~m

oldm

23 !

Ref

eren

ce

11.0

060.

0729

8.1

06

10.2

260.

0229

8.1

0.1~N

aClO

4!4

10.2

860.

0429

8.1

0.1~N

aClO

4!6

10.1

460.

0429

8.1

1.0~N

aClO

4!2

10.1

060.

0329

8.1

1.0~N

aClO

4!6

10.7

60.

130

3.1

1.0~N

aClO

41N

a 2C

O3!

3

11.0

60.

132

3.1

1.0~N

aClO

41N

a 2C

O3!

3

10.4

560.

0429

8.1

3.0~N

aClO

4!6

10.5

629

3.1

3.0

5

11.0

660.

0629

8.1

5.0~N

aClO

4!6

The

solu

bilit

ypr

oduc

tofN

aNpO

2CO

3at

diffe

rent

ioni

cst

reng

ths

has

also

been

obta

ined

byca

lcul

atio

nus

ing

the

Pitz

erm

etho

d,w

ithve

rygo

odag

reem

ent

with

expe

rimen

tald

ata.

7,9,

10

The

equi

libriu

mso

lidph

ase

isth

ehy

drat

edsa

lt,N

aNpO

2CO

3•3.

5H2O

.T

his

hydr

ate

was

first

repo

rted

byV

olko

veta

l.,8

and

sinc

eth

enre

confi

rmed

asth

eeq

uilib

rium

solid

phas

ein

the

solu

bilit

yst

udie

sby

seve

rala

utho

rs.

2,5,

9Le

mire

3re

port

edth

eso

lidph

ase

tobe

the

trih

ydra

te,

NaN

pO2C

O3•

3H2O

,at

303.

1an

d32

3.1

K.

Thi

sis

inag

reem

ent

with

the

findi

ngof

Vol

kov

et

al.8

who

repo

rted

that

NaN

pO2C

O3•

3.5H

2Otu

rned

into

the

trih

ydra

teon

heat

ing

at30

3.1

K.S

ince

the

solid

phas

eex

ists

asa

hydr

ate,

the

solu

bilit

ypr

oduc

tmay

toa

cert

ain

exte

nt,

depe

ndon

the

num

ber

ofcr

ysta

lw

ater

mol

ecul

es,

part

icul

arly

athi

ghio

nic

stre

ngth

whe

reth

ede

crea

seof

wa

activ

ityis

not

negl

igib

le.7

At

high

erca

rbon

ate

ion

conc

entr

atio

ns,

NaN

pO 2CO

3•3.

5H2O

isth

erm

odyn

amic

ally

unst

able

,an

dits

slow

tran

sfor

mat

ion

toN

a 3NpO

2~C

O3) 2•xH

2Ota

kes

plac

e.3,6

No

te:

As

apa

rtof

nucl

ear

was

test

orag

epr

ojec

tat

Yuc

caM

ount

ain,

Nev

ada,

Tuc

ker

et

al.11

mea

sure

dth

eso

lubi

lity

ofN

aNpO 2

CO

3

ingr

ound

wat

erfr

omon

ew

ell.

Thi

sdo

cum

ent

has

not

been

com

pile

dfo

rth

isvo

lum

esi

nce

the

com

posi

tion

ofth

egr

ound

wat

erw

asno

defin

ed.

The

auth

ors

obta

ined2

log

Ksp

510

.36

0.5

at33

3.1

Kan

dat

ioni

cst

reng

thof

0.146

0.05

mol

dm2

3 .T

hem

easu

rem

ents

wer

epe

rfor

med

atpH

6.0

–8.

5,an

dth

eeq

uilib

rium

solid

phas

ew

asid

entifi

edas

NaN

pO2C

O3•

H2O

.

Ref

eren

ces:

1 K.

Uen

oan

dA

.S

aito

,R

adio

chem

.R

adio

anal

.Le

tt.22,

127

~197

5!.

2 L.M

aya,

Inor

g.C

hem

.22,

2093

~198

3!.

3 R.

J.Le

mire

,G

.D

.B

oyer

,an

dA

.B

.C

ampb

ell,

Rad

ioch

im.

Act

a61

,57

~199

3!.

4 G.

Mei

nrat

h,J.

Rad

ioan

al.

Nuc

l.C

hem

.Le

tt.186,

257

~199

4!.

5 I.G

rent

he,

P.

Rob

ouch

,an

dP

.V

itorg

e,J.

Less

-Com

mon

Met

als

122,

225

~198

6!.

6 V.

Nec

k,W

.R

unde

,J.

I.K

im,

and

B.

Kan

ella

kopu

los,

Rad

ioch

im.

Act

a65

,29

~199

4!;

J.A

lloys

Com

pds.2

25,

295

~199

5!.

7 V.

Nec

k,T

.F

angh

a¨ nel

,G

.R

udol

f,an

dJ.

I.K

im,

Rad

ioch

im.

Act

a69,

39~1

995!

.8 Y

u.F

.V

olko

v,G

.I.

Vis

yash

chev

a,an

dI.

I.K

apsh

ukov

,R

adio

khim

iya

19,

319

~197

7!;

Sov

.R

adio

chem

.19,

263

~197

7!.

9 W.

Run

de,

M.

P.

Neu

,an

dD

.L.

Cla

rk,

Geo

chim

Cos

moc

him

.A

cta

60,

2065

~199

6!.

Co

~1!

@5 ~2!

~3!

Va

T/

c 2 a E Me

Iso

co so co co ob


Kspo

5@N

a1#@

NpO

21#@

CO

322#g

~Na1

!g~N

pO21

!g~C

O322

!.

Sin

cem

easu

rem

ents

wer

epe

rfor

med

atco

nsta

ntco

ncen

trat

ion

ofN

a1

ions

,th

eco

nsta

ntKsp*

was

defin

edas

Ksp*

5K

spo$@

Na1

#g~N

a1!g

~NpO

21!g

~CO

322!%

21 5

@NpO

21#@

CO

322#,

and

foun

dto

be102

(10.

146

0.04

) .T

hein

crea

sed

solu

bilit

yof

NaN

pO 2C

O3

at@C

O322

#.33

102

4m

oldm

23

was

inte

rpre

ted

byth

eau

thor

sin

term

sof

the

form

atio

nof

NpO 2

CO

32,

NpO

2~C

O3!

232,

and

NpO

2~C

O3!

352co

mpl

exes

for

whi

chth

ere

spec

tive

over

all

stab

ility

cons

tant

sw

ere

calc

ulat

edto

be104.

496

0.06

,10

7.11

60.

07,

and

108.

536

0.09

.C

ompl

exat

ion

ofN

pO21

with

HC

O32

ion

was

not

obse

rved

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.N

aNpO 2C

O3•

3.5H

2Ow

aspr

epar

edin

uin

tube

sby

addi

tion

ofN

a 2CO

3in

a1:

1m

ole

ratio

toa

O21

solu

tion.

The

tube

sw

ere

cent

rifug

ed,

and

the

pern

atan

tw

asre

plac

edw

ith1

mol

dm23

NaC

lO4

solu

tion.

eso

lidw

assu

spen

ded

and

cent

rifug

edag

ain,

and

this

oced

ure

was

repe

ated

two

mor

etim

es.

The

nal

iquo

tsof

the

rbon

ate

stoc

kso

lutio

nw

ere

intr

oduc

edto

cove

ra

rang

eof

ncen

trat

ions

upto

0.1

mol

dm23 .

The

mix

ture

sw

ere

uilib

rate

dfir

stfo

r7

days

and

then

for

anad

ditio

nal4

day

riod.

The

latte

rdi

dno

tpr

oduc

esi

gnifi

cant

chan

ges

inth

eco

ncen

trat

ion

inth

esa

tura

ted

solu

tions

.S

ome

ofth

etu

bes

reth

ensa

tura

ted

with

N 2ga

sco

ntai

ning

1%C

O 2,se

aled

deq

uilib

rate

dfo

r10

days

.A

fter

cent

rifug

atio

n,ne

ptun

ium

sde

term

ined

inth

esa

tura

ted

solu

tions

radi

omet

rical

ly,

1#

was

dete

rmin

edby

usin

ga

glas

sel

ectr

ode

fille

dw

itha

01m

oldm

23

H1

11.

0m

oldm

23 N

aClO

4so

lutio

n.T

hem

posi

tion

ofth

eso

lidph

ases

was

dete

rmin

edby

chem

ical

alys

isan

dx-

ray

diffr

actio

n.

Sto

ckso

lutio

n,0.

0665

mol

dm23 ,

ofN

p~V

!in

0.1

mol

dm2

3

HC

lO4

was

prep

ared

from

high

purit

yN

pO 2~O

RN

L!.T

heox

ide

was

diss

olve

din

hot

conc

entr

ated

HN

O3,

the

solu

tion

was

evap

orat

edto

dryn

ess,

resi

due

diss

olve

din

conc

entr

ated

HC

lO4,

the

solu

tion

evap

orat

ed,a

ndre

sidu

edi

ssol

vein

wat

er.F

rom

this

solu

tion

NpO

2OH

was

prec

ipita

ted

and

diss

olve

din

0.1

mol

dm2

3H

ClO

4.T

heso

dium

carb

onat

eus

edw

asa

reag

ent

grad

epr

oduc

t.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

1K

~aut

hor!.

Sol

ubili

typr

oduc

t:se

eab

ove.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

carb

onat

odi

oxon

eptu

nate

v~V

!;N

aNpO

2CO

3;@5

7127

-86-

3#~2

!S

odiu

mca

rbon

ate;

Na

2CO

3;@4

97-1

9-8#

~3!

Sod

ium

perc

hlor

ate;

NaC

lO 4;@7

601-

89-0#

~4!

Wat

er;

H 2O

;@7

732-

18-5#

L.M

aya,

Inor

g.C

hem

.22,

2093

–5~

1983

!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8c 2

/mol

dm2

3(C

O32

2):

1.53

102

6–

0.09

3c 3

/mol

dm2

3 :1.

0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

NaN

pO2C

O3

at25

°Cin

Na 2C

O3

solu

tions

a

2lo

g @C

O322

#b2

log @

H1

#b2

log @

Np #

b2

log @

CO

322#b,

c2

log @

H1

#b,c

2lo

g @N

p #b,

c

5.80

8.08

4.32

5.52c

6.96

4.87

5.71

8.21

4.36

4.63c

7.21

5.21

4.44

8.99

5.22

4.06c

7.51

5.41

3.98

9.31

5.40

3.52c

7.79

5.52

3.54

9.62

5.48

2.95c

8.08

5.42

3.05

9.94

5.52

4.06c

7.51

5.41

2.71

10.1

55.

383.

52c7.

795.

52

2.39

10.3

75.

132.

95c8.

085.

42

2.09

10.5

54.

89

1.64

10.7

24.

55

1.03

10.9

93.

50

a All

solu

tions

cont

aine

d1.

0m

oldm2

3N

aClO

4,an

dw

ere

ineq

uilib

rium

with

NaN

pO 2C

O3•

3.5H

2O,

@#,

asth

eso

lidph

ase.

b Equ

ilibr

ium

conc

entr

atio

ns,

inm

oldm2

3 .c M

easu

rem

ents

carr

ied

out

atpa

rtia

lpr

essu

reof

CO

2of

102

2.02

7at

m~9

22P

a!in

orde

rto

eval

uate

poss

ible

effe

cton

NaN

pO 2CO

3

solu

bilit

yof

hydr

ogen

carb

onat

eco

mpl

exat

ion

ofN

p~V

!.

Add

ition

alin

form

atio

n:T

heso

lubi

lity

data

wer

ean

alyz

edby

the

auth

ors

byus

ing

ano

nlin

ear

leas

t-sq

uare

spr

ogra

mco

nsid

erin

gdi

ssol

utio

nof

NaN

pO2C

O3,

hydr

olys

isof

NpO

21to

form

NpO

2OH

,an

dth

efo

rmat

ion

ofca

rbon

ato

com

plex

esof

NpO

21.

For

the

diss

olut

ion

reac

tion

NaN

pO2C

O3~

s!�

Na1

1N

pO21

1C

O322

the

solu

bilit

ypr

oduc

tis

Me

Iso

sit

Np

su Th

pr ca co eq pe Np

we

an wa

@H 0.0

co an

J

.16

.S

odiu

mca

rbon

ato

diox

onep

tuna

te~V!–

sodi

umpe

rchl

orat

e–

carb

ondi

oxid

e–

wat

ersy

stem

.Le

gend

toth

efig

ure:

~squ

ares!

asur

emen

tsca

rrie

dou

tby

cont

rolli

ngto

talc

arbo

nate

conc

entr

atio

n;~c

ircle

san

dtr

iang

les!m

easu

rem

ents

carr

ied

outa

tpar

tialp

ress

ure

CO

2of

0.97

and

0.11

–0.

15at

m,

resp

ectiv

ely.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

perim

enta

ltec

hniq

ueus

edw

asno

tde

scrib

ed.

The

com

pile

rsu

mes

that

mea

sure

men

tsw

ere

carr

ied

out

ina

man

ner

ilar

toth

atus

edby

the

auth

ors

inth

est

udy

ofth

elu

bilit

yof

UO

2CO

31an

dP

uO2C

O3.

2

No

deta

ilsre

port

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Ref

eren

ces:

1 I.G

rent

he,D

.Fer

ri,F

.Sal

vato

re,a

ndG

.Ric

cio,

J.C

hem

.Soc

.,D

alto

nT

rans

.24

39~1

984!

.2 P

.Rob

ouch

and

P.V

itorg

e,In

org.

Chi

m.A

cta

140,

239

~198

7!.

634634 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

carb

onat

odi

oxon

eptu

nate

~V!;

NaN

pO2C

O3;

@571

27-8

6-3#

~2!

Car

bon

diox

ide;

CO 2;

@124

-38-

9#~3

!S

odiu

mhy

drog

enca

rbon

ate;

NaH

CO

3;@1

44-5

5-8#

~4!

Sod

ium

perc

hlor

ate;

NaC

lO 4;@7

601-

89-0#

~5!

Wat

er;

H 2O

;@7

732-

18-5#

I.G

rent

he,P

.Rob

ouch

,and

P.V

itorg

e,J.

Less

-Com

mon

Met

als

122,

225

–31

~198

6!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

3pa

rtia

lpre

ssur

eof

CO 2/a

tm~k

Pa!

:0.

11–

0.15

~10.

8–

14.7!

and

0.97

~95.

15!

c 3/m

oldm

23 :

3.0

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aNpO

2CO

3at

20°C

asa

func

tion

ofeq

uilib

rium

CO 322

ion

conc

entr

atio

n

The

resu

ltsw

ere

repo

rted

ingr

aphi

calf

orm

only~see

Fig

.16

!.

Add

ition

alin

form

atio

n:T

heso

lubi

lity

ofN

aNpO

2CO

3in

carb

onat

eco

ntai

ning

3.0

mol

dm23

solu

tions

ofN

aClO 4

wer

ein

terp

rete

dby

the

auth

ors

byco

nsid

erin

gN

pO21

,N

pO2C

O32

,N

pO2~

CO

3!232

,an

dN

pO2~

CO

3!352

asso

lutio

nsp

ecie

s,an

dhy

drat

edN

aNpO

2CO

3an

dN

a 3N

pO2~

CO

3!2

asth

eeq

ui-

libriu

mso

lidph

ases

.T

heov

eral

lsta

bilit

yco

nsta

nts

ofth

eca

rbon

atoc

ompl

exes

ofN

p~V

!w

ere

repo

rted

tobe

105.09

,10

8.15

,an

d10

10.4

6 ,re

spec

tivel

y,an

dth

eso

lubi

lity

prod

ucts

ofN

aNpO 2C

O3

and

Na 3

NpO

2~C

O3!

2as

102

10.5

6an

d10

212

.44 ,

resp

ectiv

ely.

FIG

me

of Me

Ex

as sim

so


er

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.T

heso

lubi

litie

sw

ere

mea

sure

din

2CO

3/N

aClO

4so

lutio

nsw

ithin

itial

ioni

cst

reng

thof

1.0

ldm

23 .

The

solu

tions

wer

epr

epar

edus

ing

CO

2-fr

eew

ater

ich

was

prep

ared

bybo

iling

and

purg

ing

with

argo

n.E

xces

slid

was

equi

libra

ted

with

solu

tions

ofth

ede

sire

dm

posi

tion

ingl

ass

tube

sse

aled

with

aru

bber

gask

et.

The

esw

ere

subm

erge

din

ath

erm

osta

ted

bath

for

perio

dsof

era

ngin

gfr

om2

to4

wee

ks.

No

evap

orat

ion

loss

esw

ere

tect

edev

enaf

ter

seve

ralw

eeks

at75

°C.

Afte

req

uilib

ratio

n,dr

ogen

ion

conc

entr

atio

nw

asde

term

ined

atth

ete

mpe

ratu

reth

eex

perim

ent

usin

ga

mic

ropH

prob

ew

ith4.

0m

oldm23

Cls

atur

ated

with

AgC

las

fillin

gso

lutio

n.T

hepr

obe

was

libra

ted

atea

chte

mpe

ratu

reag

ains

tso

lutio

nsof

know

nH

1

OH

2io

nco

ncen

trat

ion

in1.

0m

oldm2

3N

aClO

4.A

liquo

tsth

esa

tura

ted

solu

tions

wer

ew

ithdr

awn

with

asy

ringe

uipp

edw

itha

0.2m

mfil

ter,

and

the

conc

entr

atio

nof

ptun

ium

was

dete

rmin

edra

diom

etric

ally

.T

oth

isai

m,

Np

~V!

sre

duce

dto

Np~IV

!by

Fe~

II!

sulfa

mat

e,th

eso

lutio

nw

asid

ified

to6

mol

dm2

3H

Cl,

Np~

IV!

was

extr

acte

din

to10

%m

ine

336

inxy

lene

,an

dba

ckex

trac

ted

into

0.1

mol

dm2

3

l.S

ampl

esw

ere

then

evap

orat

edto

dryn

ess

and

aco

unte

d.co

very

ofN

pin

this

proc

edur

ew

asat

leas

t95

%.

Sol

idas

esw

ere

iden

tified

byx-

ray

diffr

actio

n.

Hyd

rate

dN

aNpO

2CO

3an

dN

a 3N

pO2~

CO

3!2

wer

epr

epar

edac

cord

ing

toR

efs.

1an

d2.

Pow

der

x-ra

ydi

ffrac

tion

patte

rnof

the

solid

sw

ere

inag

reem

ent

with

thos

ere

port

edfo

rN

aNpO

2CO

3•3H

2Oan

dN

a 3NpO

2~C

O3!

2•xH

2O.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

typr

oduc

t:se

eab

ove.

Ref

eren

ces:

1 Yu.

F.

Vol

kov,

G.

I.V

isya

shch

eva,

and

I.I.

Kap

shuk

ov,

Rad

iokh

imiy

a19,

319

~197

7!.

2 Yu.

F.

Vol

kov,

G.

I.V

isya

shch

eva,

S.

V.

Tom

ilin,

I.I.

Kap

shuk

ov,

and

A.

G.

Ryk

ov,

Rad

iokh

imiy

a23,

248

~198

1!.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

carb

onat

odi

oxon

eptu

nate

~V!;

NaN

pO2C

O3;

@571

27-8

6-3#;

orso

dium

bis~c

arbo

nato!

diox

onep

tuna

te~V!;

Na 3

NpO

2~C

O3!

2;@6

4438

-44-

4#~2

!S

odiu

mca

rbon

ate;

Na

2CO

3;@4

97-1

9-8#

~3!

Sod

ium

perc

hlor

ate;

NaC

lO 4;@7

601-

89-0#

~4!

Wat

er;

H 2O

;@7

732-

18-5#

R.J

.Lem

ire,G

.D.B

oyer

,and

A.B

.Cam

pbel

l,R

adio

chim

.Act

a61

,57

–63

~199

3!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:30

3,32

3,an

d34

8E

quili

briu

mco

ncen

trat

ion

ofth

eC

O322

ion/

mol

dm2

3 :102

6–

0.1

c 3/m

oldm

23 :

vary

ing

conc

entr

atio

nto

mai

ntai

nio

nic

stre

ngth

of1.

0m

oldm

23

inN

a 2C

O3–

NaC

lO4

solu

tions

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aNpO

2CO

3or

Na 3

NpO

2~C

O3!

2at

thre

edi

ffere

ntte

mpe

ratu

res

asa

func

tion

ofeq

uilib

rium

CO

322io

nco

ncen

trat

ion

The

solu

bilit

yof

NaN

pO2C

O3

orN

a 3N

pO2~

CO

3!2

asa

func

tion

ofeq

uilib

rium

CO 322

ion

conc

entr

atio

nw

asre

port

edin

grap

hica

lfo

rmon

ly.T

heau

thor

san

alyz

edth

eso

lubi

lity

data

bya

leas

t-sq

uare

spr

oced

ure

cons

ider

ing

two

mod

els

diffe

ring

inth

eso

lidph

ases

,i.e

.,ei

thhy

drat

edN

aNpO

2CO

3~m

odel

A!or

am

ixtu

reof

hydr

ated

NaN

pO 2C

O3

and

Na 3

NpO

2~C

O3!

2~m

odel

B!.

Nep

tuni

umsp

ecie

sin

the

satu

rate

dso

lutio

nsw

ere

cons

ider

edto

beN

pO21

,N

pO2C

O32

,N

pO2~

CO

3!232

,an

dN

pO2~

CO

3!352

,w

hile

NpO

2~O

H! ~

aq!w

asno

tfou

ndto

bea

sign

ifica

ntsp

ecie

s.T

heco

nsta

nt

Ksp*

5@N

pO21

#@C

O322

#5K

sp@N

a1#g

~Na1

!g~C

O322

!g~N

pO21

!

was

calc

ulat

edfo

rdi

ffere

ntte

mpe

ratu

res

and

mod

els.

At

30an

d50

°C,

Ksp*

was

calc

ulat

edto

be102

(10.

760.

1)an

d10

2(1

1.06

0.1)

,re

spec

-tiv

ely,

irres

pect

ive

ofth

em

odel

used

.A

t75

°C,

Ksp*

was

calc

ulat

edto

be102

(10.

760.

2)~m

odel

Aw

ithN

pO2C

O32

asso

lutio

nsp

ecie

s!,10

2(1

0.86

0.2)

~mod

elB

with

NpO

2CO

32an

dN

pO2~

CO

3!352

asso

lutio

nsp

ecie

s!,an

d10

2(1

1.36

052)

~mod

elB

with

NpO

2CO

32an

dN

pO2~

CO

3!232

asso

lutio

nsp

ecie

s!.

Add

ition

alin

form

atio

n:A

t30

°C,

the

min

imum

nept

uniu

mso

lubi

lity

(;10

26

mol

dm2

3 )oc

curs

atfr

eeca

rbon

ate

conc

entr

atio

nof

abou

t10

23

mol

dm2

3 .F

orin

itial

carb

onat

eco

ncen

trat

ion

betw

een

0.01

and

0.1

mol

dm2

3th

ein

itial

solid

,ei

ther

hydr

ated

NaN

pO 2C

O3

orhy

drat

edN

a 3N

pO2~

CO

3!2,

was

reco

vere

das

the

prim

ary

solid

afte

rha

ving

been

cont

acte

dw

ithth

eso

lutio

nsfo

rm

ore

than

1m

onth

.In

afe

wex

perim

ents

usin

ghy

drat

edN

a3N

pO2~

CO

3!2

asth

ein

itial

solid

,at

leas

tpa

rtia

lcon

vers

ion

ofth

eso

lidoc

curr

ed:

Na 3

NpO

2~C

O3!

2•xH

2O�

NaN

pO2C

O3•

yH2O

12N

a11

CO

3221

(y2

x)H

2O

At

50°C

,N

a 3N

pO2~

CO

3!2

pred

omin

ated

asth

eso

lidph

ase.

Als

oat

75°C

and

at1.

0m

oldm

23

Na1

,th

est

able

solid

had

ara

tioof

Na:

Np.

1.G

ener

ally

,fo

rto

tal

carb

onat

eco

ncen

trat

ion

.0.

005

mol

dm2

3 ,on

lyhy

drat

edN

a 3NpO

2~C

O3!

2w

asid

entifi

edby

x-ra

ydi

ffrac

tion,

alth

ough

Na 8~

NpO

2!2~

CO

3!5

was

pres

ent

inso

me

sam

ples

.

Me

Iso

Na

mo

wh

so co tub

tim de hy of Na

ca or of eq ne wa

ac ala

HC

Re

ph

J

red

FIG

.17

.S

odiu

mca

rbon

ato

diox

onep

tuna

te~V!–

sodi

umpe

rchl

orat

e–

carb

ondi

oxid

e–

wat

ersy

stem

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials:

eso

lubi

lity

was

mea

sure

dby

radi

omet

ricpH

titra

tion

ina

sed

ther

mos

tate

dgl

ass

vess

el.

The

solid

phas

ew

asec

ipita

ted

inth

eve

ssel

from

a0.

02m

oldm2

3N

pO21

lutio

nin

0.1

mol

dm2

3H

ClO

4by

addi

tion

of0.

05ld

m2

3N

a 2C

O3.

The

solu

tion

with

the

prec

ipita

tew

asow

edto

stan

dfo

rab

out

3w

eeks

.T

hen

pHw

asad

just

edby

ding

solu

tions

ofei

ther

0.1

mol

dm23

HC

lO4

or0.

05ld

m2

3N

a 2C

O3.

The

solid

–liq

uid

phas

eeq

uilib

rium

ata

enpH

was

esta

blis

hed

with

in1

–3

days

.E

quili

briu

mlu

bilit

yw

asat

tain

edfr

ombo

thsu

per-

and

unde

rsat

urat

edlu

tions

toen

sure

that

are

prod

ucib

lest

eady

stat

eha

dbe

enta

blis

hed

inth

ein

vest

igat

edpH

rang

eof

6–

9.A

defin

edos

pher

ew

asm

aint

aine

dby

aco

ntin

uous

flow

ofa

cert

ified

sm

ixtu

reof

N 2co

ntai

ning

1%C

O 2th

roug

hth

eso

lutio

ner

moi

sten

ing

the

gas

inw

ashi

ngfla

sks.

Sam

ples

from

the

uid

phas

ew

ere

with

draw

naf

ter

ultr

afiltr

atio

nth

roug

ha

200

pore

size

filte

r~Adv

ante

c!.D

eter

min

atio

nof

Np~V

!in

the

tura

ted

solu

tions

was

carr

ied

out

byasp

ectr

omet

ry,

liqui

din

tilla

tion

coun

ting,

and

spec

trop

hoto

met

rical

lyat

981.

3nm

.e

pHw

asde

term

ined

acco

rdin

gto

Ref

.1.

Sol

idph

ases

rein

vest

igat

edby

usin

gx-

ray

pow

der

diffr

actio

n.

Isot

opic

ally

pure

237 N

p~C

EA

,F

ranc

e!w

asus

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

2K

~aut

hor!.

Sol

ubili

typr

oduc

t:se

eab

ove.

Ref

eren

ces:

1 G.

Mei

nrat

han

dJ.

I.K

im,

Rad

ioch

im.

Act

a52Õ5

3,29

~199

1!.

636636 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

carb

onat

odi

oxon

eptu

nate

~V!;

NaN

pO2C

O3;

@571

27-8

6-3#

~2!

Car

bon

diox

ide;

CO 2;

@124

-38-

9#~3

!S

odiu

mpe

rchl

orat

e;N

aClO 4;

@760

1-89

-0#~4

!W

ater

;H 2

O;

@773

2-18

-5#

G.

Mei

nrat

h,J.

Rad

ioan

al.

Nuc

l.C

hem

.Le

tt.186,

257

–72

~199

4!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8p

2~p

artia

lpre

ssur

e!/%

:1

c 3/m

oldm

23 :

0.1

~ioni

cst

reng

th!

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aNpO

2CO

3at

25°C

asa

func

tion

ofpH

The

solu

bilit

yof

NaN

pO2C

O3

at25

°Can

dat

ioni

cst

reng

thof

0.1

mol

dm23

ClO

42an

d1%

part

ialp

ress

ure

ofC

O2

asa

func

tion

ofpH

was

repo

rted

ingr

aphi

cal

form~

see

Fig

.17

!.U

nder

the

cond

ition

sus

ed,

i.e.,

pH,9

and

max

imum

equi

libriu

mca

rbon

ate

ion

conc

en-

trat

ion

ofab

out

1022

mol

dm2

3 ,th

eau

thor

obta

ined

for

the

solu

bilit

yof

NaN

pO 2CO

3th

eeq

uatio

n

S5K

sp@N

a1#2

1 @C

O322

#21 $

11b

1@C

O322

#1b

2@C

O322

#2%

whe

reK

sp5

@Na1

#@N

pO21

#@C

O322

#510

2~1

0.22

60.

02! ,

and

b1

and

b2

are

over

all

stab

ility

cons

tant

sof

the

NpO 2C

O32

and

NpO

2~C

O3!

232

com

plex

esw

hich

wer

eca

lcul

ated

tobe

102

(4.5

260.

02)

and

,10

26.

60,

resp

ectiv

ely.

Add

ition

alin

form

atio

n:E

quili

briu

mca

rbon

ate

ion

conc

entr

atio

nw

asob

tain

edfr

omth

eH

enry

cons

tant

,dis

soci

atio

nco

nsta

nts

ofca

rbon

icac

id,a

ndth

em

easu

pH.

Hyd

roly

sis

ofN

p~V!

was

foun

dto

bein

sign

ifica

ntun

der

the

cond

ition

sus

ed.

Me

Th

clo

pr so mo

all

ad mo

giv

so so es atm

ga aft

liq nm sa sc Th

we


mol

dm2

3N

aCl,

and

at@C

O322

#.(1

021.

9 210

21.

5 )m

oldm

23 ,

the

equi

libriu

mso

lidph

ase

was

Na

3NpO

2~C

O3!

2,@6

4438

-44-

4#.T

hein

itial

solid

used

for

mea

sure

men

tsw

asN

aNpO

2CO

3,an

din

solu

tions

with

high

erio

nic

stre

ngth

and

cont

aini

nghi

gher

CO

322co

ncen

trat

ion,

itw

asco

nver

ted

toN

a 3NpO

2~C

O3!

2w

ithin

10da

ys.

Inev

alua

ting

the

solu

bilit

yda

ta,

the

mea

sure

dpH

valu

esat

ioni

cst

reng

ths

.0.

1m

oldm

23

wer

eco

rrec

ted

for

liqui

dju

nctio

npo

tent

ials

,an

dap

pare

ntpr

otol

ysis

cons

tant

ofw

ater

was

then

calc

ulat

edfr

omth

eco

rrec

ted

valu

esan

dfr

omlit

erat

ure

valu

esof

wat

erac

tivity

.The

equi

libriu

mco

ncen

trat

ion

ofC

O322

ion

was

eval

uate

dfr

omth

eH

enry

cons

tant

and

diss

ocia

tion

cons

tant

sof

carb

onic

acid

whi

chw

ere

dete

rmin

edby

pote

ntio

met

rictit

ratio

nfo

rea

chpa

rtic

ular

ioni

cst

reng

th.

FIG

.18

.S

odiu

mca

rbon

ato

diox

onep

tuna

te~V!–

sodi

umch

lorid

e–

carb

ondi

oxid

e–

wat

ersy

stem

.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

carb

onat

odi

oxon

eptu

nate

~V!;

NaN

pO2C

O3

;@5

7127

-86-

3#;or

sodi

umbi

s~car

bona

to!di

oxon

eptu

nate~V

!;N

a 3N

pO2~

CO

3!2;

@644

38-4

4-4#

~2!

Car

bon

diox

ide;

CO 2

;@1

24-3

8-9#

~3!

Sod

ium

perc

hlor

ate;

NaC

lO 4;

@760

1-89

-0#;

orS

odiu

mch

lorid

e;N

aCl;@

7647

-14-

5#~4

!W

ater

;H 2

O;

@773

2-18

-5#

V.

Nec

k,W

.R

unde

,J.

I.K

im,

and

B.

Kan

ella

kopu

los,

Rad

ioch

im.

Act

a65,

29–

37,~

1994

!,J.

Allo

ysC

ompd

s.22

5,29

5–

302~

1995

!.

Var

iabl

es:

Pre

pare

dB

y:

T/K

:29

8p

2~p

artia

lpre

ssur

e!/%

:0.

03~3

1P

a!in

NaC

lO4

solu

tions

;1.

0~1

.03

kPa!

inN

aCls

olut

ions

c 3/m

oldm

23 :

0.1

–5.

0(N

aClO 4

);5.

0~N

aCl!

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

NaN

pO2C

O3

and

Na 3

NpO

2~C

O3!

2at

25°C

asa

func

tion

ofca

rbon

ate

ion

conc

entr

atio

nat

diffe

rent

ioni

cst

reng

ths

The

solu

bilit

yof

NaN

pO2C

O3

and

Na 3

NpO

2~C

O3!

2as

afu

nctio

nof

equi

libriu

mca

rbon

ate

ion

conc

entr

atio

nw

asre

port

edin

grap

hica

lfo

rm~s

eeF

ig.

18!.

By

usin

gno

nlin

ear

leas

t-sq

uare

san

alys

is,

the

follo

win

gva

lues

wer

eob

tain

edfo

rth

eso

lubi

lity

prod

ucts

ofN

aNpO

2CO

3an

dN

a 3N

pO3~

CO

3!2,

and

the

over

alls

tabi

lity

cons

tant

sof

the

NpO 2~C

O3)

n12

2n

com

plex

es:

Ioni

cst

reng

th~m

oldm

23 !

log

Ksp

,1a

log

Ksp

,3a

log

b1

log

b2

log

b3

02

11.0

060.

07b

214

.326

0.15

b

0.1(

NaC

lO4)

210

.286

0.04

4.58

60.

046.

606

0.07

~,6.

8!

1.0(

NaC

lO4)

210

.106

0.03

212

.236

0.15

4.50

60.

046.

966

0.06

8.67

60.

09

3.0(

NaC

lO4)

210

.456

0.04

212

.596

0.10

4.76

60.

047.

696

0.07

10.3

060.

09

5.0(

NaC

lO4)

211

.066

0.06

213

.576

0.11

5.00

60.

058.

296

0.09

11.4

760.

08

5.0

~NaC

l!c2

10.6

360.

112

12.4

860.

23

a Ksp

,15

@Na1

#@N

pO21

#@C

O32 #;

Ksp

,35

@Na1

#3@N

pO21

#@C

O32 #2

.b T

herm

odyn

amic

solu

bilit

ypr

oduc

t,ob

tain

edby

the

auth

ors

from

the

spec

ific

inte

ract

ion

theo

ry.

Cor

rect

edfo

rth

efo

rmat

ion

ofN

p~V

!ch

loro

com

plex

es.

Add

ition

alin

form

atio

n:T

hein

crea

sein

the

NaN

pO 2C

O3

solu

bilit

yat

high

erca

rbon

ate

ion

conc

entr

atio

nsor

pHw

asas

crib

edby

the

auth

ors

toth

efo

rmat

ion

ofth

eN

pO2~

CO

3) n1

22

nco

mpl

exes

.In

0.1

mol

dm23

NaC

lO4,

NaN

pO2C

O3

was

foun

dto

beth

est

able

solid

phas

eov

erth

ew

hole

CO

322

conc

entr

atio

nra

nge

stud

ied.

In1.

0m

oldm2

3N

aClO

4at

@CO

322#.

0.5

mol

dm2

3 ,an

din

3.0

and

5.0

mol

dm23

NaC

lO4,

asw

ella

sin

5.0

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

carb

onat

odi

oxon

eptu

nate

~V!;

NaN

pO2C

O3

;71

27-8

6-3#

Car

bon

diox

ide;

CO 2

;@1

24-3

8-9#

Sod

ium

chlo

ride;

NaC

l;@764

7-14

-5#W

ater

;H 2

O;

@773

2-18

-5#

W.

Run

de,

M.

P.

Neu

,an

dD

.L.

Cla

rk,

Geo

chim

.C

osm

ochi

m.

Act

a60

,20

65–

73~1

996!

.

riabl

es:

Pre

pare

dB

y:

K:

296

~par

tialp

ress

ure!/at

m:

0.01

~981

Pa!

/mol

dm2

3 :0.

1an

d3.

0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

NaN

pO2C

O3

at23

°Cas

afu

nctio

nof

carb

onat

eio

nco

ncen

trat

ion

inN

aCls

olut

ions

eso

lubi

lity

ofN

aNpO

2CO

3as

afu

nctio

nof

equi

libriu

mca

rbon

ate

ion

conc

entr

atio

n,in

the

rang

eof

@CO

322#

from

102

7to

21

mol

dm2

3 ,w

asre

port

edin

grap

hica

lfor

mon

ly.

By

usin

gno

nlin

ear

leas

t-sq

uare

san

alys

is,

the

follo

win

gva

lues

wer

eob

tain

edth

eso

lubi

lity

prod

uct

ofN

aNpO

2CO

3,an

dth

eov

eral

lsta

bilit

yco

nsta

nts

(b

n)

ofth

eN

pO2~

CO

3) n1

22

nco

mpl

exes

:

NaC

l(c

3/m

oldm

23 )

log

Ksp

alo

gb

1lo

gb

2lo

gb

3

0.1

210

.46

0.2

4.86

0.1

3.0

29.

460.

24.

360.

17.

160.

29.

260.

2

sp5

@Na1

#@N

pO21

#@C

O322

#.

ditio

nali

nfor

mat

ion:

eso

lidph

ases

wer

efo

und

tobe

NaN

pO 2CO

3•xH

2Oan

dN

a 3NpO

2~C

O3) 2•xH

2Oat

@CO

322#,

102

3an

d.

102

3m

oldm

23 ,

resp

ec-

ely.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

eso

lubi

lity

mea

sure

men

tsw

ere

perf

orm

edin

acl

osed

rmos

tate

dgl

ass

vess

elfil

led

with

argo

nga

sco

ntai

ning

0.03

1%C

O 2.

The

solid

sw

ere

prep

ared

byad

ditio

nof

0.1

mol

23

Na 2

CO

3to

anac

idic

0.01

mol

dm2

3N

pO21

solu

tion

ntai

ning

the

desi

red

conc

entr

atio

nof

NaC

l.T

heso

lidph

ases

real

low

edto

age

for

seve

ralw

eeks

inco

ntac

tw

ithth

elu

tion

until

pHan

dth

eN

p~V!

conc

entr

atio

nin

the

solu

tion

did

not

chan

ge.

The

pHof

each

solu

tion

was

adju

sted

byad

ding

Na 2C

O3

/NaC

lor

NaH

CO 3

/NaC

lsol

utio

n,an

dw

asm

easu

red

usin

ga

com

bina

tion

glas

sel

ectr

ode

~Orio

n,R

OS

S!w

hich

was

calib

rate

dag

ains

tfiv

est

anda

rdbu

ffer

solu

tions

and

eigh

tN

aCls

olut

ions

ofkn

own

H1or

OH

2co

ncen

trat

ion.

Afte

rfil

trat

ion

thro

ugh

a45

0nm

pore

size

filte

r,th

eN

p~V

!co

ncen

trat

ion

inth

esa

tura

ted

solu

tion

was

dete

rmin

edra

diom

etric

ally

byliq

uid

scin

tilla

tion

coun

ting,

disc

rimin

atin

gth

e23

7 Np

aac

tivity

from

the

over

lapp

ing

taili

ngb

activ

ityof

the

233 P

ada

ught

er,

and

spec

trop

hoto

met

rical

ly.

The

solid

phas

esw

ere

char

acte

rized

byx-

ray

pow

der

diffr

actio

n.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

typr

oduc

t:se

eab

ove.

638638 JIRI HALA

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

ym

easu

rem

ents

wer

epe

rfor

med

ina

clos

edth

erm

osta

ted

glas

sve

ssel

fille

dw

ithar

gon

gas

cont

aini

ng0.

03or

1%C

O 2.

The

gas

mix

ture

was

allo

wed

topa

ssth

roug

hth

eve

ssel

durin

gth

esa

mpl

ing

and

pHad

just

men

tw

hile

durin

gst

andi

ngpe

riods

the

vess

elw

asfil

led

with

the

gas

mix

ture

and

clos

ed.

Inea

chex

perim

ent,

som

e50

mg

Np

~V!

~;0.

002

mol

dm2

3 !w

asus

edin

50m

LH

ClO 4

/NaC

lO4

orH

Cl/N

aCl

solu

tion

~pH

3!at

the

desi

red

ioni

cst

reng

th.

The

oxid

atio

nst

ate

ofN

p~V!

inth

est

artin

gso

lutio

nw

asco

nfirm

edsp

ectr

opho

tom

etric

ally

inth

evi

sibl

ean

dne

arIR

regi

on.

The

pHof

each

solu

tion

was

rais

edto

8.0

–8.

5by

addi

ngN

aHC

O 3/N

aClO

4or

NaH

CO 3

/NaC

lsol

utio

nto

prec

ipita

teN

aNpO

2CO

3w

hich

was

then

left

for

seve

rald

ays

for

equi

libra

tion.

The

nth

eso

lubi

lity

mea

sure

men

tsw

ere

perf

orm

edby

adju

stin

gth

ede

sire

dpH

inth

era

nge

from

5.9

to9.

9,by

step

wis

ead

ding

eith

erH

ClO 4/N

aClO

4or

NaH

CO 3

/NaC

lO4

solu

tion,

orH

Cl/N

aClo

rN

aHC

O 3/N

aCl

solu

tion.

The

equi

libriu

mat

each

pHw

asco

nfirm

edby

dete

rmin

ing

pHan

dN

pco

ncen

trat

ion

inth

eso

lutio

nun

tilco

nsta

ntva

lues

wer

ere

ache

d.T

his

was

atta

ined

with

in1

–3

days

depe

ndin

gon

pHan

dio

nic

stre

ngth

.A

fter

filtr

atio

nth

roug

ha

200

nmpo

resi

zefil

ter,

the

Np

~V!

conc

entr

atio

nin

the

satu

rate

dso

lutio

nw

asde

term

ined

radi

omet

rical

lyby

liqui

dsc

intil

latio

nco

untin

g,di

scrim

inat

ing

the23

7 Np

aac

tivity

from

the

over

lapp

ing

taili

ngb

activ

ityof

the

233 P

ada

ught

er.

Aco

mbi

natio

ngl

ass

elec

trod

e~RO

SS

,O

rion!

was

used

for

pHm

easu

rem

ents

.T

heel

ectr

ode

was

calib

rate

dre

gula

rlyag

ains

tpH

buffe

rst

anda

rds~M

erck

!.T

heor

igin

alju

nctio

nel

ectr

olyt

eof

the

elec

trod

ew

asre

plac

edby

3.0

mol

dm23

NaC

lto

avoi

dpr

ecip

itatio

nof

KC

lO4.

The

solid

phas

esw

ere

char

acte

rized

byx-

ray

pow

der

diffr

actio

n.

237 N

pus

edw

aspu

rified

from

238 P

u.N

oot

her

deta

ilsre

port

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

typr

oduc

t:se

eab

ove.

Co

~1!

@5 ~2!

~3!

~4!

Va

T/

p2

c 3 Th

10 for

a K Ad

Th

tiv Me

Th

the

or dm co we

so


FIG

.19

.S

odiu

mbi

s~car

bona

to!di

oxon

eptu

nate~

V!–

sodi

umca

rbon

ate

–so

dium

nitr

ate

–ca

rbon

diox

ide

–w

ater

syst

em.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

solid

was

equi

libra

ted

with

solu

tions

ofth

ede

sire

dco

mpo

sitio

nun

der

occa

sion

alst

irrin

gfo

r3

days

whi

chw

asfo

und

suffi

cien

tfo

req

uilib

rium

tobe

reac

hed.

An

aliq

uot

ofth

esu

spen

sion

was

then

with

draw

n,ce

ntrif

uged

,an

dth

eN

pco

ncen

trat

ion

inth

esa

tura

ted

solu

tion

was

dete

rmin

edby

coul

omet

rictit

ratio

n.1

The

solid

phas

ew

asch

arac

teriz

edby

x-ra

ydi

ffrac

tion.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

5K

~aut

hor!.

Ref

eren

ces:

1 G.

A.

Sim

akin

,P

.F

.B

akla

nova

,G

.F

.K

uzne

tsov

,an

dB

.V

.C

hern

ev,

Zh.

Ana

lit.

Khi

m.2

9,15

85~1

974!

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

bis~c

arbo

nato!

diox

onep

tuna

te~V!;

3NpO

2~C

O3) 2

;@6

4438

-44-

4#S

odiu

mca

rbon

ate;

Na

2CO

3;

@497

-19-

8#S

odiu

mch

lorid

e;N

aCl;@7

647-

14-5#

Pot

assi

umch

lorid

e;K

Cl;@7

447-

40-7#

Wat

er;

H 2O

;@7

732-

18-5#

I.A

lM

aham

id,

C.

F.

Nov

ak,

K.

A.

Bec

kraf

t,S

.A

.C

arpe

nter

,an

dN

.H

akem

,R

adio

chim

.A

cta.8

1,93

–10

1~19

98!.

riabl

es:

Pre

pare

dby

:

K:

295

/mol

kg2

1 :0.

009

–95

–1.

00/m

olkg

21 :

5.00

/mol

kg2

1 :0.

10

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Na 3

NpO

2~C

O3!

2at

22°C

asa

func

tion

ofN

a 2CO

3co

ncen

trat

ion

inso

lutio

nsco

ntai

ning

NaC

land

KC

la

Na 2

CO

3

(m2

/mol

kg2

1 )N

p~V

!b

(104

mol

dm2

3 )

0.00

995c

0.14

060.

045

0.04

54c

3.55

60.

13

0.21

5c4.

096

0.13

1.00

d3.

476

0.11

llso

lutio

nsco

ntai

ned

5.00

mol

kg21

NaC

land

0.10

0m

olkg2

1K

Cl.

otal

Np~

V!

conc

entr

atio

nin

the

satu

rate

dso

lutio

n.ol

idph

ase

was

Na 3N

pO2~

CO

3!2,

@644

38-4

4-4#.

nide

ntifi

edso

lidph

ase.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.T

heso

lidw

aseq

uilib

rate

dw

ithlu

tions

ofth

ede

sire

dco

mpo

sitio

nin

poly

ethe

reth

erke

tone

ssel

s~C

adill

acP

last

ics!.

The

equi

libra

tion

time

was

170

ysw

ithst

eady

stat

ebe

ing

achi

eved

with

in10

7da

ys.

All

perim

ents

wer

eco

nduc

ted

unde

rar

gon

atm

osph

ere.

Sam

ples

the

satu

rate

dso

lutio

nsw

ere

filte

red

thro

ugh

4.1

nmnt

ricon

filte

rs~A

mic

onC

orp.!

.T

hepH

was

mea

sure

dus

ing

aR

oss

com

bina

tion

glas

sel

ectr

ode

calib

rate

din

each

ofth

eN

a1/K

1/C

l2so

lutio

nto

acco

unt

for

the

liqui

dju

nctio

npo

tent

ial.

The

Np~V

!co

ncen

trat

ion

was

mea

sure

dra

diom

etric

ally

bym

eans

ofa

high

purit

yG

ede

tect

orus

ing

the

29.4

keV

glin

eof

237 N

p.T

otal

inor

gani

cca

rbon

cont

ent

inth

esa

tura

ted

solu

tions

was

dete

rmin

edby

usin

gS

him

adzu

TO

C-5

050

carb

onan

alyz

er.

No

chan

ges

into

talc

arbo

nw

ere

obse

rved

.

Na 3

NpO

2~C

O3!

2w

aspr

epar

edby

addi

ng1

mol

dm23

Na 2

CO

3to

the

Np~

V!

stoc

kso

lutio

nto

obta

ina

final

carb

onat

eco

ncen

trat

ion

ofab

out

0.5

mol

dm23 .

Aw

hite

prec

ipita

tew

asfo

rmed

.P

urity

ofth

eN

p~V!

stoc

kso

lutio

n,in

clud

ing

oxid

atio

nst

ate

purit

y,w

asve

rified

asin

the

auth

ors’

prev

ious

wor

k.1

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

Sol

ubili

ty:

see

abov

e.

Ref

eren

ces:

1 C.

F.

Nov

ak,

I.A

lM

aham

id,

K.

A.

Bec

kraf

t,S

.A

.C

arpe

nter

,N

.H

akem

,an

dT

.P

russ

in,

J.S

olut

ion

Che

m.

26,

681

~199

7!.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

bis~c

arbo

nato!

diox

onep

tuna

te~V!;

Na 3

NpO

2~C

O3) 2

;@6

4438

-44-

4#~2

!S

odiu

mca

rbon

ate;

Na

2CO

3;

@497

-19-

8#~3

!S

odiu

mni

trat

e;N

aNO 3

;@7

631-

99-4#

~4!

Wat

er;

H 2O

;@7

732-

18-5#

G.

A.

Sim

akin

,R

adio

khim

iya1

9,51

8–

21~1

977!

.

Var

iabl

es:

Pre

pare

dB

y:

T/K

:29

8c 2

/mol

dm2

3 :0.

25–

1.0

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

a 3N

pO2~

CO

3!2

at25

°Cin

Na 2C

O3–

NaN

O 3so

lutio

nsat

ioni

cst

reng

thof

3.0

mol

dm23

The

solu

bilit

yof

Na 3

NpO

2~C

O3!

2w

asde

term

ined

at25

°Cas

afu

nctio

nof

Na

2CO

3co

ncen

trat

ion

atpH

12.0

and

cons

tant

ioni

cst

reng

thof

3.0

mol

dm2

3m

aint

aine

dby

usin

gN

aNO 3.

The

resu

ltsw

ere

repo

rted

ingr

aphi

calf

orm

only

~see

Fig

.19!.

The

equi

libriu

mso

lidph

ase

was

Na 3

NpO

2~C

O3) 2•xH

2Oin

alls

olut

ions

,th

eso

lutio

nN

p~V!

spec

ies

was

the

NpO 2

~CO

3!35

2io

n.

Co

~1!

Na

~2!

~3!

~4!

~5!

Va

T/

m2

m3

m4

a A b T c S d U Me

Iso

so ve da ex of Ce

J

no

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 R.

J.Le

mire

,G

.D

.B

oyer

,an

dA

.B

.C

ampb

ell,

Rad

ioch

im.

Act

a61

,57

~199

3!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umca

rbon

ato

diox

onep

tuna

te~V

!;pO

2CO

3;

@549

55-6

3-4#

Pot

assi

umca

rbon

ate;

K2C

O3;

@584

-08-

7#W

ater

;H 2

O;

@773

2-18

-5#

C.F

.Nov

ak,I

.AlM

aham

id,K

.A.B

eckr

aft,

S.A

.Car

pent

er,N

.H

akem

,an

dT

.P

russ

in,

J.S

olut

ion

Che

m.

26,

681

–97

~199

7!.

riabl

es:

Pre

pare

dby

:

K:

295

/mol

kg2

1 :0.

01–

4.83

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

KN

pO2C

O3

at22

°Cin

K 2C

O3

solu

tions

K2C

O3

2/m

olkg

21 )

Np~

V!a,

c

~mol

dm2

3 !S

olid

phas

edK

2CO

3

(c2

/mol

kg2

1 )N

p~V

!b,c

~mol

dm2

3 !S

olid

phas

ed

0.01

1(2

.476

0.27

)310

27

A0.

030

(3.3

060.

29)3

102

7A

0.03

0(3

.006

0.30

)310

27

A0.

070

(6.2

760.

59)3

102

7A

0.05

0(3

.656

0.34

)310

27

A0.

130

(1.7

960.

14)3

102

6A

0.07

0(6

.186

0.54

)310

27

A0.

171

(3.7

860.

29)3

102

6A

0.10

0(1

.266

0.09

)310

26

A0.

230

(9.9

460.

59)3

102

6A

e

0.24

9(1

.136

0.06

)310

25

B0.

300

(1.6

560.

10)3

102

5A

e

0.50

1(1

.846

0.06

)310

25

C0.

401

(3.5

860.

16)3

102

5A

e

0.73

9(1

.996

0.06

)310

25

C4.

83(1

.356

0.06

)310

24

B

0.99

3(2

.956

0.12

)310

25

C

0.99

3(3

.046

0.11

)310

25

C

0.99

3(2

.826

0.09

)310

25

C

1.50

(4.6

760.

18)3

102

5C

1.98

(6.7

960.

24)3

102

5C

4.81

(1.2

560.

04)3

102

4B

xper

imen

tspe

rfor

med

with

NpO 2

OH

asth

ein

itial

solid

phas

e.xp

erim

ents

perf

orm

edw

ithK

NpO 2

CO

3as

the

initi

also

lidph

ase.

otal

Np~

V!

conc

entr

atio

nin

the

satu

rate

dso

lutio

n.T

heau

thor

sdi

dno

tre

port

onth

em

eani

ngof

the

erro

r.!

KN

pO2C

O3

;@5

4955

-64-

5#;~B

!K

3NpO

2~C

O3!

2,a

mod

ifica

tion,

@#;

~C!

K3N

pO2~

CO

3!2,

b-m

odifi

catio

n,@

#.T

heau

thor

sdi

dno

txa

min

eth

ena

ture

ofth

edi

ffere

nce

betw

een

the

two

mod

ifica

tions

.T

hey

assu

med

itpe

rtai

ned

toth

ew

ater

ofhy

drat

ion

asso

ciat

edw

ithe

solid

phas

es.

rom

the

com

paris

onw

ithm

easu

rem

ents

usin

gN

pO2O

Has

the

initi

also

lidph

ase

the

auth

ors

conc

lude

dth

atin

thes

eso

lutio

ns,

i.e.,

in.2

–0.

4m

oldm

23

K2C

O3,

KN

pO2C

O3

was

met

asta

ble.

Add

ition

alin

form

atio

n:E

quili

briu

mco

nsta

nts

for

the

diss

olut

ion

reac

tions

KN

pO 2CO

3(s

)�K

11

NpO

211

CO

322an

dK 3

NpO

2~C

O3!

(s)�

3K

11

NpO

211

2CO

322

wer

eca

lcul

ated

tobe

102(1

3.66

0.1)

and

102

(15.

960.

1),

resp

ectiv

ely.

The

rmod

ynam

ican

alys

isof

the

solu

bilit

yda

taus

ing

the

Pitz

erio

nin

tera

ctio

nap

proa

chw

asal

sogi

ven.

640640 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umca

rbon

ato

diox

onep

tuna

te~V

!;K

NpO

2CO

3;

@549

55-6

3-4#

~2!

Pot

assi

umca

rbon

ate;

K 2CO

3;

@584

-08-

7#~3

!W

ater

;H 2

O;

@773

2-18

-5#

G.I

.Vis

yash

eva,

Yu.

F.V

olko

v,G

.A.S

imak

in,I

.I.K

apsh

ukov

,A

.S

.B

evz,

and

G.

N.

Yak

ovle

v,R

adio

khim

iya,1

6,85

3–

9~1

974!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

3an

d35

3c 2

/mol

dm2

3 :0.

1J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

KN

pO2C

O3

at20

and

80°C

in0.

1m

oldm2

3K

2CO

3so

lutio

na

Tem

pera

ture

~°C

!K

NpO

2CO

3

~mg

dm2

3 !K

NpO

2CO

3b

(105

c 1/m

oldm

23 )

201

0.42

2

8040

16.9

a Sol

idph

ase

was

KN

pO 2C

O3,

@549

55-6

3-4#,

inbo

thm

easu

rem

ents

.It

was

repo

rted

tobe

stab

lein

solu

tions

cont

aini

ng,

0.2

mol

dm2

3

K2C

O3.

b Cal

cula

ted

byco

mpi

ler

for

A r~N

p!5

237.

0482

.

Add

ition

alin

form

atio

n:In

Ref

.1,

the

solu

bilit

yof

KN

pO2C

O3

inK

2CO

3/K

Cl

solu

tions

ofio

nic

stre

ngth

of1.

0m

oldm2

3w

asre

port

edto

decr

ease

with

incr

easi

ngte

mpe

ratu

re.

The

data

inR

ef.

1sh

owed

rath

era

grea

tsc

atte

ran

dw

ere

pres

ente

din

grap

hica

lfo

rmon

ly.

For

this

reas

onco

mpi

latio

nw

aspr

epar

edfr

omR

ef.

1fo

rth

isvo

lum

e. Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Not

hing

spec

ified

.S

pecp

ure23

7 NpO

2w

asdi

ssol

ved

inco

ncen

trat

edH

NO

3,an

dN

p~V

!w

aspr

epar

edby

elec

troc

hem

ical

redu

ctio

nof

NpO

221at

plat

inum

elec

trod

e.T

hefin

also

lutio

nw

asad

just

edto

cont

ain

0.05

mol

dm2

3N

p~V

!an

d,

0.1

mol

dm2

3H

NO

3.O

nad

ding

0.1

–0.

2m

oldm

23

K2C

O3

solu

tion,

KN

pO2C

O3•xH

2O(x

,2

)w

asob

tain

edas

agr

een

prec

ipita

te.

Ana

lysi

s~f

ound

/cal

cula

ted

for

the

dihy

drat

e,in

mas

s%!:

K9.

3/9.

67,N

pO2

67.3

/66.

57,C

O 314

.9/1

4.85

,H 2

O~3

.2;

5.8!

/8.9

1.K 2

CO

3w

asa

chem

ical

lypu

repr

oduc

tan

dw

asre

crys

talli

zed

from

wat

er.

Co

~1!

KN

~2!

~3!

Va

T/

c 2 (c a E b E c T d ~A e th e F 0


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umca

rbon

ato

diox

onep

tuna

te~V

!;K

NpO

2CO

3;

4955

-63-

4#P

otas

sium

carb

onat

e;K

2CO

3;

@584

-08-

7#S

odiu

mca

rbon

ate;

Na

2CO

3;

@497

-19-

8#P

otas

sium

chlo

ride;

KC

l;@744

7-40

-7#S

odiu

mch

lorid

e;N

aCl;@7

647-

14-5#

Wat

er;

H 2O

;@7

732-

18-5#

I.A

lM

aham

id,

C.

F.

Nov

ak,

K.

A.

Bec

kraf

t,S

.A

.C

arpe

nter

,an

dN

.H

akem

,R

adio

chim

.A

cta.8

1,93

–10

1~19

98!.

riabl

es:

Pre

pare

dby

:

K:

295

/mol

kg2

1 :0.

001

–1.

07/m

olkg

21 :

0.00

035

–0.

0099

5/m

olkg

21 :

0.00

34–

3.20

/mol

kg2

1 :5.

00

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

KN

pO2C

O3

at22

°Cas

afu

nctio

nof

K 2CO

3or

Na 2

CO

3co

ncen

trat

ion

inso

lutio

nsof

vary

ing

com

posi

tion

a

KC

l(m

4/m

olkg

21 )

K2C

O3

(m2

/mol

kg2

1 )N

a 2C

O3

(m3

/mol

kg2

1 )N

aCl

(m5

/mol

kg2

1 )N

p~V

!b

(104

mol

dm2

3 )

0.00

340.

0010

——

(1.2

160.

08)3

102

6

0.00

320.

0101

——

(6.6

160.

57)3

102

7

0.03

230.

0010

——

(5.8

960.

28)3

102

7

0.03

200.

0101

——

(3.4

760.

24)3

102

7

0.03

210.

100

——

(2.5

060.

32)3

102

6

0.32

00.

0010

——

(2.3

260.

24)3

102

7

0.32

00.

0101

——

(3.9

260.

38)3

102

7

0.32

00.

100

——

(3.7

160.

25)3

102

6

3.20

0.00

10—

—(1

.946

0.24

)310

27

3.20

0.01

01—

—(2

.246

0.32

)310

27

3.20

0.10

0—

—(1

.466

0.12

)310

25

1.00

0.99

6—

—(1

.686

0.10

)310

25

1.08

1.07

——

(1.8

260.

12)3

102

5

0.10

0—

0.00

035

5.00

(1.0

460.

41)3

102

6

0.10

0—

0.00

100

5.00

(1.1

560.

42)3

102

6

0.10

0—

0.00

310

5.00

(2.1

160.

99)3

102

6

0.10

0—

0.00

995

5.00

(6.3

260.

23)3

102

5

a Sol

idph

ase

was

KN

pO 2C

O3,

@549

55-6

3-4#,

inal

lsol

utio

ns.

b Tot

alN

p~V

!co

ncen

trat

ion

inth

esa

tura

ted

solu

tion.

The

auth

ors

did

not

repo

rton

the

mea

ning

ofth

eer

ror,

oron

how

the

erro

rw

ases

timat

ed.

Add

ition

alin

form

atio

n:T

heau

thor

sal

som

easu

red

the

solu

bilit

yof

KN

pO 2CO

3in

thre

edi

ffere

ntsy

nthe

ticN

a–

K–

Mg

–C

lbrin

esin

the

pres

ence

ofC

O2

gas.2

Afe

wm

easu

rem

ents

ofth

eso

lubi

lity

ofK

NpO 2C

O3

wer

ere

port

ed,i

ngr

aphi

calf

orm

,by

Lem

ireet

al.3

The

mea

sure

men

tsw

ere

perf

orm

edat

30an

d75

°Cin

K 2CO

3–

KC

lsol

utio

nsco

ntai

ning

1024–

102

1m

oldm

23

equi

libriu

mca

rbon

ate

ion

conc

entr

atio

nan

d1.

0m

oldm

23

K1

ions

.



Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

edw

ithei

ther

NpO 2O

Hor

KN

pO2C

O3

asth

est

artin

gso

lid.

The

solid

was

adde

dto

K2C

O3

solu

tions

ofth

ede

sire

dco

ncen

trat

ion

inpo

lyet

here

ther

keto

neve

ssel

s~C

adill

acP

last

ics!,

and

allo

wed

toeq

uilib

rate

for

upto

200

days

.S

tead

y-st

ate

Np

~V!

conc

entr

atio

nin

the

solu

tions

was

reac

hed

in15

0da

ysor

less

.S

ampl

esfr

omth

esa

tura

ted

solu

tions

wer

efil

tere

dth

roug

h4.

1nm

Cen

tric

onfil

ters

~Am

icon

Cor

p.!th

atha

dbe

enpr

etre

ated

with

500

mL

ofth

eso

lutio

nto

bean

alyz

ed.

No

adso

rptio

nof

Np

onth

efil

ter

was

obse

rved

.N

eptu

nium

inth

esa

tura

ted

solu

tions

was

dete

rmin

edra

diom

etric

ally

bym

easu

ring

the

29.4

keVg

ray

of23

7 Np

usin

ga

high

purit

yG

ede

tect

or.

Insa

mpl

esco

ntai

ning

,10

26

mol

dm2

3 Np

itw

asne

cess

ary

tore

mov

eth

eov

erla

pfr

omth

eda

ught

er233 P

ape

akat

28.6

keV

.T

his

was

achi

eved

bysp

ectr

ade

conv

olut

ion.

The

solid

phas

esw

ere

char

acte

rized

byx-

ray

diffr

actio

n.

NpO

2OH

was

prep

ared

byad

ditio

nof

aso

lutio

nof

KO

Hto

Np~

V!

solu

tion

in0.

1m

oldm

23

HC

l.T

here

sulti

nggr

een

solid

was

was

hed

twic

ew

ithC

O 2-fr

eede

-ioni

zed

wat

er.

The

KO

Hso

lutio

nw

aspr

epar

edin

aC

O2-

free

glov

ebo

x.K

NpO

2CO

3w

aspr

epar

edby

addi

tion

ofK 2C

O3

solu

tion

toth

eN

p~V!

stoc

kso

lutio

nin

0.1

mol

dm2

3H

Cl.

The

carb

onat

eio

nco

ncen

trat

ion

was

kept

belo

w0.

05m

oldm2

3to

prev

ent

prec

ipita

tion

ofK

3NpO

2~C

O3!

2.T

here

sulti

nggr

een

solid

was

was

hed

twic

ew

ith0.

05m

oldm

23

K2C

O3

tore

mov

ean

yC

l2io

ns.

The

purit

yof

the

Np~

V!

oxid

atio

nst

ate

inth

e237 N

pst

ock

solu

tion~

sour

ceno

tre

port

ed!

was

verifi

edby

com

paris

onbe

twee

nsp

ectr

opho

tom

etric

mea

sure

men

tsan

dg

coun

ting.

No

Np~I

V!

orN

p~V

I!w

ere

pres

ent.

KO

H~J.

T.B

aker!

and

K 2C

O3

~Mat

heso

n!us

edw

ere

A.

R.

grad

e.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

Sol

ubili

ty:

see

abov

e.

Co

~1!

@5 ~2!

~3!

~4!

~5!

~6!

Va

T/

m2

m3

m4

m5

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umbi

s~car

bona

to!di

oxon

eptu

nate~V

!;N

pO2~

CO

3!2;

@549

55-6

4-5#

Pot

assi

umca

rbon

ate;

K2C

O3;

@584

-08-

7#W

ater

;H 2

O;

@773

2-18

-5#

G.I

.Vis

yash

eva,

Yu.

F.V

olko

v,G

.A.S

imak

in,I

.I.K

apsh

ukov

,A

.S

.B

evz,

and

G.

N.

Yak

ovle

v,R

adio

khim

iya16

,85

3–

9~1

974!

.

riabl

es:

Pre

pare

dby

:

K:

293

and

353

/mol

dm2

3 :1.

2J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

K3N

pO2~

CO

3!2

at20

and

80°C

in1.

2m

oldm2

3K

2CO

3so

lutio

na

Tem

pera

ture

~°C

!K

3NpO

2~C

O3!

2

~mg

dm2

3 !K

3NpO

2~C

O3!

2b

(105

c 1/m

oldm

23 !

208

3.37

8017

7.17

hew

hite

salt

K 3N

pO2~

CO

3!2

was

repo

rted

tobe

stab

lein

0.8

to1.

5m

oldm23

K2C

O3

solu

tions

.B

ased

onan

alys

isof

the

star

ting

ater

ial,

the

com

pile

ras

sum

edth

eeq

uilib

rium

solid

phas

eto

behy

drat

edK

3NpO

2~C

O3!

2.A

noth

erm

odifi

catio

nof

K 3NpO

2~C

O3!

2,pa

lello

wto

pale

gree

n,w

asob

tain

edby

prec

ipita

tion

from

solu

tions

cont

aini

ng.

1.8

mol

dm2

3K

2CO

3.S

olub

ility

data

for

this

mod

ifi-

tion

wer

eno

tre

port

ed.

alcu

late

dby

com

pile

rfo

rA r~

Np!

523

7.04

82.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

thin

gsp

ecifi

ed.

Spe

cpur

e237 N

pO2

was

diss

olve

din

conc

entr

ated

HN

O3,

and

Np~

V!

was

prep

ared

byel

ectr

oche

mic

alre

duct

ion

ofN

pO221

atpl

atin

umel

ectr

ode.

The

final

solu

tion

was

adju

sted

toco

ntai

n0.

05m

oldm

23

Np~

V!

and

,0.

1m

oldm

23

HN

O3.

On

addi

ng0.

8–

1.5

mol

dm2

3K

2CO

3so

lutio

n,K 3

NpO

2~C

O3!

2•xH

2O(x

,2

)w

asob

tain

edas

aw

hite

prec

ipita

te.

Ana

lysi

s~f

ound

/ca

lcul

ated

for

the

mon

ohyd

rate

,in

mas

s%

!:K

23.2

/22.

37,N

pO2

52.2

/51.

31,

CO 3

23.1

/22.

89,

H 2O

1.6/

3.43

.K 2

CO

3w

asa

chem

ical

lypu

repr

oduc

tan

dw

asre

crys

talli

zed

from

wat

er.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Sol

ubili

ty:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

642642 JIRI HALA

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

The

solid

was

equi

libra

ted

with

solu

tions

ofth

ede

sire

dco

mpo

sitio

nin

poly

ethe

reth

erke

tone

vess

els~

Cad

illac

Pla

stic

s!.T

heeq

uilib

ratio

ntim

ew

as17

0da

ysw

ithst

eady

stat

ebe

ing

achi

eved

with

in10

7da

ys.

All

expe

rimen

tsw

ere

cond

ucte

dun

der

argo

nat

mos

pher

e.S

ampl

esof

the

satu

rate

dso

lutio

nsw

ere

filte

red

thro

ugh

4.1

nmC

entr

icon

filte

rs~A

mic

onC

orp.!

.T

hepH

was

mea

sure

dus

ing

aR

oss

com

bina

tion

glas

sel

ectr

ode

calib

rate

din

each

ofth

eK

1/C

l2or

Na1

/K1

/Cl2

solu

tion

toac

coun

tfo

rth

eliq

uid

junc

tion

pote

ntia

l.T

heN

p~V!

conc

entr

atio

nw

asm

easu

red

radi

omet

rical

lyby

mea

nsof

ahi

ghpu

rity

Ge

dete

ctor

usin

gth

e29

.4ke

Vg

line

of23

7 Np.

Insa

mpl

esco

ntai

ning

,10

26

mol

dm2

3N

p,th

eov

erla

pfr

omth

e28

.6ke

Vglin

eof

233 P

aw

asre

mov

edby

appl

ying

spec

tral

deco

nvol

utio

n.T

otal

inor

gani

cca

rbon

cont

ent

inth

esa

tura

ted

solu

tion

was

dete

rmin

edby

usin

gS

him

adzu

TO

C-5

050

carb

onan

alyz

er.

No

chan

ges

into

talc

arbo

nw

ere

obse

rved

.

Met

hod

ofpr

epar

atio

nof

KN

pO 2C

O3

was

notr

epor

ted.

Pur

ityof

the

Np~

V!

stoc

kso

lutio

n,in

clud

ing

oxid

atio

nst

ate

purit

y,w

asve

rified

asin

the

auth

ors’

prev

ious

wor

k.1

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

Sol

ubili

ty:

see

abov

e.

Ref

eren

ces:

1 C.

F.

Nov

ak,

I.A

lM

aham

id,

K.

A.

Bec

kraf

t,S

.A

.C

arpe

nter

,N

.H

akem

,an

dT

.P

russ

in,

J.S

olut

ion

Che

m.

26,

681

~199

7!.

2 C.

F.

Nov

ak,

H.

Nits

che,

H.

B.

Sib

ber,

K.

Rob

erts

,P

.C

.T

orre

tto,

T.

Pru

ssin

,K

.B

eckr

aft,

S.

A.

Car

pent

er,

D.

E.

Hob

art,

and

I.A

lMah

amid

,R

adio

chim

.A

cta74

,31

~199

6!.

3 R.

J.Le

mire

,G

.D

.B

oyer

,an

dA

.B

.C

ampb

ell,

Rad

ioch

im.

Act

a61

,57

~199

3!.

Co

~1!

K3

~2!

~3!

Va

T/

c 2 a T m ye ca b C Me

No


Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 Ph

ysic

o-C

he

mic

alT

ab

les~S

NT

L,P

ragu

e,19

53!,V

ol.1

,p.2

68.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ces

ium

tris~

carb

onat

o!di

oxon

eptu

nate~V

!;

5NpO

2~C

O3!

3;@

#C

esiu

mca

rbon

ate;

Cs

2CO

3;@5

34-1

7-8#

Wat

er;

H 2O

;@7

732-

18-5#

D.S

.Gor

benk

oan

dR

.A.Z

enko

va,Z

h.N

eorg

.Khi

m.

11,5

20–

8~1

966!

.

riabl

es:

Pre

pare

dby

:

K:

293

/mol

dm2

3 :0.

2;10

0w2

/mas

s%

:50

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Cs 5

NpO

2~C

O3!

3at

20°C

inw

ater

and

inC

s2C

O3

solu

tions

a

Cs 2

CO

3

02w

2/m

ass%

)C

s 2C

O3

(c2

/mol

dm2

3 )N

p~V

!~m

gdm

23 !

Np~

V!b

(104

mol

dm2

3 )

00

22.7

0.95

8

—0.

287

.53.

69

50—

492.

020

.8

hena

ture

ofth

eeq

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

alcu

late

dby

com

pile

rus

ing

A r~N

p!5

237.

0482

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.2

–7

mg

ofth

edr

ysa

ltw

asui

libra

ted

with

wat

eror

Cs 2C

O3

solu

tion

ofth

ede

sire

dnc

entr

atio

nfo

r1

wee

kw

ithoc

casi

onal

stirr

ing.

The

time

cess

ary

toat

tain

equi

libriu

mw

asno

tre

port

ed.

An

aliq

uot

ofsa

tura

ted

solu

tion

was

acid

ified

with

HN

O3,

and

the

ptun

ium

conc

entr

atio

nw

asde

term

ined

radi

omet

rical

ly.

Cs 5

NpO

2~C

O3!

3w

aspr

epar

edby

prec

ipita

ting

NpO 2O

Hfr

oma

solu

tion

ofN

p~V

!in

1m

oldm

23

HN

O3

byac

tion

ofN

H 3so

lutio

n,an

dby

subs

eque

ntst

irrin

gth

epr

ecip

itate

form

edw

ithex

cess

of50

%C

s 2CO

3so

lutio

n.T

hepa

legr

een

–bl

uepr

ecip

itate

was

kept

in50

%C

s 2CO

3fo

r1

–2

days

,filte

red,

and

was

hed

with

dilu

teso

lutio

nof

Cs 2C

O3

and

acet

one.

Ana

lysi

s~fo

und/

calc

ulat

edfo

ran

hydr

ous

salt,

inm

ass

%!:

Cs

58.5

3/59

.69,

Np

20.6

8/21

.27,

CO 3

14.2

9/16

.16.

Sou

rce

and

purit

yof

Cs

2CO

3w

asno

tsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.



6.4.

Sal

tsof

Dio

xoT

ris„ca

rbon

ato…

Nep

tuna

te„V…„-5…

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umtr

is~car

bona

to!di

oxon

eptu

nate~V

!;K

5NpO

2~C

O3!

3;@

#~2

!P

otas

sium

carb

onat

e;K

2CO

3;@5

84-0

8-7#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

D.S

.Gor

benk

oan

dR

.A.Z

enko

va,Z

h.N

eorg

.Khi

m.

11,5

20–

8~1

966!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

3c 2

/mol

dm2

3 :0

–5.

57J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

K5N

pO2~

CO

3!3

at20

°Cin

wat

eran

din

K 2CO

3so

lutio

nsa

K2C

O3

(102

w2

/mas

s%)

K2C

O3

(c2

/mol

dm2

3 )N

p~V

!~m

gdm

23 !

Np~

V!b

(105

c 1/m

oldm

23 )

00

10.3

4.35

—0.

223

.09.

70

505.

57b

38.0

16.0

a The

natu

reof

the

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.b C

alcu

late

dby

com

pile

rus

ing

A r~N

P!5

237.

0482

.c C

alcu

late

dby

com

pile

rus

ing

the

dens

ityof

1.54

04g

cm2

3fo

r50

mas

s%

K 2CO

3.1

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

2–

7m

gof

the

dry

salt

was

equi

libra

ted

with

wat

eror

K 2CO

3so

lutio

nof

the

desi

red

conc

entr

atio

nfo

r1

wee

kw

ithoc

casi

onal

stirr

ing.

The

time

nece

ssar

yto

atta

ineq

uilib

rium

was

not

repo

rted

.A

nal

iquo

tof

the

satu

rate

dso

lutio

nw

asac

idifi

edw

ithH

NO

3,an

dth

ene

ptun

ium

conc

entr

atio

nw

asde

term

ined

radi

omet

rical

ly.

K5N

pO2~

CO

3!3

was

prep

ared

bypr

ecip

itatin

gN

pO 2OH

from

aso

lutio

nof

Np~

V!

in1

mol

dm2

3H

NO

3by

actio

nof

NH 3

solu

tion,

and

bysu

bseq

uent

stirr

ing

the

prec

ipita

tefo

rmed

with

exce

ssof

50%

K 2CO

3so

lutio

n.T

hepa

legr

een

–bl

uepr

ecip

itate

was

kept

in50

%K 2C

O3

for

1–

2da

ys,

filte

red,

and

was

hed

with

dilu

teso

lutio

nof

K 2C

O3

and

acet

one.

Ana

lysi

s~fo

und/

calc

ulat

edfo

ran

hydr

ous

salt,

inm

ass

%!:

K28

.43/

30.2

8,N

p34

.95/

36.8

0,C

O 327

.38/

27.9

5.S

ourc

ean

dpu

rity

ofK

2CO

3w

asno

tsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Co

~1!

Cs

~2!

~3!

Va

T/

c 2 (1 a T b C Me

Iso

eq co ne the

ne

J

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

With

refe

renc

eto

the

auth

or’s

othe

rw

ork,

1th

eco

mpi

ler

assu

med

that

fres

hly

prec

ipita

ted

NH

4NpO

2CO

3•xH

2Ow

asst

irred

with

(NH 4

! 2C

O3

solu

tions

ofth

ede

sire

dco

ncen

trat

ion

for

6–

8h.

Nep

tuni

umin

the

satu

rate

dso

lutio

nsw

asde

term

ined

radi

omet

rical

ly~m

etho

dno

tsp

ecifi

ed!.

NH

4NpO

2CO

3•xH

2Ow

asob

tain

edby

prec

ipita

tion

byad

ding

ast

oich

iom

etric

amou

ntof

(NH 4!

2CO

3to

asl

ight

lyac

idic

~pH

4–

5!so

lutio

nof

NpO

21.

Sou

rce

and

purit

yof

chem

ical

sus

edw

ere

not

spec

ified

.E

stim

ated

Err

or:

Tem

pera

ture

:pr

ecis

ion6

1K

~aut

hor;

inR

ef.

1!.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.

I.M

oskv

in,

Rad

iokh

imiy

a13,

681

~197

1!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

mon

ium

tris~

carb

onat

o!di

oxon

eptu

nate~V

I!;

H4!

4NpO

2~C

O3!

3;@

#A

mm

oniu

mca

rbon

ate;

(NH 4!

2CO

3;@5

06-8

7-6#

Wat

er;

H 2O

;@7

732-

18-5#

A.

I.M

oskv

in,

Rad

iokh

imiy

a13,

674

–81

~197

1!.

riabl

es:

Pre

pare

dby

:

K:

293a

/mol

dm2

3 :0

–2.

20J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

(NH

4!4N

pO2~

CO

3!3

at20

°Cin

(NH 4

! 2C

O3

solu

tions

b

(NH

4!2C

O3c

(c2

/mol

dm2

3 )N

p~V

I!(1

02m

oldm

23 )

010

.6

0.10

6.54

0.50

2.26

0.75

1.60

1.00

1.27

1.25

0.88

6

1.50

0.83

1

1.80

0.66

5

2.20

0.45

1

empe

ratu

rew

asno

tsp

ecifi

edin

the

orig

inal

docu

men

t.W

ithre

fere

nce

toth

eau

thor

’sot

her

pape

r1

the

com

pile

ras

sum

edth

em

easu

re-

ents

wer

epe

rfor

med

at20

°C.

hena

ture

ofeq

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

hepH

ofth

esa

tura

ted

solu

tions

varie

dfr

om8.

5to

9.1

ongo

ing

from

0to

2.0

mol

dm2

3(N

H4!

2CO

3.

ditio

nali

nfor

mat

ion:

ede

crea

sing

solu

bilit

yof

(NH 4!

4NpO

2~C

O3!

3w

ithin

crea

sing

(NH 4

! 2C

O3

conc

entr

atio

nw

asex

plai

ned

byth

eau

thor

byth

edi

ssoc

ia-

nof

the

form

erto

the

solu

ble

NpO 2

~CO

3!222

com

plex

.F

rom

the

solu

bilit

yda

tath

eau

thor

obta

ined

the

equi

libriu

mco

nsta

nt,

K83

.3,

for

the

reac

tion

~NH

4!4N

pO2~

CO

3!3~

s!�

NpO

2~C

O3!

2221

CO

3221

4NH

41

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

With

refe

renc

eto

the

auth

or’s

othe

rw

ork,

1is

othe

rmal

met

hod

used

.F

resh

lypr

ecip

itate

d(N

H 4!4N

pO2~

CO

3!3

was

stirr

edw

ith(N

H4!

2CO

3so

lutio

nsof

the

desi

red

conc

entr

atio

nfo

r6

–8

h.N

eptu

nium

inth

esa

tura

ted

solu

tions

was

dete

rmin

edra

diom

etric

ally

~met

hod

not

spec

ified!

.

(NH

4!4N

pO2~

CO

3!3

was

prep

ared

eith

erby

prec

ipita

tion

byad

ding

solid

(NH 4

! 2C

O3

toa

solu

tion

obta

ined

bydi

ssol

ving

NpO

2~O

H! 2

inco

ncen

trat

edH

NO 3,

orby

prol

onge

deq

uilib

ratio

nof

NpO

2~O

H! 2

with

.0.

5m

oldm

23

(NH

4!2C

O3.

Sou

rce

and

purit

yof

chem

ical

sus

edw

ere

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

r,in

Ref

.1!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 A.

I.M

oskv

in,

Rad

iokh

imiy

a13,

681

~197

1!.

644644 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

carb

onat

odi

oxon

eptu

nate

~V!;

NH

4NpO

2CO

3;@

#~2

!A

mm

oniu

mca

rbon

ate;

(NH 4!

2CO

3;@5

06-8

7-6#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

A.

I.M

oskv

in,

Rad

iokh

imiy

a13,

674

–81

~197

1!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

3a

c 2/m

oldm

23 :

0–

2.20

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

NH

4NpO

2CO

3at

20°C

in(N

H 4! 2

CO

3so

lutio

nsb

(NH

4!2C

O3c

(c2

/mol

dm2

3 )N

p~V

!c

(105

mol

dm2

3 )

01.

0d

0.20

1.51

0.60

4.51

1.00

6.20

1.25

10.0

1.50

12.3

2.00

10.5

2.20

7.81

a Tem

pera

ture

was

not

spec

ified

inth

eor

igin

aldo

cum

ent.

With

refe

renc

eto

the

auth

or’s

othe

rpa

per

1th

eco

mpi

ler

assu

med

the

mea

sure

-m

ents

wer

epe

rfor

med

at20

°C.

b The

natu

reof

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.S

ince

the

star

ting

mat

eria

lw

ashy

drat

edN

H4N

pO2C

O3,

the

com

pile

ras

sum

edth

isw

asal

soth

eeq

uilib

rium

solid

phas

ein

solu

tions

cont

aini

ng0.

2–

1.5

mol

dm2

3(N

H4!

2CO

3.c T

hepH

ofth

esa

tura

ted

solu

tions

varie

dfr

om8.

8to

9.0

ongo

ing

from

0.2

to2.

2m

oldm

23

(NH

4!2C

O3.

d Ext

rapo

late

d~au

thor

!.

Add

ition

alin

form

atio

n:T

hein

crea

sein

the

solu

bilit

yof

NH 4N

pO2C

O3

with

incr

easi

ng(N

H 4! 2

CO

3co

ncen

trat

ion

was

ascr

ibed

byth

eau

thor

toth

efo

rmat

ion

ofth

eso

lubl

eN

pO2~

OH

!CO

322co

mpl

ex.I

tsov

eral

lsta

bilit

yco

nsta

ntw

asob

tain

edfr

omth

eso

lubi

lity

data

at0.

2–

1.5

mol

dm2

3(N

H4!

2CO

3

as(6

.761.

2)3

104

mol

2dm

26 .

To

expl

ain

decr

ease

ofN

H 4NpO

2CO

3so

lubi

lity

at2.

00an

d2.

20dm2

3(N

H4!

2CO

3,th

eau

thor

assu

med

the

form

atio

nof

asp

arin

gly

solu

ble

salt,

(NH

4!5N

pO2~

CO

3!3.

Aux

iliar

yIn

form

atio

n

Co

Am

(N ~2!

~3!

Va

T/

c 2 a T m b T c T Ad

Th

tio 5


wer

epr

ecip

itate

dfr

om0.

3,0.

5,an

d0.

1m

oldm23

carb

onat

eso

lutio

ns,

resp

ectiv

ely,

byad

ding

Co

~NH

3!6C

l 3to

give

a0.

04m

oldm

23

solu

tion.

The

irco

mpo

sitio

n,as

dedu

ced

from

chem

ical

anal

ysis

,w

as@C

o~N

H3!

6#2N

p~IV

!~C

O3!

5•4H

2O,

@Co~

NH

3!6#

@Np~

V!O

2~C

O3!

2#•1/

6 @C

o~N

H3!

6#2~

CO

3!3•

5H2O

,an

d$@

Co~

NH

3!6#

NO

3%2N

pO2~

CO

3!3,

resp

ectiv

ely.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 W.

Bilt

z,Z

.A

norg

.A

llgem

.C

hem

.83,

177

~191

4!.

6.6.

Nep

tuni

um„IV…

Oxa

late

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Nep

tuni

um~I

V!

bis~

oxal

ate!;

Np~

C2O

4!2;

@201

96-4

8-9#

Oxa

licac

id;

C 2H

2O4

;@1

44-6

2-7#

Wat

er;

H 2O

;@7

732-

18-5#

P.

I.K

ondr

atov

aan

dA

.D

.G

elm

an,

Rad

iokh

imiy

a2,31

5–

9~1

960!

.

riabl

es:

Pre

pare

dby

:

K:

298

oxal

ate

ion!/

mol

dm2

3 :7.

6310

210

–4.

0310

25

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofN

p~C2O

4!2

inox

alic

acid

solu

tionsa

C2O

422

oldm

23 !b

Np~

C2O

4!2

(104

c 1/m

oldm

23 )

C2O

422

~mol

dm2

3 !bN

p~C

2O4!

2

(104

c 1/m

oldm

23 )

.63

102

101.

188.

7310

27

0.91

.43

102

90.

721.

753

102

61.

5

.63

102

90.

513.

153

102

62.

2

.53

102

80.

292.

5310

25

15.7

753

102

70.

283.

2310

25

24

.53

102

70.

414.

0310

25

30

hena

ture

ofeq

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

xala

teio

nco

ncen

trat

ion

was

calc

ulat

edby

the

auth

ors

from

the

conc

entr

atio

nof

oxal

icac

id,

pHof

the

solu

tion,

and

the

diss

ocia

tion

onst

ants

ofox

alic

acid~

data

not

repo

rted!

.

ditio

nali

nfor

mat

ion:

omth

eso

lubi

lity

ofN

p~C2O

4!2

inox

alic

acid

solu

tions

,th

efo

llow

ing

Np~IV

!ox

alat

ocom

plex

esw

ere

iden

tified

inth

esa

tura

ted

lutio

ns,

and

thei

rov

eral

lin

stab

ility

cons

tant

sde

term

ined

:N

p~C

2O4!

21,

K15

(2.9

62

)310

29;

Np~

C2O

4!2,

K25

(2.9

60.

05)3

102

18;

~C2O

4!322

,K

35

(1.1

60.

1)3

102

24;

and

Np~

C2O

4!442

,K

45

43

102

28.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.F

resh

lypr

epar

edN

p~C

2O4!

2•6H

2Os

stirr

edw

ithox

alic

acid

solu

tions

ofth

ede

sire

dnc

entr

atio

nfo

r5

h.T

hem

ixtu

rew

asth

ence

ntrif

uged

,an

dpt

uniu

min

the

satu

rate

dso

lutio

nsw

asde

term

ined

ectr

opho

tom

etric

ally

at32

0nm

mak

ing

use

ofab

sorb

ancy

ofth

eN

p~IV

!–H

2O2

com

plex

inal

kalin

em

ediu

m.

No

deta

ilsre

port

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.



6.5.

Hex

amm

inec

obal

t„III…

Sal

tsof

Dio

xo„ca

rbon

ate…

Nep

tuna

tes

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1A

!B

is@h

exam

min

ecob

alt~III

!#pe

ntak

is~ca

rbon

ato!a

quan

eptu

nate~IV

!;@C

o~N

H3!

6#2N

p~C

O3!

5H2O

;@

#;~1

B!

Hex

amm

inec

obal

t~III

!bi

s~ca

rbon

ato!d

ioxo

nept

unat

e~V!;

Co~

NH

3!6N

pO2~

CO

3!2H

2O;

@#;

~1C

!B

is@h

exam

min

ecob

alt~III

!ni

trat

e#tr

is~c

arbo

nato!

diox

onep

tuna

te~VI!

;$@

Co~

NH

3!6#

NO

3%2N

pO2~

CO

3!3;

@#

~2!

Wat

er;

H 2O

;@7

732-

18-5#

A.

Sai

toan

dK

.U

eno,

J.In

org.

Nuc

l.C

hem

.39

,31

5–

8~1

977!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

3J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofbi

s@hex

amm

inec

obal

t~III

!#ca

rbon

ate

nept

unat

esin

wat

era

Com

poun

dN

p~m

gdm

23 !

Np

(106

mol

dm2

3 )b

1A0.

351.

48

1B2.

18.

85

1C6.

828

.7

a The

natu

reof

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.b C

alcu

late

dby

com

pile

rfo

rA r~

Np!

523

7.04

82.

Add

ition

alin

form

atio

n:S

olub

ility

ofth

eco

mpo

und

1Ain

(NH 4!

2CO

3so

lutio

ns,

and

of1B

and

1Cin

Na

2CO

3so

lutio

nsas

afu

nctio

nof

carb

onat

eio

nco

ncen

trat

ion

wer

eal

som

easu

red,

and

pres

ente

din

grap

hica

lfor

m.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

No

expl

icit

deta

ilsw

ere

repo

rted

for

the

dete

rmin

atio

nof

solu

bilit

ies

inw

ater

.Ju

dged

from

the

othe

rso

lubi

lity

mea

sure

men

tsre

port

edin

this

docu

men

t,th

eso

lids

wer

eal

low

edto

stan

dw

itha

smal

lvol

ume

ofw

ater

for

1–

2da

ys.

Afte

rce

ntrif

ugat

ion,

nept

uniu

mw

asde

term

ined

inth

esu

pern

atan

tby

aco

untin

gof

237 N

pus

ing

aga

sflo

wpr

opor

tiona

lcou

nter

.

Fro

ma

stoc

kso

lutio

nof

Np~V

!ob

tain

edfr

om23

7 Np

purifi

edby

ion

exch

ange

,N

p~VI!

was

prep

ared

bypr

olon

ged

heat

ing

with

conc

entr

ated

HN

O 3w

hile

Np~

IV!

was

prep

ared

byre

duct

ion,

first

toN

p~III

!by

zinc

amal

gam

,an

dsu

bseq

uent

conv

ertin

gN

p~III

!to

Np~

IV!

byae

ratio

n.T

heva

lenc

ies

ofne

ptun

ium

wer

ech

ecke

dby

mea

nsof

abso

rptio

nsp

ectr

a.C

o~N

H3!

6Cl 3

was

prep

ared

acco

rdin

gto

Ref

.1.

The

com

poun

ds1A

,1B

,an

d1C

Co

~1!

~2!

~3!

Va

T/

c( ~m

7 1 3 3 1. 3

a T b O c Ad

Fr

so Np

Me

Iso

wa

co ne sp

J

mea

sure

men

tsth

eco

mpi

ler

estim

ates

the

prec

isio

n6

10%

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Nep

tuni

um~I

V!

bis~

oxal

ate!;

Np~

C2O

4!2;

@201

96-4

8-9#

Oxa

licac

id;

C 2H

2O4;

@144

-62-

7#N

itric

acid

;H

NO

3;@7

697-

37-2#

Wat

er;

H 2O

;@7

732-

18-5#

D.

W.

Luer

kens

,U

SD

OE

Rep

ort

DP

-165

5,E

.I.

Du

Pon

tde

Nem

ours

and

Com

p.,

Sav

anna

hR

iver

Lab.

,A

iken

,S

C,

1983

.

riabl

es:

Pre

pare

dby

:

K:

295,

318

and

333

/mol

dm2

3 :0.

013

–0.

80/m

oldm

23 :

0.4

–10

.0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Np~

C2O

4!2

inox

alic

acid

/nitr

icac

idso

lutio

nsat

thre

ete

mpe

ratu

res

a,b

C2H

2O422

2/m

oldm

23 )d

HN

O3

(c3

/mol

dm2

3 )dN

p~IV

!~m

gdm

23 !

Np~

C2O

4!2

(105

c 1/

mol

dm2

3 )gC

2H2O

422

(c2

/mol

dm2

3 )eH

NO

3

(c3

/mol

dm2

3 )eN

p~IV

!~m

gdm

23 !

Np~

C2O

4!2

(104

c 1/

mol

dm2

3 )g

0.01

40.

46.

12.

570.

013

0.4

45.5

1.92

0.07

80.

48.

73.

670.

077

0.4

35.5

1.48

0.15

80.

412

.85.

400.

157

0.4

94.0

3.97

0.39

70.

429

.212

.30.

397

0.4

92.5

3.90

0.80

0.4

37.4

15.8

0.79

90.

429

5.0

12.4

0.62

30.

531

.613

.30.

623

0.5

133.

05.

61

0.37

00.

614

.05.

910.

242

0.7

34.5

1.46

0.24

30.

79.

94.

180.

640

0.8

73.5

3.10

0.64

00.

820

.88.

780.

046

1.0

22.5

0.94

9

0.04

71.

04.

01.

690.

096

1.0

25.5

1.08

0.09

71.

05.

92.

490.

497

1.0

83.5

3.52

0.49

81.

09.

43.

970.

016

2.0

38.5

1.62

0.01

72.

04.

41.

860.

036

2.0

26.0

1.10

0.03

72.

04.

61.

940.

397

2.0

44.0

1.86

0.08

44.

05.

52.

320.

023

5.0

162.

56.

86

0.15

84.

05.

12.

150.

122

5.0

74.5

3.14

0.12

35.

07.

73.

250.

036

6.0

362.

515

.3

0.03

46.

035

.615

.00.

242

7.0

101.

04.

26

0.24

27.

010

.64.

470.

063

10.0

330.

013

.9

0.06

210

.035

.915

.1

646646 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Nep

tuni

um~I

V!

bis~

oxal

ate!;

Np~

C2O

4!2;

@201

96-4

8-9#

~2!

Hyd

roge

nch

lorid

e;H

Cl;@

7647

-01-

0#~3

!W

ater

;H 2

O;

@773

2-18

-5#

P.

I.K

ondr

atov

aan

dA

.D

.G

elm

an,

Rad

iokh

imiy

a,2,31

5–

9~1

960!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:28

9an

d29

2c 2

/mol

dm2

3 :1.

56–

2.09

at28

9K

;0.

41–

1.08

at29

2K

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

16an

d19

°Cof

Np~C

2O4!

2in

hydr

ochl

oric

acid

solu

tionsa

Tem

pera

ture

~°C

!H

Cl

(c2

/mol

dm2

3 )N

p~C

2O4!

2

(105

c 1/m

oldm

23 )

Np~

C2O

4!2

(105

c 1/m

oldm

23 )b

161.

5619

.819

.219

.219

.460.

20

162.

0929

.728

.229

.060.

75

190.

414.

173.

283.

373.

713.

6360.

20

191.

0812

.714

.613

.760.

95

a The

natu

reof

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.b M

ean

valu

ean

dst

anda

rdde

viat

ion

ofth

em

ean

~com

pile

r!.

Add

ition

alin

form

atio

n:T

hein

crea

sing

solu

bilit

yof

Np~C

2O4!

2w

ithin

crea

sing

HC

lco

ncen

trat

ion

was

expl

aine

dby

the

auth

ors

byco

nsid

erin

gth

ere

actio

nN

p~C

2O4!

214H

1�

Np41

12C

2H2O

4.T

heeq

uilib

rium

cons

tant

ofth

isre

actio

nw

asob

tain

edas

(6.0

61.

3)3

102

12an

d(4

.860.

3)3

102

12at

19an

d16

°C,

resp

ectiv

ely,

and

did

not

depe

ndon

HC

lco

ncen

trat

ion.

Thi

sin

dica

ted

that

Np

41/C

l2co

mpl

exes

play

eda

negl

igib

lero

lein

this

syst

em.

Fro

mth

ese

cons

tant

san

ddi

ssoc

iatio

nco

nsta

nts

ofox

alic

acid

,th

eso

lubi

lity

prod

uct

ofN

p~C

2O4!

2w

asob

tain

edas

(8.66

1.8)

310

223

and

(6.96

0.4)

310

223

at19

and

16°C

,re

spec

tivel

y.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Fre

shly

prep

ared

Np

~C2O

4!2•

6H2O

was

stirr

edw

ithox

alic

acid

solu

tions

ofth

ede

sire

dco

ncen

trat

ion

for

5h.

The

mix

ture

was

then

cent

rifug

ed,

and

nept

uniu

min

the

satu

rate

dso

lutio

nsw

asde

term

ined

spec

trop

hoto

met

rical

lyat

320

nmm

akin

gus

eof

abso

rban

cyof

the

Np~

IV!–

H2O

2co

mpl

exin

alka

line

med

ium

.

No

deta

ilsre

port

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rsfo

rth

em

easu

rem

ents

inth

eN

p~C

2O4!

2–

C2H

2O4–

H2O

syst

emre

port

edin

this

sam

edo

cum

ent!.

Sol

ubili

ty:

base

don

stan

dard

devi

atio

nsof

indi

vidu

al

Co

~1!

~2!

~3!

~4!

Va

T/

c 2 c 3 (c


y- p- ly:

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

At

room

tem

pera

ture

~22

°C!,

exce

ssN

p~C

2O4!

2•6H

2Ow

aseq

uilib

rate

dw

ithC 2H

2O4

/HN

O3

solu

tions

ofth

ede

sire

dco

ncen

trat

ion.

Inm

easu

rem

ents

at45

and

60°C

,N

p~IV

!ox

alat

ew

aspr

ecip

itate

dfr

omC

2H2O

4/H

NO

3so

lutio

nsby

addi

tion

ofN

p~IV

!ni

trat

eso

lutio

n.In

both

met

hods

,th

eso

lutio

nsco

ntai

ned

N2H

4to

prot

ect

Np~I

V!

from

oxid

atio

ndu

eto

radi

olyt

icpr

oduc

tsof

HN

O3,

and

wer

eeq

uilib

rate

dfo

r24

h.T

hem

easu

rem

ents

atro

omte

mpe

ratu

rew

ere

not

ther

mos

tate

d.S

atur

ated

solu

tions

wer

efil

tere

dan

dsa

mpl

edus

ing

a0.

25mm

mic

ropo

refil

ter

ona

syrin

ge.

The

filte

red

sam

ples

wer

eim

med

iate

lydi

lute

din

stro

ngH

NO 3

topr

even

tpr

ecip

itatio

n,an

dN

pco

ncen

trat

ion

was

dete

rmin

edby

aco

untin

g.

Ast

ock

solu

tion

ofpu

rified

237 N

pw

aspr

epar

edby

ion

exch

ange

.1N

eptu

nium

~VI!

inth

eel

uate

was

redu

ced

first

toN

p~V

!by

heat

ing

the

elua

teto

55°C

inth

epr

esen

ceof

0.1

mol

dm2

3N

2H4.

The

solu

tion

ofN

p~V!

was

cool

edto

room

tem

pera

ture

and

redu

ced

toN

p~I

V!

with

0.03

mol

dm2

3ex

cess

asco

rbic

acid

.S

olid

Np~IV

!ox

alat

ew

asob

tain

edby

prec

ipita

tion

ofN

p~IV

!w

ithex

cess

ofox

alic

acid

.T

hepr

ecip

itate

was

filte

red

and

was

hed

with

dist

illed

wat

erto

rem

ove

exce

ssox

alat

ean

dni

trat

eio

ns.

Sou

rce

and

purit

yof

othe

rch

emic

als,

and

radi

oche

mic

alpu

rity

of237 N

pus

edw

ere

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 G.

A.

Bur

ney,

US

AE

C,

Rep

ort

DP

-689

,19

62.

6.7.

Nep

tuni

um„V

I…D

ioxo

„ox

alat

e…

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Nep

tuni

um~V

I!di

oxoo

xala

te;

NpO

2C2O

4;

@#

Oxa

licac

id;

C 2H

2O4

;@1

44-6

2-7#

Nitr

icac

id;

HN

O3

;@7

697-

37-2#

Wat

er;

H 2O

;@7

732-

18-5#

M.P

.Mef

odev

a,N

.N.K

rot,

T.V

.Sm

irnov

a,an

dA

.D.G

elm

an,

Rad

iokh

imiy

a11,

193

–20

0~19

69!.

riabl

es:

Pre

pare

dby

:

K:

287

/mol

dm2

3 :0

–0.

15/m

oldm

23 :

1.0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

14°C

ofN

pO2C

2O4

inox

alic

acid

solu

tions

cont

aini

ng1.

0m

oldm2

3 HN

O3a

C2H

2O4b

~mol

dm2

3 !C

2H2O

4c

(c2

/mol

dm2

3 !N

pO2C

2O4

(103

c 1/m

oldm

23 !

00.

0017

15.7

d0.

0032

12.8

0.00

630

0.00

828.

9

0.01

250.

0137

7.15

0.02

500.

0262

6.25

0.03

790.

0390

5.85

0.05

000.

0512

4.75

0.10

0.10

14.

05

0.10

0.10

23.

65

0.15

0.15

13.

25

heeq

uilib

rium

solid

phas

ew

asN

pO 2C2O

4•3H

2O,

@#,

inal

lsol

utio

ns.

itial

conc

entr

atio

n.iti

alco

ncen

trat

ion

corr

ecte

dfo

rth

ein

crea

sedu

eto

the

reac

tion

2N

pO2C

2O41

2H1�

2N

pO

211

C2H

2O41

2CO

2.he

conc

entr

atio

nre

port

edas

1.0

mol

dm23

isob

viou

sly

am

ispr

int.

ditio

nali

nfor

mat

ion:

rom

the

solu

bilit

yda

ta,

the

auth

ors

calc

ulat

edth

eso

lubi

lity

prod

uct

ofN

pO2C

2O4

as2.

3310

29

mol

2dm

26 .

heso

lubi

lity

ofN

pO2C

2O4

was

repo

rted

toin

crea

sew

ithin

crea

sing

tem

pera

ture

~dat

are

port

edin

grap

hica

lfor

m!.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

offr

eshl

ypr

ecip

itate

dN

pO2C

2O4•

3H2O

was

equi

libra

ted

with

solu

tions

ofth

ede

sire

dco

ncen

trat

ion

ina

ther

mos

tate

dba

thfo

r20

min

.T

hen

aliq

uots

wer

ew

ithdr

awn

usin

ga

pipe

ttew

itha

filtr

atio

nad

apto

r,an

dth

eco

nten

tof

nept

uniu

min

the

satu

rate

dso

lutio

nsw

asde

term

ined

spec

trop

hoto

met

rical

ly.

The

abso

rptio

nba

ndof

Np~V

!at

981

nmw

asus

edw

hich

mad

eit

poss

ible

tode

term

ine

Np~V

!an

dN

p~V

I!si

mul

tane

ousl

y,an

dth

usco

rrec

tth

eto

talN

pco

ncen

trat

ion

inth

eso

lutio

nfo

rN

p~V

!fo

rmed

durin

geq

uilib

ratio

n.T

heso

lubi

lity

ofN

pO2C

2O4

was

calc

ulat

edfr

omth

eN

p~VI!

conc

entr

atio

n.

NpO

2C2O

4•3H

2Ow

aspr

epar

edby

prec

ipita

ting

Np

~VI!

with

oxal

icac

idfr

oma

solu

tion

cont

aini

ng20

–40

gdm2

3N

p,2

–3

mol

dm2

3 HN

O3,

and

0.05

mol

dm2

3 KB

rO3.

The

prec

ipita

tew

asw

ashe

dw

ith0.

2m

oldm2

3 HN

O3,

etha

nol

and

ethe

r,an

dai

rdr

ied

for

30m

in.

Est

imat

edE

rror

:T

empe

ratu

re:

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.



C2H

2O422

(c2

/mol

dm2

3 )fH

NO

3

(c3

/mol

dm2

3 )fN

p~C

2O4!

2

~mg

dm2

3 !

Np~

C2O

4!2

(105

c 1/

mol

dm2

3 )C

2H2O

422

(c2

/mol

dm2

3 )fH

NO

3

(c3

/mol

dm2

3 )fN

p~C

2O4!

2

~mg

dm2

3 !

Np~

C2O

4!2

(104

c 1/

mol

dm2

3 )

0.01

30.

474

.93.

160.

017

2.0

76.2

3.22

0.07

70.

460

.22.

540.

036

2.0

54.8

2.31

0.15

70.

474

.53.

140.

196

2.0

36.4

1.54

0.39

00.

417

2.4

7.27

0.39

62.

032

.41.

37

0.78

90.

426

3.7

11.1

0.45

63.

036

.71.

55

0.62

20.

511

8.9

5.02

0.01

64.

037

8.1

16.0

0.36

70.

610

6.6

4.50

0.08

34.

010

4.6

4.41

0.24

10.

761

.92.

610.

156

4.0

53.8

2.27

0.64

00.

884

.93.

580.

123

5.0

198.

28.

36

0.04

61.

068

.32.

880.

036

6.0

420.

117

.7

0.09

71.

049

.62.

090.

242

7.0

104.

64.

41

0.49

71.

084

.43.

560.

063

10.0

369.

815

.6

a The

natu

reof

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.In

inte

rpre

tatio

nof

the

resu

lts,

the

auth

oras

sum

edth

isto

beth

ehe

xah

drat

e,N

p~C2O

4!2•

6H2O

,@

#.b A

llso

lutio

nsco

ntai

ned

anun

spec

ified

conc

entr

atio

nof

hydr

azin

eus

edto

stab

ilize

Np

~IV

!va

lenc

yst

ate,

and

prev

ent

itfr

omox

idat

ion

bypr

oduc

tsof

HN

O 3ra

diol

ysis

.c In

itial

~tot

al!

conc

entr

atio

n.d R

oom

tem

pera

ture~

22°C

!.e M

easu

rem

ents

perf

orm

edat

45°C

.f M

easu

rem

ents

perf

orm

edat

60°C

.g C

alcu

late

dby

com

pile

rus

ing

A r~N

p!5

237.

0482

.

Add

ition

alin

form

atio

n:V

aria

tions

inN

p~C2O

4!2

solu

bilit

yw

ithth

eco

ncen

trat

ions

ofox

alic

and

nitr

icac

ids

wer

eas

crib

edby

the

auth

orto

the

varia

tions

offr

eeox

alat

eio

nco

ncen

trat

ion,

whi

chco

ntro

lsth

eeq

uilib

riabe

twee

nN

p~I

V!

oxal

ate

com

plex

esin

solu

tions

.M

inim

umso

lubi

lity

corr

espo

nds

toth

eco

nditi

ons

whe

reth

efo

rmat

ion

ofth

ehi

ghly

inso

lubl

eN

p~C

2O4!

2pr

edom

inat

es.

Incr

ease

dso

lubi

lity

corr

espo

nds

toth

efo

rmat

ion

ofN

p~C

2O4!

21or

Np~

C2O

4!322

com

plex

esas

the

free

oxal

ate

conc

entr

atio

nde

crea

ses

orin

crea

ses,

resp

ectiv

ely.

Bas

edon

thes

eas

sum

tions

,th

eso

lubi

lity

ofN

p~C2O

4!2

was

expr

esse

das

@Np~

IV! #

tot5

@Np~

C2O

4!21

#1@N

p~C

2O4!

2#1

@Np~

C2O

4!322

#5K

11

K1K

2/R

s1K

1K

3R

s,

whe

reK

15

@Np~

C2O

4!2#

~equ

ilibr

ium

cons

tant

for

the

reac

tion

Np

~C2O

4!2•

6H2O

~s!

Np~

C2O

4!2~

aq!)

,K

25

@Np~

C2O

4!21

#@C

2H2O

4#

3@N

p~C

2O4!

2#2

1@H

1#2

2,

K35

@Np~

C2O

4!322

#@H

1#2

@Np~

C2O

4!2#

21@C

2H2O

4#2

1,

and

Rs5

@C2H

2O4#

@H1

#225

@C2H

2O4#

@HN

O3#

22.

By

leas

tsq

uare

str

eatm

ent

ofex

perim

enta

lda

ta,

the

auth

orob

tain

edth

efo

llow

ing

cons

tant

s,al

way

sat

22,

45,

and

60°C

,re

spec

tive

K15

4.26

0.7,

14.36

6.5,

41.96

5.3;

K1K

25

0.03

060.

002,

0.34

60.

02,0

.356

0.02

;K1K

35

8.26

0.7,

60.16

5.4,

43.96

4.9.

Aux

iliar

yIn

form

atio

n

Co

~1!

~2!

~3!

~4!

Va

T/

c 2 c 3 a T b In c In d T Ad

a F b T

J

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Por

tions

ofP

uO 2CO

3w

ere

adde

dto

LiH

CO

3so

lutio

nsof

the

desi

red

conc

entr

atio

n.T

hem

ixtu

res

wer

eeq

uilib

rate

dw

ithoc

casi

onal

agita

tion

for

16h,

intw

om

easu

rem

ents

equi

libra

tion

time

of10

days

was

used

.A

fter

cent

rifug

atio

nan

aliq

uot

ofth

eda

rkre

dsa

tura

ted

solu

tion

was

drie

don

ast

ainl

ess

stee

lslid

ean

da

coun

ted

tode

term

ine

the

plut

oniu

mco

nten

t.T

heco

ncen

trat

ion

ofLi

HC

O3

inth

ein

itial

solu

tions

was

dete

rmin

edby

titra

tion

with

ast

anda

rdH

Cl

solu

tion.

PuO

2CO

3w

aspr

epar

edfr

omLi

plut

onat

e.T

hela

tter

was

obta

ined

from

aP

u~VI!

solu

tion

bypr

ecip

itatio

nw

ithso

lidLi

OH

.T

hepr

ecip

itate

was

was

hed

seve

ral

times

with

dilu

teLi

OH

,sl

urre

din

wat

er,

and

CO 2

gas

was

bubb

led

thro

ugh

the

slur

ryun

tilth

eda

rkbr

own

prec

ipita

tech

ange

dto

yello

wP

uO2C

O3.

Sou

rce

and

purit

yof

mat

eria

lsus

edw

ere

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

7.1.

1.E

valu

atio

nof

the

PuO

2CO

3¿C

O2¿

NaC

lO4¿

H2O

Sys

tem

mpo

nent

s:E

valu

ator

:

Plu

toni

um~V

I!di

oxo

carb

onat

e;P

uO 2C

O3

;@3

9292

-10-

9#C

arbo

ndi

oxid

e;C

O 2;

@124

-38-

9#S

odiu

mpe

rchl

orat

e;N

aClO 4

;@7

601-

89-0#

Wat

er;

H 2O

;@7

732-

18-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,

June

2000

Crit

ical

Eva

luat

ion:

The

mos

text

ensi

vest

udie

son

the

solu

bilit

yof

PuO

2CO

3in

NaC

lO4

solu

tions

asa

func

tion

ofeq

uilib

rium

carb

onat

eio

nco

ncen

trat

ion

sbe

enca

rrie

dou

tby

Pas

halid

iseta

l.1,2

The

data

wer

eob

tain

edat

295.

1K

inm

easu

rem

ents

cond

ucte

das

pHtit

ratio

nsin

mol

dm2

3 NaC

lO4

solu

tions

with

care

ful

cont

rol

ofex

perim

enta

lpa

ram

eter

ssu

chas

pH,

part

ial

pres

sure

ofC

O2,

atta

inin

geq

uilib

-m

,an

dch

arac

teriz

atio

nof

solid

phas

esdu

ring

solu

bilit

ym

easu

rem

ents

.B

oth

sets

ofm

easu

rem

ents

1,2

yiel

ded

solu

bilit

yda

taw

ithce

llent

repr

oduc

ibili

ty~s

eeth

eco

rres

pond

ing

com

pila

tion

shee

ts!.

InR

ef.

1,so

lubi

lity

prod

uct

ofP

uO 2C

O3

was

repo

rted

tobe

Ksp

102

(13.

986

0.12

)m

ol2

dm2

6in

0.1

mol

dm2

3N

aClO

4,an

dK

sp05

102

(14.

846

0.10

)m

ol2

dm2

6at

zero

ioni

cst

reng

th.

Sol

ubili

typr

oduc

t

p510

2(1

3.56

0.3)

mol

2dm

26

has

been

repo

rted

for

3.0

mol

dm23 N

aClO

4so

lutio

ns.B

ased

onth

ese

valu

esob

tain

edus

ing

high

prec

isio

npe

rimen

tal

tech

niqu

e,it

issu

gges

ted

that

the

valu

eK

sp5

102

12.8

mol

2dm

26 ,

obta

ined

byca

lcul

atio

nin

Ref

.4

from

the

solu

bilit

yof

H4!

2Pu 2

O7

in(N

H4!

2CO

3so

lutio

ns,

bedi

sreg

arde

das

erro

neou

sly

high

.A

sfo

rth

ede

pend

ence

ofth

eso

lubi

lity

ofP

uO 2CO

3on

equi

libriu

mca

rbon

ate

ion

conc

entr

atio

nth

esi

tuat

ion

rese

mbl

esth

atfo

r

2CO

3~s

eeC

ritic

alE

valu

atio

n!.T

heso

lubi

lity

vers

us@C

O32

2#

plot

pass

esth

roug

ha

min

imum

whe

reth

eso

lubi

lity

ofP

uO2C

O3

iste

rmin

edby

Ksp

only

,w

hile

the

incr

ease

inth

eso

lubi

lity

athi

gher @C

O32

2#

valu

esis

caus

edby

the

form

atio

nof

anio

nic

carb

onat

o-m

plex

esof

Pu~V

I!in

the

satu

rate

dso

lutio

ns.

InR

ef.

2,m

inim

umso

lubi

lity

ofap

prox

imat

ely

53

102

6m

oldm

23

was

obse

rved

inth

eO

322

#ra

nge

from

102

8to

102

6m

oldm

23 .

Thi

sis

inge

nera

lag

reem

ent

with

the

wor

kof

Rob

ouch

and

Vito

rge

3w

hoob

serv

edni

mum

solu

bilit

yof

abou

t102

5m

oldm

23

over

appr

oxim

atel

yth

esa

me @C

O32

2#

rang

eat

ioni

cst

reng

thof

3.0

mol

dm23

NaC

lO4.

fere

nces

:

Pas

halid

is,

W.

Run

de,

and

J.I.

Kim

,R

adio

chim

.A

cta

61,

141

~199

3!.

Pas

halid

is,

K.

R.

Cze

rwin

ski,

F.

Fan

gha

¨ nel

,an

dJ.

I.K

im,

Rad

ioch

im.

Act

a76,

55~1

997!

.

.R

obou

chan

dP

.V

itorg

e,In

org.

Chi

m.

Act

a140,

239

~198

7!.

.D

.G

elm

an,

A.

I.M

oskv

in,

and

V.

P.

Zai

tsev

a,R

adio

khim

iya

4,15

4~1

962!

.

648648 JIRI HALA

7.T

heS

olub

ility

ofP

luto

nium

Com

poun

ds

7.1.

Plu

toni

um„V

I…D

ioxo

carb

onat

e

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Plu

toni

um~V

I!di

oxoc

arbo

nate

;P

uO 2C

O3

;@3

9292

-10-

9#~2

!Li

thiu

mhy

drog

enca

rbon

ate;

LiH

CO 3;

@500

6-97

-3#~3

!W

ater

;H 2

O;

@773

2-18

-5#

L.J.

Witt

enbe

rgan

dR

.H.S

tein

mey

er,J

.Ino

rg.N

ucl.

Che

m.

24,

1015

–6~

1962

!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

7c 2

/mol

dm2

3 :0

–0.

94J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

24°C

ofP

uO2C

O3

inLi

HC

O3

solu

tions

a

LiH

CO

3

(c2

/mol

dm2

3 !P

u~V

I!~g

dm2

3 !P

uO2C

O3

(103

c 1/m

oldm

23 !

b

00.

043

0.18

0

0.05

1.12

4.69

0.05

c,d

1.37

5.73

0.10

3.01

12.6

0.24

10.2

42.7

0.25

11.4

47.7

0.50

14.6

61.0

0.75

c22

.393

.3

0.94

24.2

101.

2

a The

equi

libriu

mso

lidph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler

usin

gA

rr~

Pu!

523

9.05

3.c E

quili

brat

ion

time

10da

ys.

d Thi

sm

easu

rem

ents

eem

sto

indi

cate

that

16h

equi

libra

tion

may

notb

esu

ffici

entt

ogi

veth

etr

ueeq

uilib

rium

solu

bilit

yva

lues

~com

pile

r!.

Add

ition

alin

form

atio

n:T

hedi

ssol

utio

nre

actio

nw

aspo

stul

ated

byth

eau

thor

sas

PuO

2CO

3~s!

1xL

iHC

O3~

aq!�

LixP

uO2~

CO

3!~H

CO

3) x

~aq !

Aux

iliar

yIn

form

atio

n

Co

~1!

~2!

~3!

~4!

ha 0.1

riu ex 5 Ks

ex (N UO

de co @C mi

Re

1 I. 2 I. 3 P 4 A


FIG

.20

.P

luto

nium

~VI!

diox

ocar

bona

te–

sodi

umhy

drog

enca

rbon

ate

–so

dium

perc

hlor

ate

–ca

rbon

diox

ide

–w

ater

syst

em.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

pHtit

ratio

nw

asus

ed.

Fre

shly

prec

ipita

ted

O 2C

O3

was

diss

olve

din

a0.

1m

oldm2

3N

aHC

O 32.

9m

oldm

23

NaC

lO4

solu

tion.

The

gree

nso

lutio

nob

tain

ed0

mL!

was

intr

oduc

edin

toa

cell

thro

ugh

whi

cha

CO

2/A

rxt

ure,

pre-

equi

libra

ted

in3.

0m

oldm2

3N

aClO

4,w

asbb

led

atth

ede

sire

dC

O 2pr

essu

re.

Und

erco

nsta

ntag

itatio

n,w

asm

easu

red.

Whe

nat

agi

ven

pHth

eso

lubi

lity

was

nsta

nt,

3m

oldm

23

HC

lO4

or1

mol

dm2

3N

aHC

O 3w

asde

dto

vary

free

carb

onat

eio

nco

ncen

trat

ion.

At

each

nsta

ntpH

valu

e,th

eP

u~V

I!co

ncen

trat

ion

was

dete

rmin

edac

idify

ing

the

sam

ple

with

HC

lO 4,

and

mea

surin

gth

elig

htso

rptio

nof

PuO

221

spec

trop

hoto

met

rical

lyat

830.

4nm

.T

henc

entr

atio

nof

H1io

nsw

asm

easu

red

pote

ntio

met

rical

lyby

ing

aco

mbi

natio

ngl

ass

elec

trod

ew

itha

Ag/

AgC

lref

eren

celf

cell.

The

orig

inal

refe

renc

eso

lutio

nw

asre

plac

edw

itha

1m

oldm

23

NaC

l12.

99m

oldm

23

NaC

lO4

solu

tion.

The

ctro

dew

asca

libra

ted

agai

nst

ase

ries

ofbu

ffer

solu

tions

.e

equi

libriu

mso

lidph

ase

was

char

acte

rized

byx-

ray

frac

tion

seve

ralt

imes

durin

gth

eex

perim

ent.

The

pHat

ion

ofa

give

nso

lidw

ere

run

not

long

erth

an2

wee

ksin

der

toav

oid

radi

olyt

ictr

ansf

orm

atio

nof

the

solid

into

drol

yzed

prod

ucts

.

The

Pu~V

I!pe

rchl

orat

eso

lutio

nw

aspr

epar

edfr

oman

acid

stoc

kso

lutio

nby

evap

orat

ion

ofH

ClO 4

until

mos

tof

the

exce

ssac

idha

dbe

enre

mov

ed.

The

conc

entr

ated

solu

tion

was

diss

olve

din

0.1

mol

dm2

3H

ClO

4an

dP

uO2C

O3

was

prec

ipita

ted

byad

ditio

nof

NaH

CO 3

.F

orea

chpH

titra

tion,

PuO 2

CO

3w

aspr

epar

edfr

omfr

esh

perc

hlor

ate

solu

tion

toav

oid

redu

ctio

nof

Pu

~VI!

byra

diol

ysis

.

Est

imat

edE

rror

:T

empe

ratu

re:6

1K

~aut

hors!

.S

olub

ility

:pr

ecis

ion

not

repo

rted

.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Plu

toni

um~V

I!di

oxoc

arbo

nate

;P

uO 2C

O3

;@3

9292

-10-

9#~2

!C

arbo

ndi

oxid

e;C

O 2;

@124

-38-

9#~3

!S

odiu

mhy

drog

enca

rbon

ate;

NaH

CO

3;

@144

-55-

8#~4

!S

odiu

mpe

rchl

orat

e;N

aClO 4

;@7

601-

89-0#

~5!

Wat

er;

H 2O

;@7

732-

18-5#

P.

Rob

ouch

and

P.

Vito

rge,

Inor

g.C

him

.A

cta14

0,23

9–

42~1

987!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

3p

2/~

part

ialp

ress

ure

ofC

O 2!/k

Pa:

9.81

,29

.4,

and

98.1

c 4/m

oldm

23 :3

.0

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofP

uO2C

O3

at20

°Cas

afu

nctio

nof

equi

libriu

mC

O 322

ion

conc

entr

atio

nat

thre

edi

ffere

ntpa

rtia

lpre

ssur

esof

CO

2an

dat

ioni

cst

reng

thof

3.0

mol

dm23

The

solu

bilit

yof

PuO

2CO

3in

NaH

CO 3

solu

tions

with

ioni

cst

reng

thof

3.0

mol

dm23

mai

ntai

ned

byus

ing

NaC

lO 4w

asm

easu

red

atth

ree

diffe

rent

part

ial

pres

sure

sof

CO

2of

0.1,

0.3

and

1.0

atm

at20

°C.

The

equi

libriu

mso

lidph

ase

was

iden

tified

asP

uO2C

O3,

@392

92-1

0-9#.

The

resu

ltsw

ere

repo

rted

ingr

aphi

calf

orm

only

~see

Fig

.20

!.

Add

ition

alin

form

atio

n:F

ree

carb

onat

eio

nco

ncen

trat

ion

was

calc

ulat

edby

the

auth

ors

from

the

valu

esof

@H1

#,pa

rtia

lpr

essu

reof

CO 2,

and

diss

ocia

tion

cons

tant

sof

carb

onic

acid

.S

ince

ata

cons

tant

free

carb

onat

eio

nco

ncen

trat

ion

the

solu

bilit

yof

PuO

2CO

3di

dno

tde

pend

onth

ehy

drog

enca

rbon

ate

ion

conc

entr

atio

n,pH

,or

pres

sure

ofC

O2,

the

auth

ors

conc

lude

dth

atth

edi

ssol

utio

nis

cont

rolle

dby

the

reac

tion

PuO

2CO

3~s!

1~n

21

!CO

322�

PuO

2~C

O3) n2

22

n~n

51,

2,3 !

Fro

mth

eso

lubi

lity

data

,th

eau

thor

sob

tain

edth

eov

eral

lst

abili

tyco

nsta

nts

ofth

eP

uO2~

CO

3) n2

22

aco

mpl

exes

asb

15

108.

660.

3 ,b

2

510

13.6

60.

7 ,an

db

35

1018

.26

0.4 ,

and

the

solu

bilit

ypr

oduc

tof

PuO 2

CO

3as

Ksp

510

2(1

3.56

0.3)

,al

lat

3.0

mol

dm2

3io

nic

stre

ngth

.

Me

Iso

Pu

1 ~5 mi

bu pH co ad co by ab co us ha 0.0

ele

Th

dif

titr

or hy

J

e

diss

ocia

tion

cons

tant

sof

carb

onic

acid

.c M

easu

rem

ents

atpa

rtia

lpre

ssur

eof

CO

2of

1%.

d Mea

sure

men

tsat

part

ialp

ress

ure

ofC

O2

of10

0%.

e Ksp

5@P

uO221

#@C

O322

#;th

eav

erag

eva

lue

from

mea

sure

men

tsat

1%an

d10

0%pa

rtia

lpr

essu

reof

CO

2w

asre

port

edby

the

auth

ors

as10

2(1

3.98

60.

12)

mol

2dm

26 .

Thi

sw

asre

calc

ulat

edby

the

auth

ors

toze

roio

nic

stre

ngth

byus

ing

the

spec

ific

ion

inte

ract

ion

theo

rypr

oced

ure,

toob

tainK

spo5

102

(14.

846

0.10

)m

ol2

dm2

6 .

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

pHtit

ratio

nw

asus

ed.

Apo

rtio

nof

the

PuO 221

ckso

lutio

nw

asdi

lute

dw

ith0.

1m

oldm2

3N

aClO

4,ut

raliz

edto

pH7

with

NaO

H,

and

CO 2ga

sw

asbu

bble

dou

ghth

eso

lutio

n.A

whi

tepr

ecip

itate

ofP

uO 2CO

3w

asm

ed.

The

prec

ipita

tion

proc

edur

ean

dsu

bseq

uent

solu

bilit

yas

urem

ents

wer

epe

rfor

med

ina

clos

edgl

ass

vess

elw

iths

pass

ing

thro

ugh

unde

rpa

rtia

lpre

ssur

eof

CO

2of

1%O

2/A

rm

ixtu

re!

or10

0%.

The

pHof

the

solu

tion

inco

ntac

tth

PuO

2CO

3w

asad

just

edst

epw

ise

byad

ditio

nof

0.1

mol

23

HC

lO4

orN

aOH

.T

hega

sw

asbu

bble

dth

roug

hth

ess

elco

ntin

uous

ly.

The

pHw

asm

easu

red

with

aR

OS

S-t

ype

mbi

natio

nel

ectr

ode

cont

aini

ng3

mol

dm23

NaC

lO4

asa

ing

solu

tion.

The

elec

trod

ew

asca

libra

ted

agai

nst

six

fere

ntbu

ffer

solu

tions

.T

hetim

eof

equi

libra

tion

afte

rea

chju

stm

ent

ofpH

was

not

repo

rted

.T

heeq

uilib

rium

plut

oniu

mnc

entr

atio

nin

the

satu

rate

dso

lutio

nw

asde

term

ined

byui

dsc

intil

latio

nco

untin

gto

obta

inth

eto

talp

luto

nium

ncen

trat

ion,

and

byU

Vsp

ectr

osco

pyto

obta

inth

eP

uO221

ncen

trat

ion.

The

solid

phas

esw

ere

char

acte

rized

byx-

ray

wde

rdi

ffrac

tion,

IR,

and

UV

spec

tros

copy

.

242 P

uof

99.9

%is

otop

icpu

rity

was

used

.T

heP

uO 221st

ock

solu

tion

was

prep

ared

byfu

min

gw

ithco

ncen

trat

edH

ClO

4in

apl

atin

umcr

ucib

le,

and

subs

eque

nttr

eatm

ent

with

ozon

ean

dA

rga

s.T

heva

lenc

yst

ate

ofP

uin

the

stoc

kso

lutio

nw

asve

rified

byco

mpa

ring

Pu

conc

entr

atio

nsas

dete

rmin

edby

spec

trop

hoto

met

ryan

dliq

uid

scin

tilla

tion

coun

ting.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

Sol

ubili

ty:

prec

isio

nno

tre

port

ed.

650650 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Plu

toni

um~V

I!di

oxoc

arbo

nate

;P

uO 2C

O3;

@392

92-1

0-9#

~2!

Car

bon

diox

ide;

CO 2;

@124

-38-

9#~3

!S

odiu

mpe

rchl

orat

e;N

aClO 4;

@760

1-89

-0#~4

!W

ater

;H 2

O;

@773

2-18

-5#

I.P

asha

lidis

,W

.R

unde

,an

dJ.

I.K

im,

Rad

ioch

im.

Act

a61

,14

1–

6~1

993!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

5p

2(p

artia

lpr

essu

re)/

%51

and

100

c 3/m

oldm

23 5

0.1

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

PuO

2CO

3in

0.1

mol

dm2

3so

lutio

nof

NaC

lO4

at22

°C,

and

1%or

100%

part

ialp

ress

ure

ofC

O2a

pH2

log @

CO

322#b

2lo

g @P

uO221

#c2

log

Ksp

epH

2lo

g @C

O322

#b2

log @

PuO

221#d

2lo

gK

spe

4.23

11.1

72.

9414

.11

3.51

10.6

03.

4014

.00

4.24

11.1

42.

8113

.95

3.70

10.2

23.

7713

.99

4.28

11.0

62.

9413

.99

3.84

9.94

3.91

13.8

5

4.31

10.9

93.

067

14.0

63.

859.

924.

0313

.95

4.33

10.9

63.

067

14.0

23.

899.

844.

0313

.87

4.35

10.9

32.

8113

.74

4.01

9.60

4.54

14.1

4

4.51

10.6

03.

2513

.85

4.30

9.02

5.18

14.2

0

4.53

10.5

63.

2513

.81

4.65

10.3

23.

8614

.18

4.75

10.1

23.

8814

.00

5.22

9.19

4.73

13.9

2

5.55

8.52

5.64

14.1

6

5.58

8.47

5.47

13.9

4

5.60

8.43

5.47

13.8

9

5.60

8.41

5.64

14.0

5

5.62

8.39

5.47

13.8

5

a Equ

ilibr

ium

solid

phas

ew

asP

uO 2C

O3,

@392

92-1

0-9#,

inal

lso

lutio

ns.

The

solid

was

mos

tst

able

unde

rva

cuum

.It

chan

ged

with

in2

wee

ksin

HC

O 32so

lutio

n,an

dw

asno

tsta

ble

atal

lwhe

nin

cont

actw

ithai

r.M

easu

rem

ents

wer

eal

sope

rfor

med

at0.

03%

part

ialp

ress

urof

CO

2.A

tth

ispr

essu

resl

ight

tran

sfor

mat

ion

ofP

uO 2CO

3in

toP

uO2~

OH

! 2in

the

surf

ace

laye

rof

PuO 2

CO

3cr

ysta

lsto

okpl

ace,

asde

duce

dby

the

auth

ors

from

the

depe

nden

ceof

log

@PuO

221

#ve

rsus

pHpl

ots

obta

ined

atdi

ffere

ntpa

rtia

lpre

ssur

esof

CO

2.b C

once

ntra

tion

offr

eeca

rbon

ate

ion~m

oldm

23 !.

Itw

asca

lcul

ated

from

the

mea

sure

dpH

,pa

rtia

lpre

ssur

eof

CO

2,H

enry

cons

tant

,an

d

Me

Iso

sto

ne thr

for

me

ga ~C wi

dm ve co fill

dif

ad co liq co co po


3.69

10.1

83.

774.

578.

425.

09

3.70

10.1

63.

775.

167.

245.

11

3.81

9.94

3.97

5.18

7.20

5.27

3.83

9.90

3.91

5.73

6.10

5.27

3.84

9.88

4.03

5.94

5.68

5.07

3.85

9.86

3.91

6.04

5.48

4.77

3.88

9.80

4.03

a At

part

ialp

ress

ure

ofC

O 2of

1%an

d10

0%,

the

solid

phas

ew

asP

uO2C

O3,

@392

92-1

0-9#,

inal

lsol

utio

ns.

b Equ

ilibr

ium

conc

entr

atio

nof

the

carb

onat

eio

n;it

was

calc

ulat

edby

the

auth

ors

from

the

equa

tion

log

@CO

322#5

Slo

gK

1lo

gp(

CO

2)1

2pH

,w

here

Slo

gK

52

17.5

5(6

0.09

)in

clud

esH

enry

cons

tant

for

CO

2,an

ddi

ssoc

iatio

nco

nsta

nts

ofca

rbon

icac

id.

c Con

cent

ratio

nsin

mol

dm23 .

Add

ition

alin

form

atio

n:U

sing

the

repo

rted

solu

bilit

yda

ta,

and

the

solu

bilit

ypr

oduc

tof

PuO

2CO

3fr

omth

eau

thor

s’ea

rlier

wor

kof

102(1

3.98

60.

12) ,1

the

over

all

stab

ility

cons

tant

sfo

rth

efo

llow

ing

carb

onat

ocom

plex

esof

the

PuO

221io

nw

ere

calc

ulat

ed:

PuO 2

CO

3,b

15

108.

760.

3 ;P

uO2~

CO

3!222

,b

25

1014

.16

0.5 ;

and

PuO

2~C

O3!

342,

b35

1017

.86

0.2 .

By

appl

ying

the

ion

inte

ract

ion

Pitz

erap

proa

ch,

the

ther

mod

ynam

icso

lubi

lity

prod

uct

ofP

uO2C

O3

was

obta

ined

asKspo

510

214

.85m

ol2

dm2

6 .

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

lubi

lity

expe

rimen

tsw

ere

cond

ucte

das

pHtit

ratio

nsin

0.1

ldm

23

NaC

lO4

unde

r1~

CO

2/A

rm

ixtu

re!

or10

0%pa

rtia

les

sure

ofC

O 2in

acl

osed

glas

sve

ssel

.A

port

ion

ofth

e~V

I!st

ock

solu

tion

was

adde

dto

0.1

mol

dm23

NaC

lO4

lutio

n,th

epH

was

adju

sted

to7

with

0.1

mol

dm23

NaO

H,

dC

O 2ga

sw

asbu

bble

dth

roug

hit.

Aw

hite

crys

talli

neec

ipita

teof

PuO

2CO

3w

asfo

rmed

.T

hepH

was

mea

sure

dby

ing

com

bina

tion

glas

sel

ectr

odes~R

OS

S-t

ype,

Orio

n!w

ith3

ldm

23

NaC

lO4

asa

fillin

gso

lutio

n,w

hich

wer

eca

libra

ted

ains

tsi

xst

anda

rdbu

ffer

solu

tions

inth

epH

rang

eof

2–

8.e

equi

libriu

mco

ncen

trat

ion

ofP

u~VI!

atea

chpH

was

term

ined

byliq

uid

scin

tilla

tion

coun

ting

and

abso

rptio

nec

tros

copy

at83

0.4

nmto

obta

into

talc

once

ntra

tion

ofP

ud

conc

entr

atio

nof

PuO 221

,re

spec

tivel

y.T

heso

lidph

ases

rech

arac

teriz

edby

IRsp

ectr

osco

pyan

dx-

ray

diffr

actio

n.

244 P

uof

99.9

%is

otop

icpu

rity

was

used

topr

epar

eth

eP

uO2C

O3

solid

phas

e.P

luto

nium~

VI!

stoc

kso

lutio

n~0.

01m

oldm

23 !

was

prep

ared

byfu

min

gw

ithco

ncen

trat

edH

ClO

4in

apl

atin

umcr

ucib

le,

and

furt

her

oxid

atio

nby

ozon

e.T

hepu

rity

ofth

eva

lenc

yst

ate

ofP

uw

asve

rified

byco

mpa

ring

ofpl

uton

ium

conc

entr

atio

nsas

dete

rmin

edby

abso

rptio

nsp

ectr

osco

pyan

dliq

uid

scin

tilla

tion

coun

ting.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 I.P

asha

lidis

,W.R

unde

,and

J.I.

Kim

,Rad

ioch

im.A

cta

61,1

41~1

993!

.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Plu

toni

um~V

I!di

oxoc

arbo

nate

;P

uO 2C

O3;

@392

92-1

0-9#

~2!

Car

bon

diox

ide;

CO 2;

@124

-38-

9#~3

!S

odiu

mpe

rchl

orat

e;N

aClO 4;

@760

1-89

-0#~4

!W

ater

;H 2

O;

@773

2-18

-5#

I.P

asha

lidis

,K

.R

.C

zerw

insk

i,T

.F

angh

anel

,an

dJ.

I.K

im,

Rad

ioch

im.

Act

a76,

55–

62~1

997!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

5p

2(p

artia

lpre

ssur

eof

CO 2)

/%5

1an

d10

0c 3

/mol

dm2

3 50.

1

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

PuO

2CO

3as

afu

nctio

nof

carb

onat

eio

nco

ncen

trat

ion

in0.

1m

oldm

23

NaC

lO4

at22

°Ca

pH2

log @

CO

322#b,

c2

log @

PuO

221#c

pH2

log @

CO

322#b,

c2

log @

PuO

221#c

Mea

sure

men

tsat

1%pa

rtia

lpre

ssur

eof

CO

2

4.22

11.1

22.

944.

999.

584.

09

4.23

11.1

02.

815.

219.

144.

73

4.27

11.0

22.

945.

578.

425.

09

4.30

10.9

63.

075.

578.

425.

09

4.32

10.9

23.

077.

065.

444.

69

4.34

10.8

82.

817.

065.

444.

71

4.50

10.5

63.

257.

404.

764.

34

4.52

10.5

23.

257.

424.

724.

60

4.64

10.2

83.

867.

474.

624.

47

4.69

10.1

83.

777.

534.

504.

31

4.70

10.1

63.

777.

544.

484.

30

4.74

10.0

83.

887.

634.

303.

85

4.81

9.94

3.97

7.64

4.28

4.14

4.83

9.90

3.91

7.72

4.12

3.76

4.84

9.88

4.03

7.81

3.94

3.58

4.85

9.86

3.91

7.82

3.92

3.36

4.88

9.80

4.03

7.87

3.82

3.67

Mea

sure

men

tsat

100%

part

ialp

ress

ure

ofC

O2

3.49

10.5

83.

403.

999.

584.

09

3.50

10.5

63.

404.

578.

425.

09

Me

So

mo

pr Pu

so an pr us mo

ag Th

de sp an we

J

NaC

lsol

utio

nof

the

desi

red

conc

entr

atio

nco

ntai

ned

ina

loos

ely

clos

edve

ssel

,w

ithC

O 2ga

sbu

bblin

gth

roug

h.S

olut

ion

pHw

asad

just

edby

addi

tion

ofN

aOH

/NaC

lor

HC

l/NaC

lso

lutio

ns.

The

elec

trod

ew

asca

libra

ted

agai

nst

buffe

rso

lutio

ns.

Equ

ilibr

atio

ntim

ew

asno

tre

port

ed.

Sam

ples

with

draw

nfr

omth

esa

tura

ted

solu

tions

wer

efil

tere

dus

ing

250

nmpo

resy

ringe

filte

rs~M

illip

ore

!,an

dth

eP

u~VI!

conc

entr

atio

nw

asde

term

ined

in25m

Lal

iquo

tsof

the

filtr

ate

byliq

uid

scin

tilla

tion

coun

ting.

dryn

ess

with

conc

entr

ated

HC

lO 4.T

here

sidu

ew

asdi

lute

dw

ithw

ater

,th

eP

uco

ncen

trat

ion

was

dete

rmin

edby

liqui

dsc

intil

latio

nco

untin

g,an

dpl

uton

ium

oxid

atio

nst

ate

purit

yw

asve

rified

usin

gab

sorb

ance

spec

tros

copy

.P

uO2C

O3

was

prep

ared

bybu

bblin

gC

O 2ga

sth

roug

ha

stirr

edac

idic

stoc

kso

lutio

nfo

r3

–5

days

,w

ashi

ngth

ere

sulti

ngpr

ecip

itate

with

dist

illed

de-io

nize

dw

ater

,re

diss

olvi

ng,

and

repe

atin

gpr

ecip

itatio

n.O

zone

was

also

bubb

led

thro

ugh

the

susp

ensi

onfo

rth

efin

al2

days

tore

oxid

ize

any

plut

oniu

mre

duce

dby

radi

olys

is.

The

resu

lting

pale

tan

solid

was

char

acte

rized

usin

gpo

wde

rx-

ray

diffr

actio

n,ex

tend

edx-

ray

abso

rptio

nfin

est

ruct

ure

~EX

AF

S!,

and

diffu

sere

flect

ance

spec

tros

copy

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

Sol

ubili

ty:

erro

rof

Ksp

not

repo

rted

.

7.2.

Am

mon

ium

Tris

„ca

rbon

ato…

Dio

xopl

uton

ate

„V

I…„-4…

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

tris~

carb

onat

o!di

oxop

luto

nate~

VI!

;H

4!4P

uO2~

CO

3) 3

;@3

6568

-63-

5#A

mm

oniu

mca

rbon

ate;

(NH 4!

2CO

3;@5

06-8

7-6#

Wat

er;

H 2O

;@7

732-

18-5#

L.E

.D

rabk

ina,

Rad

iokh

imiy

a2,

377

–8

~196

0!.

riabl

es:

Pre

pare

dby

:

K29

30w

2/m

ass%

:5

–25

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

(NH

4!4P

uO2~

CO

3!3

at20

°Cin

(NH 4

! 2C

O3

solu

tions

a

(NH

4!2C

O3

100w

2/m

ass%

)P

u~g

kg2

1 !b(N

H4!

4PuO

2~C

O3!

3

~gkg

21 !b,

c

53.

253.

807.

72

102.

001.

804.

16

150.

973

0.97

42.

13

200.

628

0.69

31.

45

250.

384

0.41

80.

877

hena

ture

ofeq

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

ram

spe

rkg

satu

rate

dso

lutio

n.al

cula

ted

byco

mpi

ler

for

the

aver

age

ofth

etw

oso

lubi

lity

valu

esre

port

ed,

usin

gA

r~P

u!5

239.

053.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.(N

H 4!2C

O3

solu

tions

wer

est

irred

thso

lid(N

H4!

4NpO

2~C

O3!

3fo

r2

hw

hich

was

foun

dffi

cien

tto

reac

heq

uilib

rium

.M

etho

dof

anal

ysis

ofth

etu

rate

dso

lutio

nsw

asno

tre

port

ed.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

r!.S

olub

ility

:the

scat

ter

ofth

edu

plic

ate

mea

sure

men

tsin

dica

tes

aner

ror

of6

5%–

10%

~com

pile

r!.

652652 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Plu

toni

um~V

I!di

oxoc

arbo

nate

;P

uO 2C

O3;

@392

92-1

0-9#

~2!

Car

bon

diox

ide;

CO 2;

@124

-38-

9#~3

!S

odiu

mch

lorid

e;N

aCl;@7

647-

14-5#

~4!

Wat

er;

H 2O

;@7

732-

18-5#

M.

P.

Neu

,S

.D

.R

eily

,an

dW

.H

.R

unde

,M

ater

.R

es.

Soc

.S

ymp.

Pro

c.46

5,75

9–

65~1

997!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

5p

2/%

~par

tialp

ress

ure!:

100

m3

/mol

kg2

1 :0.

1–

5.0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

typr

oduc

tof

PuO

2CO

3in

NaC

lsol

utio

nsat

22°C

and

100%

part

ialp

ress

ure

ofC

O2a,

b

NaC

l(m

3/m

olkg

21 )

2lo

gK

spc

0.1

12.9

0.2

12.4

0.5

12.5

112

.3

212

.2

512

.3

a The

equi

libriu

mso

lidph

ase

was

confi

rmed

byus

ing

vario

ussp

ectr

osco

pic

met

hods

tobe

PuO

2CO

3,@3

9292

-10-

9#.b N

umer

ical

data

ofP

uO 2C

O3

not

repo

rted

.c K

sp5

@PuO

221#@

CO

322#;

Ksp

data

repo

rted

inm

ol2kg

22 .

Equ

ilibr

ium

carb

onat

eio

nco

ncen

trat

ion

was

calc

ulat

edas

log

@CO

322#5

log

K1

log

p(C

O2)

12

pH,

whe

reK

isth

eeq

uilib

rium

cons

tant

for

the

form

atio

nof

CO

322fr

omC

O2

gas

ineq

uilib

rium

with

NaC

lsol

utio

ns.

Add

ition

alin

form

atio

n:R

educ

tion

ofP

u~VI!

toP

u~V

!w

asob

serv

edsp

ectr

osco

pica

llyat

low

NaC

lcon

cent

ratio

ns.

The

Pu

~V!

pres

ent

inth

eso

lutio

ndi

spro

por-

tiona

ted

toP

u~VI!

~aq!

and

poly

mer

icP

u~IV

!hy

drox

ide.

On

equi

libra

tion

prol

onge

dup

to4

mon

ths,

the

equi

libriu

mso

lidph

ase

was

PuO

2CO

3.S

ince

equi

libra

tion

time

used

inso

lubi

lity

expe

rimen

tsw

asno

trep

orte

dit

isno

tcle

arho

w,a

ndif,

this

coul

dha

veaf

fect

edth

eK

spda

taat

low

NaC

lcon

cent

ratio

ns.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Sol

ubili

tyex

perim

ents

wer

epe

rfor

med

aspH

titra

tion

proc

edur

eus

ing

appr

oxim

atel

y50

mg

PuO 2C

O3

and

5m

LP

luto

nium

~VI!

stoc

kso

lutio

nw

aspr

epar

edby

diss

olvi

ng239 P

um

etal

in7

mol

mol

dm2

3H

ClO

4an

dfu

min

gth

eso

lutio

nto

near

Co

~1!

(N ~2!

~3!

Va

T/

10

(

a T b G c C Me

Iso

wi

su sa


Sol

ubili

ty:

dupl

icat

em

easu

rem

ents

at40

and

50m

ass

%N

H4N

O3

indi

cate

aner

ror

ofup

to610

%~c

ompi

ler!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Tet

raam

mon

ium

tric

arbo

nato

diox

oplu

tona

te~V

I!;

H4!

4PuO

2~C

O3!

3;@3

6568

-63-

5#A

mm

oniu

mca

rbon

ate;~

NH

4!2C

O3;

@506

-87-

6#W

ater

;H 2

O;

@773

2-18

-5#

A.D

.Gel

man

,A.I

.Mos

kvin

,and

V.P

.Zai

tsev

a,R

adio

khim

iya

4,15

4–

62~1

962!

.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

dm2

3 :0.

438

–2.

19J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

of~N

H4!

4PuO

2~C

O3!

3in

~NH

4!2C

O3

solu

tions

a

~NH

4!2C

O3

(c2

/mol

dm2

3 )~N

H4!

4PuO

2~C

O3!

3

(103

c 1/m

oldm

23 )

0.43

821

.8

0.87

69.

29

1.31

46.

65

1.75

24.

26

2.19

03.

29

hena

ture

ofeq

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

ditio

nali

nfor

mat

ion:

eau

thor

sst

ated

that

the

PuO 2~C

O3!

342io

nw

asun

stab

lein

solu

tion,

and

that

inth

esy

stem

stud

ied

Pu

~VI!

exis

ted

asP

uO 2~C

O3!

222in

satu

rate

dso

lutio

ns.

The

equi

libriu

mco

nsta

ntfo

rth

ere

actio

nP

uO2~

CO

3!342�

PuO

2~C

O3!

2221

CO

322w

asre

port

edto

be(8

.261.

1)10

23

mol

dm2

3 .

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

xces

sso

lid~NH

4!4P

uO2~

CO

3!3

was

rred

with

~NH

4!2C

O3

solu

tions

ofth

ede

sire

dco

ncen

trat

ion

4–

6h

whi

chw

asfo

und

suffi

cien

tfo

req

uilib

rium

tobe

ache

d.P

luto

nium

conc

entr

atio

nin

the

satu

rate

dso

lutio

nss

dete

rmin

edra

diom

etric

ally

.

~NH

4!4P

uO2~

CO

3!3

was

prep

ared

byre

actin

g~NH

4!2P

u 2O

7w

ithco

ncen

trat

edso

lutio

nof~

NH

4!2C

O3.

The

salt

was

obta

ined

asa

dark

-gre

enso

lid.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

tris~

carb

onat

o!di

oxop

luto

nate~

VI!

;~N

H4!

4PuO

2~C

O3!

3;@3

6568

-63-

5#~2

!A

mm

oniu

mni

trat

e;N

H 4N

O3;

@648

4-52

-2#~3

!W

ater

;H 2

O;

@773

2-18

-5#

L.E

.D

rabk

ina,

Rad

iokh

imiy

a2,

377

–8

~196

0!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

310

0w2

/mas

s%

:10

–64

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

~NH

4!4P

uO2~

CO

3!3

at20

°Cin

NH 4

NO

3so

lutio

nsa

NH

4NO

3

(100

w2

/mas

s%

)P

u~g

kg2

1 !b~N

H4!

4PuO

2~C

O3!

3

~gkg

21 !b,

d

102.

325.

02

200.

866

0.79

91.

803

300.

423

0.91

6

400.

152

0.19

20.

372

500.

070

0.08

30.

167

63.9

0.02

10.

0455

c0.

027

0.05

84

a The

natu

reof

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.b G

ram

spe

rkg

satu

rate

dso

lutio

n.c S

olut

ion

satu

rate

dw

ithN

H 4NO

3;co

ncen

trat

ion

ofth

ela

tter

not

repo

rted

.d C

alcu

late

dby

com

pile

rus

ing

A r~P

u!5

239.

053.

Whe

retw

om

easu

rem

ents

wer

eav

aila

ble,

the

aver

age

valu

ew

asus

ed.

Add

ition

alin

form

atio

n:T

heau

thor

also

repo

rted

data

for

the

solu

bilit

yof~N

H4!

4PuO

2~C

O3!

3in

solu

tions

cont

aini

ng5

–25

mas

s%

NH

4NO

3w

hich

wer

esa

tura

ted

with

~NH

4!2C

O3.

The

data

are

not

give

nhe

resi

nce

the

conc

entr

atio

nof

~NH

4!2C

O3

inth

ese

solu

tions

was

not

repo

rted

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

NH 4N

O3

solu

tions

wer

est

irred

with

solid

~NH

4!4N

pO2~

CO

3!3

for

2h

whi

chw

asfo

und

suffi

cien

tto

reac

heq

uilib

rium

.M

etho

dof

anal

ysis

ofth

esa

tura

ted

solu

tions

was

not

repo

rted

.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

r!.

Co

~1!

~N ~2!

~3!

Va

T/

c 2 a T Ad

Th

the

3 Me

Iso

sti

for

re wa

J

7.4.

Hex

amm

inec

obal

t„III…

Sal

tof

Pen

taki

s„ca

rbon

ato…A

quap

luto

nate

„IV…„-6…

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Bis

~hex

amm

inec

obal

t~III

!!nt

acar

bona

toaq

uapl

uton

ate

~IV

!;o~

NH

3!6# 2

@Pu~

CO

3!5H

2O#;

@#

Wat

er;

H 2O

;@7

732-

18-5#

orE

than

ol;

C 2H

6O;

@64-

17-5

#

K.

Uen

oan

dM

.H

oshi

,J.

Inor

g.N

ucl.

Che

m.32,

3817

–22

~197

0!.

riabl

es:

Pre

pare

dby

:

K:

293

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

of@C

o~N

H3!

6#2@P

u~C

O3!

5H2O

#in

wat

eran

det

hano

la

Sol

vent

Pu

~mg/

100

gso

lven

t!@C

o~N

H3!

6# 2

@Pu~

CO

3!5H

2O#

(105

c 1/m

oldm

23 )b

wat

er1.

12.

15

etha

nol

0.4

0.43

1

quili

briu

mso

lidph

ases

wer

eno

tin

vest

igat

ed.

alcu

late

dby

com

pile

rus

ing

A r~P

u!5

239.

053.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

xces

sof

dry

plut

oniu

mco

mpo

und

sal

low

edto

stan

din

the

solv

ent

for

24h.

The

satu

rate

dlu

tion

was

anal

yzed

radi

omet

rical

lyfo

rpl

uton

ium

cont

ent.

@Co~

NH

3!6# 2

@Pu~

CO

3!5H

2O#

was

prep

ared

bypr

ecip

itatio

nw

ithC

o~N

H3!

6Cl 3

from

1m

L2m

oldm

23 ~

NH

4!2C

O3

cont

aini

ng1

mg

Pu~

IV!.

The

prec

ipita

tew

asva

cuum

drie

dun

der

102

3m

mH

gat

room

tem

pera

ture

.A

naly

sis:

foun

d/ca

lcul

ated

for

@Co~

NH

3!6# 2

@Th~

CO

3!5H

2O#•

4H2O

~mas

s%!

:P

u26

.1/2

5.2,

Co~

NH

3!6

33.0

0/33

.9,

CO 3

30.0

/31.

5.P

luto

nium

~IV

!so

lutio

nin

2.5

mol

dm2

3w

aspr

epar

edby

redu

ctio

nof

Pu

~VI!

with

NaN

O2.

Co~

NH

3!6C

l 3w

aspr

epar

edac

cord

ing

toR

ef.

1.~NH

4!2C

O3

reag

ent

grad

e,so

urce

not

spec

ified

.D

istil

led

wat

eran

dre

agen

tgr

ade

etha

nolw

ere

used

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n62

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 W.

Bilt

z,Z

.A

norg

.A

llgem

.C

hem

.83,

177

~191

4!.

654654 JIRI HALA

7.3.

Am

mon

ium

Hyd

roxo

carb

onat

oD

ioxo

plut

onat

e„V

I…„-1…

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

hydr

oxoc

arbo

nato

-dio

xopl

uton

ate

~VI!

;N

H4P

uO2~

CO

3!O

H;

@#

~2!

Am

mon

ium

carb

onat

e;~N

H4!

2CO

3;

@506

-87-

6#~3

!W

ater

;H 2

O;

@773

2-18

-5#

A.D

.Gel

man

,A.I

.Mos

kvin

,and

V.P

.Zai

tsev

a,R

adio

khim

iya

4,15

4–

62~1

962!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

at25

°Cof

NH 4

PuO

2~C

O3!

OH

inw

ater

The

solu

bilit

yat

25°C

ofN

H 4P

uO2~

CO

3!O

Hin

wat

erw

asre

port

edto

bec15

1.05

310

23

mol

dm2

3 .E

quili

briu

mso

lidph

ase

was

not

inve

stig

ated

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

solid

was

stirr

edin

wat

erfo

r4

–6

h.P

luto

nium

conc

entr

atio

nin

the

satu

rate

dso

lutio

nsw

asde

term

ined

radi

omet

rical

ly.

NH

4PuO

2~C

O3!

OH•3H

2Ow

aspr

epar

edby

diss

olvi

ng~N

H4!

2Pu 2

O7

in0.

17–

0.40

mol

dm2

3~N

H4!

2CO

3.F

rom

the

dark

-red

solu

tion

the

com

plex

salt

prec

ipita

ted

asa

pink

solid

onad

ditio

nof

aneq

ual

volu

me

of96

%et

hano

l.It

was

was

hed

seve

ralt

imes

from

exce

ssca

rbon

ate

with

70%

–80

%et

hano

land

ethe

r,an

ddr

ied

over

CaC

l2.

Ana

lysi

s~f

ound

/cal

cula

ted

for

the

trih

ydra

te,m

ass

%!:N

H4

5.3/

4.3,

Pu

54.1

2/56

.9,C

O 211

.4/1

0.5.

Sou

rce

and

purit

yof~

NH

4!2P

u 2O

7an

d~N

H4!

2CO

3no

tspe

cifie

d.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

Sol

ubili

ty:

prec

isio

nno

tre

port

ed.

Co

~1!

pe @C ~2!

Va

T/

a E b C Me

Iso

wa

so


drie

dby

aspi

ratio

n.A

llch

emic

als

used

wer

ere

agen

tgr

ade.

Est

imat

edE

rror

:T

empe

ratu

re:

not

repo

rted

.S

olub

ility

:va

lues

repo

rted

wer

eob

tain

edfr

omsi

ngle

dete

rmin

atio

ns;

this

did

not

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 L.R

.C

risle

r,J.

Inor

g.N

ucl.

Che

m.34

,32

63~1

972!

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Plu

toni

um~I

II!

tris

~for

mat

e!;

Pu~

CH

O2!

3;@3

4501

-13-

8#F

orm

icac

id;

CH 2

O2;

@64-

18-6

#S

odiu

mfo

rmat

e;C

HO 2N

a;@1

41-5

3-7#

Hyd

roxy

alam

ine

hydr

ochl

orid

e;N

H 2OH•H

Cl;

@547

0-11

-1#W

ater

;H 2

O;

@773

2-18

-5#

J.D

.N

avra

til,

Roc

kwel

lIn

t.,G

olde

n,C

O~p

rivat

eco

mm

unic

atio

n!.

riabl

es:

Pre

pare

dby

:

K:

296

/mol

dm2

3 :0.

5–

2.0

/mol

dm2

3 :0.

1–

0.5

/mol

dm2

3 :0.

05

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

23°C

ofP

u~CH

O2!

3in

CH

2O2

/CH

O2N

aso

lutio

nsa

CH

2O2

2/m

oldm

23 )

CH

O2N

a(c

2/m

oldm

23 )

Pu~

CH

O2!

3

~gdm

23 !

Pu~

CH

O2!

3

(104

c 1/

mol

dm2

3 )bC

H2O

2

(c2

/mol

dm2

3 )C

HO

2Na

(c2

/mol

dm2

3 )P

u~C

HO

2!3

~gm

dm2

3 !

Pu~

CH

O2!

3

(104

c 1/

mol

dm2

3 )b

0.5

0.1

1.35

56.4

1.5

0.1

0.07

83.

27

0.2

0.39

16.3

0.2

0.04

01.

67

0.3

0.02

51.

040.

30.

023

0.96

3

0.4

0.02

10.

879

0.4

0.02

61.

09

0.5

0.02

00.

837

0.5

0.02

81.

17

1.0

0.1

0.08

23.

432.

00.

10.

066

2.76

0.2

0.02

41.

000.

20.

034

1.42

0.3

0.02

41.

000.

30.

029

1.21

0.4

0.01

70.

714

0.4

0.03

31.

38

0.5

0.02

71.

130.

50.

034

1.42

hena

ture

ofeq

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

All

solu

tion

cont

aine

d0.

05m

oldm

23

NH

2OH•H

Clt

om

aint

ain

the

Pu~III

!le

ncy

stat

e.al

cula

ted

byco

mpi

ler

usin

gA r~P

u!5

239.

053.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

xces

sP

u~C

HO

2!3

was

equi

libra

ted

with

CH

2O2

/CH

O2N

aso

lutio

nsof

the

desi

red

conc

entr

atio

nfo

r16

h.It

was

not

stat

edw

heth

erth

eso

lutio

nsw

ere

ther

mos

tate

ddu

ring

equi

libra

tion.

The

filte

red

satu

rate

dso

lutio

nsw

ere

anal

yzed

for

Pu

cont

ent

byan

unsp

ecifi

edm

etho

d.

Pu~

CH

O2!

3w

aspr

epar

edac

cord

ing

toR

ef.

1.P

luto

nium

met

al~9

9.99

%!

was

diss

olve

din

conc

entr

ated

HC

l,an

dth

eso

lutio

nw

asfil

tere

dth

roug

ha

0.25m

mM

illip

ore

Sol

vine

rtfil

ter.

Inth

efil

trat

eth

epH

was

adju

sted

to8

byco

ncen

trat

edam

mon

iaso

lutio

n,an

dco

ncen

trat

edfo

rmic

acid

was

adde

dto

diss

olve

plut

oniu

mhy

drox

ide

and

prec

ipita

teP

u~C

HO

2!3.

The

prec

ipita

tew

asag

edfo

r1

h,w

ashe

dw

ithco

ncen

trat

edfo

rmic

acid

,an

ddr

ied

byas

pira

tion.

All

chem

ical

sus

edw

ere

reag

ent

grad

e.

Est

imat

edE

rror

:T

empe

ratu

re:

not

repo

rted

.S

olub

ility

:va

lues

repo

rted

wer

eob

tain

edfr

omsi

ngle

dete

rmin

atio

ns;

this

did

not

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 L.R

.C

risle

r,J.

Inor

g.N

ucl.

Che

m.34

,32

63~1

972!

.



7.5.

Plu

toni

um„III…

For

mat

e

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Plu

toni

um~I

II!

tris

~for

mat

e!;

Pu~

CH

O2!

3;@3

4501

-13-

8#~2

!F

orm

icac

id;

CH 2

O2;

@64-

18-6

#~3

!H

ydro

xyal

amin

ehy

droc

hlor

ide;

NH 2O

H•H

Cl;

@547

0-11

-1#~4

!W

ater

;H 2

O;

@773

2-18

-5#

J.D

.N

avra

til,

Roc

kwel

lIn

t.,G

olde

n,C

O~p

rivat

eco

mm

unic

atio

n!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

6c 2

/mol

dm2

3 :0.

5–

23.5

c 3/m

oldm

23 :

0.05

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

23°C

ofP

u~CH

O2!

3in

form

icac

idso

lutio

nsa

CH

2O2

(c2

/mol

dm2

3 )P

u~C

HO

2!3

~gdm

23 !

Pu~

CH

O2!

3

(104

c 1/m

oldm

23 )b

0.5

1.81

48.8

1.0

1.40

37.7

20.

7620

.4

50.

4111

.0

100.

141

3.79

150.

052

1.40

23.5

0.01

50.

404

a The

natu

reof

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.A

llso

lutio

nco

ntai

ned

0.05

mol

dm2

3N

H2O

H•H

Clt

om

aint

ain

the

Pu~III

!va

lenc

yst

ate.

b Cal

cula

ted

byco

mpi

ler

usin

gA r~P

u!5

239.

053.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

Pu

~CH

O2!

3w

aseq

uilib

rate

dw

ithfo

rmic

acid

solu

tions

ofth

ede

sire

dco

ncen

trat

ion

for

16h.

Itw

asno

tst

ated

whe

ther

the

solu

tions

wer

eth

erm

osta

ted

durin

geq

uilib

ratio

n.T

hefil

tere

dsa

tura

ted

solu

tions

wer

ean

alyz

edfo

rP

uco

nten

tby

anun

spec

ified

met

hod.

Pu~

CH

O2!

3w

aspr

epar

edac

cord

ing

toR

ef.

1.P

luto

nium

met

al~9

9.99

%!

was

diss

olve

din

conc

entr

ated

HC

l,an

dth

eso

lutio

nw

asfil

tere

dth

roug

ha

0.25m

mM

illip

ore

Sol

vine

rtfil

ter.

Inth

efil

trat

eth

epH

was

adju

sted

to8

byco

ncen

trat

edam

mon

iaso

lutio

n,an

dco

ncen

trat

edfo

rmic

acid

was

adde

dto

diss

olve

plut

oniu

mhy

drox

ide

and

prec

ipita

teP

u~C

HO

2!3.

The

prec

ipita

tew

asag

edfo

r1

h,w

ashe

dw

ithco

ncen

trat

edfo

rmic

acid

,an

d

Co

~1!

~2!

~3!

~4!

~5!

Va

T/

c 2 c 3 c 4 (c a T va b C Me

Iso

J

~196

7!.

7.6.

Plu

toni

um„III…

Oxa

late

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Dip

luto

nium

~III

!tr

is~o

xala

te!;

Pu 2

~C2O

4!3;

@331

6-65

-2#A

mm

oniu

mox

alat

e;(N

H 4!2C

2O4;

@111

3-38

-8#W

ater

;H 2

O;

@773

2-18

-5#

A.

D.

Gel

man

,N

.N

.M

ator

ina,

and

A.

I.M

oskv

in,

Dok

l.A

kad.

Nau

kS

SS

R117

,88

–91

;~19

57!

Sov

.J.

At.

Ene

rgy3

,11

5–

20~1

957!

.

riabl

es:

Pre

pare

dby

:

K:

343

/mol

dm2

3 :0

–0.

70J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Pu 2

~C2O

4!3

at70

°Cin

wat

eran

din

(NH 4!

2C2O

4so

lutio

nsa

NH

4!2C

2O4

2/m

oldm

23 )

Pu 2

~C2O

4!3

(104

c 1/m

oldm

23 )

(NH

4!2C

2O4

(c2

/mol

dm2

3 )P

u 2~C

2O4!

3

(104

c 1/m

oldm

23 )

00.

188

0.41

8.19

0.07

2.02

0.49

9.75

0.13

2.90

0.56

11.4

0

0.22

54.

700.

6215

.00

0.28

5.66

0.66

20.5

0

0.35

6.90

0.70

22.5

0

hena

ture

ofth

eeq

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

The

initi

also

lidus

edfo

rth

em

easu

rem

ents

isre

port

edto

beu 2

~C2O

4!3•

9H2O

.In

Ref

.1

the

crys

tallo

hydr

ate

ofpl

uton

ium~III

!ox

alat

ew

asre

port

edto

bede

cahy

drat

e,P

u2~

C2O

4!3•

10H

2O.

ditio

nali

nfor

mat

ion:

omth

ein

crea

seof

the

solu

bilit

yof

Pu

2~C

2O4!

3w

ithin

crea

sing

(NH 4

! 2C

2O4

conc

entr

atio

nth

eau

thor

sca

lcul

ated

the

cons

ecut

ive

tabi

lity

cons

tant

sof

the

Pu

2~C

2O4)

n(32

2n

)co

mpl

exes

.F

rom

the

solu

bilit

yof

Pu

2~C

2O4!

3in

wat

erth

eau

thor

sob

tain

edth

eso

lubi

lity

oduc

tof

the

salt

asKsp

5@P

u31#2

@C2O

422#3 5

2.53

310

222

mol

5dm

215

at70

°C.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.S

olut

ions

ofth

ede

sire

dco

ncen

trat

ion

rest

irred

with

exce

ssP

u2~

C2O

4!3•

9H2O

ina

ther

mos

tate

dth

for

4–

6h,

whi

chw

ases

tabl

ishe

das

suffi

cien

tto

reac

hui

libriu

m.

To

avoi

dox

idat

ion

ofP

u31,

ast

ream

ofN 2

gas

spa

ssed

thro

ugh

the

solu

tion

durin

gst

irrin

g.T

henc

entr

atio

nof

plut

oniu

min

the

satu

rate

dso

lutio

nsw

asde

term

ined

byan

unsp

ecifi

edra

diom

etric

met

hod.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 I.L.

Jenk

ins,

F.H

.Moo

re,a

ndM

.J.W

ater

man

,J.I

norg

.Nuc

l.C

hem

.27,

77~1

965!

.

656656 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Plu

toni

um~I

II!

tris

~for

mat

e!;

Pu~

CH

O2!

3;@3

4501

-13-

8#~2

!F

orm

icac

id;

CH 2

O2;

@64-

18-6

#~3

!P

erch

loric

acid

;H

ClO 4

;@7

601-

90-3#

~4!

Sod

ium

perc

hlor

ate;

NaC

lO 4;@7

601-

89-0#

~5!

Wat

er;

H 2O

;@7

732-

18-5#

A.

V.

Ana

nev

and

N.

N.

Kro

t.R

adio

khim

iya26

,75

5–

8~19

84!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8c 2

/mol

dm2

3 :0.

2c 3

/mol

dm2

3 :0

–0.

1c 4

/mol

dm2

3 :1.

9–

2.0

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

at25

°Cof

Pu~C

HO

2!3

inC

H2O

2/H

ClO

4/N

aClO

4so

lutio

ns

Sol

ubili

tyat

25°C

ofP

u~CH

O2!

3w

asm

easu

red

in0.

2m

oldm2

3so

lutio

nsof

form

icac

idco

ntai

ning

0–

0.1

mol

dm23

HC

lO4,

and

NaC

lO4

tom

aint

ain

ioni

cst

reng

thof

2.0

mol

dm23 .

The

resu

ltsw

ere

repo

rted

ingr

aphi

calf

orm

.F

rom

the

solu

bilit

yda

tath

eso

lubi

lity

prod

uct

ofP

u~CH

O2!

3w

asca

lcul

ated

tobe

5.463

102

12m

ol4

dm2

12at

ioni

cst

reng

thof

2.0

mol

dm23 .

Inth

ese

calc

ulat

ions

,th

eex

iste

nce

inth

esa

tura

ted

solu

tions

ofth

eP

u~C

HO

2!21

and

Pu~C

HO

2!21

com

plex

esw

asta

ken

into

acco

unt.

The

irst

abili

tyco

nsta

nts

wer

eal

soca

lcul

ated

.T

heeq

uilib

rium

solid

phas

ew

asP

u~C

HO

2!3,

@345

01-1

3-8#.

Als

ore

port

ed,

ingr

aphi

calf

orm

,w

asth

eso

lubi

lity

at25

°Cof

Pu~

CH

O2!

3in

sodi

umfo

rmat

e–

NaC

lO 4so

lutio

ns,a

ndth

eso

lubi

lity

ofP

u~CH

O2!

3in

wat

eras

7.143

102

3m

oldm

23 .

Itw

asno

tsta

ted

expl

icitl

yif

the

latte

rva

lue

was

obta

ined

byca

lcul

atio

nor

expe

rimen

tally

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

Pu

~CH

O2!

3w

aseq

uilib

rate

dw

ithso

lutio

nsof

the

desi

red

conc

entr

atio

nfo

r10

hin

ther

mos

tate

dfla

sks.

Bef

ore

mea

sure

men

ts,

the

solu

tions

wer

efr

eed

from

air

bypa

ssin

gth

roug

hth

ema

stre

amof

argo

nga

s.In

the

filte

red

satu

rate

dso

lutio

ns,

pHw

asde

term

ined

pote

ntio

met

rical

ly,

and

the

conc

entr

atio

nof

Pu

~III

!sp

ectr

opho

tom

etric

ally

in;0.

6m

oldm

23

HC

lO4

at60

3nm

.T

hepH

met

erus

edw

asca

llibr

ated

agai

nst

2.0

mol

dm2

3

NaC

lO4.

Sol

idph

ases

wer

eid

entifi

edby

x-ra

ydi

ffrac

tion.

239 P

u~C

HO

2!3

was

prep

ared

from

fres

hly

prec

ipita

ted

Pu

~OH

! 3an

dco

ncen

trat

edfo

rmic

acid

acco

rdin

gto

Ref

s.1,

2.T

heso

lidpr

oduc

tw

asce

ntrif

uged

,w

ashe

dw

ith10

mol

dm23

form

icac

idan

d50

%et

hano

l,an

dke

ptov

erK

OH

.A

llot

her

chem

ical

sw

ere

reag

ent

grad

epr

oduc

ts.

Dou

bly

dist

illed

wat

erw

asus

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

erro

rno

tre

port

ed.

Ref

eren

ces:

1 L.R

.C

risle

r,J.

Inor

g.N

ucl.

Che

m.34

,32

63~1

972!

.2 F

.W

eige

lan

dN

.te

rMee

r,In

org.

Nuc

l.C

hem

.Le

tt.3,40

3

Co

~1!

~2!

~3!

Va

T/

c 2

((c a T P A

dF

rin

spr M

e

Iso

we

ba eq wa

co


e

equi

libriu

m.

To

avoi

dox

idat

ion

ofP

u31,

the

solu

tions

cont

aine

d10

–15

gdm2

3so

dium

form

alde

hyde

sulfo

xyla

te,

and

ast

ream

ofN 2

gas

was

pass

edth

roug

hth

eso

lutio

nsdu

ring

stirr

ing.

The

conc

entr

atio

nof

plut

oniu

min

the

satu

rate

dso

lutio

nsw

asde

term

ined

byan

unsp

ecifi

edra

diom

etric

met

hod.

Tem

pera

ture

:no

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 I.L.

Jenk

ins,

F.H

.Moo

re,a

ndM

.J.W

ater

man

,J.I

norg

.Nuc

l.C

hem

.27,

77~1

965!

.

7.6.

1.E

valu

atio

nof

the

Pu

2„C

2O4…

3¿C

2H2O

4¿H

NO

3¿A

scor

bic

Aci

d

orH

ydra

zine

¿H

2OS

yste

m

mpo

nent

s:E

valu

ator

:

Dip

luto

nium

~III

!tr

is~o

xala

te!;

Pu 2

~C2O

4!3;

@331

6-65

-2#O

xalic

acid

;C 2

H2O

4;@1

44-6

2-7#

Nitr

icac

id;

HN

O3;

@769

7-37

-2#A

scor

bic

acid

;C 6

H8O

6;@5

0-81

-7#;

orH

ydra

zine

;N 2

H4;

02-0

1-2#

Wat

er;

H 2O

;@7

732-

18-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,

June

2000

Crit

ical

Eva

luat

ion:

The

solu

bilit

yof

Pu 2~

C2O

4!3

inox

alic

acid

–H

NO 3

solu

tions

has

been

stud

ied

inth

ree

refe

renc

es.

Che

neau

1re

port

edte

mpe

ratu

repe

nden

ceof

the

solu

bilit

yat

one

fixed

HN

O3

and

oxal

icac

idco

ncen

trat

ion

whi

leH

asilk

areta

l.2an

dB

urne

yan

dP

orte

r3

mea

sure

dth

elu

bilit

yof

Pu 2

~C2O

4!3

asa

func

tion

ofox

alic

acid

conc

entr

atio

nfo

rva

rious

HN

O3

conc

entr

atio

nsat

one

tem

pera

ture

,i.e

.,at

298.

1an

d4.

1K

,re

spec

tivel

y.A

llm

easu

rem

ents

wer

epe

rfor

med

inth

epr

esen

ceof

are

duci

ngag

ent,

eith

eras

corb

icac

id2,

3or

hydr

azin

e,1to

sure

the

triv

alen

tst

ate

ofpl

uton

ium

.T

here

sults

inR

ef.

3w

ere

repo

rted

ingr

aphi

calf

orm

only

.A

lthou

ghth

epu

blis

hed

data

allo

wfo

rra

ther

limite

dco

mpa

rison

,it

can

clea

rlybe

seen

from

som

esy

stem

s~0

.1m

oldm

23

C2H

2O4/

2.0

mol

dm2

3H

NO

3;0.

2m

oldm

23

H2O

4/1.

5or

2.0

mol

dm2

3H

NO

3!th

atth

eda

taof

Bur

ney

and

Por

ter

3ar

ehi

gher

than

thos

eof

Has

ilkaret

al.2

bya

fact

orof

upto

2.ee

ms

that

this

disc

repa

ncy

corr

elat

esw

ithth

eeq

uilib

ratio

ntim

eus

ed,i

.e.,

16h

inR

ef.3

and

1h

only

inR

ef.2

.The

only

mea

sure

men

tC

hene

au1th

atca

nbe

com

pare

dw

ithth

ose

ofR

efs.

2,3,

i.e.,

that

take

nin

0.2

mol

dm2

3C

2H2O

4/1.

45m

oldm

23

HN

O3,

seem

sto

agre

ell

with

that

obta

ined

inR

ef.

3fo

r0.

2m

oldm2

3C

2H2O

4/1.

5m

oldm

23

HN

O3,

alth

ough

Che

neau

used

equi

libra

tion

time

of30

min

ly.

Unc

erta

inty

inte

mpe

ratu

rem

ayal

sobe

impo

rtan

tfo

rth

epu

blis

hed

solu

bilit

yda

tasi

nce

Che

neau

1sh

owed

that

the

solu

bilit

yof

2~C

2O4!

3is

dist

inct

lyte

mpe

ratu

rede

pend

ent.

With

resp

ect

ofth

isit

may

bere

leva

ntto

note

that

itis

not

clea

rfr

omth

epu

blis

hed

orm

atio

nw

heth

erB

urne

yan

dP

orte

r3

perf

orm

edeq

uilib

ratio

nin

ath

erm

osta

ted

appa

ratu

s,an

dth

atH

asilk

are

ta

l.2de

scrib

edth

epe

ratu

reof

thei

rm

easu

rem

ents~298

.1K!

asap

prox

imat

ero

omte

mpe

ratu

re.

Mor

eove

r,it

isap

pare

ntfr

omda

tain

Ref

.3

that

the

lubi

lity

ofP

u 2~C

2O4!

3in

oxal

icac

id–

HN

O 3so

lutio

nsw

as,

toso

me

exte

nt,

depe

nden

ton

asco

rbic

acid

conc

entr

atio

n.T

heev

alua

tor

sum

edth

isto

bedu

eto

the

form

atio

nof

solu

ble

Pu

~III

!co

mpl

exes

with

asco

rbic

acid

inth

esa

tura

ted

solu

tions

.T

akin

gal

lth

isin

toco

unt,

the

syst

emw

ould

obvi

ousl

yne

eda

thor

ough

rein

vest

igat

ion

with

part

icul

arem

phas

ison

equi

libra

tion

time,

tem

pera

ture

cont

rol,

dth

ety

pean

dco

ncen

trat

ion

ofth

ere

duci

ngag

ent

used

.F

orth

isre

ason

,no

neof

the

publ

ishe

dda

taca

nbe

reco

mm

ende

dal

thou

ghth

eta

ofB

urne

yan

dP

orte

r,3

ifdi

gitiz

edfr

omth

egr

aphi

calr

epre

sent

atio

n,co

uld

serv

eas

are

ason

able

appr

oxim

atio

nfo

rth

eco

nditi

ons

ed.

fere

nces

:

.C

hene

au,

Rep

ort

CE

A-R

-410

9,19

71.

.P

.H

asilk

ar,

N.

B.

Khe

deka

r,K

.C

hand

er,

A.

V.

Jadh

av,

and

H.

C.

Jain

,J.

Rad

ioan

al.

Nuc

l.C

hem

.18

5,11

9~1

994!

.

.A

.B

urne

yan

dJ.

A.

Por

ter,

Inor

g.N

ucl.

Che

m.

Lett.3,

79~1

967!

.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Dip

luto

nium

~III

!tr

is~o

xala

te!;

Pu 2

~C2O

4!3;

@331

6-65

-2#~2

!P

otas

sium

oxal

ate;

K 2C2O

4;@5

83-5

2-8#

~3!

Pot

assi

umch

lorid

e;K

Cl;@7

447-

40-7#

~4!

Wat

er;

H 2O

;@7

732-

18-5#

A.

D.

Gel

man

,N

.N

.M

ator

ina,

and

A.

I.M

oskv

in,

Dok

l.A

kad.

Nau

kS

SS

R117

,88

–91

~195

7!;

Sov

.J.

At.

Ene

rgy3

,11

5–

20~1

957!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

3c 2

/mol

dm2

3 :0

–2.

41J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Pu 2

~C2O

4!3

at20

°Cin

wat

eran

din

K 2C2O

4so

lutio

nsa,

b

K2C

2O4

(c2

/mol

dm2

3 )P

u 2~C

2O4!

3

(104

c 1/m

oldm

23 )

K2C

2O4

(c2

/mol

dm2

3 )P

u 2~C

2O4!

3

(104

c 1/m

oldm

23 )

00.

0432

0.6

10.1

0.01

0.35

30.

817

.1

0.02

50.

754

0.9

22.7

0.05

1.00

1.2

34.6

0.07

51.

091.

5159

.1

0.10

1.55

1.81

84.5

0.2

2.7

2.00

106

0.3

4.04

2.41

187

a The

natu

reof

the

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.T

hein

itial

solid

used

for

the

mea

sure

men

tsis

repo

rted

tob

Pu 2

~C2O

4!3•

9H2O

.In

Ref

.1

the

crys

tallo

hydr

ate

ofpl

uton

ium~III

!ox

alat

ew

asre

port

edto

beth

ede

cahy

drat

e,P

u2~

C2O

4!3•

10H

2O.

b Inso

lutio

nsco

ntai

ning

0.01

–1.

5m

oldm2

3K

2C2O

4io

nic

stre

ngth

was

mai

ntai

ned

atan

unsp

ecifi

edco

nsta

ntva

lue

byus

ing

KC

l.

Add

ition

alin

form

atio

n:F

rom

the

incr

ease

ofth

eso

lubi

lity

ofP

u2~

C2O

4!3

with

incr

easi

ngK 2

C2O

4co

ncen

trat

ion

the

auth

ors

calc

ulat

edth

eco

nsec

utiv

ein

stab

ility

cons

tant

sof

the

Pu~C

2O4)

n(32

2n

)co

mpl

exes

.F

rom

the

solu

bilit

yof

Pu

2~C

2O4!

3in

wat

erth

eau

thor

sob

tain

edth

eso

lubi

lity

prod

uct

ofth

esa

ltas

Ksp

5@P

u31#2

@C2O

422#3 5

1.62

310

225

mol

5dm

215

at20

°C.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Sol

utio

nsof

the

desi

red

conc

entr

atio

nw

ere

stirr

edw

ithex

cess

Pu

2~C

2O4!

3•9H

2Oin

ath

erm

osta

ted

bath

for

4–

6h,

whi

chw

ases

tabl

ishe

das

suffi

cien

tto

reac

h

Not

hing

spec

ified

.

Est

imat

edE

rror

:

Co

~1!

~2!

~3!

~4!

@3 ~5!

de so 29 en a C2

Its

of we

on Pu

inf

tem

so as ac an da us Re

1 G 2 S 3 G

J

FIG

.21

.D

iplu

toni

um~I

II!–

tris

~oxa

late!

–ox

alic

acid

–ni

tric

acid

–w

ater

syst

em.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

xces

sP

u2~

C2O

4!3•

10H

2Ow

asad

ded

solu

tions

ofth

ede

sire

dco

mpo

sitio

n,an

dag

itate

din

plas

ticttl

eson

am

echa

nica

lsha

ker.

Asc

orbi

cac

idw

asus

edto

oid

oxid

atio

nof

Pu~I

II!.

At

inte

rval

sal

iquo

tsof

the

lutio

nsw

ere

with

draw

n,fil

tere

d,an

dan

alyz

edfo

rto

nium

,ac

id,

and

oxal

ate.

Ana

lyse

sw

ere

cont

inue

dun

tilsy

stem

reac

hed

equi

libriu

m,

whi

chto

ok16

h.T

henc

entr

atio

nsof

acid

and

oxal

ate

wer

ede

term

ined

bytit

ratio

nth

NaO

Han

dK

MnO

4so

lutio

ns,

resp

ectiv

ely.

The

met

hod

plut

oniu

man

alys

isw

asno

tsp

ecifi

ed.

239 P

u~III

!ox

alat

ew

aspr

epar

edby

diss

olvi

ngpu

reP

um

etal

insu

lfam

icac

id,

addi

ngto

this

solu

tion

0.05

mol

dm23

asco

rbic

acid

tost

abili

zeth

eP

u~III

!st

ate,

and

prec

ipita

ting

Pu

~III

!ox

alat

eby

addi

ng0.

1m

oldm

23

oxal

icac

idso

lutio

n.T

hepr

ecip

itate

was

filte

red,

was

hed

with

0.1

mol

dm23

oxal

icac

id,

and

air

drie

d.T

hepr

oduc

tw

asth

ebr

ight

blue

–gr

een

deca

hydr

ate.

All

othe

rch

emic

als

wer

ere

agen

tgr

ade.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 I.L.

Jenk

ins,

F.H

.Moo

re,a

ndM

.J.W

ater

man

,J.I

norg

.Nuc

l.C

hem

.27,

77~1

965!

.

658658 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Dip

luto

nium

~III

!tr

is~o

xala

te!;

Pu 2

~C2O

4!3;

@331

6-65

-2#~2

!O

xalic

acid

;C 2

H2O

4;@1

44-6

2-7#

~3!

Nitr

icac

id;

HN

O3;

@769

7-37

-2#~4

!A

scor

bic

acid

;C 6

H8O

6;@5

0-81

-7#

~5!

Wat

er;

H 2O

;@77

32-1

8-5#

G.A

.Bur

ney

and

J.A

.Por

ter,

Inor

g.N

ucl.

Che

m.L

ett.

3,79

–85

~196

7!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

4c 2

/mol

dm2

3 :0.

09–

0.3

c 3/m

oldm

23 :

0.5

–3.

1c 4

/mol

dm2

3 :0.

05

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

at21

°Cof

Pu 2~

C2O

4!3

inH

NO

3–

C2H

2O4–

asco

rbic

acid

solu

tions

The

solu

bilit

yof

Pu 2~

C2O

4!3

at21

°Cin

HN

O 3–

C2H

2O4

solu

tions

cont

aini

ng0.

05m

oldm2

3as

corb

icac

idw

ere

pres

ente

din

grap

hica

lfo

rm~s

eeF

ig.

21!.

The

natu

reof

the

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.P

resu

mab

lyit

was

the

deca

hydr

ate,

Pu 2

~C2O

4!3•

10H

2O,

@#,

whi

chw

asre

port

edto

prec

ipita

tefr

omH

NO

3-C

2H2O

4so

lutio

ns.1

Me

Iso

to bo av so plu

the

co wi

for


e

plut

oniu

mw

asde

term

ined

byaco

untin

g.T

hepr

oced

ure

was

repe

ated

until

equi

libriu

mw

asre

ache

d,w

hich

usua

llyto

okle

ssth

en30

min

.

acid

solu

tion.

Afte

r30

min

stirr

ing,

the

prec

ipita

tew

asfil

tere

dan

dw

ashe

dw

ith0.

1m

oldm2

3ox

alic

acid

.Sou

rce

and

purit

yof

othe

rch

emic

als

wer

eno

tsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Dip

luto

nium

~III

!tr

is~o

xala

te!;

Pu 2

~C2O

4!3;

@331

6-65

-2#O

xalic

acid

;C 2

H2O

4;@1

44-6

2-7#

Nitr

icac

id;

HN

O3;

@769

7-37

-2#A

scor

bic

acid

;C 6

H8O

6;@5

0-81

-7#

Wat

er;

H 2O

;@7

732-

18-5#

S.

P.

Has

ilkar

,N

.B

.K

hede

kar,

K.

Cha

nder

,A

.V

.Ja

dhav

,an

dH

.C

.Ja

in,

J.R

adio

anal

.N

ucl.

Che

m.

185,

119

–25

~199

4!.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

dm2

3 :0.

02–

0.20

/mol

dm2

3 :0.

5–

2.0

/mol

dm2

3 :0.

01–

0.1

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Pu 2

~C2O

4!3

at25

°Cin

HN

O 3–

C2H

2O4–

C6H

8O6

solu

tions

a

HN

O3

3/m

oldm

23 )

C2H

2O4

(c2

/mol

dm2

3 )P

u~m

gdm

23 !

Pu 2

~C2O

4!3b

(104

c 1/

mol

dm2

3 !c

HN

O3

(c3

/mol

dm2

3 )C

2H2O

4

(c2

/mol

dm2

3 )P

u~m

gdm

23 !

Pu 2

~C2O

4!3b

(104

c 1/

mol

dm2

3 !c

0.5

0.20

10.7

0.22

41.

50.

2024

.10.

504

1.0

0.02

123.

42.

582.

00.

0213

79.5

28.8

0.05

51.5

1.08

0.05

417.

38.

73

0.10

19.9

0.41

60.

1017

1.7

3.59

0.20

14.6

0.30

50.

2052

.51.

10

0.20

10.9

0.22

80.

2044

.80.

937

hena

ture

ofth

eeq

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

The

initi

also

lidus

edfo

rth

em

easu

rem

ents

isre

port

edto

beu 2

~C2O

4!3•

10H

2O.

llso

lutio

nsco

ntai

ned

0.05

mol

dm23

asco

rbic

acid

.al

cula

ted

byco

mpi

ler

usin

gA r~P

u!5

239.

053.

HN

O3

3/m

oldm

23 )

C6H

8O6

(c4

/mol

dm2

3 )P

u~m

gdm

23 !

Pu 2

~C2O

4!3b

(105

c 1/

mol

dm2

3 )cH

NO

3

(c3

/mol

dm2

3 )C

6H8O

6

(c4

/mol

dm2

3 )P

u~m

gdm

23 !

Pu 2

~C2O

4!3b

(104

c 1/

mol

dm2

3 !c

1.0

0.01

18.6

3.89

2.0

0.01

63.7

1.33

0.02

16.2

3.39

0.02

61.5

1.29

0.05

12.5

2.61

0.05

60.1

1.26

0.10

13.6

2.85

0.10

58.1

1.22

b All

solu

tions

cont

aine

d0.

20m

oldm2

3ox

alic

acid

.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Dip

luto

nium

~III

!tr

is~o

xala

te!;

Pu 2

~C2O

4!3;

@331

6-65

-2#~2

!O

xalic

acid

;C 2

H2O

4;@1

44-6

2-7#

~3!

Nitr

icac

id;

HN

O3;

@769

7-37

-2#~4

!H

ydra

zine

;N 2

H4;

@302

-01-

2#~5

!W

ater

;H 2

O;

@773

2-18

-5#

G.C

hene

au,C

ente

rP

rod.

Plu

toni

um,M

arco

ule,

Fra

nce,

Rap

port

CE

A-R

-410

9,19

71.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

6–

341

c 2/m

oldm

23 :

0.20

c 3/m

oldm

23 :

1.45

c 4/m

oldm

23 :

0.16

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Pu 2

~C2O

4!3

inH

NO

3–

C2H

2O4–

N2H

4so

lutio

nsas

afu

nctio

nof

tem

pera

ture

a

Tem

pera

ture

~°C

!P

u~m

gdm

23 !

Pu 2

~C2O

4!3

(104

c 1/m

oldm

23 )b

2346

0.94

9

3067

1.40

4012

12.

53

5020

54.

29

6036

57.

67

6854

711

.5

a The

natu

reof

the

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.T

hein

itial

solid

used

for

the

mea

sure

men

tsis

repo

rted

tob

Pu 2

~C2O

4!3•

10H

2O.

All

solu

tions

cont

aine

d1.

45m

oldm2

3H

NO

3,0.

20m

oldm

23

oxal

icac

id,

and

0.16

mol

dm23

hydr

azin

e.b C

alcu

late

dby

com

pile

rus

ing

A r~P

u!5

239.

053.

Add

ition

alin

form

atio

n:A

lso

repo

rted

,in

grap

hica

lfor

m,

was

the

solu

bilit

yof

Pu

2~C

2O4!

3at

23°C

inH

NO 3

–C

2H2O

4so

lutio

nsco

ntai

ning

eith

er0.

1m

oldm2

3

N2H

4or

0.05

mol

dm2

3as

corb

icac

id.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Sol

utio

nsof

the

desi

red

conc

entr

atio

nw

ere

stirr

edw

ithex

cess

Pu

2~C

2O4!

3•10

H2O

ina

ther

mos

tate

dba

th.

At

inte

rval

sal

iquo

tsw

ere

with

draw

n,fil

tere

d,an

d

Gre

enP

u 2~C

2O4!

3•10

H2O

was

obta

ined

bypr

ecip

itatin

gP

u31

from

aso

lutio

nco

ntai

ning

11g

dm23

Pu,

1.2

mol

dm2

3H

NO

3,an

d0.

05m

oldm

23

asco

rbic

acid

with

0.70

mol

dm23

oxal

ic

Co

~1!

~2!

~3!

~4!

~5!

Va

T/

c 2 c 3 c 4 (c a T P b A c C (c

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Dip

luto

nium

~III

!tr

is~o

xala

te!;

Pu 2

~C2O

4!3;

@331

6-65

-2#O

xalic

acid

;C 2

H2O

4;@1

44-6

2-7#

Hyd

roge

nch

lorid

e;H

Cl;@

7647

-01-

0#A

scor

bic

acid

;C 6

H8O

6;@5

0-81

-7#

Wat

er;

H 2O

;@7

732-

18-5#

S.

P.

Has

ilkar

,N

.B

.K

hede

kar,

K.

Cha

nder

,A

.V

.Ja

dhav

,an

dH

.C

.Ja

in,

J.R

adio

anal

.N

ucl.

Che

m.

185,

119

–25

~199

4!.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

dm2

3 :0.

02–

0.20

/mol

dm2

3 :0.

5–

2.0

/mol

dm2

3 :0.

01–

0.1

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Pu 2

~C2O

4!3

at25

°Cin

HN

O 3–

C2H

2O4–

C6H

8O6

solu

tions

a

HC

l

3/m

oldm

23 )

C2H

2O4

(c2

/mol

dm2

3 )P

u~m

gdm

23 !

Pu 2

~C2O

4!3b

(104

c 1/

mol

dm2

3 )cH

Cl

(c3

/mol

dm2

3 )C

2H2O

4

(c2

/mol

dm2

3 )P

u~m

gdm

23 !

Pu 2

~C2O

4!3b

(104

c 1/

mol

dm2

3 )c

0.5

0.20

13.5

0.28

21.

50.

2032

.80.

686

1.0

0.02

120.

82.

532.

00.

0275

3.3

15.8

0.05

35.1

0.73

40.

0529

1.6

6.10

0.10

24.1

0.50

40.

1099

.52.

08

0.20

14.6

0.30

50.

2039

.70.

830

0.20

10.9

0.30

50.

2061

.61.

29

hena

ture

ofth

eeq

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

The

initi

also

lidus

edfo

rth

em

easu

rem

ents

isre

port

edto

beu 2

~C2O

4!3•

10H

2O.

llso

lutio

nsco

ntai

ned

0.05

mol

dm23

asco

rbic

acid

.al

cula

ted

byco

mpi

ler

usin

gA r~P

u!5

239.

053.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.A

bout

450

mg

ofP

u~I

II!

oxal

ate

wde

rw

aseq

uilib

rate

dw

ith10

mL

solu

tion

ofth

ede

sire

dm

posi

tion

for1

hin

40m

Leq

uilib

ratio

ntu

beus

ing

ach

anic

alsh

aker

.T

hepr

ecip

itate

was

allo

wed

tose

ttle

for

h,an

dce

ntrif

uged

.M

etho

dof

plut

oniu

mde

term

inat

ion

inth

esa

tura

ted

solu

tions

not

spec

ified

.

Plu

toni

umst

ock

solu

tion

in4

mol

dm23

HN

O3

was

prep

ared

from

plut

oniu

mfr

eshl

ypu

rified

byio

nex

chan

gepr

oced

ure

acco

rdin

gto

Ref

.1.

All

othe

rch

emic

als

used

wer

eof

A.R

./G.R

.gr

ade.

Pu 2~

C2O

4!3•

10H

2Ow

asob

tain

edby

prec

ipita

tion.

Plu

toni

umw

asre

duce

dto

Pu

31by

mea

nsof

asco

rbic

acid

soas

tom

aint

ain

0.05

mol

dm2

3ex

cess

ofth

ela

tter.

Cal

cula

ted

exce

ssov

erth

est

oich

iom

etric

amou

ntof

oxal

icw

asad

ded

soth

atth

esu

pern

atan

tco

ntai

ned

0.02

–0.

2m

oldm

23

oxal

icac

id.

The

prec

ipita

tew

asal

low

edto

settl

efo

r30

min

,an

dth

ence

ntrif

uged

.

Est

imat

edE

rror

:T

empe

ratu

re:

tem

pera

ture

repo

rted

asap

prox

imat

eva

lue

ofro

omte

mpe

ratu

re;

the

syst

ems

wer

eno

tth

erm

osta

ted

durin

geq

uilib

ratio

n.S

olub

ility

:fr

omth

edu

plic

ate

mea

sure

men

tsin

0.2

mol

dm2

3

oxal

icac

idso

lutio

nsth

eco

mpi

ler

estim

ates

prec

isio

nas

low

as6

20%

.

Ref

eren

ces:

1 J.L.

Ray

nan

dJ.

Whe

elw

right

,U

SA

EC

,R

epor

tH

W-5

5893

,19

59.

660660 JIRI HALA

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Abo

ut45

0m

gof

Pu

~III

!ox

alat

epo

wde

rw

aseq

uilib

rate

dw

ith10

mL

solu

tion

ofth

ede

sire

dco

mpo

sitio

nfor

1h

in40

mL

equi

libra

tion

tube

usin

ga

mec

hani

cals

hake

r.T

hepr

ecip

itate

was

allo

wed

tose

ttle

for

1/2

h,an

dce

ntrif

uged

.M

etho

dof

plut

oniu

mde

term

inat

ion

inth

esa

tura

ted

solu

tions

not

spec

ified

.

Plu

toni

umst

ock

solu

tion

in4

mol

dm23

HN

O3

was

prep

ared

from

plut

oniu

mfr

eshl

ypu

rified

byio

nex

chan

gepr

oced

ure

acco

rdin

gto

Ref

.1.

All

othe

rch

emic

als

used

wer

eof

A.R

./G.R

.gr

ade.

Pu 2~

C2O

4!3•

10H

2Ow

asob

tain

edby

prec

ipita

tion.

Plu

toni

umat

the

desi

red

conc

entr

atio

nw

asre

duce

dto

Pu

31by

mea

nsof

asco

rbic

acid

soas

tom

aint

ain

0.05

mol

dm2

3ex

cess

ofth

ela

tter.

Cal

cula

ted

exce

ssov

erth

est

oich

iom

etric

amou

ntof

oxal

icw

asad

ded

soth

atth

esu

pern

atan

tcon

tain

ed0.

02–

0.2

mol

dm2

3ox

alic

acid

.T

hepr

ecip

itate

was

allo

wed

tose

ttle

for

30m

inan

dth

ence

ntrif

uged

.

Est

imat

edE

rror

:T

empe

ratu

re:

tem

pera

ture

repo

rted

asap

prox

imat

eva

lue

ofro

omte

mpe

ratu

re;

the

syst

ems

wer

eno

tth

erm

osta

ted

durin

geq

uilib

ratio

n.S

olub

ility

:fr

omth

edu

plic

ate

mea

sure

men

tsin

0.2

mol

dm2

3

oxal

icac

idso

lutio

nsth

eco

mpi

ler

estim

ates

prec

isio

nas

low

as6

15%

.

Ref

eren

ces:

1 J.L.

Ray

nan

dJ.

Whe

elw

right

,U

SA

EC

,R

epor

tH

W-5

5893

,19

59.

Co

~1!

~2!

~3!

~4!

~5!

Va

T/

c 2 c 3 c 4 (c a T P b A c C Me

Iso

po co me

1/2


n.mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Plu

toni

um~I

V!

bis~

oxal

ate!;

Pu~

C2O

4!2;

@132

78-8

1-4#

Per

chlo

ricac

id;

HC

lO 4;

@760

1-90

-3#W

ater

;H 2

O;

@773

2-18

-5#

A.

I.M

oskv

inan

dA

.D

.G

elm

an,

Zh.

Neo

rg.

Khi

m,3,

956

–6

~195

8!;

Dok

l.A

kad.

Nau

kS

SS

R118

,49

3–

6~1

958!

.

riabl

es:

Pre

pare

dby

:

K:2

93/m

oldm

23 :0

–1.

0J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofP

u~C2O

4!2

inw

ater

and

HC

lO 4so

lutio

nsa

HC

lO4

2/m

oldm

23 )

Pu~

C2O

4!2•

6H2O

~mg

dm2

3 !P

u~C

2O4!

2

(104

c 1/m

oldm

23 )

Ksp

c

(1022

mol

3dm

29 )

0b

1.01

1.14

0.96

b

0.1

290.

5b

0.5

531.

017

0.75

b1.

294

1.0

811.

573

hena

ture

ofth

eeq

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

The

com

pile

ras

sum

esth

eso

lidph

ase

isth

ehe

xahy

drat

e,u~

C2O

4!2•

6H2O

,@2

6588

-74-

9#,w

hich

prec

ipita

tes

from

acid

icso

lutio

ns.

1

otre

port

ed.

sp5

@Pu4

1#@

C2O

422#2

;ca

lcul

ated

byth

eau

thor

sas

Ksp

5K

Ka12

Ka22

usin

gth

eeq

uilib

rium

cons

tant

for

the

reac

tion

u~C

2O4!

2•6H

2O~s

!14H

1�

Pu41

12C

2H2O

416H

2O,

K5

@Pu4

1#@

C2H

2O4#

2@H

1#2

45

13

102

11m

ol2

1dm

3 ,an

dth

edi

ssoc

iatio

nco

n-an

tsof

oxal

icac

idKa1

50.

108

andK

a25

6.43

102

5m

oldm

23

~sou

rce

ofth

eco

nsta

nts

not

repo

rted!.

ditio

nali

nfor

mat

ion:

epH

ofth

esa

tura

ted

solu

tions

ofP

u~C

2O4!

2in

wat

erw

as4.

460.

05.

By

anal

ogy

with

U~C2O

4!2,

2th

eau

thor

sex

plai

ned

this

inte

rms

acid

prop

ertie

sof

Pu~C

2O4!

2,i.e

.,by

the

equi

libriu

mP

u~C2O

4!2~

H2O

! n�

Pu~

C2O

4!~H

2O! n

211

H1

1C

2O422

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

eis

othe

rmal

met

hod3w

asus

ed.

Fre

shly

prec

ipita

ted

~C2O

4!2•

6H2O

was

agita

ted

with

wat

eror

HC

lO 4so

lutio

nsth

ede

sire

dco

ncen

trat

ion

ina

ther

mos

tate

dba

thfo

r4

–6

hic

hw

asfo

und

suffi

cien

tfo

req

uilib

rium

tobe

reac

hed.

The

toni

umco

ncen

trat

ion

inth

esa

tura

ted

solu

tions

was

dete

rmin

edra

diom

etric

ally

.

Pu~

C2O

4!2•

6H2O

was

obta

ined

bypr

ecip

itatio

nof

Pu

~IV

!w

ithox

alic

acid

,an

dw

ashi

ngth

epr

ecip

itate

with

wat

er.

1

Est

imat

edE

rror

:T

empe

ratu

re:6

0.02

K~a

utho

rs!.

Sol

ubili

ty:

from

the

mea

sure

men

tsin

wat

erth

eco

mpi

ler

estim

ates

the

prec

isio

nof6

10%

.

Ref

eren

ces:

1 I.L.

Jenk

ins,

F.H

.Moo

re,a

ndM

.J.W

ater

man

,J.I

norg

.Nuc

l.C

hem

.27,

81~1

965!

.2 A

.A

.G

rinbe

rgan

dI.

Pet

rzha

k,T

rudy

Rad

iev.

Inst

.,K

him

.G

eokh

im.,7

,50

~195

6!.

3 A.

I.M

oskv

inan

dA

.D

.G

elm

an,

Zh.

Neo

rg.

Khi

m.3,

962

~195

8!.



7.7.

Plu

toni

um„IV…

Oxa

late

7.7.

1.E

valu

atio

nof

the

Pu

„C

2O4…

2¿H

2OS

yste

m

Com

pone

nts:

Eva

luat

or:

~1!

Plu

toni

um~I

V!

bis~

oxal

ate!;

Pu~

C2O

4!2;

@132

78-8

1-4#

~2!

Wat

er;

H 2O

;@7

732-

18-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

611

37B

rno,

Cze

chR

epub

lic,

May

2000

Crit

ical

Eva

luat

ion:

Thr

eeva

lues

for

the

solu

bilit

y,in

mol

dm23 ,

ofP

u~C

2O4!

2in

wat

erha

vebe

enpu

blis

hed,

i.e.,

4.71310

23

at29

8K

,11.

883

102

4at

300

K,2

and

1.03

310

24

at29

3K

.3T

here

seem

sto

beso

me

unce

rtai

nty

inth

ese

valu

es.

Firs

t,th

eva

lue

repo

rted

byD

awso

n1

ishi

gher

bym

ore

than

1or

der

ofm

agni

tude

com

pare

dto

othe

rtw

ova

lues

.The

reas

onfo

rth

isca

nnot

beid

entifi

edfr

omth

epu

blis

hed

info

rmat

ioP

artic

ular

ly,

mis

sing

info

rmat

ion

oneq

uilib

ratio

ntim

ein

Ref

.1

mak

esan

yco

nclu

sion

diffi

cult.

Inth

isre

spec

tit

isno

tew

orth

yth

ata

diffe

renc

eof

the

sam

ety

pebe

twee

nD

awso

n’s

and

othe

rau

thor

s’w

ork

isal

soob

serv

edfo

rth

eso

lubi

lity

ofP

u~C

2O4!

2in

aque

ous

solu

tions

ofH

NO 3

~see

Eva

luat

ion

for

the

Pu~C

2O4!

2–

HN

O3–

H2O

syst

em!.

Sec

ond,

itse

ems

that

anal

mos

ttw

ofol

din

crea

sein

the

solu

bilit

yon

goin

gfr

om29

3K3

to30

0K2

isra

ther

unus

ual.

For

thes

ere

ason

sno

neof

the

valu

espu

blis

hed

can

begi

ven

pref

eren

ce.

Ref

eren

ces:

1 J.K

.D

awso

n,A

.E.R

.E.~H

arw

ell!,

Rep

ort

C/M

92,

1950

.2 C

.J.

Man

dleb

erg,

K.

E.

Fra

ncis

,an

dR

.S

mith

,J.

Che

m.

Soc

.24

64~1

961!

.3 A

.I.

Mos

kvin

and

A.

D.

Gel

man

,Z

h.N

eorg

.K

him

.3,95

6~1

958!

;A

.D

.G

elm

anan

dA

.I.

Mos

kvin

,D

okl.

Aka

d.N

auk

SS

SR11

8,49

3~1

958!

.

Co

~1!

~2!

~3!

Va

T/

c 2 (c a T P b N c K P st Ad

Th

of Me

Th

Pu

of wh

plu

J

rs

is es is

FIG

.22

.P

luto

nium

~IV

!bi

s~ox

alat

e!–

nitr

icac

id–

wat

ersy

stem

.

Ref

eren

ces:

1 W.

H.

Rea

s,N

atl.

Nuc

l.E

nerg

yS

er.

Div

.IV1

4B,

423

~194

9!.

2 J.K

.D

awso

n,A

.E

.R

.E

.~Har

wel

l!,R

epor

tC

/M92

,19

50.

3 A.

I.M

oskv

inan

dA

.D

.G

elm

an,

Zh.

Neo

rg.

Khi

m.3,

956

~195

8!.

4 A.

D.

Gel

man

and

A.

I.M

oskv

in,

Dok

l.A

kad.

Nau

kS

SS

R118,

493

~195

8!.

5 C.

J.M

andl

eber

g,K

.E

.F

ranc

is,

and

R.

Sm

ith,

J.C

hem

.S

oc.

2464

~196

1!.

6 G.

C.

Cha

prue

ta

l.,P

roce

edin

gsN

atio

nalC

hem

ical

Rad

ioch

emic

alS

ympo

sium

1981

,p.

561

~198

3!.

662662 JIRI HALA

7.7.

2.E

valu

atio

nof

the

Pu

„C

2O4…

2¿H

NO

3¿H

2OS

yste

m

Com

pone

nts:

Eva

luat

or:

~1!

Plu

toni

um~I

V!

bis~

oxal

ate!;

Pu~

C2O

4!2;

@132

78-8

1-4#

~2!

Nitr

icac

id;

HN

O3;

@769

7-37

-2#~3

!W

ater

;H 2

O;

@773

2-18

-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

611

37B

rno,

Cze

chR

epub

lic,

May

2000

Crit

ical

Eva

luat

ion:

Sol

ubili

tyda

tafo

rth

issy

stem

are

avai

labl

ein

six

docu

men

ts,a

ndth

ere

sults

offiv

eof

them

are

sum

mar

ized

inF

ig.2

2.In

the

pape

ofM

andl

eber

get

al.,

5an

dR

eas1

the

solu

bilit

ies

wer

ere

port

edfo

rth

equ

arte

rnar

ysy

stem

Pu

~C2O

4!2–

HN

O3–

oxal

icac

id–

H 2O

,fr

omw

hich

the

valu

esfo

rze

roco

ncen

trat

ion

ofox

alic

acid

have

been

extr

acte

dfo

rth

esa

keof

com

paris

onw

ithot

her

Pu

~C2O

4!2–

HN

O3–

H2O

data

.E

xcep

tfo

rtw

osi

ngle

valu

esfo

r0.

75m

oldm2

3H

NO

3re

port

edat

298

K,1,2

othe

rm

easu

rem

ents

wer

eca

rrie

dou

tat

diffe

rent

tem

pera

ture

s.T

heda

tapu

blis

hed

byIn

dian

auth

ors

6ha

veno

tbe

enco

mpi

led

sinc

eth

eau

thor

sdi

dno

tre

port

the

tem

pera

ture

ofth

eir

mea

sure

men

ts,

and

pres

ente

dth

eso

lubi

lity

data

for

Pu

~C2O

4!2

inH

NO

3–

oxal

icac

idso

lutio

nsin

grap

hica

lfo

rmof

poor

qual

ity.

The

irva

lues

ofP

u~C2O

4!2

solu

bilit

yin

1an

d2

mol

dm2

3H

NO

3ar

ehi

gher

byro

ughl

y1

orde

rof

mag

nitu

deth

anth

ose

ofR

ef.

5.F

orth

eev

alua

tion

ofth

eso

lubi

lity

inth

eP

u~C

2O4!

2–

HN

O3–

H2O

syst

em,

the

obse

rvat

ion

ofR

eas

1se

ems

tobe

ofim

port

ance

.T

heau

thor

cons

ider

edhi

sso

lubi

lity

valu

eas

erro

neou

sly

high

due

toox

idat

ion

ofox

alic

acid

byH

NO

3un

der

cata

lytic

actio

nof

plut

oniu

m.

Thi

sm

aybe

the

reas

onfo

rth

edi

scre

panc

esam

ong

the

resu

ltsob

tain

edby

diffe

rent

auth

ors.

Afa

ctw

hich

seem

sto

supp

ort

this

view

that

aqu

alita

tive

corr

elat

ion

can

befo

und

betw

een

the

solu

bilit

yda

taan

dth

ere

spec

tive

equi

libra

tion

time

appl

ied.

Thu

sth

elo

wes

tval

uw

ere

repo

rted

byM

oskv

inan

dG

elm

an3,4

who

used

4–

6h

equi

libra

tion

time

whi

leR

eas

1an

dM

andl

eber

get

al.5

equi

libra

ted

the

syst

ems

for

1–

2w

eeks

,an

d2

–3

wee

ks,

resp

ectiv

ely.~D

awso

n2di

dno

tre

port

the

equi

libra

tion

time

used

.!

Thu

sit

seem

sth

atth

eP

u~C

2O4!

2–

HN

O3–

H2O

syst

emis

ano

nequ

ilibr

ium

one,

and

the

publ

ishe

dda

taca

nse

rve

asa

qual

itativ

ele

adon

ly.

The

cata

lytic

oxid

atio

npr

oces

sco

uld

wel

lbe

ofgr

eate

rim

prot

ance

than

are

the

diffe

renc

esin

tem

pera

ture

used

bydi

ffere

ntau

thor

s.N

otew

orth

yin

thre

spec

tse

ems

also

tobe

the

fact

that

whi

lese

vere

alst

udie

sw

ere

perf

orm

edon

the

solu

bilit

yof

U~C

2O4!

2in

aque

ous

solu

tions

ofhy

droc

hlor

ic,

perc

hlor

ic,

and

sulfu

ricac

ids,

nosu

chst

udy

has

been

repo

rted

onth

eU

~C2O

4!2–

HN

O3–

H2O

syst

em.


te,

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Plu

toni

um~I

V!

bis~

oxal

ate!;

Pu~

C2O

4!2;

@132

78-8

1-4#

Nitr

icac

id;

HN

O3;

@769

7-37

-2#W

ater

;H 2

O;

@773

2-18

-5#

J.K

.D

awso

n,R

epor

tA

.E

.R

.E

.,H

arw

ell,

C/M

92,

1960

.

riabl

es:

Pre

pare

dby

:

K:2

98/m

oldm

23 :0

.75

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofP

u~C2O

4!2

in0.

75m

oldm

23

HN

O3

isre

port

edto

be0.

13g

dm23

Pu

~5.3

3310

24

mol

dm2

3;

com

pile

r!.T

hem

posi

tion

ofth

eeq

uilib

rium

solid

phas

ew

asno

trep

orte

dbu

tpre

sum

ably

itis

the

hexa

hydr

ate,

Pu

~C2O

4!2•

6H2O

,@26

588-

74-9#

,whi

chec

ipita

tes

out

from

acid

solu

tions

.1

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

was

used

.G

lass

stop

pere

dco

ntai

ner

ntai

ning

the

acid

solu

tion

and

exce

ssP

u~I

V!

oxal

ate

was

ced

ina

met

alco

ntai

ner

toex

clud

elig

ht,

and

this

intu

rns

susp

ende

din

ath

erm

osta

ted

bath

.T

heco

ntai

ner

was

aken

man

ually

from

time

totim

e.T

heac

tual

equi

libra

tion

ew

asno

tre

port

ed.

The

satu

rate

dso

lutio

nw

asce

ntrif

uged

,d

aliq

uots

wer

eta

ken

for

the

dete

rmin

atio

nof

Pu

byaun

ting.

An

argo

npr

opor

tiona

lcha

mbe

rw

ith35

%ge

omet

ryan

elec

tros

cope

wer

eus

edfo

rco

untin

g.

Pu~

IV!

oxal

ate

was

prep

ared

byad

ding

oxal

icac

idcr

ysta

lsto

anal

mos

tne

utra

lso

lutio

nof

Pu~IV

!ni

trat

e.T

hepr

ecip

itate

was

cent

rifug

edan

dw

ashe

dtw

ice

with

wat

er.

Ana

lysi

sof

the

prod

uct

was

not

repo

rted

.

Est

imat

edE

rror

:T

empe

ratu

re:

not

repo

rted

.S

olub

ility

:65%

~aut

hor!.

Ref

eren

ces:

1 I.L.

Jenk

ins,

F.H

.Moo

re,a

ndM

.J.W

ater

man

,J.I

norg

.Nuc

l.C

hem

.27,

81~1

965!

.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Plu

toni

um~I

V!

bis~

oxal

ate!;

Pu~

C2O

4!2;

@132

78-8

1-4#

~2!

Nitr

icac

id;

HN

O3;

@769

7-37

-2#~3

!W

ater

;H 2

O;

@773

2-18

-5#

A.

I.M

oskv

inan

dA

.D

.G

elm

an,

Zh.

Neo

rg.

Khi

m,3,

956

–6

~195

8!;

Dok

l.A

kad.

Nau

kS

SS

R118

,49

3–

6~1

958!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:293

c 2/m

oldm

23 :0

.025

–1.

0J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofP

u~C2O

4!2

inH

NO

3so

lutio

nsa

HN

O3

(c2

/mol

dm2

3 )P

u~C

2O4!

2•6H

2O~m

gdm

23 !

Pu~

C2O

4!2

(105

c 1/m

oldm

23 )

0.02

525

4.8

0.1

305.

7

0.25

5410

.3

0.5

7213

.8

1.0

144

27.5

a The

natu

reof

the

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.T

heco

mpi

ler

assu

mes

the

solid

phas

ebe

the

hexa

hydr

aP

u~C

2O4!

2•6H

2O,

@265

88-7

4-9#

whi

chpr

ecip

itate

sfr

omac

idic

solu

tions

.1

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

isot

herm

alm

etho

d2w

asus

ed.

Fre

shly

prec

ipita

ted

Pu~

C2O

4!2•

6H2O

was

agita

ted

with

wat

eror

HC

lO 4so

lutio

nsof

the

desi

red

conc

entr

atio

nin

ath

erm

osta

ted

bath

for

4–

6h

whi

chw

asfo

und

suffi

cien

tfo

req

uilib

rium

tobe

reac

hed.

The

plut

oniu

mco

ncen

trat

ion

inth

esa

tura

ted

solu

tions

was

dete

rmin

edra

diom

etric

ally

.

Pu~

C2O

4!2•

6H2O

was

obta

ined

bypr

ecip

itatio

nof

Pu

~IV

!w

ithox

alic

acid

,an

dw

ashi

ngth

epr

ecip

itate

with

wat

er.

1

Est

imat

edE

rror

:T

empe

ratu

re:6

0.02

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 I.L.

Jenk

ins,

F.H

.Moo

re,a

ndM

.J.W

ater

man

,J.I

norg

.Nuc

l.C

hem

.27,

81~1

965!

.2 A

.I.

Mos

kvin

and

A.

D.

Gel

man

,Z

h.N

eorg

.K

him

.3,96

2~1

958!

.

Co

~1!

~2!

~3!

Va

T/

c 2 co pr Me

Iso

co pla

wa

sh tim an co or

J

te,

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Plu

toni

um~I

V!

bis~

oxal

ate!;

Pu~

C2O

4!2;

@132

78-8

1-4#

Am

mon

ium

oxal

ate;

(NH 4!

2C2O

4;@1

113-

38-8#

Wat

er;

H 2O

;@7

732-

18-5#

J.K

.D

awso

n,R

epor

tA

.E

.R

.E

.,H

arw

ell,

C/M

92,

1960

.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

dm2

3 :0

–0.

13J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofP

u~C2O

4!2

inw

ater

and~

NH

4!2C

2O4

solu

tions

a

~NH

4!2C

2O4

(c2

/mol

dm2

3 )P

u~g

dm2

3 !P

u~C

2O4!

2

(103

c 1/m

oldm

23 )b

01.

154.

81

0.02

1.38

5.78

0.07

32.

08.

37

0.13

2.62

10.9

2

heco

mpo

sitio

nof

the

equi

libriu

mso

lidph

ase

was

not

repo

rted

.al

cula

ted

byco

mpi

ler

usin

gA r~P

u!5

239.

053.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

was

used

.G

lass

stop

pere

dco

ntai

ner

ntai

ning

the

(NH 4

! 2C

2O4

solu

tion

and

exce

ssP

u~I

V!

oxal

ate

spl

aced

ina

met

alco

ntai

ner

toex

clud

elig

ht,

and

this

inn

was

susp

ende

din

ath

erm

osta

ted

bath

.T

heco

ntai

ner

was

aken

man

ually

from

time

totim

e.T

heac

tual

equi

libra

tion

ew

asno

tre

port

ed.

The

satu

rate

dso

lutio

nw

asce

ntrif

uged

,d

aliq

uots

wer

eta

ken

for

the

dete

rmin

atio

nof

Pu

byaun

ting.

An

argo

npr

opor

tiona

lcha

mbe

rw

ith35

%ge

omet

ryan

elec

tros

cope

wer

eus

edfo

rco

untin

g.

Pu~

IV!

oxal

ate

was

prep

ared

byad

ding

oxal

icac

idcr

ysta

lsto

anal

mos

tne

utra

lso

lutio

nof

Pu~IV

!ni

trat

e.T

hepr

ecip

itate

was

cent

rifug

edan

dw

ashe

dtw

ice

with

wat

er.

Ana

lysi

sof

the

prod

uct

was

not

repo

rted

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:6

5%~a

utho

r!.

664664 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Plu

toni

um~I

V!

bis~

oxal

ate!;

Pu~

C2O

4!2;

@132

78-8

1-4#

~2!

Sul

furic

acid

;H 2

SO

4;@7

664-

93-9#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

A.

I.M

oskv

inan

dA

.D

.G

elm

an,

Zh.

Neo

rg.

Khi

m.3,

956

–61

~195

8!;

Dok

l.A

kad.

Nau

kS

SS

R118

,49

3–

6~1

958!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:293

c 2/m

oldm

23 :0

.012

5–

0.50

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofP

u~C2O

4!2

inH

2SO

4so

lutio

nsa

H2S

O4

(c2

/mol

dm2

3 )P

u~C

2O4!

2•6H

2O~m

gdm

23 !

Pu~

C2O

4!2

(104

c 1/m

oldm

23 )

0.01

2568

1.3

0.05

971.

9

0.25

200

5.0

0.50

418

8.0

a The

natu

reof

the

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.T

heco

mpi

ler

assu

mes

the

solid

phas

ebe

the

hexa

hydr

aP

u~C

2O4!

2•6H

2O,

@265

88-7

4-9#,

whi

chpr

ecip

itate

sfr

omac

idic

solu

tions

.1

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

isot

herm

alm

etho

d2w

asus

ed.

Fre

shly

prec

ipita

ted

Pu~

C2O

4!2•

6H2O

was

agita

ted

with

H 2SO

4so

lutio

nsof

the

desi

red

conc

entr

atio

nin

ath

erm

osta

ted

bath

for

4–

6h

whi

chw

asfo

und

suffi

cien

tfo

req

uilib

rium

tobe

reac

hed.

The

plut

oniu

mco

ncen

trat

ion

inth

esa

tura

ted

solu

tions

was

dete

rmin

edra

diom

etric

ally

.

Pu~

C2O

4!2•

6H2O

was

obta

ined

bypr

ecip

itatio

nof

Pu

~IV

!w

ithox

alic

acid

,an

dw

ashi

ngth

epr

ecip

itate

with

wat

er.

1

Est

imat

edE

rror

:T

empe

ratu

re:6

0.02

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 I.L.

Jenk

ins,

F.H

.Moo

re,a

ndM

.J.W

ater

man

,J.I

norg

.Nuc

l.C

hem

.27,

81~1

965!

.2 A

.I.

Mos

kvin

and

A.

D.

Gel

man

,Z

h.N

eorg

.K

him

.3,96

2~1

958!

.

Co

~1!

~2!

~3!

Va

T/

c 2 a T b C Me

Iso

co wa

tur

sh tim an co or


te,

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

Pu

~C2O

4!2•

6H2O

was

shak

enfo

rat

leas

t10

days

ina

ther

mos

tat

with

solu

tions

ofth

ede

sire

dco

mpo

sitio

n.In

mos

tca

ses,

one

ortw

oal

iquo

tsw

ere

take

nfo

rP

ude

term

inat

ion

atth

een

dof

1w

eek,

and

then

agai

ntw

oto

four

aliq

uots

afte

rab

out

5da

ysto

ensu

reth

attr

ueeq

uilib

rium

solu

bilit

yva

lues

wer

eob

tain

ed.

Plu

toni

umw

asde

term

ined

bya

coun

ting

afte

rev

apor

atin

gth

eal

iquo

tsof

the

satu

rate

dso

lutio

nson

plat

inum

dish

es.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

05K

~aut

hor!.

Sol

ubili

ty:

from

the

para

llel

coun

ting

data

the

com

pile

res

timat

edth

epr

ecis

ion

tobe6

10%

inso

lutio

nsco

ntai

ning

0.00

68an

d0.

0179

mol

dm23

oxal

icac

id,

and6

5%at

high

erox

alic

acid

conc

entr

atio

ns.

Ref

eren

ces:

1 I.L.

Jenk

ins,

F.H

.Moo

re,a

ndM

.J.W

ater

man

,J.I

norg

.Nuc

l.C

hem

.27,

81~1

965!

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Plu

toni

um~I

V!

bis~

oxal

ate!;

Pu~

C2O

4!2;

@132

78-8

1-4#

Oxa

licac

id;

C 2H

2O4;

@144

-62-

7#N

itric

acid

;H

NO

3;@7

697-

37-2#

Wat

er;

H 2O

;@7

732-

18-5#

C.

J.M

andl

eber

g,K

.E

.F

ranc

is,

and

R.

Sm

ith,

J.C

hem

.S

oc24

64–

8~19

61!.

riabl

es:

Pre

pare

dby

:

K:

300

/mol

dm2

3 :0

–0.

6/m

oldm

23 :

0–

3.52

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

27°C

ofP

u~C2O

4!2

inC

2H2O

4/H

NO

3so

lutio

nsa

HN

O3

3/m

oldm

23 )

C2H

2O4

(c2

/mol

dm2

3 )P

u~m

gdm

23 !b

Pu~

C2O

4!2

(104

c 1/

mol

dm2

3 )cH

NO

3

(c3

/mol

dm2

3 )C

2H2O

4

(c2

/mol

dm2

3 )P

u~m

gdm

23 !b

Pu~

C2O

4!2

(104

c 1/

mol

dm2

3 )c

00

45.9

1.92

1.18

0.00

7116

.30.

682

00.

0533

414

.01.

610.

002

65.8

2.76

00.

2524

210

.11.

610.

015

150.

628

0.1

026

.61.

112.

000

128

5.36

0.1

0.5

132

5.52

2.00

0.05

9.7

0.40

6

0.5

069

.02.

892.

000.

2515

.10.

632

0.5

0.05

26.6

1.11

2.34

0.01

15.3

0.64

0

0.5

0.25

97.1

4.06

2.34

0.00

524

.91.

04

0.5

0.60

361

15.1

2.52

0.02

516

.70.

661

0.78

0.40

144

6.02

3.52

0.00

592

.13.

85

1.0

012

25.

103.

520.

0145

.81.

92

1.0

0.05

13.3

0.55

63.

520.

0518

0.75

3

1.0

0.25

36.9

1.54

3.52

0.1

18.2

0.76

1

1.0

0.60

133

5.56

3.52

0.5

31.4

0.89

5

heco

mpo

sitio

nof

the

equi

libriu

mso

lidph

ases

was

not

repo

rted

.T

heco

mpi

ler

assu

mes

the

solid

phas

eis

the

hexa

hydr

ate,

u~C

2O4!

2•6H

2O,

@265

88-7

4-9#,

whi

chpr

ecip

itate

sat

25°C

from

C 2H2O

4/H

NO

3so

lutio

ns.1

the

orig

inal

docu

men

tth

epl

uton

ium

conc

entr

atio

nis

repo

rted

,ob

viou

sly

bym

ista

ke,

ing/

dm3 .

Inth

egr

aphi

calr

epre

sent

atio

nof

the

ata,

how

ever

,th

eau

thor

sre

port

the

solu

bilit

ies

inm

g/dm

3 ,w

hich

also

agre

esw

ithP

u~C2O

4!2

solu

bilit

yas

repo

rted

byot

her

auth

ors.

2,3

alcu

late

dby

com

pile

rus

ing

A r~P

u!5

239.

053.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Por

tions

ofP

u~C

2O4!

2•6H

2Ow

ere

cont

inuo

usly

agita

ted

with

C 2H2O

4/H

NO

3so

lutio

nsof

the

desi

red

com

posi

tion

ina

ther

mos

tat.

Equ

ilibr

ium

was

achi

eved

afte

rag

itatio

nfo

r2

–3

wee

ks.

The

plut

oniu

mco

ncen

trat

ion

inth

esa

tura

ted

solu

tions

was

dete

rmin

edby

pipe

tting

port

ions

ofth

esu

pern

atan

tliq

uid

onto

coun

ting

tray

s,an

dm

easu

ring

aac

tivity

ina

prop

ortio

nalc

ount

er.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

the

auth

ors

stat

edth

atth

eda

tare

port

edw

ere

the

resu

ltsof

repe

ated

dete

rmin

atio

nsw

hich

agre

edw

ithin

afe

wpe

rcen

t.

Ref

eren

ces:

1 I.L.

Jenk

ins,

F.H

.Moo

re,a

ndM

.J.W

ater

man

,J.I

norg

.Nuc

l.C

hem

27,

81~1

965!

.2 A

.I.

Mos

kvin

and

A.

D.

Gel

man

,Z

h.N

eorg

.K

him3

,95

6~1

958!

.3 W

.H

.R

eas,

Nat

l.N

ucl.

Ene

rgy

Ser

.,D

iv.

IV14B

,42

3~1

949!

.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Plu

toni

um~I

V!

bis~

oxal

ate!;

Pu~

C2O

4!2;

@132

78-8

1-4#

~2!

Oxa

licac

id;

C 2H

2O4;

@144

-62-

7#~3

!N

itric

acid

;H

NO

3;@7

697-

37-2#

~4!

Wat

er;

H 2O

;@7

732-

18-5#

W.

H.

Rea

s,N

atl.

Nuc

l.E

nerg

yS

er.,

Div

IV14B

,42

3–

33~1

949!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8c 2

/mol

dm2

3 :0.

001

–0.

40c 3

/mol

dm2

3 :0.

75

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofP

u~C2O

4!2

inox

alic

acid

solu

tions

cont

aini

ng0.

75m

oldm2

3H

NO

3a

C2H

2O4

(c2

/mol

dm2

3 )P

u~C

2O4!

2

(104

c 1/m

oldm

23 !

C2H

2O4

(c2

/mol

dm2

3 )P

u~C

2O4!

2

(104

c 1/m

oldm

23 )

0.00

034b

3.4c

0.04

330.

826

0.00

10.

522d

0.09

411.

39

0.00

316

0.38

9e0.

145

2.04

0.00

680.

421

0.19

62.

54

0.01

790.

521

0.40

04.

89

a The

com

posi

tion

ofth

eeq

uilib

rium

solid

phas

esw

asno

tre

port

ed.

The

com

pile

ras

sum

esth

eso

lidph

ase

isth

ehe

xahy

dra

Pu~

C2O

4!2•

6H2O

,@2

6588

-74-

9#,w

hich

prec

ipita

tes

at25

°Cfr

omC 2H

2O4

/HN

O3

solu

tions

.1

b No

oxal

icac

idw

asad

ded

inth

ism

easu

rem

ent.

The

auth

oras

sum

edth

atP

u~C

2O4!

2•6H

2Odi

ssol

ved

topr

oduc

eP

u~C2O

4!21

and

C 2H

2O4,

and

cons

ider

edth

ede

term

ined

solu

bilit

yto

beeq

ualt

oth

eox

alic

acid

conc

entr

atio

nin

the

solu

tion.

c The

auth

orco

nsid

ered

this

valu

eas

erro

neou

sly

high

due

toox

idat

ion

ofox

alic

acid

byH

NO

3un

der

cata

lytic

actio

nof

Pu~IV

!.d M

echa

nica

lst

irrin

gw

asus

edin

this

expe

rimen

t.T

heap

proa

chto

equi

libriu

mw

asra

pid,

and

equi

libriu

mso

lubi

lity

coul

dbe

obta

ined

afte

rle

ssth

an2

heq

uilib

ratio

n.e S

olub

ility

obta

ined

byth

eau

thor

byex

trap

olat

ion.

Itco

uld

not

beob

tain

edex

perim

enta

llysi

nce

eith

erca

taly

ticox

idat

ion

ofox

alic

acid

orP

u~IV

!ox

idat

ion

byan

unkn

own

impu

rity

inte

rfer

ed.

Add

ition

alin

form

atio

n:T

heau

thor

inte

rpre

ted

the

solu

bilit

yda

tain

term

sof

the

form

atio

nof

Pu

~C2O

4!21

,P

u~C

2O4!

2an

dP

u~C2O

4) 32

2co

mpl

exes

inth

esa

tura

ted

solu

tions

.E

quili

briu

mco

nsta

nts

for

the

reac

tions

Pu

~C2O

4!21

1C

2H2O

4�

Pu~

C2O

4!21

2H1

and

Pu~C

2O4!

21C

2H2O

4�P

u~C

2O4!

3221

2H1

wer

eob

tain

edas

965

and

25.1

mol

dm23 ,

resp

ectiv

ely. A

uxili

ary

Info

rmat

ion

Co

~1!

~2!

~3!

~4!

Va

T/

c 2 c 3 (c a T P b In d c C

J

whe

re@C

2O422

# tot

isth

eto

talo

xala

teco

ncen

trat

ion.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dw

asus

ed.

Fre

shly

prec

ipita

ted

Pu~

C2O

4!2•

6H2O

was

agita

ted

with

solu

tions

ofth

ede

sire

dco

ncen

trat

ion

ina

ther

mos

tate

dba

thfo

r4

–6

hw

hich

was

foun

dsu

ffici

ent

for

equi

libriu

mto

bere

ache

d.T

hepl

uton

ium

conc

entr

atio

nin

the

satu

rate

dso

lutio

nsw

asde

term

ined

byan

unsp

ecifi

edra

diom

etric

met

hod.1

Pu~

C2O

4!2•

6H2O

was

obta

ined

bypr

ecip

itatio

nof

Pu

~IV

!w

ithox

alic

acid

,an

dw

ashi

ngth

epr

ecip

itate

with

wat

er.

2

Est

imat

edE

rror

:T

empe

ratu

re:6

0.02

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 I.L.

Jenk

ins,

F.H

.Moo

re,a

ndM

.J.W

ater

man

,J.I

norg

.Nuc

l.C

hem

.27,

81~1

965!

.2 A

.A

.G

rinbe

rgan

dI.

Pet

rzha

k,T

rudy

Rad

iev.

Inst

.,K

him

.G

eokh

im.7

,50

~195

6!.

7.8.

Plu

toni

um„V

I…D

ioxo

„ox

alat

e…

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Plu

toni

um~V

I!di

oxoo

xala

te;

PuO

2C2O

4;@5

2689

-31-

3#O

xalic

acid

;C 2

H2O

4;@1

44-6

2-7#

Nitr

icac

id;

HN

O3;

@769

7-37

-2#W

ater

;H 2

O;

@773

2-18

-5#

1 L.E

.D

rabk

ina,

A.

I.M

oskv

in,

and

A.

D.

Gel

man

,Z

h.N

eorg

.K

him

.3,

1934

–6~

1958

!.2 A

.D.G

elm

anan

dL.

E.D

rabk

ina,

Zh.

Neo

rg.K

him

.3,

1105

–8

~195

8!.

riabl

es:

Pre

pare

dby

:

K:

293

/mol

dm2

3 :0

–0.

75or

100w

2/m

ass

%:

0–

8/m

oldm

23 :

1.1

–3.

08

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofP

uO2C

2O4

inC

2H2O

4/H

NO

3so

lutio

nsa

NO

3b

(c3

/ld

m2

3 )

C2H

2O4b

(c2

/m

oldm

23 )

PuO

2C2O

4b

(103

c 1/

mol

dm2

3 )

Ksp

d

(1010

mol

3dm

29 )

HN

O3c

(c3

/m

oldm

23 )

C2H

2O4c

(100

w2

/m

ass

%)

Puc

~gdm

23 !

PuO

2C2O

4

(103

c 1/

mol

dm2

3 )e

1.10

013

.49.

31.

10

3.20

13.3

0.11

4.0

10.

950

3.97

0.23

2.69

20.

642

2.69

0.45

2.46

40.

588

2.46

0.75

2.21

60.

528

2.21

2.01

016

.38

0.49

12.

05

0.11

5.35

4.2

2.0

03.

9116

.4

0.23

3.81

11.

301.

265.

35

0.45

2.61

20.

877

0.94

63.

82

0.75

2.40

40.

623

2.64

3.08

028

.06

0.57

42.

40

0.11

9.83

80.

487

0.49

72.

06

0.23

5.40

5.5

3.08

06.

7528

.2

0.45

3.19

12.

32.

419.

85

0.75

2.55

21.

201.

301.

365.

40

40.

795

0.72

40.

766

3.19

60.

617

0.61

20.

605

2.66

80.

567

0.60

00.

589

2.45

a The

com

posi

tion

ofth

eeq

uilib

rium

solid

phas

esw

asno

tre

port

ed.

The

com

pile

ras

sum

esth

eso

lidph

ase

isth

etr

ihyd

rate

,P

uO2C

2O4•

3H2O

,@

#,w

hich

prec

ipita

tes

from

acid

icso

lutio

nsby

actio

nof

oxal

icac

id.

1

b Dat

afr

omor

igin

aldo

cum

ent.1

c Dat

afr

omor

igin

aldo

cum

ent.2

d Ksp

5@P

uO221

#@C

2O422

#.It

was

calc

ulat

edby

the

auth

ors

unde

rth

eas

sum

ptio

nth

atth

eco

ncen

trat

ion

ofP

uO221

was

equa

lto

the

expe

rimen

tal

solu

bilit

yof

PuO 2

C2O

4si

nce

spec

trop

hoto

met

ricm

easu

rem

ents

did

not

indi

cate

any

com

plex

form

atio

nbe

twee

nP

uO221

and

C 2O

422io

ns.

Equ

ilibr

ium

oxal

ate

ion

conc

entr

atio

nw

asob

tain

edfr

omth

eto

tal

conc

entr

atio

nof

oxal

icac

idan

ddi

ssoc

iatio

nco

nsta

nts

ofth

ela

tter,K

a15

0.10

8m

oldm

23

~Ref

.2!

and

Ka2

56.

4310

25

mol

dm2

3 .3

e Cal

cula

ted

byth

eco

mpi

ler

usin

gA

r~P

u!5

239.

053.

Whe

rem

ore

than

one

mea

sure

men

tsw

ere

repo

rted

,ca

lcul

atio

nw

asdo

nefo

rth

eav

erag

eva

lue.

666666 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Plu

toni

um~I

V!

bis~

oxal

ate!;

Pu~

C2O

4!2;

@132

78-8

1-4#

~2!

Am

mon

ium

oxal

ate;

(NH 4!

2C2O

4;@1

113-

38-8#

~3!

Nitr

icac

id;

HN

O3;

@769

7-37

-2#~4

!W

ater

;H 2

O;

@773

2-18

-5#

~1!

A.

I.M

oskv

inan

dA

.D

.G

elm

an,

Zh.

Neo

rg.

Khi

m.3,

962

–74

~195

8!.

~2!

A.

I.M

oskv

inan

dA

.D

.G

elm

an,

Zh.

Neo

rg.

Khi

m.3,

956

–61

~195

8!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

3c 2

/mol

dm2

3 :0.

001

–0.

35c 3

/mol

dm2

3 :1.

0;3.

8

J.H

ala

Exp

erim

enta

lDat

a

(NH

4!2C

2O4

(c2

/mol

dm2

3 )P

u~C

2O4!

2

(104

c 1/m

oldm

23 )

0.00

1b0.

619

0.00

20.

502

0.00

30.

458

0.00

40.

406

0.00

50.

355

0.01

0.43

0.05

0.57

7

0.14

1.8

0.17

52.

38

0.21

3.35

0.23

34.

18

Add

ition

alin

form

atio

n:T

hein

crea

sein

the

solu

bilit

yof

Pu~C

2O4!

2in

1.0

mol

dm2

3H

NO

3so

lutio

nsat

(NH 4

! 2C

2O4

conc

entr

atio

ns.

0.01

mol

dm2

3w

asas

crib

edby

the

auth

ors

toth

efo

rmat

ion

ofox

alat

ocom

plex

esof

Pu

~IV

!.T

heir

over

all

inst

abili

tyco

nsta

nts,K

n5

@Pu4

1#

3@C

2O422

#n@P

u~C

2O4!

n42

n#2

1,

wer

eob

tain

edfr

omex

perim

enta

lso

lubi

litie

sasK

15

1.83

102

9m

oldm

23 ,

K25

1.23

102

17m

ol2

dm2

6 ,K

35

4.03

102

24m

ol3

dm2

9 ,an

dK

45

3.23

102

28m

ol4

dm2

12.

Als

oca

lcul

ated

wer

eeq

uilib

rium

cons

tant

sfo

rth

ere

actio

nsP

u~C

2O4!

2•6H

2O~s

!12H

1�

Pu~

C2O

4!21

1C

2H2O

416H

2O,P

u~C

2O4!

2•6H

2O~s

!�P

u~C

2O4!

216H

2O,

Pu~

C2O

4!2•

6H2O

~s!1

C2H

2O4

�P

u~C

2O4!

3221

2H1

16H

2O,

and

Pu~C

2O4!

2•6H

2O~s

!12

C2H

2O4�

Pu~

C2O

4!442

14H

11

6H2O

as3.

1310

28,

3.23

102

5m

oldm

23 ,

6.8

310

24

mol

2dm

26 ,

and

7.03

102

5m

ol3

dm2

9 ,re

spec

tivel

y.In

thes

eca

lcul

atio

ns,

the

auth

ors

used

diss

ocia

tion

cons

tant

sof

oxal

icac

idK

a15

0.10

8m

oldm

23

and

Ka2

56.

4310

25

mol

dm2

3 ,an

dca

lcul

ated

equi

libriu

mhy

drog

enan

dox

alat

eio

nco

ncen

trat

ions

as@H

1#5

~12

2@C

2O422

# tot)1

Ka1

@C2O

422# t

ot/(

122 @

C2O

422# t

ot),

and

@C2O

422#5

@C2O

422# t

ot/(

11@H

1#K

a1211

@H1

#2K

a121K

a221),

resp

ectiv

ely,

Co

~1!

~2!

~3!

~4!

Va

T/

c 2 c 3

H

mo


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Plu

toni

um~V

I!di

oxoo

xala

te;

PuO

2C2O

4;@5

2689

-31-

3#A

mm

oniu

mox

alat

e;(N

H 4!2C

2O4;

@111

3-38

-8#N

itric

acid

;H

NO

3;@7

697-

37-2#

Wat

er;

H 2O

;@7

732-

18-5#

1 A.D

.Gel

man

and

L.E

.Dra

bkin

a,Z

h.N

eorg

.Khi

m.

3,11

05–

8~1

958!

.2 A

.D

.G

elm

an,

L.E

.D

rabk

ina,

and

A.

I.M

oskv

in,

Zh.

Neo

rg.

Khi

m.

3,15

46–

50~1

958!

.

riabl

es:

Pre

pare

dby

:

K:

293

0w2

/mas

s%

:1

–6

orc2

/mol

dm2

3 :0.

07–

0.4

/mol

dm2

3 :0.

5–

3.0

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofP

uO2C

2O4

in~N

H4!

2C2O

4/H

NO

3so

lutio

nsa

HN

O3b

3/m

oldm

23 )

(NH

4!2C

2O4b

(100

w2

/mas

s%

)P

ub

~gdm

23 !

PuO

2C2O

4

(103

c 1/m

oldm

23!

dH

NO

3c

(c3

/mol

dm2

3 )(N

H4!

2C2O

4c

(c2

/mol

dm2

3 )

PuO

2C2O

4c

(103

c 1/m

oldm

23 )

0.5

10.

707

2.96

1.0

0.07

03.

76

20.

916

3.83

0.14

03.

30

31.

606.

690.

256

3.39

1.0

10.

900

3.76

0.28

43.

60

20.

760

0.81

23.

290.

305

3.87

30.

789

0.73

83.

190.

355

4.40

40.

889

0.84

53.

620.

369

4.60

61.

251.

064.

810.

398

4.88

2.0

11.

666.

94

21.

194.

98

30.

807

3.38

40.

709

2.97

60.

634

2.65

3.0

12.

5110

.5

21.

446.

02

31.

174.

89

40.

931

3.89

60.

761

3.18

heco

mpo

sitio

nof

the

equi

libriu

mso

lidph

ases

was

not

repo

rted

.b D

ata

from

orig

inal

docu

men

t.1

c Dat

afr

omor

igin

aldo

cum

ent.2

d Cal

cula

ted

byth

eco

mpi

ler

usin

gA

r~P

u!5

239.

053.

Whe

rem

ore

than

one

mea

sure

men

tsw

ere

repo

rted

,ca

lcul

atio

nw

asdo

nefo

rth

eav

erag

eva

lue.

Add

ition

alin

form

atio

n:T

hein

crea

sein

the

solu

bilit

yof

PuO 2

C2O

4w

ithin

crea

sing

(NH 4

! 2C

2O4

conc

entr

atio

nin

solu

tions

cont

aini

ng1.

0m

oldm2

3H

NO

3w

asex

plai

ned

byth

eau

thor

sby

the

form

atio

nof

the

PuO

2~C

2O4!

222co

mpl

exin

the

solu

tions

.U

sing

diss

ocia

tion

cons

tant

sof

oxal

icac

id,

Ka1

50.

108

mol

dm2

3~R

ef.

1!an

dK

a25

6.43

102

5m

oldm

23 ,2

and

the

solu

bilit

ypr

oduc

tof

PuO 2

C2O

4,K

sp5

5.93

102

10m

ol2

dm2

6

~Ref

.2!

for

the

calc

ulat

ion

ofeq

uilib

rium

conc

entr

atio

nsof

the

PuO

221an

dC 2

O422

ions

,th

eov

eral

lins

tabi

lity

cons

tant

sw

ere

obta

ined

asK

15

@PuO

221#@

C2O

422#@

PuO

2C2O

4#2

15

2.23

102

7m

oldm

23

and

K25

@PuO

221#@

C2O

422#2

@PuO

2~C

2O4!

222#2

15

4.33

102

12m

ol2

dm2

6 .



Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

ofP

uO2C

2O4•

3H2O

was

stirr

edw

ithso

lutio

nsof

the

desi

red

com

posi

tion

ina

ther

mos

tate

dap

para

tus

for2

hw

hich

was

esta

blis

hed

assu

ffici

ent

for

equi

libriu

mto

bere

ache

d.T

hepl

uton

ium

conc

entr

atio

nin

the

satu

rate

dso

lutio

nsw

asde

term

ined

byan

unsp

ecifi

edra

diom

etric

met

hod.

Pur

eP

uso

lutio

nin

HN

O 3w

asus

edas

ast

artin

gm

ater

ial.

Plu

toni

umw

asox

idiz

edto

Pu~V

I!in

0.5

–1.

0m

oldm

23

HN

O3

byhe

atin

gth

eso

lutio

nw

ithK 2C

r 2O

7or

MnO

2at

90°C

for

1–

2h.

The

cour

seof

oxid

atio

nw

asfo

llow

edsp

ectr

opho

tom

etric

ally

.B

yad

ding

crys

talli

neox

alic

acid

toth

eP

u~V

I!so

lutio

nin

1–

2m

oldm

23

HN

O3,

api

nkcr

ysta

lline

prec

ipita

tew

asob

tain

edw

hich

was

show

nby

grav

imet

ric(P

u,H

2O)

and

titrim

etric

~oxa

late!

anal

ysis

tobe

PuO 2

C2O

4•3H

2O.

Est

imat

edE

rror

:T

empe

ratu

re:6

1K

~aut

hors!

.S

olub

ility

:ba

sed

onth

edu

plic

ate

ortr

iplic

ate

mea

sure

men

tsas

repo

rted

inor

igin

alre

fere

nce,2co

mpi

ler

estim

ated

prec

isio

nto

be<

10%

.

Ref

eren

ces:

1 I.L.

Jenk

ins,

F.H

.Moo

re,a

ndM

.J.W

ater

man

,J.I

norg

.Nuc

l.C

hem

.27,

77~1

965!

.2 G

.S

eabo

rg,

J.K

atz,

and

P.

Man

ning

.,E

ds.,

Th

eT

ran

sura

niu

mE

lem

en

ts~1

949!

,1,

p.42

3.3 B

.P

.N

ikol

skii,

Ed.

,S

pra

voch

nik

Kh

imik

a~C

he

mis

try

Ha

nd

bo

ok!

~195

2!,

Vol

.3,

p.50

5.

Co

~1!

~2!

~3!

~4!

Va

T/

10 c 3 (c a T

J

7.9.

Plu

toni

um„III…

o-h

ydro

xybe

nzoa

te

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Plu

toni

um~I

II!

tris

~o-h

ydro

xybe

nzoa

te!;P

u~C

7H5O

3!3;

@#

Sol

vent

sO

.E

.Z

vyag

ints

evan

dB

.N

.S

udar

ikov

,Z

h.N

eorg

.K

him

.3,

975

–85

~195

8!;

Rus

s.J.

Inor

g.C

hem

.3,21

7–

33~1

958!

.

riabl

es:

Pre

pare

dby

:

K:

293

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

20°C

ofP

u~C7H

5O3!

3in

thre

eso

lven

tsa

Sol

vent

Pu31

~gkg

21 !b

Pu~

C7H

5O3!

3

(103

m1

/mol

kg2

1 )b

ter;

H 2O

;@7

732-

18-5#

0.12

0.50

2

anol

;C 2

H6O

;@6

4-17

-5#

0.50

2.09

eton

e;C 3H

6O;

@67-

64-1

#3.

5014

.9

heco

mpo

sitio

nof

the

equi

libriu

mso

lidph

ase

was

not

repo

rted

.ra

ms

per

kgso

lutio

n.al

cula

ted

byco

mpi

ler

usin

gA r~P

u!5

239.

053.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

was

used

.E

xces

sP

u~C

7H5O

3!•1.

5H2O

was

uilib

rate

dby

stirr

ing

for1

hw

ithth

ede

sire

dso

lven

t.ut

oniu

mco

ncen

trat

ion

inth

esa

tura

ted

solu

tions

was

term

ined

byan

unsp

ecifi

edra

diom

etric

met

hod.

Pu~

IV!

solu

tion

was

redu

ced

toP

u~I

II!

byei

ther

SO 2

orso

dium

sulfo

xyla

te,

and

Pu~C

7H5O

3!•1.

5H2O

was

obta

ined

asa

light

-blu

eso

lidon

prec

ipita

ting

with

salic

ylic

acid

atpH

2.8

–3.

8.A

naly

sis

~fou

nd/c

alcu

late

dfo

rth

ehy

drat

e,m

ass

%!:

Pu

35.3

4/35

.30,

salic

ylat

e60

.44/

60.7

1.S

ourc

ean

dpu

rity

ofso

lven

tsus

edw

asno

tsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

tem

pera

ture

ofth

em

easu

rem

ents

was

give

nas

appr

oxim

ate

valu

e.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

668668 JIRI HALA

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

ofP

uO2C

2O4•

3H2O

was

stirr

edw

ithso

lutio

nsof

the

desi

red

com

posi

tion

ina

ther

mos

tate

dap

para

tus

for

2h,

whi

chw

ases

tabl

ishe

das

suffi

cien

tfo

req

uilib

rium

tobe

reac

hed.

The

plut

oniu

mco

ncen

trat

ion

inth

esa

tura

ted

solu

tions

was

dete

rmin

edby

anun

spec

ified

radi

omet

ricm

etho

d.

Pur

eP

uso

lutio

nin

HN

O 3w

asus

edas

ast

artin

gm

ater

ial.

Plu

toni

umw

asox

idiz

edto

Pu~V

I!in

0.5

–1.

0m

oldm

23 H

NO

3

byhe

atin

gth

eso

lutio

nw

ithK 2C

r 2O

7or

MnO

2at

90°C

for

1–

2h.

The

cour

seof

oxid

atio

nw

asfo

llow

edsp

ectr

opho

tom

etric

ally

.B

yad

ding

crys

talli

neox

alic

acid

toth

eP

u~V

I!so

lutio

nin

1–

2m

oldm

23

HN

O3,

api

nkcr

ysta

lline

prec

ipita

tew

asob

tain

edw

hich

was

show

nby

grav

imet

ric(P

u,H

2O)

and

titrim

etric

~oxa

late!

anal

ysis

tobe

PuO 2

C2O

4•3H

2O.

Est

imat

edE

rror

:T

empe

ratu

re:6

1K

~aut

hors!

.S

olub

ility

:fr

omth

efo

urdu

plic

ate

mea

sure

men

tspr

ecis

ion

of6

~3–

8!%

can

bees

timat

ed.

Ref

eren

ces:

1 G.

Sea

borg

,J.

Kat

z,an

dP

.M

anni

ng.,

Eds

.,T

he

Tra

nsu

ran

ium

Ele

me

nts

~194

5!,

Vol

.1,

p.42

3.2 L.

E.

Dra

bkin

a,A

.I.

Mos

kvin

,an

dA

.D

.G

elm

an,

Zh.

Neo

rg.

Khi

m.

3,19

34~1

958!

.

Co

~1!

~2!

Va

T/

wa

eth

ac a T b G c C Me

Iso

eq Pl

de


Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Dip

luto

nium

~IV

!tr

ioxo

~o-h

ydro

xybe

nzoa

te!;

2O3~

C7H

5O3!

;@

#H

ydro

gen

chlo

ride;

HC

l;@76

47-0

1-0#;

orA

mm

onia

;N

H 3;

664-

41-7#

Wat

er;

H 2O

;@7

732-

18-5#

O.

E.

Zvy

agin

tsev

and

B.

N.

Sud

arik

ov,

Zh.

Neo

rg.

Khi

m.

3,97

5–

85~1

958!

;R

uss.

J.In

org.

Che

m.3,

217

–33

~195

8!.

riabl

es:

Pre

pare

dby

:

K:

283

–37

1~in

HC

lor

NH

3so

lutio

ns!:

0.7

–9.

4J.

Hala

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Pu 2

O3~

C7H

5O3!

asa

func

tion

ofte

mpe

ratu

rean

dpHa

Sol

ubili

tyof

Pu 2

O3~

C7H

5O3!

asa

func

tion

ofte

mpe

ratu

rebS

olub

ility

ofP

u 2O

3~C

7H5O

3!as

afu

nctio

nof

pHe

empe

ratu

re~°

C!

Pu41

~mg

kg2

1 !cP

u 2O

3~C

7H5O

3!(1

06m

1/m

olkg

21 )d

pHP

u41

~mg

kg2

1 !cP

u 2O

3~C

7H5O

3!(1

06m

1/m

olkg

21 )d

100.

31.

250.

723

.698

.7

251.

35.

442.

32.

410

.0

503.

916

.34.

22.

08.

37

706.

326

.45.

71.

35.

44

851.

04.

187.

20.

31.

25

980.

52.

099.

40.

72.

93

heco

mpo

sitio

nof

the

equi

libriu

mso

lidph

ase

was

not

repo

rted

.he

pHof

the

satu

rate

dso

lutio

nsno

tre

port

ed.

ram

spe

rkg

satu

rate

dso

lutio

n.al

cula

ted

byco

mpi

ler

usin

gA r~P

u!5

239.

053

negl

ectin

gth

esm

allp

luto

nium

conc

entr

atio

nin

the

satu

rate

dso

lutio

ns.

hepH

was

adju

sted

byus

ing

HC

lor

NH

3.A

ctua

lcon

cent

ratio

nof

HC

lor

NH 3

was

not

spec

ified

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

was

used

.E

xces

sP

u2O

3~C

7H5O

3)•xH

2Os

equi

libra

ted

with

the

desi

red

solu

tion

and/

orat

the

desi

red

pera

ture

byst

irrin

gfo

r1

–2

h.P

luto

nium

conc

entr

atio

nin

satu

rate

dso

lutio

nsw

asde

term

ined

byan

unsp

ecifi

eddi

omet

ricm

etho

d.

Pu 2

O3~

C7H

5O3)•xH

2Ow

aspr

epar

edas

amor

phou

sgr

ay–

yello

wto

brow

nso

lidby

boili

ngso

lutio

nsof

PuO~

C7H

5O3!

2in

amm

onia

cal

solu

tions

ofam

mon

ium

salic

ylat

eor

inal

kalin

eso

lutio

nsof

sodi

umsa

licyl

ate.

The

Pu

~IV

!:sa

licyl

ate

ratio

inth

epr

oduc

tw

asw

ithin

2:0.

92–

2:1.

09.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.



7.10

.P

luto

nium

„IV…

oxo„o

-hyd

roxy

benz

oate

s…

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Plu

toni

um~I

V!

oxob

is~o-

hydr

oxyb

enzo

ate!;

PuO

~C7H

5O3!

2;@

#~2

!H

ydro

gen

chlo

ride;

HC

l;@76

47-0

1-0#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

O.

E.

Zvy

agin

tsev

and

B.

N.

Sud

arik

ov,

Zh.

Neo

rg.

Khi

m.

3,97

5–

85~1

958!

;R

uss.

J.In

org.

Che

m.3,

217

–33

~195

8!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8pH

~inH

Cls

olut

ions

!:0.

4–

5.7

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofP

uO~C

7H5O

3!2

inH

Cls

olut

ions

asa

func

tion

ofpHa

pHb

Pu41

~mg

kg2

1 !cP

uO~C

7H5O

3!2

(105

m1

/mol

kg2

1 )c,d

0.4

71.0

29.7

1.5

50.0

20.9

2.0

6.2

2.59

3.0

1.3

0.54

4

5.2

0.5

0.20

9

5.7

0.3

0.12

5

a The

com

posi

tion

ofth

eeq

uilib

rium

solid

phas

ew

asno

tre

port

ed.

b The

pHw

asad

just

edby

addi

ngH

Cl.

Act

ualc

once

ntra

tion

ofth

ela

tter

was

not

spec

ified

.c G

ram

spe

rkg

satu

rate

dso

lutio

n.d C

alcu

late

dby

com

pile

rus

ing

A r~P

u!5

239.

053.

Add

ition

alin

form

atio

n:A

tpH

.6,

PuO

~C7H

5O3!

2w

asre

port

edto

hydr

olyz

eto

yiel

da

spar

ingl

yso

lubl

epr

oduc

t,w

hich

was

iden

tified

asP

u2O

3~C

7H5O

3)•xH

2O.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dw

asus

ed.

Exc

ess

PuO

~C7H

5O3!

2w

aseq

uilib

rate

dby

stirr

ing

for1

hw

ithso

lutio

nsof

thed

esire

dpH

.P

luto

nium

conc

entr

atio

nin

the

satu

rate

dso

lutio

nsw

asde

term

ined

byan

unsp

ecifi

edra

diom

etric

met

hod.

PuO

~C7H

5O3!

2w

aspr

epar

edby

prec

ipita

tion

ofa

Pu

~IV

!so

lutio

nw

ithsa

licyl

icac

idat

pH0

–5

asa

brow

npr

ecip

itate

.A

naly

sis

~fou

nd/c

alcu

late

dfo

rP

uO~C

7H5O

3!2,

mas

s%!

:P

u45

.50/

45.1

8,sa

licyl

ate

51.8

0/51

.80.

Co

~1!

Pu

~2!

@7 ~3!

Va

T/

pH

T

a T b T c G d C e T Me

Iso

wa

tem

the

ra

J

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Dip

luto

nium

~IV

!tr

ioxo

~o-h

ydro

xybe

nzoa

te!;

2O3~

C7H

5O3!

;@

#A

mm

oniu

mo-

hydr

oxyb

enzo

ate;

C 7H9N

O3;

@#

Wat

er;

H 2O

;@7

732-

18-5#

O.

E.

Zvy

agin

tsev

and

B.

N.

Sud

arik

ov,

Zh.

Neo

rg.

Khi

m.

3,97

5–

85~1

958!

;R

uss.

J.In

org.

Che

m.3,

217

–33

~195

8!.

riabl

es:

Pre

pare

dby

:

K:

298

and

333

/mol

kg2

1 :0.

02–

4.3

:1.

2–

10.2

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25an

d60

°Cof

Pu 2O

3~C

7H5O

3!in

amm

oniu

msa

licyl

ate

solu

tionsa

mpe

ratu

re~°

C!

C7H

5O32

~gkg

21

solu

tion!

bC

7H9N

O3

(m2

/mol

kg2

1 )cpH

Pu41

~mg

kg2

1so

lutio

n!P

u 2O

3~C

7H5O

3!(1

06m

1/m

olkg

21 )c

255

0.03

241.

22.

510

.5

50.

0324

1.7

1.5

6.31

50.

0324

2.7

0.5

2.10

50.

0324

5.5

0.3

1.26

50.

0324

6.2

0.3

1.26

50.

0324

7.4

0.2

0.84

50.

0324

9.2

0.1

0.42

50.

0324

10.2

0.1

0.42

00

70.

31.

25

30.

0194

70.

41.

68

50.

0324

70.

20.

841

500.

339

71.

46.

16

750.

526

72.

913

.1

100

0.71

66

0.5

2.32

100

0.71

67

3.0

13.9

100

0.71

68.

91.

56.

97

100

0.71

69.

72.

813

.0

200

1.61

4.2

1.5

7.84

200

1.61

73.

417

.8

200

1.61

7.4

3.4

17.8

300

2.76

74.

929

.3

300

2.76

7.3

4.9

29.3

300

2.76

9.2

6.5

38.8

400

4.30

6.9

6.8

47.4

400

4.30

74.

934

.2

400

4.30

9.8

9.0

62.7

600

0d

6.4

26.7

100

0.71

6d

50.0

232

170

1.32

d68

.034

3

250

2.15

d87

.048

5

400

4.30

d23

9.0

1670

a The

com

posi

tion

ofth

eeq

uilib

rium

solid

phas

ew

asno

tre

port

ed.

b Con

cent

ratio

nof

the

salic

ylat

eio

n;gi

ven

byau

thor

sas

appr

oxim

ate

valu

es.

c Cal

cula

ted

byco

mpi

ler.

For

plut

oniu

m,

Ar~

Pu!

523

9.05

3w

asus

ed.

d Not

repo

rted

.

670670 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Dip

luto

nium

~IV

!tr

ioxo

~o-h

ydrx

yben

zoat

e!;P

u 2O

3~C

7H5O

3!;

@#

~2!

Am

mon

ium

chlo

ride;

NH 4

Cl;

@121

25-0

2-9#;

orA

mm

oniu

mni

trat

e;N

H 4N

O3;

@648

4-52

-2#~3

!W

ater

;H 2

O;

@773

2-18

-5#

O.

E.

Zvy

agin

tsev

and

B.

N.

Sud

arik

ov,

Zh.

Neo

rg.

Khi

m.

3,97

5–

85~1

958!

;R

uss.

J.In

org.

Che

m.3,

217

–33

~195

8!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8m

2/m

olkg

21 :

3.42

;8.

44~N

H4C

l!;0

–12

.5~N

H4N

O3!

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

and

pH6

ofP

u 2O3~

C7H

5O3!

inN

H4C

lor

NH

4NO

3so

lutio

nsa

Sal

tS

alt

~gkg

21 !b

Sal

t(m

2/m

olkg

21 )c

Pu41

~mg

kg2

1 !bP

u 2O

3~C

7H5O

3!(1

06m

1/m

olkg

21 )c

NH

4Cl;

@121

25-0

2-9#

157

3.42

0.5

2.48

315

8.44

0.1

0.61

1

NH

4NO

3;@6

484-

52-2#

500.

658

0.5

2.20

100

1.39

0.4

1.86

300

5.35

0.3

1.79

500

12.5

0.1

0.84

a The

com

posi

tion

ofth

eeq

uilib

rium

solid

phas

ew

asno

tre

port

ed.

b Gra

ms

per

kgsa

tura

ted

solu

tion.

c Cal

cula

ted

byco

mpi

ler.

Form

1,

Ar~

Pu!

523

9.05

3w

asus

edan

dth

esm

all

plut

oniu

mco

ncen

trat

ion

inth

esa

tura

ted

solu

tions

was

negl

ecte

d.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dw

asus

ed.

Exc

ess

Pu

2O3~

C7H

5O3!•xH

2Ow

aseq

uilib

rate

dby

stirr

ing

with

solu

tions

ofth

ede

sire

dco

ncen

trat

ion

for

1–

2h.

Plu

toni

umco

ncen

trat

ion

inth

esa

tura

ted

solu

tions

was

dete

rmin

edby

anun

spec

ified

radi

omet

ricm

etho

d.

Pu 2

O3~

C7H

5O3!•xH

2Ow

aspr

epar

edas

amor

phou

sgr

ay–

yello

wto

brow

nso

lidby

boili

ngso

lutio

nsof

PuO~

C7H

5O3!

2in

amm

onia

cal

solu

tions

ofam

mon

ium

salic

ylat

eor

inal

kalin

eso

lutio

nsof

sodi

umsa

licyl

ate.

The

Pu

~IV

!:sa

licyl

ate

ratio

inth

epr

oduc

tw

asw

ithin

2:0.

92–

2:1.

09.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Co

~1!

Pu

~2!

~3!

Va

T/

m2

pH Te


7.11

.P

luto

nium

„IV…

8-H

ydro

xyqu

inol

inat

es

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Plu

toni

um~I

V!

tetr

akis~

halo

geno

-8-h

ydro

xy-q

uino

linat

es!A

mm

oniu

mpe

rchl

orat

e;N

H 4ClO

4;@7

790-

98-9#

Sod

ium

acet

ate;

C 2H3O

2Na;

@127

-09-

3#W

ater

;H 2

O;

@773

2-18

-5#

C.

Kel

ler

and

S.

H.

Ebe

rle,

Rad

ioch

im.

Act

a4,14

1–

5~1

965!

.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

dm2

3 :0.

09;

0.1

/mol

dm2

3 :0;

0.01

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofpl

uton

ium~

IV!

tetr

akis~

8-hy

drox

y-qu

inol

inat

es!in

NH

4ClO

4/C

2H3O

2Na

solu

tions

a

mpl

exin

glig

and

Pu~

IV!

com

plex

~for

mul

a!N

H4C

lO4

(c2

/mol

dm2

3 )C

2H3O

2Na

~c3

/mol

dm2

3 )P

u~IV

!co

mpl

ex~1

06c 1

/mol

dm2

3 )

hydr

oxyq

uino

line,

C 9H7N

OP

u~C

9H6N

O! 4

;0.

10

2.0

@#

~I!

0.09

0.01

1.5

chlo

ro-8

-hyd

roxy

quin

olin

e,P

u~C9H

5ClN

O! 4

;0.

10

0.69

H6C

lNO

@#

~II!

0.09

0.01

3.9

-dic

hlor

o-8-

hydr

oxyq

uino

line,

Pu~C

9H4C

l 2N

O! 4

;0.

10

0.59

H5C

l 2N

O@

#~I

II!

0.09

0.01

5.3

-dib

rom

o-8-

hydr

oxyq

uino

line,

Pu~C

9H4B

r 2N

O! 4

;0.

10

0.21

H5C

l 2N

O@

#~I

V!

0.09

0.01

1.6

chlo

ro-7

-iodo

-8-h

ydro

xyqu

inol

ine,

Pu~C

9H4C

lINO

! 4;

0.1

00.

82

H5C

l 2N

O@

#~V

!0.

090.

010.

92

heco

mpo

sitio

nof

the

equi

libriu

mso

lidph

ase

was

not

repo

rted

.S

atur

ated

solu

tions

show

edpH

of6.

ditio

nali

nfor

mat

ion:

rth

eP

u~C9H

6NO

! 4ch

elat

e~I!

the

solu

bilit

yw

asal

som

easu

red

asa

func

tion

ofpH

inth

etw

oso

lutio

nssh

own

abov

e.T

here

sults

wer

epo

rted

ingr

aphi

calf

orm

.



Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dw

asus

ed.

Exc

ess

Pu

2O3~

C7H

5O3!•xH

2Ow

aseq

uilib

rate

dby

stirr

ing

with

solu

tions

ofth

ede

sire

dco

ncen

trat

ion

for

1–

2h.

Plu

toni

umco

ncen

trat

ion

inth

esa

tura

ted

solu

tions

was

dete

rmin

edby

anun

spec

ified

radi

omet

ricm

etho

d.C

hem

ical

sus

edto

adju

stpH

not

repo

rted

.

Pu 2

O3~

C7H

5O3!•xH

2Ow

aspr

epar

edas

amor

phou

sgr

ay–

yello

wto

brow

nso

lidby

boili

ngso

lutio

nsof

PuO~

C7H

5O3!

2in

amm

onia

cal

solu

tions

ofam

mon

ium

salic

ylat

eor

inal

kalin

eso

lutio

nsof

sodi

umsa

licyl

ate.

The

Pu

~IV

!:sa

licyl

ate

ratio

inth

epr

oduc

tw

asw

ithin

2:0.

92–

2:1.

09.

Sou

rce

and

purit

yof

plut

oniu

man

dot

her

chem

ical

sno

tsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

~4!

Va

T/

c 2 c 3 Co

8- 5- C9

5,7

C9

5,7

C9

5- C9

a T Ad

Fo

re

J

7.12

.P

luto

nium

„IV…

N-H

ydro

xy-N

-Nitr

osob

enze

neam

inat

e

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Plu

toni

um~I

V!

raki

s~N-h

ydro

xy-N

-nitr

oso-

benz

enea

min

ate

!;C

24H

20N

8O8P

uP

u~C

6H5N

2O2!

4;@

#N

-hyd

roxy

-N-n

itros

oben

zene

amin

e~cup

ferr

on!;

C6H

6N2O

2;48

-97-

0#S

ulfu

ricac

id;

H 2S

O4;

@766

4-93

-9#W

ater

;H 2

O;

@773

2-18

-5#

I.V

.Moi

seev

,N.N

.Bor

odin

a,an

dV

.T.T

svet

kova

,Zh.

Neo

rg.

Khi

m.6

,54

3–

8;~1

961!

Rus

s.J.

Inor

g.C

hem

.6,27

7–

9~19

61!.

riabl

es:

Pre

pare

dby

:

K:

294

/mol

dm2

3 :0.

0018

9–

0.01

52/m

oldm

23 :

0.25

–1.

5

J.D

.N

avra

til

Exp

erim

enta

lDat

a

Sol

ubili

tyat

21°C

ofP

u~IV

!te

trak

is~c

upfe

rrat

e!,P

u~C

6H5N

2O2!

4,in

H2S

O4

solu

tions

a

H2S

O4

3/m

oldm

23 )b

@H1

#c

~mol

dm2

3 !C

upfe

rron

d

(103

c 2/m

oldm

23 )

Pu~

C6H

5N2O

2!4e

(106

c 1/m

oldm

23 )

0.25

0.27

81.

893.

477.

9~0.7

9!f

2.07

~0.1

53!f

0.50

0.53

83.

485.

074.

93~0.

416!

f2.

53~0

.116

!f

1.0

1.05

510

.11.

76~0

.386

!

1.5

1.56

815

.21.

38~0

.056

6!

hena

ture

ofth

eeq

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

itial

conc

entr

atio

nof

sulfu

ricac

id.

ydro

gen

ion

conc

entr

atio

nat

equi

libriu

m.

Itw

asob

tain

edfr

omth

ein

itial

conc

entr

atio

nof

sulfu

ricac

id,

and

the

appa

rent

diss

ocia

tion

nsta

nts

ofth

eac

idta

ken

from

Ref

.1.

quili

briu

mco

ncen

trat

ion

ofcu

pfer

ron.

Itw

asca

lcul

ated

from

the

initi

alco

ncen

trat

ions

ofP

u~I

V!

and

cupf

erro

n,th

efin

alvo

lum

eof

the

olut

ion,

and

the

Pu~IV

!co

ncen

trat

ion

inth

esa

tura

ted

solu

tion.

vera

geva

lues

and

stan

dard

devi

atio

ns~inpa

rent

hese

s!ca

lcul

ated

byth

eco

mpi

ler

from

thre

epa

ralle

lexp

erim

ents

.hi

spa

irof

mea

sure

men

tsdi

ffere

din

the

initi

alcu

pfer

ron

conc

entr

atio

n.

ditio

nali

nfor

mat

ion:

eeq

uilib

rium

cons

tant

for

the

prec

ipita

tion

ofP

u~I

V!

bycu

pfer

ron

~HR

!,K

5@H

1#4

@Pu~

IV! #

21@H

R#2

4w

asca

lcul

ated

tobe

6.6

102

13m

ol2

1dm

3 .F

rom

this

cons

tant

the

solu

bilit

ypr

oduc

tof

Pu

~IV

!cu

pfer

rate

,w

asob

tain

edasK

sp5

Ka4K

215

@Pu~

IV! #

@R2

#4

1.23

102

31m

ol5

dm2

15us

ing

the

diss

ocia

tion

cons

tant

ofcu

pfer

ron,Ka5

5.33

102

4.2

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

yof

Pu~I

V!

cupf

erra

tew

asde

term

ined

acco

rdin

gto

Ref

.3.

Abo

ut10

mL

Pu~IV

!in

0.5

mol

dm2

3H

2SO

4an

dth

eca

lcul

ated

quan

titie

sof

wat

er,

acid

,an

dth

ecu

pfer

ron

solu

tion

wer

est

irred

for

abou

t3

min

ina

50m

Lbe

aker

.T

hen

the

prec

ipita

tew

asfil

tere

dof

fus

ing

aN

o.4

glas

sfil

ter

cruc

ible

.T

hefir

st15

mL

offil

trat

ew

ere

reje

cted

,an

dth

eP

u~IV

!co

nten

tin

the

rem

aini

ngso

lutio

nw

asde

term

ined

radi

omet

rical

ly.

Aso

lutio

nof

Pu~I

V!

was

prep

ared

bydi

ssol

ving

pure

Pu

~OH

! 4,

fres

hly

prec

ipita

ted

inth

eco

ld,i

n1:

1H 2S

O4.

Afte

rdi

lutio

nw

ithw

ater

the

conc

entr

atio

nof

H 2SO

4w

as0.

5m

oldm

23 .

The

plut

oniu

mco

ncen

trat

ion

inth

isso

lutio

nw

asde

term

ined

grav

imet

rical

lyby

prec

ipita

ting

Pu~O

H! 4

with

amm

onia

,an

dig

nitin

gto

PuO

2at

1000

°C.C

upfe

rron

solu

tion

was

prep

ared

byw

ashi

ngth

ere

agen

tre

peat

edly

with

etha

nol,

diss

olvi

ngit

inw

ater

,an

dst

anda

rdiz

ing

bytit

ratio

nw

itha

stan

dard

Fe

~III

!so

lutio

nin

ast

ream

ofC

O 2us

ing

apl

atin

umin

dica

tor

elec

trod

e.

Est

imat

edE

rror

:T

empe

ratu

re:6

0.02

K~a

utho

rs!.

Sol

ubili

ty:

stan

dard

devi

atio

nca

lcul

ated

byth

eco

mpi

ler.

Ref

eren

ces:

1 T.

F.

You

ngan

dL.

A.

Bla

tz,

Che

m.

Rev

.44,

93~1

949!

.2 I.

V.

Pya

tnits

kii,

Zh.

Ana

l.K

him

.1,

135

~194

6!.

3 I.V

.P

yatn

itski

i,Z

h.A

nal.

Khi

m.1

,57

~194

6!.

672672 JIRI HALA

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dw

asus

ed.

The

rmos

tatin

gof

the

solu

tions

and

equi

libra

tion

time

not

repo

rted

.P

luto

nium

conc

entr

atio

nin

the

satu

rate

dso

lutio

nsw

asde

term

ined

byan

unsp

ecifi

edra

diom

etric

met

hod.

Plu

toni

um~9

9.8%

purit

y!w

asdi

ssol

ved

inac

idan

dth

e241 A

mac

cum

ulat

edby

bde

cay

of24

1 Pu

was

rem

oved

bypr

ecip

itatio

nof

plut

oniu

mas

pero

xide

.T

heab

senc

eof24

1 Am

was

chec

ked

bypa

per

chro

mat

ogra

phy

acco

rdin

gto

Ref

.1.

The

Pu

solu

tion

was

fum

edw

ithH 2

SO

41H

NO

3m

ixtu

reto

obta

inP

u~IV

!.T

hech

elat

e~I!

was

prep

ared

byad

ding

drop

wis

e0.

05m

mol

Pu

~IV

!in

10m

L1

mol

dm2

3H

2SO

4to

aso

lutio

nof

0.25

mm

ol8-

hydr

oxyq

uino

line

in50

mL

0.1

mol

dm23

C2H

3O2N

aso

lutio

nun

der

vigo

rous

stirr

ing.

The

pHw

asco

ntin

uous

lyad

just

eddu

ring

prec

ipita

tion

to4.

5–

4.9

with

NH 3so

lutio

n.T

hem

ixtu

rew

ashe

ated

to50

–60

°C,

slow

lyco

oled

toro

omte

mpe

ratu

re,

filte

red,

the

prec

ipita

tew

asw

ashe

dw

ithw

arm

wat

er,

and

drie

dov

erP 2

O5.

The

chel

ates

~II!

–~V

!w

ere

prep

ared

byad

ding

drop

wis

e0.

05m

mol

Pu~IV

!in

10m

L1

mol

dm2

3H

2SO

4to

50m

L0.

1m

oldm

23

C2H

3O2N

ain

40%

–60

%di

oxan

e.T

heso

lutio

nsco

ntai

ned

2%–

5%ex

cess

ofth

ech

elat

ing

agen

tov

erth

est

oich

iom

etric

amou

nt.

The

pHw

asco

ntin

uous

lyad

just

eddu

ring

prec

ipita

tion

to4.

5–

4.9

with

NH 3so

lutio

n.T

hem

ixtu

rew

asth

endi

lute

dw

ithw

ater

toa

diox

ane

cont

ent

of30

%,

the

prec

ipita

tew

assu

cked

dry,

was

hed

with

30%

diox

ane

at60

°C,

and

drie

dat

110

°C.

Ana

lysi

sof

the

chel

ates

,fo

und/

calc

ulat

edfo

rP

u~lig

and!

4~m

ass

%!:

~I!

Pu

29.2

/29.

30,

ligan

d71

.2/7

0.70

;~I

I!P

u25

.2/2

5.06

,lig

and

78.0

/74.

94;~III

!22

.4/2

1.91

,lig

and

79.7

/78.

09;~

IV!

Pu

16.6

/16.

51,

ligan

d83

/83.

49;~V

!P

u16

.0/

16.4

0,lig

and

82/8

3.60

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 C.

Kel

ler,

J.C

hrom

atro

grap

hy7,

535

~196

2!.

Co

~1!

tet

or ~2!

@1 ~3!

~4!

Va

T/

c 2 c 3 (c a T b In c H co d E s e A f T Ad

Th

3 5


re by as s,

510

2(2

1.76

0.2)

mol

3dm

29

~Kw

isth

eio

npr

oduc

tof

wat

er,K

a2is

the

seco

nddi

ssoc

iatio

nco

nsta

ntof

carb

onic

acid

!.A

lthou

ghth

isva

lue

iscl

ose

toth

atof

Fel

my,5

the

eval

uato

rre

com

men

dsth

eva

lue

ofR

unde

and

Kim

3be

used

sinc

eit

was

obta

ined

unde

rw

ell

defin

edco

nditi

ons.

Ref

eren

ces:

1 G.

Mei

nrat

han

dJ.

I.K

im,

Rad

ioch

im.

Act

a52Õ5

3,29

~199

1!.

2 G.

Mei

nrat

han

dJ.

I.K

im,

Eur

.J.

Sol

idS

tate

Inor

g.C

hem

.28

,38

3~1

991!

.3 W

.R

unde

,G

.M

einr

ath,

and

J.I.

Kim

,R

adio

chim

.A

cta

58Õ5

9,93

~199

2!.

4 R.

J.S

ilva,

Mat

er.

Res

.S

ol.

Sym

p.P

roc.26

,87

5~1

989!

.5 A

.R

.F

elm

y,D

.R

ai,

and

R.

W.

Ful

ton,

Rad

ioch

im.

Act

a50,

193

~199

0!.

6 M.

Shi

loh,

M.

Giv

on,

and

Y.

Mar

cus,

J.In

org.

Nuc

l.C

hem

.30

,18

07~1

969!

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Dia

mer

iciu

mtr

is~ca

rbon

ate!;

Am

2~C

O3) 3

;@

#P

otas

sium

carb

onat

e;K

2CO

3;

@584

-08-

7#W

ater

;H 2

O;

@773

2-18

-5#

M.

Shi

loh,

M.

Giv

on,

and

Y.

Mar

cus,

J.In

org.

Nuc

l.C

hem

.30

,18

07–

14~1

969!

.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

dm2

3 :0.

12–

0.6

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofA

m2~

CO

3!3

at25

°Cin

K 2C

O3

solu

tions

eso

lubi

lity

ofA

m2~

CO

3!3

at25

°Cas

afu

nctio

nof

K 2CO

3co

ncen

trat

ion,

inm

oldm

23 ,

was

repo

rted

tobe

give

nby

the

equa

tion

S5K

@CO

32 #2

thK

51.

8310

23

mol

21

dm3 .

Exp

erim

enta

ldat

aw

ere

repo

rted

ingr

aphi

calf

orm

.Als

oin

grap

hica

lfor

mw

asre

port

edth

eso

lubi

lity

of

2~C

O3!

3as

afu

nctio

nof

pH.T

heA

m~III

!sp

ecie

spr

esen

tin

0.12

–0.

6m

oldm2

3K

2CO

3so

lutio

nsw

asid

entifi

edas

Am~O

H!~

CO

3) 34

2.

eeq

uilib

rium

solid

phas

ew

asA

m 2~C

O3!

3,@

#,in

alls

olut

ions

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.25m

Lof

the

Am

~III

!st

ock

solu

tion

H3,

dilu

teH

ClO

4!w

asin

trod

uced

into

2.5

mL

K 2CO

3

lutio

nof

the

desi

red

conc

entr

atio

nin

ace

ntrif

uge

cone

.te

rst

andi

ng24

hat

room

tem

pera

ture

with

occa

sion

alak

ing,

the

prec

ipita

tew

asce

ntrif

uged

off,

and

amer

iciu

min

satu

rate

dso

lutio

nw

asde

term

ined

byaco

untin

g.T

heui

libriu

mso

lidph

ases

wer

ean

alyz

edfo

rca

rbon

ate

and

eric

ium

,an

dth

eC

O 3/A

mra

tiow

asfo

und

tobe

1.60

.

241 A

m~U

.S.A

.E.C

.!w

asdi

ssol

ved

inH

ClO 4

solu

tion

tofo

rma

stoc

kso

lutio

nof

abou

t0.

1m

oldm2

3A

m~I

II!.

Por

tions

ofth

isso

lutio

nw

ere

used

topr

ecip

itate

amer

iciu

mca

rbon

ate

dire

ctly

inth

eso

lubi

lity

expe

rimen

ts.

K 2CO

3w

asa

reag

ent

grad

epr

oduc

t.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.



8.T

heS

olub

ility

ofA

mer

iciu

mC

ompo

unds

8.1.

Am

eric

ium

„III…

Car

bona

tean

dA

mer

iciu

m„III…

Hyd

roge

ncar

bona

te

8.1.

1.E

valu

atio

nof

the

Am

„O

H…C

O3

orA

m2„

CO

3…3¿

CO

32À¿

NaC

lO4¿

H2O

Sys

tem

Com

pone

nts:

Eva

luat

or:

~1!

Am

eric

ium

hydr

oxoc

arbo

nate

;A

m~OH

!CO

3;

@101

362-

32-7#

;or

Dia

mer

iciu

mtr

is~ca

rbon

ate!;

Am

2~C

O3) 3

;@

#~2

!C

arbo

nate

ion;

CO 322

;@3

812-

32-6#

~3!

Sod

ium

perc

hlor

ate;

NaC

lO 4;

@760

1-89

-0#~4

!W

ater

;H 2

O;

@773

2-18

-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,

June

2000

Crit

ical

Eva

luat

ion:

The

two

amer

iciu

mca

rbon

ates

,Am~O

H!C

O3

and

Am

2~C

O3!

3,ar

eso

lidph

ases

impo

rtan

tfro

mth

epo

into

fvie

wof

pote

ntia

llea

chin

gof

amer

iciu

mfr

omra

dioa

ctiv

ew

aste

repo

sito

ries.

The

irso

lubi

lity

inca

rbon

ate

cont

aini

ngN

aClO

4so

lutio

nsha

sbe

enst

udie

din

Ref

s.1

–4.

The

hydr

oxoc

arbo

nate

isth

eth

erm

odyn

amic

ally

stab

leso

lidph

ase

inso

lutio

nsth

atar

ein

cont

act

with

atm

osph

eric

part

ialp

ress

uof

CO

2(,

1%

),3

and/

orat

low

equi

libriu

mca

rbon

ate

ion

conc

entr

atio

n,4

whi

leat

high

erpa

rtia

lpr

essu

res

ofC

O2

itis

the

crys

talli

neca

rbon

ate,

Am 2

~CO

3!3.

1–

3T

hese

solid

phas

esha

veal

sobe

enst

udie

din

rela

ted

syst

ems

not

cont

aini

ngN

aClO

4.T

hus

Fel

mye

ta

l.5

obse

rved

Am~

OH

!CO

3as

the

solid

phas

ein

solu

tions

cont

aini

ng,0.

1m

oldm

23

Na 2

CO

3,an

dat

pH5.

5–

13,a

ndS

hilo

heta

l.6ob

serv

edA

m2~

CO

3!3

ineq

uilib

rium

with

solu

tions

cont

aini

ng.

0.12

mol

dm2

3K

2CO

3.T

heso

lubi

lity

data

wer

eob

tain

edin

mea

sure

men

tsco

nduc

ted

aspH

titra

tions

1–

3or

byus

ing

the

isot

herm

alm

etho

d,4,

5w

ithca

refu

lco

ntro

lof

pHan

dot

her

expe

rimen

tal

para

met

ers.

The

carb

onat

eio

nco

ncen

trat

ion

inth

esa

tura

ted

solu

tions

was

cont

role

dei

ther

satu

ratin

gth

eso

lutio

nsw

ithC

O 2ga

sat

vario

uspH

,1

–3,

5or

byus

ing

NaH

CO 3

4,5

orN

a 2C

O3.

5E

xcep

tfo

rm

easu

rem

ents

inR

efs.

1,2

whe

reeq

uilib

ratio

ntim

eof

2–

3da

ysw

asus

ed,o

ther

auth

ors

equi

libra

ted

the

syst

ems

for

seve

ralw

eeks

.The

long

equi

libra

tion

time

wne

eded

beca

use

ofth

esl

owtr

ansi

tion

ofin

itial

lyam

orph

ous

solid

tocr

ysta

lline

form

.5

Thi

sis

poss

ibly

also

the

reas

onfo

rra

ther

wid

esc

atte

rof

expe

rimen

tal

solu

bilit

yda

taob

serv

edev

enaf

ter

long

equi

libra

tion.

1,5

Num

eric

also

lubi

lity

data

have

been

repo

rted

byS

ilva

4

only

,oth

erau

thor

sre

port

edth

eir

data

ingr

aphi

calf

orm

,1,

5or

repo

rted

solu

bilit

ypr

oduc

tson

ly.

2,3

Thi

ssi

tuat

ion

does

notm

ake

ade

taile

dco

mpa

rison

poss

ible

.As

with

the

carb

onat

esof

uran

ium

,nep

tuni

um,a

ndpl

uton

ium

,the

solu

bilit

ies

ofbo

thA

m~O

H!C

O3

and

Am

2~C

O3!

3

pass

thro

ugh

am

inim

umw

hen

plot

ted

agai

nst

equi

libriu

mca

rbon

ate

ion

conc

entr

atio

n.1,

2,5

The

enha

nced

solu

bilit

yat

high

er @CO

322#

valu

esha

sbe

enas

crib

edto

the

form

atio

nof

Am

~III

!ca

rbon

atoc

ompl

exes

,i.e

.,A

m~CO

3) 22

,1,5

Am

~CO

3) 33

2,5

orA

m~O

H!~

CO

3) 34

2.6

Like

wis

e,no

dire

ctco

mpa

rison

ofso

lubi

lity

prod

uct

valu

esis

poss

ible

.F

orK

spof

Am

2~C

O3!

3,th

ere

sults

ofth

eG

erm

angr

oup

1–

3ar

eav

aila

ble

only

.T

heau

thor

sob

tain

edth

eso

lubi

lity

prod

uct

inse

vera

lrep

eate

dm

easu

rem

ents

with

very

good

repr

oduc

ibili

ty.

The

valu

eas

2lo

gK

sp,

for

0.1

mol

dm2

3N

aClO

4,ar

e29

.896

0.18

at29

8.1

Kan

dp(C

O2)

of1%

,129

.576

0.10

at29

5.1

Kan

dp(C

O2)

of10

0%,2

29.3

260.

08at

295.

1K

andp

(CO

2)of

1%,2

and

29.4

560.

18at

298.

1K

andp

(CO

2)of

1%or

100%

.3T

heev

alua

tor

sugg

ests

thes

eva

lues

asre

com

men

ded

ones

.T

heso

lubi

lity

prod

uct

ofA

m~O

H!C

O3

has

been

repo

rted

tobe

102(1

8.70

60.

12)

mol

3dm

29

~298

.1K

,p

(CO

2)

0.03

%,0

.1m

oldm

23

NaC

lO4)

,3an

d10

222

.5m

ol3

dm2

9at

unsp

ecifi

edio

nic

stre

ngth

and

room

tem

pera

ture

.5

Silv

a4ob

tain

edth

eeq

uilib

rium

cont

ant,

K5

@Am

31

#@C

O322

#@H

1#2

25

5836

206

~0.1

mol

dm2

3N

aClO

4)fo

rth

ere

actio

nA

m~O

H!C

O3

(s)

12H

1�

Am

311

HC

O32

1H

2O.

Fro

mth

isco

nsta

ntth

eev

alua

tor

calc

ulat

edth

eso

lubi

lity

prod

uct

asKsp

5K

KwK

a2

Co

~1!

~2!

~3!

Va

T/

c 2 Th

wi

Am

Th

Me

Iso

~p so Af

sh the

eq am

J

FIG

.23

.D

iam

eric

ium

tris~c

arbo

nate!

–so

dium

perc

hlor

ate

–ca

rbon

diox

ide

–w

ater

syst

em.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

eso

lubi

lity

expe

rimen

t,co

mbi

ned

with

pHtit

ratio

n,w

asnd

ucte

din

a10

0m

Lth

erm

osta

ted

vess

elin

the

pHra

nge

m6.

0to

9.2

unde

rar

gon/

1%C

O2

atm

osph

ere.

The

desi

red

rbon

ate

conc

entr

atio

nw

asat

tain

edby

pHco

ntro

l.T

he31

ion

0.1

mol

dm2

3H

ClO

4w

asin

trod

uced

into

the

vess

elm

31

# tot

553

102

4m

oldm

23 )

and

prec

ipita

ted

byad

ditio

n0.

05m

oldm

23

Na 2

CO

3.T

heso

lutio

nw

ithth

epr

ecip

itate

sle

ftto

stan

dun

der

Ar/

CO 2at

mos

pher

efo

r2

wee

ks.

The

npH

ofth

eso

lutio

nw

asgr

adua

llyad

just

edby

addi

tions

ofhe

r0.

1m

oldm

23

HC

lO4

or0.

05m

oldm

23

Na 2

CO

3fo

rth

era

nge

of6

–8

inth

epr

esen

ceof

0.1

mol

dm23

NaC

lO4,

or0.

3m

oldm

23

HC

lO4

or0.

1m

oldm

23

Na 2

CO

3fo

rth

epH

nge

of8

–9

inth

epr

esen

ceof

0.3

mol

dm23

NaC

lO4.

mbi

natio

ngl

ass

elec

trod

es~RO

SS

-typ

e,O

rion!

used

for

pHas

urem

ent

wer

eca

libra

ted

agai

nst

stan

dard

buffe

rso

lutio

nsju

sted

toth

ede

sire

dio

nic

stre

ngth

.E

quili

briu

mat

agi

ven

was

esta

blis

hed

in2

–3

days

.T

heam

eric

ium

conc

entr

atio

ns

mea

sure

daf

ter

filtr

atio

nof

the

satu

rate

dso

lutio

nth

roug

h0

nmpo

resi

zefil

ter

byliq

uid

scin

tilla

tion

coun

ting

eckm

anLS

6800!

.In

anu

mbe

rof

sam

ples

,th

eA

mnc

entr

atio

nw

asal

sode

term

ined

byei

ther

UV

spec

tros

copy

t @A

m3

1# t

ot.

102

5m

oldm

23 !

orby

lase

r-in

duce

dot

oaco

ustic

spec

tros

copy~a

t @A

m3

1# t

ot,

102

6m

oldm

23 !

.e

equi

libriu

mso

lidph

ases

wer

ein

vest

igat

edby

mea

nsof

31as

am

odel

ion

whi

chis

know

nto

beve

rycl

ose

inem

ical

beha

vior

toA

m31.

The

Nd31

ion

was

prec

ipita

ted

der

the

sam

eco

nditi

ons

asw

asA

m31

inth

eso

lubi

lity

perim

ent,

and

the

prec

ipita

tew

asco

nfirm

edto

be

2~C

O3!

3•8H

2Oby

x-ra

ydi

ffrac

tion

and

IRsp

ectr

osco

py.

Isot

opic

ally

pure

241 A

mw

asus

ed.

The

Ar

11%

CO 2

gas

mix

ture

was

apr

oduc

tof

Lind

e.N

oot

her

deta

ilsw

ere

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n61

K~a

utho

rs!.

pH:

prec

isio

n60.

03un

its~a

utho

rs!.

Sol

ubili

typr

oduc

t:st

anda

rdde

viat

ion

see

abov

e.

674674 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Dia

mer

iciu

mtr

is~ca

rbon

ate!;

Am

2~C

O3) 3

;@

#~2

!C

arbo

ndi

oxid

e;C

O 2;

@124

-38-

9#~3

!S

odiu

mpe

rchl

orat

e;N

aClO 4

;@7

601-

89-0#

~4!

Wat

er;

H 2O

;@7

732-

18-5#

1 G.

Mei

nrat

han

dJ.

I.K

im,

Rad

ioch

im.

Act

a52Õ5

3,29

–34

~199

1!.

2 G.

Mei

nrat

han

dJ.

I.K

im,

Eur

.J.

Sol

idS

tate

Inor

g.C

hem

.28

,38

3–

8~1

991!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8;29

5p

2~p

artia

lpre

ssur

eof

CO 2!

/%:

1;10

0c 3

/mol

dm2

3 :0.

1;0.

3

J.H

ala

Exp

erim

enta

lDat

aIn

the

orig

inal

Ref

.1,

the

solu

bilit

yof

Am 2~

CO

3!3

asa

func

tion

ofpH

and

equi

libriu

mco

ncen

trat

ion

ofC

O322

ion,

at25

°Can

dpa

rtia

lpr

essu

reof

CO 2

of1%

,w

ere

repo

rted

ingr

aphi

calf

orm~s

eeF

ig.

23!.

The

conc

entr

atio

nof

CO 322

ion

was

calc

ulat

edfr

omth

em

easu

red

pH,

and

ase

ries

ofeq

uilib

riain

clud

ing

part

ialp

ress

ure

ofC

O2,

Hen

ryco

nsta

nt,

and

diss

ocia

tion

cons

tant

sof

carb

onic

acid

:

CO

2~g

!�KH

CO

2~a

q !�K

*H

2CO

3�Ka1

HC

O3�K

a2

CO

322

aslo

g @C

O322

#5lo

gK

1lo

gp(

CO

2)1

2pH

,w

ithlo

gK

5lo

g(K

HK

* Ka1

Ka2

)52

17.7

8.T

heco

urse

ofth

eso

lubi

lity

curv

ew

asin

terp

rete

dby

the

auth

ors

inte

rms

ofth

efo

rmat

ion

ofA

m(C

O3)

n32

2n

com

plex

esin

the

solu

tion.

Usi

ngth

eeq

uatio

n @Am

# tot

5$K

sp/ @

CO

322#3

%1/2 S

bn@C

O322

#n,

whe

re@A

m# t

otis

the

tota

lco

ncen

trat

ion

ofA

m~III

!in

the

satu

rate

dso

lutio

n,K

sp

5@A

m3

1#2

@CO

322#3

,an

db

n5

@Am

(CO

3) n3

22

n#/

@Am

31

#@C

O322

#n~o

vera

llst

abili

tyco

nsta

nts

ofth

eA

m(C

O 3)n3

22

nco

mpl

exes!

,th

efo

l-lo

win

gva

lues

wer

eob

tain

ed: b15

10(5

.976

0.15

)m

ol2

1dm

3 ,b

25

10(9

.586

0.24

)m

ol2

2dm

6 ,an

dK

sp5

102

(29.

896

0.18

)m

ol5

dm2

15.

The

seco

nsta

nts

wer

ere

port

edto

beva

lidfo

rso

lutio

nsw

ithio

nic

stre

ngth

of0.

1–

0.3

mol

dm2

3N

aClO

4.In

the

orig

inal

refe

renc

e,2th

eva

lue

oflo

gKw

asre

fined

tobe

2(1

7.62

60.

07),

and

the

solu

bilit

ypr

oduc

tofA

m 2~C

O3!

3at

22°C

was

obta

ined

as102

(29.

326

0.08

)m

ol5

5 dm2

15at

100%

and

1%pa

rtia

lpr

essu

reof

CO

2,re

spec

tivel

y,an

dio

nic

stre

ngth

of0.

1m

oldm2

3

NaC

lO4.

Inbo

thdo

cum

ents

,th

eeq

uilib

rium

solid

phas

ew

asA

m2~

CO

3) 3

,@

#,ov

erth

ew

hole

pHra

nge

inve

stig

ated

.

Me

Th

co fro

ca Am

( @A

of wa

the

eit

pH by ra Co

me

ad pH wa

45 ~B co ~a ph Th

Nd

ch un ex Nd


The

equi

libriu

mso

lidph

ases

wer

ech

arac

teriz

edby

ther

mog

raph

ican

alys

isco

mbi

ned

with

DT

A,

byF

TIR

spec

tros

copy

,an

dx-

ray

pow

der

diffr

actio

n.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

eric

ium

hydr

oxoc

arbo

nate

;A

m~OH

!CO

3;

0136

2-32

-7#S

odiu

mhy

drog

enca

rbon

ate;

NaH

CO

3;

@144

-55-

8#S

odiu

mpe

rchl

orat

e;N

aClO 4

;@7

601-

89-0#

Wat

er;

H 2O

;@7

732-

18-5#

R.

J.S

ilva,

Mat

er.

Res

.S

oc.

Sym

p.P

roc.26,

875

–81

,~198

4!.

Am

erici

um

an

dC

uriu

mC

he

mis

try

an

dT

ech

no

log

y,e

dite

dby

N.

M.

Ede

lste

ine

ta

l.,~R

eide

lDor

drec

ht,

1985!

,pp

.22

5–

238.

R.

J.S

ilva

and

H.

Nits

che,

NU

RE

G/C

P-0

052,

Pro

ceed

ings

U.S

.N

RC

,Nuc

l.W

aste

Geo

chem

.’83

,Res

ton,

VA

,198

3,pp

.70

–93

.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

dm2

3 :2

310

24

/mol

dm2

3 :0.

1

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofA

m~O

H!C

O3

in2

310

24

mol

dm2

3N

aHC

O 3/0

.1m

oldm

23

NaC

lO4

solu

tions

a

quili

brat

ion

time

~day

s!pH

HC

O32

(104

c 2/m

oldm

23 )

Am

~OH

!CO

3

(106

c 1/m

oldm

23 )

102

2K

d

1b6.

132.

0928

.662.

563

.261.

0

36.

132.

0911

.960.

426

.363.

6

76.

152.

192.

1760.

545.

516

1.56

146.

132.

092.

3960.

215.

286

0.85

216.

142.

142.

0260.

044.

796

0.65

306.

142.

142.

2960.

03e

5.43

60.

73

1.54

60.

13f

3.65

60.

58

1.40

60.

13g

3.32

60.

07

1c6.

091.

9136

6613

6146

82

36.

112.

0031

565

6076

82

76.

122.

0535

6613

7356

102

146.

101.

9578

.6616

.714

1635

226.

132.

097.

6760.

7217

.062.

8

316.

142.

143.

2160.

147.

606

1.07

376.

132.

094.

4260.

179.

776

1.36

446.

132.

094.

7160.

3010

.461.

5

516.

112.

004.

8860.

11e

9.40

61.

33

quili

briu

mso

lidph

ase

was

Am~O

H!C

O3,

@101

362-

32-7#

,in

alls

olut

ions

.hi

san

dth

efo

llow

ing

five

mea

sure

men

tspe

rfor

med

usin

gpr

oced

ure

~a!.

c Thi

san

dth

efo

llow

ing

seve

nm

easu

rem

ents

perf

orm

edus

ing

proc

edur

e~b

!.d E

quili

briu

mco

nsta

ntfo

rth

ere

actio

nA

m~OH

!CO

3~s!

12H

1�

Am

311

HC

O32

1H

2O.

Itw

asca

lcul

ated

from

the

mea

sure

dam

eric

ium

and

HC

O32

conc

entr

atio

ns,

and

the

calc

ulat

edH

1io

nco

ncen

trat

ion,

whi

chw

asob

tain

edfr

omth

em

easu

red

pHva

lue

usin

gth

eac

tivity

coef

ficie

ntof

0.78

.B

ased

onlit

erat

ure

data

for

the

hydr

olys

isof

Cm

31io

n,as

acl

ose

anal

ogof

Am31

,an

dth

est

abili

tyco

nsta

ntof

the

Am

~CO

3!1

com

plex

,th

eco

ncen

trat

ion

ofth

eA

m31io

nsw

asfo

und

tobe

equa

lto

(95.

96

1.3)

%of

the

mea

sure

dco

ncen

trat

ion

ofA

m~I

II!

inth

eso

lutio

ns.

The

valu

esof

the

cons

tantKob

tain

edin

met

hod~a

!by

the

thre

edi

ffere

ntso

lid–

liqui

dse

para

tion

proc

edur

esaf

ter

30da

yeq

uilib

ratio

ntim

e,an

din

met

hod~b!

afte

r51

day

equi

libra

tion

time

wer

eav

erag

edby

the

auth

ors

toob

tain

K5

583

620

6.U

sing

activ

ityco

effic

ient

sof

0.46

,0.

76,

and

0.78

for

the

Am

31,

HC

O32

,an

dH1

ions

,re

spec

tivel

y,th

eco

nsta

ntat

zero

ioni

cst

reng

thw

asob

tain

edasK

05

3356

120.

e Cen

trifu

gatio

non

ly.

f Cen

trifu

gatio

nan

dfil

trat

ion

thro

ugh

a0.

2mm

filte

r.g C

entr

ifuga

tion

and

filtr

atio

nth

roug

ha

0.01

5mm

filte

r.



Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Dia

mer

iciu

mtr

is~ca

rbon

ate!;

Am

2~C

O3) 3

;@

#;or

Am

eric

ium

hydr

oxoc

arbo

nate

;A

m~OH

!CO

3;

@101

362-

32-7#

~2!

Car

bon

diox

ide;

CO 2

;@1

24-3

8-9#

~3!

Sod

ium

perc

hlor

ate;

NaC

lO 4;

@760

1-89

-0#~4

!W

ater

;H 2

O;

@773

2-18

-5#

W.

Run

de,

G.

Mei

nrat

h,an

dJ.

I.K

im,

Rad

ioch

im.

Act

a58

Õ59,

93–

100~

1992

!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8p

2~p

artia

lpre

ssur

eof

CO 2!

/%:

0.03

;1;

100

c 3/m

oldm

23 :

0.1

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofA

m2~

CO

3!3

and

Am

~OH

!CO

3in

0.1

mol

dm2

3N

aClO

4so

lutio

nw

asm

easu

red

asa

func

tion

ofpH

and

equi

libriu

mco

ncen

trat

ion

ofC

O 322io

n,at

25°C

and

part

ial

pres

sure

sof

CO

2of

0.03

%,

1%,

and

100%

.T

heex

perim

enta

lda

taw

ere

not

repo

rted

.U

sing

the

sam

eco

mpu

tatio

nal

proc

edur

eas

inth

eau

thor

s’pr

evio

usw

ork

1,2

the

auth

ors

obta

ined

the

follo

win

gso

lubi

lity

prod

ucts

:K

sp5

@Am

31

#2@C

O322

#35

102

(29.

456

0.18

)m

ol5

dm2

15at

part

ial

pres

sure

ofC

O 2of

1%or

100%

,an

dKsp

5@A

m3

1#@

OH

2#@

CO

322#

510

2(1

8.70

60.

12)

mol

3dm

29

atpa

rtia

lpr

essu

reof

CO 2of

0.03

%.

Sol

idph

ases

ateq

uilib

rium

wer

eid

entifi

edas

Am

2~C

O3) 3

,@

#at

part

ialp

ress

ure

ofC

O 2of

1%or

100%

,an

dA

m~OH

!CO

3,@1

0136

2-32

-7#,

atpa

rtia

lpre

ssur

eof

CO 2of

0.03

%.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

yex

perim

ent,

com

bine

dw

ithpH

titra

tion,

was

cond

ucte

din

a10

0m

Lth

erm

osta

ted

vess

elun

der

diffe

rent

CO

2pa

rtia

lpre

ssur

esus

ing

argo

n/C

O2

gas

mix

ture

s.T

heA

m31

inac

idic

0.1

mol

dm2

3N

aClO

4so

lutio

nw

aspr

ecip

itate

dby

the

addi

tion

of0.

1m

oldm2

3N

aOH

.T

heso

lutio

nw

ithth

epr

ecip

itate

was

left

tost

and

unde

rth

ede

sire

dA

r/C

O2

atm

osph

ere

for

mor

eth

an2

wee

ks.

The

gas

with

agi

ven

com

posi

tion

was

cont

inuo

usly

pass

edth

roug

hth

eve

ssel

tom

aint

ain

aco

nsta

ntpr

essu

reof

CO

2.T

hen

the

pHof

the

solu

tion

was

grad

ually

adju

sted

byad

ditio

nsof

eith

er0.

1m

oldm

23

NaH

CO 3

orN

aOH

.A

fter

equi

libriu

mha

dbe

enat

tain

ed,

the

pHw

asm

easu

red

bya

com

bina

tion

glas

sel

ectr

ode

~RO

SS

-typ

e,O

rion!,

whi

chw

asca

libra

ted

with

mor

eth

anfiv

est

anda

rdbu

ffer

solu

tions

.T

heeq

uilib

rium

Am

31co

ncen

trat

ion

inth

esa

tura

ted

solu

tions

was

dete

rmin

edby

UV

spec

tros

copy

mea

surin

gth

eab

sorb

ance

at50

3.2

nm.

The

tota

lam

eric

ium

conc

entr

atio

nw

asde

term

ined

byliq

uid

scin

tilla

tion

coun

ting.

Not

hing

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

n60.

2K

~aut

hors!

.pH

:pr

ecis

ion6

0.02

units

~aut

hors!

.S

olub

ility

prod

uct:

stan

dard

devi

atio

n,se

eab

ove.

Ref

eren

ces:

1 G.

Mei

nrat

han

dJ.

I.K

im,

Rad

ioch

im.

Act

a52Õ5

3,29

~199

1!.

2 G.

Mei

nrat

han

dJ.

I.K

im,

Eur

.J.

Sol

idS

tate

Inor

g.C

hem

.28

,38

3~1

991!

.

Co

~1!

@1 ~2!

~3!

~4!

Va

T/

c 2 c 3

E

a E b T

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

eric

ium

hydr

oxoc

arbo

nate

;A

m~OH

!CO

3;01

362-

32-7#

met

hod~

a!:

Sod

ium

hydr

ogen

carb

onat

e;N

aHC

O3;

@144

-55-

8#C

arbo

ndi

oxid

e;C

O 2;@1

24-3

8-9#;

Wat

er;

H 2O

;@7

732-

18-5#

met

hod~

b!:

Sod

ium

carb

onat

e;N

a2C

O3;

@497

-19-

8#;S

odiu

mhy

drox

ide;

NaO

H;@1

310-

73-2#

Wat

er;

H 2O

;@7

732-

18-5#

A.

R.

Fel

my,

D.

Rai

,an

dR

.W

.F

ulto

n,R

adio

chim

.A

cta50,

193

–20

4~19

90!.

riabl

es:

Pre

pare

dby

:

K:

unsp

ecifi

edro

omte

mpe

ratu

rean

dc 3

/mol

dm2

3 :se

eth

ete

xtbe

low

J.H

ala

Exp

erim

enta

lDat

ae

solu

bilit

yof

Am

~OH

!CO

3w

asm

easu

red

inN

aHC

O 3/C

O2

and

Na 2

CO

3/N

aOH

solu

tions

.T

here

sults

,w

hich

show

eda

rath

erw

ide

atte

r,w

ere

repo

rted

ingr

aphi

calf

orm

only

.In

met

hod

~a!

~see

belo

w;p

25

0.00

1at

m,

NaH

CO 3

solu

tions

!,us

ing

Am

~OH

!CO

3pr

epar

edtw

odi

ffere

ntm

etho

ds,

the

syst

ems

requ

ired

36da

yeq

uilib

ratio

nto

obta

inst

eady

stat

eA

mco

ncen

trat

ion

inth

eso

lutio

ns.

The

auth

ors

plai

ned

this

byco

nver

sion

ofth

ein

itial

lyam

orph

ous

solid

tocr

ysta

lline

Am

~OH

!CO

3,@1

0136

2-32

-7#.

The

sam

eeq

uilib

rium

solid

ase

was

foun

dal

soin

met

hod

~b!

with

eith

er0.

07m

oldm

23

Na 2

CO

31N

aOH

atpH

10.5

–13

,or

with

0.00

3–

0.1

mol

dm23

Na 2

CO

3at

8.5

–11

afte

r61

days

ofeq

uilib

ratio

n.T

hus

Am

~OH

!CO

3is

the

equi

libriu

mso

lidph

ase

inso

lutio

nsco

ntai

ning,

0.1

mol

dm2

3

2CO

3,an

dat

pH5.

5–

13.

The

auth

ors

conc

lude

dth

atth

eso

lubi

lity

ofA

m~O

H!C

O3

unde

rth

eco

nditi

ons

used

coul

dbe

stbe

expl

aine

das

sum

ing

Am31

and

Am

~CO

3!n3

-2n

spec

ies

inth

esa

tura

ted

solu

tions

.A

tpH,7,

the

unco

mpl

exed

Am31

ion

isth

edo

min

ant

spec

ies.

pH7

–8.

5,an

dat

pH.

8.5

the

com

plex

esA

m~CO

3!1

and

Am

~CO

3!22

and

Am

~CO

3!22

and

Am

~CO

3!332

pred

omin

ate,

resp

ectiv

ely.

No

icat

ion

ofso

lutio

nco

mpl

exes

cont

aini

ngei

ther

OH

2or

HC

O32

ligan

dsw

asob

serv

ed.

The

follo

win

gco

nsta

nts,

atze

roio

nic

stre

ngth

,re

obta

ined

byap

plyi

ngth

eio

nin

tera

ctio

nth

eory

toex

perim

enta

lda

ta~ b

nar

eov

eral

lst

abili

tyco

nsta

nts

!:~O

H!C

O3~

s,cr

yst!�

Am

311

OH

21

CO

322,

Ksp0

510

222

.5A

m31

1C

O322�

Am

~CO

3!1

,b

15

107.

6A

m31

12C

O322�

Am

~CO

3!22

,b

2

1012

.3A

m31

13C

O322�

Am

~CO

3!332

,b

35

1015

.2

676676 JIRI HALA

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

yof

Am

~OH

!CO

3w

asm

easu

red

byis

othe

rmal

met

hod

intw

ose

ries

ofex

perim

ents

.In

the

first

met

hod

~a!

the

solu

tions

wer

eco

ntac

ted

with

crys

talli

neA

m~O

H!C

O3.

8m

gof

Am

~OH

!CO

3w

ere

plac

edin

apo

lypr

opyl

ene

cell

with

50m

Laq

ueou

sph

ase.

Sam

ples

wer

eta

ken

afte

rdi

ffere

nttim

ein

terv

als,

cent

rifug

ed,

and24

3 Am

inth

esa

tura

ted

solu

tions

was

dete

rmin

edby

liqui

dsc

intil

latio

nco

untin

g.T

heco

untin

gw

aspe

rfor

med

perio

dica

llyfo

r3

–4

wee

ksto

allo

wse

cula

req

uilib

rium

with

239 N

pto

bees

tabl

ishe

d.In

the

30da

ysex

perim

ent,

addi

tiona

laliq

uots

wer

eta

ken

and

filte

red

thro

ugh

0.2

and

0.01

5mm

filte

rsaf

ter

cent

rifug

atio

n.In

the

seco

ndm

etho

d~b!

the

satu

rate

dso

lutio

nsfr

omth

eab

ove

proc

edur

ew

ere

mad

e0.

1m

oldm2

3H

ClO

4to

diss

olve

the

solid

Am

~OH

!CO

3,th

evo

lum

ew

asm

ade

upto

50m

Lw

ithw

ater

,an

dN

aHC

O 3or

NaO

Hso

lutio

nsto

prod

uce

agai

nth

esa

me

com

posi

tion

asin

met

hod~a

!,an

dth

ere

mai

nder

ofth

epr

oced

ure

was

adop

ted

asde

scrib

edfo

rm

etho

d~a

!.A

llm

easu

rem

ents

wer

eco

nduc

ted

atfix

edpH

whi

chw

asco

ntro

lled

with

apo

tent

iost

at.

The

pHof

the

mea

sure

men

tsw

asse

lect

edso

asto

bew

ithin

aw

ellb

uffe

red

regi

on,

and

atth

esa

me

time

with

inth

epH

inte

rval

nece

ssar

yto

avoi

dhy

drol

ysis

ofA

m~III

!~o

ccur

sat

pH.

6.5!

,an

ddi

ssol

utio

nof

allA

m~O

H!C

O3

~occ

urs

atpH

,5.

0!.

The

conc

entr

atio

nof

HC

O32

ion

was

fixed

byco

ntac

ting

the

solu

tions

with

anat

mos

pher

eof

0.79

2%C

O 2199

.2%

Ar.

The

solid

phas

esw

ere

iden

tified

byx-

ray

diffr

actio

npa

ttern

sw

hich

wer

efo

und

tobe

near

lyid

entic

alw

ithth

ose

ofN

d~OH

!CO

3.1

Am

~OH

!CO

3w

aspr

epar

edby

hydr

olys

isof

Am~III

!tr

ichl

oroa

ceta

teac

cord

ing

toth

epr

oced

ure

for

lant

hani

des.

2

Est

imat

edE

rror

:~a

utho

rs!T

empe

ratu

re:

prec

isio

n61

K.

pH:

prec

isio

n60.

03un

its.

Sol

ubili

ty:

the

erro

r~se

eth

eta

ble!

isth

ede

viat

ion

from

the

aver

age

oftw

oal

iquo

tsta

ken

atea

chsa

mpl

ing

perio

d.H

CO

32io

nco

ncen

trat

ion:6

(0.1

7–

0.19

)310

24

mol

dm2

3 .

Ref

eren

ces:

1 H.

Dex

pert

and

P.

Car

o,M

at.

Res

.B

ull.9,

1577

~197

4!.

2I.

Sal

utsk

yan

dL.

L.Q

uill,

J.A

m.C

hem

.Soc

.72

,330

6~19

50!.

Co

~1!

@1 In ~2!

~3!

~4!

In ~2!

~3!

~4!

Va

T/

c 2 Th

sc by ex ph pH Na

by At

ind

we

Am

5


8.2.

Sal

tsof

Car

bona

todi

oxoa

mer

icia

te„V…„-1…

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Dia

mer

iciu

mtr

is~ca

rbon

ate!;

Am

2~C

O3!

3;@

#;or

Sod

ium

carb

onat

odio

xoam

eric

iate~V!;

Na~

Am

O2!

CO

3;@

#C

arbo

nate

ion;

CO 322

;@3

812-

32-6#

Sod

ium

chlo

ride;

NaC

l;@764

7-14

-5#W

ater

;H 2

O;

@773

2-18

-5#

E.

Giff

aut

and

P.

Vito

rge,

Mat

er.

Res

.S

oc.

Sym

p.P

roc.

294,

747

–51

~199

3!.

riabl

es:

Pre

pare

dby

:

K:

294

/%:

100

~par

tialp

ress

ure!

/mol

dm2

3 :0.

1;4

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

typr

oduc

tsof

Am 2

~CO

3!3

and

Na~A

mO

2!C

O3

at21

°Cin

NaC

lsol

utio

ns

NaC

l(c

3/m

oldm

23 )

2lo

gK

sp~1

!a,c

2lo

gK

sp~2

!b,c

0.1

34.26

0.3

—

430

.46

0.4

10.56

0.3

sp5

@Am

31#2 @

CO

322#3 .

sp5

@Na1

#@A

mO

21#@

CO

322#.

once

ntra

tions

inm

oldm2

3 .

ditio

nali

nfor

mat

ion:

4m

oldm

23

NaC

lthe

Am

solu

bilit

yw

asfo

und

tobe

high

erby

1–

3or

ders

ofm

agni

tude

than

that

in0.

1m

oldm

23

NaC

l,an

dcl

ose

Np~

V!

solu

bilit

yun

der

sim

ilar

cond

ition

s.1,2

Inth

epr

esen

ceof

met

allic

iron

asa

redu

cing

agen

t,th

eA

mso

lubi

lity

decr

ease

dw

ithin

eek

toth

at0.

1m

oldm

23

NaC

l.T

his

beha

vior

was

expl

aine

dby

the

auth

ors

asbe

ing

due

tora

diol

ytic

oxid

atio

nof

Am

~III

!to

Am

~V!.

3

pH,

6.5,

NaA

mO 2

CO

3w

asth

eeq

uilib

rium

solid

phas

eat

equi

libriu

mC

O322

ion

conc

entr

atio

ns.

102

5m

oldm

23 .

Sol

ubili

tyda

tare

repo

rted

ingr

aphi

cal

form

only

,an

dsh

owth

atm

inim

umA

m~I

II!

and

Am

~V!

solu

bilit

yoc

curs

atap

prox

imat

ely

25–

102

4m

oldm

23

carb

onat

eio

nco

ncen

trat

ion.

Als

ore

port

edw

ere

stab

ility

cons

tant

sof

ofA

m~I

II!~

CO

3!3

22

n(n

51

–3

)co

mpl

exes

0.1

and

4m

oldm

23

NaC

l,an

dA

mO 2

~CO

3!1

-2n

~n5

1an

d2!

com

plex

esin

4m

oldm

23

NaC

l.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

lubi

lity

mea

sure

men

tsw

ere

perf

orm

edas

pHtit

ratio

noc

edur

ew

ithA

m 2~C

O3!

3as

the

star

ting

solid

inca

rbon

ate

ffer

solu

tions

.T

hesu

spen

sion

was

stirr

edat

the

desi

red

pHfo

r13

wee

ks.

Afte

req

uilib

ratio

n,sa

mpl

esof

the

satu

rate

dso

lutio

nsw

ere

filte

red,

the

pHw

asm

easu

red

with

aco

mbi

ned

glas

sel

ectr

ode

that

was

calib

rate

dw

ithN

aHC

O 3/N

a 2C

O3

/NaC

lor

HC

l/NaC

lsol

utio

ns,

and

the

Am

solu

bilit

yw

asde

term

ined

byliq

uid

scin

tilla

tion

coun

ting.

Am

2~C

O3!

3w

aspr

epar

edby

equi

libra

ting

anam

eric

ium

solu

tion

in0.

5m

oldm

23

carb

onat

ew

ithbu

bblin

gC

O 2ga

sth

roug

hth

eso

lutio

nfo

ra

perio

dof

3w

eeks

.

Est

imat

edE

rror

:N

oin

form

atio

nre

port

ed.

Ref

eren

ces:

1 L.M

aya,

Inor

g.C

hem

.22,

2093

~198

3!.

2 I.G

rent

he,P

.Rob

ouch

,and

P.V

itorg

e,J.

Less

-Com

mon

Met

als

122,

225

~198

6!.

3 S.

Mag

irius

,W

.T

.C

arna

llan

dJ.

I.K

im,

Rad

ioch

im.

Act

a38,

29~1

985!

.



Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Tw

ose

ries

ofm

easu

rem

ents

wer

eco

nduc

ted.

Inon

e@m

etho

d~a

!#,

afix

edpa

rtia

lpre

ssur

eof

CO 2o.

d.0.

001

atm

inul

trap

ure

Ar

gas

was

adju

sted

ina

glov

ebo

x.A

llH

CO

3so

lutio

nsw

ere

initi

ally

equi

libra

ted

with

the

cham

ber

gas

for

2–

3da

ysbe

fore

thes

eso

lutio

nsw

ere

adde

dto

the

prec

ipita

ted

mat

eria

lin

cent

rifug

etu

bes.

The

tube

sw

ere

kept

slig

htly

capp

edto

allo

wex

chan

geof

CO 2

with

the

glov

ebo

xat

mos

pher

e,an

dw

ere

shak

enon

anor

bita

lsha

ker.

Inth

ese

cond

serie

sof

expe

rimen

ts@m

etho

d~b!

#,th

epr

ecip

itate

dA

m~OH

!CO

3

obta

ined

inm

etho

d~a!

was

was

hed

with

de-io

nize

dw

ater

,re

susp

ende

din

eith

er0.

003

–0.

1m

oldm23

Na 2

CO

3~in

itial

pH10

.6–

11.3!

,or

in0.

07m

oldm

23

Na 2

CO

3w

hose

pHw

asad

just

edw

ithC

O 2-f

ree

NaO

Hto

reac

hpH

11.7

–13

,an

dsh

aken

.E

ach

ofth

ese

two

proc

edur

esw

ere

run

with

Am

~OH

!CO

3pr

epar

edby

proc

edur

es~A!

and

~B!

~see

belo

w!.S

uspe

nsio

nsof

Am~O

H!C

O3

wer

eeq

uilib

rate

dfo

rpr

olon

ged

perio

dsof

time,

and

sam

ples

from

the

satu

rate

dso

lutio

nsw

ere

take

naf

ter

inte

rval

sra

ngin

gfr

om2

to78

days

.T

hepH

ofth

esu

spen

sion

sw

asm

easu

red

with

aco

mbi

natio

ngl

ass

elec

trod

eO

rion/

Ros

s,ca

libra

ted

with

pHbu

ffers

.T

hesa

mpl

esw

ere

cent

rifug

edat

2000

gfo

r7

–10

min

,al

iquo

tsof

the

supe

rnat

ant

wer

efil

tere

dth

roug

hA

mic

onty

peF

-25

Cen

trifl

om

embr

ane

cone

s~;0.

0018

mm

pore

size!

.F

iltra

tes

wer

eac

idifi

ed,

and

befo

reA

man

alys

isst

ored

for

;30

days

toal

low

the

239 N

p~p

rodu

ced

from

the24

3 Am

~OH

!CO

3in

the

orig

inal

susp

ensi

ons!to

deca

yto

near

secu

lar

equi

libriu

mw

ith24

3 Am

pres

ent

inea

chvi

al.

Sam

ples

wer

eco

unte

dus

ing

high

-pur

ityG

epl

anar

dete

ctor

s.T

otal

chem

ical

anal

ysis

ofth

esa

tura

ted

solu

tions

was

perf

orm

edby

the

indu

ctiv

ely

coup

led

plas

ma~

ICP!

met

hod.

Tot

alin

orga

nic

carb

onw

asde

term

ined

byus

ing

aC

oulo

met

rics

Inc.

Mod

el50

20to

talc

arbo

nan

alyz

er.

Sol

idph

ases

wer

ech

arac

teriz

edby

x-ra

ydi

ffrac

tion.

Am

~OH

!CO

3w

aspr

epar

edby

two

met

hods

:~A

!by

prec

ipita

tion

byad

ding

0.1

mL~

;4.

5m

gA

m!

of24

3 Am

stoc

kso

lutio

nto

30m

L0.

01m

oldm

23

NaH

CO 3

atpH

7in

apo

lypr

opyl

ene

cent

rifug

eco

ne;

the

prec

ipita

tew

asw

ashe

dtw

ice

with

20m

L0.

0004

mol

dm2

3N

aHC

O 3at

pH8;

~B!

byho

mog

eneo

uspr

ecip

itatio

nof

Am~

III!

tric

hlor

oace

tate

.1S

olut

ions

with

Am

~OH

!CO

3pr

ecip

itate

wer

ehe

ated

for

about6

hat

50°C

,al

low

edto

cool

over

nigh

t,an

dth

enw

ashe

dw

ith0.

0004

mol

dm2

3N

aHC

O 3at

pH8.

Ref

eren

ces:

1 R.

G.

Cha

rles,

J.In

org.

Nuc

lChe

m.

27,

1489

~196

5!.

Co

~1!

~2!

~3!

~4!

~5!

Va

T/

p2

c 3 a K b K c C Ad

In to 1w

At

we

10 in Me

So

pr bu

J

8.3.

Am

eric

ium

„III…

For

mat

e

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

eric

ium

~III

!tr

is~f

orm

ate!

;A

m~C

HO

2!3;

@182

74-7

1-0#

For

mic

acid

;C

H 2O

2;@6

4-18

-6#

Per

chlo

ricac

id;

HC

lO 4;

@760

1-90

-3#S

odiu

mpe

rchl

orat

e;N

aClO 4;

@760

1-89

-0#W

ater

;H 2

O;

@773

2-18

-5#

A.

V.

Ana

nev

and

N.

N.

Kro

t,R

adio

khim

iya26

,75

5–

8~19

84!.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

dm2

3 :0.

2/m

oldm

23 :

0–

0.1

/mol

dm2

3 :1.

9–

2.0

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

at25

°Cof

Am~

CH

O2!

3in

CH

2O2

/HC

lO4

/NaC

lO4

solu

tions

lubi

lity

at25

°Cof

Am~

CH

O2!

3w

asm

easu

red

in0.

2m

oldm2

3so

lutio

nsof

form

icac

idco

ntai

ning

0–

0.1

mol

dm23

HC

lO4,

and

ClO

4to

mai

ntai

nio

nic

stre

ngth

of2.

0m

oldm2

3 .T

here

sults

wer

ere

port

edin

grap

hica

lfor

m.

Fro

mth

eso

lubi

lity

data

the

solu

bilit

yod

ucto

fAm~

CH

O2!

3w

asca

lcul

ated

tobe

1.053

102

9m

ol4

dm2

12at

ioni

cst

reng

thof

2.0

mol

dm23 .T

heca

lcul

atio

nsw

ere

perf

orm

edin

gth

edi

ssoc

iatio

nco

nsta

ntof

form

icofK

a52.

7310

24

mol

dm2

3at

ioni

cst

reng

thof

2.0

mol

dm23 ,

and

taki

ngin

toac

coun

tth

eis

tenc

ein

the

satu

rate

dso

lutio

nsof

the

Am

~CH

O2!

21an

dA

m~C

HO

2!21

com

plex

es.

The

irst

abili

tyco

nsta

nts

wer

eal

soca

lcul

ated

.T

heui

libriu

mso

lidph

ase

was

Am~C

HO

2!3,

@182

74-7

1-0#.

Als

ore

port

ed,

ingr

aphi

calf

orm

,w

asth

eso

lubi

lity

at25

°Cof

Am

~CH

O2!

3in

dium

form

ate-

NaC

lO 4so

lutio

ns.T

heso

lubi

lity

ofA

m~C

HO

2!3

inw

ater

was

repo

rted

tobec

15

7.32

310

23

mol

dm2

3 .It

was

nots

tate

dpl

icitl

yif

the

latte

rva

lue

was

obta

ined

byca

lcul

atio

nor

expe

rimen

tally

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

xces

sA

m~C

HO

2!3

was

equi

libra

ted

thso

lutio

nsof

the

desi

red

conc

entr

atio

nfo

r10

hin

rmos

tate

dfla

sks.

Bef

ore

mea

sure

men

ts,

the

solu

tions

wer

eed

from

air

bypa

ssin

gth

roug

hth

ema

stre

amof

argo

nga

s.th

efil

tere

dsa

tura

ted

solu

tions

,pH

was

dete

rmin

edte

ntio

met

rical

ly,

and

the

conc

entr

atio

nof

Am

~III

!ec

trop

hoto

met

rical

lyin;

0.6

mol

dm2

3H

ClO

4at

503

nm.

epH

met

erus

edw

asca

llibr

ated

agai

nst

mol

dm2

3 NaC

lO4.

Sol

idph

ases

wer

eid

entifi

edby

x-ra

yfr

actio

n.

243 A

m~C

HO

2!3

was

prep

ared

from

fres

hly

prec

ipita

ted

Am

~OH

! 3an

dco

ncen

trat

edfo

rmic

acid

acco

rdin

gto

Ref

s.1,

2.T

heso

lidpr

oduc

tw

asce

ntrif

uged

,w

ashe

dw

ith10

mol

dm23

form

icac

idan

d50

%et

hano

l,an

dke

ptov

erK

OH

.A

llot

her

chem

ical

sw

ere

reag

ent

grad

epr

oduc

ts.

Dou

bly

dist

illed

wat

erw

asus

ed.

Est

imat

edE

rror

:T

empe

ratu

repr

ecis

ion6

0.5

K~a

utho

rs!S

olub

ility

:er

ror

not

repo

rted

.

Ref

eren

ces:

1 L.R

.C

risle

r,J.

Inor

g.N

ucl.

Che

m.34

,32

63~1

972!

.2 F

.W

eige

lan

dN

.te

rMee

r,In

org.

Nuc

l.C

hem

.Le

tt.3,40

3~1

967!

.

678678 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Rub

idiu

mca

rbon

atod

ioxo

amer

icia

te~V!;

RbA

mO

2CO

3;@

#~2

!R

ubid

ium

carb

onat

e;R

b 2CO

3;@

#~3

!W

ater

;H 2

O;

@773

2-18

-5#

J.P

.Nig

on,R

.A.P

enne

man

n,E

.Sta

ritzk

i,T

.K.K

eena

n,an

dL.

B.

Asp

rey,

J.P

hys.

Che

m.58

,40

3–

4~1

954!

.

Var

iabl

es:

Pre

pare

dby

:

100

w2

/mas

s%

:5.

64;

6.73

J.H

a´ l

a

Exp

erim

enta

lDat

a

Sol

ubili

tyof

RbA

mO 2

CO

3in

Rb 2

CO

3so

lutio

nsa

Rb 2

CO

3

(100

w2

/mas

s%

)R

b 2C

O3

(m2

/mol

kg2

1 )b~A

mO

2!2C

O3

(100

w/m

ass

%)

RbA

mO

2CO

3

(100

w1

/mas

s%

)bR

bAm

O2C

O3

(m1

/mol

kg2

1 )b

5.64

0.25

90.

0043

0.00

590.

0001

49

6.73

0.31

40.

376

0.51

80.

0133

a Com

posi

tion

ofth

eeq

uilib

rium

solid

phas

ew

asre

port

edto

beR

bAm

O2C

O3,

@#.

The

auth

ors

stat

ed,

how

ever

,th

ata

hydr

ate

ofth

esa

ltco

uld

not

beru

led

out.

Tem

pera

ture

ofth

em

easu

rem

ents

was

not

spec

ified

.b C

alcu

late

dby

com

pile

r.F

oram

eric

ium

,A

r524

3.06

~243 A

m!

was

used

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Ver

ydi

lute

solu

tions

ofA

m~III

!in

1m

oldm

23

Rb 2

CO

3w

ere

oxid

ized

byoz

one

toA

m~V!.

The

resu

lting

prec

ipita

tew

asce

ntrif

uged

and

then

slur

ried

in0.

1m

oldm2

3R

b 2C

O3.

Wei

ghed

sam

ples

ofth

esu

pern

atan

tliq

uid

wer

ew

ithdr

awn

for

anal

ysis

.A

mer

iciu

mw

asde

term

ined

radi

omet

rical

ly,

CO

2w

asde

term

ined

byev

olut

ion

into

Ba~O

H! 2

solu

tion

acco

rdin

gto

Ref

.1

usin

ga

clos

edsy

stem

with

ape

rista

ltic

pum

pto

circ

ulat

eth

ega

san

den

sure

com

plet

eab

sorp

tion

ofC

O2.

Com

posi

tion

ofth

eso

lidph

ases

was

dete

rmin

edby

Sch

rein

emak

ers’

met

hod.

Tem

pera

ture

and

equi

libra

tion

time

was

not

repo

rted

.

Not

hing

spec

ified

.

Est

imat

edE

rror

:S

olub

ility

:pr

ecis

ion6

1%~a

utho

rs!.

Ref

eren

ces:

1 W.

C.

Sch

roed

eran

dE

.P

.P

artr

idge

,In

d.E

ng.

Che

m.,

Ana

l.E

d.4,

262

~193

5!.

Co

~1!

~2!

~3!

~4!

~5!

Va

T/

c 2 c 3 c 4 So

Na

pr us ex eq so ex Me

Iso

wi

the

fre

In po sp Th

2.0

dif


te

perio

dica

llyst

irred

with

HC

lO 4so

lutio

nsin

ther

mos

tate

dte

sttu

bes

for

3–

5h,

the

time

requ

ired

tore

ach

equi

libriu

m.

The

conc

entr

atio

nof

amer

iciu

min

the

satu

rate

dso

lutio

nsw

asde

term

ined

radi

omet

rical

ly.

Det

ails

ofth

em

etho

dw

ere

not

spec

ified

.

oxal

icac

idor

sodi

umox

alat

eon

a0.

5m

oldm

HN

O3

solu

tion

cont

aini

ng10

–15

gdm

23

of24

1 Am

.T

hepr

ecip

itate

was

anal

yzed

grav

imet

rical

lyby

igni

tion

toA

mO 2.

Pre

cipi

tate

sob

tain

edat

20–

90°C

had

the

com

posi

tion

ofA

m2~

C2O

4!3•

9H2O

.S

ourc

ean

dpu

rity

of24

1 Am

and

othe

rch

emic

als

used

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 C.E

.Cro

utha

mel

and

D.S

.Mar

tin,J

.Am

.Che

m.S

oc.

72,1

382

~195

0!.

2 L.S

.D

arke

n,J.

Am

.C

hem

.S

oc.63,

1007

~194

1!.

3 G.

D.

Pin

chin

gan

dR

.G

.B

ates

,J.

Res

.N

at.

Bur

.S

td.

40,

405

~194

8!.

4 C.

E.

Cro

utha

mel

and

D.

S.

Mar

tin,

J.A

m.

Che

m.

Soc

.73

,56

9~1

951!

.5 T

.L.

Mar

kin,

J.In

org.

Nuc

l.C

hem

.7,29

0~1

958!

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Dia

mer

iciu

m~III

!tr

is~o

xala

te!;

Am

2~C

2O4) 3

;@6

5113

-20-

4#P

otas

sium

oxal

ate;

C 2O4K

2;

@583

-52-

8#W

ater

;H 2

O;

@773

2-18

-5#

A.

Lebe

dev,

S.

V.

Piro

zhko

v,V

.M

.R

azbi

tnoi

,an

dG

.N

.Y

akov

lev,

Rad

iokh

imiy

a2,

351

–6

~196

0!.

riabl

es:

Pre

pare

dby

:

K:

298

/mol

dm2

3 :0.

1–

1.45

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofA

m 2~C

2O4!

3in

C2O

4K2

solu

tions

atco

nsta

ntio

nic

stre

ngth

of4.

35m

oldm23

a

C2O

4K2

(c2

/mol

dm2

3 )A

m(1

04m

oldm

23 )

Am

2~C

2O4!

3

(104

c 1/m

oldm

23 )b

0.10

01.

420.

71

0.20

04.

642.

32

0.35

19.

324.

66

0.60

032

.816

.4

1.00

70.5

35.3

1.45

8.86

44.3

hena

ture

ofth

eeq

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

The

salt

used

tom

aint

ain

cons

tant

ioni

cst

reng

thw

asno

tsp

ecifi

ed.

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

xces

sA

m2~

C2O

4!3•

9H2O

was

riodi

cally

stirr

edw

ithC 2

O4K

2so

lutio

nsin

ther

mos

tate

dte

stes

for

3–

5h,

the

time

requ

ired

tore

ach

equi

libriu

m.

The

ncen

trat

ion

ofam

eric

ium

inth

esa

tura

ted

solu

tions

was

term

ined

radi

omet

rical

ly,

the

tota

loxa

late

conc

entr

atio

nw

aste

rmin

edby

titra

tion

with

stan

dard

KM

nO 4so

lutio

n.

Am

~III

!ox

alat

ew

aspr

epar

edby

actio

nof

asa

tura

ted

solu

tion

ofox

alic

acid

orso

dium

oxal

ate

ona

0.5

mol

dm23

HN

O3

solu

tion

cont

aini

ng10

–15

gdm

23

of24

1 Am

.T

hepr

ecip

itate

was

anal

yzed

grav

imet

rical

lyby

igni

tion

toA

mO 2.

Pre

cipi

tate

sob

tain

edat

20–

90°C

had

the

com

posi

tion

ofA

m2~

C2O

4!3•

9H2O

.S

ourc

ean

dpu

rity

of24

1 Am

and

othe

rch

emic

als

used

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.



8.4.

Am

eric

ium

„III…

Oxa

late

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Dia

mer

iciu

m~III

!tr

is~o

xala

te!;

Am

2~C

2O4!

3;@6

5113

-20-

4#~2

!P

erch

loric

acid

;H

ClO 4

;@7

601-

90-3#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

A.

Lebe

dev,

S.

V.

Piro

zhko

v,V

.M

.R

azbi

tnoi

,an

dG

.N

.Y

akov

lev,

Rad

iokh

imiy

a2,

351

–6

~196

0!.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8c 2

/mol

dm2

3 :0.

05–

0.28

6J.

D.

Nav

ratil

and

J.H

a´ l

a

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofA

m 2~C

2O4!

3in

HC

lO4

solu

tions

a

HC

lO4

(c2

/mol

dm2

3 )A

m(1

04m

oldm

23 )

Am

2~C

2O4!

3

(104

c 1/m

oldm

23 )b

Ksp

c

(1031

mol

5dm

215

)

0.05

00.

557

0.27

9d

0.10

01.

160.

580

d

0.19

24.

402.

202.

28

0.28

67.

693.

852.

31

a The

natu

reof

the

equi

libriu

mso

lidph

ases

was

noti

nves

tigat

ed.B

ased

onth

eau

thor

s’ch

emic

alan

alys

isof

amer

iciu

mox

alat

epr

ecip

itaob

tain

edin

0.5

mol

dm2

3H

NO

3,th

eso

lidph

ase

coul

dbe

take

nto

beA

m2~

C2O

4!3•

9H2O

,@

#,or

,ac

cord

ing

toR

ef.

5,A

m2~

C2O

4!3•

7H2O

.b C

alcu

late

dby

com

pile

r.c C

alcu

late

dby

auth

ors

asKsp

5g

32a

ox3@A

m3

1#2

,w

here

g3

isth

eac

tivity

coef

ficie

ntof

the

Am31

ion

and

aox

isth

eac

tivity

ofth

eC 2

O422

ion

calc

ulat

edas

aox

5K

a1K

a2c o

x/ $

aH2

1K

a1a

H/g

11

Ka1

Ka2

/g2%.

1H

ere

c ox

isth

eto

talc

once

ntra

tion

ofox

alat

ein

solu

tion

~obt

aine

das

c ox5

3/2 @

Am

31

#!,

aH

isth

eac

tivity

ofH1

ion,

Ka1

and

Ka2

are

the

diss

ocia

tion

cons

tant

sof

oxal

icac

id,

Ka1

55.

363

102

2m

oldm

23 ,2

and

Ka2

55.

423

102

5m

oldm

23 ,3

both

at25

°C,

andg

1an

dg

2ar

eth

eac

tivity

coef

ficie

nts

ofth

eH

C 2O42

and

C2O

422io

ns,

resp

ectiv

ely.

Num

eric

alva

lues

ofth

eac

tivity

coef

ficie

nts

ofio

nsin

oxal

ate

solu

tions

wer

eta

ken

from

Ref

.4.

d Not

repo

rted

.

Add

ition

alin

form

atio

n:T

heau

thor

sal

sore

port

edon

thei

run

succ

essf

ulat

tem

pts

tode

term

ine

the

solu

bilit

yof

Am

2~C

2O4!

3in

wat

er.

Inre

peat

edm

easu

rem

ents

,th

eso

lubi

lity

fluct

uate

dbe

twee

n102

5an

d10

24

mol

dm2

3 ,A

m~I

II!

and

the

auth

ors

ascr

ibed

this

toth

ehy

drol

ysis

ofA

m31

ion.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

Am

2~C

2O4!

3•9H

2Ow

asA

m~I

II!

oxal

ate

was

prep

ared

byac

tion

ofa

satu

rate

dso

lutio

nof

23

Co

~1!

~2!

~3!

Va

T/

c 2 a T b C Me

Iso

pe tub

co de de

J

0.10

00.

138

5.00

40.

537

0.10

00.

196

5.25

70.

693

0.10

00.

285

5.54

70.

839

0.10

00.

382

5.78

01.

44

0.05

00.

359

6.03

11.

76

0.00

066

0.15

57.

261

44.0

a The

natu

reof

the

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.B

ased

onth

eau

thor

s’an

alys

isof

Am

~III

!ox

alat

eob

tain

edin

0.5

mol

dm2

3H

NO

3so

lutio

nsth

eco

mpi

ler

assu

mes

the

solid

phas

ew

asA

m2~

C2O

4!3•

9H2O

,@

#.b A

ctiv

ityof

the

H1

ion.

c Act

ivity

ofth

eC

2O

422

ion

calc

ulat

edas

aox

5K

a1K

a2c o

x/ $

aH2

1K

a1a

H/g

11

Ka1

Ka2

/g2%.

1H

ere

c ox

isth

eto

talc

once

ntra

tion

ofox

alat

ein

solu

tion,

aH

isth

eac

tivity

ofH1

ion,

Ka1

and

Ka2

are

the

diss

ocia

tion

cons

tant

sof

oxal

icac

id,

Ka1

55.

363

102

2m

oldm

23 ,2

and

Ka2

55.

423

102

5m

oldm

23 ,3

both

at25

°C,

andg

1an

dg

2ar

eth

eac

tivity

coef

ficie

nts

ofth

eH

C 2O42

2io

ns,

resp

ectiv

ely,

take

nfr

omC

rout

ham

elan

dM

artin

.4

d Con

cent

ratio

nof

Am~

III!

inth

esa

tura

ted

solu

tions

.

Add

ition

alin

form

atio

n:F

rom

the

depe

nden

ceof

the

solu

bilit

yof

Am~III

!ox

alat

eon

the

oxal

ate

ion

activ

ityth

eco

nsec

utiv

ein

stab

ility

cons

tant

s,at

zero

ioni

cst

reng

th,

ofth

eA

m~C

2O4!

1,

Am

~C2O

4) 22

,an

dA

m~C

2O4) 33

2co

mpl

exes

wer

eob

tain

edasK

15

(5.0

60.

3)3

102

8,

K25

(6.9

60.

7)3

102

5,

and

K35

(1.6

60.

2)3

102

1,

alli

ndm

3m

ol2

1 ,re

spec

tivel

y.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.E

xces

sA

m2~

C2O

4!3•

9H2O

was

riodi

cally

stirr

edw

ithso

lutio

nsof

the

desi

red

com

posi

tion

ther

mos

tate

dte

sttu

bes

for

3–

5h,

the

time

requ

ired

tore

ach

uilib

rium

.T

heco

ncen

trat

ion

ofam

eric

ium

inth

esa

tura

ted

lutio

nsw

asde

term

ined

radi

omet

rical

ly,

the

tota

loxa

late

ncen

trat

ion

was

dete

rmin

edby

titra

tion

with

stan

dard

nO4

solu

tion.

The

pHof

the

satu

rate

dso

lutio

nsw

aste

rmin

edw

itha

quin

hydr

one

elec

trod

e.

Am

~III

!ox

alat

ew

aspr

epar

edby

actio

nof

asa

tura

ted

solu

tion

ofox

alic

acid

orso

dium

oxal

ate

ona

0.5

mol

dm23

HN

O3

solu

tion

cont

aini

ng10

–15

gdm

23

of24

1 Am

.T

hepr

ecip

itate

was

anal

yzed

grav

imet

rical

lyby

igni

tion

toA

mO 2.

Pre

cipi

tate

sob

tain

edat

20–

90°C

had

the

com

posi

tion

ofA

m2~

C2O

4!3•

9H2O

.S

ourc

ean

dpu

rity

of24

1 Am

and

othe

rch

emic

als

used

not

spec

ified

.

Est

imat

edE

rror

:T

empe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 C.E

.Cro

utha

mel

and

D.S

.Mar

tin,J

.Am

.Che

m.S

oc.

72,1

382

~195

0!.

2 L.S

.D

arke

n,J.

Am

.C

hem

.S

oc.63,

1007

~194

1!.

3 G.

D.

Pin

chin

gan

dR

.G

.B

ates

,J.

Res

.N

at.

Bur

.S

td.

40,

405

~194

8!.

4 C.

E.

Cro

utha

mel

and

D.

S.

Mar

tin,

J.A

m.

Che

m.

Soc

.73

,56

9~1

951!

.

680680 JIRI HALA

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Dia

mer

iciu

m~III

!tr

is~o

xala

te!;

Am

2~C

2O4) 3

;@6

5113

-20-

4#~2

!P

otas

sium

oxal

ate;

C 2O4K

2;

@583

-52-

8#~3

!P

erch

loric

acid

;H

ClO 4

;@7

601-

90-3#

~4!

Wat

er;

H 2O

;@7

732-

18-5#

A.

Lebe

dev,

S.

V.

Piro

zhko

v,V

.M

.R

azbi

tnoi

and

G.

N.

Yak

ovle

v,R

adio

khim

iya2

,35

1–

6~1

960!

.

Var

iabl

es:

Pre

pare

dby

:

T/K

:29

8c 2

/mol

dm2

3 :0.

05–

0.23

8ac

tivity

ofH

1io

n/m

oldm

23 :

0.00

022

–0.

359

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofA

m 2~C

2O4!

3in

C2O

4K2–

HC

lO4

solu

tions

a

C2O

422

~mol

dm2

3 !H

1b

~mol

dm2

3 !2

log

a~C

2O

422

)c

~mol

dm2

3 !A

m~I

II!d

(105

mol

dm2

3 )

0.23

8—

1.30

124

.6

0.21

4—

1.34

721

.8

0.13

0—

1.49

58.

04

0.09

19—

1.60

23.

99

0.05

54—

1.74

52.

57

0.14

00.

000

224

1.81

83.

79

0.11

50.

000

316

1.98

33.

15

0.10

00.

000

447

2.22

11.

30

0.09

00.

000

852

2.41

71.

41

0.08

00.

001

552.

695

0.89

2

0.12

00.

003

162.

857

0.54

4

0.10

00.

005

133.

143

0.52

3

0.10

00.

009

143.

411

0.34

1

0.10

00.

0123

3.55

80.

400

0.10

00.

0199

3.80

10.

456

0.10

00.

0289

4.00

40.

483

0.10

00.

0489

4.31

30.

407

0.10

00.

0562

4.30

40.

290

0.10

00.

0832

4.65

20.

393

0.10

00.

115

4.87

30.

425

Me

Iso

pe in eq so co KM

de


ofmpo

nent

s:O

rigin

alM

easu

rem

ents

:

Dia

mer

iciu

m~III

!tr

is~o

xala

te!;

Am

2~C

2O4) 3

;@1

3278

-81-

4#O

xalic

acid

;C 2

H2O

4;

@144

-62-

7#N

itric

acid

;H

NO

3;

@769

7-37

-2#W

ater

;H 2

O;

@773

2-18

-5#

S.A

.Zak

olup

inan

dE

.V.K

orab

lin,R

adio

khim

iya,19

,698

–70

1~1

977!

.

riabl

es:

Pre

pare

dby

:

K:

287

–33

3/m

oldm

23;

0.01

–0.

4/m

oldm

23 :

0–

1.0

J.D

.N

avra

tilan

dJ.

Ha

´ la

Exp

erim

enta

lDat

a

Sol

ubili

tyof

Am

2~C

2O4!

3in

C2H

2O4–

HN

O3

solu

tions

asa

func

tion

ofte

mpe

ratu

rea

mpe

ratu

re~°

C!

C2H

2O4

(c2

/mol

dm2

3 )

HN

O3

(c3

/mol

dm2

3 )

00.

10.

30.

50.

71.

0

Sol

ubili

tyof

Am

2~C

2O4!

3re

port

edas

mg

Am~I

II!/

dm3 :

140

36.4

137

283

592

718

992

0.01

0.19

0.66

5.6

2983

232

0.05

0.16

0.5

1.13

3.48

10.5

26.4

0.1

0.16

0.38

0.7

1.7

4.2

13.5

0.2

0.21

0.4

0.58

1.36

2.6

6.1

0.3

0.30

0.38

0.68

1.3

2.0

4.1

0.4

0.40

0.44

0.78

1.26

1.84

3.54

300.

019.

117

.673

.520

1.6

414

1077

0.05

5.2

12.6

26.1

58.4

113.

622

5

0.1

3.7

6.4

10.4

16.4

37.8

57.6

0.2

2.6

3.3

4.3

6.1

11.8

19.6

0.3

2.1

3.2

3.7

5.4

9.2

14.2

0.4

3.0

3.3

4.0

5.9

9.5

12.6

450.

0119

.245

.328

053

711

9518

40

0.05

12.0

25.9

46.1

99.2

323

702

0.1

5.0

8.9

16.2

38.3

115.

623

2

0.2

2.0

3.42

8.1

1839

.687

.3

0.3

2.3

3.65

8.73

18.4

533

.375

.5

0.4

5.5

6.9

14.1

323

534

.569

.5

600.

0178

164

480

1248

2752

—

0.05

2555

76.8

149.

667

2—

Sol

ubili

tyof

Am

2~C

2O4!

3as

c 1/m

oldm

23

~com

pile

rs!:

140

7.55

310

25

2.84

310

24

5.87

310

24

1.23

310

23

1.49

310

23

2.06

310

23

0.01

3.94

310

27

1.37

310

26

1.16

310

25

6.02

310

25

1.72

310

24

4.81

310

24

0.05

3.32

310

27

1.04

310

26

2.34

310

26

7.22

310

26

2.18

310

25

5.48

310

25

0.1

3.32

310

27

7.88

310

27

1.45

310

26

3.53

310

26

8.71

310

26

2.80

310

25

0.2

4.36

310

27

8.30

310

27

1.20

310

26

2.82

310

26

5.39

310

26

1.26

310

25

0.3

6.22

310

27

7.88

310

27

1.41

310

26

2.70

310

26

4.15

310

26

8.51

310

26

0.4

8.30

310

27

9.13

310

27

1.62

310

26

2.61

310

26

3.82

310

26

7.34

310

26

300.

011.

893

102

53.

653

102

51.

523

102

44.

813

102

48.

593

102

42.

233

102

3

0.05

1.08

310

25

2.61

310

25

5.41

310

25

1.21

310

24

2.36

310

24

4.67

310

24

0.1

7.68

310

26

1.33

310

25

2.16

310

25

3.40

310

25

2.84

310

25

1.20

310

24

0.2

5.39

310

26

6.85

310

26

8.92

310

26

1.26

310

25

2.45

310

25

4.07

310

25

0.3

4.36

310

26

6.64

310

26

7.68

310

26

1.12

310

25

1.91

310

25

2.95

310

25

0.4

6.22

310

26

6.85

310

26

8.30

310

26

1.22

310

25

1.97

310

25

2.61

310

25

450.

013.

983

102

59.

403

102

55.

813

102

41.

113

102

32.

483

102

33.

823

102

3



Com

pone

nts:

Eva

luat

or:

~1!

Dia

mer

iciu

m~III

!tr

is~o

xala

te!;

Am

2~C

2O4) 3

;@6

5113

-20-

4#~2

!O

xalic

acid

;C 2

H2O

4;

@144

-62-

7#~3

!N

itric

acid

;H

NO

3;

@769

7-37

-2#~4

!W

ater

;H 2

O;

@773

2-18

-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

611

37B

rno,

Cze

chR

epub

lic,

May

2000

Crit

ical

Eva

luat

ion:

The

solu

bilit

yof

Am

2~C

2O4!

3in

oxal

icac

id/H

NO 3

solu

tions

has

been

stud

ied

intw

ore

fere

nces

.Z

akol

upin

and

Kor

ablin

1re

port

ednu

mer

ical

data

for

the

solu

bilit

yof

Am 2~

C2O

4!3

asa

func

tion

ofox

alic

acid

conc

entr

atio

nat

vario

usco

ncen

trat

ions

ofH

NO

3an

dte

mpe

ratu

res

whi

leB

urne

yan

dP

orte

r2

repo

rted

thei

rda

taat

one

tem

pera

ture~296

.1K!

ingr

aphi

cal

form

only

~see

the

resp

ectiv

eco

mpi

latio

ns!.

Bec

ause

ofth

is,

apr

ecis

eco

mpa

rison

betw

een

the

two

sets

ofda

tais

not

poss

ible

.H

owev

er,

anap

prox

imat

ere

ad-o

utth

eso

lubi

lity

data

for

0.05

and

0.1

mol

dm23

HN

O3

from

the

grap

hin

Bur

ney

and

Por

ter

2re

veal

sth

atth

ese

data

fall

reas

onab

lyw

ell

betw

een

thos

ein

Ref

.1

obta

ined

at28

7.1

and

303.

1K

.F

orth

isre

ason

the

data

ofZ

akol

upin

and

Kor

ablin

1ca

nbe

reco

mm

ende

das

tent

ativ

eva

lues

for

Am 2~

C2O

4!3

solu

bilit

yin

oxal

icac

id/H

NO 3

solu

tions

.

Ref

eren

ces:

1 S.

A.

Zak

olup

inan

dE

.V

.K

orab

lin,

Rad

iokh

imiy

a19,

698

~197

7!.

2 G.

A.

Bur

ney

and

J.A

.P

orte

r,In

org.

Nuc

l.C

hem

.Le

tt3,

79~1

967!

.

Co

~1!

~2!

~3!

~4!

Va

T/

c 2 c 3 Te

J

241 A

mis

otop

e.E

xces

sof

fres

hly

prec

ipita

ted

Am

~III

!ox

alat

ew

aseq

uilib

rate

dw

ithso

lutio

nsof

requ

ired

com

posi

tion

with

blad

em

ixer

ina

ther

mos

tat

for

1h.

Exp

erim

ents

esta

blis

hed

30m

inas

the

equi

libriu

mtim

e.A

fter

20m

inst

andi

ng,

asa

mpl

eof

the

satu

rate

dso

lutio

nw

asco

llect

ed,

cent

rifug

ed,

and

amer

iciu

mco

ncen

trat

ion

was

dete

rmin

edbygco

untin

g.D

etai

lsof

gco

untin

gan

dpH

dete

rmin

atio

nno

tsp

ecifi

ed.

Est

imat

edE

rror

:T

empe

ratu

re:6

1K

~aut

hors!

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 T.

J.M

arki

n,J.

Inor

g.N

ucl.

Che

m.7,

290

~195

8!.

2 I.A

.Le

bede

v,S

.V

.P

irozh

kov,

V.

M.

Raz

bitn

oi,

and

G.

N.

Yak

ovle

v,R

adio

khim

iya2

,35

1~1

960!

.3 C

.E.C

rout

ham

elan

dD

.S.M

artin

,J.A

m.C

hem

.Soc

.72

,138

2~1

950!

.4 C

.E

.C

rout

ham

elan

dD

.S

.M

artin

,J.

Am

.C

hem

.S

oc.

73,

569

~195

1!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Dia

mer

iciu

m~III

!tr

is~o

xala

te!;

Am

2~C

2O4!

3;@6

5113

-20-

4#O

xalic

acid

;C 2

H2O

4;@1

44-6

2-7#

Nitr

icac

id;

HN

O3;

@769

7-37

-2#W

ater

;H 2

O;

@773

2-18

-5#

G.A

.Bur

ney

and

J.A

.Por

ter,

Inor

g.N

ucl.

Che

m.L

ett.

3,79

–85

~196

7!.

riabl

es:

Pre

pare

dby

:

K:

296

/mol

dm2

3 :0.

02–

0.5

/mol

dm2

3 :0.

1–

4.0

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

at23

°Cof

Am 2

~C2O

4!3

inH

NO

3–

C2H

2O4

solu

tions

eso

lubi

lity

ofA

m2~

C2O

4!3

at23

°Cin

HN

O 3–

C2H

2O4

solu

tions

wer

epr

esen

ted

ingr

aphi

cal

form~s

eeF

ig.

24!.

The

natu

reof

the

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

Bas

edon

the

wor

kof

Mar

kin

1th

eau

thor

sas

sum

edth

eeq

uilib

rium

solid

phas

ebe

the

ptah

ydra

te,

Am 2~

C2O

4!3•

7H2O

,@

#.

FIG

.24

.D

iam

eric

ium

~III

!–tr

is~o

xala

te!–

oxal

icac

id–

nitr

icac

id–

wat

ersy

stem

.

682682 JIRI HALA

0.05

2.49

310

25

5.37

310

25

9.56

310

25

2.06

310

24

6.70

310

24

1.46

310

23

0.1

1.04

310

25

1.85

310

25

3.36

310

25

7.95

310

25

2.40

310

24

4.81

310

24

0.2

4.15

310

26

7.10

310

26

1.68

310

25

3.73

310

25

8.22

310

25

1.81

310

24

0.3

4.77

310

26

7.57

310

26

1.81

310

25

3.83

310

25

6.91

310

25

1.57

310

24

0.4

1.44

310

25

1.43

310

25

2.93

310

25

4.88

310

25

7.16

310

25

1.44

310

24

600.

011.

623

102

43.

403

102

49.

963

102

42.

603

102

35.

713

102

3—

0.05

5.19

310

25

1.14

310

24

1.59

310

24

3.10

310

24

1.39

310

23

—

HN

O3

(c3

/mol

dm2

3 )C

2H2O

4

(c2

/mol

dm2

3 )A

mb

~mol

dm2

3 !

Ioni

cst

reng

th~m

oldm

23 !

aox

c

~mol

dm2

3 !a

H1

d

~mol

dm2

3 !g

3e

Ksp0

~mol

5dm

215

!

Sol

ubili

typr

oduc

tof

Am 2

~C2O

4!3

at14

°Cca

lcul

ated

byth

eau

thor

s:

00.

056.

7310

27

0.15

8.84

310

26

0.10

0.09

93.

0310

230

0.1

0.00

085

5.73

102

40.

104

1.52

310

27

0.10

0.12

31.

76310

229

0.1

0.01

2.74

310

26

0.13

1.32

310

26

0.12

0.10

72.

0310

231

0.1

0.05

2.07

310

26

0.25

2.75

310

26

0.20

0.07

4.33

102

31

0.1

0.10

1.57

310

26

0.4

2.66

310

26

0.3

0.05

31.

36310

231

0.3

0.00

175

1.173

102

30.

304.

7310

28

0.3

0.06

15.

35310

231

a The

natu

reof

the

equi

libriu

mso

lidph

ases

was

not

inve

stig

ated

.B

ased

onth

eau

thor

s’an

alys

isof

Am

~III

!ox

alat

eob

tain

edin

0.5

mol

dm2

3H

NO

3at

<30

°Cth

eco

mpi

ler

assu

mes

the

solid

phas

ew

asA

m2~

C2O

4!3•

9H2O

,@

#.M

arki

n1re

port

edth

eex

iste

nce

ofA

m2~

C2O

4!3•

7H2O

.b C

once

ntra

tion

ofA

m~III

!in

the

satu

rate

dso

lutio

ns.

c Act

ivity

ofth

eC

2O422

ion

calc

ulat

edac

cord

ing

toR

ef.

2asa

ox5

Ka1

Ka2

c ox

/ $a

H21

Ka1

aH

/g11

Ka1

Ka2

/g2%.

Her

ec o

xis

the

tota

lco

ncen

trat

ion

ofox

alat

ein

solu

tion,a

His

the

activ

ityof

H1io

n,K

a1an

dK

a2ar

eth

edi

ssoc

iatio

nco

nsta

nts

ofox

alic

acid

,K

a15

5.37

310

22

mol

dm2

3an

dK

a25

5.63

102

5m

oldm

23 ,

both

at14

°C,

andg

1an

dg

2ar

eth

eac

tivity

coef

ficie

nts

ofth

eH

C 2O422

and

C 2O

422

ions

,re

spec

tivel

y,ta

ken

from

Ref

s.3,

4.d A

ctiv

ityof

H1

ions

.e A

ctiv

ityof

the

Am

31io

n.S

ourc

eno

tre

port

ed.

f Obt

aine

das

Kspo

5g

32@A

m31

#2a

ox3.

The

auth

ors

expl

aine

dth

esc

atte

rofKspo

valu

esas

bein

gdu

eto

varia

tions

inio

nic

stre

ngth

.

Add

ition

alin

form

atio

n:A

tH

NO

3co

ncen

trat

ions

of0.

1an

d0.

3m

oldm2

3 ,th

eso

lubi

lity

ofA

m~I

II!

oxal

ate

asa

func

tion

ofox

alic

acid

conc

entr

atio

nsh

owed

am

inim

um.

With

refe

renc

eto

Ref

.2,

the

auth

ors

ascr

ibed

this

toth

efo

rmat

ion

ofA

m~I

II!

oxal

atoc

ompl

exes

,th

epr

edom

inat

ing

spec

ies

bein

gA

m31

atlo

wox

alat

eco

ncen

trat

ions

,A

m~C2O

4!1

and

Am

~C2O

4!22

inth

era

nge

ofth

em

inim

um,

and

Am~C

2O4!

332at

high

oxal

ate

conc

entr

atio

ns.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

The

wor

kw

asco

nduc

ted

with

the

Not

hing

spec

ified

.

Co

~1!

~2!

~3!

~4!

Va

T/

c 2 c 3 Th

eq he


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Dia

mer

iciu

m~III

!tr

is~o

xala

te!;

Am

2~C

2O4!

3;@6

5113

-20-

4#O

xalic

acid

;C 2

H2O

4;@1

44-6

2-7#

Pot

assi

umox

alat

e;C 2O

4K2;

@583

-52-

8#N

itric

acid

;H

NO

3;@7

697-

37-2#

Wat

er;

H 2O

;@7

732-

18-5#

E.

M.

Paz

ukhi

n,A

.S

,K

rivok

hats

kii,

and

S.

M.

Koc

herg

in,

Rad

iokh

imiy

a29,

11–

16~1

987!

.

riabl

es:

Pre

pare

dby

:

K:

298

uilib

rium

conc

entr

atio

nof

the

C 2O422

ion/

mol

dm2

3 :1.

710

26–

0.3

J.H

ala

Exp

erim

enta

lDat

a

Sol

ubili

tyat

25°C

ofA

m 2~C

2O4!

3in

C2H

2O4–

C2O

4K2

orC

2H2O

4–

HN

O3

solu

tions

a

talo

xala

teol

dm2

3 !Io

nic

stre

ngthe

~mol

dm2

3 !g

6e

aH

1

@H1

#~m

oldm

23 !

@C2O

422#f

(102

mol

dm2

3 )2

log

CA

m

~mol

dm2

3 !

1.50

b15

02.

80

1.00

b10

03.

07

0.60

b60

3.37

0.30

c0.

901.

045.

62310

29

5.41

310

29

303.

84

0.15

c0.

450.

875.

62310

29

6.49

310

29

154.

44

0.10

b10

4.57

0.07

0c0.

210.

826.

31310

29

7.72

310

29

74.

80

0.03

0c0.

090.

836.

17310

29

7.48

310

29

35.

36

0.02

0c0.

060.

843.

16310

29

3.77

310

29

25.

47

0.01

0c0.

030.

874.

47310

29

5.16

310

29

15.

67

0.00

8c0.

020.

888.

91310

29

1.01

310

28

0.80

5.81

0.00

5c0.

020.

885.

50310

29

6.24

310

29

0.50

5.88

0.30

d0.

270.

827.

76310

23

9.42

310

23

0.84

5.81

0.03

0d0.

040.

851.

78310

24

2.08

310

24

1.42

5.84

0.01

0d0.

010.

913.

98310

23

4.36

310

23

3.90

310

22

5.89

0.01

0d0.

010.

911.

07310

22

1.18

310

22

1.40

310

22

5.90

0.01

0d0.

010.

911.

82310

22

2.00

310

22

7.60

310

23

5.88

0.01

0d0.

006

0.92

3.803

102

24.

143

102

22.

803

102

35.

73

0.00

5d0.

003

0.94

3.803

102

24.

033

102

21.

603

102

35.

25

0.00

5d0.

002

0.95

5.503

102

25.

773

102

29.

903

102

44.

73

0.00

5d0.

002

0.95

1.073

102

11.

123

102

13.

703

102

44.

29

0.00

5d0.

0001

0.97

1.783

102

11.

843

102

11.

703

102

43.

72

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.b C

once

ntra

tion

adju

sted

bym

eans

ofC

2O4K

2.c C

once

ntra

tion

adju

sted

bym

eans

ofC

2O4H

2ne

utra

lized

byC

O 2-fr

eeN

H 3ga

s.d C

once

ntra

tion

adju

sted

bym

eans

ofC

2O4H

2an

dH

NO 3

.e S

eeA

dditi

onal

Info

rmat

ion.

f Obt

aine

das

seco

ndap

prox

imat

ion.

Add

ition

alin

form

atio

n:A

sth

efir

stap

prox

imat

ion,

equi

libriu

mco

ncen

trat

ions

ofC

2O422

and

HC 2

O42

ions

wer

eca

lcul

ated

usin

gth

edi

ssoc

iatio

nco

nsta

nts

ofox

alic

acid

take

nfr

omLu

rye,1

and

the

mea

sure

dpH

valu

e.F

rom

the

conc

entr

atio

nsso

obta

ined

,io

nic

stre

ngth

was

calc

ulat

edan

dus

edto

calc

ulat

eac

tivity

coef

ficie

nts

and

conc

entr

atio

nof

the

H1

ion.

Fro

mth

ese

valu

es,

and

usin

gdi

ssoc

iatio

nco

nsta

nts

ofox

alic

acid

ofK

a15

1.05

310

21

and

Ka2

51.

883

102

4fo

rio

nic

stre

ngth

of0.

1m

oldm

23 ,

the

equi

libriu

mco

ncen

trat

ion

ofth

eC

2O422

ion

was

then

obta

ined

asth

ese

cond

appr

oxim

atio

n.W

ithin

crea

sing

oxal

ate

ion

conc

entr

atio

n,th

eso

lubi

lity

ofA

m~I

II!

oxal

ate

first

decr

ease

d,th

enpa

ssed

thro

ugh

am

inim

um,

and

incr

ease

dat

high

erox

alat

eco

ncen

trat

ions

beca

use

ofth

efo

rmat

ion

ofox

alat

oco

mpl

exes

ofA

m~I

II!.

Ove

rall

stab

ility

cons

tant

sof

the

Am

~C2O

4!n3

22

nco

mpl

exes

,bn5

@Am

~C2O

4)n3

22

n]3

@Am

31#2

1@C

2O422

#2n,

wer

eob

tain

edgr

aphi

cally

for

zero

ioni

cst

reng

thasb

1

54.

8310

6m

ol2

1dm

3 ,b

25

8.73

109

mol

22

dm6 ,

and

b35

4.15

310

11m

ol2

3dm

9 .T

hefit

with

expe

rimen

tald

ata

was

furt

her

impr

oved

whe

nal

soth

eco

mpl

exA

m~HC

2O4!

21,

b1

h5

4.37

310

4m

ol2

1dm

3w

asco

nsid

ered

.



Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

An

aliq

uot

ofA

m~III

!st

ock

solu

tion,

enou

ghto

ensu

reex

cess

ofA

m2~

C2O

4!3•

7H2O

ateq

uilib

rium

,w

asad

ded

toso

lutio

nsof

the

desi

red

com

posi

tion,

ina

poly

ethy

lene

bottl

e.T

hebo

ttle

was

mec

hani

cally

shak

enun

tileq

uilib

rium

was

achi

eved

,w

hich

took

less

than

16h.

The

nal

iquo

tsof

the

solu

tions

wer

ew

ithdr

awn,

filte

red,

and

conc

entr

atio

nof

amer

iciu

mde

term

ined

byasp

ectr

omet

ry.

The

conc

entr

atio

nsof

acid

and

oxal

ate

wer

ede

term

ined

bytit

ratio

nw

ithst

anda

rdN

aOH

and

KM

nO 4so

lutio

ns,

resp

ectiv

ely.

Dep

letio

nof

oxal

ate

orH

1io

nsby

radi

olys

isdi

dno

toc

cur

for24

3 Am

.A

fter

the

first

4–

12h

inso

me

3da

yeq

uilib

ratio

ns,

ther

ew

ere

node

tect

able

varia

tions

inso

lutio

nco

mpo

sitio

nor

chan

ges

inso

lubi

lity.

Sto

ckso

lutio

nof

Am~

III!

nitr

ate

was

prep

ared

bypr

ior

sepa

ratio

nfr

omne

utro

nirr

adia

ted23

9 Pu,

lant

hani

des,

and

curiu

mw

ithtr

ibut

ylph

osph

ate/

tert

iary

amin

eex

trac

tion,

and

K2C

O3

prec

ipita

tion.

The

K 3Am

~CO

3!2

was

diss

olve

d,A

m~III

!re

prec

ipita

ted

asox

alat

e,ca

lcin

ed,

diss

olve

din

HC

l,pu

rified

byan

ion

exch

ange

,an

dpr

ecip

itate

dw

ithN

H3

solu

tion.

The

amer

iciu

mhy

drox

ide

was

diss

olve

din

HN

O3.

The

amer

iciu

mw

aspu

re24

3 Am

cont

aini

ng,

2000

ppm

curiu

man

d,10

00pp

mof

othe

rca

tioni

cim

purit

ies.

The

amer

iciu

mw

assh

own

tobe

triv

alen

tby

spec

trop

hoto

met

rican

alys

is.

All

othe

rch

emic

als

wer

ere

agen

tgr

ade

prod

ucts

.

Est

imat

edE

rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Ref

eren

ces:

1 T.

L.M

arki

n,J.

Inor

g.N

ucl.

Che

m.7,

290

~195

8!.

Co

~1!

~2!

~3!

~4!

~5!

Va

T/

eq 3 To ~m

J

9.T

heS

olub

ility

ofC

uriu

mC

ompo

unds

9.1.

Cur

ium

„III…

Oxa

late

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Dic

uriu

m~I

II!

tris

~oxa

late!

;C

m2~

C2O

4!3;

@#

Oxa

licac

id;

C 2H

2O4;

@144

-62-

7#N

itric

acid

;H

NO

3;@7

697-

37-2#

Wat

er;

H 2O

;@7

732-

18-5#

G.A

.Bur

ney

and

J.A

.Por

ter,

Inor

g.N

ucl.

Che

m.L

ett.

3,79

–85

~196

7!.

riabl

es:

Pre

pare

dby

:

K:

296

/mol

dm2

3 :0.

025

–0.

5/m

oldm

23 :

0.1

–4.

0

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

at23

°Cof

Cm 2

~C2O

4!3

inH

NO

3–

C2H

2O4

solu

tions

eso

lubi

lity

ofC

m 2~C

2O4!

3at

23°C

inH

NO 3

–C

2H2O

4so

lutio

nsw

aspr

esen

ted

ingr

aphi

cal

form~s

eeF

ig.

25!.

The

natu

reof

the

uilib

rium

solid

phas

esw

asno

tin

vest

igat

ed.

Rad

ioly

ticde

com

posi

tion

ofox

alat

eby

ara

diat

ion

from

244 C

maf

fect

edth

eac

cura

cyof

lubi

lity

dete

rmin

atio

n.T

hera

teof

radi

olyt

icde

plet

ion

ofox

alat

ew

asre

lativ

ely

rapi

dat

solu

bilit

ies

.50

0m

g24

4 Cm

/dm

3an

dat

,0.

5ld

m2

3ox

alat

eco

ncen

trat

ion.

The

data

obta

ined

inth

ese

regi

ons

wer

eco

nsid

ered

byth

eau

thor

sas

appr

oxim

ate.

FIG

.25

.D

icur

ium

~III

!–tr

is~o

xala

te!–

oxal

icac

id–

nitr

icac

id–

wat

ersy

stem

.

684684 JIRI HALA

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Exc

ess

Am

~III

!ox

alat

ew

aseq

uilib

rate

dfo

r6

–10

hw

ithso

lutio

nsof

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icac

idan

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ium

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ate

cont

aini

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rious

conc

entr

atio

nsof

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ate

ions

.S

ampl

esw

ere

take

npe

riodi

cally

from

each

solu

tion

toch

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rium

had

been

atta

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the

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rate

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mea

sure

d,an

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II!

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rmin

edby

anun

spec

ified

radi

omet

ricm

etho

d.

Am

2~C

2O4!

3•7H

2Ow

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tion,

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olve

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solu

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filte

red

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the

carb

onat

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com

pose

dw

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HN

O3.

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CO 2

was

rem

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atin

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oric

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into

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lized

with

amm

onia

topH

2.T

heA

m~III

!ox

alat

ew

asw

ashe

dse

vera

ltim

esw

ith0.

1m

oldm

23

C2H

2O4/

0.1

mol

dm2

3H

NO

3so

lutio

n,an

dke

ptun

der

dist

illed

wat

er.

Tw

ice

recr

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llize

dox

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acid

and

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ssiu

mox

alat

ew

ere

used

.2

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edE

rror

:T

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ratu

re:6

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rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 Yu.

Yu.

Lury

e,H

an

db

oo

ko

fA

na

lytic

alC

he

mis

try~in

Rus

sian

!~K

him

iya,

Mos

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,19

71!,

p.95

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tepa

nov

and

E.M

.Paz

ukhi

n,Z

h.N

eorg

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m.

15,1

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~3!

~4!

Va

T/

c 2 c 3 Th

eq so mo


Aux

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form

atio

n

etho

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ppar

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re:

Sou

rce

and

Pur

ityof

Mat

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ls:

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rmal

met

hod

used

.A

nal

iquo

tof

Cm

~III

!st

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toen

sure

exce

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solid

Cm

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!ox

alat

eat

uilib

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ded

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mpo

sitio

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apo

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nebo

ttle.

The

bottl

ew

asec

hani

cally

shak

enun

tileq

uilib

rium

was

achi

eved

,w

hich

okle

ssth

an16

h.T

hen

aliq

uots

ofth

eso

lutio

nsw

ere

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awn,

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red,

and

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entr

atio

nof

curiu

mw

aste

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edby

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The

conc

entr

atio

nsof

acid

and

alat

ew

ere

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rmin

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titra

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with

stan

dard

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Han

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ns,

resp

ectiv

ely.

Cur

ium

was

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rate

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omne

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ted

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uin

the

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gw

ay.

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ylph

osph

ate,

then

curiu

man

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ium

wer

ese

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sw

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mer

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mw

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para

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from

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ofK 3A

m~C

O3!

2,an

dcu

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was

final

lypr

ecip

itate

das

oxal

ate

and

calc

ined

toth

eox

ide.

The

latte

rw

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ssol

ved

inH

Cl,

curiu

mw

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rified

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ange

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itate

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H 3so

lutio

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Pur

ified

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95%24

4 Cm

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ium

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her

chem

ical

sw

ere

reag

ent

grad

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ts.

Est

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rror

:T

empe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

;3%

for

solu

bilit

y,

10m

g24

4 Cm

/dm

3;

;5%

for

solu

bilit

y,;

50m

g24

4 Cm

/dm

3an

d,

0.1

mol

dm2

3ox

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eto

radi

olys

isef

fect

s~aut

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.



M Is en eq co m to w de ox KM

J

he symbol

5

7

6

34

10. System Index

Page numbers preceded by E refer to evaluation texts whereas those not preceded by E refer to compiled tables. T~aq! stands for water as an additional component in the respective system.

Actinium oxalate1water 539Actinium oxalate~aq!

1nitric acid 5401nitric acid1oxalic acid 5401oxalic acid 539

Americium~III ! carbonate~aq!1carbon dioxide1sodium perchlorate 674, 671carbonate ion1sodium chloride 6771carbonate ion1sodium perchlorate E6731potassium carbonate 673

Americium~III ! formate~aq!1formic acid1perchloric acid1sodium perchlorate 678

Americium~III ! hydroxocarbonate~aq!1carbon dioxide1sodium hydrogencarboante 676-671carbon dioxide1sodium perchlorate 6751carbonate ion1sodium perchlorate E6731sodium carbonate1sodium hydroxide 676–6771sodium hydrogencarbonate1sodium perchlorate 675–67

Americium~III ! oxalate~aq!1oxalic acid1nitric acid E681, 681–682, 682–681oxalic acid1nitric acid1potassium oxalate 683–681perchloric acid 6791potassium oxalate 6791potassium oxalate1perchloric acid 680

Ammonium carbonato dioxoneptunate~V! ~aq!1ammonium carbonate 644

Ammonium hydroxy~carbonato! dioxoplutonate~VI ! ~aq!1ammonium carbonate 654

Ammonium tetra~oxalato!thorate~aq! 1 ammonium oxalate 569Ammonium tris~carbonato! dioxoneptunate~V! ~aq!

1ammonium carbonate 644Ammonium tris~carbonato! dioxoplutonate~VI ! ~aq!

1ammonium carbonate 652, 6531ammonium nitrate 653

Ammonium tris~carbonato! dioxouranate~VI !1water 585Ammonium tris~carbonato! dioxouranate~VI ! ~aq!

1sodium tris~carbonato!dioxouranate~VI ! 585Ammonium tris~hydroxybenzoato! dioxouranate~VI ! ~aq!

1ammonium hydroxybenzoate 625–626Calcium tris~carbonato!dioxouranate~VI !1water 586Cesium tris~carbonato!dioxouranate~VI !1water 582Cesium tris~carbonato!dioxoneptunate~V! ~aq!

1cesium carbonate 643Curium~III ! oxalate~aq!

1oxalic acid1nitric acid 684–685Guanidinium pentakis~carbonato!thorate~aq!

1guanidinium carbonate1guanidinium nitrate 5441guanidinium hydrogencarbonate1guanidinium nitrate 544

Guanidinium trifluorotris~carbonato!thorate~aq!1guanidinium carbonate1guanidiunium fluoride 544

Hexamminecobalt~III ! pentakis~carbonato! aquaneptunate~IV !1water 645Hexamminecobalt~III ! bis~carbonato! dioxoneptunate~V!1water 645Hexamminecobalt~III !nitrate tris~carbonato! dioxoneptunate~VI !1water 645Hexamminecobalt~III ! pentakis~carbonato!aqua plutonate~IV !

0047-2689Õ2001Õ30„2…Õ686Õ168Õ$35.00 J. Phys. Chem. Ref. Data, Vol. 30, No. 2, 2001686

1

1

2

2

2

2

2

0


1ethanol 6541water 654

Hexamminecobalt~III ! penta~carbonato!thorate1acetone 5451water 545

Magnesium tricarbonatodioxouranate~VI !1water 586Neptunium~VI ! dioxo~carbonate! ~aq!

1carbon dioxide1sodium perchlorate 630–63Neptunium~VI ! dioxo~oxalate! ~aq!

1oxalic acid1nitric acid 647Neptunium~IV ! oxalate~aq!

1hydrogen chloride 6461oxalic acid 6451oxalic acid1nitric acid 646–647

Plutonium~VI ! dioxocarbonate~aq!1carbon dioxide1sodium chloride 6521carbon dioxide1sodium perchlorate E648, 650, 651carbon dioxide1sodium hydrogencarbonate1sodium perchlorate 6491lithium hydrogen carbonate 648

Plutonium~VI ! dioxo~oxalate! ~aq!1ammonium oxalate1nitric acid 667–6681oxalic acid1nitric acid 666–667

Plutonium~VI ! formate~aq!1formic acid1hydroxylamine hydrochloride 6551formic acid1perchloric acid1sodium perchlorate 6561formic acid1sodium formate1hydroxylamine hydrochloride 655

Plutonium~IV ! 5-chloro-8-hydroxyquinolinate~aq!1ammonium perchlorate1sodium acetate 671–67

Plutonium~IV ! 5-chloro-7-iodo-8-hydroxyquinolinate~aq!1ammonium perchlorate1sodium acetate 671–67

Plutonium~IV ! 5,7-dibromo-8-hydroxyquinolinate~aq!1ammonium perchlorate1sodium acetate 671–67

Plutonium~IV ! 5,7-dichloro-8-hydroxyquinolinate~aq!1ammonium perchlorate1sodium acetate 671–67

Plutonium~IV ! 8-hydroxyquinolinate~aq!1ammonium perchlorate1sodium acetate 671–67

Plutonium~IV ! N-nitroso-N-benzeneaminate~aq!1N-nitroso-N-benzeneamine1sulfuric acid 672

Plutonium~III ! oxalate~aq!1ammonium oxalate 6561oxalic acid1hydrogen chloride1ascorbic acid 6601oxalic acid1nitric acid1ascorbic acid E657, 658, 659–661oxalic acid1nitric acid1hydrazine E657, 6591potassium oxalate1potassium chloride 657

Plutonium~IV ! oxalate1water E661Plutonium~IV ! oxalate~aq!

1ammonium oxalate 6641ammonium oxalate1nitric acid 6661nitric acid E662, 663, 6631oxalic acid1nitric acid 665, 6651perchloric acid 6611sulfuric acid 664

Plutonium oxobis~o-hydroxybenzoate! ~aq!1hydrogen chloride 669

Plutonium~III ! tris~o-hydroxybenzoate!1ethanol 6681water 668


8

6

5

688688 JIRI HALA

Plutonium~IV ! trioxo~o-hydroxybenzoate! ~aq!1ammonia 6691ammonium chloride 6701ammonium nitrate 6701ammoniumo-hydroxybenzoate 6691hydrogen chloride 669

Potassium bis~carbonato! dioxoneptunate~V! ~aq!1potassium carbonate 642

Potassium carbonato dioxoneptunate~V! ~aq!1potassium carbonate 640, 640–641

1potassium carbonate1sodium carbonate1potassium chloride1sodium chloride 641–642Potassium tris~carbonato! dioxoneptunate~aq!

1potassium carbonate 643Potassium tris~carbonato!dioxouranate~VI !1water 582Rubidium carbonato dioxoamericiate~V! ~aq!

1rubidium carbonate 678Rubidium tricarbonatodioxouranate~VI !1water 582Sodium bis~carbonato! dioxoneptunate~V! ~aq!

1carbon dioxide1sodium chloride 637–6381carbon dioxide1sodium perchlorate 635, 637–631sodium carbonate1sodium chloride1potassium chloride 6391sodium carbonate1sodium nitrate 6391sodium carbonate1sodium perchlorate 635

Sodium carbonato dioxoamericiate~V! ~aq!1carbonate ion1sodium chloride 677

Sodium carbonato dioxoneptunate~V! ~aq!1carbon dioxide1sodium chloride 637–638, 6381carbon dioxide1sodium perchlorate E631–E632, 631carbon dioxide1sodium hydrogencarbonate1sodium perchlorate 6341sodium carbonate 6321sodium carbonate1sodium perchlorate 633, 63

Sodium dicarbonatodioxouranate~VI !1water 581Sodium pentacarbonato bis~dioxouranate~VI !!1water 587Sodium pentakis~carbonato!thorate~aq!

1sodium carbonate E542, 543, 5431sodium hydrogencarbonate 543

Sodium tris~acetato! dioxouranate~VI ! ~aq!1acetic acid1sodium acetate 591, 5921acetic acid1sodium acetate1ammonium acetate 5921acetic acid1sodium acetate1ammonium nitrate 5921acetic acid1sodium acetate1sodium nitrate 5921acetic acid1sodium acetate1sodium perchlorate 592

Sodium tris~carbonato!dioxouranate~VI !1water 582Sodium tris~carbonato!dioxouranate~VI ! ~aq!

1ammonium tris~carbonato!dioxouranate 5851sodium carbonate 5821sodium carbonate1sodium chloride 5841sodium chloride 5831sodium perchlorate 5841sodium sulfate 583

Sodium zinc tris~dioxouranium~VI !!nonakis~acetate! ~aq!1ethanol 593Strontium tris~carbonato!dioxouranate~VI !1water 587Thorium acetate

12-Aminoethanol 54711,2-Ethanediamine 54711,2-Ethanediol 5471water 546


61

6

0

2


Thorium carbonate~aq!1thorium oxalate1sodium carbonate1sodium oxalate 578Thorium decanoate~aq!1potassium nitrate 547Thorium dodecanoate~aq!1potassium nitrate 547Thorium formate~aq!1formic acid 545Thorium formate trihydrate

1acetone 5461benzene 5461carbon tetrachloride 5461ethanol 5461methanol 5461oxirane~ethylene oxide! 54612-propanol 5461trichloroethylene 546

Thorium hexadecanoate~aq!1potassium nitrate 547Thorium hydroxyquinolinate~aq!1hydrogen chloride1sodium chloride 571Thorium 5-nitro-barbiturate1water 570Thorium O-butylcarbonodithioate~aq!1potassium nitrate 548Thorium O-decylcarbonodithioate~aq!1potassium nitrate 548Thorium O-ethylcarbonodithioate~aq!1potassium nitrate 548Thorium O-hexylcarbonodithioate~aq!1potassium nitrate 548Thorium oxalate1water E548, 549, 562Thorium oxalate~aq!

1ammonium chloride 5621ammonium oxalate E557, 558, 559, 559–51 ammonium perchlorate1perchloric acid 5631ammonium sulfate 5621hydrogen chloride 550, 550, 5511 hydrogen chloride1oxalic acid 5631hydrogen chloride1sodium chloride 5621nitric acid E551, 552, 552–5531nitric acid1oxalic acid E564, 564, 565, 565–566, 561oxalic acid 5551oxalic acid1perchloric acid 5671potassium hydrogen sulfate 5621potassium oxalate 556, 5571sodium chloride 5621sodium oxalate 5561sodium sulfate 5621sulfuric acid E553, 5541thorium carbonate1sodium carbonate1sodium oxalate 578

Thorium oxalate dihydrate1ammonia 549Thorium oxobis~hydroxybenzoate! ~aq!1ammonium hydroxybenzoate 569–57Thorium oxocarbonate~aq!

1sodium perchlorate 5411sodium carbonate1sodium perchlorate 541–54

Thorium pentadecanoate~aq!1potassium nitrate 547Thorium phthalocyaninate

1benzene 57111-chloronaphthalene 571

Thorium tetradecanoate~aq!1potassium nitrate 547Thorium tridecanoate~aq!1potassium nitrate 547Thorium undecanoate~aq!1potassium nitrate 547Uranium~VI ! dioxocarbonate~aq!

1carbon dioxide 573, 5741sodium carbonate 581

Uranium~VI ! dioxo~acetate!1water 588, 589Uranium~VI ! dioxo~acetate! ~aq!


580

690690 JIRI HALA

1acetic acid 5891phosphoric acid tri-n-butylester 590

Uranium~VI ! dioxo~acetate! dihydrate1phosphoric acid di-n-butyl ester 5911phosphoric acid tri-n-butyl ester 5911phthalic acid di-n-butyl ester 5911phthalic acid di-n-octylester 591

Uranium~VI ! dioxo~benzenesulfonate! ~aq!1phosphoric acid tri-n-butyl ester 600–601

Uranium~VI ! dioxo~benzoate!1water 588Uranium~VI ! dioxo bis~8-hydroxyquinolinate!1trichloromethane 628Uranium~VI ! dioxo bis~8-hydroxyquinolinate!~8-hydroxyquinoline!

1dioxane 6261ethanol1trichloromethane 6281water 627

Uranium~VI ! dioxo bis~8-hydroxyquinolinate!~8-hydroxyquinoline! ~aq!1ammonium carbonate1ammonium chloride 627

Uranium~VI ! dioxo bis@4,4,4-trifluoro-1-~2-thienyl!-1,3- butanedionate#1benzene 6291chlorobenzene 6291cyclohexane 6291o-dichlorobenzene 6291dichloromethane 6391n-heptane 6291n-hexane 6291isopropylbenzene 6291toluene 6291tetrachloromethane 6291trichlorobenzene 6291trichloromethane 629

Uranium~VI ! dioxo~butyrate!1water 588Uranium~VI ! dioxocabonate~aq!

1carbon dioxide1sodium perchlorate E572, 575, 576, 577, 578, 578–579, 579–Uranium~VI ! dioxo~ethylenediaminetetraacetate!1water 629Uranium~VI ! dioxo~formate!1water 588Uranium~VI ! dioxo~formate! ~aq!1formic acid 588Uranium~VI ! dioxo~glycolate!1water 588Uranium~VI ! dioxo~hydroxybenzoate!1water 588Uranium~VI ! dioxo~iso-butyrate!1water 588Uranium~VI ! dioxo~lactate!1water 588Uranium~VI ! dioxo~monochloroacetate!~aq!

1diethyl ether 595–5961phosphoric acid tri-n-butylester 596–597

Uranium~VI ! dioxo~nitrate! ~aq!1uranium~VI ! dioxo~oxalate! 6231uranium~VI ! dioxo~oxalate!1oxalic acid1nitric acid 623–624

Uranium~VI ! dioxo~oxalate!1water E609, 610Uranium~VI ! dioxo~oxalate! ~aq!

1ammonium oxalate 617–6181ammonium oxalate1nitric acid 6221ammonium oxalate1perchloric acid 6221barium oxalate 6201calcium oxalate 6191hydrogen chloride 6141nitric acid E611, 611–612, 6131oxalic acid 615–6161oxalic acid1nitric acid 621


.


1oxalic acid1perchloric acid 6211perchloric acid 6131phosphoric acid 6141potassium oxalate 618–6191sodium oxalate 616–6171strontium oxalate 6201sulfuric acid 6151uranium dioxo~nitrate! 6231uranium dioxo~nitrate!1oxalic acid1nitric acid 623–624

Uranium~VI ! dioxo~oxalate! N,N8-dimethylformamide monosolvate~aq!1N,N8-dimethylformamide1nitric acid1oxalic acid 6241N,N8-dimethylformamide1sodium perchlorate 625

Uranium~VI ! dioxo~propionate!1water 588Uranium~VI ! dioxo~tartrate!1water 588Uranium~VI ! dioxo~trichloroacetate! ~aq!

1diethyl ether 597–59814-methyl-2-pentanone 599–6001phosphoric acid tri-n-butylester 598–599

Uranium~VI ! dioxo~trifluoroacetate! ~aq!1diethyl ether 593–5941phosphoric acid tri-n-butylester 594–595

Uranium~VI ! dioxo~valerate!1water 588Uranium~IV ! oxalate1water E601, 602, 602–603Uranium~IV ! oxalate~aq!

1hydrogen chloride E603, 604, 6051hydrogen chloride1ammonium oxalate 6081hydrogen chloride1oxalic acid 6081oxalic acid 6071perchloric acid 6061sodium oxalate 6061sulfuric acid 605

Uranium~IV ! phthalocyaninate1benzene 63011-chloronaphthalene 630

11. Registry Number Index

Page numbers preceded by E refer to evaluation texts whereas those not preceded by E refer to compiled tables

50-81-7 E657, 658–66056-23-5 546, 62960-29-7 593–59662-76-0 556, 578, 606, 616–61764-17-5 546, 593, 628, 654, 66864-18-6 545, 588, 655–656, 678764-19-7 588, 591, 59267-56-1 54667-63-0 54667-64-1 546, 66867-66-3 628–62968-12-2 624–62571-43-2 546, 571, 629–63075-09-2 62979-01-6 54684-74-2 59190-13-1 571, 630


4–677

58–660,

–677

84

–668

4–5788

692692 JIRI HALA

95-21-8 54695-50-1 62998-82-8 629107-15-3 547107-21-1 547107-66-4 591108-10-1 599–600108-88-3 629108-90-7 629110-54-3 629110-82-7 629117-84-0 591123-91-1 626124-38-9 E572, 573–580, 630–631, E631–E632, 634, 636–638, E648, 649–652, 67124-46-9 544126-73-8 590–591, 594–601127-09-3 591–592, 671–672141-43-5 547141-53-7 655142-82-5 629144-55-8 543, 634, 649, 675–677144-62-7 539–540, 555, 563, E564, 564–567, 607–608, 615–616, 621, 623–624, 645–647, E657, 6

666–667, E681, 681–685148-97-0 672302-01-2 E657, 659497-19-8 541–542, E542, 543, 578, 582, 584, 632–633, 635, 639, 641–642, 676506-87-6 627, 644, 652, 654506-93-4 544506-97-3 648516-02-9 620534-17-8 643541-09-3 589–590562-99-2 545563-72-4 619583-52-8 556–557, 618–619, 657, 679–680, 683–6584-08-7 640–643, 673593-85-1 544, 581631-61-8 592814-95-9 6201113-38-8 E557, 558–561, 569, 608, 617–618, 622, 656, 664, 6661310-73-2 676–6772031-89-2 E609, 610, E611, 611–6242040-52-0 E548, 549–551, E551, 552–553, E553, 554–557, E557, 558–563, E564, 562847-15-6 E601, 602–603, E603, 604–603316-65-2 656–657, E657, 658–6603812-32-6 E673, 6775470-11-1 6555794-28-5 6196000-70-7 5606132-02-1 5786153-56-6 555, 615–616, 623–6246159-44-0 588–5916484-52-2 592, 653, 6706487-48-5 556, 618–6197264-35-9 539–5407447-40-7 639, 641–642, 657


51, 656,

680

, 669677

20, E662,

3, E564,–631,E673,

568

4


7601-89-0 541–542, E572, 575–580, 584, 592, 625, 630–631, E631–E632, 633–638, E648, 649–6E673, 674–676, 678

7601-90-3 563, 567, 575, 606, 614, 621–622, 656, 661, 678–7631-99-4 592, 6397646-93-7 5627647-01-0 550–551, 562–563, 571, E603, 604–605, 608, 615, 6607647-14-5 562, 571, 583–584, 637–639, 641–642, 652,7647-15-5 5627664-38-2 6147664-41-7 549, 6697664-93-9 E553, 554, 605, 615, 664, 677697-37-2 540, E551, 552–553, E564, 565–566, E611, 611–613, 621–624, 646–647, E657, 658–66

663–668, E681, 681–6857732-18-5 539–542, E542, 543–548, E548, 549–551, E551, 552–553, E553, 554–557, E557, 558–56

564–571, E572, 573–601, E601, 602–603, E603, 604–609, E609, 610, E611, 611E631–E632, 632–648, E648, 649–657, E657, 658–660, E661, 661, E662, 663–672,

673–680, E681, 681–6857757-79-1 5487757-82-6 562, 5837783-20-2 5627790-98-9 563, 671–67210102-06-4 612, 623–62412076-52-7 582–58512125-01-8 62712125-02-9 562, 67012274-95-2 E572, 573–58112386-47-9 541–542, 56812581-78-1 57113075-28-0 546–54713266-86-9 54613278-81-4 E661, 661, E662, 663–66613520-83-7 623–62414041-32-8 54914286-13-6 591, 59215221-09-7 595–59716788-62-8 550–551, 552–553, 554–556, 558, 560, 563–16984-59-1 58817855-75-3 626–62818077-77-5 58518153-67-8 57118274-71-0 67818581-89-0 62018581-91-4 62018860-43-0 610–612, 614–620, 623–6219024-62-5 56819610-62-9 E542, 54320196-48-9 645–64620593-39-9 57621740-41-0 597–60026588-74-9 661, 663–66534501-13-8 655–65636568-63-5 652–65338078-70-5 54439292-10-9 648, E648, 649–65251407-02-4 54452689-31-3 666–66854955-63-4 640–642


.

24

620

694694 JIRI HALA

54955-64-5 64254974-80-0 593–59555328-36-4 54457127-86-3 E631–E632, 632–63864438-44-4 635, 637–63965113-20-4 679–680, E681, 681–68483835-49-6 624–62594667-45-5 600–601101362-32-7 E673, 675–677107176-04-5 547107305-72-6 547134893-75-7 547134893-76-8 547134902-18-4 548134902-19-5 548134902-20-8 548134902-21-9 548184444-18-3 629

12. Author Index

Page numbers preceded by E refer to evaluation texts whereas those not preceded by E refer to compiled tables

Akiba, K. 629Al Mahamid, I. 639, 640–641, 641–642Amphlett, C. B. E611, 611Ananev, A. V. 656, 678Anjaneyalu, B. 547Asprey, L. B. 678Babko, A. K. E572Bachelet, M. 581–582, 586–587Baluev, A. V. 590, 593–601Beckraft. K. A. 639–642Bevz, A. S. 640, 642Bischoff, H. E572, 579–580Blake, C. A. 581–584Bolshakov, K. A. E609, E611, 612, 615–616, 623–6Borodina, N. N. 672Boyer, G. D. E631–E632, 635Brauner, B. 569Britton, H. T. S. 556Brown, K. B. 581–584Bryzgalova, R. V. E551, 553, E564, 565–566Burney, G. A. E657, 658, E681, 682–685Bykhovskii, D. N. 624–625Campbell, A. B. E631–E632, 635Carpenter, S. A. 639–642Chander, K. E658, 659–660Chapru, G. C. E662Charles, R. G. 626Cheneau, G. E657, 659Chernitskaya, I. V. E551, 553, E564, 565–566Cheylan, E. 581–582, 586–587Clark, D. L. E631–E632, 638Claudel, B. 541–542, 546, E557, 560Colani, M. E548, 550, 555, 563, 588–589, E609, 610, E611, 612, 614–Coleman, C. F. 581–584


8

51

–668

47

–6751


Courtois, C. 588Czerwinski, K. R. E572, 577, E648, 651Davidge, O. T. E611, 611Dawson, J. K. E661, E662, 663, 664Dervin, J. E542, 543–544Dorough, G. D. E603, 604–605, 608Drabkina, L. E. 652–653, 666–667, 667–66Duis, M. 581–582, 586–587Ebelmen, M. E609, 610Eberle, S. H. 671–672Elovskikh, N. N. 585Ermakova, T. A. E609, 615–616Essen, L. N. 563, 567Evteev, L. I. E548, 549, 602Fanghanel, F. E572, 577, E631–E632, E648, 6Faucherre, J. E542, 543–544Feldman, C. V. 547–548Felmy, R. W. E673, 676–677Ferri, D. E572, 575Francis, K. E. E661, E662, 665Freiser, H. 626Fromage, F. 544Fulton, A. R. E673, 676–677Gelman, A. D. 645–647, E648, 653–654, 656, E661, 661, E662, 663–664, 666Giffaut, E. 677Giolitti, F. 585Givon, M. E673, 673Goheen, M. W. 570Gorbenko, D. S. 643Goulette, J. C. 581–582, 586–587Grenthe, I. E572, 575, E631–E632, 63Grinberg, A. A. E548, 549, E601, 602–603, 60Hakem, N. 639–642Hall, R. E564, 565Hasilkar, S. P. E657, 659–660Hauser, G. E553, 554, E557, 558Hill, D. G. 581–584Holden, H. C. E557, 559Hoshi, M. 545, 654Jadhav, A. V. E657, 659–660Jain, H. C. E657, 659–660James, C. E557, 559Jarrett, M. E. D. 556Jenkins, W. A. 549Kadenskaya, V. S. E572Kanellakopulos, B. E631–E632, 637–638Kanno, T. 629Kapshukov, I. I. E631–E632, 640, 642Kato, Y. E572, 576, 578, 630–631Kazachenko, D. V. 546Keenan, T. K. 678Keller, C. 671–672Khedekar, N. B. E657, 659–660Khodakovskii, I. L. E572, 573Kim, J. I. E572, 577, 580, E631–E632, 637–638, E648, 650–651, E673, 674Kimura, T. E572, 576, 578–579, 630–63Kirby, H. W. 540


84

24

84

64

675

–657,8

696696 JIRI HALA

Klygin, A. E. 627, 629Kochergin, S. M. 557, E557, 561, E564, 566, 683–6Kolyaga, N. S. 627Kondratova, P. I. 645–646Korablin, E. V. E681, 681–682Korenmen, I. M. 562, 571Korolikhin, V. V. 562, 571Korovin, S. S. E609, E611, 612, 615–616, 207, 623–6Kotchevanova, L. G. 591, 592Kovalenko, K. N. 546Kovaleva, I. S. E542, 543, E548, 556, 568Krammer-Schnabel, U. E572, 579–580Krivokhatskii, A. S. E551, 557, E557, 561, E564, 566, 683–6Krot, N. N. 647, 656, 678Kurnakova, A. S. E548, E551, 552, 555, E564, 5Kuzmina, M. A. 548, 625Lang, G. E557, 560Lebedev, A. 679–680Lemire, R. J. E631–E632, 635Lingen, van der, G. W. B. 593Lowrie, R. S. 581–584Luerkens, D. W. 646–647Lumpov, A. A. 594–599Luzhnaya, N. P. E542, 543, E548, 556, 568Mandleberg, C. J. E661, E662, 665Marcus, Y. E673, 673Martell, A. E. E572Marx, G. E572Matorina, N. N. 656–657Maya, L. E572, E631–E632, 633McCuiston, J. M. 549Mefodeva, M. P. 647Meinrath, G. E572, 576, 578–579, E631–E632, 636, E673, 674–Mentzen, B. 545–546Mikhailov, G. G. 541–542Misko, Yu. S. 571, 630Moiseev, I. V. 672Monson, P. R. E564, 565Moskalev, P. N. 571, 630Moskvin, A. I. 563, 567, E601, E603, 604, 608, E611, 613, 621–622, 644, E648, 653–654, 656

E661, 661, E662, 663–664, 666–66Muniyappan, T. 547Myagkova-Romanova, M. A. 599–600Naumov, G. B. E572, 573Navarro, A. E557, 560Navratil, J. D. 655Neck, V. E631–E632, 637–638Neu, M. P. E631–E632, 638, 652Nigon, J. P. 678Nikitin, A. A. E572, 573Nikolaeva, N. M. E572, 574, 606Nikolskii, B. P. 591–592Nikolskii, N. A. 629Nitani, N. 578, 630–631Nitsche, H. E631–E632, 675–676Novak, C. F. E631–E632, 639, 642Oki, S. 628


184

66

625

9

675

64

66

7

7

4


Pamfilova, G. G. 591–592Paramonova, V. I. 591–592Pashalidis, I. E572, 577, 580, E648, 650–65Pazukhin, E. M. E551, 557, E557, 561, E564, 566, 683–6Pazukhina, Yu. L. E551, 557, E557, 561, E564, 5Penneman, R. A. 678Perlova, C. V. 547–548Petrzhak, G. I. E548, 549, E601, 602–603, 607, 624–Pirozhkov, S. V. E572, 574, 679–680Plyushchev, V. E. E609, 615–616Porter, J. A. E657, 658, E681, 682–685Prussin, T. 640–641Rai, D. E333, 676–677Razbitnoi, V. M. 679–680Reas, W. H. E662, 665Reily, S. D. 652Riccio, G. E572, 575Roberts, K. E. E631–E632Robinson, R. J. 570Robouch, P. E631–E632, 634, E648, 64Rogozin, Yu. M. E551, 553, E564, 565–566Rudolf, G. E631–E632Runde, W. E572, 104, E631–E632, 637–638, 638, E648, 650, 652,Saito, A. E631–E632, 632Salutsky, M. L. 540Salvatore, F. E572, 575Samsonova, O. N. 546Sazonova, V. F. 546–548Schmitt, J. M. 581–584Sergeeva, E. I. E572, 573Shapkin, G. N. 571, 630Shestakova, I. A. 539–540Shiloh, M. E333, 673Shubochkin, L. K. E548, E551, 552, 555, E564, 5Silin, A. Yu. 590Silva, R. J. E631–E632, E333, 339Simakin, G. A. 639–640, 642Skrylev, L. D. 547–548Smirnova, E. A. E551, 557, E557, 561, E564, 5Smirnova, I. D. 627, 629Smirnova, T. V. 647Smith, R. E661, E662, 665Smith, R. M. E572Spitsyn, V. I. E548, E551, 553, 557, 603, 60Stabrovskii, A. I. 585Standifer, E. M. E631–E632Starzicky, E. 678Steinmeyer, R. H. 648Sudarikov, B. N. 569–570, 625–626, 668–32Suglubova, I. G. 590, 593–601Suzuki, N. 629Szilagy, M. 591Taranov, A. P. 590, 600–601Tsvetkova, V. T. 672Tucker, D. B. E631–E632Ueno, K. 545, E631–E632, 632, 645, 65Vdovenko, V. M. 593–598


7

622

27

698698 JIRI HALA

Vecchiarelli, V. 585Visyashcheva, G. I. E631–E632, 640, 642Vitorge, P. E631–E632, 634, E648, 649, 67Volkov, Yu. F. E631–E632, 640, 642Watt, G. W. 549Whittemore, C. F. E557, 559Wirth, F. 550, E553, 554, E557, 558Wittenberg, L. J. 648Xi, R. H. E572, 579–580Yakovlev, G. N. 640, 642, 679–680Yoshida, Z. E572, 576, 578, 630–631Zaitseva, V. P. E648, 653–654Zakharov, O. I. 541–542Zakharova, F. A. E601, E603, 604, 608, E611, 613, 621–Zakolupin, S. A. E681, 681–682Zehenter, J. 589Zenkova, R. A. 643Ziv, D. M. 539–540Zvyagintsev, O. E. 569–570, 625–626, 668–3

IUPAC –NIST SOLUBILITY DATA SERIESEditor-in-Chief

M. SalomonSub-editor

solid/Liquid SystemsW. Voigt

EDITORIAL BOARDM. W. Chase~USA! C. Magalhaes~Portugal!R. Cohen-Adad~France! J. Sangster~Canada!J. Eysseltova` ~Czech Republic! K. Sawada~Japan!P. G. T. Fogg~UK! M.-Th. Saugier Cohen-Adad~France!H. Gamsja¨ger ~Austria! P. Scharlin~Finland!M. Gaune-Escard~France! D. G. Shaw~USA!A. Goto ~Japan! A. Skrzecz~Poland!C. Guminski~Poland! R. P. T. Tomkins~USA!E. Konigsberger~Austria! J. Vanderdeelen~Belgium!J. W. Lorimer~Canada! V. M. Valyashko~Russia!

Managing EditorM. Chase

National Institute of Standards and Technology


iupac-nist solubility data series. 74. actinide carbon compounds

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