CONTENTS

CHAPTER I THE TBEORETICbL BABIIl OF Q U A m I T A r n OHEmcAL

~ A L Y 8 E 8 PAGE

I, 1. Electrolytic dissociation . 1 I, 2. The law of mass action . 4 I, 8. Application of the law of mass action to solutions of

electrolytes . 6 'I, 4. Strengths of acids and bases . . 6 I, 6. Activity and activity coefficient . . 8 I, 6. Ionisation of polybasic acids . . I . . 9 I, 7. Common iofi effect . . 11 I, 8. Solubility product . 13 I, 0. Completeness of precipitatioh. ~ i a n t i t k v e 'effects oi a

common ion . . 17 I, 10. Limitations of the solubility iroduct pii~ciple ' . 18 I, 11. Fractional precipitation . . 21 I, 1I1. Complex ions . . 22 I, 18. Effect of acids upon the solubility of aprecipitate . . 26 I, 14. Effect of temperature upon the solubility of a precipitate 26 I, 16. Effect of the solvent upon the solubility of a precipitate 26

, I, 16. The ionic product of water . . 26 I, 17. The hydrogen ion exponent, pH . . 28 I, 18. The hydrolysis of salts . . 30 I, la. Hydrolysis constant and degree of hydrolysis . 33 I, W). Buffer solutions . . 38

VOLUMETRIC ANALYSIS I, $l. Volumetric analysis .

JI, a. Classification of reactions in ;olum&ric analy& : I, m. Eqmvalent weights. Normal solutions . . .. I, 24. Advantages of the use of the equivalent system for the

preparation of standard solutions . I, S. Preparation of standard solutions . L, m. Primary standard substances . --. Xe&r@ation indicators .

$B. Prepara-of indicator solutions . . . 29. Mixed indicatbrs

4 I, 80. Universal or multipkrange indicators . -- I, 81. Neutralisation curves .

I, 33. Neutralisation of a strong acid and a strong base . I, 88. Neutralisation of a weak acid with a strong base . I, 84. Neutralisation of a weak base with a strong acid . I, 86. 'Neutralisation of a weak acid with a weak base, . I, 88. Xeutralisation of apolybasic acid with a strong base . .

/I, 87. Tibration of solutions of hydrolysed salts. Displacement titrations

fi 88.' Choice of indicators in neutralisation reactions . ix D

x Contents THEORY OF PRECIPITATION' AND COMPLEX-FORMATION

PROCESSES PAGE 89, Precipitation reactions . . 86

40. Cqmplex-formation reactions . . -89 41. Determination of end points in precipitation and in

complex-formation reactions . . 90

& k. THEORY OF OXIDATION-REDUCTION REACTIONS I, 48. Electrode potentials . I, 44. Concentration cells . 1 46. Calculation of the e.m.f. of a voltaic Eel1 I, 46. Oxidation-reduction cells . I, 47. Calculation of the oxidation potential . . . I, 48. Equilibrium constants of oxidation-reduction reactions I, 49. Change of the electrode e e n t i a l during the titration of an

oxidant and a reductant. Oxidation-reduction curve 4 60. Indicators for the determination of end points in oxidation-

reduction titrations I, 61. Potestiometric titration . I, 62. Determination of $H . I, 68. Experimental details concerning potentiometric titmtions..

Recent developfnents in the technique of potentiometric titration and of other physical methods of analysis

THEORY OF GRAVIMETRIC ANALYSIS 'I, 64. Gravimetric analysis . . 138

I, 66. Precipitation methods . . 136 I, 66. The colloidal state . . 140 I, 67. Supersaturation and precipitate formation . . 145 I, 68. The purity of the precipitate. Cbprecipitation . . 147 I, 69. Conditions of precipitation . . . 149

/ I , 60. Washing of the precipitate . . 160 I, 61. Fractional precipitation . . 16% I, 62. Organic precipitants . . 158 I, 68. Volatilisation or evolution methods . . 169

ELECTRO-ANALYTICAL METHODS

I, 84. Theory of electro-analysis . I, 85. Decomposition potentials . I, 66. Electrode reactions . I, 67. Overvoltage . I, 68. Completeness of deposiiion

'

I, 69. Electrolytic separation of m e k s : I, 70. Character of the deposit . I, 71. Separation by mlscellaneoue physical methods. I, 7% Errors in quantitative analysis . . I, 78. Classification of errors I, 74. Minimisation of errors . I, 76. Significant figures and compubtio& : ,

Contents 4 CHAPTER I1

-AL -52- OF QU

Balance, weights, and weighing . Description of a typical analytical The requirements of a good balance . Weights. Reference masses . . . Care and use of the balance . . Methods of weighing Errors in weighing . . . . Calibration of weights . Other types of balances .

GENERAL APPARATUS, REAGENTS

10. General apparatus . 11. Reagents 12. Purification 4f substances . 18. Heating apparatus . 14. Sampling of solids . 15. Crushing and grinding. . 16. Solution of the sample . - .

1 TECHNIQUE OF VOLUMETRIC 4 II, 17. Unit of volume . . , * a 18. Standard temperature . . . a 19. Volumetric apparatus . , . XI, 20. Measuring flasks . a. Pipettes . . . C

I& 22. Burettes . a 23. Weight burettes . XI, 24. Graduated cylinders . IX, 25. Storage and preservation of soln

analysis .

lS, a. Precipitation . . . . 11, m. Filtration . . . 11, 28. Filter papers . . .. -n, B. Macerated filter paper . . I& 80. Filter mats. Cooch crucibles . 11, 81. Preparation of a Gooch crucible . I& 83. Munroe crucibles . . . a 88. Crucibles fitted with permanent porous

-3II, 84. Washing of precipitates . . I& 86. Technique of atration . . ./a

86. Drying and ignition of precipitates . 2 XI, 87. The care and use of platinum vessels . j

88. Perforated screens for crucibles . .

PAGE 86

-89

, I Contents xi

CHAPTER I1

-AL 'rEmMIQllE OF Q U r n A T I V E ANALYSIS PAGE

II, 1. ~alance, weights, and weighing . . 194 II, 2. Description of a typical analytical balance . . 196 II, 5. The requirements of a good balance . . 197 II, 4. Weights. Reference masses . 198 11, 5. Care and use of the balance . 200 II, 6. Methods of weighing . 201 II, 7. Errors in weighing . . 208 II, 8. Calibration of weights 1 . . . 212 II, 9. Other types of balances . . 216

GENERAL APPARATUS, REAGENTS AND OPERATIONS

II, lo. General apparatus . . 218 II, 11. Reagents . 226 II, 12. Purificatio~! qf substances . . 228

. II, 18. Heating apparatus . . 230 II, 14. Szimpling of solids . . 233 . II, 15. Crushing and grinding. . . 234 II, 16. Solution of the sample . - . . 236 c

-. -- TECHNIQUE OF VOLUMETRIC ANALYSIS

II, 17. Unit of volume . . 238 II, 18. Standard temperature . . 239 II, 19. Volumetric apparatus . 239 II, 20. Measuring flasks . . 240 II, %I. Pipettes . . 243 - II, 23. Burettes . . 246 II, 23. Weight burettes . 263 II, 24. Graduated cylinders . . 254 II, 25. Storage and preservation of solutions in volumetric

analysis . . . 264 .

I TECHNIQUE OF GRA VIMETRIC ANALYSIS

II, 243. Precipitation . . 268 fL 27. Filtration . . 269

- - II, 28. Filter papers . . 269 m, %. %rated @ter paper . , 262 II, 80. Filter mats. Gooch crucibles . , 263 II, 81, Preparation of a Gooch crucible . . . . 263 - II, 82. Munroe crucibles . . . 266 JI, 88. Crucibles fitted with permanent porous plates . . 266

+I& 54. Washing of precipitates . . 267 I& 85. Technique of filtration , . 269 I& 36. Drying and ignition of precipitates . . 270 II, 87. The care and use of platinum vessels . . 274 . II, 88. Perforated screens for crucibles . , 277

xii Contents

1 CHAPTER I11

VOLuME!mIC ANALYSIS $

ACIDIMETRY AND ALRALIMETRY

III, 1: Preparation of a standard acid . . 278 / III, 8. Preparation of constant boiling point hydrochloric acid 279 IU, 8. Direct preparation of 0.1N hydrochloric acid from the

constant boiling point acid . . 280 III, 4. Preparation of 0.1N hydrochloric acid and standardisa-

tion . . 281 III, 6. Preparation of standard alkali . . 286 a 6. Standardisation of approx. 0.1N sodium hydroxide . 289 III, 7. Other standard substances for acidimetry and alkali-

metry . . 291 III, 8. Standard barium hydroxide (baryta) solution . . 296 ID, 9. D. * of the Na,CO, content of washing soda . 296 a lo. D. of the strength of glacial acetic acid . . 297

.h& 11. D. of sulphuric acid in the concentrated acid . . 297 ./bO[, 12. D. of sulphuric acid in the fuming acid . . 298

ID, 18. D. of carbon dioxide in the atmosphere . . 298 /XI, 14. D. of a mixture of carbonate and hydroxide. Analysis

of commercial caustic soda . . 299 a 16. D. of a mixture of carbonate and .bicarbonate . . 301 IU, 18. D. of phosphoric acid in commercial orthophosphoric

acid . -. 302 ID, 17. D. of boric acid and Lrax' : . 303 IU, 18. D. of ammonia in an ammonium salt . . 306 IU, 19. D. of nitrates (sodium nitrate in Chile saltpetre) : . 306 IU, 20. D. of nitrogen by Kjeldahl's method. . 307

PRECIPITATION AND COMPLEX FORMATION REACTIONS

IU, a. General discussion . 310 IU, a. Preparation of 0.1N iiver kitratk : . 310 IU, m. Standardisation of the silver nitrate solution . . 311

/IU, M. D. of chlorides . . 313 IU, a. D. of bromides . 313 XU, m. D. of chlorides and bromides with standard mercurous

- perchlorate solution . . 315 II1, 81. D. of iodides . . 316 IU, a. D. of thiocyanates . . 317

k ID, a. D. of mixtures of halides with absorption indicators . 317 IU, 80. D. of mixtures of halides by an indirect method - . 317 III, 81. Preparation and use of 0.1N ammonium or potassium

thiocyanate: Titrations according to Volhard's method . . 318

,ID, a. D. of silver in a silver alloy . 320 a m. D. of chlorides (Volhard's method) . . 3% III, W. D. of bromides (Volhard's niethod) . . 322

i IU, 86. D. of iodides (Volhard's method) . . 322

k , *D. = Determination.

Contents

I& m. D. of hyposulphites S

III, 87. D. of cobalt . III, 88. D. of nickel . m, 89. D. of fluoride as lead chlorofluorihe ; III, 40. D. of arsenic as silver arsenate . . III, 41. D. of cyanides . . . III, 4% D. of nickel by potassium cyanide . IU, 68. D. of thiocyanates . III, 44. D. of barium and of sulphates . . OXIDATION-REDUCTION TITRATZONS.

REDUCTIMETRY III, 66. General discussion . . .

OXIDATIONS WITH POTASSIUM PE III, 46. Discussion . IU, 47. Preparation of 0.1N potassium pe III, QS. Standardisation of permanganate so

48. Permanence of potassium permang 60. D. of ferrous iron . u. Reduction of ferric tp ferrous iron .

4 68. D. of iron in ferric ammonium sulphate [III, 68. D. of total iron in an iron ore . . /lIl, #. D. of calcium in calcium carbonate . III, 56. Analysis of hydrogen peroxide . - . III, 56. Analysis of sodium peroxide . .

M. D. of manganese dioxide in pplusite III, 68. D. of nitrites .

' III, 69. D. of persulphates . I /m, 60. D. of manganese in steel (bismuthate III, 81. D. of formates and of formic acid . III, 82. D. of selenium .

OXIDATIONS WITH POTASSIUM IU, 68. General discussion III, 64. Preparation of 0.1N potassium dic IU, 65. Standardisation of potassium dic

against iron . I a 86. D. of ferrous iron . . . -- I IIJ, 87. D. of ferric iron (iron in fe&c ammonid

III, 68. D. of total iron in an iron ore . . : IU, 6B. D. of ferrous and femc iron in an iron 4 a 70. D. of chromium in a chromic salt . 3

III, 7 l . D. of chromium in chromite . . < III, 7% .D. of manganese in steel or in mangam

sonIs method) . . . r

OXIDATIONS WITH CERIC SUL III, 78. General discussion . . ID, 74. Preparation of 0.1 N ceric sulphate . IU, 76. Standardisation of ceric sulphate solutiq

f I ' -

".,

/,,, Contents

"CHAPTER I11

r)LmE!mC A#ALm WETRY AND ALKALIMETRY

~ric acid rom the

dardisa-

:ide alkali-

d m hydroxide (barvtal Llutio; :

Irk acid in the fuming acid . c dioxide in the atmosphere .

ire of carbonate and hydroxide. Analysis cial caustic soda .

idd and borax' : h in an ammonium salt .

n COMPLEX FORMATION RBACTIO

011 I. 1~ dver hitratk '

)n of the silver nitrate sdlution r). . . n and bromides with standard mercurous ldiltion .

= - 5: Titrations according to Volhard's

n a silver allov

*D. 4: Determination.

---n,d,a . L - . . C . --

PAGE

278 279

280

28 1 286 289

29 1 296 296 297 297 298 298

299 301

302 303 305 306 307

f NS

310 310 31 1 313 313

316 316 317 317 317

318 320 3% 322 322

..A

I

Contents

f, 88. D. of hyposulphites -*

I, 87. D. of cobalt . I, 88. D. of nickel . I, 89. D. of fluoride as 1eaa'chlorLfluohae E, 40. D. of arsenic as silver arsenate . D, 41. D. of cyanides U, 4. D. of nickel by potassium cyanide U, 48. D. of thiocyanates . U, 44. D. of barium and of sulphates .

xiii PACE

. 322

OXIDATION-REDUCTION TITRATIONS. OXIDIMETRY AND REDUCTIMETRY

III, 46. General discussion . 334

OXIDATIONS WITH POTASSIUM PERMANGANATE III, 46. Discussion . . 334 III, 47. Preparation of 0.1 N potassium permanganate . . 338 III, 48. Standardisation of permanganate solutions . . 339

4.3 49. Permanence of potassium permanganate solutions . 343 60. D. of ferrous iron . . 344

/III, 61. Reduction of femc $0 ferrous iron . . - . 344- 5% D. of iron in femc ammonium sulphate . . 361

f III, 68. D. of total iron in an iron ore . . 352 /m, 64. D. of calcium in calcium carbonate . . 362

III, 66. Analysis of hydrogen peroxide . - . . 354 III, 56. Analysis of sodium peroxide . . 356

/III, 67. D. of manganese dioxide in pyrolusite . . 356 . XI& 68. D. of nitrites . . 367

XI& 69. D. of persulphates . . 358 /XI& 60. D. of mangaqese in steel (bismuthate method) . . 358

XI& 82. D. of formates and of formic acid . . 361 111, 6% D. of selenium . 363

OXIDATIONS WITH POTASSIUM DICHROMATE 1, 88. General discussion 1, _ 64. Preparation of 0.1N potassium dichromate I, 66. Standardisation of potassium dichromate solution

against iron . I, 66. D. of ferrous iron . & .87. D. of femc iron (iron in feqic ammonium sulphate) . 3, 68. D. of total iron in an iron ore . E, a. D. of ferrous and femc iron in an iron ore . D, 70. D. of chromium in a chromic salt . E, n. D. of chromium in chromite . U, 72. .D. of manganese in steel or in manganese ore (Pattin-

sonls method) . r

OXIDATIONS WITH CERIC SULPHATE 111, 78. General discussion 111, 74. Preparation of 0.1 N ceric s;lpha;e : 111, 76. Standardisation of ceric sulphate solution .

xiv Contents Contents . , PAGE III , 76. D. of oxalates . . .

, . . 382 IU, 77. D. of iron in an iron ore . . 383. rn 78. D. of ferrocyanides . 383 Ill, 79. D. of nitrites. . . 384 III, 80. D. of tellurium . 386. m, 81. D. of thallium . . 385 I& 82. D. of cerium . 386

OXIDATIONS WITH MANGANIC SULPHATE

III, 88. General discussion . 387 84. Plleparation and standardisation of manganic sulphate

solutions . . , . . 387 III , 86. Applications of manganic sulphate solutions . . 388

REDUCTIONS WITH TITANOUS SALTS

III, 86. Generirl discussion . 389 JII, 87. Preparation of titanous solutions . . 390 III , 88. Standardisation of titanous solutions . 391 III, 09. D. of iron in an ore . 392

REDUCTIONS WITH AMALGAMATED ZINC AND WITH LIQUID AMALGAMS -

III, BO. General discussio~l . 3 W III, 91. D. of uranium . . 394 'm, @& D. of titanium . 394 III, 93. D. of molybdenum , . . 395 III, 94. D. of vanadium . . 596

95. D. of titanium (zinc amdgam method) . . 396 m, 96. D. of tungsten . 398

III, 97. Reductions with chromous salts . 399 III, 98. Reductions with vanadous salts . 400

OXIDATION AND REDUCTION PROCESSES INVOLVING & D I N E

IODIMETRY AND IODOMETBY

III, 99. General discussion III, 100. Detection of the end point .

101. Preparation of 0.1N sodium thiosulphate . III , 10% Standardisation of sodium thiosulphate solutions III, 108. Preparation of 0.1 N iodine . III, 104. Standardisation of iodine solutions . III, 105. D. of copper in crystallised copper sulplate . ISI, 106. D. of copper in an ore . III, 107. D. of manganese dioxide in pyrolusite . III, 108. D. of chloratea and of bromates III , 100. Volumetric D. of lead . III , 110. Analysis of hydrogen peroxide . III, 111. n. of the available chlorine in bleaching powder .

of hypochhrites . of antimony . of antimony in antimonic oxide a of arsenic in arsenic oxide and in of tin of antimony and tin in type metal of sulphurous acid and of sulphites of hydrogen sulphjdes and of silphi of femcyanides . of femc iron (iodometric method) .

OXIDATIONS WITH WTASSIUY 4 I& la. General discussion . . III, 138. Preparation of 0.1N (0.02671f) .potassium IXI, 124. D. of iodides . . . III, m. D. of arsenic or of antimony . . - I IL 1s. D. of copper . . .

mercurv tin peroxides (lead, barium hydrogen peroxide . hydrazine . thallium . iodides by ceric sulphate

' vanadium .

and

OXIDATIONS WITH POTASSIUM B I ( ~ III, 186. General discussion I& 11. Preparation of 0.1 N potassium bromate III, 187. D. of antimony or of arsenic . III, 1%. D. of metals by means of 8-hydroxyqu III, 189. D. of hydroxylamine .

OXIDATIONS WITH CHLO

- III, 140. General discussion. Preparation III, la. D. of antimwy . III, 14% D. of nitrites . In, 14a. D. of tin IU, 144. D. of ferrocyanides

MISCEUANEO US VOL UMETRZC D

146. D. of zinc with standard potassi solution . . . :

IU, 146. D. of phosphorus . . . I

m 147. D. of temporav and peminent hardn$ IU, 148. D. of sodium . III, 149. D. of potassium . . .

J IU, 160. D. of cadmium . .

Contents xv PAGE

I, 112. D. of hypochlorites . . 428 1,113. D. of antimony . . 428 , 1,114. D. of antimony in antimonic oxide and in antimonates 429 I, 116. D. of arsenic in arsenic oxide and in arsenates . . 430 & 116. D. of tin . 430 & 117. D. of antimony and tin in type metal . . 432 & 118. D. of sulphurous acid and of sulphites . . 433 [I, 119. D. of hydrogen sulphjdes and of silphides . . 434 & l20. D. of femcyanides . . 435 [I, 121. D. of ferric iron (iodometric method) . . 436

OXIDATIONS wrrH PoTAssIuM IODATE$

a 122. General discussion III, 138. Preparation of 0.1N (0.026Af) .potassium iodate . III, 124. D. of iodides . IU, 1%. D. of arsenic or of antimony . IU, 128. D. of copper . IU, 127. D. of mercury

, III, US. D. of tin III, 129. D. of peroxides (lead, barium and manganese dioxides) III, 130. D. of hydrogen peroxide . III, la; D. of hydrazine . m, 132. D. of thallium . III, 18% D. of iodides by ceric sulphate III, 134. D. of vanadium . . - .

OXIDATIONS WITH POTASSIUM BROMATE

IU, 1%. General discussion . 460 IE, 136. Preparation of 0.1N potassium bromate . . 451 III, 187. D. of antimony or of arsenic . . 451

188. D. of metals by means of 8-hydroxyquinoline (" oxine ") 452 III, 188. D. of hydroxylamine . . 458

OXIDATIONS WITH CHLOUMINE-T

' III, 140. General discussion. Preparation of 0.1N solution . 459. III, 141. D. of antimwy . . 460 III, 142: D. of nitrites . . 460 III, 143. D. of tin . 461 m, 144. D. of ferrocyanides . 462

III, 146. D. of zinc with standard potassium ferrocyanide solution . . 463

III, 146. D. of phosphorus . . 464 III, 147. D. of temporary and permanent hardness of water . 466 III, 148. D. of sodium . . 472 ,

III, 149. D. of potassium . . 472 J IKI, 160. D. of cadmium . . 472

xvi Contents

b CHAPTER IV

PAGE IV, 1. General discussion . I . 473 IV, 2. Note book entries, and calculations . . 473 IV, 8. Calculations of gravirnetric analysis. Chemical factors 473

SIMPLE GRAVIMBTRIC DETERMINATIONS

IV, 4. D. of water of hydration in crystallised barium IV, 6. D. of chloride as silver chloride . IV, 6. D. of sulphate as barium sulphate . IV; 7. D. o! sulphur in iron pyrites . IV, 8. D. of iron as femc oxide .

.--- IV, a. D. of aluminium as aluminium oxide . IV, lo. D. of calcium as oxalate, carbQnate or oxide IV, ll. D. of magnesium as pyrophosphate . IV, 12. D. of nickel as the dimethylglyoxime complex

SYSTEMATIC

W, 18. General discussion IV, 14. Lead IV, 15. Silver . IV, 16. Mercury . IV, 17. Bismuth IV, 18. Cadmium . IV, 19. Copper .

/ IV. B. Arsenic .

chloride

GRAVIMETRIC ANALYSIS

IV; 21. Antimony /IV, 2% Tin IV, as. ~01~bdenuA : . . . IV. 24. Selenium and telluriurd. . : IV; 86. Platinum IV, H. Palladium . IV, 87. Gold IV, Aluminium IV, 2B. Beryllium IV, 80. Chromium IV, 81. Iron IV, 38. Nickel . . IV, 88. Cobalt '. IV, 34. Zinc IV, 86. Manganese IV, 86. Vanadium IV, 87. Uranium . IV, 88. Thorium . IV, 89. Cerium . IV, 40. Titanium IV; 4l. Zirconium . IV, 4% Thallium . ,IV, 48. Calcium .

i - m, a. Strontium . IV, 45. Barium IV, 46. Magnesium IV, 47. Sodium .

' .IP; 48. Potassium m, a. Lithium . m, m. Ammonium IV, 51. Tungsteo IV. 62. Chlonde .

Contents

*; &. Bromide . . m, 64. Iodide . m, 55. Thiocyanate . . . . N, 56. Cyanide . IP; 57. Fluoride . IP; 68. Chlorate . . * .

W, as. Perchlorate . IP; 80. Iodate . . . IP; 81. Sulphate . . . IP; 68. Sulphide . m, 68. Sulphite . . . IV, a Thiosulphate . . . . w, 65. Phosphate . . . m, 68. Phosphite . . . IV, 67.. Hypophosphite . . . m, 68. Oxalate . . . IV, 6Q. Borate . . . IV, 70. Silicate . . . . IV, 71. Fluosilicate . . . W, 72. Ferrocyanide . . . IV, 78. Facyanide . . . W, 74. Nitrite . . . . IV, 75. Nitrate . . . , IV, 76. Carbonate . . . .

F ELECTROLYTIC DETERMINA

IV, 77. Apparatus . IV, 78. Copper m, 70. Lead . IV 80. Cadmium . IV: 81. Nickel . IV, w. Cobalt . . . IV, 88. Silver .

/ IV, 84. zinc w, 86. Electrolytic separation and dete nickel . . . -

IV, MI. SIMPLE GRAVIMETRIC SEPARATI

ANALYSIS OF C O M P W

IV, 87. Analysis of brass . . . IV, a. Analysis of bronze . . R, 8. Analysis of German siiver (ni&el lihr

TC ANAZ . YSIS

PAGE 473 473 473

m, 44. Strontium . IV, 46. Barium . IV, 46. Magnesium

, IV.47. Sodium . .lV, 48. Potassium m, 49. Lithium . IV, M). Ammonium IV, Sl. Tungstea IV. 62. Chloride . N, 68. Bromide m, 64. Iodide . IV, M. Thiocyanate IV, 66. Cyanide . IV, 57. Fluoride . IV, 68. Chlorate . IV, MI. Perchlorate IV, 80. Iodate . IV. 01. su l~hate .

Contents xvii. PAGE

. 664

. 666

. 667 . 667 . 670

. 674

. 674

. 576

. 676 . t . 666

. 676 . 677

. 678 : 678 . 680 . 681 . 682 . 682 C"'

62. ~u&hide . . 683 IV, 88. Sulphite . . 683

I IV, 64. Thiosulphate . . 684 IV, 65. Phosphate I

. -684 1 IV, M. Phosphite . 686 i IV, 67.. Hypophosphite . . 687

. IV, SS. Oxalate . . 687 m, 69. Borate . . 688 IV, 70. Silicate . . 688 IV, 71. Fluosilicate . . 691 IV, 72. Ferrocyanide . . 691 IV, 78. Facyanide . . 692 IV, 74. Nitrite . . 692 IV, 75. Nitrate . . 692 IV, 7%. Carbonate . . 69%

ELECTROLYTIC DETERMXNATIONS IV, 77. Apparatus . 686 IV, 78. Copper . . 606 IV, 7@. Lead . _ . . 610 IV, 80. Cadmium . . 611 IV, 8l. Nickel . . 612 IV, 82. Cobalt . . . . 613 IV, 88. Silver . . 614

0 IV, 84. Zinc . 614 IV, 86. Electrolytic separation and determination of copper and

nickel . . 616

W, 86. SIMPLE G ~ V I M E T R I C SEPARATIONS . . 617

ANALYSIS OF COMPLEX MATERIALS lV, 87. Analysis of brass . . 626 IV, 88. Analysis of bronze . 631 lV, 89. Analysis of German siker (iickel iilverj : - : . 634 .

xviii Contefits . E IV, 80. Analysis of solder . IV, 91. Analysis of a silvercoinage alloy . . IV, 98. Analysis of steel . lV, 98. Analysis of an aluminium alloy . IV, 94. Analysis of a limestone or dolomite . JV, 96. Analysis of a fekpar . IV, 98. Analysis of portland cement' :

CHAPTER V

COLORJRUEtWC ANALY8I8 Vs 1. General discussion . V, 2. .Theory of spectrophotometry and colorimetry . V, 8. Classification of methods o t " colour " measurement or

comparison . A,. Standard series method . B. Duplication method . D. Balancing method E. Gradation or step-photometer method . F. Photo-electric photometer method Turbidimetry and nephelometry . D. of the pH of solutions by colorimetric methods . Some general remarks upon colorimetric determinations D. of ammonia . D. of nitrites . D. of iron . . . Manganese Titanium . Vanadium . Chromium Aluminium . . . Molybdenum . Nickel . Cobalt . Arsenic . Antimony . Tin

, V; eS. Lead a: W). Copper . t54. Bismuth .

V, jB. Silver V, MI. Silicate . V, e7. D. of other elements and radicals

CHAPTER VI

PAGE 636 638 639 652 664 661 666

QAS ANALYSIS k 'VI, 1. General discussion . . 732 PI, & Sampling . 733 VI, 8. Purification of mkrcur;l : . . . . . . 734

Cmtents C

V& - 4 . r r w @ n of volume of gas for tern VI, 5. 9ibrat lon of gas measuring vessels VI, 6. Apparatus employed in gas analysis . - VI, 7. Absorbents for w e various gases . . VI, 8. D. by explosion and combustion methods VI, 9 Exercises in gas analysis .

GAS- VOLUMETRIC METHODS ANALYS LIQUIDS

The Lunge nitrometer . VI, D. of nitrates . "h VI, D. of hydrogen peroxide . Vf. 18. Evaluation of pyrolusite . Vf. 14. D. of available chlorine in bleach* VI, ).5. Evaluation of zinc dust . . . VI, 18. D. of ammoniunl salts .

LIST OF PLATES'

RATE I. Cambridge pH meter, electrical and electrodes for use with

PLATE*. B. D. H. hvibond nesslerim PLATE III. Ihusch. and Lomb Duboscq PLATE IV. " Spekker " photo-electric a

a

PAGE . 636 . 638 . 639 - 652 . 664 . 661 . 666

CHAPTER V

n . . . m h h + f i - ~ . --.a . 670

colorimetry . . 761 -, bd10~r " measurement or

csda method . 675 atsthod . . 678 whod . 682 : *photometer method . 683

,,A-

uyvn colonmetric determinations 697

- - - CHAPTER VI

i mALm

e PAGE

VI, -4. Qme€@n of volume of gas for temperature and pressure 736 VI, 5.wibrat ion of gas measuring vessels . . 739 VI, 6. Apparatus emplo3'ed in gas analysis . . 740 VI, 7. Absorbents far fie various gases . . 762 VI, 8. D. by explosion' and cambustion methods . . 767 VI, t Exercises in gas analysis . '* . 770

GAS- VOLUMETRIC METHODS ANALYSIS FOR SOLIDS AND LIQUIDS -

The Lunge nitrometer . . 771 VI, D. of nitrates . -9 . 772 VI, &. D. of hydrogen peroxide . . 774 VI, 18. Evaluation of pyrolusite . . . . . 776 ,

VI, 14. D. of available chlorine in bleaching: powdm . 776 VI, 115. Evaluation of zinc dust . . . . 776 ll& 16. a. of ammonium salts . 776

APPENDH . '. 778 A, ! . Internqtiona~ atomic weights. 1939 .

A, 2. Chemical factors . 779 A, 3. 'I'he literature of analytical chemistry . . 783 A, 4. l)ens~ties of acids a t 200C . . 788 A, 5. Densities of alkaline solutions a t 2WC . . 790 & 6. Data on the strength of aqueous solutions af the common

acids and am~nonium hydroxide . . 790 & 7. Samples and solut~ons for elementary analysis . . 791

8. Anal* samples . 798. . A . 798 2

&, 9. Adytical reagents - & 10. Buffer solutions . . 808 A, 11. Comparison of metric and other units . . 813 n

A, la. Decimals of an inch, I.S.W.G., and millimetres . . Slfj . -:2 & 18. The Greek alphabet . . 816 -. 7 A, 14. Suggested scheme of study for Intermediate Science and

Engineering, Higher School Certificate, and Ordinary National Certiticates in Chemjstry, and Examinations 4 similar character . . . . 811)

A, 15. Suggested scheme of study for B.Sc. Special Chemistry, Honours BSC., Chemistry. Associateship of the Institute C of Chemistry, and minations ~ f~s imi l a r scope . 817 P . . .

g . B B A, 16. Four-figure logarithm A, 17. Five-figure logarithms . . - . . 8%

. 813 a-4

Indes . . . s

LIST OF PLATES 4 To f a e page .a%- ,%

F'LATB I. Cambridge pH meter, electrical circuit of lattet, * : and electrodes for use with this instrument . 131

PLATE*. B. D. H. L-uvibond nesslerimeter . 682 PLATE 111. 13ausch. and Lomb Duboscq c e i m . . 684 PLATE IV. " Spekker " pho t~ l ec t r i c a h r p t i o $!& -1 -. 689