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NIST–JANAF Thermochemical Tables for theBromine OxidesCite as: Journal of Physical and Chemical Reference Data 25, 1069 (1996); https://doi.org/10.1063/1.555993Submitted: 25 July 1995 . Published Online: 15 October 2009

M. W. Chase

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NIST -JANAF Thermochemical Tables for the Bromine Oxides

Malcolm W. Chase Standard Reference Data Program, National Institute of Standards and Technology, Gaithersburg, Maryland 20899

Received July 25, 1995; revised manuscript received May I, 1996

The thermodynamic and spectroscopic properties of the bromine. oxide species have been reviewed. Recommended NIST -JANAF Thermochemical Tables are given for six gaseous bromine oxides: BrO, OBrO, BrOO, BrOBr, BrBrO, and Br03' Sufficient information is not available to generate thermochemical tables for any condensed phase species. Annotated bibliographies (over 280 references) are provided for all neutral bromine oxides which have been reported in the literature. There are needs for additional experimental and theoretical data to reduce the uncertainties in the recommended values for these six species. Of all the species mentioned in the literature, many have not been isolated and characterized. In fact some do not exist. Throughout this paper, uncertainties attached to recommended values correspond to the uncertainty interval, equal to twice the standard deviation of the mean. © 1996 American Institute of Physics and American Chemical Society.

Key words: bromine oxides; evaluated/recommended data; literature survey; spectroscopic properties; thermodynamic properties.

Contents 1. Introduction............................... 1069

1.1. References for the Introduction. . .. . . . . . .. 1071 2. Chemical Species Coverage .................. , 1072 3. Historical Perspective of Bromine Oxide Studies. 1072 4. Summary of the Data for the Bromine Oxide

Species. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1073 4.1. Spectroscopic Information. . . . . . . . . . . . . .. 1073 4.2. Thermodynamic Information. .. . . . . . . . . .. 1073

5. Discussion of the Literature Data ............. , 1073 5.1. BrO................................. 1074 5.2. OBrO................................ 1079 5.3. BrOO................................ 1085 5.4. Br03 ................................ 1085 5.5. Br04................................ 1086 5.6. BrOBr............................... 1086 5.7. BrBrO............................... 1088 5.8. Br2(02).............................. 1089 5.9. Br203................................ 1089 5.10. BrOBr02............................. 1089 5.11. 02BrBr02'" . . . . . . . . . . . . . . . . . . . . . . . .. 1090 5.12. 02BrOBrO ........................... 1090 5.13. BrBr04.............................. 1090

5.14. Br20S ................................ 1090 5.15. Br206 ............................... 1091 5.1fi. Rr207' 1091 5.17. Br30g ................................ 1091

6. NIST-JANAF Thermochemical Tables ......... 1092 6.1. BrO(g)............................... 1093

(i) 1996 by tlw C.S. Secretary of Commerce on behalf of the United States. All rights resem~d. This copyright is assigned to the American Institute of Phy..;j(,<; :lnd rhi' .... meril'an Ch.?mical Society.

Reprint~ available from ACS; see Reprints list at back of issue.

6.2. OBrO(g)............................. 1094 6.3. BrOO(g)............................. 1095 6.4. Br03(g).............................. 1096 6.5. BrOBr(g)............................. 1097 6.6. BrBrO(g)............................. 1098

7. Conclusions................................ 1099 8. Acknowledgments.......................... 1099 9. References-Annotated Bibliographies. . . . . . . . .. 1100

List of Tables 2.1. Bromine Oxide Species. . . . . . . . . . . . . . . . . .. 1072 5.1.1. KotatlOnal Constants tor 131'0. . . . . . . .. . . . .. l.O75 5.1.2. Rotational.and Electronic State Splitting

5L3 6.

7.1.

Constants for BrO. . . . . . . . . . . . . . . . . . . . . .. 1077 Dissociation Energy of BrO. . . . . . . . . . . . . .. 1079 Bromine Oxide Species: Structure and Vibrational Frequencies. . . . . . . . . . . . . . . . . .. 1081 Thermodynamic Properties of the Bromine Oxides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1099

1. Introduction

As a continuation of previous studies which dealt with the thermodynamic properties of the chlorine oxides I and oxygen fluorides,2 this study deals with the neutral bromine oxides. A succeeding article will deal with iodine oxides. We will Hul lli~CllS~ lhe: aSlatine uxilles, as there appears to be

only an estimated D~ value reported in the literature for AtO(g). Specifically, this study examines the thermodynamic properties of the neutral oxides. not the gaseous ionic and aqueous ionic species. The main purpose of this article is to

0047 -2689/96/2S( 4)/1 069/43/S14.00 1069 J. Phys. Chern. Ref. Data, Vol. 25, No.4, 1996

1070 MALCOLM W. CHASE

generate thermochemic.al tables for bromine oxide species. In generaL there are scant data available for the description of the spectroscopic and thermodynamic data for any of the bromine oxides, except for BrO, OBrO, and BrOBr. Although the prime emphasis was on the diatomic and triatomic species, a thorough search of all bromine oxygen species was conducted to decide which species had sufficient data.

For the time period 1907 to 1994, there are only 280 citations in Chemical Abstract Services (CAS) dealing with all phases of the bromine oxides; of these 147 deal with BrO, 45 deal with OBrO. and 25 with BrOBr. Of the approximately 25 oxides mentioned in the literature, however, there is not conclusive evidence as to the existence of all of them.

The major interest in the numerous bromine oxides is due to the important role these compounds play in stratospheric chemistry. For this reason, the spectroscopic characterization of these species is mandatory in order to explain possible reactions thermodynamically and kinetically and to monitor the species in real time. In addition, numerous researchers are examining bonding trends within all halogen oxide species. There are no commercial uses of the bromine oxides

mentioned in the literature. The current study is aimed at providing a complete and

thorough coverage of the literature for spectroscopic and thermodynamic information. Although it is not the purpose of this article to summarize and critique the chemistry of the bromine oxides, all such references are provided here. The references were obtained primarily by use of commercial abstracting services and all NIST Data Centers. (Chemical Kinetics Data Center; Chemical Thermodynamics Data Center; Ion Kinetics and Energetics Data Center; Molecular Spectra Data Center; Vibrational and Electronic Energy Levels of Small Polyatomic Transient Molecules; Crystal and Electron Diffraction Data Center.) Since the literature survey revealed so few references in total for all neutral bromine oxides, all citations are listed in Sec. 10 (References Annotated Bibliography). It should be noted that the reading of the individual articles yielded additional references. many of which are included in the attached bibliography. Not included are those articles or books (textbooks and handbooks) which are simply presenting a summary of properties. with no critical evaluation. Note that the earliest reference for any bromine oxide species was in 1928. Even though many of these citations are not relenmt to this study. future investigators will not h~lxe to ,:earch the past literature. but simply concentrate

on the publications since 199-1-. The current version (1985) of the JANAF Thermochemi

cal Tables" does not include any bromine oxygen species. whereas the 1989 version of the Thermophysical Properties of fndi\idual Substances..j. only includes BrO(g). for which 14 references are given: the latest of these being dated 1975. This latter critical review referred to data from four spectroscopic studies. two micrO\vave studies. three EPR studies. four dissociation energy studies. and two earlier reviews. There are sufficient new data available to warrant a revision to this tabulation. The NBS Thermodynamic Tables:' and its

J. Phys. Chern. Ref. Data, Vol. 25, No.4, 1996

Russian counterpart by Glushko and Medvedev6 listed values (C;,HO, S°, and ~"fHO) at 298.15 K for BrO(g), but only an enthalpy of formation for Br02(cr). [The NBS Tables also listed values for three aqueous ions, Glushko and Medvedev listed two aqueous ions.J It should be noted that the NBS study was performed in 1964 and the Russian study in 1965, and were based on the same references.

There are many NASA-JPL publications on chemical kinetics in which enthalpy of formation tables are given. Of all the bromine oxides, only BrO(g) is listed by NASA-JPL.7

These data are presented without citation or reference to the original source. Most of the recommendations are based upon data in the IUPAC Evaluation (Atkinson et al., 1989,S 19929

). Some of the values are different from the current IUPAC recommendations. reflecting recent studies that have not yet been accepted and incorporated into that publication. IUPAC cites the origin of their values. All citations given by IUP AC are included in this article.

Lewis 10 in 1932 reVIewed the kinetics of reactions that proceeded with velocities ranging from the flammable region to detonation. As part of this review the author summarized the kinetics of the explosion of ozone as sensitized by bro

mine. Lewis raised the question as to the possible formation of bromine oxides.

In a 1963 review article, Schmeisser and Brandle II summarized the data pertaining to the properties and chemistry of the halogen-oxide compounds. Although these authors did not discuss BrO, they examined BrOBr and OBrO in detail. A measured enthalpy of formation of OBrO(cr) was noted. Brief mention was made of BrO 3, Br205, and Br308' although it was clear that the authors were not convinced that these "compounds" existed.

A 1972 review by Brisdon,12 discussed seven bromine oxide species: BrO, OBrO, BrOO, Br03, BrOBr, Br202. and Br:P4' Whereas there was a complete spectroscopic characterization of BrOBr presented, only a partial identification of BrO was made. General comments proposing the existence (or nonexistence) of the remaining compounds were made.

Clyne and Curran 13 surveyed the reaction kinetics of halogen atoms, excited molecular halogens, and halogen oxide radicals. The authors covered the literature through early 1976. Their discussion provided a summary of the bimolecular reactions ot CIU and BrU with a variety of species. In the case of BrO, one of the products formed was BrOO. Thermodynamic enthalpies of reaction given in this review were extracted from earlier studies by Clyne

Bromine and its oxides were reviewed (through 1992) by Keller-Rudek et af. 14 for the Gmelin series. An earlier review by Kotowski et af. I:' for this series was published in 1931. The Keller-Rudek review discussed in detail many oxides [BrO, Br02, Br03' Br20, BrBrO, Br202, Br203' Br20..j.. Br20:" and Br206J, but only briefly mentioned others [BrO..j., Br06' Br207' Br30S' Br..j.O. Br..j.02, and Br..j.O..j.]. Four species were listed in this review for which we do not have bibliographies. Two of these species [Br..j.O, BrO(J were stated to be weak complexes, whereas the other two [Br..j.02' Br..j.0-lJ were assumed to be unstable intermediates.

NIST -JANAF THERMOCHEMICAL TABLES FOR THE BROMINE OXIDES 1071

On the other hand, this JPCRD article mentions two species [BrOO, 02BrOBrO] which were not discussed by KellerRudek et al. l~

[After this article was written and reviewed, we became aware of the existence of another review article by Wayne et aI.21 This article provides discussion on the thermodynamic and spectroscopic data on many bromine oxides. Although not of imponance for our purposes, the ankle abo discusses many other topics, including photochemistry and kinetics.]

In reading Sec. 5, the reader will soon learn that the existence of many of the bromine oxide compounds is questionable. The thermal instability of the bromine oxides has led to numerous difficulties in characterizing specific bromine oxides. The syntheses are not always reproducible. The following summarizes our interpretations of the probable existence of the compounds mentioned:

Exist and have been observed: BrO; OBrO; BrOO; BrOBr: BrBrO

Postulated: Br03; BrO~; Br06; Br202 Ohserved as crystalline solid: OBrOBrO: BrOBr02;

02Br-Br02; 02BrOBrO; BrBr04; Br205 No conclusive confirmation as to existence: Br206;

Br207: Br308; Br40; Br402; Br404

In the following discussions, analyses and calculations, the 1993 atomic weights of the elements 16 are used: ArCBr) =79.904±0.001; Ar(O)= 15.9994±0.0003. Since the mid-1950s, the relative atomic weight of oxygen has changed by 0.0006 to 15.9994. Similarly for bromine, the relative atomic weight has changed by 0.012 to 79.904. Relatively speaking, these ch3nres 3rt" sufficiently small that we \-vill not consider any conversions due to relative atomic weights.

In addition, the 1986 fundamental constants are used. 17

The key constant of interest in this work is the ideal gas constant: R=~.3145lU± 0.000070 J mol I K I. In companson to the 1973 fundamental constants,18 R has cham!ed bv +0.0001 J mol- 1 K- 1

• The effect on the thennal fu~ction-s with this change is ~SO (298.15 K)=O.004 J mol- 1 K- 1 for OBrO(g) and BrOBr(g).

SI units are used for the final recommendations. Since we are dealing only \\/ith ideal gases and spectroscopic information. the resulting calculated thermodynamic tables refer to thermodynamic temperatures. Thus, no temperature scale conversions are necessary.

In the follO\ving dit;cut,sions, the numeric values (and their

uncertainties jf given) presented are those reported in the original publication in addition to the Sl value. This is to ensure quick confirmation of the extracted results and their uncertainties. These uncertainties (not ahvays based on experimental and mathematical analyses) are the values quoted bv the ori£inal authors and are often not fullv described as to their origi~1S. Our reported uncertainties for sv and .1rE-f are calculated llsing a propagation of errors approach.

The recommended data presented in the NIST -JANAF Thermochemical Tables are a result of a combined appraisal of results from experimental studies. calculations (e.g.

quantum-mechanical treatments) and estimations. All tables are calculated using the full significance of all numeric values. Rounding occurs at the<end of the calculations. The uncertainty given represents our best attempt for twice the standard deviation.

The NIST -JANAF Thermodynamic Tables (Sec. 6) are calculated using the current atomic weights and fundamental constants, as well as the thermochemical tables for the mon

atomic and diatomic bromine and oxygen. These latter reference state thermochemical tables, as originally calculated, were based on the 1973 fundamental constants l8 and the 1981 relative atomic weights. I 9 This will cause a slight offset in the formation properties of the order 0.01 kJ/mol; such an offset is well outside the uncertainty range of the enthalpy of formation of the bromine oxides. Neumann20 has presented an identical thermochemical table for BrO(g); this table was prepared jointly with this authorY

1.1. References for the Introduction

I S. Abramowitz and M. W. Chase, "Thermodynamic properties of gas phase species of importance to ozone depletion," J. Pure. App!. Chern. 63(10), 1449-54 (1991).

2M. W. Chase, "NIST-JANAF Thermochemical Tables for the oxygen fluorides," J. Phys. Chern. Ref. Data 25(2), 551-603 (1996).

3M. W. Chase, Jr, C. A. Davies, 1. R. Downey, 11'., D. A. Frurip, R. A. McDonald, and A. N. Syverud, "1ANAF Thermochemical Tables. 3rd Edition," 1. Phys. Chern. Ref. Data 14, Supplement No. 1. 1856 pp. (1985).

.jL. V. Gurvich. I. V. Veyts, and C. B. Alcock, Thermodynamic Properties of Illdividual Substances, 4th ed., two parts (551 pp. and 340 pp.) (Hemisphere, New York, 1989).

5D. D. Wagman. W. H. Evans, V. B. Parker, R. H. Schumm, 1. Halow. S. M. Bailey, K. L. Chumey, and R. L. NuttalL "The NBS Tables of Chemical Thermodynamic Properties. Selected Values for Inorganic and C I and

C2 organic substances in SI units," 1. Phys. Chem. Ref. Data 11. Supple

ment No.2. 393 pp. (1982). 6 y . P. Olushko and Y. A. Medvedev, Thermal COllSWIITS Of SubSTances.

(145 pp.) (Academy of Sciences, Moscow, 1965). VoL 1. 7W. B. De More, S. P. Sander, D:M. Golden, R. F. Hampson. M. J.

Kurylo. C. J. Howard, A. R. Ravishankara. C. E. Kolb, and M. 1. Molina. . 'Chemical kinetics and photochemical data for use in stratospheric modeling," NASA-1PL Publication 92-20 (1992); this is one of a series of similar publications.

~R. Atkinson. D. L. Baulch. R. A. Cox, R. F. Hampson. Jr., J. A. Kerr, and J. Troe. "Evaluated kinetic and photochemical for atmospheric chemistry: supplement IlL" J. Phys. Chem. Ref. Data 18(2). 881-1095 (1989).

tlR. Atkinson. D. L. Baulch. R. A. Cox, R. F. Hampson. Jr .. J. A. Kerr, and 1. Troe. "Evaluated kinetic and photochemical for atmospheric chemistry: supplement IV:' 1. Phys. Chern. Ref. Data 2](6). 1125-1568 (1992).

lOB. Lcwis. "Explo:>ion in gascs and thcir kinctics," Chcll1. Rcv. 10.40- 80

(1932): particularly pp. 72-5. II M. Schmeisser and K. Brandle, "Oxides and oxyftuorides of the halo

gens." Ad\". Inorg. Radiochem. 5. 41-89 (1963). I:B. 1. Brisdon. "Oxides and oxvacids of (he halogens:' Int. Rev. Sci.:

[norg. Chem .. Ser. One 3. 2i5-51 <l9721. \1 M. A. A. Clyne and A, H. Curran. "Reactions of halogen atoms. free

radicals. and excited slates." Gas Kinet. Energy Transfer 2. 239-95 ( 19771.

J.lH. Keller-Rudek. D, KoscheIl. P. Meriel. G. Ohms-Brudemann. 1. Wagner. and A. Wietchmann. "Bromine." System No.7. Suppl. B2. GIIl(!lill

Handbook of IllorgGlIic alld OrgwlOl1I(!w/lic Chemistry (Springer, Berlin. 19921.

15 A. Kotowski. R. Gagarin. M. du Maire. G. Glauner-Breittinger. W. Roman. A. Eisner. and F. Seuferling. "Bromine:' System No.7. Main Vol-



ume Gmelins Handbuch der Anorganisclzen Chemie (Verlag Chemie G.M.B.H., Berlin, 1931), 342 pp.

16IUPAC Commission on Atomic Weights and Isotopic Abundances, "Atomic weights of the elements 1993," J. Phys. Chern. Ref. Data 24(4), 1561 (1995); Pure & App!. Chern. 66(12), 2423 (1994).

17E. R. Cohen and B. N. Taylor, "The 1986 CODATA recommended values of the fundamental physical constants," 1. Phys. Chern. Ref. Data 17(4), 1795 (1988).

18E. R. Cohen and B. N. Taylor, "The 1973 least-squares adjustment of the fundamental constant!;," J. Phys. Chem. Ref. Data 2,663 (1973).

19N. E. Holden and R.L. Martin, "Atomic Weights of Elements - 1981," Pure App!. Chern. 55, 1101 (1983).

2oD. B. B. Ne'umann, "NIST -JANF Thermochemical Tables, Supplement 1995," J. Chern. Phys. Ref. Data, (submitted).

21 R. P. Wayne, H. Poulet, P. Briggs, J. P. Burrows, R. A. Cox, P. J. Crutzen, G. D. Hayman, M. E. Jenkin, G. Le bras, G. K. Moortgat, U. Platt, and R. N. Schindler, "Halogen oxides: radicals, sources, and reservoirs in the laboratory and in the atmosphere," Atmos. Env. 29(20), 2675-2884 (1995).

2. Chemical SpeCies Coverage

The following is a list of all bromine oxide species cited in the Chemical Abstract Services (CAS) Indices (formula and substance). Aqueous ions and gaseous ions are not included in this study. The chemical name, formula, and CAS Regis

try Number (when available) are given. This list is complete through Volume 121 of Chemical Abstracts Services (December 1994). It is important to note that this listing gives species whose existence is now questioned. Deleted CA Registry Numbers are given to assure the reader that all past citations were retrieved. There is limited information on the existence of asymmetric isomers of the triatomic speeies

BrOO and BrBrO. Such asymmetric isomers exist for the chlorine oxides, although for the oxygen fluorides, FOO has been observed (but not FFO). (See Table 2.1.)

3. Historical Perspective of the Bromine Oxides

. It is informative to briefly summarize the types of studies which have been conducted through the years on the bromine oxides. Specific references are given in Sec. 9. This section is intended to simply highlight developments through the years. not to provide specific references.

Using the Chemical Abstracts Services Collective Indices as a backdrop for these historical comments, the period of 1907 to 1926 (the 1 st and 2nd Collective Indices) revealed no citations for any bromine oxide species. Even the later citations do not refer to any studies in this time period or

earlier. In the time period 1927 to 1946 (the 3rd and 4th Collec

tive Indices). Chemical Abstracts listed a total of ten citations dealing with bromine oxides. All citations can be grouped in two classes: (1) preparation of solid bromine oxides (from the reaction of bromine and ozone) and (2) preparation of 8r20 in CCI-1- solutions (from the reaction of bro

mine \vith HgO). It is not always clear whether the studies' prime motive was the preparation of bromine oxides or the decomposition of 0 3, In all cases. the stability of the products was examined. The first citation (by Lewis and Schuma-


TABLE 2.1. Bromine oxide species.

Chemical Abstracts and Registry

Formulaa Name Deleted # Current #b

BrO Bromine oxide 23878-08-2 BrO(BrO) Bromine oxide 77968-12-5 15656-19-6

16651-29-9 12233-84-0

79BrO e9BrO) Bromine oxide 24050-34-8 81BrO(81BrO) Bromine oxide 23878-08-2 BrO:! (OBrO) Bromine oxide 21255-83-4 79BrO:! (079BrO) Bromine oxide 29044-85-7 81BrO:! (081 BrO) Bromine oxide 29051-09-0 Br02 (BrOO) bromodioxy 67177-47-3 Br03 (pyr) Bromine oxide 26670-64-4 32062-14-9 BrO.j (Br04) Bromine oxide 56310-08-8 11092-92-5 Br20 (BrOBr) Bromine oxide 21308-80-5 Br2180 (BrI8OBr) Bromine oxide 21364-13-6 Br20(BrBrO) Bromine oxide 68322-97-4 79Br20 (Br79BrO) 151921-01-6 81Br20 (Br81 BrO) 151921-02-7 Br202 (BrOOBr) Bromine peroxide 96028-01-2 Br103 (OBrOBrO) Bromine oxide 55589-63-4 53809-75-9 Br203 (BrBrOJ) Bromine bromate 152172-79-7 Bri0.j (Br(BrO.j) Bromine 141438-65-5

perbromate Br20.j (02Br- Br02) Bromine oxide 53723-86-7 Br20.j (02Br-0-BrO) Bromine oxide 55589-64-5 Br205 Bromine oxide 58572-43-3 Br20 6 Bromine oxide Brl07 Bromine oxide

Br308 Bromine oxide 121992-88-0

a A secondary formula is intended to suggest the assigned structure. If there is no secondary formula given, this means that no structure has been determined for this species, but the atomic ratio is known.

blf no CA Registry Number appears in this column, the species is assumed not to exist.

cher in 1928) dealt with a study in which, upon mixing bromine and ozone in a flask (no temperature specified), a white deposit appeared.,Soon thereafter, an explosion destroyed the apparatus. With such an auspicious debut, further studies of the bromine reaction with ozone were performed more carefully and at lower temperatures (15 °C).

For the time period 1947 to 1961 (the 5th and 6th Collective Indices), 16 additional articles were indexed in Chemical Abstracts Services. Again, this work concentrated on the preparation of condensed phase bromine oxides and was more definitive as to the exact composition of the compound formed during a specified reaction scheme. In addition, the

absorption spectra and dissociation energy of BrO(g) were reported, and the enthalpy of formation of Br02(cr) was measured.

For the time period 1962 to 1971 (the 7th and 8th Collective Indices). 37 references were cited. The dominant theme was the formation of a particular bromine oxide species through radiolysis. photolysis, or shock waves of solutions of

bromates (BrO, Br02' Br03) and EPR studies of y-irradiated crystalline bromates (BrO, Br02, Br03, and Br0-1-)' There was some additional information on the spectroscopic properties of BrO(g), Br03' and Br20.


In the time period of the 9th and 10th Collective Indices (1972-1981), there was considerable activity in the area of the study of the reaction and formation of various bromine oxides. In addition to the spectral studies on BrO(g), Br02' Br03, and Br20, many were published on the preparation, structure, and Raman spectra of many of the oxides (Br203' Br204, Br20s) in the condensed phases: EPR studies on BrO, Br02, BrOj, and Br04 were continued.

For the lith and 12th Collective Indices (1982-1991), there were extensive studies of the formation and reaction of BrO (includiI1gmany dealing with the kinetics) in the troposphere and stratosphere. Fortunately, there are numerous definitive studies of the spectroscopic properties of the triatomic oxides.

In the past three years there has been experimental studies in which Br02 and Br20 have been observed in the gas phase. Additionally, more definitive studies have examined the crystalline oxides in an attempt to confirm the existence of some of the higher valence bromine oxides.

In summary, there are no heat capacity, enthalpy, or vapor pressure studies for any of the bromine oxides. There are a few articles which detail the preparation and report decom

position temperatures for the condensed phases. There is one direct experimental enthalpy of formation measurement for Br02(cr), one enthalpy of formation measurement for Br20(g), and one equilibrium study for Br20(g). The spectroscopic properties and dissociation energy for BrO(g) have been studied adequately, but the complete spectroscopic detennination and enthalpy of fonnation values for any of the other bromine oxides is lacking. Except for Br20, not all vibrational frequencies have been observed for these oxides. The identification and characterization of the crystalline phase is not always definitive.

4. Summary of the Data for the Bromine Oxide Species

4.1 Spectroscopic Information

The construction of thennodynamic tables for polyatomic gas phase species requires a knowledge of the spectroscopic constants of the molecule including electronic energy levels and degeneracies, vibrational frequencies and molecular structure (including bond angles and bond lengths). This information is necessary for any low-lying excited electronic states. as well as the ground state. These data are obtained

either from direct spectroscopic measurements, from theory, or by analogy with other similar chemical compounds. In some cases, theoretical quantum mechanical calculations are used. There is some spectral information available on a limited number of bromine oxides in the condensed phase. Recent gas spectroscopic studies reveal structural and vibrational frequency information for BrOBr and OBrO. However. relying on information from the fluorine and chlorine oxides. estimates can be made for the structure allJ spectroscopic properties of the asymmetric triatomic oxides. BrOO(g). and BrBrO(g).

For diatomic molecules, spectroscopic information on the electronic energy levels and vibrational-rotational structure is necessary. Experimental data of these types are available for BrO(g). Similar information on CIO(g) is available for comparison.

4.2 Thermodynamic Information

The literature survey revealed little or no information on the thermodynamic properties of any of the bromine oxides, except for BrO(g) which was derived from spectroscopic data. There is a reference for the enthalpy of formation for Br02(cr). Although not explicitly cited in Chemical Abstracts, there is a reference for the enthalpy of fonnation of Br03(g). There are, however, numerous citations as to the thermal stability of the various condensed phase oxides.

For the gas phase species, BrO(g) has dissociation energy infonnation available so that an enthalpy of fonnation may be calculated. Only experimental formation information has been reported in the literature for Br20(g), but not for any of the other gaseous bromine oxides.

There are insufficient data available to permit the calcula

tion of thennodynamic functions for the condensed phase of any of the bromine oxides. No heat capacity or enthalpy data are reported in the literature for any of these oxides. There are some ambiguous data for the melting of the various condensed phase.

5. Discussion of the Literature Data

The information is discussed in terms of the individual bromine oxide species. This is not to imply that all those

species exist or have been isolated and characterized. For example, current information suggests that Br206, Br207, and Br30g do not exist, whereas compounds such as Br03 and Br04 have been proposed but have not been isolated. The proposed existence of the former three was based on a chemical analysis which is now known to be in error. The references for each of the following subsections are found in the References-Annotated Bibliographies (Sec. 9). The squib notation is used to denote the references. The squib is fonned by taking the last two digits of the year and the first three letters of the lead two authors.

Early studies, prior to 1960. which deal with the bromine oxides fall into three categories: (1) the reaction of bromine vvith ozone at low temperatures « -40 DC), (2) the bromine

sensitized decomposition of ozone, and (3) the reaction of bromine with HgO. In the former case, depending on the temperature and relative concentration of the two gases, the products have been stated to be Br308, Br03' Br~05.

Br20, and Br02. all in the condensed phase. However. due to the instability of these oxides and the lack of definitive characterization of the crystals, it was not possible to clearly define the reaction and its products. Reproducibility appeared not to be commonplace. It was also stated that Br02 decomposed to Br20 as the temperature was raised above -40 DC, with Br::;07 proposed as an intermediate. Since the

J. Phys. Chem. Ref. Data, Vol. 25, No.4, 1996


actual chemistry is not of prime importance in this article, and the fact that the characterization of the compounds is not definitive, these articles will not be discussed or critiqued in detail in the sections dealing with these six species.

The early studies revealed the presence of condensed phase products which were stable only at low temperatures, typically below IS 0c. Three articles by Lewis and coworkers examined the reaction of ozone and bromine to form an unstable oxide which they interpreted to be (Br30 8) n .

Schwarz and co-workers examined reaction schemes which produced Br02' Br20, and Br207' Zentl and Rienacher and Brenschede and Schumacher prepared Br20 by the reaction of bromine vapor on specially prepared HgO and HgO in CC14 solution, respectively. As already stated, these reaction ,,('h~m~" pr()nll('~n pronllctc;: which were unstable above ap

proximately IS °C. In fact, the species of presumed composition Br308 was found to be very unstable, explosively un-. stable. [This compound was later shown to be most likely Br03 . J These early preparative reports gave no quantitative information, other than a temperature at which a (presumed) compound appeared to decompose. The reason for emphasizing these points is that, even to the present, most reaction

schemes for any of the bromine oxides still rely on the reaction of bromine gas and ozone in the gas phase or solution. Isolation and characterization is difficult and has led to ambiguous results.

5.1 BrO

The references for BrO can be grouped into numerous categories. Although these categories are somewhat arbitrary, the intent is to provide the reader with a general understanding of the information available. For the purpose of this article, we will discuss only the spectroscopy, EPR, and dissociation energy studies; others may not be addressed as these do not necessarily provide sound thermodynamic information.

1. Spectroscopy: Cross sections

[88W AH/RA V], [77VOG/DRE] Microwave

[69POW/JOH], [72AMA/YOS], [74LOV/TIE]. [SOLOEIMIL], [81 COH/PIC]

IR -[7STEVIWAL], [SIMCK], [S4BUT/KAW]. [9 IORLI BUR]

UV (emission) -[37VAI]. [3SVAI], [47COLIGAY]

UV (absorption) -[SOHER]. [SSDURlRAM], [SSZEE]. [SOLOE/MIL]. [SI BARlCOH]. [SSDUIIHUD]

Other -[72YAN]. [73BYB/SPA], [73PAN/MlT]. [74DHAI CLE]. [74DHAlCLE2]. [74TIS]. [81 DORIMEH]. [81GROILAU]. [85POY/PIC]. [88IGE/STO].


[89BOWIBOY], [93MON/STI] 2. EPR-

[66CARlLEV], [67CAR], [67CARlLEV], [67CARI LEV2], [67CAR/LEV3], [67CARlLEV4], [69CAR], [70CARlDYE], [71MIL], [71BYF/CAR], [72ADL]. [72BRO/BYF], [7SDALILIN], [86BYB], [86BYB2]

3. Dissociation energy/IPIEA -[4 7COL/GA Y], [48GA Y], [SOB RE/B RO], [50HER], [53BRE], [S3GA Y], [54COT], [S8BRE], [58DURI RAM], [63SCH], [6SGLUIMED], [66VED/GUR], [68GA Y], [68WAGIEVA], [69BREIROS], [70DAR], [77GLI], [77VOGIDRE], [78DUNIDYK], [79HUBI HER], [81BOH/SEN], [82WAGIEVA], [84SAU/TAT], [86GIN], [97BAS/GA V], [S8IGE/STO], [88SIN]. [88TYK], [89GURlVEY]: [92GILIPOL], [94RUSI BER]

4. Formationldecompositionlreaction/detection -[40MUN/SPI], [60BRIIMAT], [60MATIDOR], [61UUb/UUU], [62UUb/PAN], [6JBUJ{JNUK], [64TRE/YAH], [66BUXlDAI], [68BUXIDAI], [70AMIITRE], [70TOM/STU], [71KAU/KOL]. [710SL], [73DIXIPAR], [73PARlHER], [74CAH/RILl [77GIL/GAR], [77TAD/SHI], [78TEVIW AL]. [80SEHI SUD], [80YUNIPIN], [86BRU/AND], [86KREIFAB], [86RAZ/DOD], [86HILIMCC], [89BARlBEC], [90S0L], [91ARS/ZIV], [9IJAD/LON], [91NEUI DOR], [91SZAIWOJ], [92FAN/JAC], [92MCC/HEN], [92W AT], [94ARP/JOH] , [94COXlCOX], [94GARI SOL], [94HAUIPLA], [94INO], [94MARlCOR], [94POMIPIQ], [95FLE/CHA]

5. Kinetics -[70BRO/BUR], [70CL Y/CRU]. [70CL Y/CRU2], [71 CL Y ICR U], [7 5CL Y IW AT], [75RADIWHI], [75WOFIMCE], [76CL YIMON]. [76MOIlYUR], [77CLY/CUR], [77CLYIWAT], [79LEU], [79WATI SAN], [80JAFIMAI], [80MOLIMOL], [80NIC]. [80SAN], [8JCLYIMAC], [8 1 DON/ZEL] , [8IMENI SAT]. [81RAYIWAT], [81SAN/RAY], [81SANIWAT], [82ANT], [82COX/SHE], [82COX/SHE2], [82FERI SMI], [83BUTIMOR], [82BAU/COX]. [84CLA], [85BYKlGOR], [86BRU/STI], [86MCE/SAL], [86MOX], [86SAN], [86TUN/KO], [87ELO/RYN], [~"/HIUCIC], [~~BAJ{JSUL], [88tlKUrrOO], [88HIL].

[88HILlCIC], [88SALIWOF]. [88SAN/FRI], [88TOOI AND], [88TOO/BRU], [89AND/BRU], [89ATK/BAU]. [89ATKlBAU21 [89AUS/JONl [89FRIISA N] [R9KOI ROD], [89MEL/POU], [89SAN/FRI], [89S0LlSAN], [90DAN/CAR], [90PHI], [90POUILAN], [90POUI LAN2], [90TUR]. [90TURlBIR]. [91AND/TOO]. [91BARlBAS], [91LANILAV]. [91MUR], [91TUR], [91 TURlBIR]. [92POU/PIR], [92ROS/TIM]. [92W AHI SCH], [93BRIIVEY]. [93CURlRAD]. [93MAUIW AH]. [93SALIWOF], [93THO/DA Y], [93WININIC], [94CHIICAR]. [94THO], [94TOU], [94WEN/COH].

[95THOICRO] 6. Review -

[48GA Y]. [50BRE/BRO], [53BRE], [53GA YJ,


TABLE 5.1.1. Rotational constants for BrO (Bo/cm -I).

Source 79BrO

58DURIRAM 0.455

69POW/JOH 0.4277893 ±0.0000037

72AMAlYOS 0.4277789 ±0.0000017

74TIS 0.4282 ±0.0005

81COH/PIC 0.42960660 ± 0.00000013

8IMCK 0.42960660 ± 0.000000 13

0.426278

84BUT/KAU 0.42778722 ± 0.00000007

910RLlBUR 0.42778706 ± 0.00000025

[S7RAM], [66VED/GUR], [68GA Y], [69BREIROS], [70DAR], [74LOEITIE], [74SCH], [77CLY/CUR], [79HUB/HER], [84BAU/COX], [84BURlLAW], [84SAU/TAT], [89ATKlBAU]

Spectroscopic b~fomzation The microwave data which result in rotational constants

are summarized in Table S.1.I. Vaidya [37VAI, 38VAIJ assigned a system of bands in the

region 4000-4600 A to the radical Bra. The compound was obtained in a flame of ethyl bromide burning with oxygen. Vaidya proposed a provisional vibrational analysis. Coleman and Gaydon [47COLIGAY] studied the emission of BrO in flames. A vibrational analysis yielded w~ = 713 em - I and w~x~ = 7 cm - I. Zeelenberg [S8ZEE], using flash photolysis techniques with four brominated compounds, observed an absorptIon spectra WhICh was attributed to tirU. No vIbrational analysis was provided.

Durie and Ramsay [S7RAM. 58DURJRAM] observed the ;)bsorptinn spectn) of 8rO during: the flash photolysis of

Br2-02 mixtures. Twenty absorption bands were recorded in the region 2890-2550 A. Rotational and vibrational analyses \-vere performed. leading to values for 1'0, and Bo, as well as We and wexe values. Only approKimate rotational constants \vere observed:

'l)BrO Bn = 0.455 cm - I ro = 1.669 A SIBrO B()=0.472 em-I l'o=1.635 A

I?urie and Ramsay adopted a mean value of 1'0 = 1.65 :!:0.02 A. The authors were able to describe the absorption bands in

the same \'ibrational scheme as used by 47COL/GA Y for

81BrO Comments

0.472 B determined by plotting VR(J)

vs (J -2)2

0.4260164 Beff ; microwave spectrum ±0.0000030

0.4260037 Beff ; reported in MHz; ±0.0000030 microwave spectrum

0.4264 Review ±0.0005

0.42782007 Beff(Be2); rotational spectrum ±0.00000013

0.42782007 Beff ; values taken from ± 0.00000013 81COHIPIC; held fixed in this

spectral analysis; 0.424510 Bo values

0.42601182 Beff(BO); states this values ± 0.00000007 (from infrared and microwave

data) to be same as that derived by 81 COHIPIC

0.42601176 derived from infrared ± 0.000000 11 measurements

emission, with a slight adjustment in the numbering scheme. The vibrational analysis yielded we=771.9 cm- I and wexe =6.82 em-I.

Powell and Johnson [69POW/JOH] detected the microwave spectra of the gas phase BrO radical in the 2TI312

ground state. They reported rotational constants BeffC9BrO) 12824.80:!:0.11 (0.42779 cm -1) and Beff(8IBrO) 12771.6S±0.09 (0.42602 cm- I). These results are in good

agreemeIll wiLlI Lhe EPR rneasuremenlS which are memioned later in this section.

Using microwave detection techniques, Amano et al. [72AM A/YOS] oe:termine:o the e:qnilihrinm strncturf', and di

pole moment of the gas phase BrO. They reported Beff C9BrO, 2TI3/2' 12824.49:!:0.OS MHz (0.42779 em-I) and Beft< 8I BrO, v=0)=12771.27±0.09 MHz (0.42600 cm -I). The authors recommended r e = 1. 7171 :!:0.00I3 A for both isotopic species as derived from Be.

Yanishevskii [72Y AN] studied the relationship between vibrational frequencies and dissociation energies. No new

data were presented. Byberg and Spanget-Larsen [73BYB/SPA] used a modi

fied extended Huckel method to calculate nuclear quadrupole coupling constants. No new structural information for BrO was provided.

Pandey et al. [73PAN/MIT] calculated the mean amplitudes ot Vlbration ot tirU at the temperatures T=LYl:).lb and 500 K. The bond and molecular polarizabilities have been computed using the Lipincott-Stutman Ll-potential function model of chemical bonding.

Dhar and Cleveland [74DHA/CLE, 74DHA/CLE2] pre-



sen ted calculations relating the Morse-potential energy function with force constants, vibrational frequencies and dissociation energies. Calculations refer back to the Durie and Ramsay (1958) study. No new data were provided.

In their review of microwave spectra of diatomic molecules, Lovas and Tiemann [74LOVITIE] recommended rotational constants and ground state splitting based on data from Amano et al. (1972). However, they also referred to the EPR results of [67CARlLEV3] and [71BYF/CAR].

Tischer [74TIS] analyzed the x2rr3/2 spectrum of the BrO radical by calculating energy eigenvalues of the corresponding Hamiltonian. The author adopted [70CARlDYE]'s EPR value of Bo=0.4282 cm- 1 C9BrO); Bo=0.4264 cm- I

(81 B rO) for the rotational constants and Ao = - 815 ± 120 cm -I for the splitting of the two isotopic species (see the next section). An ro = 1.7205 A C9BrO) value was also quoted from [70CARlDYE]. re values of 1.717 A were likewise reported, based on the work of Amano et al. (I972) for both isotopic species.

Tevault et al. [78TEVIW AL] studied the reaction of atomic and molecular bromine with atomic and molecular oxygen in argon matrices (photolysis of bromine and ozone

containing matrices). Several bromine oxygen compounds were stated to have been formed and identified by infrared spectroscopy-BrO, OBrO, BrBrO, BrOBr, and (BrOh. The authors assigned a very weak absorption at 729.9 cm -I to BrO. The force constant calculated from this frequency was 4.18 mdynJA, a value which was not unexpected on the basis of the FO and CIO constants of 5.41 and 4.66 mdynJA respectively, obtained from their argon matrix frequencies. A reinterpretation of the data yielded We = 751 em -I and wexe = 5.0 cm -I for the ground state. The excited state was reported to lie at 27740 cm -I.

Absorption spectra of BrO were observed from argon matrix samples prepared by microwave discharge of mixtures of argon, bromine and oxygen by Loewenschuss et at. [80LOEI MILl The authors reported an excited state of Te=26363 cm- I with we=514.8 cm- I and wexe=4.8 cm- I. Vibrational const::lnts for the erollnn st::ltf' ::lrf' frle=741.') cm- I ::lnn (,leXe

=6 cm- I. These values result from a reanalysis of earlier data and the current matrix work of [80LOEIMIL].

The absorption spectra and rotational analysis of the A~lli-X :::U i state of isotopically enriched 151BrO and normal BrO have been obtained by Barnett et al. [81 BARICOH] using the flash photolysis of mixtures of bromine and ozonized oxygen. The authors quoted and used [81MCKJ's value of

-968 em -I as the spin splitting in the ground state. The lower state rotational constants were taken to be those deri ved from the microwave study [Sl COH/PICl The rotational constants for the excited state were estimated as: B ~ =0.31-+ cm- I and a; =0.003-+ em-I. with an internuclea-~ distance of 1.95 A. From the analysis of vibrational assignments for BrO. a value for ~ G'{/2 of 722.1 ± 1.1 em -I was obtained. tv'lolecular constant values of w~: =730.6 em -I. w;=516.1 em-I. and D~=19694 em- I w~re used for the calculations of the v' and v' bands.

Rotational spectrum of the v=O and 1 bands and moleeu-


lar parameters of BrO in the 2rr 3/2 state were observed by Cohen et al. [81COHIPICl Rotational constants for the 2rr3/2 state were determined to be Be2=0.42960133 cm- I

C9BrO) and 0.42781482 cm- 1 ( 81 BrO). The values of We2 =726 cm- 1 C9BrO), 724 cm- 1 (81BrO) and We2Xe2=4.92 cm- I C9BrO), 4.90 cm -I (81BrO) derived from the mechanical constants were in good agreement with results obtained by [81BARlCOH], [7STEVIWAL] and [80LOEI MILl An re2 value of 1.717263 A was also determined for both of the isotopic species.

Doraiswamy and Mehrotra [81DORIMEH] examined the collision-induced linewidths of BrO.

Grodzicke et al. [81GROILAU] calculated the dipole moment of BrO.

Using laser magnetiC resonance spectroscopy on three CO2 laser lines, McKellar [81MCK] detected magnetic dipole transitions between the 2Il1/2 and 2Il3/2 components of the grollnn staff' of RrO This W::lS thf' first direct observ3tion

of the 2Il1/2 state of Bra. A spectrum lying between 964.77 and 969.14 cm -1 was recorded for this state. The spin-orbit splitting parameter A and rotational constants BeffeIl ll2 )

were determined to be -967.9831 cm- I (I'JBrO), -967.9981 cm- I (81BrO) and 0.4248 cm- 1 C9BrO), 0.4230 cm- 1

(8IBrO), respectively. The author also predicted micro

wave rotational transition frequencies for the x 2rr 1I2 state of BrO.

Butler et al. [84BUT/KA W] observed the fundamental vibration-rotation band of the 79BrO and 81BrO radicals in the 2rr3/2 ground electronic state (700-760 cm - 1) by using Zeeman-modulated IR diode laser spectrometry. The authors assigned a 721. 92814 cm - I value for the 81 BrO A 2rr ix 2rr j transition, which agrees well with the 714 cm - I value estimated by [81COHIPIC] and the 722.1±1.1 cm- I value derived by [81BARICOH] from optical spectra. Rotational constants 8 0 =0.427781964 cm- 1 C9BrO),=0.426006591 cm- 1 (8I BrO), Q.armonic .frequency we=732.S9 cm- I

e9BrO),=731.37 -cm- 1 ( 8I BrO), and vibrational anharmo

nicity W eXe=4.74 cm- 1 e9BrO),=4.72 cm- I ( 81 BrO) were calculated. But based on the equilibrium spin-orbit coupling constant Ae , assumed to be independent of isotopic mass, the "true" we=72S.69 and 724.18 cm- I for the two isotopic species. The Ae value of -975.19 cm- 1 e9BrO) was based on the results of [82MAKILOV] for CIa. The eqUilibrium internuclear distance was calculated from rotational constants to be r c= 17207') A for hoth of th~ i(mtopic. species.

Duignan and Hudgens [85DUI/HUD] reported the resonance enhanced multi photon ionization spectra of CIO and BrO free radicals between 415 and 475 nm. BrO showed three new vibrational progressions starting from transitions between the X 2rr3/2 state to Rydberg states with assignments of E22:( voo=65003 em-I), F2L( voo=67470 em-I), and an apparently inverted state, G( voo=70504 em -I). No doublet originating from the ground state 2rr 1/2-2rr 312 spin-orbit splitting was observed. The authors proposed a ground state vibrational frequency of 714 em -I. obtained from the difference of the hot band at 466.51 nm and the E(O,O) band. This

NIST-JANAF THERMOCHEMICAL TABLES FOR THE BROMINE OXIDES 1077

TABLE 5.1.2. Rotational and electronic state splitting constants for BrO.

Source Species Balcm- 1 Alcm- 1 ra/A

66CARILEV 79BrO 0.45 81BrO 0.47

70CARIDYE 79BrO 0.4282::!:: 0.0005 -8 IS::!:: 120 1.720" 81BrO 0.4264::!:: 0.0005 -815::!:: 120

71MIL BrO adopted values of [70CARIDYE] 72ADL RrO adopted values of [70CARJDYE]

72BROIBYF 79BrO 0.4281 -980 81BrO 0.4263 -980

81MCK 79BrO O.4278b -967.983(2) 81BrO 0.4260b -967.9981 (2)

"Unspecified which BrO isomer e9BrO or 81BrO) it dealt with.

"These values are Befferr 3/2).

value differed from the 722 cm -1 value proposed by [78TEV/w AL, 81BAR/COH, 84BUT/KA W], and the FZL (we=822 cm- I

), E2L(We=897 cm- I), and G2(LlGl/z =848

cm - I) values for the Rydberg states. Values for EZL( wexe =2.6 cm- I ) were also given.

Poynter and Plckett [~5POY/PIC] have created a computer-accessible catalog of submillimeter, millimeter and microwave spectral lines which was constructed by using

. theoretical least square fits to the observed spectral lines. Ground-state properties of the fourth row main group

monohydrides XH and monoxides XO (X = K through Br) were determined by Igel-Mann et al. [88IGE/STO] by means of self-consistent field/configuration interaction (SCF/CI)

calculations. Bond lengths re= l.741 A (3.29 a.u.), dissociation energy De= 10646 cm- 1 (1.32 eV) and vibrational frequency w e=726± 10 cm -1 were calculated. The authors referred to the dissociation energy recommended by Huber and Herzberg (1979).

Wahner et al. [88WAHIRAV] measured the absolute UV cross section of BrO at 338.1±0.1 nm, the peak of the (7,0) band of the A 2n f- X zn transition. The absorption spectra of BrO in the wavelength range 312-385 nm were measured at 298±2 and 223±4 K using a flow tube reaction.

Bowmaker and Boyd [89BOW/BOY] performed a SCF-MS-Xa study of the bonding and nuclear quadrupole coupling in oxygen compounds with the halogens. Calculations were performed using structural information from [69POW/JOH].

The v= 1-0 band of BrO in the X 2n312 spin state was measured by Orlando et al. [910RLIBUR] using high

resolution Fourier transform absorption spectroscopy. The values obtained were vo=723.4l4 e9BrO) and vo =72l.927 (8I BrO)' One hundred and thirty transitions were assigned and analvzed to determine the band origins and rotational constant; of 79BrO and 8IBrO. The BrO line positions were fit using the same expression as [84BUT/KA W]. The fits also included the micfO\vavc data of [81 COHIPICl This fit

involved the band origin rotational constant and centrifugal distortion constant. UV measurements recorded an A2nX 2n transition' of BrO in the region 285-355 nm (28169-35088 em-I). Rotational c~nstants. 8 0 =0.42778706

C9BrO) and 8 0 =0.42601176 (81BrO) were also obtained. The molecular constants are in good agreement with those reported by [84BUT/KAU].

The photoionization spectrum of 79BrO was measured by Monks et al. [93MON/STI] over the wavelength range A = 1 U~-122 nm (~196 7 -92593 cm -I) using a dischargeflow photoionization mass spectrometry. The structure shown by the equivalent 81 BrO spectrum was indistinguishable. This is the first determination of the ionization energy for BrO(X2nD to be obtained via direct photoionization threshold measurement, although it had been attempted by Dunlavey et al. [78DUNIDYK] earlier. A vertical excitation energy for the X --* A transition was calculated (using MC-SCF method) to be 30539 em -1 which compares favorably with an experimental adiabatic excitation energy 27926 em -I. This study also provides calculated values for three other excited electronic states. The authors quoted the three excited states of [85DUIIHUD]. An re= 1.824 A value was also proposed.

EPR Information There are numerous EPR studies involving BrO. These

studies can provide information as to the rotational constant (to yield an ro value) and the electronic spin orbit splitting constant (A), and are summarized in Table 5.1.2. In many of these studies this information has not been provided.

Carrington and co-workers have studied the EPR spectrum of BrO in the gas phase. In all cases there were difficulties in preparing the sample and observing the full spectrum due to the intensity of O2 lines in the same region.

66CARILEV - A preliminary EPR study in which techniques for measurements were given for BrO. Eighteen lines of the 24 expected were detected, the remaining being obscured by the intense spectrum of O2. The authors were confident that the spectrum arises from BrO (2n 312) in its lowest rotational level. The data were consistent with Durie and Ramsay's (1958) calculations for the rotational

constant 8 0 =0.45 (79BrO); =0.47 (8I BrO). 67CAR - A review article of EPR and other forms of micro

wave spectroscopy in which the BrO spectra was mentioned but no data was given.



67CARILEV - Attempted to study the EPR gas phase spectra of BrO. The relatively weak BrO lines were often obscured by the many intense O2 lines which occur in the same field region.

67CARlLEV2 - The effects of an electric field on the electron resonance spectra in the gas-phase were used to measure the dipole moment of BrO in its electronic ground state.

67CARILEV3 - Examined the EPR spectrum of BrO and detected ,double quantum transitions.

67CARlLEV4 - A gas phase EPR cavity was developed which allows the application of a parallel Stark field. The spectra of BrO were observed clearly in the presence of O2 ,

69CAR - High-resolution spectroscopic studies of the rotational levels of BrO. The author reviewed his previous studies involving the 2n 312 electronic state of BrO.

70CARfDYE - The gas phase EPR spectra of BrO in its 2IT 312, J = 3/2 levels were described. The analysis con

firmed that the radical has a 2 rr 3/2 ground electronic state (8612.200 MHz). Values of the fine-structure splitting A = - 815 ± 120 cm -I and rotational constant B 0 = 0.4282 ±0.0005 cm- I e9BrO); =0.4264±0.0005 cm- I (8IBrO) were obtained. The determination of A as negative showed conclusively that the ground state was 2rr 3/2 (an inverted doublet). The authors favor their values over those obtained by 58DURlRAM, leading to a calculation of "0= 1.720 A. Byfleet et al. [7lBYF/CAR] measured the dipole moment

of BrO using Stark splitting of the molecule's gas phase electron resonance spectra.

Miller [71MIL] reanalyzed the data from electron resonance experiments for BrO and 10. Although he stated that the splitting of the ground state was anomolously low for 10 and questioned the treatment for BrO. he did not give a new value for the splitting of the ground state for BrO. Miller quoted the earlier results tabulated by [70CARfDYE] for the spin-orbit coupling constant (A = - 815 cm -I).

Adl [72ADL] examined the EPR spectrum of gaseous BrO. He identified as the ground state a 2rr electronic state for the radical \vhere J=312. [72ADL] compares and contrasts ground and first excited rotational states of BrO, assigning the radical a spectra of 8775.5 MHz for both the Qround state (J=312) and the excited state (J=512l. The molecular parameters presented by [70CARIDYE] were used to calculate the "pectra for the .1=112 and .1=':>12 levels of BrO_ No new parameters were presented by Ad!.

The EPR spectrum of the gaseous BrO J=5/2 rotational lewis of 2n ground state \vas observed by Brown et al. [72BRO/BYF]. A comparison with the results of J=312 levels lead to values for corrections. Spectra were recorded at 9720.26 YIHz at J=512 levels using Stark modulation. This value. -980 cm -I. is preferred to that of [70CARIDYE] because of the more extensive data in the higher order data treatment method used by [72BRO/BYF] in comparison with that used by [70CAR/DYE].

Although secondary references imply that the article by

J. Phys. Chem. Ref. Data. Vol. 25, No.4, 1996

[75DALILIN] deals with BrO, in fact it examines the EPR of Br02' Br04, and Br06 and is strictly a theoretical study.

Byberg [86BYB] studied the EPR of [XO, O2], X=Br, CI, formed from the decomposition of CI03 - and Br03 - in solid KCI04 : KBr03' The main features of the spin Hamiltonian [BrO, O2] correspond to BrO err) in a crystal field, coupled through an isotropic exchange interaction to O2 (3I ~) to form a spin-doublet ground state. Hamiltonian values were given as experimental and calculated values at 26 K. Molecular hyperfine parameters in MHz for 79BrO in the gas phase were also given.

In a subsequent study by Byberg [86BYB2]. the preparation of BrO in the crystal state was examined. The EPR and x-irradiation of solid KBr03 is shown to produce complex defects of the composition [BrO, 02]. The EPR spectra of

KBr03(cr) recorded at 26 K after x-irradiation contained signals from at least six defects in spin-doublet and ground state. But the thermal formation of [BrO, O2] in the photolyzed KBr03(cr) indicated that BrOt produced [BrO, O2] by reaction with a photoinduced precursor R, BrOj + R -+[BrO, 02]. (See Table 5.1.2.)

The cunclusiuns tu be drawn from Ihe EPR smdies are Ihar the ground state is 2rr 3/2 (inverted doublet). For comparison, the laser magnetic resonance study of [8IMCK] yielded rotational and spin orbit coupling constants. These values are included in Table 5.1.2.

Dissociation Energy Studies There are two experimental spectroscopic studies which

yield dissociation energy values: [47COL/GA Y, 58DURI RAM]. It is important to note that the excited state dissociates to Brep3/2 ) +0(,D2).

1. A linear Birge-Sponer extrapolation of the Coleman and Gaydon (1947) data gave 17800 cm- l (2.21 eV or 50.9 kcal) for the dissociation energy of the ground state. Assuming that this extrapolation is high by perhaps as much as 20% [53GAY], Coleman and Gaydon recommended 14240 cm- I (1.75±0.3 eV or 40.7 kcal).

2. As stated by Durie and Ramsay .[58DURlRAM], the

absorption spectrum of BrO was not observed to the dissociation energy limit. The limit was determined by extrapolating an equation representing the band heads and by a graphical Birge-Sponer technique. The limit was determined to be approximately 35200 em -I. Subtracting the ID2- 3P2 excitation energy of the oxygen arom (15867.862 cm-'), the dissociarion energy is calculated to be 19332±200 cm- I (2.40±0.02 eV or 55.3 kcaIlmol). Durie and Ramsay reported the dissociation energy to be 19330 cm -I whereas the actual calculation yields 19332 cm -I.

Table 5.1.3 lists all studies which mention the dissociation energy of BrO. There are numerous articles which refer to dissociation studies, some of which simply extract earlier reported values or calculate them anew, and others which reassess data from the two experimental spectroscopic studies listed above.


TABLE 5.1.3. Dissociation energy of BrO (DoO).

Source

Experimental 47COLIGAY 58DURIRAM

Calculation 77GLl

881GE/STO

Comparisons 77VOGIDRE 78DUNIDYK

81 BOH/SEN 84SAlJITAT 88TYK 92GILIPOL

Re-assignments 50BRE/BRO 50HER 53BRE 53GAY

54COT

58BRE 63SCH 65GLU/MEO 66VED/GUR

68GAY

68WAGIEVA 70DAR

70Hl'B/HER

:-::2\\'.-\G/I::V'\ ~9CiCR/VEY

94Rl'SIBER

eV

1.32

2.2

1.8:±:0.5

2.2 1..8:±:0.5

1.8:±:0.5

2.40:±: 0.02

:2.39::::0.01

kcallmol

40.7 55.3

50.9

42

5J

55.3:±:0.6 55.3:±: 0.6

55.2

55.3:±: 0.6 55.2

55.3:±:0.6 55.27

55.3:±: 0.1

55.3=0.6 55.28=0.6

55.3=0.6

kllmol

170 231

213

127

212

176:±:48

212 176:±:48

213 176:±:48 231:±: 3 231 :±:3

231

231 :±:3 231

231=3 231

231:±: I ::1:<0.6:::: I.n

231:!: .3 23\J:±: 3

231 =3

Clyne and CO-\v'orkers [77CL YfW AT. 77CL Y/CUR] tabulated enthalpy of reaction for reactions involving BrO. The enthalpy of formation in these calculutions was not specifi

cally gi\en but was said to have been taken from the best <)\'ailabk information at the time (1976).

\Ve adopt the interpretation of [79HUB/HER] for the disc-;uciarion energy uf BrO. (See Table: 5.1.3. )

See discussion See discussion

Comments

Used experimental !1Hr values to calculate mean bond dissociation energies; the calculated DI value was derived from a t1Hr value of [S3BRE] but this latter value was not reported SCF/CI calculations of the fourth row main group oxides (for the oxides K through Br the De values are consistently underestimated except for KO); dissociation energy value compared with a 2.45 cV value presumably from [79HUB/HER) (This is not what appears in these authors' book); bond length re= 1.741 A and vibrational frequency w c =726= 10 cm -I were also calculated

Used value extracted from [68GA Y] Photoelectron spectroscopy study of ionization potential: quotes dissociation value of [S8DURIRAM] Mentioned dissociation energy but did not give a value Adopted value recommended by [79HUB/HER] Reported values extracted from existent sources: no new data Photoelectron spectroscopic study: no new values given

No direct values are given Also refers to US eV as derived from f.47COLIGA YJ No value given but reference made to an earlier study [SOBRO/BRE] Linear Birge-Spone extrapolation (L.B.x.) (v. 0-7) 2.2 e V. but signs of negative curvature: analogy with CIO and 10 favors high value; [47COLIGAY] Values extracted from [50HER] and [53GA YJ respectively: spectroscopic evidence is uncertain; Gaydon's upper limit. which agrees with [50HER] LBSX value, is more in accord \vith Dc.(CIO), but even this seems low Value reported by Brewer with no explanation as to its origin Value extracted from [53GAY] Values hased primarily on the study of [58DUR/RAM] Extrapolation of A 2n levels: assumed dissociation I imi l goes to

BreP3/:)+O('D); interpretation taken from Gurvich's carly review (I <)62)

L.B-S.Xcn 2.7. eV. Good .G.B.-S.A 2ft assuming limit is to O(,D). 2.402:0.02. [58DURIRAM] Results hased solely on the work of [58DCRIRAM] Spectroscopy. adopted !:38DUR/RAMJ value: Extrapolation of Acn [66VEDlGUR]: Extracted from[65W AG/EV A]; Recommended by [70DAR] Tuken from nellr convergence of the i1b~Orplion b'lI1d~ A - X I .

assumes dissociation of A into Br(2Pld -or '02)

Results based solely on the work of [580UR/RAM] Based on short extrapolation of the levels in the A:n; state: authors tnenli()ll rhree kint'lir ~1lJ(lif''' whi"h If'ilel III I,',,, :1('('llnltt' \':1111<"<;

Value given at () K: source of \'aluc unknown

5.2. Br02 (OBrO)

All references dealing with RrO~ are listed in the follow

ing eight categories. This listing is somewhat arbitrary but is intended to give the reader a purview of the reported data. Of prime interest for this article are the spectroscopic and bond dissociation energy ~tl\dies.



1. Formation/preparation/decomposition [37SCH/SCH], [3SSCHlWIE], [39SCHlJAB], [39SCHlWIE],. [40MUN/SPI], [59SCHlJOE], [62GUEIPAN], [71SHErrUR], [74S0L/KEI], [SOJAFIMAI], [S3BUTIMOR], [90LEV/OGD]

2. Formation in crystal matrix or solution -[62BOY/GRA], [6SBUXlDAI], [69AMIICZA], [69BARlGIL], [70AMIffRE], [710SL], [91SZAI WOJ]

3. Br02 a$ an intermediate -[S5BEN/KRI], [S5STE], [S6BEN/KRI, [90SASIHUI]

4. Reaction -[53PFL], [55PFL], [72FIEIKOR], [76HERlSCH], [7SFOE/SCH], [SOFOEILAM], [SOFOEILAM2], [S2FOEILAM], [S2FOEILAM2], [S2FIE/RAG], [83FIEIRAG], [S3FOEILAM], [S5FOEILAM], [S6HUIINET], [SSNETIHUI], [89FOEINOS], [91SZAlWOJ], [94HJEIROS]

5. Enthalpy of formation/bond di~~ociatioIl eIlelgy -

[51PFLlSCH], [54COT], [66VED/GUR], [68WAGI EVA], [S2WAGIEVA], [S9STA], [95HUIILAS]

6. Spectroscopy/structure -[73BYB/SPA], [73PASIPOT], [76PAS/PAV], [78TEVIW AL], [83BUTIMOR], [S9BOWIBOY], [94RAT/JON] , [95MAIIBOT], [95MUEIMIL]

7. EPR-[66CHAlBOY], [70COL/COS], [71BYB], [72RAOI SYM], [75BYBILIN], [75DALILIN], [77SASIRAO], [79CARISAH]

8. Review -[60GEO], [63SCHIBRA], [72BRI], [S4BURlLAW], [S4JAC], [90JAC], [94JAC]

Br02 was first mentioned in the literature in 1937 [37SCHI SCH]. Schwarz et al. [37SCHlSCH], [3SSCHIWIE], [39SCH/JAB], [39SCHIWIE] discussed the preparation of Br02'

Schwarz and Schmeisser [37SCH/SCH] studied the reaction of bromine with ozone which produced Br02 as a light yellow solid. This compound did not melt but decomposed spontaneously to the elements at approximately O°c.

Schwarz and Wiele [3SSCHIWIE] studied the thermal decomposition of Br02' In addition to the formation of the elements. the authors also detected a white oxide which they presumed was Br207 or Br206 and a dark-brown oxide. 8r20. Schwarz and Wiele [39SCHIWIE] continued their <;;tlld y· of thf' thE'rmal dE'composition of BrO:! Their study

shO\\'ed that Br02 is completely stable at -40°C, but that decomposition can be detected manometrically as the temperature is increased. Br20 is stable at -40°C. Again 8r:::07 was suggested as one of the decomposition products of BrO,.

\lungen and Spinks [40i\1UN/SPI]. in examining the decomposition of ozone in the presence of bromine, detected the formation of a number of bromine oxides. including Br02'

The remaining studies of the formation of Br02 are based on \·ariations of these abO\·e-mentioned procedures. Solomon


and Keith [74S0L/KEI] made several ~ttempts to prepare Br02, including the glow-discharge method of [37SCHI SCH]. The techniques used produced bromine oxides of variable composition including Br02, Br03 and Br02.71 (very close to Br308)' Much of this work was reviewed by [63SCHlBRA] and [72BRI], as well as in the Gmelin series mentioned in the Introduction.

There are numerous EPR studies. None of these studies provide any information as to the structure of Br02 .

Chase and Boyd [66CHAlBOY]: radiolysis of crystalline alkaline earth bromates by cobalt-60 y-ray, suggested that Br02 was produced and stabilized in the crystal lattice.

Collins et al. [70COL/COS]: irradiated zinc bromate, experimental evidence suggested the formation of a paramagnetic center In the crystal which was attributed to

Br02'

Byberg [71BYBJ: x-ray irradiated KBr04 crystals at 10 or 26 K, spectra interpreted to indicate the existence of Br04 which then, thermally dissociated to Br02'

Rao and Symons [72RAO/SYM]: x-ray irradiated crystalline bromate5, EPR 5peclra of Br02 ill pilll uil~eu UIl ~eeing the effects of two isotopes 79Br and 81Br, both having 1=3/2, proposed a formation route for Br02, results stated to differ from the Collins et al. [70COL/COS] data.

Byberg and Linderberg [75BYBILIN]: x-ray irradiated perbromate crystals, suggested the formation of a weakly bound complex of the composition (Br02- O2), no evidence that Br02 existed as a separate entity.

Dalgard and Linderberg [75DALILIN]: molecular theory calculational model for the EPR study of quadrupole and hyperfine interaction tensors of Br02, Br04, and Br06; x-ray irradiation of KBr04 led to the formation of the (Br02 . O2) complex.

Sastry and Rao [77SASIRAO]: EPR identification of the formation of Br02 in a y-irradiated cadmium bromate dihydrate.

Carlier et al. [79CARIISAH]: EPR of Br02' spectrum was similar to that observed by [72RAO/SYM].

There are a number of spectroscopic studies which provide vibrational frequencies and sIrucrural information. These are summarized in Table 6.

Byberg et al. [73BYB/SPA], stated that in 1973, no structural information was availahle for Br02. Modified extended Huckel theory was used to calculate nuclear quadrupole coupling constants. Comparing calculated values with observed values helped confirm the geometry of Br02: C 2L, symmetry with a bond length of 1.625 A and a bond angle of 117.6°. This geometry was that of CI02 with an adjustment for the presumed differences in BrO and CIO. The nuclear quadrupole coupling constants are not as sensitive to the bond angle as they are to the bond distances. The authors stated that any reasonable changes will not improve interpretation.

Pascal et al. [73PASIPOT, 76PASIPAV] indicated that Br02 exists as Br20-i with a Br-Br bond. The authors ob-


Table 6. Polyatomic bromine oxide species: Structure and vibrational frequencies.

Bond Distance rCA)

Source Structure Br-O 0-0 Br-Br

Br02 (OBrO) 73BYB/SPA C 2v ' 117.6° 1.625

73PASIPOT

78TEVIWAL '*1l0:±:2°

83BUTIMOR C2l" 118°

84JAC, 90JAC 94JAC

2.9

89BOW /BOY C tV' 117.6° 1.625

95MAVBOT Czv

95MUEIMIL C 2v , 114.4° 1.649

BrOO

70CLY/CRU

78TEV/SMA

79MICIPAY

83BUTIMOR

84JAC. 90JAC

95MAVBOT

56VEN/SUN

63VEN/RAJ

6.+RAO/SYM

Cs ,120° 2

Cs

C ol,,89° 1.68

1.5

Vibrational Frequencies

081BrO

791-797 079BrO

794-799

1487

872

1487

Brl602 1'+75.5-1484.0

Brl60180

1.+30-1432.1

VI V2

442 800

.+42 800

.+39 806

100

V3

35 0

35 0 35

0

852

852

comments

Modified extended Huckel theory used to calculate nuclear quadrupole coupling constants; calculated values for structure

Raman spectra in crysralline form indicated that Br02 exists as Br20~ with a Br-Br bond

Infrared spectra of the isolated radical in an Ar matrix; *apex angle

determined on identification of v3 asymmetric stretch; 180 isotopic enrichment experiments used to identify molecules

Mass spectrometry; discharge-flow system; reaction of 0+ Bf2 ; assumed structure (in analogy with OCIO) and calculated rotational consrants

Review recommended V3 value from Ar matrix study of 78TEV/ WAL

SCF multiple scattering X-a calculations of the bonding and nuclear quadrupole coupling in Br02; adopted geometry of [73BYB/SPA]

o 81BrO IR absorption; matrix isolation at 12 K

842-844 079BrO

845-847

V~

828

828 815

Microwave study, preliminary analysis also supportive of V2

approximately equal to 300 cm- I

Electronic absorption spectrophotometry in a discharge-flow system of BrO; formation of BrOO in BrO+BrO-kr -+Br+BrOO-)Br+02 disproportionation reaction

Infrared spectra of the isolated radical in an argon matrix

BEBO calculations, stated to be indeterminate for the bending frequency; value suggested for Vz is consistent with the authors' kinetic data in the region 200-360 K

Mass spectrometry\discharge-fiow system; assumed structure (in analogy with Br-O-O-Br structure suggested by 70CLY/CRU) and calculated rotational constants

Review recommended VI value from Ar matrix study of 78TEV/ SMA

IR absorption; matrix isolation at 12 K; the vibrational frequency assigned to Brl60lS0 is in fact a mixture of Brl60180 and Br\80160

References observed Raman frequencies, however it appears adopted frequencies are approximations derived from the ion: bond distance calculated by Badger's rule; calculation of force constants

Urey-Bradley potential force field; although the authors refer to observed vibrational frequencies there is no specific reference to these observations; observed and calculated frequencies given

respectively: calculation of force constants

Vibrational mean square amplitude theory; two totally symmetric AI and identifies six vibrations, modes; no data provided: two doubly degenerate E mean square amplitudes calculated


1082

Table 6. (Continued.)

Source

70BEG/SUB

72RAO

74BYB/KIR

77LEE/BEN

78THIIMOH

85BYB

86UMAIRAM

BrOBr

54ANT/DOJ

68CAMIJON

72BRI

77PASIPAV

78PAS

78TEVIWAL

8-1-BOLIBAL

84CPIILAR

8-1-JAC. 90JAC. 9-1-JAC 87ALLIPOL

90LEY/OGD

Bond Distance rCA)

Structure Br-O 0-0 Br-Br

* Cs

1.66

1.79

1.57

105S 1.56 1.72 1.64

Linear

*IIV or 8r

C~l' Ill::::::''' 1.85 3.07


MALCOLM W. CHASE


800 442 82

504 197

504 197

504 197

506

526.1

250 245

526.1

526.1

508

Comments

ESR; formation of Br03 from y-radiolysis of potassium bromate at 77 K; structure identified; magnetic parameters given

Centrifugal distortion constants; classifies the six vibrations as two totally symmetric AI and two doubly degenerate E modes but no values were given

*ESR crystal study of paramagnetic defects in x-in'adiated KBr03 suggests that the species is Br03 rather than Br03; KN03 : KBr03 exhibits the Br03 species with a cylindrical spin Hamiltonian analogous to that of CI03 ; calculated bond distance based on CI03

EXAFS spectra: prediction of bond length

350 Group theoretical method; vibrational frequencies calculated for VI and V2 are reversed, the same is true for V3 and v -I: force constants are calculated

581

583

590

592

504

800

623,4

623,4

595

Values proposed earlier by 74BYB/KIR to account for the spin

Hamiltonian of Br03 in KN03 : KBr03 ;

ESR spectra in KCI04 : KBr03; author proposes a new asymmetric

structure for Br03 with bond distances for (Br-O~), (Br-02) and (Br-03), respectively

ESR y-irradiation of crystal KBr03 and Sr(Br03h·Hp; MO calculations using the CNDO/2 method; NQR experimental values

UV absorplion spectra of Br20 in CC14 ; strong absorprion band ar 2800 A (35714 em-I)

IR spectra of the crystal Br20 and 180-enriched Br20;spectra most satisfactorily explained in terms of C 2v symmetry; comparisons with F20 and Cl20 were used in explaining data; force constants were calculated

Review based crystal study by 68CAMIJON; calculation of force conSlams

Raman analysis' (species observed in a matrix at 50°C) corroborates

previous IR studies; assumed the formation of Br20 from decomposition of Br20J

IR spectra of the crystal Br20

IR spectra of the isolated radical in an argon matrix; states that the

values assigned by 68CAM/JON for VI and V3 are reversed and questioned the V3 reasonableness of the bond angle: 180 isotopic enrichment experiments used

Extended x-ray absorption spectra of thermally excited vibrations; frequencies were used to calculate force constants; no preferred structure was recommended; estimates of the vibrational frequencies

as a furction of bond angles

MOVD theory: no data provided

Re\'iew recommended j)1 and P, values from Ar matrix studies by 78TEV/WAL and 87ALLIPOL

IR spectra of matrix isolated radical: *bond angle depend on relative

assignment of VI and fl.,

IR and CY -YIS spectroscopy and bromine k-edge EXAFS of the solid radical: consislem Wilh the resulLs of 68CAMIJON allli 78PAS



Source

92NOV

95LEE

95MUE/COH

BrBrO

73DIXfPAR

73PARIHER

78TEVIWAL

80VELIDUR

82FERISMI

84JAC. 9OJAC. 94JAC 87LOE/AND

9SLEE

68EDW/GRE

70CLY/CRU

78TEVIWAL

8.f.EPIILAR

Br20.,

7.f.PAS/PAV

76PAS/PAV

77PAS/PAV

87ALLJPOL

Structure

e 2L·,

1IS.69°

e 2L" 112.9°

elL' '

112.24°

150°

3A"

c,

Bond Distance rCA)

Br-O 0-0 Br-Bf

1.80902

1.865

1.8429

1.690 2.5\0

Br-O 0-0 Br-O

1.64 1.5 2.0


VI V2

512 180

180

804 <200

804

793 215

V3

613

236

236

153

Comments

Ab initio calculations and an extended basis set; comparable with the results of 90LEV/OGD

Ab initio calculations-CCSD(T)

Microwave spectra for three isotopomers

Reaction complex O-Br-Br; plausible triplet ground state at a= 180°, however, an improved approximation might change a to 150°

Cross-beam experiments involving collision ·of 0 atoms with Br molecules; predicts an O-Br-Br nonlinear complex with a triplet ground state

Infrared spectra of the Ar-Brr03 matrix isolated radical: the Br-Br bending mode are based on comparison with the Cl-Cl stretch and CICIO bending mode of CICIO

Cross-beam scattering; stated reactive results are consistent with the long-lived triplet of the OBrBr complex as suggested by 78TEV/ WAL and 73PARIHER

Reactive scattering of 0 atoms with Br2; proposed existence of a shortlived OBrBr collision complex with a bent configuration and with a modest Eo of approximately 110 kJ/mol; supports the conclusion of 73P ARIHER

Review recommended VI and V3 from Ar matrix study by 78TEV/ WAL Frontier orbital theory and Lewis electronic structure theory: proposed existence of a long-lived intermediate of a cyclic BrBrO structure

Ab initio calculations-CCSD(T)

Rate law stoichiometry; classified as BrBr02

Electronic absorption spectrophotometry in a discharge-flow system of BrO', tran~ition-\;tat" theory: a symmetrical planar bent chain

triplet species with a structure (BrOOBr) was assumed; estimated in comparison with .cZlOOCI

IR argon matrix spectroscopy; photolysis; weak bands appeared at 831.7, 830.2. and 760.3 cm -I; identified the most likely structure of Br202 as an open chain when the Br-Br bond remains intact (OBrBrO), and a (ErOBrO) structure formed by the insertion of an oxygen atom into the weakened Br-Br bond

MOVB theory: reference to this species in table but no data provided

Prepared from the thermal decomposition of Br20 I: Raman absorption and IR spectra; the vibrational spectrum of Br203 shows the presence of a BrOBr bond but it was not possible to distinguish between the two forms (OBrOBrO and BrOBr02l

Raman specrra: suggesred a (05r08rO) sIrucmre for 8r203: some vibrational frequencies have been assigned to specific vibrational modes

Raman spectra; sug.2:ested a svmmetric structure (OBrOBrO); some frequencies have been assigned to specific vibrational modes

973.1-1029.6 IR spectra of a crystalline Br20, in argon matrix: not able to determine which structure (BrOBr02 or OBrOBrO) existed; the ~)TlIllIctrical structure wa~ adopted based on compari~on of Raman

spectra of Br203 and Br20.j




Bond Distance rCA) Vibrational Frequencies

Source Structure Br-O 0-0 Br-O Comments

93STI Proposed anionic structure of Br+Br03 for Br203

BrZ04 73PASIPOT C 2t' or C z 861-882 205 910-919 Raman spectra at -180°C;

(02BrBr02)

74PASIPAV. (02BrBr02) 76PASIPAV (OzBrOBrO)

77PASIP A V C 2v or C 2

(OzBrOBrO)

92GILILEV (BrBr04)

Br205 77PASIPAV

served the Raman spectra of the crystalline bromine dioxide at - 180°C in a sealed tube in vacuo. There is no structural or vibrational information provided directly for Br02(g), although tentative assignments had been made for the crystalline dimer.

Tevault et al. [78TEV/w AL] studied the reaction of atomic and molecular bromine with atomic and molecular oxygen in argon matrices (photolysis of bromine and ozone containing matrices). Several bromine oxygen compounds were stated to have been formed and identified by infrared spectroscopy - BrO, OBrO, BrBrO, BrOBr, and (BrOh. The apex angle of Br02 was calculated to be 110± 2° based on three facts:

1. The proper identification of the symmetric stretching frequency V3 to be 852 cm -1,

2. Observed frequency shifts with the use of 180 3 , and 3. Splitting due to the naturally occurring bromine iso

topes (79Br and 8IBr).

Bowmaker and tloyd [~~tlUW/tlUY] assumed the BrU2

geometry as suggested by [73BYB/SPA] in performing an SCF-Xa study of the bonding and nuclear quadrupole coupling in BrOz . Butkovskaya et ai. [83BUTIMOR], in their kinetic studies, proposed a C2v structure with a bond angle of I 18° and a bond distance of 2.9 A by analogy with OCIO. This series was detected by modulated beam mass spectrometry. Magnetic and electric field beam focusing revealed that OBrO is a paramagnetic molecule with a C2v symmetry.

Jacox [84JACl [90JAC], [94JAC], in her reviews, recommended a v3=852 cm- 1 asymmetric stretch value, based on the work of [78TEV!W ALl

Rattigan et al. [94RAT/JON] observed a visible absorption spectrum arising from OBrO in the bromine sensitized decomposition of ozone. The authors provided spectral evi-


Br204 is classified as having a dimeric structure (02Br-Br02) with a Br-Br bond Raman spectra; suggested structure to be (02BrBr02) Raman spectra; suggested structure of the two isomers of Br204 to be (02BrBr02) and (02BrOBrO); some vibrational frequencies have been assigned to specific vibrational modes of the two symmetric and asymmetric isomers

Raman spectra; suggested structures (02BrBr02) and (02BrOBrO) for thc two isomcrs of Bl20 4 , :'IOlUC [lc4ucudt:s havt: bt:t:Il assignt:ll

to specific modes of the symmetric and asymmetric isomers

Spectroscopic and EXAFS data on solid compound; interatomic distance given

Based on the Raman spectra and structure of Br203 and BrZ04' an 120 5 analogous polymer structure is proposed for BrZ05

dence for the A 2 A2f- x2B 1 electronic transition. They reported vO,o,o= 16178 cm- 1 and approximate vibrational frequencies for the excited state (VI =600 cm -1 and v2=200 cm- I ).

Preliminary results of a microwave study of OBrO(g) by Mueller et al. [95MUEIMIL] suggested a bent structure, r(Br-O)= l.649 A and «OBrO)= 114.4°. They also observed the V2 and 2V2 states, but the relative intensities were not measured. Results are consistent with a V2 value of approximately 300 cm -1.

Maier and Bothur [95MAIIBOT] studied the flash photolysis of a gas mixture containing bromine, oxygen and argon. Br02 was f9rmed by rhe matrix irradiation of BrOO. The IR absorptio~ of two isomers (081 BrO and 0 79BrO) was observed at three different concentration ratios of Br21 02/Ar and values for VI ~nd V3 were assigned.

Pfiugmacher et al. [51PFL/SCH] experimentally measured the enthalpy of formation of Br02 (cr). The value reported wa~ -12.5-'-.0.7 kL:ul whidl, ill fUL:l, rdt:rs lu lht: ut:L:umpu

sition heat. The formation reaction is the reverse of what was measured. Wagman et al. [68WAGIEVA], [82WAGIEVA], in their reviews. assumed that the measured value referred to the energy of the reaction (not the enthalpy) and corrected the value for a ~(pv) term, adjusted the value from -45°C to 25°C, thus resulting in a value of 11.6 kcallmol for the enthalpy of formation of Br02(cr). Glushko and Medvedev (1965) adopted 12.5 kcallmol as the enthalpy of formation.

Cottrell [54COT] reported D(O-BrO) ~ 70± 10 kcal/mol. (This converts to ~fH=87.3 kJ/mol.) This value was based on the enthalpy of formation of Br02(cr) reported by [51PFL/SCH] and Do(BrO)=2.25 eV or 50 kcallmol. Cottrell expressed doubt as to the validity of this value based on comparison with CI02 . The enthalpy of dissociation re-


ported by [66VED/GUR] is ilH(298) ;?! 70 kcallmol for the reaction Br02-+ BrO+O. This is an estimated value based on the work by Cottrell (1954). In contrast Huie [95HUIILAS] has estimated the ethalpy of formation of OBrO(g) in the following manner. According to Stanbury [89STAN], the enthalpy of formation of OBrO in the gas phase can be estimated from the value of il GO = 144 kJ mol- 1 in the aqueous phase by comparison with the gas and aqueous phase values for OCIO~ Taking il GO = 120.5 kJ mol- 1 for OCIO(g) and aGo= 117.6 kJ mol- 1 for OCIO(aq) [Wagman, 1968] and assuming the same ratio applies for OBrO, we obtain ilGo= 148.0 kJ mol- I for OBrO(g) and ilfHo= 130 kJ mol-I.

5.3. Br02 (BrOO)

All references dealing with BrOO are listed in the following four categories. This listing is somewhat arbitrary but is intended to give the reader a purview of the data. The structure and vibrational frequencies of this molecule are summarized in Table 6.

I. Formation as an intermediate in kinetic schemes -[69IPIBUR], [70BLAlBRO], [70CL Y/CRU], [77CLY/CUR], [8OJAFIMAI], [81SANIW AT], [83BUTIMOR], [86SAN], [88TOOIBRU], [93MAUI WAH]

2. Reviews -[77CL Y/CUR] , [84BURILA W], [84JAC], [90JAC], [94JAC]

3. Spectroscopy/structure -[70CLY/CRUl, f78TEV/SMA 1, r79MICIPAY1, [83BUTIMOR], [95MAIIBOT]

4. Enthalpy of formationl dissociation energy -[69IP/BUR], [70BLAlBRO], [70CL Y/CRU], [81SANIWAT], [83BUTIMOR], [88TOOIBRU],

[95HUIILAS]

Butkovskaya et al. [83BUTIMOR], in their kinetic studies, proposed a C s structure with a bond angle Br-O--O"- 1200

and bond distances of r(Br-0)=2 A and r(O-O)= 1.5 A. [83BUTIMOR] referred to the [70CL Y/CRU] study to aid in estimating a structure for BrOO.

Michael and Payne [79MIC/PA Y] discussed a calculational approach (BEBO) in which they detemlined VI =872 em -I. Although this method was stated to be indeterminate for the bending frequency. the a.uthors did suggest that a

value of V2 = 100 cm - I was consistent with their kinetic data in the region of 200-360 K.

Jacox [84JAC]. [90JAC], [94JAC] reviewed the spectroscopic properties of BrOO: the sole reference being the spectroscopic work by Tevault and Smardzewski [78TEV/SMA] on the infrared spectrum of the Ar matrix isolated radical. Tbe 1IIea~U1elllelll PIU\ ideu all 0-0 ~tlctchillg ftequcncy of

1487 cm -I. There are no gas phase studies which characterize this molecule.

Maier and Bothur f95MAIIBOTl studied the flash photolysis of a gas mixture containing bromine, oxygen and ar-

gon. BrOO was produced by this process. The IR absorption of three isomers (Br160 ISO, BrlSO 160, and Br1602) was observed and values for V I were assigned.

A number of authors have cited an enthalpy of formation [81SANIWAT],[88TOOIBRU] or a bond dissociation energy [70CLY/CRU], [83BUTIMOR], [95HUIILAS] for BrOO. However, all of these studies are based on the work by Blake et al. [70BLAlBRO].

Ip and Bums [69IPIBUR] determined the recombination rate constants of bromine atoms in the presence of six different third bodies (helium, neon, argon, krypton, oxygen and nitrogen) over the temperature range of 300 and 1273 K. The authors refer to two earlier studies: Rabinowitch and Wood [36RABIWOO] and Strong et al. [57STRlCHI]. Based on these data, Blake et ai. [70BLAlBRO] calculated interaction potentials between atomic bromine, oxygen and an inert third body (such as a rare gas). A value was given for Br-02' BrOO was thought to be unstable with a bond energy (Br-OO) of approximately 1 kcallmol which translated to an enthalpy of formation of 108 kJ/mol.

5.4. Br03

The articles pertaining to Br03 may be classified as follows.

1. Formation/preparation -[28LEW/SCH], [29LEW/SCH], [29LEW/SCH2], [30LEW/SCH], [38CSHlWIE], [39SCHlWIE], [40MUN/SPI], [53PFL], [55PFL], [55PFL/RAB], [58ARV/AYM], [59ARV/AYM], [59PFL], [59SCH], [60BRI/MAT], [62GUEIPAN], [74S0L/KEI], r82MuKlKHIl

2. Radiolysis -[60MATIDOR], [62BOY/GRA], [70AMIITRE], [70BEG/SUB], [71SERIZAK]

3. Spt::l:lruSl:upY!SllUl:lUH: -

[56VEN/SUNJ, [63VEN/RAJ], [64RAO/SAN]. [72RAO], [77LEEIBEN], [78THIIMOH], [84SASI RAO]' [85BYB], [86UMAlRAM]

4. EPR [70BEG/SUB], [71SERlZAK], [72RAO/SYM], [74BYB/KIR], [85BYB]

5. Review -[34BRAJ, [60GEO], [63SCH/BRA], [80KOL], [84JAC]

6. Enthalpy of formation - [4RFAR/KLEJ

Early work refers to the formation in the condensed phase of the trioxide (or its dimer, the hexoxide).

There is no confirmatory information as to the proper characterization. There are many articles dealing with the formation or reaction of Br03' Pflugmacher et al. [55PFLI RAB] studied the reaction of bromine with excess O2 in a gluw uisduuge al 0 "C. Bt03 wa~ daiweu tu ue the product.

Although the ratio was 1 :3, it is not clear that the product was Br03' The compound formed was claimed to decompose above - 70°C. Also, the method of Lewis and Schumacher [29LEW ISCH], in which the reaction of bromine



with ozone was claimed to produce Br30g, was reproduced here with a larger excess of ozone and yielded Br03 (in the condensed phase). .

Arvia et al. [59ARV/A YM] studied the thermal reaction between bromine and ozone. Under different conditions, they observed Br20S and Br30g. The authors specifically stated that Br03 or Br206 was not observed, contrary to the result of Pftugmacher. Pftugmacher [59PFL] and Schumacher [59SCH] responded to this article and further discussed possible interpretations of the results.

Solomon and Keith [74S0LlKEI] made several attempts to prepare Br02, including the glow-discharge method of [37SCHlSCH]. The techniques used produced bromine oxides of variable composition including Br02, Br03' and Br02.71 (very close to Br30g).

EPR studies often provide information as to the structure of the molecule and the nature of the electronic ground state. In the case of Br03, the EPR studies were consistent with a C3v symmetry but thele wa:s 11U lldi11itive evillellce LO con

firm this. Br03 was produced by the y-radiolysis of KBr03 at 77 K

[70BEG/SUB]. From the EPR measurements of Br03 and an assumed C 3v symmetry, they calculated the bond angle to be 114 0 • The structure was distorted in the crystalline environment. The authors stated that the radical must be distorted from C 3v symmetry presumably because of an asymmetric environment of the potassium ions around the oxygen atoms of Br03' Similar results were reported in 1985 by Byberg [85BYB], in which the author reported that the Br03 radical had C 3 v symmetry but some distortion might occur due to the nature of the host crystal. He discussed a bond angle of 112° and a bond length of 1.57 A. The other studies provide no additional information.

The spectroscopic articles for the gas phase radical involved force field calculations of pyramidal XY3 type molecules [56YEN/SUN, 63YEN/RAJ, 64RAO/SAN, 72RAO, 78THIIMOH]. Contrary to the implications of these five articles, there was no observed structural information nor was there any observed vibrational information. Upon examination of the earlier literature cited by these authors, vibrational frequency information was found for BrO~ in a crystalline environment. Two of the four vibrational frequencies IIlUlched exaclly Wilh those reponed for Br03 . These articles have assumed a pyramidal structure with an O-Br-O angle of 89'J (the same angle was used for the chlorine, bromine. and iodine trioxides): a bond distance Br-O of 1.68 A (from Badger's rule L and vibrational frequencies (in cm -I) of 1'1=442 [AI]. v::=800 [A::]. v3=350 [E], and v-l=828 [El

T\vo additional studies provide insight into the structure of BrO.,. Electric field gradients at the halogen site in X03 and XO~ - radicals (X =CL Br), formed by the y-irradiation of single crystals of NaCIO.<. KCIO-,. KBrO.< and Sr(BrO .. ~)~·H20 have been evaluated by MO calculations using the CNDO/2 method. The symmetry of the XO" radicals \\as aS~llll1ed h) be that of Xo.~ ions \\hich haw C,\ symmetry [86l:\IA/RA\I]. Lee anu Beni [77LEE/BE~]. in their


calculation of atomic phase shifts (as applied to extended x-ray absorption and fine structure in molecules and crystals) predicted a Br-O bond length of 1.66 A in solution. No other information of Br03 was provided.

There is no reported information as to the experimental determination of the enthalpy of formation of this radical. There is a calculated value reported by [48F ARlKLE] of +23 kcallmol. Although the authors, Farkas and Klein, stated that they calculated the enthalpy of formation of Br03 the formula given was BrO; .

5.5. Br04

It is important to note that this oxide has not been isolated. There is no thermodynamic information and no spectro scopic information.

Br04 has been proposed to be formed:

(1) As a weak adduct, RrO.OJ , in thp di"proportionation of BrO [90TURlBIR] .

(2) In the 60Co y-irradiation of an acidic aqueous glass containing perbromate ions [75GIN/SYM]

(3) In the X-irradiatIon.ot .K.Hr04 crystalS [71BYB] (4) As a complex (Br02·02) during the X-irradiation of

KBr04 (calculational model and EPR study) [75DAL/ LIN]

(5) By the X-irradiation of KCI04 single crystals doped with KBr04 [85BJEIBYB]

(6) During the X-irradiation of KBr04 single crystals in which a weakly bound complex (Br02' 202) was formed which decayed to Br04 [75BYBILIN].

5.6. Br20 (BrOBr)

All references dealing with Br20 are listed in the following six categories. Of prime interest are the spectroscopic studies and the ep.thalpy of .formation calculation. The structure and vibrational frequencies of this molecule are summarized in Table 6. Br20 has been experimentally studied in condensed media and in the gas phase.

1. Preparation/decomposition [30ZIN/RIE], [31LEWIFEI], [35BRE/SCH], [36BRE/SCH], [38SCHIWIE], [j9SCHIWIE]. [40MUN/SPI], [6 1 GUE/GOU], [62GUE/PAN]

2. Review -[:14RRA], [AOGFO], [A~SrHfRRAl [72RRT]. [84BURlLAW], [84JAC], [9OJAC], [94JAC]

3. Reaction -[47KLAlBOL], [53KAN], [69JEN/ZIE], [72BUN], [72BUB2], [760DYINEC], [79MIT], [89FLE/SWA], [87SW AlFLE] , [94DNEIELI], [95HEU/HAN]

4. Spectroscopy/structure -(In solution) -[54ANB/DOS] (In crystal) [68CAMIJON], [77PASIPA V], [90LEY/OGD] (In matrix) [90LEY/OGD]

[78TEVIWAL]. [87ALLlPOL].


(In gas) - [73PARlHER], [84BOL/BAL], [84EPII LAR], [92NOV], [9SLEE], [9SMUE/COH], [9S0RLI BUR]

6. Enthalpy of formation -[92NOV], [9SLEE], [9S0RLIBUR], [9STHOIMON]

S. Physical properties (viscosity, thermal conductivity) -[62SVE]

6. Misclassified (should be BrO) -

[ 66CARILEV]

The earliest studies dealing with the preparation of Br20 are based on work by [30ZIN/RIE], [31LEWIFEI], and [3SBRE/SCH].

In a review article. Brady [34BRA] stated that Zintl and Rienacker [30ZINIRIE] obtained small quantities of a volatile OXIde. perhaps Hr20, by two methods; (l) by passing bromine vapor over a specially prepared HgO at SO-60 °C, and (2) by mixing bromine vapor with ozone under reduced pressure at O°c. A subsequent study by Brenschede and Schumacher [3SBRE/SCH] examined the reaction between HgO and bromine in a carbon tetrachloride solution. The method of preparation is given, as well as the self decompositIon and the reactIon WIth carbon tetrachlorIde In lIght [the same reaction occurred in dark in a few days]. The decomposition in light was presumed to be Br20----+Br2+ 11202 and Br20+CCI4----+COCI2+Br::>+CI2' A subsequent study by the same authors [36BRE/SCH] examined the same formation

. reaction. In addition, they studied the extinction curve of Br::p dissolved in CCl4 and the thermal and photochemical decomposItion.

Schwarz and Wiele [38SCHIWIE] studied the thermal decomposition of Br02' In addition to the formation of the elements. the authors also detected a white oxide which they presumed was Br207 or Br206 and a dark-brown oxide, Br:;O. Schwarz and Wiele [39SCHIWIE] continued their study of the thermal decomposition of Br02' Their study showed that BrO:; is completely stable at ~40 °C but that decomposition can be detected manometrically. BrO:; sub-

- limes with extensive decomposition. melting in dry air at approximately -17.5°C Br:;O is stable at 40°C. Again Br207 was suggested as one of the decomposition products

of Br02' Le\\'is and Feitknecht [31 LEW /FE I]. in examining the de

composition of ozone in the presence of bromine. detected the formation of a number of oxides. but not Br20. The specitic oxide formed was not identified. The remaining studie,; dealing with the formation of Br~O are based on

\'ariation~ of these procedures, All studies inyolving the formation. preparation and decomposition of Br:;O are reviewed by [34BRA]. [63SCH/BRA] and [72BRI]. as well as in the Gmelin series discussed in the Introduction.

Anthar and DustrovsKY [5.-J.AI\'T/DOS] measured the ultra\iokt absorption spectra of Br20 in CCl-1.' A strong absorption band wa:'i obscrycd at 2800 A (35714 em ·-1),

Parrish and Herschbach [73PARJHER] observed. in their cross beam experiments. that the reaction of O( -'P) \vith Br2(:~;) yielded BrO(2rli+Br(2p). The authors stated that

thi~ re:lcti()ll occurred . '\'ia a persistent collision complex

with large reaction yield and no activation energy, but the known, stable B[20 molecule does not correlate with the reactants.' ,

The IR spectra of the solid was most satisfactorily explained [68CAM/JON] in terms of a bent triatomic molecule with C2v symmetry and a vI=504 cm- I , v:;=197 em-I, and v3=S87 cm- I

. The assumed bond angle was 113°. Pascal et al. [77PASIPAV] assumed that BrzO was formed

from the decomposition of Br203' The authors observed the symmetric stretch of Br20 to be 504 cm -I, the asymmetric stretch, 590 em -I, and assumed the bend to be 197 cm- I .

The Raman analysis of Br20 corroborated the previous infrared work by Campbell et al. In a later study, Pascal [78PAS] reported vI=S06 cm- I and v3=592 cm- I values.

The results of Tevault et al. [78TEV IW AL] arc in contrast

to those observed by Campbell et af. [68CAM/JON]. It appears that these authors assigned v I a value of 526.1 cm- t

and they implied that the assignments of VI and v3 by [68CAM/JON] are reversed. Using Tevault's value of V3' a minimum value of 87° was calculated for the bond angle.

Bolander and Baldeschwieler [84BOL/BAL] examined the dependence of the extellded x-ray dU:'lOljJlivlI fllle :'lllUclUle,

amplitude, and phase on thermally excited vibrations. The model system the authors studied was Br20. They assumed the symmetric stretch and bend occurred at 250 and 245 em -I in the linear structure, while the asymmetric stretch occurred at 800 cm -I. These assumed frequencies were used

to calculate force constants which were then assumed to be independent of the geometry of the molecule. No experimental data were referred to and no preferred structure was recommended. This article provided estimates of the vibrational frequencies as a function of bond angles.

Epiotis et al. [84EPIILAR]. using a MOVB theory. referred to Br]O in a table but provided no information.

Allen ef al. [87 ALLIPOL] studied the IR spectra of matrix isolated Br20 and assigned v3 to be 623.4 cm J and VI to be 526.1 cm -[. The authors referred to a bond angle of 113 ° or 87° based on the V3 isotopic shift information.

Levason et al. [90LEV/OGD] studied Br:?O (cr) by infrared and UV -VIS spectroscopy and bromine K -edge extended x-ray absorption fine structure (EXFAS). This is the first

definitive structural analysis study for the bromine oxides (Br20~ was definitively analyzed at a later date by others). The authors' results are consistent with the IR spectra of Br20 obtained by Campbell et al. [68CAM/JON). the 180 results which demonstrated that ~;olid Br~O is molecular. and

with experimenrs by Pascal [78PAS] who reported lit =506 em ~ I and /);, = 592 cm ~ J. The data were consistent with

C'2c symmetry and a bond angle (Br-O-Br) of ! 12::1::::2° and

bond distance 1'(81'-0)= 1.85 A. With the aid of ab illitio calculations and an extended

basis set. Novak [92NOV] calculated 3 C:;.\ geometry with r!Dr-O)= 1.80902 A and <l bond angk of 115.69:::. Thi:) caJ

culation yielded a shorter bond distance but a larger bond angle than the v,;ork of [90LEV lOG D J and \vas stated to be due to the exclusion of electron correlation in the calculation.

Jacox [84JAC], [901 ACl [941 ACl in her reviews, reCO\11-

J. Phys, Chern. Ref. Data, Vol. 25, No.4, 1996


mended an al symmetric stretch of 526.1 cm- I (Ar) based on the studies by [78TEV /W AL, 87 ALLIPOL], and a V3 asymmetric stretch of 623.4 cm- I (Ar) based on the work by [90LEV/OGD]. Jacox did not report a value for V2'

Lee [95LEE], using ab initio techniques, calculated the equilibrium structure and harmonic vibrational frequencies of Br20. The results suggested a C 2v symmetry with a bond angle of 112.9° and a bond distance of 1.865 A.

Mueller and Cohen [95MUE/COH], from the microwave spectra of three isotopomers of BrOBr(g), determined ro = 1.8429 A and a bond angle of 112.24°. Their study implied v2=180±5 cm- I

.

. Novak [92NOV] estimated the enthalpy of formation, AfHO(Br20, 0 K)=83± 8 kJ/mol from a sum of bond enthalpies that were deduced from the data of H)O and HOBr. The enthalpy of formation corresponds to AatHO(O K)=399.6 kJI

mol or an average bond dissociation energy of roughly 200 kJ/mo!. The author did not specify the temperature; we assume T/K -0.

Orlando and Burkholder [950RLIBUR] recorded the UVI visible absorption spectra and observed maxima near 200 nm and 314 nm. They also determined the equilibrium constant for the reaction Br20+H20-+2HOBr, K=0.02. Using auxiliary data, [950RLIBUR] derived AfH(Br20, 298 K) = 138 kJ/mol.

Thorn et al. [95THOIMON] quoted the enthalpy of formation value derived by [950RLIBUR] to encompass the range of 113-159 kJ/mol. From a study of the photoionization efficiency spectrum of Br20, along with the ionization energy and the appearance energy of BrO+, the authors derived ArH(BrzO, 298 K)=107.1 kllmol and AfH(Br20, 0 K) = 124.1 kJ/mol. The uncertainty was estimated to be ± 3.5 kJ/mol.

Lee [95LEE], using the CCSD(T) electron correlation method in conjunction with the basis set of triple zeta double polarized (TZ2P) quality, calculated the enthalpy of formation of Br20. The author reported a value of 33 kcaVmol at 0 K (138 kJ/mo!).

5.7. Br20 (BrBrO)

There are no gas phase spectroscopic studies on this molecule. All experimental work is in the condensed phase???:

pure solid and isolated ·in an argon matrix. The reviews by Jacox [84lAC]. [90JAC], [94JAC] summarized these structural and spectroscopic studies in which two of the three vibrations have been observed. The structure and vibrational frequencies of this molecule are summarized in Table 6.

There are numerous articles which provide specific spectroscopic information:

( 1 ) Reaction complex OBrBr follows the 0+ Br2 reaction -[73DIX/PAR]. [73PARIHER]

(2) Infrared spectra in an argon matrix [7STEVIWAL] (3) Structure in an argon matrix [SOVELIDUR], [S2FERI

SMI]. [87LOE/AND] (4) Reactive scattering of oxygen atoms with chlorine

molecules: observed results which are consistent with


OCICI with a 3n sym1!letry when colinear and 3 A" symmetry when bent. Browett et al. [81BROIHOB] referred to the analogous 0-X-X study as described by [78TEV/w AL] and [73PARlHER]

(5) The vibrational frequency information (vI' V3) was reviewed by Jacox [84JAC], [9OJAC], [94JAC] and was based on the data reported by [78TEV/w AL]

(6) [93SCH/ ABD] used Fourier transform infrared (FTIR) techniques to study BrBrO in an argon matrix; their observations supported the conclusions of Tevault et at. [78TEV/w AL]

(7) Burdett et al. [84BURlLAW], in a review, discussed the stability and spectroscopic properties of BrBrO but referred back to the work of [78TEV /w AL ] as the

only source of information (8) Lee [95LEE], using ab initio techniques, calculated the

equilibrium structure and harmonic vibrational frequencies of BrBrO.

In examining cross beam experiments involving the colli

sion of ° atoms with bromine molecules. Parrish and coworkers [73DIXlPAR, 73PARlHER] proposed the existence of an asymmetric OBrBr complex with the possibility of a rather substantial bond angle, 150°C. However, neither of the two 1973 studies [73DIXlPAR, 73PARlHER] provided definitive structural information. The kinetic studies suggested a triplet electronic ground state.

Tevault et al. [78TEV/w AL] studied the reaction of atomic and molecular bromine with atomic and molecular oxygen in argon matrices (photolysis of bromine and ozone containing matrices). Several bromine oxygen compounds were stated to have been formed and identified by infrared spectroscopy-BrO, OBrO, BrBrO, BrOBr. and (BrOh. The authors observed the spectra of BrBrO in a photolyzed Ar-Br2-01 matrix. The a~signments were assumed to be vl=804 C~-I (B~-O stretch), v3=236 cm- I (Br-Br stretch) and the V2 value (the bending mode) was expected to be below 200 cm -I.

Veltman et al. [80VELIDUR] stated that reactive scattering results were consistent with the long-lived triplet of the OBrBr configuration suggested by 178TEV/w ALJ.

Fernie et af. [82FERISMI] proposed the existence of a short-lived OBrBr collision complex with a bent configuration and 3 A" symmetry with a modest well of an Eo approximately 110 kllmo!.

Loewenstein and Anderson [87LOEI AND] proposed the existence of a long-lived intermediate of a cyclic BrBrO structure.

lacox [84JAC], [90JAC]. [94JAC], in her reviews, recommended an a' BrO stretch value, in argon matrix, of 804 cm -I and a BrBr stretch value, in argon matrix, of 236 cm- I , based on the study by [78TEVIWAL]. Lee [95LEE], using ab initio techniques, calculated an enthalpy of formation at 0 K of 47.4 kcallmol 098.3 kJ/mol).


This oxide has been proposed as an activated complex to aid in the description of kinetic processes. Although the m~jority of experimental studies whic.h refer to Br202 ~ere III aqueous solutions, there were some gas phase studIes. In addition, there were two spectroscopic studies in which an absorption was attributed to Br202' Tevault et al. [78TEVI WAL] tentatively identified a molecule as (BrOh through oxygen-i8 isotopic enrichment experiments in argon matrices. They suggested that the most likely structures were an open chain such as OBr-BrO and BrOBrO. Mauldin et al. [93MAU/w AH), in their study of the self-reaction of the BrO radical, attributed an absorption structure to Br202, but assumed a Br-O-O-Br structure.

Epiolis et al. [84EPIILAS] listed this species in tables (with many related molecules), but there were no structural data provided. The article implied that calculations could

have been made on this species, but there was absolutely no mention of this species in their discussion.

The pertinent articles may be grouped as follows:

1. Proposed intermediate in aqueous solution -[30BRA], [34SKR], [52EDW], [58SIG], [68BUKI DAI), [68EDWfGRE), [72FIEfKOR], [73S0KJ DOR], [76HERfSCH], [78ROV/ZHA] , [79NOSI BOD], [86THO]

2. Proposed as intermediate in gas phase reaction sys-terns -

[70BROIBUR], (70CL YICRU], [80JAFIMAI], [81SANIWAT], [83BUTIMOR], [86SAN], [90TURI BIR], [93MAUIW AH]

3. Proposed structure -l30BRAj: BrOOBr or OBrBrO (possible) [52EDW]: Donor-acceptor intermediate BrBr02 [66SPRJPIM]: Calculation, BrOOBr (staggered or trapezoidal) [68EDW IGRE]: BrBr02 [70CL Y/CRU]: Symmetric planar bent BrOOBr (120°) [73S0KIDOR]: BrOOBr [78TEV IW AL]: Possibly OBr-BrO or BrOBrO [80JAFIMAI]: Possibly staggered or trapezoidal (Br-O-O-Br) [SlSANIWAT]: Trapezoidal (Br-O-O-Br) [S6THO]: BrOOBr [90TURfBIR]: BrOOBr [93MAUIW AH1: BrOOBr

4. Spectroscopy -[78TEVIW AL], [93MAUIW AH]

The citations listed in the bibliography for Br203 can be classified as follows:

1. Dissertations (full copy not available at this time) -[66CAM], [78PAS], [83ALL]

2. Formation with crystal characterization -

[74PASIPAV], [76PASIPAV), [77PASIPAV], [94LEO/SEP]

3. Comment/formation without characterization -

[87ALLIPOL] 4. Patent (lubricants) -

[84STE]

The status of the characterization of solid Br203 is best summarized by statements provided by Allen et al. [87 ALLI POL]: "There has also been considerable work on the vibrational spectra of the solid higher oxides of bromine (Br203, Br204), but structural conclusions had to be somewhat tentative." Pascal et al. [74PASIPAV) prepared Br203 by the thermal decomposition of Br204' The authors stated that the vibrational spectrum of Br203 shows the presence of a BrOBr bond, but that it was not possible to distinguish between structural possibilities: OBrOBrO and BrOBr02. Chemical analysis established the stoichiometry. Br203 was said to be a stable intermediate in the decomposition of Br204 to Br20. A subsequent study [76PASIPAV], using Raman spectra, indicated that the structure was OBrOBrO. At a conference, these same authors [77P ASIP A V] summarized their work by discussing the synthesis of the two isomers of Br204, Br203, and Br20 in a Raman tube and the spectra obtained at 93 K. The stepwise decomposition of Br204 to Br20 was presented and vibrational frequencies assigned. In summary, analysis of the vibrational spectra of the crystalline phase by Pascal et al. [76PASIPAV, 77PASIPAV] of the various possible isomers of Br203 and Br204, suggested that Br203 has the structure (OBrOBrO) and that the two Br204 isomers have the structure (02BrBr02) and (02BrOBrO).

Leopold and Seppelt [94LEO/SEP] stated that because of thp. similarity of Raman spectra, the BrZ03 identified by

[74PASIPAV] is probably identical with the Br203 investigated by the crystal structure analysis of [93KUS/SEP] (see Sec. 5.10).

Allcll et ul. [87ALLIPOL] ~tuuieu the comlensa[ion of 03/Ar and Brz/Ar mixtures. TheIR spectrum was interpreted to· suggest the formation of a Brzl03 complex. However, the structure could not be unambiguously determined.

5.10. BrOBr02 (Br+BrOi)

Kuschel and Seppelt [93KUSISEP, 93STI] prepared Br203 by the reaction of bromine with ozone at -50 to - 60°C. The authors stated that other workers used this same rCB.I,,;\.ion 35 yt:m:::. ag,U uul, iu <..:uutralSt, cl1ant<.:lerized the prod

uct as BrO')· the identification may have been based on impure mated;1. Kuschel and Seppelt deduced the structure of the crystal (bond distances and bond angles) by the use of the EXAFS-method (extended x-ray absorption fine structure) and the Raman spectra.

The authors compared the structural data of their Br+Br03 with that described by [92GILILEV] for BrBr04' The comparison suggested that these products may have been the same. Thus, there is some question raised as to the existence of BrBr04'



There is no gas phase or thermodynamic information on this molecule, however, some crystalline data (structure and vibrational frequencies) are available. Of the eight articles, the studies can be grouped as follows:

1. Formation and characterization -[73PASIPOT], [74PAS/PAV], [76PASIPAV], [77PAS/PAV], [87ALLIPOL], [94LEO/SEP]

2. Intermediate in solution -[80FOEILAN], [83FIE/RAG], [91SZAlWOJ).

Pascal and Potier [73PASIPOT] interpreted the Raman spectrum of the Br02 crystalline form (-180°C) in terms of a dimeric structure with a Br-Br bond. They specifically ruled out a chain or ring structure with bridging oxygen at

oms. Tentative assignments were made for some of the observed frequencies. In a subsequent study [74PAS/PAV] of the vibrational spectra of Br20::l, the authors discussed the corresponding spectra of Br20-l- and suggested the structure to be O]BrBr02' In studying the reaction between ozone and Br]03, Pascal et al. [76PASIPAV, 77PASIPAV] observed lwu i~Ullle1::' uf B1]04' The a~yHuHelril.; isumer

[02BrOBrO], was not isolated and rapidly transformed to the symmetric isomer [02BrBr02). An analysis of the vibrational spectra of the various possible isomers of Br]03 and Br204 suggested that Br203 has the structure (OBrOBrO) and that the two Br204 isomers have the structure (02BrBrO]) and (0 ]BrOBrO). Some tentative spectral assignments have been made. [94LEO/SEP] questioned the existence of this com~ pound.

Allen et al. [87 ALL/POL] mentioned the formation and characterization of Br20-l- but did not perform any additional work on this species.

The dimerization of BrO] to Br]O-l- was proposed to ex-. plain aqueous reaction kinetics:

(1) The Belousov-Zhabotinsky-system-(HBr02)/BrO; reaction [80FOEILAN],

(2) The pulse radiolysis of the bromine dioxide radical and hexacyanoferrate (4-), manganese (II), phenoxide ion, or phenol [83FIE/RAG], and

(3) The pulse radiolysis of the hexacyanoferrate (II)hrnm;ltf' cy:1nirlf' I;Yl;tf'm in :1C!11f'()11I; f'thylf'nf' !?lyC'()l

[91 SZAIWOJ].

5.12. 02BrOBrO

There is no gas phase or thermodynamic information on this molecule, however, some crystalline data (structure and vibrational frequencies) are available. All three articles can be classified as formation and characterization: [7 4P AS/ PAY]. [76PAS/PAV] and [77PAS/PAY].

In attempting to study Br]O, Pascal et at. have examined the decomposition of Br20-1- and the formation of an intermediate Br20~. In the analysis of the vibrational spectra of Br20., ' [7 -l-P AS/PA V] discussed the corresponding spectra of Br20-l- and suggested the structure to be 02BrBr02' Subsequent studies by Pascal et al. [76PAS/PAY, 77PAS/PAY]


prepared two isomers of Br204' These authors observed a slow reaction between ozone and Br203' The asymmetric isomer [02BrOBrO] formed was not isolated and rapidly transformed to the symmetric isomer [O]BrBrO]). An analysis of the vibrational spectra of the various possible isomers of Br203 and Br]04 suggested that Br203 has the structure (OBrOBrO) and that the two Br20-l- isomers have the structure (0]BrBr02) and (02BrOBrO). Some tentative spectral assignments have been made. [94LEO/SEP] questioned the existence of this compound.

5.13. BrBr04

Gilson et al. [92GILILEV] discussed the formation of BrBrO.1 by passing a mixture of bromine and oxygen through a discharge tube. The authors were surprised that with the hydrolysis of the yellow solid, BrO; was identified in the solution. Bromine K-edge EXFAS data on this solid detected vibrations which were assignable to a Br-O-Br bridge. This is in contrast to the results of [73PASIPOT]. Three distinct shells were observed corresponding to terminal Br-O, bridging Br-O, and nonbonded Br-Br distances at 1.61 (2L 1.86(2), and 3.05(3) A respectively, concomitant with the proposed structure. A Br-O-Br bridging angle of 11O± 3° was calculated by triangulation. [94LEO/SEP] supported the existence of this isomer.

Of the 13 articles, the studies can be classified as follows:

1. Patent (cellulose esterification) -[47PRA]

2. Preparation -[39SCHIWIE], [58ARV/A YM], [59ARY/A YM]. [59PFL], [59SCH]

3. Review -[63SCH/,J3RA]

4. Formation with characterization -f]6PAS/PAV21, f]7PASIPAVl, r94LEO/SEPl

5. Misclassified (really deal with BrO) -[88BAR/BOT] and [88COS/TEN], and

6. Archeology/vitrified slag (uncharacterized) -[88FLE/SWA] and [90HARlWHI].

Arvia et al. [58ARV/A YM, 59ARV/A YM] studied the thermal reaction between bromine and ozone. Under different conditions, they observed Dr]OS and DrJOs. The authors

specifically stated that BrO" or Br]06 was not observed, contrary to the result of Pftugmacher. Pftugmacher [59PFL] and Schumacher [59SCH] responded to this article and further discussed possible interpretations of the results. These studies do not conclusively suggest the existence of Br20S .

Pascal et al. [76PAS/PA Y2] recorded the Raman spectra of the white solid Br20". The authors deduced that the structure (0]BrOBr02) was a symmetric, polymeric structure similar to I20 5 . Comparison of the observed Raman spectra with that known for the ions bromite, bromate and perbromate resulted in the identification of vibrations which were


attributed to a bromine-terminal oxygen and a -bridging oxygen. Additional assignments were presented by the authors to justify their selection of the structure. In a later study, [77P ASIP A V] suggested that in the reaction of ozone with bromine, whenever Br:z05 was form~d, it was always mixed with Br203 or Br204' The authors continued to propose a polymeric structure (for Br205) analogous to that of 1205 .

Leopold and Seppelt [94LEO/SEP] presented a crystal structure analysis which characterized Br20S which crystallized with three molecule propionitrile. The structure was depicted as 0;B~OBr02' The Raman spectra of solvate-free Br20S was in agreement with this structure. The Raman spectra determined by [94LEO/SEP] differs from that by [76PASIPAV2].

The available information does not conclusively confirm the existence of Br206' The nine articles listed in the bibliography refer to the preparation of the condensed phase oxide Br~06 (or Br03)' All articles involved the reaction of ozone with bromine, except Mungen and Spinks [40MUN/ SPI] who were actually investigating [he decomposition of ozone. No property data have been reported. There is no gas phase information.

Schwarz and Wiele [38SCHIWIE] studied the thermal decomposition of Br02' In addition to the formation of the elements, the authors also detected a white oxide which they presumed was Br207 or Br206 and a dark-brown oxide, Br20. Schwarz and Wiele [39SCHIWIE] continued their study of the thermal decomposition of Br02' Their study showed that Br02 is completely stable at -40°C, but that decomposition can be detected manometrically. Br02 sublimes with extensive decomposition, melting in dry air at approximately 17.5 dc. Br20 is stable at -40°C. Again Br207 was suggested as one of the decomposition products of BrO:::.

Pflugmacher et aI. [55PFL. 55PFL/RAB], in studying the reaction of Br2 and O2 in a glow discharge, stated that the product was B,r03 (or Br206) but did not isolate the compound.

Arvia et al. [59ARV/A YM. 59ARV/A YM] studied the thermal reaction bet\veen bromine and ozone. Under different conditions. they observed Br205 and Br308' The authors specifically stated that Bro., or Br::06 was not observed. contrary to the result of Pflugmacher. Pflugmacher [59PFLJ and Schumacher [59SCH] responded to this article and further discllssed possible interpretations of the results. Refer to Sec. 5.-+ on BrO" for additional information.

Although two articles allude to the formation of the heptoxidc [38SCH/\VIE. 30SCH/\VIE]. no definitive informa

tion is available to confirm its existence. At this time, \ve assume that such an oxide does not exist. as suggested by [55PFL 5SPFLlRAB].

Sch\\'arz and Wiele [38SCHIWIE] studied the thermal de-

composition of Br02' In addition to the formation of the elements, the authors also detected a white oxide which they presumed was Br207 or Br206 and a dark-brown oxide, Br:zO. Schwarz and Wiele [39SCHlWIE] continued their study of the thermal decomposition of Br02' Their study showed that Br02 is completely stable at -40°C, but that decomposition can be detected manometrically. Br02 sublimes with extensive decomposition (to Dr2), melting in dry

air at approximately 17.5°C. Br20 is stable at -40°C. Again Br207 was suggested as one of the intermediate decomposition products of Br02. According to Pflugmacher [55 PFL, 55PFLIRAB], Br207 probably did not exist.

5.17. Br30s

There are numerous pre-1960 studies which mention the preparation of a presumed condensed phase oxide with the composition Br30S' Although 28LEW/SCH, 29LEW/SCH, 29LEW/SCH2. and 30LEW/SCH discussed the preparation of this oxide, 55PFL, 55PFL/RAB, 58ARV/AYM, and 59ARV/AYM repeated the procedure and determined that the product was Br03 (or Br206) not Br308' No property information is available. Based on existing information, there is no conclusive evidence that this compound exists.

Of the articles published since 1975 and indexed (by CAS) to this oxide, only three (of which two are both patents) may deal with Br308' The other four, in fact, deal with BrO in the stratosphere and troposphere, and are misclassified.

All citations can be grouped into five categories.

1. Patent -[90100] and [91BEN/GER]

2. Misclassified as Br30S (really BrO) -[89DRU/AND], [89CARlSAN], [90DOTIDAR], and [9 1 MOUIJAK]

3. Review -[34BRA], [60GEOl [63SCHIBRA]

4. Formation/preparation/decomposition -[28LEW ISCHl [29LEW ISCH],[29LEW ISCH2], [30LEW/SCH], [55PFL], [55PFL/RAB], [58ARV/ AYM], [59ARV/A YM], [59PFLJ. [59SCH], [74S0Ll KEI]

5. Sensitized decomposition of ozone -[31LEW/FEI], [31SPil [40MUN/SPI].

6. Reaction -[90BIGIBRO]

When Lewis and Schumach~r [28LEW/SCH] allowed bromine and ozone to mix in a flask (no temperature was specified), a white deposit appeared on the walls on the flask. This solid was thought to be an. oxide of bromine, later described as Br50 tl . Shortly after the formation of the solid, an

explosion destroyed the apparatus. In subsequent work by Lewis and Schumacher [29LEW/SCH] at low temperatures, - 5 to 10 0 C. an oxide of bromine was formed which had the composition Br"Os and existed in two crystalline modifica-



tions. Two subsequent studies by the same authors [29LEWI SCH, 29LEW/SCH2] examined the thermal reaction in more detail to observe the formation and the rate of decomposition. The transition temperature between the two presumed crystalline forms was determined to be -35±3 0c. The thermal reaction between bromine and ozone was studied again in 1930 [30LEW/SCH] to determine the kinetics of decomposition.

In a review article, Brady [34BRA] mentioned that the method used by Lewis and Schumacher [29LEW/SCH] to obtain Br308, was used by Zintl and Rienacker [30ZINIRIE] for the preparation of Br20 [refer to the Br20 discussion for these references]. The implication is that Br308 is not a pure, single compound.

Arvia et al. [58ARV/A YM, 59ARV/A YM] studied the thermal reaction between bromine and ozone. Under differ-ent conditions, they observed Br20S and Br30S' The authors specifically stated that Br03 or Br206 was not observed, contnuy tu tht: rt:sult uf Pflugllladlt:L Pflugllladlt:l [59PFL]

Schumacher [59SCH] responded to this article and further discussed possible interpretations of the results.


In the 1960 review by George [60GEO], the author stated that the proposal of a Br03 oxide raises doubt about the authenticity of Br30S'

The 1963 review by Schmeisser and Brandle [63SCH/ BRA] discussed the numerous experimental studies which led to the presumed formation of Br308' The authors also referred to other related studies which stated the product really was Br20S' It appears that the reaction of bromine with ozone can lead to a mixture of different bromine oxides. In addition, part of the problem may lie in the precise characterization of the products.

6. NIST JANAF Thermochemical Tables

NIST-JANAF Thermochemical Tables for BrO(g) (Sec. G.l), OBIO(g) (Sec. G.2), BrOO(g) (Sec. G.3), Br03(g) (Sec.

6.4), BrOBr(g) (Sec. 6.5), and BrBrO(g) (Sec. 6.6) are presented on the following pages.

~ "0 :T '< !" o :T (l)

? JJ

~ o Q)

~ < ~ I\)

.!Jl z !' _.f>.

<0 <0 (j)

Bromine Oxide (BrO) Ideal Gas Mr =95.9034

f);; = 19.1.'2 :t. 200 <"Ill I

.\"(2')1-1.1:; K) o~ 2.1"2')7 ~. 0.1 J K 1'11101 I

t:;.,IIO(O K) = 133.3 :± 2.4 kJ '0101- 1

t:;. ,II"(298.15K)= 125.8:± 2.4kJ·mol- '

Stall'

X'II, X'II, A'II, A'III.

r

%8 27~71

[2<)321 [

g, Electronic Levels and Molecular O',nstants e~BrIhO). cm"

('),. (<leX,' (l),.Y,. B,. n,. De-IO'

727.0:; 4.9,,2 727.0) 4.9,,2 511 .. 1 4.83 .i 11.3 4.8

-0.074 -0.074

Point Group: C. v

0.4299 0.4299 0.314 0.314

0.003639 0.003639 0.00.\4 0.0034

0.594 0.)94 0.474 0.474

(T=I

rJA

1.717 1.717 1.95 1.95

Enthalpy of ('orlnation The I\~'O exisling speclroscopic sludies by Cckman and Gaydon' and Durie and Ramsay< yield dissociation energi values for BrO(g). One

should nOll'. witl I"L'SPl'CI to those studies. tilit the first hound excited state A1n of BrO(g) dissociates to Br( P.1/2) t 0(ID2). A linear Birge-Sponn l':>vt-apolalion of Ihe Coleman and Gaydon ' data gave 17800 em .. 1 or 213.2 kJ·mol- ' for the ground state dissociation energy. Assul11illg Ihl' l'xlI'apolation was high by up to 20%. they recolllmended 1.75:± 0.3 eV or 170:± 29 kJ·mol- l

. Durie anj Ramsay,2 from a graphical Birge .. Spoiler eXlrapolation. calculaled a dissociation energy of D~ = 19332 :± 200 cm- I or 231.6 :± 2.4 kJ ·mol- I. The latter value leads to Ihe pn.'St'lIt adopled value for t:;. ,lr(298.15 K) for BrO(g) of 125.8 :± 2.4 kJ 'mol- I. Additional data needed for the calculations prl'senled here. e.g. thennal functions for the Br(g). and Br2(ref). O(g), and 02(ref), are t"ken from the JANAF Thermxhemical Tables:1

IIl'at Cap<ldty al1d Entropy The spct"lrosco:Jic resuits wbulatcd above al:? for tht' 7"8rl"0 isotopomer. Isotopic relati,)nships4 are used to convert the above constants

10 those for Ihe IIcrmally lx-curring. i.e. nalural Ibundance. sprcies. The latter values are thea used in the calculatioll of the thermal functions. On Iy Ihe X alld I'. slall's are included in the c,ilculatioll of the thernlal functions; a sllm-over-states technique is used.

Values of ('),. alld (')eX,' given in Ihe table above for the r,round state are from Butler et vl./ while those for the first excited state are from Barnell <'I al." Th:se values in fact described al average II state; there are differences in the vibrational constants for the X2n1i2 and X2rr l12 slates bUI lhey art not consitit'red in this calcukilion. The Be value for the ground state is from Amano el £11.7 The internuclear distance and value for B,. for the A state are from Barnell £'/ vI." The value of D,. for the excited state was estimated.4 Barnett 1'1 al.~ gave a dissociation l'nl'rgy of H960 CIIl' I for the A slate which is lIsed in conjunction with Tc to provide an energy cutoff from the sum-over-states calculation on Ihe exc iled state.

I'rl'viously, Ihe value of the spin orbit constmt. A". for the inverted doublet x2n prounj state adopted by Huber and Herzberg8 was an averaw' based on two values derived from the EI'R spectra studies: Au = -815 cm- of Carrington et vl.~ and Au = -980 em-I of Brown <'luI. t I The ITcenl Ill<.'asured value of McKellal. " A" = -968 COl ,1. for the spin-orbit splitting of the ground state is adopted here. For CIO Ihl' spin-orbit splitting of the A statl" is apprmimately 1.5 times the value found for the ground slate. 1l Using the sam~ factor of 1.5, the spin-orbit splitting for the A state in BrO is e~timated to be 1450 cm- I.

Numerous excited slates have been estimal~d by Monks ('{ vI. J\ and observed by Duignan and Hudgens.14 These ~tates are not fully characlerized in t:nns of vibrational and rotational conslants and do not contribute signilicantly to the thermal functions below 6000 K.

References :1:. 11. Coit'man ,uld A. (;. Gaydon. DiscussiolS Faraday Soc. (2). 166 (1947). 'R. A. Durie and I). A. Ramsay. Can. J. I'hys.36. 35 (1958). 'JANAF ThenlHxhemical Tables: Br(g). June 1982; Br,(ref). June 1982; O(g), Sept. 1982; 02(ref). Sept. 1982. \;. Herzbl'rg. Sp~ctra of Dialomic Molecules. D. Van Nostrand Co .. New York, p.'·107 (1950). ;.1. E. BUller. K. Kawaguchi ~tI1d E. Hirota. 1. 1.-101. Speclrosc. 104(2). 372-9 (1984). ('M. Barnett. E. A. Cohen and D. A. Ramsay. Can. J. I'hys. 59(12).1908-\6 (1981). 7'1". Amano. A. Y'Jshinaga and E. Hirota. J. Mol. Spectrosc. 44(33), 594-8 (1972). 'K. 1'. Huber and C •. Herzberg. Mlliecular Spertra and Molecular Structure. IV. Conslants of Diatomic Molecules. ':(,'0. CUTingloll. l' N. Dyer and D. H. Levy. J.Chem. Phys. 52(1),309-14 (1970).

.I. M. Brown. C R. Bytleet. B. J. Howard. aud D. K. Russell, Mol. Phys. 23(3). 4§7-68(1972). "A. R. W. Ml·Kdlar. J. Mol. Speclrosc. 86( I) 4.1-54 (1981).

Bromine Oxide (BrO) Br101(g)

EnthaljJY Reference Temperature; T,; 2911.15 K Standard State Pressure; pO ; 0.1 MPa ---J·K-'mol-'____ kj·mol-' ___ _

T/I\ C; So -[Go-If(T,))fT HO-W(T,) ArW ArGO log Kr

o 50

100 ISO 200 250

29H.15

300 400 500

600 700 xno <)O{)

1000

1100 1200 1300 1400 1500

1600 1700 IXOO 1900 2000

2100 2200 2300 2400 2500

260{) 2700 2HOO 2900 3000

3100 3200 3300 3400 3500

3600 3700 3HOO 3900 40(1)

4100 4200 4300 44(~)

4500

4600 4700 4HOI) 4\1{~)

5000

5100 5201) 5300 540) 55(1)

56(~)

S7(1) 5HOl) 5')(~) 6()(~)

PREVIOUS

0.0 29.103 29.13'.1 2'.1.5'.12 30.HOS 32.4<)3

34.IX2

34.244 37.062 3X.71'.1

3'.1.525 3'.1JB'.I 39.'.101 3'.1.X46 3'.1.746

3'.1.634 3 '.I.S 2'1'-. 3<).437 3'.1.361 3'.1.301

3'.1.256 39.225 3'.1.205 3'.1.194 3'.1. I X '.I

3'.1. I X '.I 3'.1.IX9 3'.1.IXX 3'.1.IX2 39.16X

3'.1.145 39.110 3'.1.061 3X.9\!6 3X.915

3H.H 17 3H.701 3H.56H 3X.4IH 3X.2S1

3~Ul6H 37.H71 37.661 37.43<) 37.205

36.%3 36.712 36.454 36.191 35.924

35.654 35.3X2 35.IOH 34X35 34.562

34.291 34.021 33.755 33.491 33.232

32.976 32.724 32.477 32.235 31.9'.1H

0.0 179.334 199.S11 2 I 1.3HX 220.050 227.101

232.970

233.IH2 243.447 251.'.IIS

259.055 265.176 270.S02 275.199 279.392

2X3.175 2X6.619 2'1'-.9.779 292.699 295.412

297.'.147 300.326 302.56X 304.6X7 306.697

30H.6()9 310.432 312.174 313.K42 315.441

316.977 31 H.454 319.K75 321.245 322.S66

323.X40 325.071 326.260 327.409 32K520

329.595 330.635 331.643 332.61X 333.563

334.479 335.366 336.227 337'(l62 337.X73

33H.659 339.423 340.165 340.XX6 341.5X7

342.269 342.932 343.S7H 344.206 344.X IX

345.415 345.996 346.563 347.116 347.656

Brorrine Oxide (BrO)

[NFI'l[TE 331.631 2tl.I04 2~2.6XI 235.9X5 2]3.523

232.970

232.971 234.351 237.042

2~0.132 2~3.2X3 2~6.36()

249.30X 252.1 I I

254.766 257.279 259.659 261.916 264.06()

2f6.099 26!U)43 269.\I{)() 2,1.675 2,3.377

2,S'()()9 2j6.57X 2jK.OKR 2,9.544 2Hl.94K

2U.304 2i3.616 2i4.KX6 2i6.[ 16 2i7.309

2i,X.467 2i,9.S92 2~0.6K5 2~1.74X 292.7X3

293.791 2~4.773 2~5.730 2~6.663 2~7.S74

2~X.463 299.331 300.179 301.00R 30l.XIX

302.611 303.3X6 304.[44 304.XX7 305.614

306.326 307.024 307.707 30X.377 309.034

309.679 310.311 310.93[ 311.S40 312.137

-9.(l61 -7.615 -6.159 -4.694 -3.IX7 -1.6()6

o.()()()

0.(l63 3.63X 7.436

1l.354 IS.325 19.313 23.301 27.2XI

31.2S0 35.20X 39.156 43,(196 47.029

50.957 54.XXI 5X.X02 62.722 66.641

70.560 74.479 7X.39X X2.316 X6.234

90.ISO 94.(l62 97.971

10l.X74 IOS.770

109.656 113.532 117.396 121.245 125.079

12X.X95 132.692 136.469 140.224 I 43.9S6

147.665 151.349 155.()()7 15X.639 162.245

165.X24 169.376 I 72.90() 176.397 179.'1167

I X3.310 IX6.725 190.114 193.476 I <)6.X13

2()().123 203.40X 206.66X 209.903 213.115

133.3)5 133.611 133.JSK I 32.9U 132.424 13UiJ9

125.770

125.736 110.5~6 III.(X)K

111.4'i6 111.950 112.4)5 112.Hl)K 113.170

[ 13.493 113.7K0 114.(J36 114.265 114.4'>7

114.647 114.R)5 114.<)42 115'<)57 115.153

[ 15.226 115.279 IIS.310 115.31X 115.3:)3

115.264 115.201 115.112 114.WX 114.~X

114.{90 114.'196 114.276 114.C2X I 13.i55

113.~53 113.124 112.-.69 112.:X9 Ill.SiiO

IIL,,47 IIIJKX I IO.e03 IIO.{')3 109.S59

Iml.W9 IOX.~16 IOU09 107.177 106.523

105.M4 !OS. 143 104.LIH 103.{69 102.~9X

102.103 101.'HS [()().L44

99.S79 9X.{90

133.305 129.149 124.765 120.S55 116.505 112.SRX

109.SH2

109.4H2 !o7.2()() 106.307

105.321 104.256 103.125 101.94() 1()().713

99.451 9X.162 96.\i50 \/5.S19 94.173

92.X[4 91.445 \I{).066 XX.6XI X7.291

X5.X95 X4.497 X3.0<)X X 1.697 HO.296

7lUI97 77.49X 76.103 74.711 73.325

71.945 70.S6X 69.19X 67.X36 66.4li3

65.136 63.7<)6 62.471 61.150 5Y.X40

5X.545 57.255 55.9XO 54.717 53.463

52.222 SO.9\/4 49.7XO 4X.579 47.3XX

46.213 4S.04H 43.900 42.76S 41.646

40.537 39.445 3K.367 37.305 36.256

INF[N[TE ·-134.9IK -65.169 -41.9KO -30.427 -23.523

-19.19X

- 19.(l62 -13.999 -1l.l05

-9.169 -'PHO -6.733 -5.916 -5.261

-4.722 -·4.273 -3.X91 -3.564 -3.279

-3.030 -2.KI0 -2.614 -2.43X -2.2KO

-2.136 -2.llO6 -I.XX7 -1.77X -1.67X

-·1.S'1'-.5 -1.499 -1.420 -1.346 -1.277

-1.212 -1.l52 -1.0<)S -1.042 -0.992

-0.945 -0.90[ -0.X59 -0.XI9 -0.7XI

-0.746 -0.7[2 -O.6XO -0.6S0 -0.621

-0.593 -0.567 -0.542 -0.5IX -0.495

-0.473 '-0.452 -0.433 -OAI4 -0.396

-0.37H -:-0.361 -0.346 -0.330 -0.316

CURRENT: March J 996 (I bar

Br101(g)

z

r » z » '"T1 -I :::t m :IJ 3: o o :::t m 3: o » .--I » OJ .m en '"T1 o :D -I :::t m OJ :IJ o 3: Z m o >< a m en

.-. o (0 ~

~

"'0 :T '< ~ o :T CJ)

~ :0

~ o Q)

¥ < ~ I\)

_01

Z ~ -~

co CO Q)

Bromine Oxide (OBrO)

.'>..J r(o 1\.1 "' [.j ,I) , .)~! k I" 1101 I

\ ,.{ .'():-;.I.~ 1\.1 , .. ) II. I' I r... '11I()1

Ideal Gas Mr = 111.9028

:!1,lI0(OK)=[161,5:!:25]kJ'mol I :!1[1I"{.29X. I) K) = ! 152.0 :!: 251 kJ 'mol I

Lit', lroni,' Level and QuanlUnl Wl'ii!1!1 SI,!il' C,.cm ' ,1:,

v'n; lI.O

VihratiolJ; I h,'qlll'i1\'il;~ ~~:~~I !)l'g,'nl'r<lcil's

Enthalpy of Formation h'r I ill' s('li,'S ().\()(;.~) 1"IIl'I\' X=I:. Cl.h. II.

.\.,,/I"(OCi().g) '!lld n;:(clo) :trl' 1'c·<Is(lfI<lbk. W.' ad( alld O!lrOI g l. TilliS we l'akulatl' :!1."ff"(OBrO, g. ()

Co!tI\'11 [ reporll.'<1 [l(O ·llrO) .. ~ 7n .f· 10k,,; I'mol 1', H'lllation of IlrO~(cr) rep(lIwd by l'f1uglllachl.'r ('1 al. 2

01 Iilis vallll' b;ISI'd Oil clJlllparison with CIO" "hl' t.' for 1IIl' !\';ll'lioll Br(),·-7BrO·jO. This is <lnl'stimatl'd

In cOlltrast. H uil' ;'lllt! l.asl.lo' haw l'~tilllated the I l'lltilalpy of fOl'lllatioll <:1' OBrO in thl' gas ph;lll' ran appli\,,; for till.' brollline' SllL"'il's. Usillg a valul, .. r 2.9 kJmol k.\·IIl()1 [. we <lillain J.(i" = 146,<) kj'nll11 [ 1'01 OBrO(gJ and

xoo (I) -'(Xl (I) X52 (I)

(1 = 2.

14Bl e = 409.()X44" 10 ' [I g '(111"

rdiahk l'xpnillll'ntal data 1'01 OCIO(g). Assuming that the values (~'1.94) to apply for a similar relationship between BrO(g) :!: 25 kJ·llloj!.

= '8.7 khl10l ',This value was based on the enthalpy of kcd·l11ol· [, Cottrl'1I expressed doubt as to the validity

Vedcneyev ('I ul.' was :J.fI(298 K) ~ 70 kcal'mol- I

(1954) although a diff..,rent temperature was given. the following manner. According to Stanbury,S the differencl' in the !J.,G for CI2(g) and CI02(aq) also £'1 af." as this dilTerence and !J.C (I3r02, aq) = 144.0

. In comparison [)~:(I3rO) = 231.6 kJ·mol- l.

Ileal Caparity and Entropy . MUl'Ikr ('1111. 7 havl' lIll'asul'l'd the Illicrowaw speclra of 0 3rO(g). Preliminary analysis of the data suggested a bent structure (r" = 1.649 A and <(( lI~r()) = I 14.4"), This structure is adoilled all}! is consistent Wilh t!lt eXI?,l'cted trl.'nds in the l'll\!;esponding chlorine and i()~ine oxide nl<)ic-cuit's. I iK' prlllcipallllollll'nis 01 IIll'I11a (In g nn ) arl': jA = 3.0275 X 10 . , III = 10,2087 X 10 , and 1(' = 1-'.2361 X 10 ..

In support ,)1' Ihi, study. Bylll'rg and Spallg'.'t .. Larsl'nx use.! modified eXlended Huckel Iheory to calculate nuclear quadrupole coupling (Oll,tallts for a snil'.s of oxyg,'n halogen cOll1pounds.:nll' comparison of calculated values with observed values helped confinn the geometry of BrO,: C" sylllllll'lry with a hond kngth of 1.625 A and a h:lIld angle of 117,6". This geometry was assumed to Lx: similar to that of C102,

using a 0.15 A difkrcllcc hl'lWl'l'1l the envaic'III radii of the chlorine and bromine atoms. Tl'vault £'1 "I." ,)I>s,'r\'('<1 Ihc infrared sperm of BrO, in a solid argon lIlalrix. As.suming the proper identification of the antisymmetric

strelching I', to lx' X52 (Ill '. tile apl'\ angie \\as calculated to bt.' 110::':: 2" This was close to the value observed for Ihe analogous matrix isolated O() •.

The rel'<.1I1;llll'nded vihrali,lI1ai frequency (1',) is tilat sugge:aed by Jacox. 10 This data is based on Ihe infrared spectra of the argon matrix isolated radiI al a~: stlldi,'d by Tevauit ,'I (/1." I'rl'liminary micowave sludie~ by Mueller ('{ ill.1 suggested an approximate value for V2 (300 ('Ill '). The uno!l,,'rved vihratioll,tI frequellcy , v,) is estimaltd from those which describe the other halogen oxide molecules." Maier and BOlhur." usillg flash photolvsis, trapped OBrO in a matrix allc measured VI ;)nd v, for.two isotopes. Their values for Vl are within a few wave nUlllbl'r, of the valul's dnived by Tcvaull 1'1111." 1', val lies arc of the order of79 1-799 cm '1, depending on the concentration of the pyrolized mixture (Br2/0c/Ar).

Rl'ferenc('s [T. L. Cottrell. The Strt'll~ths of Chemical Bonds, Illlllerwor.ns. 'A. l'f1ugmacitt-r. R, S('Il\~'all and H. J. Rabbin, Z. 'V, l. Vcdcnl'Yl'v. L V. C;urvirh, v, N. Electroll Affinilies. Amold. London, 7'1)· ·'R. Huic and B. Laszlo, ALlv. ChI.' Ill. Series. 'I), M. Stanhurry. Adv. In()!g. ('he Ill. 33, 6(; ''D, D. Wagman. W. 11. Evans. V, n, Parker, R. 71 I. S. 1'. MU"lIer, C. Milkr ;lIId E, A. Cohen. s 'J, R. l3ybl'rg and J, Spangl,t·Larsen. ChcllI. I'hys. 1.,'11 "D. E, Tevaull. N, Walkl'!'. R. R. Slllardl.t~\Vski. and W, "'M. E. Jacox. J. I'hys. Chcm, Rcf. Data. Monograph No. "JANAF TherlnoL'ill'lIIical Tables: ()CIO(~): Sell!. 19')): 010: [2(1, Maia :llId ,\. Bothur. '/., anorf!, allg. ('hell, 621. 74.,-4'1

221-'8.1 (1<)54). 11 264. 204-8 (1951 ),

and Yc. L Frankevich. Bond Energies, Ionization pOlenlials and

82.27-'-' (1918).

Bromine oxidE (OBrO)

Emh,IIlY Hcfcr('occ Temperature = 7, = 298,15 K

TIK

(I

50 IO() 150 20\1 250

___ '·K·'mol"' ____ _

c; SO -[Go-if'(T,)11T

INfiNITE 0<)X.X61 ](IK.07K :K3.<)56 "75.11 I :71,X46

2\1X,15 4'U64 271.112 :71.112

:71.113 :72.<)44 :76.516 :X(),626 :X4.K36 :XX.969 :92.<)52 :\16.760 j(XUX7 j03Xl\l j07.125 jl(),254 013,23<)

300 4U\1 500

600 70{) KilO

PREVIOUS:

360,6XI 364,164 367.453 370,567 373,525

421.792 423'<)42 424.265 425.463 426.637

Bromine oxide (OBrO)

.;16.0'10 JIK.KI6 j21.42X j2J.<)33 j26.33\1

j2X.654 j30.XX3 j33.0J2 :,35. 10K j37,1 t3 :,39.053 ;40.'133 j42,754 j44.521 A6,237

347.905 j4<).527 351.106 :52.643 354.141

:55.602 :'57.02X 35X.420 j5'1.7XO 361.10'1

:62.409 :63.6X() 364.925 366.143 36V37

;6X,507 :69.654 :'70.77'1 371,XX3 372.966

374.030 375.075 376.101 j77.II0 j7H,IOI

j7\!.076 jKO.035 :;XO,97LJ jX1.907 3X2,x21

Br102(g)

Standard State Pressure = pO = 0.1 I\1Pa ____ .. kJ·mol-' ____

II°_II°(T,) !:i.,lI c !:i.,G0 log K,

-11.395 161.500 161.500 INFINITE -Y,731 16t.299 159.420 -166.544 -X,020 160.57:- I 57.XO') -X2.431 -6,IX5 15').7')0 156.5<)6 -54.531 - 4.222 15,),010 155,64') -40.651 -2,131 15X,236 154.X9X -32,364

,(XIO 151.')57 I 54,97Y -27.152

,OX4 151.')16 I 54 ,<)\IX -26.9XX 4.X26 136.447 15'),21 I 20.7\11 \I.X77 136,5,)4 IM.XXX -17.226

15.1J3 I 36.X311 170.525 -·14.x46 20.526 137.100 176,120 - 13,142 26.1115 137.375 IKI.675 -·II.X62 31.570 137.643 Ix7,1\16 .- to.X65 37.174 I 37.X')X In.6XX "'IO,()65

42.K16 13X.13,) I')X.156 ·\1.410 4X,4X5 13X.3M 2113,602 --X.X63 54.177 13X.572 209.0311 -x.3Y') 5'),XX7 13K.764 214,442 - X.OOl 65.61 I 13X.\l37 21').X42 -7,656

7U46 t3')'()')O 225,230 -7.353 77.0<)1 13(),223 230,610 -7.0K6 X2,H45 13<).334 235,')X2 -6.H4X XX.605 13\1.42() 241.34<) -6.635 \14,371 13Y.4KI 246,712 -6.443

100.142 13')515 252.073 -6,270 I05.9IK 13'1.520 257.433 -6,112 I I 1.6YX 13\1.497 262,7')2 -5,'16K 117.4X() 139.443 26X.154 -'5.836 12-'.266 139,358 273.519 -5.715

12\1,054 LW,244 27K.XX7 -5.603 134,K45 13'1,I(X) 2X4,261 -·5.499 140.63H 138.'!26 2K9.640 -5.403 146.433 I3K.725 2'15,026 ·-5,314 152,229 13X.496 3(X).420 -5.231

15KJ)27 13K.243 305.X22 -5.153 163,H26 137.965 311.231 -5.0XO 16'.1,626 137.666 316.650 -5.012 I 75.42X 137.347 322.079 -4.94X IHI.231 137.010 327.517 -4.XXX

IX7.035 136.657 332.965 -4.H31 In.H39 I 36.2K9 33K.423 -4.77X 19X.644 135.90X 343.X92 -4.727 204.451 135.517 349.370 -4.679 210.257 135.116 354.H5K -4.634

216.065 134.707 360.357 -4.591 221.K73 134,291 365.X66 -4.550 227,6H2 133.X70 37t.3x5 -4.511 233.491 133.444 376.913 -4.475 239.300 133,014 3H2.451 -4.439 245.111 132.5XI 3X7.99X -4.406 25(),'121 132.145 393.556 -4.374 256,732 131.707 399.122 -4.343 262.543 131.266 404.69X -4.314 26K.355 130.H23 41O.2X3 -4.2x6 274,167 130.377 415.H77 -4.259 27'.1.979 I 29.'!2X 421.479 -4.234 2H5.7'!2 129.475 427.091 -4.2()<) 291.605 129.01X 432.710 -4.IX6 297.4IH 12H,557 43H.33K -4.163

303,231 12H.OX'! 443.975 -4.141 30'1,045 127.615 44'.J.620 -4.120 314.X59 127.U4 455.273 -4.I<X) 320,673 126.644 460.934 -4.0XI 326.4X7 126.143 466.605 -4.062

CURRENT: March 1996 (J bar

Br102(g)

..... o <0 ~

s: » r(") o r-s: ?E (") ::r: » en m

~ "0 ::T '< !J' () ::T CD

? Jl

~ o III

Ju < ~ I\) _01

Z ~

_.f:>.

<.0 <.0 Ol

Bromodioxy (BrOO) Ideal Gas Mr = 111.9028 Bromine Oxide (BrOO) Br102(g)

S"(2()~.I) K)= l2~~.~ I 3\.1 K "111<11 I

Electronic Level and Quantum Weight state E" cnl-

I K,

---~\I'A;i--- 0.0 [2]

Vibr<ltilln<ll Frequencies and Degeneracie~ v, em'"

1487 (I) [250] (I) [160] (I)

0. ,/1"(0 K) = [116.1 2: 4D] kJ·mo!-1 0. ,11°(298.15 K) = [108.0 2: 4D] kj.mol- I

Point (,roup: C, 0 0 .T = I Bond DiSl<lnces: Br-O = [2.0\ A; 0-0 = [1.25] A Bond AI~;le: Br-O-O = [115]" Product of the MOJllellls of Inertia: I"/,J(" = [588.4497 X '10 117] g'cm'

Enthalpy of Foromtion Ip and Bums I detenllined the recombination rate con slants of bromine atoms in the presence of six different third bodies (helium, neon,

argon, kry~Jlon, ?xygen <lnd p itrogcn) over the emperature ra~ge of 300 ,!nd 127~o K. The .~uthors refer to t~o earli~r studies: Rabino~itch and Wood- <lnd Stwng ('[ al. Based Oil these daa, Blake l'I al. calculated IIlteraclJon potenwls between atomIc brommI', oxygen and an mert third body (such ;IS a rare gas). A value is givel for Br-O,. BrOO was thought to be unstable with a bond energy (8r-00) of approximately I keti-mol I (at 298.15 K) which translated te, <In enthalpy of formation of 108.0 kl mol-I.

lIeat Capacity and Entropy " Butko\'skaya ('wi.' l'sJimated the structure' of this moil'cule to be bent with a Br-O-O angle of [115]" and bond lengths, r(Br-O) '" [2.0]

A and r(O-O) = /1.251 A. Butkovskaya ('{ al. assuml'd this structure in an attempt to explain the formation of Br02 fDm the reaction of (~ + Br, i-!, <I flow disch<lrge ~ystelll.,,~nder the ~xperimelltal,&'onditions studied, OBrO \~~;' actually formed. The principal moments of inertia (III gcm') are: I A =[1.2011 X 10 \./ II =[215417X 10 J, and Ic= [22.7428 X 10 "].

The rl'COmllll'IHled vibrational frequl'llcy for 1'1 is that suggested b~ Jacox." In addition, we adopt v2=[250] and v,=[150] cm- I based on an assumed trelld C)f the FOO(g) and CIOO(gJ vibrational frequencies. VI is based on the infrared spectra of the argon matrix isolated radical as studied by Tev.lult and Smardzewski! Michael and Payne" calculated (BEBO method) ,I stretching frequency of872cm- 1 for VI which is ill conflict with the observed frequency by T('vault and Smardzl'wskix and the corresponding value for CIOO. POO(g) and CIOO(g) have ]11(0-0 stretch) values of 114X7 and 144-' em I, respectiwly.7 Thus, v,= 1487 CI11-

1 for BrOO appears reasonable. The aUllors suggested that the bending frequwcy of 100 cm I was consisll'nt with their kinetic data. The recent stlld~ by Maier and BothurJ{) suggested a V, value in' agreement with tl'c adopted value.

References 'J. K. K. Ip and G. Burns, J. Chem. l'hys. 51. .~414 (1969). 'I:. Rabinowitch ;nd W. C. Wood. Trans. Randay Soc. 32,907 (1936). 'R. L. Strong, J. W. Chien, P. E, Graf. and .I. E. Willard, 1. Chelll. Phys. 26, 1287 ('1957). 4D. 11.. Blake, R ... Browne. and G. Burns, J. Chclll. Phys. 53, 3320 (1970). 'N. I. BlltkovskaJ,I, I. I. Mommv. V. L. Tal'rose. and E. S. Vasiliev, Chern. Phys. 79, 21 (1983). I'M. E. Jacox, 1. rhys. Chem. Ref. Data. Monq~raph No.3, 461 pp. (1994). 7111.NAF Thl'nnochelllical Tables: FOO(gl. Sept. 1995; CIOO(g). Sept. 1995. xI). E. Tevault and R. R. Sinardzl'wski . .I. Am. Chem. Soc. 100, 3955 (1978). "J. V. Michael anll W. 11.. Payne, Int. J. Chell1. Kim'!. II. 799 (1979).

Enthal~y Reference Temperature", T, = 298. IS K Standar' State Pressure = pO = 0.1 MPa ___ '·K-'mol-'____ kJ·mor' ___ _

Tm C; So -[Go-If(T,»)1T II°-W(T,) Arll" ArGO log Kr

C .O()O 5(1 35.~'X2

100 41.HIH ISO 45.376 2()(1 47.12H 25(1 4H.143

2YH.15 4H.x75

3()(1 4H.'!01 40(1 50.265 50(1 51.562 60(1 52.707 7()(1 53.657

H()(I 54.421 <)()(I 55.031

1 ()()(1 55.517 1100 55.Y07 12()(1 56.222

130(1 56.4XO 1400 56.692 1500 56.H6'! 16()(1 57.017 17()(1 57.142

I HOtl 57.24'! 1 'XXI 57.341 2tX)0 57.421 2100 57.4'X) 220(1 57.550

2300 57.6()3 24(XI 57.650 25(XI 57.692 26(XI 57.72Y 2700 57.763

2X()(1 57.7n 2 'XXI 57.XI'! 3(X)0 57.X44 310Q 57.X66 3200 57.HX6

3300 57.Y05 34()0 57.922 3500 57.Y37 3600 57.'!51 3700 57.%5

3HOO 57.'!77 3'Xl(I 57.YHH 4(Xl(I 57.WX 4Hl(I 5H.(X)X 4200 5H.017

4300 5H.025 44(l(I 5X.033 4500 58.04() 46(l(I 5K.047 4700 5H.054

4Xtl(l 5X.060 4YOO 58.065 5000 5H.071 5100 5X.076 5200 5H.OX I

5300 5H.OX5 54()0 5H.OX9 5500 5H.OY3 56()0 5H.097 5700 5X.IOI

5HOO 5X.104 5'X)0 5H.107 6(X)O 5X.1 II

PREVIOUS:

.000 212.021 23H.630 256.347 26'!.66H 2XO.301

2X8.H45

2X9.14H 303.404 314.761 324.266 332.465

339.6H2 346.12H 351.952 357.263 362.141

366.652 370.X45 374.763 37X.43H 3HI.X'!Y

3H5.16H 3HH.266 391.209 394,(>12 396.6HH

3Y9.247 4()1.700 4()4.054 4()6.3IH 4()X.497

410.59X 412.627 414.5H7 416.41\4 41H.322

420.104 421.H32 423.512 425.144 426.732

42X.278 429.7H4 431.252 432.6H5 434.0H)

435.44X 436.7X2 43H.OH6 43'!.362 44().61O

44I.X33 443.030 444.203 445.353 446.41\1

447.5X7 448.673 44'!.739 450.7H6 451.HI4

452.H24 453.HIH 454.7'!4

Bromine Oxide (BrOO)

INFINITE 435.344 3:'1:).YOH 303.261 2'!3.267 2HY.646

2HH.X45

2HH.H46 29:).7xl 294.479 2%.672 302.nx

3(f1.0XO 311.067 314.H69 318.4X5 321.n2

325.192 32lU05 331.273 334.107 336.X 17

339.414 3~1.'X)4 3<14.2% 3~6.597 34K.H 14

350.'!51 353.015 355.010 356.Y4() 35H.XIO

3t'O.622 3~2.3XO 3M.OHX 3~5.74X 30.362 3~X.934 370.464 371.,!56 373.411 374.X31

376.217 377.571 3iX.X,!5 3~0.IH'! 3~1.456

3~2.696 3~3.91O 3~5.0<J9 3~6.265 3~7.4()X

3~X.529 3~Y.630 3S0.7OY 3SI.76Y 3S2.XII

3S3.X34 3S4.X)'! 3S5.X2H 3S6.H(X) 3S7.756

3~H.697 3S'!.623 4(0.534

-12.X51 ' -11.166 -'!.22X -7'<)37 -4.720 -2.336

'(XX)

.090 5J)4'!

10.141 15.356 20.676

26.0H2 31.555 37'()H4 42.656 4X.263

53.H,!H 59.557 65.235 70.930 76.63X

H2.35H HX.OX7 93.X25 99.571

105323

III.OXI 116.X43 122.611 12X.3X2 134.156

\39.Y34 145.715 151.4'!X \ 57.2X3 I 63'()7 I

16X.X61 174.652 I HO.445 IH6.239 192.035

IY7.X32 203.630 209.430 215.230 221.031

226.H33 232.636 23H.440 244.244 250.04'!

255.X55 261.661 267.46X 273.276 279.0H3

2X4.Xn 290.700 2%.510 302.3 I'! 30H.129

313.939 31'!.750 325.561

116.017 115.YI)7 115.4>)<) 114.Y!1 114.555 114.073

10X.OX)

107.Y&6 92.714 n.YJ) I Y3.nn 93.2'13

93.4~5 93.671 93.Hil Y4.012 Y4.H4

94.316 Y4.471 Y4.6)S 94.717 94.X13

94.X)O '!4.Y16 Y4.YlY Y4.Y17 94.YS9

Y4.YZ3 94.X49 '!4.716 Y4.614 94.454

Y4.2S6 Y4.050 Y3.XW 93.543 '!3.254

92.944 92.614 92.257 9I.Y:)S YI.5ZH

YI.I3'! 90.740 'XU3I X9.Y15 X9.413

X9.OJS XX.633 xX.m H7.759 87.317

H6.X74 X6.4ZX X5.979 X5.5ZY H5.07S

X4.61H X4.157 H3.6n x3.220 X2.743

H2.25X X1.7S4 X 1.250

116.0H7 113.639 111.569 109.743 IOX.(161 106.4YI

105.736

105.722 IOH.119 111.949 115.741 11'!.4'!Y

123.230 I 26.Y36 130.623 134.292 137.946

14i.5H6 145.215 14H.X35 152.'446 156.051

159.651 163,247 166.X41 170.434 174.02H

177.622 IHI.219 IX4.H20 IXH.425 In.036

195.654 I <J9.27X 202.911 206.553 210.202

213.H61 217.531 221.20Y 224.X9Y 22X.5,!X

232.30H 236.02X 23'!.75Y 243.49Y 247.250

251.(>12 254.7X3 25x.563 262.354 266.154

269.964 273.7x4 277.612 2XI.449 2X·5.294

2XY.150 293.013 296.HX4 3()().766 304.654

30X.552 312.457 316.372

INFINITE -IIX.7IK

-5H.27H -3H.216 -2H.223 -22.250

- IX.524 -IK4()X -14.119 -11.695 -10.076 -H.'!17

-XJ)46 -7.367 -6.H23 -6.377 -6.(X)5

-5.6X9 -5.4IX -5.IX3 -4.Y77 -4.795

-4.633 -4.4XX -4.357 -4.23'! -4.132

-4.034 -3.944 -3.K62 -3.7X6 '-3.715

-3.650 -3.5x'! -3.533 -3.4l\O -3.431

-3.385 -3.342 -3.301 -3.263 -3.227

-3.193 -3.161 -3.131 -3.102 -3.075

-3.04Y -3.025 -3.001 -2.97'! -2.95X

-2.93X -2.YI'! -2.'!OO -2.XH3 -2.X66

-2.X50 -2.X34 -2.X20 -2.X05 -2.792

-2.77Y -2.766 --2.754

URRENT: Marcht <J96 (I bar

Br102(g)

z

r » z » "T1 -t :x: m :D 3: o o :x: m 3: o » r--t » OJ rm (J)

"T1 o :D -t :x: m CD :D o 3: Z m o X 6 m (J)

-" o co (11

~ "U ::l" '< !" () ::l" (1)

~ :0 ~ o Q)

Ju < ~ I\)

~Ol

z !' ~~

<0 <0 0'1

Bromine Oxide (Br03)

L1,,//,,(2<)X.I ~ K) = [625 ::+: 50] khll!)1 I

S"(29X.15 K) = [2X4.5 :+~ 2] 1 K 1'll101

Ideal Gas

';ta~~tl'trollic I.t.'vtl a~~ ~~arltum Weight

["Ad 0.0

Vibrational Fr~qul'ncies and Degeneracies v. em'"

[442J(I) [800)(1) [350J(2) [828](2)

g,

[2)

Mr = 127.9022

L1rI/O(O K) = [233 ± 50] kj'mol- I

Ll,II"(29X.15 K) = [221 ± 50] kJ'mol- 1

u=3 Point Bond Bond Product

= [1.68]A [89t of Inertia: IJ/uh' = 2198.7927 x 10- 117 g'cm"

Enthalpy of Formation We adopt an enthalpy of fomlation value ",hich is based on ,m assumed relationship of Ll.,II°(BrO."g)/3=0.9Dr,(BrO). An enthalpy of fomJation value (at 29& 15 KI has heen repo<1ed by Farkas and Klein.' This value, 23 keal'mol" , (96 kJ 'mol-'), was derived

from absorption spectra measurements of bromate ions in solutions. There is considerable uncertainty in this value, both in terms of the experimental measurements and the fact that the authors have interch;mged BrO., and BrO.l-' This corresponds to an average bond energy of 254 kJ'mol' '. In comparison Do(BrO) = 231 U'J11ol' '.

Heat Capacity and Entropy • The structure of this molecule is estimated to he pyramida, with a 0-8r-O angle of [89]" and a bond length of [1.68] A, in analogy with

the corresponding chlorine and iodine oxide molecules. Venkateswarlu and Sundaram.2 Venkateswarlu and Rajalakshmi;' Rao and SanthaIllma,4 Rao,5 and Thirugnanasamballdam anti Mohan" assumed the same slructure and bond ;mgle for CIO" BrO." and 10.,. Using Badgers' rule, the authors examined the relationship betwet.'11 the vibrational frequencies and force constants for the three pyramidal molecules - CIa." BrO.\, and 10,. Although these authors reft.'r to early meaSUffments of the vibrational frequencies, the values appear to be in part, those of the ion BrO,·'. The vibrational frequencies are derived frolll the force constants which describe the other halogen oxide molecules. The principal moments of int.'rtia (in g cm2

) arc: IA = 12.2156 X IO- w, In = 12.2156 x IO-'w, and Ie = 14.7352 X 1O-1~. • Byberg,7 in an EPR study, suggested the molecule had C" symmetry with a bond angle of 1120 and bond length of 1.57 A. In contrast,

Begum etal} in a radiolysis stltdy, suggested a bond length of 1140 with C.'v symmetry. In calculating atomic phase shifts, Lee and BeniY

calculated a bond length of 1.66 A in solution. In these cases, there is no definitive evidence as to the geometry. Values were suggested which would be consistent with experimental observations.

References 'L, Farkas and P. S. Klein, 1. Chem. Phys. 16(9), 886-93 (E>48). "K. Venkateswarlu and S. Sundaram, Proc. PLys. Soc. (London) A69. 180(1956). 'K. Venkateswarlu and K. V. Rajalakshmi, InJian J. Pure A)pl. Phys. I, 3~0 (1963). 4c. G. R. Rao and C. Santhamma, Current Sci. 33(22). 677 : 1964). 5c. G. R. Rao. Sci. Cull. 38( 12), 522 (1972). "P. Thirugnanasambandam and S. Mohan, Indian J. Phys. 51U(3), 173 (19'78). 71. R. Byberg, J. Chem. Phys. 83(3), 919 (1985). xA. Begum, S. Subramanuan, and M. C. R. Symons. J. Chem. Soc. 6, 918(1970).

Bromine oxide (Br03)

Enthalpy Reference Temperature = 1, = 2911.15 K ---.!·K-'01o\-' ___ _

TIK C: So -[Go-.'i"(T,)\fT

IN:'INITE 50 33.333 20<).520 nX.271

100 36.646 233.32<) B0.43X ISO 43.0XS 24\1.376 .HXJ.X50 200 49.535 262.667 1X<).6X4 250 55.2<)7 274..'154 lX5.471

29KI5 59.9<)9

300 <IOC) 500

1100 1200 130() 1400 1500

160n 170() IXOO I<J()() 2000

2100 220() 2300 24()() 250{)

2600 2700 2XOO 2<J()() 30()O

3100 3200 331)() 341)0 3500

360n 371)() 3HOO 3<)1X) 4()I)()

41')() 42'Xl OX) 44I)(}

451)()

4600 470() 4KIXl 4<)1)() 5(~X)

5100 521)() 531)() 54J)() 55')()

56JO 57'X) SiI')O 59'X) 6OX)

PREviOUS:

XO.377 XO.XOI X 1.\36 KI.4()4 X 1.623

KI.X03 X 1.'.153 X2.0XO X2.IX7 X2.27<)

X2.35X X2.42X K2.4KX X2.541 X2.5XX

X2.630 H2.667 X2.7{)() X2.730 X2.7S7

K2.7KI X2Ji04 X2.H24 X2.K43 XVi5<)

K2.X75 K2.KX<) K2.<)03 K2.915 X2.926

X2.937 X2.946 X2.956 X2.964 X 2.972

2X4.509

379.465 3X6.4n 392.<)59 39X.9X2 404.606

409.XXO 414.H44 41'.1.532 423.<)72 42X,190

432.207 436.04() 439.705 443.217 446.5X7

449.X27 452.'.147 455.954 4SX.X56 461.661

464.375 467.()(l4 469.552 472.1)25 474.427

476.761 479.032 4XI.243 4X3.396 4X5.496

Bromine oxide (Br03)

1K4.5O\J

1H4.S10 lX6.%5 19 Uil 5 197.452 303.263 30X.9<)5 )\4.S4t 31'}.X5X

324.\135 32<).775 334.3X9 J3x.79t 342.'.1'.13

347.010 350.X56 354.542 35X.OXO 361.4XI

)64.754 367.'.I0X 370.<)51 3D.KX<) 376.730

37<).4XO .1K2.143 3H4.726 3H7.232 3K<).667

)<)2.033 394.335 396.576 39K.75'.1 4()().XX7

4()2.%2 oI04.<)XK 4()6.'.I65 4(}K.X,}H ~1O.7x6

~12.634 ~14.441 ~16.21(J ~17.943 ~1<).641

~21.305 422.936 424.537 426.107 427.64X

42<).162 nO.64i1 B2.IO\l B3.544 B4.955

B6.343 B7.70X -139.052 -140.373 +41.675

Ir-lr(T,)

-13.101 --11.43X

-<).711 -7.721 -5.403 -2.779

.()()()

.tll 6.511

13.4X5

20.X27 2X.41 I 36.15<) 44.023 51.<)72

59.9X3 6X.043 76.140 X4.26X 92.420

1()().5,} I IOX.779 tI6.,}XI 125.1,}5 133.4IX

141.650 14,}.XX'.1 15X.135 166.3X7 174.643

IH2.'.I04 1<)1.I6'.1 1,}'.I.437 207.70'.1 215.'.IX3

224.260 232.53\1 24().X21 24'.1.104 257.3X\I

265.676 273.%4 2X2.254 2'.10.545 2'.1X.X37

307.130 315.424 323.71\1 332.015 34().312

34X.609 356.\lOX 365.207 373.506 3H I.X07

3<)0.107 3'.1X.4()'.1 4()6.710 415.ot3 423.315

431.61X 43'.1.n2 44H.226 456.530 464.X35

Br103(g)

Standard State Pressure = pO = 0.1 MPa "1·0101-' ____

ilrllO il,G° log Kr

233.000 233.!X)0 INFINITE 132.073 233.75<) -244.206 130.636 235.<)n - 123.26<) 229.279 23X.97 I -X3.217 22X.126 242.3XI -63.303 227.156 246.060 -51.411

220.X21 250.432 -43.X75

220.7XI 250.616 -43.636 205.4X3 263.72X -34.43<) 206.024 27X.233 -29.067

206.767 2n.607 -25.474 207.599 306.X49 -22.X<)7 20X.466 320.<)6<) -·20.<)57 209340 334.<)79 - 19.442 210.20X 34X.xn - IX.224

211.065 362.719 -t7.224 211.905 376.469 -16.3X7 212.72X 3<)0.14<) -15.676 213.530 403.767 -15.()65 214.311 417327 - 14.533

2t5.067 430.X37 -14.()65 2t5.7'}7 444.3(X) - 13.652 216.4<)X 457.721 - 13.2X3 217.16X 471.104 -12.<)52 2t7.X05 4X4.452 - 12.653

2IX.4()6 4<)7.770 -12.3XI 2 I X.\J7 I 511.060 -12.134 2 I <).4<),} 524.324 -II.<)OX 2t'.l.<)H7 537.566 -11.7(X) 220.436 550.7<)0 -11.50X

220.X46 563.'.1% -11.331 221.217 577.IX7 -11.166 221.551 5'.10.365 -11.013 221.X47 603.531 -10.X71 222.IOX 616.6XX -10.737

222336 62\1.X3X -10.613 222.532 642.<)7'.1 -10.4% 222.6<)X 656.115 - to.3X5 222.X37 66'.1.247 - 10.2H2 222.<)50 6X2.374 - IO.IX4

223.04() 695.500 - 1O.()91 223.1O,} 70X.622 - IO'(X)4 223.15X 721.745 -<).921 223.190 734.X65 -9.X42 223.207 747.9X4 -<).76X

223.20<) 761.104 -9.697 223.19<) 774.223 -9.62,} 223.17X 7X7.343 -'}.564 223.145 HOO.463 -<).503 223.104 X13.5H4 -''.1.444

223.053 X26.706 -'.I.3XX 222.\I'}4 X3<).X30 -9.334 222.926 X52.'.I55 -'.I.2X2 222.X4\1 X66.0H2 -'.1.233 222.764 X7<).210 -'}.IX5

222.670 xn.34() -<).139 222.565 '.105.471 -9.096 222.451 \I I X.606 -9.053 222.324 <)31.741 -9.013 222.IX5 ,}44.X79 -X.974

222.032 \l5x.022 - X.936 22t.X63 <)71.165 -x'900 221.67X '}X4.313 - X.X65 221.474 '.1'.17.462 -X.X31 221.250 1010.617 - H.7<)X

CURRENT: March 1996 (I bar

Br103(g)

-" o co 0)

3: » r-0 0 r-3:

:cE 0 ::I: » (JJ m

!'"0 :::T '< ~ o :::T (I)

~ :D

~ o ! -0)

< ~ I\)

Y' z ?

_.f:>. .... CD CD CJ)

Bromine Oxide (BrOBr) Ideal Gas Mr = 175.8074 Bromine oxide (BrOBr) Br201(g)

1::..,,11°(0 K) = JS~ ::':: 5 kJ'mol- 1

,\'°(298.15 K) = 290.8 ::':: 2 J K -I'moll

Electronic Level and Quantum Weight state E,; cm- I

XIA 0.0

Vibrational Frequencies and Degeneracies v, cm- I

526.1 (I) 180 (I) 623.4 (I)

Xi

I::..r1/0(0 K) = 124.1 ::':: 3.5 kJ'mol- 1

I::.. r1/0(298.15 K) = 107.6::':: 3.5 kJ·mol- 1

Point Group: C2v • <T = 2 Bond Distance: Br-O = 1.8429 A Bond Algie: Br-O-Br = 112.240 Product Df the Moments of Inertia: IA/sle= 10238.8:>84 X 10- 117 g.1cm6

Enthalpy of Formation Thorn et al.' u.,ing experimental results fromphotoionization efficiency spectrum of Br20 1

along with the ionization and appearance energy. have derived a value of the enthalpy of formation I::..rH (Br20, 0 K) = 124.1 ::':: 3.5 kJ 'mol- , which we adopt.

There are three other related studies leading to an enthalpy of formation. Orlando and Burkholder l mea~ured the equilibrium constant for the reaction: Br20+H20=2HOBr. They determined I::..,GO(298 K) = 9.70 kJ·mol- ' . Using the thermal functions present~d in this table and thermal functions for HOBr(g) given by JANAF,2 we calculatel::..rHO(Br20,g, 298.15) = 107.6::':: 3.5 kJ·mol- l

• This value supports our adopted value. Assuming that the values Dg(CIO) and ~,lr(OCIO,g) are reasonable, we would anti~ipate the ratio of the numbers (1.52) to apply for a similar relationship between BrO(g) and BrOBr(g). This would yield a value of 114 kJ'mol- 1 which is in good agreement with our adopted value. Using the estimation scheme of Novak4 (in part based on ab initio calculations and an extended basis set). the enthalpy of formation wa~ calculated tc be 83 ::':: 8 kJ'mol- 1 at 0 K

Heat Capacity and Entropy • Mueller and Cohen,S from the microw2ve spectra of three isotopomers of BrOBr(g), have determined '0 = 1.8429 A and

« BrOBr) = 112.24°, which we adopt. Supporti1g evidence was derived from bromine K-edge EXAFS study o(Levason et aZ.6 The structure of this molecule was bent with a Br-O-Br an~le of 112 ::':: 2° and the Br-O bond length was 1.85 ::':: 0.0 I A. The bond angle is in good agreement with the value derived from matrix IR studies7 where a value pf 1130 was estimated from isotope shifts. In comparison, Novak,4 with the aid of ab initio calculations, determined a bond length of 1.809 A and a bond angle of 115.7°. The principal moments of inertia (in g cm2) are: IA = 2.5488 X 10-.19, In'" 62.1189 X 1O-.1~, and Ie = 64.6677 X 10-.19•

111e recommended vibrational frequencies (VI, v~) are those su;gested by Jacox.R These remits are based on the infrared >pectra of the argon matrix isolated radical as studied by Tevault et ~l., Allen et al.s and Levason et al.6 A value of V2 = 197 em -I reported in the solid IR spectra study of Campbell et al. lO However, the Mueller and Cohen studr implied V2 = 180 cm- I

(::':: 5). Lee, II using ab hitio calculations -CCSD(T) - derhed vibrational frequencies (513, 180 and 613 cm- ) which are in reasonable agreeJ11ent with our adopted values. Similar calculations by Lee yielded a structure in a~re~ment with our recommendations (112.9° and 1.865 A).

All specific studies (condensed or matrix)" 12yielded values for VI and V3 which are in reasonable agreement. Although Tevault et al.9 stated that the values fer VI and v, reported by Campbell et al. lo are reversed, this does not affe,:t the thermal functions. •

Anthar and Dostrovskyl.1 measured the ultra,iolet absorption spectra of Br20 in eC14 • A strong absorption band was observed at 2800 A (35714 em-I). We assume this refers to the position of (he first excited electronic state. This state is not included in the calculations.

References IJ. J. Orlando and J. B. Burkholder, J. Phys. Chern. 99, 1143-50 (1995). 2JANAF Thermo:hemical Tables: HOBr(g), June 1995. 'R. P. Thorn Jr., P. S. Monks, L. J. Stief, S.-C. Kuo, Z. Zhang and R. B. Klemm, ~rookhaven National Laboratory, BNL #62126, Ilpp. ~ 1995); J. Phys. Chern. (1996, in press). I. Novak, Struct. Chem. 3(6), 377-9 (1992).

5H. S. P. Mueller lmd E. A. Cohen, submitted for publication in J. Phys. Chern. 6W. Levason, J. S. Ogden, M. D. Spicer, and N". A. Young, J. Am. Chern. Soc. 112, 1019 (1990). 7D. Allen. M. Poliakoff, and J. J. Turner, J. rvbl. Strnct. 157, I (1987). xM. E. Jacox. J. Phys. Chern. Ref. Data, Monograph No.3, 461 pp. (1994). ~p. E. Tevault, l\. Walker, R. R. Smardzewsk, and W. B. Fox, J. Phys. Chem. 82, 2733 (1978).

C. Campbell, J. P. M. Jones, and J. J. Turner, Chern. Commun. (15). 888 (1968). liT. J. Lee, J. Phys. Chern. 99, 15074-80 (1995). 12J. L. Pascal, A. C. Pavia, J. Potier, IUJd A Potier, Proc. Int. Conf. Raman Spectrosc. 5th (1976), No. 210447, 120-1 (pub. 1977).

Enthalpy Reference Temperature = T,= 298.15 K Standard State Pressure = pO = 0.1 MPa ----I·K-'mol-'____ kj·md-' ___ _

TIK. c: So -[Go-H'(T,»)rr HO-W(T,) 4 rH' .irG° log Kr

) .000 j) 34.529

HD 38.4l!O 15) 41.918 20') 45.264 25l> 4l\.(l75

29lU 5 50.168 30') 50.238 40) 53.068 S(X) 54.685 60) 55.664 70') 56.293 80') 56.717 90:) 57.016

1(0) 57.234 110') 57.397 120') 57.523 13m 57.621 14aJ 57.700 150') 57.763

160) 57.816 170') 57.859 18m 57.896 190') 57.927 2(0) 57.953 21m 57.976 22m 57.996 23m 58.014 24aJ 58.029 25m 58.042 260) 58.054 270') 58.065 280') 58.074 290') 58.0R3 3(0) 5R.091 310') 58.()98 32m 58.104 330') 58.110 340) StU 15 350') 58.120

360) 58.125 37m 58.129 380') 58.132 39O'J 58.136 4(0) 5KI39 410) 58.142 42()) 58.145 43()) 58.14l! 44aJ 5KI50 450') 58.152

460') 58.154 470) 58.156 48()) 58.158 49m 58.160 50()) 58.162 510) 58.163 520') 58.165 530) 58.166 540) 58.167 550) 58.169 560) 58.170 57fJ.l 58.171 58fJ.l 58.172 590) 58.173 6(0) 5t\.l74

PREVIOUS:

.000 217.773 242.978 259.228 271.753 282.16ll 290.823 291.133 306.013 318.044 328.108 336.739 344.285 350.984 357.003 362.466 367.466 372.074 376.347 380.330 384.060 387.566 390.875 394.006 396.978 399.806 402.503 405.082 407.551 409.920 412.197 414.388 416.500 418.538 420.507 422.412 424.257 426'()45 427.780 429.464 431.102 432.694 434.245 435.755 437.227 438.662 440.063 441.432 442.768 444.075 445.353 446.604 447.828 449.028 450.203 451.354 452.4l!4 453.592 454.679 455.746 456.794 457.824 458.836 459.830 460.80l!

Bromine oxide (BrOBr)

INFINITE 4,2.252 3>1.921 305.126 295.272 291.638 290.823 290.824 292.833 296.711 301.128 305.614 309.986 314.176 318.163 321.946 325.534 328.939 332.174 335.254 338.189 340.991 343.671 346.239 348.702 351.069 353.346 355.540 357.656 359.699 3&1.675 3&3.587 3&5.439 3&7.235 368.978 370.671 372.317 373.918 375.477 376.996 378.476 379.920 381.329 332.706 384.050 3&5.365 3&6.651 3&7.909 389.140 390.347 391.529 392.687 393.823 394.938 396.031 397.105 398.159 399.194 400.212 401.212 402.195 403.162 404.113 405.049 405.970

-12.399 -10.724 -8.894 -6.885 -4.704 -2.367

.000

.()93 5.272

10.667 16.188 21.788 27.440 33.127 38.840 44.572 50.318 56.076 61.842 67.615 73.394 79.178 84.966 90.757 96.551

102.347 I OIU 46 113.947 119.749 125.552 131.357 137.163 142.970 148.778 154.587 160.396 166.206 172.017 I 77J!28 183.640 189.452 195.265 201.078 206.891 212.705 218.519 224.334 230.14l! 235.963 241.778 247.593 253.409 259.225 265.041 270.857 276.673 282.4R9 2811.306 294.123 299.939 305.756 311.573 317.390 323.2011 329.025

124.100 124.:19 123.,59 122.,14 121.193 119.~1l5

107.048 107.:74 76.~1l7 76.061 77.183 77.417 77.64l! 77.b69 78.077 78.;71 78.451 78.616 78.:66 78.900 79.016 79.113 79.:89 79.142 79.;69 79.;69 79.139 79.79 79.087 78.963 7lU07 78.61B 78.400 78.152 77.!77 77.!77 77.154 76.912 76.J54 76 .. 81 75.'9B 75.407 75.011 74.612 74.114

73.818 73.427 73.042 72.666 72.199 7l.944 71.600 71.170 70,953 70.650 70.,62 70.08H 69.!29 69.!83 69.,52 69.134 6X.930 68.:311 68.:57 68.;88

t24.100 118.511 113.112 108.209 103.675 99.433 96.902 96.835 99.594

105.277 110.920 116.524 122.095 127.637 133.156 138.654 144.135 149.602 155.057 160.501 165.938 171.367 176.791 182.212 187.631 193.049 198.468 203.889 209.313 214.741 220.175 225.616 231.064 236.521 241.986 247.462 252.947 258.442 263.949 269.465 274.994 280.532 286.081 29.1.641 297.211 302.791 308.380 313.979 319.5116 325.202 330.826 336.458 342.097 347.743 353.395 359.053 364.715 370.384 376.057 381.734 387.416 393.102 398.791 404.4l!2 410.178

INFINITE -123.808 -59.083 -37.682 -27.077 -20.775 -16.977 -16.861 -13.006 -10.998 -9.656 -8.695 -7.972 -7.408 -6.955 -6.584 -6.274 -6.011 -5.785 -5.589 -5.417 -5.265 -5.130 -5.009 -4.900 -4.802 -4.712 -4.630 -4.556 -4.4l!7 -4.423 -4.365 -4.311 -4.260 -4.213 -4.170 -4.129 -4.091 -4.055 -4.022 -3.990 -3.960 -3.932 -3.906 -3.881 -3.1158 -3.835 -3.814 -3.794 -3.775 -3.757 -3.739 -3.723 -3.707 -3.692 -3.677 -3.664 -3.650 -3.638 -3.625 -3.614 -3.602 -3.591 -3.581 -3.571

RRENT: March 1996 (I bar

Br201(g)

z en L » z » -n -i ::I: m :0 s:: o (') ::I: m s:: (; » r--i » CD rm (J)

-n o :0 -i ::I: m CD :0 o 3: Z m o >< 6 m (J)

..... o <0 .......

!="'0 :::r '< ~ o :::r (1)

~ JJ ~ o OJ

iii < ~ I\)

.!JI z ?

_.f:>.

<0 <0 en

Bromine Oxide (BrBrO)

.'1'''(2<)8.15 K)= [312.7 -~ 21 J K '-mol I

Ideal Gas

El<:ctrDnic L('wl and Quantum Weight state E" Clll '

[ 'A") 0.0

Vibrational Frequencies and Degeneracies v, cm- I

804 (I) [ISO] () 236 (l)

Point Group: C Br-Br = [2.SI] A.

K,

[3]

Mr = 175.8074

D.,/nO K) = [183.7 ::!: 20] kJ'mol- 1

D.rl/"(298.IS K) = [168::!: 20) kJ'mol-'

(T= I Bond Distances: Br-C = Bond Angle: Br--Br-C =

Product of the Momerts 1~/PJc= [13784.9110 X 10- 117] g'cmh

Enthalpy of Formation 1'01' the four halogcn oxide species. XXO(g'

detcmlined tilt' cnthalpies of formation of mary isodcsmic rcaction energies. The calculated results 2()S.IS K.

Br, I, there is no experimental data related to the enthalpy of formation. Lee I compounds using a combination of theoretical isomeric

i homodesmic and

BrBrO is less stable than BrOBr by 14.6 kcal'mol- (61.1 kJ·mol) at

I1eat Capacity and Entropy 0

Lee.' using ah initio calculations - CCSD(T> - derived a bond angle of 113.10 and bond distances r(Br-Br) = 2.510 A and r(Br-O) = 1.690 A. which we a<lnpl. The principal moments cf inenia(in g crn2

) are: IA = L.7079 X 10-3~, III = SI.8084 X IO- w, and Ie = S6.S163 X 10-.19. The 1'l'col1lmentkd vi hrat ional f requenc ies are those sugge~ted by Jacox.2 These results are based on the infrared spectra of the arlion matrix

isolated radical as studied by Tevault ('[ al.' L2 is estimated lased on comparisons of the vibrational frequencies with CIOO. Lee, using ab initio calculations. derived the vihrational fre1luencies to be 793. IS3 and 115 cm- I

. These are in excellent agreement with our recommendations.

Tevault ('[ al. ' observed very intense bands at 804 nm light. The assignments for BrBrO were aswlIled to bending mode) was expected 10 be below 201) elll--

I.

References

em - I which appeared when Ar-BrrO, matrices were photolyzed with 632.8 VI = 804 cm- I (Er-O stretch). v, = 236 cm- I (Br-Br stretch) and the V2 value (the

'T, J. Lee. J, I'hys. Chern. 99. IS074-RO (19QS). 2M. E. Jacox. J. Phys. Chern. Ref. Data. MOllograph No. 3.461 pp. (1994). 'D. E. Tevalill. N. Walker. R. R. Smardzews(i, and W. B. :ox. J. Phys. Chern. 82. 2733 (1978).

Bromine oxide (BrBrO) Br201(g)

Enthalpy Reference Temperature = r, = 298.15 K Standard Slate Pressure = pO = 0.1 MPa ---l·K-'mol-'____ kJ·mol- I ___ _

TfK C; So -[Go-fr(T,))fT W-W(T,) tl.rW tl.rG° log Kr

o 5()

I{)()

150 ,{)O ,SO

29U5 5J.3X5 ~oo 51.433 £()O 53.530 :00 54.X6X (()O 55.735 ~oo 56.316 W() 56.719 \{)() 57.()()X

Il()() 57.222

PREvIOUS:

312.704

384.677 389.676 394.2H3 39H.555 4{)2.537

422.01() 424.707 427.285 429.754 432.123

444.614 446.459 44H.246 449.981 451.666 453.303 454.896 456.446 457.956 459.428

460.863 462.264 463.632 464.<)69 466.276

473.555 474.6K4 475.792 476.8KO 477.947

Bromine oxide (BrBrO)

I1>FINITE 463.229 356.090 327.647 317.312 313.543 312.704 312.705 314.750 318.676

323.132 327.647 332'()4t 336.249 340.250 344.044 347.642 351.054 354.297 357.381 360.32t 363.128 365.812 36083 370.849 373.219 375.498 377.694 379.812 381.858 383.X35 385.749 387.602 389.400 391.144 392.838 394.485 396.088 397.647 399.t67 400.648 402.093 403.503 404.880 406.225 407.540 408.827 410.085 411.318 412.524 413.707 414.866 416.()o2 417.117 418.21t

419.285 420.34{) 421.376 422.393 423.394

424.377 425.345 426.296 427.232 42H.154

-13.hx -11.447 -9.479 -7.259 -4.899 -2.442

.()()O

.095 5.351

10.776

16.309 21.913 27.566 33.253 38.965 44.696 50.441 56.197 61.962 67.734

73.512 79.295 85.081 90.872 96.665

102.461 108.259 I t4.059 119.860 125.663 131.467 137.273 143.079 148.887 154.695 160.504 166.314 172.124 177.935 183.747

IX9.559 195.371 201.184 206.997 212.811 218.624 224.438 230.253 236.06X 241.883 247.698 253.513 259.329 265.144 270.960 276.776 282.593 2X8.4{)9 294.226 3(XJ.042

305.859 311.676 317.493 323.310 329.127

IX3.713 183.7 JJ INFINITE IK3.8~ 177.315 - 185.239 183.126 17U)47 -89.346 182.292 165.183 -57.522 181.349 159.619 -41.68X 180.262 154.309 -32.241 16X.O()O 150.730 -26.407

167.928 150.623 -26.226 137.218 151.179 -19.742 137.422 154.646 -16.156

137.656 15X,069 -t3.76t 137.895 161.453 -12.0~ 138.127 164.802 -10.760 138.347 168.123 -9.758 138.554 171.420 -8.954

138.747 174.698 -x'296 138.925 177.958 -7.746 I 39'()89 18J.204 -7.281 I 39.23X 184.438 -6.881 139.371 187.662 -6.535

139.~6 190.877 -6.231 139.582 194.086 -5.964 139.657 197.290 -5.725 139.708 2()().490 -5.512 139.735 203.6X9 -5.320

139.734 206.886 -5.146 139.704 210.085 -4.988 139.643 213.285 -4.844 139.550 216.~8 -4.712 139.426 219.697 -4.590

139.269 222.910 -4.478 139.080 226.131 -4.375 138.861 229.359 -4.279 138.613 232.595 -4.189 138.337 235.841 -4.106 t38'()37 239.096 -4.029 137.714 242.361 -3.956 137.372 245.636 -3.8XX 137.013 248.922 -3.824 136.640 252.219 -3.764 136.256 255.527 -3.708 135.865 258.845 -3.654 135.469 262.175 -3.604 135.070 265.514 -3.556 134.671 268.864 -3.511 134.275 272.224 -3.468 133.884 275.593 -3.427 133.499 278.972 -3.389 133.122 282.359 -3.352 132.756 285.755 -3.317 132.400 2X9.15X -3.283 132.056 292.570 -3.252 131.726 295.989 -3.221 131.4{)9 299.415 -3.192 131.106 302.846 -3.164 130.817 306.284 -3.137 130.543 309.727 -3.111 130.284 313.176 -3'c)87 130'()38 316.629 -3.063 129.807 320.086 -3.04{)

129.589 323.548 -3.018 129.384 327.013 -2.997 129.192 33(J.~2 -2.976 129.oJ2 333.954 -2.957 I 28){42 337.429 -2.938

CURRENT: March 1996 (l bar

Br201(g)

..... o <0 OJ

s: » I (') 0 I s: ~ (') ::I » C/I m


7. Conclusions

Of the bromine oxides mentioned in the literature, only

nine have been prepared (as a single crystal, or in the gas phase, or a matrix) and (at least, partially) characterized:

BrO, BrBrO, BrOBr, OBrO, BrOO, Br203, 02BrBr02' 02BrOBrO, and Br20S' Only early studies exist which men

tion Br206 and Br207; it would appear that these species do not exist. Br93 and Br04 are proposed as intermediates in solutions or crystalline environments, with only an absorp

tion maximum as a characterization. Early references to Br30g are undoubtedly incorrect. Dif

ficulties in the experimental determination of the true identity and composition of the solid oxides caused difficulty for all the condensed bromine oxides in the period before 1970.

Recent references to this oxide are also incorrect in the sense that they should have been indexed to the monoxide-BrO. Thus, at this time, there is considerable uncertainly as to the existence of this compound. Finally, even recent evidence suggests that the characterization of the various isomers of

Br204 may not be correct. In the following table, a summary of the recommended

thermodynamic properties at ambient conditions for six bromine oxides are given. The brackets indicate estimated values. The recommended values contain significant uncertainties. In all cases, experimental enthalpy of formation data are

needed. However, due to its importance in atmospheric

chemistry, the prime effort should be directed at determining experimentally the enthalpy of formation of OBrO(g). Further eUorts should be dIrected towards confirmmg the disso

ciation energy of BrO and the enthalpy of formation of BrO

Br(g), and establishing the enthalpies of formation for BrOO{g), BrDrO(g) and Br03(g). Por any of the polyatomic

gaseous species, except BrOBr, spectroscopic measurements

for the geometry and vibrational frequencies would greatly reduce the uncertainties in the resulting thermal functions.

Confirmation as to the existence of the various condensed

phases is needed, although this is a much lower priority.

Heat capacity and enthalpy are not necessary at this time. (See Table 7.1.)

TABLE 7.1. Thennodynamic Properties of the Bromine Oxides.

OK 298.15 K

AfHo AfHo Apo CO p

SO

Compound kJ mol- 1 J mol- 1 K- 1

BrO(g) 133.3±2,4 125.8±2,4 109.6 34.2 232.97±0.1

OBrO(g) [161.5±25] [152.0±25] [155.0] 45.4 271.1±2

BrOO(g) [116.1±40] [108.0±40] [105.7] [48.9] [288.8±3]

Br03(g) [233±50] [221±50] [250,4] [60] [284.5±2]

BrOBr(g) 124.1±3.5 107.6±3.5 96.9 50.2 290.8±2

BrBrO(g) [183.7±20] [168±20] [150.7] [51.4] [312.7±2]

8. Acknowledgments

This work was undertaken as part of a larger study to provide NIST -JANAF Thermochemical Tables for as many halogen oxide species as possible. This particular study for the bromine oxides was supported by the Standard Reference Data Program at the U.S. National Institute of Standards and Technology. The author is particularly grateful for the help of Sabina erisen who confirmed the completeness of the annotated bibliographies, created the numerous tables which

summarize the reported experimental studies, and obtained

copies of the pertinent articles. In addition to the anonymous

reviewers of this article, the contribution of Stanley Abramowitz in discussions on the spectroscopic properties of

the triatomic molecules is greatly appreciated; Edward A.

Cohen (JPL) for providing data prior to publication and for n:vh::wing puniuw; u[ lhis anick; Hulger Mueller (JPL) [or

reviewing portion~ .. of this . article; Cl:nd R. B. Klemm

(Brookhaven National Lab) for information pertaining to the enthalpy of formation of BrzO as well as reviewing this ar~

ticle. The BrO calculations were performed by David Neu

mann.



9. References-Annotated Bibliographies

The following articles are a combination of all references dealing with the bromine oxides. Where possible, we have tried to include all authors, title, journal, a citation to Chemical Abstracts, and an annotation indicating the type of study. In general, dissertations (especially non-US) have not been obtained and read.

28LEW/SCH B. Lewis and H.-J. Schumacher, "The existence of an oxide of bromine," Z. Phys. Chern., Abt. A 138, 462 (1928); CA 23 3416(7); preparation.

29LEW/SCH B. Lewis and H.-J. Schumacher, "Preparation and properties of a bromine oxide," Z. Anorg. Allgem. Chern. 182, 182-6 (1929); CA 23 5426(3); preparation, decomposition.

29LEW/SCH2 B. Lewis and H.-J. Schumacher, "Thermal reaction between bromine and ozone," Z. Elektrochem. 35, 64~-52 (1929); CA 24 2033(8); preparation.

30BRA W. C. Bray, "An oxide of iodine, 12°2 , An intermediate compound," J. Am. Chern. Soc. 52, 3580-6 (1930); CA 24 5654; in aqueous solution.

30LEW/SCH B. Lewis and H.-J. Schumacher, "A first order solid phase reaction," Nature 125, 129 (1930); CA 24 2033(8); kinetics.

30ZINIRIE E. Zintl and G. Rienacker, "Existence of a volatile bromine oxide," Ber. 63B, 1098-1104 (1930); CA 24 5249(3); preparation.

31LEWIFEI B. Lewis and W. Feitknecht, "The kinetics of gas explosions: the thermal decomposition of ozone sensitized by bromine vapor," J. Am. Chern. Soc. 53, 2910-34 (1931); decomposition of ozone.

31SPI J. W. T. Spinks, "Photosensitized decomposition of ozone by bromine," Nature 128, 548 (1931); decomposition of ozone.

34BRA 0. L. Brady, "Recent advances in science: general and organic chemistry," Sci. Prog. 29, 101-9 (1934); CA 28 6598(8); review.

34SKR A. Skrabal, "Reactions of alkaline halogen bleaches [hypohalites]," Z. Elektrochem. Angew. Phys. Chern. 40, 232-46 (1934); CA 28 4997(1); re-examination of available data in aqueous solution.

35BREISCH W. Brenschede and H. J. Schumacher, "Bromine oxide, Br20," Z. Phys. Chern. B29, 356-8 (1935); CA 30 37(3); preparation, decomposition.

36BRE/SCH W. Brenschede and H. J. Schumacher, "The preparation and a few properties of bromine oxide of the formula Br~O," Z. Anorg. Allgem. Chern. 226, 370-84 (1936); CA 30 4419(7); preparation. properties.

36RABIWOO E. Rabinowitch and W. C. Wood, "Kinetics of recombination of bromine atoms. II," Trans. Faraday Soc . .52, YU} -l/ (iY36); LA :;U )~62(l.); dISSOCIatiOn of Br2 in the presence of O2 .

37SCH/SCH R. Schwarz and M. Schmeisser, "A new oxide of bromine of the formula Br02' I," Ber. 70B, 1163-6 (1937); CA 31 6125(6); formation, decomposition.

37V Al W. M. Vaidya, "Flame spectra of some aliphatic halides. I. Methyl iodide." Proc. Indian Acad. Sci. 6A, 122-8 (1937); CA 32 50(8); spectra.

38SCHI\VIE R. Schwarz and H. Wiele. "The bromine oxide. Br}O," Naturwissenschaften 26. 742 ([938): CA 33 2430(9); preparation.

38VAI W. M. Vaidya, "Flame spectra of some aliphatic halides. II. Ethylbromide," Proc. Indian Acad. Sci. 7a, 321-6 (1938); CA 32 6550(7); spectra.


39SCHIJAB P. W. Schenk and H. Jablonowski, "Reactions between atoms at low temperatures," Z. Anorg. Allgem. Chern. 244, 397 (1940); Z. Elektrochem. 45, 650 (1939); preparation.

39SCHlWIE R. Schwarz and H. Wiele, "The bromine oxides. II," J. Prakt. Chern. 152(2), 157-76 (1939); CA 33 4541(5); formation.

40MUN/SPI R. Mungen and J. W. T. Spinks, "The bromine sensitized photodecomposition of ozone," Can. J. Res. 18B, 363-71 (1940); CA 35 692(6); formation.

47COLIGAY E. H. Coleman and A. G. Gaydon, "The radicals BrO and CBr in flames," Discussions Faraday Soc. (2), 166-9 (1947); CA 43 5312g; spectra, dissociation energy.

47KHAIBOL M. Kharasch, P. B. Bolen, and W. HUrry, "Formation of quinone by the action of bromine oxide on benzene," J. Am. Chern. Soc. 69, 2566 (1947); CA 42 146f; reaction with benzene, toluene, and cyclohexane.

47PRA A. H. Pratt, "Esterification of cellulose," U.S. 2,429,644 (1947); CA 42 P3178h; dehydration of HBr03 to Br205' catalyst in celluluse:: e::sle::rtflcaliull.

48FARlKLE L. Farkas and F. S. Klein, "On the photochemistry of some ions in solution," J. Chem. Phys. 16(9), 886-93 (1948); CA 50 16345h; enthalpy of formation.

48GA Y A. G. Gaydon, Spectroscopy and Combustion Theory, 2nd ed. (Chapman and Hall, London, 1948), p. 92; review, dissociation energy.

50BREIBRO L. Brewer, L. A. Bromley, P. W. Gilles, and N. L. Lofgren, "Paper 6: The thermodynamic properties of the halides," National Nuclear Energy Series 19B, edited by L. L. Quill (McGraw-Hill, New York, 1950); dissociation energy.

50RER G. Herzberg, Molecular Spectra and Molecular Structure. /. Spectra of Diatomic Molecules, 2nd ed. (Van Nostrand, Princeton, 1950); spectroscopy.

51ABE E. Abel, "Halate formation," Monatsh. Chern. 82, 751-4 (1951); CA 46 3890g; intermediate in aqueous solution (does not specifically mention Br202)'

51PFLISCH A. Pflugmacher, R. Schwarz, and H. J. Rabbin, "Oxides of bromine. III. The heat of formation of bromine dioxide," Z. Anorg. Allgem. Chem~264, 204-8 (1951); CA 47 6752i; enthalpy of formation.

52EDW 1. 0. Edwards, "Rate laws and mechanisms of oxyanion reactions with bases," Chern. Rev. 50, 455--82 (1952); CA 46 8482f; in aqueous solution, review.

53BRE L. Brewer, "The thermodynamic properties of the oxides and their vaporization processes," Chem. Rev. 52, 1-66 (1953); review, dissociation energy.

53GA Y A. G. Gaydon, Dissociation Energies and Spectra of Diatomic Molecules, 2nd ed. (Chapman and Hall, London, 1953); dissociation energy.

53KAN N. P. Kanyaev, "Bromination of unsaturated compounds. III. Reaction of addition of hypobromous acid to allytrimethyammonium perchlorate," Sbomik Statei Obshchei Khim. 2, 1172-7 (1953); CA 49 5087f; formation, bromination with HBrO.

53PFL A. Pflugmacher, "Bromine oxides. IV. Trinitrobromo dioxide," Z. Anorg. Allgem. Chem. 273,41-7 (1953); CA 48 489f; compound with N02 , questions if the compound is not Br206 .

54ANTIDOS M. Anthar and 1. Dostrovsky, "Ultraviolet absorption spectra of some organic hypohalites," J. Chern. Soc. 1105-8 (1954); CA 48 6827h; spectrum in CC14 .

54COT T. L. Cottrell, The Strengths of Chemical Bonds (B utterworths, London, 1954), pp. 221-81; estimated bond dissociation energy.

55PFL A. Pftugmacher, "About bromine trioxide." Angew. Chem. 67, 524 (1955); discussion of reaction scheme.

55PFLIRAB A. Pftugmacher, H. J. Rabben, and H. Dahmen, "Bromine oxides. V. Bromine trioxide," Z. Anorg. Allgem. Chem. 279, 313-20 (1955); CA 49 14550f; preparation, properties.

56VEN/SUN

57RAM

C;7ST1VCHT

58ARV/AYM

58BRE

58DURIRAM

58MCGINOR

58SIG

58ZEE

58ARV/AYM

58PFL

59SCH/JOE

59SCH

60BRI/MAT

60GEO

60MATIDOR

61GUE/GOC


K. Venkateswarlu and S. Sundaram, "Evaluatio~ of force constants from Raman effect data: molecules, radIcals, and groups of pyramidal XY3 type," Proc. Phys. Soc. (London) A 69, 180-3 (1956); CA 50 16345h; vibrational frequencies. . D. A. Ramsay, "Electronic spectra of polyatomlc free

radicals." Ann. NY Acad. Sci. 67,485-98 (1957); CA 51 16094a; review of electronic spectra, only passing reference to BrO (no data). R L. Strong, I. C. W. Chien, P. E. Graf, and J. E. Willard,

"Studies of iodine atom and bromine atom recombination

following flash photolysis of gaseous 12 and Br2 , " J. Chern. Phys.26, 1287-95 (1957); CA 51 13580d. A. J. Arvia, P. J. Aymonino and H.-J. Schumacher. "Formation of solid oxides of bromine in the thermal

reaction between bromine and ozone," Anales Asoc. Quim.

Arg. 46, 55-65 (1958); CA 52 18048i; refer to CA 53

7849c; formation from Br and 0 3 •

L. Brewer, "Dissociation energies of gaseous oxides," UCRL 8356, 4 pp. (1958); critical evaluation of

dissociation energy. R. A. Durie and D. A. Ramsay, "Absorption spectra of the halogen monoxides," Can. 1. Phys. 36, 35-53 (1958); CA 52 4315b; absorption spectra; rotational and vibrational analysis, dissociation energy. W. D. McGrath and R. G. W. Norrish, "The study of energy transfer und energy distribution in fast chemical reaction by flash photolysis and kinetic spectroscopy," Z.

Phys. Chern. (Frankfurt) 15,245-61 (1958); CA 52 11591f; dissociation energy. J. Sigalla. "Reduction of bromates hy halide~ ::lnci th~

mechanism of oxidation-reduction reactions," 1. chim.

phys. 55, 758-67 (1958); CA 53 7851a; in aqueous solution

(Br20 2· HP)· A. P. Zeelenberg, "Absorption spectrum of the OBr radical," Nature 181,42 (1958); CA 52 10717c; absorption spectrum. A. J. Arvia, P. J. Aymonino, and H. J. Schumacher, "Formation of solid oxides of bromine in the thermal reaction between bromine and ozone," Anales Asoc. Quim.

Arg. 46. 55-65 (I958); Z. Anorg. Allgem. Chern. 298, 1-8 (1959); CA 53 7849c; solid formation from bromine and ozone. A. PRugmacher, "Formation of solid oxides of bromine in

the thermal reaction between bromine and ozone," Z.

Anorg. Allgem. Chern. 298, 9-10 (1959); CA 53 784ge; response to Arvia et al. M. Schmeisser and K. Joerger. "Reactions with !WonI'

solutions. I. Synthesis of Br02 ," Angew. Chern. 71. 523-4 (1959); CA 54 5315e: preparation from Br,:? and ozone in CFCI, solutions. H. J. -Schumacher. "Formation of solid oxides of bromine

in the thermal reaction between bromine and ozone," Z.

Anorg. Allgem. Chern. 298. 11 (1959): CA 53 7849f: response to Pflugmacher. N. K. Bridge and M. S. Matheson, "The flash photolysis of hal ate and~ other ions in solution:' J. Phys. Chern. 64. 1280-5 (I960): CA 55 7006e: formation in hypobromate solutions.

1. W. Geor2:e. "Halides and oxyhalides of the elements of groups Vb~ and Vlb," Progr. Inorg. Chern. 2, 33-107

(1960): CA 57 10507c: review.

M. S. tvlatheson and L. M. Dorfman. "Detection of short-li\'ed transients in radiation chemistry," 1. Chem. Phvs.32. 1870-1 (960): CA 55 1150c: pulse radi()ly~i, H. Guenebaut and P. Goudmand. "Molecular

spectroscopY--Dn the excitation in shock wave. of a

resulting Q.aseous mixture of the action of H2S04 on

KBr03:- Compt. Rend. 253. 1926-8 (1961): CA 56

15056c: shock wave. formation.

62BOY/GRA

62GUEIPAN

62SVE

63BURINOR

63SCH

63SCHIBRA

63VENIRAJ

64RAO/SAN

64TREIYAA

65GLUIMED

66BUXIDAI

66CAM

66CARILEV

66CHAIBOY

66SPRIPIM

66VED/GUR

67CAR

67CAR/LEV

G. E. Boyd, E. W. Graham, and Q. V. Larsan, "Recoil reactions with high intensity slow neutron sources. IV. Radiolysis of crystal alkali metal bromates with {'-rays," 1. ,Phys.Chem. 66, 300'--7 (1962); CA 57 313h; radiolysis. H. Guenbaut, G. Pannetier, and P. Goudmand, "Excitation

of gases or gas mixtures in a shock tube," Bull. Soc. Chim. France 1962, 80-6 (1962); CA 57 1753a; formation in reaction of H2S04 and KBr03 induced by shock waves.

R. A. Svehla, "Estimated viscosities and thermal conductivities of gases at high temperatures," NASA Tech.

Rep. R132, 140 pp. (1962); CA 57 79c; thermal conductivity, viscosity.

G. Bums and R. G. W. Norrish, "Mechanism of the formation of halogen monoxides during flash photolysis

of halogen + oxygen mixtures," Proc. R. Soc.

(London) A 271, 289-95 (I963); CA 58 4076d; flash photolysis.

C. J. Schexnayder Jr., "Tabulated values of bond dissociation energies, ionization potentials and electron affinities for some molecules found in high-temperature chemical reactions," NASA Tech. Note D-179I. 62 pp.

(1963); dissociation energies. M. Schmeisser and K. Brandle, "Oxides and oxyfluorides

of the halogens," Adv. Inorg. Chern. Radiochem. 5, 41-89 (1963); CA 60 7657b; review. K. Venkateswarlu and K. V. Raj::llak~hmL "Tlrf'y-Rrnrlley force field and thermodynamic properties: pyramidal XY3 type molecules," Indian 1. Pure App!. Phys. 1, 380-2 (1963); CA 60 4823e; vibrations.

C. G. Rama Rao and C. Santhamma, "The mean square amplitudes of vibration in Br03, 103 , and SiBr3 ," Current Sci. 33(22), 677-8 (1964); CA 62 6001e; molecular vibrations.

A. Trei~in and M. Yaacobi, "The electronic spectra of the hal ate ions in solution," 1. Phys. Chern. 68, 2487-92 (1964); CA 61 10192e; rejection of Matheson et al. (1960) data.

V. P. Glushko and V. A. Medvedev, "Thermal Constants of Substances," Volume I (145 pp.), Academy of Sciences, Moscow (1965).

G. V. Buxton, F. S. Dainton, and F. Wilkerson, "The BrO

radical in aqueous solution," Chern. Commun. (l I). 320-1 (1966); CA 65 8231 a: formation and reaction.~ in prl'<;pnce of ultraviolet light.

C. CaIY!pbell, "Spectroscopic studies of bromine oxides,"

Ph.D. thesis, Cambridge, England (1966); full citation is not

available at this time. A. Carrington and D. H. Levy, "Electron resonance studies of free radicals in the gas phase. Detection of ClO, BrO.

and NS," J. Chern. Phys. 44(3), 1298-9 (1966); CA 64 15218a; magnetic resonance absorption. ESR of BrO.

1. W. Chase and G. E. Boyd. "Radiolysis of the crystal alkaline earth bromates by cobalt-60 {'-rays," J. Phys.

Chern. 70. 1031-6 (1966): proposed formation of BrOc . R. D. Spratley and G. C. Pimentel. "The [p-IT*J{}' and [sIT*]{}' bonds. FNO and 02F2'" 1. Am. Chem. Soc. 88. 2394-7 (1966); CA 65 3106b; structure,

V. I. Vedeneyev. L. V. Gurvich, V. N. Kondrafyev, V. A. Mf'civf'cif'v, and Yeo L. Frankevich, Bond Energies,

/oni:.;ation Potentials, and Electronic Affinities (Edward Arnold. London, 1966). p. 33 (English translation of Russian 1962 publication)~ dissociation energy, review. A. Carrington, "Electron resonance of .gaseous free radicals," Proc. R. Soc. London, Ser. A 302(1470). 291-304 (J 967): CA 68 109411 q: ESR. A. Carrington and D. H. Levy, . 'Electron resonance of free

radicals in the gas phase." 1. Phys. Chem. 71 (j), 2-11. discussion 11-12 (1967)~ CA 67 69326m: EPR.



67CARlLEV2 A. Carrington, D. H. Levy, and T. A. Miller, "Stark effect in gas-phase electron resonance. The dipole moments of CIO, BrO, SH, and III SO," J. Chern. Phys. 47(10), 3801-9 (1967); CA 68 34133q;EPR, dipole moment.

67CARlLEV3 A. Carrington, D. H. Levy, and T. A. Miller, "Double quantum transitions in gas-phase electron resonance," J. Chern. Phys. 47(11), 4859-60 (1967); CA 68 64047q; EPR.

67~ARlLEV4 A. Carrington, D. H. Levy, and T. A. Miller, "Stark-modulated gas phase electron resonance cavity," Rev. Sci. Instrum. 38(8), 1183-4 (1967); CA 68 64426e; EPR.

68BUXIDAI G. V. Buxton and F. S. Dainton, "The radiolysis of aqueous solutions of oxybromine compounds: the spectra and reactions of BrO and Br02 , " Proc. R. Soc. London, Ser. A 304(1479), 427-39 (1968); CA 68 110274d; radiolysis, formation, BrZ02 as an intermediate.

68CAM/JON C. Campbell, J. P. M. Jones, and 1. J. Turner, "Spectroscopic studies of bromine oxides: the infrared spectrum of solid bromine monoxide," Chern. Commun. (15), 888-9 (1968); CA 69 81958t; force constants, IR spectrum, structure, also for Br21s0.

68EDW/GRE J. O. Edwards, E. F. Greene and J. Ross, "From stoichiometry and rate law to mechanism," J. Chern. Educ. 45, 381-5 (1968); CA 69 24473g; proposed structure (BrBr02), aqueous solutions, review.

68GA Y A. G. Gaydon, DissociaTion energies and spectra Of

diatomic molecules, 3rd ed. (Chapman and Hall, London, 1968), p. 265; review, dissociation energy.

68WAGIEV A D. D. Wagman, W. H. Evans, V. B. Parker, R. H. Schumm, I. Halow, and S. M. Bailey, "Selected values of chemical thermodynamic properties. Part 1. Tables for the first 23 elements in the standard order of arrangement," NBS-TN7270-3, 31 (1968); enthalpy of formation reported.

69AMUCZA O. Amichai, G. Czapaki, and A. Treinin, "Flash photolysis of the oxybromine anions," Isr. J. Chern. 7(3), 351-9 (1969); CA 71 I 18332d; formation in photolysis of bromate and bromite.

69BARIGIL F. Barat, L. Gilles, B. Hickel, and J. Sutton, "Flash photolysis of aqueous solutions of halate ions," 1. Chern. Soc. D (24), 1485 (1969); CA 72 61336x; formation in flash photolysis of aqueous bromate.

69BRE/ROS L. Brewer and G. M. Rosenblatt, "Dissociation energies and free energy functions of gaseous monoxides," Adv. High Temp. Chern. 2, 1-33 (1969); review.

69CAR A. Carrington, "Electron resonance of gaseous diatomic molecules. Magnetic and electric interactions in zil states," Proc. Colloq. AMPERE (At. Mol. Etud. RadiO Elec. lY6!:l)

15, 23-41 (pub. 1969); CA 71 l30594y; EPR. 69IP/BUR 1. K. K. lp and G. Bums, "Recombination of Br atoms by

flash photolysis over a wide temperature range. II. Br2 in Ht:. Nt:. Ar. Kr. N2 . ami O 2 ,'' J. ChclII. Phy~. 51, 3414-24

(I 969): CA 71 129273m; rate constants. 69JENIZIE P. W. Jennings and T. D. Ziebarth, "Mechanism of the

modified Hunsdiecker reaction," J. Org. Chern. 34(10), 3216-7 (1969); CA 71 123267r; intermediate in

Hunsdiecker reaction. 69POW/JOH F. X. Powell and D. R. Johnson, "Microwave spectrum of

the BrO free radical," J. Chern. Phys. 50(10),4596 (1969); CA 71 34844j; microwave spectrum, 79BrO and 81BrO data.

70AMIITRE O. Amichai and A. Treinen, "Oxybromine radicals," J. Phys. Chern. 74(20), 3670-4 (1970); CA 73 104276t; formation in the photolysis and radiolysis of bromate.

70BEG/SliB A. Begum. S. Subramanuan, and M. C. R. Symons, . 'Oxides and oxyions of the nonmetals. Xl. Electron spin resonance study of the bromate radical in 'Y-irradiated potassium bromate," 1. Chern. Soc. (6), 918-21 (1970); CA 72 138214r: EPR in potassium bromate during radiolysis.


70BLAIBRO D. A. Blake, R. J. Browne, and G. Bums, "Interaction potentials involving Br atoms," J. Chern. Phys. 53, 3320-3 (1970); CA 73 113370w; enthalpy of formation.

70BROIBUR J. Brown and G. Bums, "Decomposition of bromine monoxide studied by kinetic spectroscopy," Can. J. Chern. 48(22), 3487-90 (1970); CA 74 25483a; kinetics and mechanism of decomposition.

70CARIDYE A. Carrington, P. N. Dyer, and D. H. Levy, "Gas-phase electron resonance spectra of bromosyl iodosyl," J. Chern. Phys. 52(1), 309-14 (1970); CA 72 49474h; ground state configuration, splitting, rotational constant, EPR.

70CLY/CRU M. A. A. Clyne and H. W. Cruse, "Rates of elementary reactions involving the BrO (X2II) and 10 (XzII) radicals. 1. Formation and decay of the BrO radical," Trans. Faraday Soc. 66(9), 2214-26 (1970); CA 73 70238q; kinetics of formation and disproportionation, structure.

70CLY/CRU2 M. A. A. Clyne and H. W. Cruse, "Rates of elementary reactions involving the BrO (X2II) and 10 (X2II) radicals. 2. Reactions of the BrO and 10 radicals," Trans. Faraday Soc. 66(9), 2227-36 (1970); CA 73 70239r; reaction with nitrogen dioxide.

70COLICOS M. A. Collins, M. M. Cosgrove, and G. P. Bettertidge, "Bromine dioxide center in irradiated ZIllC bromate," J.

Phys. B 3(5), L48-L52 (1970); CA 73 50570p; ESR in 'Y-irradiated zinc bromate, 79Br02 and 81Br02'

70DAR B. de B. Darwent, "Bond dissociation energies in simple molecules," NSRDS-NDS 31, 1-48 (1970); CA 72 9J85c;

review, dissociation energy. 70SERIZAK L. V. Serikov, Yu. A. Zakharov, and A. A. Vasil'ev,

"Radiolysis of alkali metal halates," Tr. Mehvuz. Konf. Radiats. Fiz. 1967, 321-5 (1970); Ref. Zh., Khim. 1971, Abstr. No. 2IB1193; CA 77 95304d; EPR study, formation of Br03 during radiolysis.

70TOMISTU R. E. Tomalesky and J. E. Sturm, "Bromine monoxide from the flash photolysis of bromine-nitrous oxide and bromine-nitrogen dioxide mixtures," J. Chern. Phys. 52(1), 472-3 (1970); CA 72 61332t; formation.

71BYB J. R. Byberg, "ESR spectra from paramagnetic centers in irradiated potassium perbromate," J. Chern. Phys. 55(10), 4867-72 (1971); CA 75 156727b; EPR in potassium perbromate.

7IBYF/CAR C. R. Byfleet, A. Carrington, and D. K. Russell, "Electric dipole moments of open-shell diatomic molecules," Mol. Phys. 20(4), 271-8 (1971); CA 74 147751g; dipole moment, EPR.

71CLY/CRU M. K A. Clyne an'd H. W. Cruse, "Studies of ground-state 2p 312 halogen atoms using atomic resonance absorption," Trans. Faraday Soc. 67, 2869-85 (1971); CA 75 145664c;

kinetics, cross-sections. 71KAU/KOL M. Kaufman and C. E. Kolb, "Molecular beam analyzer for

identifying transient intermediates in gaseous reactions," Chern. lnstrum. 3(2). 175-89 (I 97 \): CA 76 76557b: detection.

71MlL T. A. Miller, "Alternative explanation for anomalous molecular parameters from electron resonance experiments," 1. Chern. Phys. 54, 3156-61 (1971); CA 74 118155k; questions earlier EPR spectra value of X"II 312

state. 710LS K. J. Olsen, "Radiolysis of frozen solutions containing

oxybromine anions," Trans. Faraday Soc. 67(4), 1041-8 (1971); CA 74 132925t; stability in aqueous solution.

71SHEITUR P. M. A. Sherwood and J. J. Turner, "'The reactions of hydrogen atoms with solids at low temperature. Part I. Apparatus, hydrocarbon, and hydrogen cyanide reactions," J. Chern. Soc. A 1971,2474; no bromine oxides data, only a reference to another study.

72ADL T. Adl, "Electron resonance study of gaseous bromine oxide," Ph.D. thesis, Pennsylvania State University, 92 pp. (1972); Diss. Abstr. lnt. B 33(12) [Part I], 5710; Order No. 73-13945; CA 79 131120t; EPR.


72AMONOS T. Amano, A. Yoshinaga, and E. Hirota, "Microwave spectrum of the BrO radical. Equilibrium structure and dipole moment," J. Mol. Spectrosc. 44(33), 594-8 (1972); CA 78 50058f; moleqIlar constants, 79BrO and 81BrO,

microwave spectroscopy. 72BRI B. J. Brisdon, "Oxides and oxyacids of the halogens," Int.

Rev. Sci.: Inorg. Chern. Ser One 3,21551 (1972); CA 76 R120933x: review.

72BROIBYF 1. M. Brown, C. R. Byfieet, B. 1. Howard, and D. K. Russell, "Electron resonance spectra of bromine monoxide,

iodine monoxide, and selenium monofiuoride in J =5/2 rotational levels," Mol. Phys. 23(3), 457-68 (1972); CA 77 107377v; EPR.

72BUN N. J. Bunce, "Mercury salt pathway for the degradation of

carboxylic acids to alkyl halides using halogen and mercuric salts," J. Org. Chern. 37(4), 664-9 (1972); CA 76 98849z; reaction with mercuric oxide and pivalic acid.

72BUN2 N. J. Bunce, "Free radical bromination of saturated hydrocarbons using bromine and mercuric oxide," Can. J. Chern. 50(19), 3109-16 (1972); CA 78 28887d; bromination of alkanes.

72FIE/KOR R. J. Field, E. Koros and R. M. Noyes, "Oscillations in chemical systems. II. Thorough analysis of temporal oscillation in the bromate-cerium-malonic acid system," J. Am. Chern. Soc. 94(25), 8649-64 (1972); CA 78 48508j; formation of Br202 in aqueous solution.

72RAO C. G. R. Rao, "Centrifugal distortion constants in bromine

trioxide (Br03), iodine trioxide (103), and silicon tribromide (SiBr3) molecules," Sci. Cult. 38(12), 522 (1972); CA 78 166312p; molecular centrifugal distortion constants.

72RAO/SYM K. V. S. Rao and M. C. R. Symons, "Oxides and oxyanions of the nonmetals. XV. Electron spin resonance spectra

of selenium and bromine radicals," J. Chern. Soc .. Dalton Trans. (2), 147-50 (1972); CA 76 66023k; EPR.

72YAN V. M. Yanishevskii, "On certain regularities in the

variation of the fundamental stretching vibration frequencies of diatomic molecules," Opt. Spcktrosk. 33(4), 636-41 (1972); Eng. trans!., Opt. Spectrosc. 33, 349-52 (1972); CA 78 64392x; correlation vibrational frequencies and dissociation energies.

73BYB/SPA J. R. Byberg and J. Spanget-Larsen. "Relation between molecular geometries and nuclear quadrupole coupling constants for some oxy-compounds of bromine and chlorine," Chern. Phys. Lett. 23, 247-51 (1973); CA 80 125084p; correlation nuclear quadrupole constants and geometry.

73DIXIPAR D. A. Dixon, D. D. Parrish, and D. R. Herschbach,

"Molecular beam scattering, general discussion." Faraday

Discuss. Chern. Soc. 55, 385-7 (1973); formation. 73PANfMIT A. N. Pandey, A. K. Mithal. M. M. Shukla. and G. C.

Singh, "Mean amplitUdes of vibrational and molecular

polarizabilities for some diatomic molecules." Indian 1. Pure App!. Phys. 11(1).69-71 (1973); CA 79 47266n; molecular vibrational amplitudes.

73PARIHER D. D. Parrish and D. R. Herschbach. "Molecular beam

chemistry. Persistent collision complex in reaction of

oxygen atoms with bromine molecules," J. Chern. Soc.

95(18). 6133-4 ([ 973); CA 79 129458r; formation, ground state.

73PASIPOT J. L. Pascal and 1. Potier. "Raman spectrum and structure

of bromine dioxide." 1. Chern. Soc .. Chern. Commun. (13).

446-7 ( 1973): CA 79 98776m: Raman spectra. structure is LiillICIil.:. BI20-l willI i.1 BI-BI uund.

73S0LlDOR D. V. Sokol'skii, Ya. A. Dorfman. and T. L. Rakitskaya.

"Induction period in the reduction of sodium bromate by

phosphine:' Zh. Fiz. Khim. 47. 59-61 (1973); Russ. J. Phys. Chern. 47. 3 J -2 (1973); CA 79 35500\\1: intermediate

in aqueous solutions.

74BYB/KIR J. R. Byberg and B. S. Kirkegaard, "ESR spectra of

Br03 and BrO~- ," J. Chern. Phys. 60(7), 2594-97 (1974); EPR.

74CAHIRIL R. W. Cahill and J. F. Riley, "Bromine oxide (BrO) disappearance in the pulse radiolysis of molecular oxygen + molecular bromine and nitrogen dioxide + molecular bromine systems," Radiat. Res. 58(1), 25-37 (1974); CA 80 l51056a; formation, disappearance.

74DHNCLE A. 1. Dhar and F. F. Cleveland, "Bond strengths and other constants for diatomic molecules. IV. Calculated values of

the energies at zero Kelvin. energies equilibrionic, and constants in the exponential part of the Morse potential energy function, for bonds of the types B-C, B-D, and B-E," Spectrosc. Mol. 23(268), 42":"4 (1974); CA 82 7815w; calculation of force constants, dissociation energies, and vibrational frequencies.

74DHNCLE2 A. 1. Dhar and F. F. Cleveland, "Bond strengths and other constants for diatomic molecules. V. Calculated values of the bond strengths, and of the quantities Cr (force-constant ratio) and Cw (bond-energy ratio), for molecules of several bond types," Spectrosc. Mol. 23(269), 48-9 (1974); CA 82 7814v; calculation offorce constants, dissociation energies, and vibrational frequencies.

74LOVITIE F. J. Lovas and E. Tiemann, "Microwave spectral tables. 1. Diatomic molecules," 1. Phys. Chern. Ref. Data 3(3).609-769 (1974); CA 82 104977h; review, microwave spectral data.

74PASIPAV J. L. Pascal, A. C. Pavia, J. Potier, and A. Potier, "New

bromine oxide Br203," C. R. Acad. Sci., Ser. C 279(1), 43-6 (1974); CA 81 98807p; thermal decomposition.

74SCH J. Schneider, "Internal partition function of two atom molecules in a polynomial representation," Z. Phys. Chern. (Leipzig) 255(5), 986-96 (1974); CA 82 145259u; coefficients, partition function.

74S0LlKEI 1. J. Solomon and J. N. Keith, "Synthesis of halogen compounds in high valence states," AD 775942/6GA, 66 pp. (1974); CA 81 57742v; formation.

74TIS R. Tischer, "5. Constants of Radicals. 5.1 Diatomic

Radicals," Landolt-Bornstein New Ser. Group II 6, 5-90 (1974); review, molecular spectra.

75BYBILIN J. R. Byberg and J. Linderberg, "ESR Spectra of chloryl

and bromyl (Br02) exchange coupled to molecular oxygen," Chern. Phys. Lett. 33(3), 612-5 (1975); CA 83 105899s; EPR of oxygen exchange coupled complex.

75CLYIWAT M. A. A. Clyne and R. T. Walson, "Kinelics sludks [or

diatomic free radicals using mass spectrometry. 3.

Elementary reactions involving bromine oxide (BrO

[X2I1]) radicals," 1. Chern. Soc., Faraday Trans. 1 71 (2), 336 50 (1975); CA 82 160763K; kinetics of reactions.

75DALILIN E. Dalgard and J. Linderberg, "Energy weighted overlap in

magnetic fields. Applications to electron spin resonance

problems," lnt. 1. Quantum Chern., Symp. 9, 269-77 (1975): CA 84 51901m: structure.

75GIN/SYM 1. S. Ginns and M. C. R. Symons. "Radiation mechanisms.

r. Inorganic salts in aqueous solutions. Electron spin

resonance studies of y-irradiated aqueous glasses

containing oxyanions." 1. Chern. Soc., Dalton Trans. (6), 514-21 (1975); CA 83 88617d; formation during

radiolysis. EPR.

75RADfWHl D. St. A. G. Radlein, J. C. Whitehead. and R. Grice,

"Reactive scattering of oxygen atoms. Oxygen + diiodine, iodine chloride. dibromine," Mol. Phys. 29(6), 1813-28 (I975)~ CA 83 103946f; angular distribution.

75WOF/MCE S. C. Wofsy, M. B. McElroy and Y. L. Yung, "The

chemistry of atmospheric bromine," Geophys. Res. Lett. 2, 215-1:) (1975); CA 84 110882[, Ul:l;UllClllX uC BIO.

76CLY/MON M. A. A. Clyne. P. B. Monkhouse. and L. W. Townsend,

"'Reactions of oxygen (0 3pJ) atoms with halogens: The rate constants for the elementary reactions 0 + BrCI, O+Br" and O+CL." Int. J. Chern. Kinet. 8(3),425-49 (1976)-; CA 85 25845x; reaction with 0, kinetics.



76MOIIYUR F. B. Moin, Ya. P. Yurkevisc and V. M. Drogovvishkii, "Reaction kinetics of atomic oxygen with chlorine and

bromine," Dokl. Akad. Nauk SSSR 226(4),866-8 (1976). 76HERISCH C. Herbo, G. Schmitz and M. Van Glabbeke, "Belousov

oscillating reaction. I. Kinetics of the bromate-cerium (III)

reaction," Can. J. Chern. 54, 2628-38 (1976); CA 85 16726Ic; Br202 as an intermediate in aqueous solution.

760DYINEC K. Ody, A. Nechvatal, and J. M. Tedder, "Liquid-phase bromination of bromo-butane: variation of the ratio of 1,2-to 1,3-dibromobutanes produced," J. Chern. Soc., Perkins

Trans. 2 (5), 521-4 (1976); CA 84 179208h; mechanism of the bromination of halobutanes.

76PASIPAV J. L. Pascal, A. C. Pavia, J. Potier, and A. Potier, "Synthesis and Raman structural analysis of an isomeric form of dibromine tetroxide (Br20 .. (B)). Geometric structure of this isomer and of bromine trioxide," C. R. Hebd. Seances Acad. Sci .. Ser. C 280(10), 661-4 (1976); CA 83 18208x; Raman spectra, structure, reactions with ULune.

76PAS/PA V2 J. L. Pascal, A. C. Pavia, J. Potier, and A. Potier,

"Synthesis and Raman spectroscopic study of bromine

hemipentoxide." C. R. Hebd. Seances Acad. Sci., Ser. C 282(1), 53-6 (1976); CA 84 98742a; preparation,

polymeric structure.

77CLY/CUR M. A. A. Clyne and A. H. Curran, "Reactions of halogen

atoms, free radicals, and excited states," Gas Kinet. Energy Tnm'&~r 2, ?'N-Q"i (lQ77): r~vi~w nf kin~tir"

77CLYIW AT M. A. A. Clyne and R. T. Watson, "Kinetic studies of

diatomic free radicals using mass spectrometry. Part 4. The bromine atom + chlorine dioxide radical and bromine oxide radical + chlorine oxide radical reactions," J. Chern. Soc., Faraday Trans. 1 73(8), 1169-87 (1977); CA 87 173377c; reactions, thermodynamics.

77GILIGAR H. M. Gillespie, J. Garraway, and R. J. Donovan,

"Reaction of atomic oxygen (2 ID2) with halomethanes," J. Photochem. 7(1), 29-40 (1977); CA 87 60675e; formation.

77GLI C. Glidewell, "Bond energy terms in oxides and

oxo-anions," Inorg. Chim. Acta 24(2),149-57 (1977); CA 87 157428q; bond energy. dissociation energy.

77LEE/BEN P. A. Lee and G. Beni. "New method for the calculation of atomic phase shifts: application to extended x-ray absorption fine structure (EXAFS) in molecules and

crystals." Phys. Rev. B 15(6). 2862-83 (1977); CA 86 163150p: bond length. spectroscopy.

77PAS/PAV J. L. Pascal. A. C. Pavia, J. Potier. and A. Potier. "Structural studies of bromine oxides by Raman laser spectroscopy:' Proc. Int. Conf. Raman Spectrosc. 5th (1976).110-1 (pub. 1977): CA 87 210447y: Raman spectra,

structure, thermal decomposition.

77SAS/RAO D. L. Sastry and K. V. S. R. Rao, "ESR study of

y-irradiated cadmium bromate dihydrate." Proc. Nuc!. Phy" Snlici StMe Phys Symp 20(,. 'iI1f> (1977): CA 90 1125981': EPR in y-irradiated cadmium bromate dihydrate.

77TAD/SHI K, Tado. T. Shioda. and K. Tanaka. "Removal of halogen

gas from waste gas." J. Kokai Tokkyo Koho IP 7799966

(1977): CA 88 PI09907u; reduction. 77VOGIDRE D. Vogt. \V. Dreves. and 1. Mische. "Energy dependence of

differential cross sections in endoergic ion-molecule collision processes of negative ions:' Intern. J. Mass

Spectrom. Ion Phys. 24. 285-96 (1977); CA 87 74078z: dissociation energy.

78DL':--<IDYK S. J. Dunlavey. 1. M. Dyke. and A. Morris. "The first ionization potential of the bromine monoxide (X2n i) radical obtained using photoelectron spectroscopy: Chem. Phys. Lett. 53C~). )82--+ (1978): CA 88 l13036b: IP.

78FOE/SCH H. D. Foersterling. H. Schreiber. and \V. Zittlau. "Detection of bromine dioxide (8r02) in the BelousO\-Zhabotinskii system. Z, Naturforsch. A 33:\(12). 1552-6 (1978): CA 90 94765m: electronic absorption spectra of cerium containing solutions.


78PAS J. L. Pascal, "Contribution to the studies on halogen oxides," Ph.D. Thesis, U.S.T.L. Montpelier, France (1978);

oxidation of bromine by ozone, full citation not available at

this time. 78ROV/ZHA A. B. Rovinskii and A. M. Zhabotinskii, "Mechanism of

the autocatalytic oxidation of cerium (3 +) by bromate," Teor. Eksperim. Khim. 14, 183-92 (1978); Theor. Exptl. Chem. [USSR] 14, 142-50 (1978); CA 89 31486e; Br202 in aqueous solution yields Br02 radicals.

78TEV/SMA D. E. Tevault and R. R. Smardzewski, "Matrix infrared spectrum of the 02Br radica!' Bonding in the 02X species, ., J. Am. Chern. Soc. 100(12), 3955-7 (1978); CA 89 119979d; matrix spectrum, IR.

78TEVIWAL D. E. Tevault, N. Walker, R. R. Smardzewski, and W. B. Fox, "Infrared spectra of the BrO and OBrO free radical

and of BrOBr and BrBrO molecules in solid argon at 10 K," 1. Phys. Chern. 82(25), 2728-33 (1978); CA 90 14201m; formation, dimerization, IR spectrum.

78THIIMOH P. Thirugnanasambandam and S. Mohan, "A new look at

molecular vibrations: Part II," Indian J. Phys. 528(3), 173-8 (1978); CA 90 44141j; molecular vibrations, force constants.

7YADl)fDON M. C. AddIson, J.{. J. Donovan, and J. Garraway,

"Reactions of 0(2 ID2) and 0(23PJ) with halomethanes," Faraday Discuss. Chern. Soc. 67, 286-96 (1979); kinetics.

79CARISAH M. Carlier, K. Sahetchian, and L. R. Sochet, "ESR evh.lelH.:t: [UI halugell u!l.yraLlical fUlilIatiulI ill the sluLly uf

the heterogeneous decomposition of gaseous hydrogen peroxide on halides," Chern. Phys. Lett. 66(3), 557-60 (1979); CA 92 11795p; formation.

79HUB/HER K. P. Huber and G. Herzberg, Molecular spectra and molecular structure (Van Nostrand, New York, 1979), vol. 4, pp. 110-1 (1979); CA 90 B195497f; review, EPR spectra.

79LEU M.-T. Leu, "Rate constant for the reaction bromine oxide (BrO)+nitric oxide-atomic bromine+nitrogen dioxide," Chern. Phys. Lett. 61(2), 275-9 (979); CA 90 157672b; reaction with NO(g).

79MICIPA Y 1. V. Michael and W. A. Payne. "Absolute rate constants for the reaction of bromine atoms with ozone from 234 to 360 K," Int. J. Chem. Kinet. 11, 799-809 (1979); rate constant for formation of BrO.

79MIT Mitsubishi Electric Co., "Bromine recovery from wastewater containing bromide ion," Jpn. Kokai Tokkyo Koko.80, 154, 305 (1979); CA 94 177468a; manufacture from ·wastewater.

79NOS/BOD Z. Noszticzius and J. Bodiss, "A heterogeneous chemical o:>cillator. The Dclousoy-Zhdbotin~kii-type reaction of

oxalic acid," J. Am. Chern. Soc. 101, 3177-82 (1979); CA 91 90866t; Br202 as an intermediate in aqueous solution.

79WAT/SAN R. T. Watson. S. P. Sander, and Y. L. Yung, "Pressure and temperature dependence kinetics ~ttldy of the· nitric oxide

+bromine oxide - nitrogen dioxide + bromine reaction.

Implications for stratospheric bromine photochemistry:' J. Phys. Chem. 83(23). 2936-44 (1979); CA 92 47875d; reaction with NO(g).

80BAU/COX D. L. Baulch. R. A. Cox. R. F. Hapson Jr., J. A. Kerr, J. Troe and R. T. Watson. "Evaluated kinetic and photochemical data for atmospheric chemistry." J. Phys.

Chem. Ref. Data 9(2). 2950471 (1980); kinetics.

80FOEILAM H. D. Foersterling. H. J. Lanberz. and H. Schreiber. . 'Formation of bromine dioxide in the Belousov

Zhabotinskv-svstem investi2:<ltion of the bromous acid (HBrO, )ib;on;ate reaction::- Z. Naturforsch. A 35A(l2), 1354-60 (1980); CA 94 7227lc; formation.

80FOE/LAM,2 H. D. Foersterling, H. Lamberz, and H. Schreiber, . 'Formation of bromine oxide (8r02) in the Belousov-Zhabotinsky system investigation of the cerium (r )/bromate reaction." Z. Naturforsch. A 35M3). 329-31 (1980); CA 92 221569u; formation.


80JAFIMAI S. Jaffe and W. K. Mainquist, "Bromine decomposition of ozone," J. Phys. Chern. 84, 3277-80 (1980); CA 93 228487v; dissociation, transition states.

80KOL L. Kolditz, "Bromine pxygen compounds," Sitzungsber. Akad. Wiss. DDR Math. Naturwiss. Tech. N14, 11-7 (1980); CA 94 166675q; review, formation.

80LOEIMIL A. Loewenschuss, J. C. Miller, and L. Andrews, "Argon matrix absorption spectra of chlorine monoxide, bromine monoxide, iodine monoxide, and emission spectra of iodine monoxide," J. Mol. Spectrosc. 80(2), 351-62 (1980); CA 93 16053a; vibrational analysis. from absorption and emission spectra.

80MOLIMOL 'L. T. Molina and M. J. Molina, "Impact of brominated compounds on the stratosphere," EPA-600/9-80-003 [Proc. Conf. Methyl Chloroform Other Halocarbon Pollut.] WI 1-10/6 (1980); CA 94 144590f; in stratosphere.

80NIC M. Nicolet, "The chemical equations of stratospheric and mesospheric ozone," FAA-EE-RO-20 [Proc NATO Aclv

Study Inst. Atmos. Ozone: Var. Hum. Influences], 823-64 (1980); CA 94 160302u; AD A088889; in atmosphere.

80SAN S. P. Sander, "Kinetic studies of bromine-monoxide and methylperoxy free radicals by flash photolysis," Ph.D. thesis, California Institute of Technology, 259 pp. (1980); CA 93 140860a; Diss Abstr. Int. B 40(12, Pt. 1), 5698; Order No. 8012213; full dissertation not available at this time, reaction kinetics.

80SEDILAZ W. A. Sedlacek, A. L. Lazrus, and B. W. Gandrud, "Measurement of stratospheric bromine," FAA-EE-80-00 [Proc. NATO Adv. Study Inst. Atmos. Ozone: Var. Hum. Influences], 273-80 (1980); CA 94 195482e; AD A08889; determination in stratosphere.

80SUBILOD M. S. Subhano and S. F. Lodhi, "A mechanism for the photolytic decomposition of hypobromite in aqueous solution at 365 nm, 313 nm, and 253.7 nm," Rev. Roum. Chim. 25(11-12), 1567-78 ,(1980); CA 95 141909b; formation.

80VELIDUR I. Veltman, A. Durkin, D. J. Smith, and R. Grice, "Reactive scattering of hydroxyl radicals: OH + Br2 " Mol. Phys. 40, 213-24 (1980); CA 93 156174r; structure in Ar matrix.

80YUNIPIN Y. L. Yung, J. P. Pinto, R. T. Watson and S. P. Sander, . 'Atmospheric bromine and ozone perturbations' in the lower stratosphere," J. Atmos. Sci. 37, 339-53 (1980).

81BARICOH M. Barnett, E. A. Cohen, and D. A. Ramsay, "The A 2rr j_X2rr j absorption spectrum of bromine oxide (BrO)," Can. J. Phys. 59(12), 1908-16 (1981); CA 96 94301f; electronic absorption spectrum, 81 BrO.

81BOH/SEN M. C. Bohm, K. D. Sen, and P. C. Schmidt, "Molecular orbital electronegativity," Chern. Phys. Lett. 78(2), 357-60 (1981); CA 94 163058e; electronegativity.

81BROIHOB R.1. Browett, J. H. Hobson, F. E. Davidson and R. Grice, "Reactive scattering of a supersonic oxygen atom beam 0 -r el2 at threshOld," Mol. Phys. 4.i, 113-21 (1':181); CA 95 139050w; BrBrO detected in Ar matrix.

8lCLYIMAC M. A. A. Clyne and A. 1. Macrobert, "Kinetic studies of frce radical reactions by mass spectroscopy. II. The reactions of SO I cia. so -r OCIO. aml so -r Bra," Inr. 1. Chern. Kinet. 13(2), 187-97 (1981); CA 94 91106u; reaction with SO(g).

81 COHIPIC E. A. Cohen, H. M. Pickett, and M. Geller, . 'The rotational spectrum and molecular parameters of bromine monoxide in the 2rr 3/2 state," 1. Mol. Spectrosc. 87(2), 459-70 (198 Il: CA 95 52007p: microwave spectrum. molecular constants.

8lDON/ZEL A. F. Donodov, V. V. Zelenov, and V. L. Tal'roze, "Mechanism of reactions in the oxygen + ozone + bromine system." Kinet. Katal. 22(1), 245-7 (I981); CA 94 128159s; formation. decay kinetics.

81DORIMEH S. Doraiswamy and S. C. Mehrotra, "The collision-induced linewidths of chlorine and bromine monoxide perturbed by nitrogen," JSR, J. Geophys. Res., Sect. C 86(C6), 5381-2 .. ' (1981); CA 95 51875h; collision-induced linewidths.

81GROILAU M. Grodzicke, S. Lauer, A. X. Trautwein, and A. Vera, "Application of molecular orbital calculations to Moessbauer and NMR spectroscopy of halogen-containing compounds," Adv. Chern. Ser. 194 (Moessbauer Spectrosc. Its Chern. Appl.) , 3-37 (1981); CA 96 43242e; dipole moment.

81MCK A. R. W. McKellar, "Laser magnetic resonance spectrum

of bromine oxide (BrO) err lIr 2rr 3/2)," J. Mol. Spectrosc. 86(1), 43-54 (1981); CA 94 112118s; laser magnetic resonance spectrum, 79BrO and 81BrO.

81MEN/SAT A. Menon and N. Sathyamurthy, "Negative activation energy for the Cl(Br)O + NO-CI(Br) + N02 reactions," J. Phys. (;hem. R~(R), 1021-3 (1981); CA 94 198165q; reaction with NO(g).

81RAYIWAT G. W. Ray and R. T. Watson, "Kinetics study of the reactions of nitric oxide with oxygen fluoride, chlorine oxide, bromine oxide, and iodine oxide at 298 K." J. Phys. Chern. 85(20), 2955-60 (1981); CA 95 139403p; reaction with NO(g).

81SANIRAY S. P. Sander, G. W. Ray, and R. T. Watson, "Kinetic study of the pressure dependence of the BrO + N02 reaction at 291S K.," J. Phys. Chern. 85(2), 199-210 (1981); CA 94 91082h; reaction with N02(g).

81SANIWAT S. P. Sander and R. T. Watson, "Kinetics and mechanism of disproportionation of BrO radicals," J. Phys. Chern. 85, 4000-7 (1981); CA 95 226406k; formation.

81SEG/SUT C. Sehgal, R. G. Sutherland, and R. E. Verralll, "Sonoluminescence from aqueous solutions of bromine and iodine," J. Phys. Chern. 85(4), 315-7 (1981): CA 94 111776t; sono1uminescence.

82ANT S. Antonik, "Kinetic and analytical study of the oxidation of trifluoro- bromo methane between 450 and 550°C," Bull. Soc. Chim. Fr. (3-4, Pt 1), 83-9 (1982); CA 97 109370z; lack of abstraction reaction.

82BAU/COX D. L. Baulch, R. A. Cox, P. J. Crutzen, R. E. Hampson, 1. A. Kerr, J. Troe and R. T. Watson, "Evaluated kinetic and photochemical data for atmospheric chemistry. Supplement 1. CODATA Task Group on Chemical Kinetics," J. Phys. Chern. Ref. Data 11, 327-496 (1982); review of the kinetics of reaction involving BrO, references a BrO enthalilY of formation value.

82COx/SHE R. A. Cox and D. W. Sheppard, "Rate coefficient for the reaction of bromme oxide with hydroperoxy at 303 K," 1. Chern. Soc., Faraday Trans. 278(8),1383-9 (1982); CA 97 169579t; reaction with hydroperoxy, kinetics.

82COX/SHE2 R. A. Cox, D. W. Sheppard, and M. P. Stevens, "Absorption Lvdfidcllt~ amI k.inetics of me bromine oxide (BrO) radical using molecular modulation," 1. Photochem. 19(3),189-207 (1982); CA 97 11811Os; formation, spectra.

R?FFRISMI D. P. Fernie, D. J. Smith, A. Durkin, and R. Grice,

"Reactive scattering of a supersonic oxygen atom beam: 0 + Br2'" Mol. Phys. 46, 41-54 (1982); CA 97 98653r; ground state.

82FIE/RAG R.1. Field, N. V. Raghaven, and 1. G. Brummer, "A pulse radiolysis investigation of the reactions of bromine dioxide radical (Br02) with hexacyanoferrate(II), manganese(II), phenoxide ion, and phenol," J. Phys. Chern. 86(13), 2443-9 (1982); CA 97 12499k; reduction.

82FOEILAM H. D. Foersterling, H. 1. Lamberz, H. Schreiber, and W. Zittlau. "Bromine dioxide as an intermediate product of the Belousov-Zhabotinskii reaction," Kern. Kozl. 57(3-4), 283-93 (1982); CA 97 155341p; formation.

J. Phys. Chern. Ref. Data, Vol. 25, No. 4,1996


82FOEILAM H. D Foersterling, H. L. Lamberz, H. Schreiber, and W. Zittlau, "Bromine dioxide (Br02) as an intermediate in the BelousovcZhabotinskii reaction," Acta Chim. Acad. Sci. Hung. 110(3), 251-60 (1982); CA 97 188870p; formation.

82MUKlKHI V. N. Mukhin, B. A. Khisamov, and A. G. Kotov, "Radiation-induced formation of paramagnetic centers in ionic crystals," Khimn. Fiz. (12), 1637-41 (1982); CA 101 101095u; formation of paramagnetic center.

82WAGIEVA D. D. Wagman, W. H. Evans, V. B. Parker, R. H. Schumm, I. Halow, S. M. Bailey, K. L. Churney, and R. L. Nuttall, "The NBS tables of chemical thermodynamic properties.

. Selected values for inorganic and C1 and C2 organic substances in SI units," J. Phys. Chern. Ref. Data 11 Suppl. No.2, 2-50 (1982); CA 99 B219862k; enthalpy of formation reported, supersedes 65W AGIEV A.

83ALL S. D. Allen, "Spectroscopy and photochemical studies of the bromine oxides," Ph.D. thesis, Nottingham, England (1983); full citation not available at this time.

83BUS/SIB R. J. Buss, S. J. Sibener and Y. T. Lee, "Reactive scattering of Oep) + CF3I," 1. Phys. Chern. 87(24), 4840 (1983); ground state assumed by analogy with other halogen oxides.

83BUTIMOR N. I. Butkovskaya. L L Morozov. V. L. Tal' rose. E. S. Vasiliev, "Kinetic studies of the bromine-oxygen system: a new paramagnetic particle, bromine dioxide," Chern. Phys. 79(1), 21-30 (1983); CA 99 146907s; formation, structure.

83FIEIRAG R. J. Field, N. N. Raghavan, and J. G. Brunimer, "Pulse radiolysis study of the reaction between the bromine dioxide radical and hexacyanoferrate(4-) ion, manganese(II), phenoxide ion, or phenol,' , Kern. Kozl. 59(1-2), 235-50 (1983); CA 101 237999z; formation and reaction in pulse radiolysis of bromite solutions.

83FOEILAM H. D. Foersterling, H. J. Lamberz, and H. Schreiber, "Formation of bromine dioxide (Br02) in the Be1ousov-Zhabotinskii reaction of aliphatic alcohols with bromate," Z. Naturforsch. A 38A(4), 483-6 (1983); CA 99 52982k; formation.

84BAU/COX D. L. Baulch, R. A. Cox, R. F. Hampson Jr., J. A. Kerr, J. Troe, and R. T. Watson, "Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement II. CODATA task group on gas phase chemical kinetics," 1. Phys. Chern. Ref. Data 13, 1259-380 (1984); CA 102 152285j; review, kinetics.

84BOLIBAL J. J. Boland and J. D. Baldeschwieler, "The effect of thermal vibrations on extended x-ray absorption fine structure. II," J. Chern. Phys. 81(3), 1145-59 (1984); CA 101 100730k; thermal vibrations effect on EXAFS.

84BURlLA W J K RlInip.tt, N J. T .1lWTp.nce, and I .. L Turner. "Oxygen

fluorides, non-metal halides, van der Waals molecules, and related species: a linking theoretical thread," Inorg. Chern. 23,2419-28 (1984); CA 101 60416; review.

84BUT/KA W J. E. Butler. K. Kawaguchi, and E. Hirota, "Infrared diode laser spectroscopy of the bromine oxide (BrO) radical," J. Mol. Spectrosc. 104(2), 372-9 (1984); CA 100 l47790z; IR spectrum, 79BrO, 81 BrO.

84CLA D. C. Clary, "Rates of chemical reactions dorriinated by long-range inter-molecular forces," Mol. Phys. 53(1), 3-21 (1984); CA 101 198902r; reaction with NO(g).

84EPIILAR N. D. Epiolis, J. R. Larson, and H. H. Eaton, "Common denominator by the MOVB method: the structures of water, hydrogen peroxide, and their derivatives," Croat. Chern. Acta, 57(S), 1031-S3 (1984); CA 102 172905q; MO-VB theory in study of molecular structure.

84JAC M. E. Jacox, "Ground-state vibrational energy levels of polyatomic transient molecules," 1. Phys. Chem. Ref. Data 13(4), 94S-1068 (1984); CA 103 4S024x; review of ground state vibrational levels.

84STE Kobe Steel, "Lubricant coatings for petroleum-drilling pipe threads," Japan 841744699 (1984); CA 102 I I 6422t; lubricant.


84SASIRAO D. L. Sastry and K. V. S. Rama Rao, "Comparative study of quadrupole coupling constants of Br03 and BrO-31

paramagnetic radical derived from bromate (Br03) ion," Proc. Nuc!. Phys. Solid State Phys. Symp. 25C, 201-2 (1984); CA 102 141172u; quadrupole coupling constants of . paramagnetic radicals.

84SAUITAT J. Sauval and J. B. Tatum, "A set of partition functions and equilibrium constants for 300 diatomic molecules of astrophysical interest," Astrophys. J., Supp!. Ser. 56(2), 193-209 (1984); CA 101 200866c; equilibrium constant, partition function.

85BENIKRI V. A. Benderskii and A. G. Krivenko, "Time resolutions of polarograms of intermediate species," Elektrokhimiya 21(11), 1507-13 (1985); CA 104 58296h; polarograms.

85BJEIBYB N. Bjerre and J. R. Byberg, "Formation of complex defects involving molecular oxygen by electronhole reactions in X-irradiated KCI04 and KBr04, studied by ESR and IR spectroscopy," J. Chern. Phys. 82(5), 2206-11 (1985); CA 102 194277p; EPRlIR formation of LX02 , O2].

85BYB 1. R. Byberg, "Oxidation of bromate ion in solid matrices studied by ESR," J. Chern. Phys. 83(3), 919-24 (1985); CA 103 147964w; electronic levels within potassium jJcldllulliU::.

85BYKlGOR I. B. Bykhalo, E. B. Gordon, A. P. Perminov, and V. V. Filatov, "EPR study of reactions of excited atoms. The atomic oxygen + molecular bromine bromine monoxide

I· atomic bromine ( 2P IIZ' 2P3/Z)' Formation of atomic

bromine (2pI/2) in the reaction of hydrogen deuterium and fluorine with molecular bromine," Khim. Fiz. 4, 770-8 (1985); CA 103 60060z; ground and excited states of BrO.

85DUIIHUD M. T. Duignan and J. W. Hudgens, "Multiphoton ionization spectroscopy of chlorine monoxide (ClO) and bromine monoxide (BrO)," J. Chern. Phys. 82(10), 4426-33 (1985); CA 103 14011m; ionization spectra.

85FOEILAM H. D. Foersterling, H. J. Lamberz, and H. Schreiber, "Kinetics of the cerium (3+ )lbromine oxide (Br02) reaction in sulfuric acid medium," Z. Naturforsch. A: Phys., Phys. Chem., K'osmophys. 40A(4), 368-72 (1985); CA 102 210074c; redox reaction with cerium(III) in sulfuric acid.

85POYIPIC R. L. Poynter and H. M. Pickett, "Submillimeter, millimeter, and microwave spectral line catalog," App!. Opt. 24(14), 2235-40 (1985); CA 103 78568f; submillimeter, millimeter, microwave spectral line catalog.

85STE H. 1. Sternal, "Device for testing blood alcohol content," Ger. -:3418373 (1985); CA 104 47016r; pill containing Br02 for alcohol determination.

86BEN/KRI V. A. Benderskii, A. G. Krivenko, and N V Fedorich,

"Electrode reactions of intermediate species formed during the reduction of the bromate anion on mercury," Elektrokhimiya 22(6), 728-34 (1986); CA 105 68947f; reduction on mercury.

86BRU/AND W. H. Brune and J. G. Anderson, "In situ observations of midlatitude stratospheric chlorine oxide (CIO) and bromine oxide (BrO)," Geophys. Res. Lett. 13(13), 1391-4 (1986); CA 106 87998k; in stratosphere.

86BRU/STI J. Brunning and L. Stief, "Rl:llt: \.:UIlStlinl fUI thc relictivlI sulfur monoxide + bromine monoxide --> sulfur dioxide + atomic bromine." 1. Chern. Phys. 85(5), 2591-4 (1986); CA 105 IS9527k; kinetics of reaction with SO(g).

86BYB 1. R. Byberg, "ESR study of the complexes chlorine oxide -molecular oxygen (CIO,Oz) and bromine oxide -molecular oxygen (BrO,02) formed by decomposition of chlorate and bromate anions in solid potassium perchlorate," J. Chern. Phys. 84(8), 4235-42 (1986); CA 104 234l14h; complex with molecular oxygen.

86BYB2 J. R. Byberg, "ESR study of the formation of complex defects involving molecular oxygen by electron-hole reactions in x-irradiated potassium chlorate and potassium bromate." J. Chem. Phys. 84(11), 6204-9 (1986); CA 105 32826b; EPR of complex defects.


86GIN M. L. Ginter, "Spectral studies related to dissociation of hydrogen bromide, hydrogen chloride, and bromine monoxide," NASA-CR-176698, 92 pp. (1986); CA 105 1776S7g; dissociation. , '

86HILIMCC G. W. Hills, W. J. McCoy, and R. E. Muenchausen, "Infrared spectroscopy using optogalvanic detection of a radio-frequency discharge," AlP Conf. Proc. 146 [Adv. Laser Sci.-l], 456-7 (1986); CA 105 143232z; detection technique.

86HUI/NET R. E. Huie and P. Neta, "KmetIcs ot one-electron transfer reactions involving chlorine dioxides and nitrogen dioxide," J. Phys. Chern. 90(6), 1193-8 (1986); CA 104

. 116829x; I-electron transfer reactions. 86KRE/FAB B. C. Kreuger and P. Fabian, "Model calculations about the

reduction of atomospheric ozone by different halogenated hydrocarbons," Ber. Bunsen-Ges. Phys. Chern. 90(11), 1062-6 (1986); CA 106 37743c; formation.

86MCE/SAL M. B. McElroy, R.I. Salawitch, and S V. Wofsy,

"Antarctic ozone: mechanism for the spring decrease," Geophys. Res. Lett. 13(12), 1296-9 (1986); CA 106 36327h; Antarctic stratosphere.

86MOZ M. Mozurkewich, "Reactions of hydroperoxo with free radicals," J. Phys. Chern. 90(10), 2216-21 (1986); CA 104 194019x; reaction with hydroperoxo.

86RAZIDOD V. V. Raznikov, A. F. Dodonov, and V. V. Zelenov, "Disentangling the fine structure of ionization efficiency curves," Int. J. Mass Spectrom. Ion Processes 71(1), 1-27 (1986); CA 104 142768s; ionization efficiency curves.

86SAN S. P. Sander, "Kinetics and mechanism of the 10-10 reaction," J. Phys. Chern. 90, 2194-9 (1986); CA 104 194017v; formation.

86THO R. C. Thompson, "Reaction mechanisms of the halogens and oxo-ha10gen species in acidic, aqueous solution," Adv. Inorg. Bioinorg. Mech. 4, 65-106 (1986); .CA 105 2141/5I/m; review, intermediate in aqueous solutions.

86TUN/KO K. K. Tung, M. K. W. Ko, J. M. Rodriguez, amd N. D. Sze, " Are Antartic ozone variations a manifestation of dynamics or chemistry?" Nature (London) 322(6082),811-4 (1986); CA 105 137411r; reaction with CIO(g).

86UMAIRAM Y. Umasasidhar, S. Ramaprabhu, and K. V. S. Rama Rao, "Investigation of EFG parameters at the halogen site in

X03 and XO~- radicals (X=chlorine, bromine) in certain inorganic solids," Z. Naturforsch. A: Phys., Phys. Chem., Kosmophys. 41A(1-2), 169-70 (1986); CA 105 12341m; thermal vibrations effects on EXAFS.

87ALLIPOL S. D. Allen, M. Poliakoff, and J. J. Turner, "Photochemistry of an ozone-bromine complex; the IR spectrum of matrix isolated Br20," J. Mol. Struct. 157, 1-15 (1987); CA 106 186247w; critique of earlier vibrational data.

87BAS/GAV N. G. Basov, V. F. Gavrikov, S. A. Pozdneev and V. A. Shcheglov, "Possible expansion of the spectral emission range of electronic-transition chemical lasers," Sov. J.

Quantum Electron. 17(9), 1139-52 (1987). 87ELO/RYN A. Elofson, K. Rynefors, and L. Holmlid, "Monte Carlo

~iml1htion of RRKM I1nimoll'rlllilr nl'rompo<;ition in

molecular beam experiments. V. Product oxygen halide (OX) angular and energy distributions from atomic oxygen (3p) + X2 (X = bromine, iodine)," Chern. Phys. 118(1), 1-16 (1987); CA 108 44232e; unimolecular decomposition.

87FLE/SW A S. J. Fleming and C. P. Swann, "Color additives and trace elements in ancient glasses: specialized studies using PIXE spectrometry," Nucl. Instrum. Methods Phys. Res., Sect. B B22(1-3), 411-8 (1987); CA 106 195455q; determination.

87HILICIC A. J. Hills, R. J. Cicerone, J. G. Calvert, and J. W. Birks, "Kinetics of the bromine monoxide + chlorine monoxide reactions and implications for stratospheric ozone," Nature (London) 328(6129), 405-8 (1987); CA 107 100125r; full citation not available at this time, reaction with CIO(g), kinetics.

87LOE/AND L. M. Loewenstein and 1. G. Anderson, "Reactions of radicals with halogen molecules: a frontier orbital interpretation," J. Phys. Chern. 91, 2993-7 (1987); CA 106 202539a; proposed cyclic BrBrO sirucLUre.

87SW AlFLE C. P. Swann and S. J. Fleming, "PIXE spectrometry in archaeometry: the development of a system with high spatial resolution," Nucl. Instrum. Methods Phys. Res., Sect. B B22{1-3), 407-10 (1987); CA 106 195454p; determination.

88BARIBOT L. A. Barrie, J. W. Bottenheim, R. C. Schnell, P. J. Crutzen, and R. A. Rasmussen, "Ozone destruction and photorh~mical r~ilrtiom; i\t polar ~lInri~e in the lower Arctic

atmosphere," Nature 334(6178), 138-41 (1988); CA 109 115299r; in air, ozone destruction in relation to; deals with BrO (not Br20S)'

88BARISOL J. W. Barrett, P. M. Solomon, R. L. DeZafra, M. Jaramillo, L. Emmons, and A. Parrish, "Formation of the Antractic ozone hole by the chlorine monoxide dimer mechanism," Nature (London) 336(6198), 455-8 (1988); CA 110 99189t; in lower stratosphere.

88BRUITOO W. H. Brune, D. W. Toohey, J. G. Anderson, W. L. Starr, J. F. Vedder, and E. F. Danielson, "In situ northern mid-latitude observations of chlorine monoxide, ozone, and bromine monoxide in the wintertime lower stratosphere," Sci. 242(4878), 558-62 (1988); CA 110 26966j; in lower stratosphere.

88COSITEN R. C. Costen, G. M. Tennille, and J. S. Levine, "Cloud pumping in a one- dimensional photochemical model," 1. Geophys. Res. D: Atmos. 93(D12), 159;1 1-5;1 (1988);

CA 110 158021g; in troposphere; deals with BrO (not

Br20s)' 88FLE/SW A S. J. Fleming and C. P. Swann, "The Bartol PIXE

microprobe facility: recent applications in archaeology," Nucl. lnstrum. Methods Phys. Res., Sect. B B30(3), 444-53 (1988); CA 108 166628j; determination in archaeological artifacts.

88HIL A. J. Hills, "Kinetics investigations of atmospheric chemical reactions," Ph. D. thesis, University of Colorado, 108 pp. (1987); .Univ. Microfilms lnt., Order No. DA8723465; Diss. Abstr. Int. B 48(10), 2951 (1988); CA 107 100125s; reaction with ClO(g).

88HILICIC A. J. Hills, R. J. Cicerone, J. G. Calvert, and J. W. Birks, "Temperature dependence of the rate constant and product channels for the bromine oxide + chlorine oxide reaction," J. Phys. Chern. 92(7), 1853-8 (1988); CA 108 157109p; kinetics of reaction with CIO(g).

88IGE/STO G. Igel-Mann, H. Stoll, and H. Preuss, "Pseudopotential study of monohydrides and monoxides of main group elements potassium through bromine," Mol. Phys. 65(6), 132C)-36 (l c)&&): CA 111 202162a; calculation of r" ide'

and De. 88NET/HUI P. Neta, R. E. Huie, and A. B. Ross, "Rate constants for

reactions of inorganic radicals in aqueous solution," J. Phys. Chern. Ref. Data 17(3), 1027-284 (1988); CA 109 R198144k; reactions, review.

88SALIWOF R. J. Salawitch, S. C. Wofsy, and M. B. McElroy, "Chemistry of OCIO in the Antarctic stratosphere: implications for bromine," Planet Space Sci. 36(2), 213-24 (1988); CA 108 226063h; reaction with CI02 ·



88SANIFRI S. P. Sander and R. R. Friedl, "Kinetics and product studies of the bromine oxide (BrO) + chlrorine oxide (CIO) reaction: implications for Antarctic chemistry," Geophys. Res. Lett. 15(8), 887"":90 (1988); CA 109 173873j; reaction with CIO(g).

88SIN M. Singh, "Thirty-one new diatomic molecules in cosmic objects spectra," Astrophys. Space Sci. 140(2), 421-7 (1988); CA 109 82624n; dissociation energy, IP .•

88TOO/AND D. W. Toohey and J. G. Anderson, "Formation of bromine

chloride eIIuO+) in the reaction of bromine monoxide with chlorine monoxide," J. Phys. Chern. 92(7), 1705-8 (1988); CA 108 157132r; kinetics of reaction with CIO(g).

88TOOIBRU D. W. Toohey, W. H. Brune, and J. C. Anderson, "Rate

constant for the reaction Br + 0 3 -4 BrO + O2 from 248 to 418 K: kinetics and mechanism," Intern. J. Chern. Kinet. 20, 131-44 (1988); CA 108 157114m; reaction, titration with NO, enthalpy of formation.

88TYK R. J. Tykodi, "Estimated thermochemical properties of some noble-gas monoxides and difluorides." J. Chern. Educ. 65(11), 981-5 (1988); CA 110 220036w; enthalpy of atomization.

88W AfIIRA V A. Wahner, A. R. Ravishankara, S. P. Sander, and R. R. Friedl, "Absorption cross secTion of BrO between 312 and 385 nm at 298 and 223 K," Chern. Phys. Lett. 152(6), 507-12 (1988); CA 110 6604lk; UV absorption cross sections.

S9ANDIBRU J. G. Anderson, W. H. Brune, S. A. Lloyd, D. W. Toohey,

S. P. Sander, W. L. Starr, M. Loewenstein, and 1. R. Podolske, "Kinetics of ozone destruction by chlorine oxide and bromine oxide within the Antarctic vortex: an analysis based on in situ ER-2 data," J. Geophys. Res., D: Atmos. 94(D9), 11480-520 (1989); CA 113 62842m; reactions.

89ATKIBAU R. Atkinson, D. C. Baulch, R. A. Cox, R. F. Hampson Jr., J. A. Kerr, and J. Troe, "Evaluated kinetics and photochemical data for atmospheric chemistry. Supplement III," J. Phys. Chern. Ref. Data 18, 881-1097 (1989); CA 111 l21638h; review, reaction enthalpy.

89ATKlBAU2 R. Atkinson, D. C. Baulch, R. A. Cox, R. F. Hampson Jr., 1. A. Kerr, and J. Troe, "Towards a quantitative understanding of atmospheric ozone," Planet. Space Sci. 37(12), 1605-20 (1989); reactions with ClO.

89AUS/JON 1. Austin, R. L. Jones, D. S. McKenna, A. T. Buckland, 1. G. Anderson, D. W. Fahey, C. B. Farmer, L. E. Heidt, M. H. Proffitt, and others, "Lagrangian photochemical modeling studies of the 1987 Antarctic spring vortex. 2. Seasonal trends in ozone," J. Geophys. Res. (Atmos) 94(DI4), 16717-35 (1989); CA 114 68161f; in stratosphere.

89BARIBEC 1. Barnes, K. H. Becker. D. Martin, P. Carlier, G. Mouvier, J. L. Jourdain, G. Laverdet, and G. Le Bras, "Impact of halogen oxides on dimethyl sulfide oxidation in the marine

atmosphere," ACS Symp. Ser. 393 [Biog. Sulfur Environ.]. 464-75 (1989); CA 112 238441a; reaction.

89BOW/BOY G. A. Bowmaker and P. D. W. Boyd, "An SCF-MS-Xa study of the bonding and nuclear quadrupole coupling in oxygen compounds of the halogens," THEOCHEM 60. 161-75 (1989); CA 112 84498k; bonding, nuclear quadrupole coupling.

89BRU/AND W. H. Brune. J. G. Anderson, and K. R. Chan, "In situ observations of bromine oxide (BrO) over Antarctica: ER-2 aircraft results from 54° S to 72° S latitude." 1. Geophys. Res. (Atmos.) 94(DI4), 16639-47 (1989); CA 113 236826b: in stratosphere. deals with BrO (not Br308)'

89CARISAN M. A. Carroll. R. W. Sanders, S. Solomon. and A. Schmeltekopf. "Visible and near-ultraviolet spectroscopy at McMurdo Sation, Antarctica. 6. Observations of bromine oxide (BrO)." J. Geophys. Res. (Atmos.) 94(D14), 16633-8 (1989); CA 113 236825a: in stratosphere, deals with BrO (not BrJOR)'


89FOEINOS H. D. Foersterling and Z. Noszticzius, "An additional negative feedback loop in the classical Belousov-Zhabotinsklii reaction: malonyl radical as a second control intermediate," J. Phys. Chern. 93(7), 2740-8 (1989); CA 110 142188f; reaction.

89FRIISAN R. R. Friedl and S. P. Sander, "Kinetics and product studies of the reaction chlorine monoxide + bromine monoxide using discharge-flow mass spectrometry," J. Phys. Chern. 93(12), 4756-64 (1989); CA 111 13080m; reaction with CIO(g).

89KOIR00 M. K. W. Ko, J. M. Rodriquez, N. D. Sze, M. H. Proffitt, W. L. Starr, A. Krueger, E. V. Browell, and M. P. McCormick, "Implications of AAOE observations of the seasonal and interannual behavior of Antarctic ozone," J. Geophys. Res. (Atmos) 94(014), 16705-15 (1989); CA 114 68160e; in stratosphere.

89MELIPOU A. Mellouki, G. Poulet, G. Le Bras, R. Singer, J. P. Burrows, and G. K. Moortgat, "Discharge flow kinetic study of the reactions of nitrate radical with bromine, bromine monoxide, hydrogen bromide, and hydrogen chloride," J. Phys. Chern. 93(24), 8017-21 (1989); CA III 241084w; kinetics of reaction with N03 -, EPR.

89SANIFRI S. P. Sander and R. R. Friedl, "Kinetics and product studies of the reaction chlorine monoxide + bromine monoxide using flash photolysis-ultraviolet absorption," J. Phys. Chern. 93(12), 4764-71 (1989); CA III 15161n; reaction with N02 •

89S0LlSAN S. Solomon, R. W. Sanders, M. A. Carroll, and A. L. Schmeltekopf, "Visible and near-ultraviolet spectroscopy at McMurdo Station, Antarctica 5. Observations of the diuranal variations of bromine oxide and chlorine dioxide," J. Geophys. Res., D: Atmos. 94(D9), 11393-403 (1989); CA 113 27063n; in lower stratosphere.

89STA D. M. Stanbury, "Reduction potentials involving inorganic free radicals in aqueous solutions," Adv. Inorg. Chern. 33, 69-138 (1989); CA 111 162816h.

90BIG/BRO P. Biggs, A. C. Brown, C. Canosa-Mas, P. Carpenter, P. S. Monks, and R. P. Wayne, "The reactions of nitrate radical with atoms and radicals," Phys.-Chem. Behav. Atmos. Pollut., (Proc. Eur. Symp. 1989) 5th, 204-9 (pub. 1990); CA 115 77627k; reactions with nitrate radical.

90BOT/BAR J. W. Bottenheim, L. A. Barrie, E. Atlas, L. E. Heidt, H. Niki, R. A. Reinholt, and P. B. Shepson, "Depletion of lower tropospheric ozone during Arctic spring: the Polar Sunris.~ Experiment 1988," J. Geophys. Res. (Atmos.) 95(Dl1), 18555-68 (1990): CA 115 12675e; in troposphere, deals with BrO (not Br308)'

90DAN/CAR F. Danis, F. Caralp, J. Masanet, and R. Lesclaux, "Kinetics of the reaction bromine monoxide + nitrogen dioxide M .....; bromine nitrate + M in the temperature range 263-343 K." Chern. Phys. Lett. 167(5), 450-6 (1990); CA 113 473 16z; reaction with NO} .

90HARIWHI G. L. Harlow, C. A. Whitehurst, H. Robards, D. Deville, and B. V. Rao, Ash vitrification-a technology ready for transfer, Proc. Shale Waste Process. Conf. 14th, 143-50 (1990), CA 115 986l3t; in vitrified slag.

901AC M. E. Jacox, "Vibrational and electronic energy levels of polyatomic transient molecules. Supplement," J. Phys. Chern. Ref. Data 19(6), 1387-1546 (1990); CA 115 263718r; electronic and vibrational energy levels, review.

90100 F. Jooste, "Stabilized sterilizing or disinfecting halogen-containing composition, method, and apparatus," PCT lnt. Appl. WO 90 08,558 (j 990); CA 114 P88678h; stable disinfectant containing.

90LEV/OGO W. Levason, J. S. Ogden. M. D. Spicer. and N. A. Young, "Characterization of dibromine oxide (Br20) by bromine K-edge EXAFS and IR spectroscopy," 1. Am. Chern. Soc. 112(3), 1019-22 (1990); CA 112 68662d; preparation of Br

20. decomposition of Br02 .


90PHI L. F. Phillips, "Collision-theory calculations of rate constants for some atmospheric radical reactions over the

temperature range 10-600 K," J. Phys. Chern. 94(19), 7482-7 (1990); CA 113 135958r; rate constants of reactions.

90POUILAN G. Poulet, I. T. Lancar, G. Laverdet, and G. Le Bras. "The BrO and CIO reaction and the polar stratospheric ozone," in Phys.-Chem. Behav. Atmos. Pollut. [Proc. Eur. Symp.,

5th, eds. G Restelli and G. Angeletti], 190-5 (1990); CA 115 77625h; reactiun wittI CIO(g).

90POUILAN2 G. Poulet, I. T. Lancar, G. Laverdet, and G. Le Bras,

"Kinetics and products of the bromine monoxide . + chlorine monoxide reaction," J. Phys. Chern. 94(19), 218-84 (1990); CA 112 43481f; reaction with CIO(g).

90SASIHUI L. V. Sastry, R. E. Huie, and P. Neta, "Formation and reactivity of hypophosphite and phosphite radicals and their

peroxyl derivatives," J. Phys. Chern. 94(5), 1895-9 (1990); CA 112 126245h; electron exchange reaction.

90S0L S. Solomon, "Progress towards a quantitative

understanding of Antartic ozone depletion," Nature 347, 347-54 (1990).

90TUR A. A. Turnipseed, "Kinetics of the reactions of bromine monoxide radicals with chlorine monoxide and bromine monoxide, and the chemiluminescent reactions of fluorine

with dimethyl sulfide," PB90-256322, 155 pp. (1990); CA 114 172367p; self reaction with CIO(g), kinetics, self dlsproportlOnatlOn.

90TURIBIR A. A. Turnipseed, J. W. Birks, and 1. G. Calvert, "Kinetics of the bromine monoxide radical + bromine monoxide

radical reaction," J. Phys. Chem. 94(19), 7477-82 (1990); CA 113 139614y; self disproportionation, Br202 as an intermediate.

91ANDrrOO 1. G. Anderson, D. W. Toohey, and W. H. Brune, "Free radicals within the Antarctic vortex: the role of CFC's in Antarctic ozone loss," Sci. 251(4989), 39-46 (1991); CA

114 128100x; in Antarctic vortex. 91ARS/ZIV M. Arsenovic, M. Zivanovic. and R. Sovljanski, "Weed

control on railways in Yugoslavia," Brighton Crop Prot. Conf. - Weeds 3, 1159-64 (1991): CA 116 250367w.

91BARIBAS 1. Barnes, V. Bastian, K. H. Becker. and R. D. Overath, "Kinetic studies of the reactions of iodine oxide. bromine oxide, and chlorine oxide with dimethyl sulfide," Int. 1. Chern. Kinet. 23(7),579-91 (1991); CA 115 113768a; reaction.

91BEN/GER C. R. Bennett and J. Gerlach, "Removal of selenium from

wastewaters:' U.S. Patent No. 5,071,568 (1991); CA 116

P 180462x: oxidizing agents.

9lJADILON D. B. Jadhav and A. L. Londhe, "A portable spectrometer with source intensity variation compensation for visible twilight spectroscopy," Ind. J. Techno!. 29(9). 455-8 (1991); CA I 15 286115 f: determination in troposphere.

91 LANILA V I. T. Lancar, G. Laveret. G. Le Bras, and G. Poulet. "Rate constant and products of the bromine oxide + bromine monoxide reaction at 298 K," Int. J. Chern. Kinet. 23! I). 37-45 (1991): CA 114 172324x: kinetics of recombination.

91~IOL1fJAK G. H. Mount. R. O. lakoubek. R. W. Sanders. 1. W. Harder. R. Winkler. T. Thompson. and W. Harrop. "New spectroscopic IIlstrumentatlOn tor measurement or

stratospheric trace species by remote sensing of scattered skylight.·· Proc. SPIE-Int. Soc. Opt. Eng. 1491 (Remote Sens. Atmos. Chern.). 188-93 (1991); CA 115 286129p: determination in stratosphere. most likely deals BrO (not Br,O~).

91NICR D. M. ~Iurphy. "Ozone loss rates calculated along ER-2

flight tracks," 1. Geophys. Res. (Atmos.) 96(D3). 5045-53 11 qq 1,"- C A 11-1. "") 1 OqqSb: r,>aC'tion~

91 ~El'/DOR R. ~euroth. H. P. Dorn. and U. Platt. "High resolution

spectral features of a series of aromatic hydrocarbons and bromine oxide (8rO): potential interferences in atmospheric

hydroxyl-measurements:' 1. Atmos. Chern. 1213 l. 287-98 ( 1991 l: CA 114 252978d: interference.

9 10 RLIBUR J. J. Orlando, J. B. Burkholder, A. M. R. Bopegedera, and C. J. Carleton, "Infrared measurements of bromine monoxide (X2n3/2)," 1. Mol. Spectrosc. 45(2), 278-89 (1991); CA 114 l10997k; IR spectra, spectral constants.

91SZAlWOJ E. Szabo-Bardos, L. Wojnarovits, and A. Horvath, "Pulse radiolysis studies on hexacyanoferrate(II)-bromate-cyanide system in ethylene glycol-water solutions," J. Radioana!.

Nucl. Chem. 147(2), 215-24 (1991); CA 114 174775u; formation, reaction/).

91 TUR A. A. Turnipseed. "Kinetics of the reactions of bromine monoxide radicals with chlorine monoxide and bromone

monoxide, and the chemiluminescent reactions of fluorine with dimethyl sulfide," Ph.D. thesis, University of

Colorado, 151 pp. (1991); Unlv. Microfilms lnt. Order No. DA9117088; Diss Abstr. lnt. B 52(1), 206-7 (1991); CA 115 240971j; full citation not available at this time, self reaction, reaction with ClO(g).

91TURIBIR A. A. Turnipseed, J. W. Birks, and J. G. Calvert, "Kinetics

and temperature dependence of the bromine monoxide + chlorine monoxide reaction," J. Phys. Chern. 95(1 1), 4356-64 (1991); CA 114 235796a; temperature dependence, kinetics.

92FAN/JAC S.-M. Fan and D. J. Jacob, "Surface ozone depletion in Arctic spring sustained by bromine reactions on aerosols," Nature 359, 522-24 (1992).

92GILfLEV T. R. Gilson and W. Levason, "Bromine perbromare: synthesis and bromine K-edge EXAFS studies," J. Am.

Chern. Soc. 114(13), 5469-70 (1992); CA 117 19295f; hydrolysis, molecular structure.

92GILIPOL M. K. Gilles, M. L. Polak, and W. C. Lineberger,

"Photoelectron spectroscopy of the halogen oxide anions oxygen fluoride ion (I -), oxygen chloride ion (1-), oxygen bromide ion (1-), oxygen iodide ion (1-), chlorine rlim:irl~ ion (1-), anrl iodine rlimide ion(1 -)," J Chern.

Phys. 96(11), 8012-20 (1992); CA 117 79197k; electron affinity.

92MCC/HEN J. C. McConnell, G. S. Henderson, L. Barrie, J. Bottenheim, H. Nikis, C. H. Langford and E. M. 1. Templeton.

"Photochemical bromine production implicated in Arctic boundary-layer ozone depletion:' Nature 355, 150-52 (1992).

92NOV I. Novak. "Molecular and electronic structure of bromine oxide (Br~O)," Stmct. Chern. 3(6). 377-9 (1992); CA 118 46210b; ab initio calculation of structure.

92POUIPIR G. Poulet. M. Pirr"e, F. Maguin, R. Ramaroson, and

G. Le Bras, "Role of the bromine oxide + hydroperoxo reaction in the stratospheric chemistry of bromine," Geophys. Res. Lett. 19(23), 2305-8 (1992); CA 118 216913c; kinetics.

92ROSrrIM V. V. Rosanov. Yu. M. Timofeev, 1. Burrows. and W.

Scheider, "Sensitivity of transmission functions in tangential directions to variations in atmospheric gas

composition." Izv. Akad. Nauk, Fiz. Atmos. Okeana 28(7), 714-20 (1992); CA 119 143361e: detection of BrO. CIO and OCIO.

92WAH/SCH A. Wahner and C. Schiller. "Twilight variation of vertical column abundances of chlorine ~ dioxide and bromine monoxide in the North Polar region," 1. Geophys. Res. [Atmos.] 97(D8), 8047-55 (1992); CA 118 63563m: vertical column abundances.

92W AT 1. W. Waters. "Submillimeter-wavelength heterodyne spectroscopy and remote sensisng of the upper

atmosphere:' Proc. IEEE 80(11), 1679-701 (1992): CA II)!, 4R')f)')v' nf"If"C'lion of 79Br() :1nn O'Rr()

93BRIIVEY I. Bridier. B. Veyret. and R. Lesclaux, "Flash photolysis

kinetic study of reactions of the bromine oxide (BrO) radical with BrO and hydrogen dioxide (HO~) radicals," Chern. Phys. Lett. 201(5-6). 563-8 (1993): CA 118 90600c; kinetics.



93CURIRAD J. A. Curry and L. F. Radke, "Possible role of ice crystals in ozone destruction of the lower Arctic atmosphere,"

Atmos. Environ. Part 27A(17-18), 2873-8 (1993); CA 120: 139704x; kinetics, reaction in troposphere.

93KUS/SEP R. Kuschel and K. Seppelt, "Bromine bromate, Br203'" Angew. Chern. 105(11), 1734-5 (1993); Eng. transl., Angew. Chern. lnt. Engl. 32(11), 1632-33 (1993); CA 120 67967k; crystal data.

93MAUIW AH R. L. Mauldin III, A. Wahner and A. R. Ravishankara, "Kinptir,<; ilno mpc.hilni<;m of the self-reaction of the bromine oxide radical," J. Phys. Chern. 97(27), 7585-96 (1993); CA 119 81169n; kinetics, an absorption peak of Br7 0 7 , formation.

93MON/STI P. S. -Monks, L. J. Stief, M. Krauss, S. C. Kuo, and R. B.

Klemm, " A discharge-flow photoionization mass

spectrometric study of the bromine oxide (BrO)(X2rr) radical. Photoionization mass spectrum and ionization energy," Chern. Phys. Lett. 211(4-5), 416-20 (1993); CA llY 169/02s; dIscharge-flow photoionizarion mass spectroscopy of 79BrO and 8IBrO.

93SALIWOF R. J. Salawitch, S. C. Wofsy, E. W. Gottlieb, L. R. Lait, P. A. Newman, M. R. Schoeberl, M. Lowenstein, J. R.

Podolske, S. E. Strahan, et aI., "Chemical loss of ozone in the Arctic polar vortex in the winter of 1991-1992," Sci. 261(5125), 1146-9 (1993); CA 119 185156x; kinetics.

93SCHIABD L. Schriver-Mazzuoli, O. Abdelaoui, C. Lugez, and A. Scriver, "MiltriX rpilrtion of ozone with chlorine and bromine. Fourier transform IR identification of BrClO and CIBrO," Chern. Phys. Lett. 214(5), 519-26 (1993); CA 120 41778z; IR spectra.

93STI S. Stinson, "New oxides of bromine, nitrogen prepared," Chern. & Eng. News, 51-2 (Nov. 29, 1993); confirms

existence of Br203 . 93THOIDA Y R. P. Thorn, E. P. Daykin. and P. H. Wine, "Kinetics of the

bromine oxide + nitrogen dioxide association reaction. Temperalun: ami pre~sUlc lkpcndcncc in the falloff region," lnt. 1. Chern. Kinet. 25(7), 521-37 (1993); CA 119 147452h; kinetics.

93WIN/NIC P. H. Wine, 1. M. Nicovich, A. J. Hynes, R. E. Stickel, R. P. Thorn. M. Chian, 1. A. Cronkhite, 1. C. Shackelford, and Z. Zhao, "Laser flash photolysis studies of atmospheric free radical chemistry using optical diagnostic techniques," SPIE-Int. Opt. Eng. 1715,2-14 (1993); CA 119 166708n; kinetics.

94ARP/JOH K. H. Alpag, P. V. Johnston, II. L. Miller, R. W. Sanders and S. Solomon, "Observations of the stratospheric BrO column over Colorado, 40 ON," J. Geophys. Res. [Atmos.] 99(D4), 8175-81 (1994); CA 121 235108x; UV BrO absorption bands at 349 and 355nm.

94CHI/CAR M. p, Chipperfield, D. Cariolle and P. Simon, "A 3D

transport model study of chlorine activation during EASOE." Geophys. Res. Lett. 21(13), 1467-70 (1994); CA III 262298r.

9-1-COXICOX 1. P. Cox and R. W. D. Cox. "Devolatilizing and stabilizing \'olatile pollutants using halogen containing treatment

agents." PCT Int. App!. WO 9414.524,118 pp. (1994); CA 121 P 163030r; reaction.

Y4D]\;tJI:::Ll A. ~, uneprovskii, E. V. Eliseenkov and A. V. Pullusenill.

. 'Mechanisms of free-radical reactions. XXIX. Free-radical halogenations by chlorine(I) oxide and bromine(I) oxide.

Selectiyity ofhaloxy radicals." Zh. Org. Khim. 30(2). 221-6 II 994); CA 122 9259m; kinetics.

94GARISOL R. R. Garcia and S. Solomon. "A new numerical model of the middle atmosphere 2. Ozone and related species." J. Geophys. Res, 99(06), 12937-12,951 (1994): CA 121 160l61"

9-1-HAC/PLA ~L Hausmann and U. Platt. "Spectroscopic measurement of bromine oxide and ozone in the high Arctic during

polar sunrise experiment 1992." J. Geophys. Res. [Atmos.] 99(012) 25. 399--1-13 (1994); CA 122 166007v: detection.


94HJEIROS A. Hjelmfelt and 1. Ross, "Electrochemical experiments on thermodynamics at nonequilibrium steady states," 1. Phys.

Chern. 98(39), 9900-2 (1994); CA 121 189795u; reaction. 94INO A. Inoe, "Electrodeless discharge lamps," Jpn. Kokai

Tokkyo Koho JP 06.111,790 [94,111,790], 5 pp. (1994); CA 121 P267357u.

94JAC M. E. Jacox, "Vibrational and electronic energy levels of

poly atomic transient molecules," J. Phys. Chern. Ref. Data, Monograph No.3, 461 pp. (1994); supersedes 84JAC.

94.LEOfSFP n T ,p,opo'o ilno K. Seppelt. "Dibromine pentoxide Br205'" Angew. Chern. 33(9), 975-6 (1994).

94MARICOR A. Mariani, E. Corpaccioli, M. Fibbi, R. Veratti, A. Hahne,

J. Callies and A. Lefebvre, "GOME: a spectrometer for ozone monitoring from space," Proc. SPIE-Int.

Soc. Opt. Eng. 2209 (Space Optics 1994: Earth Observation and Astronomy), 57-67 (1994); Ca 122

168487a; detection.

94POMIPIQ J.-P. Pommereau and J. Piquard, "Observations of the vertical distribution of stratospheric OCIO," Geophys. Res. Lett. 21(13), 1231-4 (1994); CA 121 262270a; implication of OCIO distribution on spectral observations and reactivity of BrO (which was not observed).

94RAT/JON O. V. Rattigan, R, L. Jones and R. A. Cox, "The visible spectrum of gaseous OBrO," Chern. Phys. Lett. 230(1-2), 121-6 (1994); CA 122 41328u; visible spectra (gas).

94RUS/DER D. RU3eie and J. Berkowitz, "Experimental determination

of LlH~(HOBr) and ionization potentials (HOBr): implications for corresponding properties HOI," J. Chern. Phys. 101(9), 7795-7803 (1994); CA 121 308799k.

94THO R. P. Thorn, "Laboratory studies of stratospheric bromine

chemistry: kinetics of the reactions of bromine monoxide with nitrogen dioxide and atomic oxygen," 259 pp. (1993); Diss. Abstr. lnt. B 54 (12, Pt.l), 6255 (1994); CA 121 138046t.

94TOU R. Toumi, "BrO as a sink for dimethylsulfidein the marine atmosphere," Geophys. Res. Lett. 21(2), 117-20 (1994); CA 121 87975k.

94WEN/COH P. O. Wennberg, R. C. Cohen, R. M. Stimpfle,

J. P. Koplow, 1. G. Anderson, R. J. Salawitch, D. W. Fahey, E. L. Woodbridge, E. R. Keirn, R. S. Gao, C. R. Webster, R. D. May, D. W. Toohey, L. M. Avallone, M. H. Proffit, M. Loewenstein, J. R. Podolske, K. R. Chan, and S. C. Wuf:,y, "Removal of stratospheric 0 3 by radicals: in

'situ measurements. of OH, H02 , NO, N02 , CIO, and BrO"-: Sci. 266, 398-404 (1994); CA 121 283972w; kinetics.

95FLE/CHA E. L. Flemings, S. Chandra, C. H. Jackman, D. B. Considine and A. R. Douglass, "The middle atmospheric

response to short and long term solar UV variations: analysis of observations and 20 model; results," J. Atmos.

Terr. Phys. 57(4), 333-65 (1995); CA 122 246828b; detection.

95HUEIHAN L. G. Huey, D. R. Hanson and C. 1. Howard, "Reactions of

SF6 - and 1- with atmospheric trace gases," 1. Phys. Chern. 99(14),5001-8 (1995); CA 122 193002w; kinetics.

95HUIILAS R. Huie and B. Laszlo, "Atmospheric chemistry ot IOdme compounds," Adv. Chern. SeT.. in press.

95LEE T. J. Lee, .. Ab initio characterization of triatomic bromine

molecules of potential interest in stratospheric Chemistry," 1. Phys. Chern. 99, 15074-80 (I 995); geometry, enthalpy of formation.

95MAIIBOT G. Maier and A. Bothur, "Bromine superoxide: generation

and photo isomerization into bromine dioxide," Z. Anorg. Allg. Chcl11. 621. 743-6 (1995); vibrational frequencies.

95MUE/COH H. S, P. Mueller and E. A. Cohen, J. Phys. Chem. (to be

published). 95MUE/MIL H. S, P. Mueller, C. Miller and E. A. Cohen, Angew, Chem.

(to be published).


950RLIBUR J. J. Orlando and J. B. Burkholder, "Gas-phase UV/visible absorption spectra of HOBr and Br20," J. Phys. Chern. 99(4), 1143-50 (1995); CA 122 60571j; UV/visible absorption spectra (gas phase).

95THOICRO R. P. Thorn, J. M. Cronkhite, J. M. Nicovich and P. H. Wine, "Laser flash photolysis studies of a radical-radical reaction kinetics: OePJ) + BrO reaction," J. Chern. Phys. 102(10),4131-42 (1995); CA 122 193003x; kinetics.

95THOIMON R. P. Thorn Jr., P. S. Monks, L. J. Stief, S.-C. Kuo, Z. Zhang and R. B. Klemm, (a) 'A preliminary report on the photoionization efficiency spectrum, ionization energy and heat of formation of Br20; and the appearance energy of BrO+(Br20),' Brookhaven National Laboratory, Report BNL No. 62126, 11 pp. (1995); (b) 'The photoionization efficiency spectrum, ionization energy and heat of formation of Br20,' J. Phys. Chern. (in press).


25, 1069 (1996); https:// doi.org/10.1063/1.555993 bromine ...journal of physical and chemical...

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