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A TEXT-BOOK OF QUANTITATIVE INORGA-NIC ANALYSIS THEORY AND PRACTICE BY ARTHUR L VOGEL, D.Se. (LOND.);
A
TEXT-BOOK
OF
QUANTITATIVE
INORGA-NIC ANALYSIS
THEORY
AND
PRACTICE
BY
ARTHUR L VOGEL, D.Se. (LOND.); D.Le., F.I.C.
HEAD
OF
CHE}IISTRY
DEPARTMENT.
\VOOLWICH
POLYTECHNIC:
LATELy'
BElT
SCIE:NTIFIC
RESE;ARCH
FELLOW
OF
THE
IMPERIAL
COLLEGE
With Plates and Diagrams
LONGM~NS: GREEN
AND
CO.
LONDON
NEW YORK-
TORONTO
4
By the, same al'tnor A TEXT BOOK OF QUALITATIVE CHEMICAL ANALYSIS With Illusttations " An
By the, same al'tnor
A TEXT BOOK OF
QUALITATIVE
CHEMICAL
ANALYSIS
With
Illusttations
" An exceilent guide to the student from
the early stages in his career up to the
Honours courses."-Nature.
~.'t. ~o. 64. l Imperial Veterinary Res~ .:', Library,! '540\(OG "'''' MUKTESW ~~
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Book No.
~QIPC-S2-rrr·6.25(PD)-6.6.38-250.
QUANTITATIVE INORGANIC ANALYSIS
QUANTITATIVE INORGANIC ANALYSIS
LONGMANS, GREEN AND CO . LTD. OF PATERNOSTER ROW 43 ALBERT DRIVE, LONDON, S.W.19 17
LONGMANS, GREEN AND CO . LTD.
OF PATERNOSTER ROW
43
ALBERT DRIVE,
LONDON, S.W.19
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LONGMANS, GREEN AND
Cpo
2 I 5 VICTORIA ST.REET, TORONTO
First Published 1939
Reprinted June 1941
and November 1942
CODE NUMBER:
85287.
Printed In Great Britain by
Lowe and Bryd6.ne Printers Limited, London. N.\V.IO
PREFACE IN ~ritingthis bot>k, the author had as his primary object the proyision of a
PREFACE
IN ~ritingthis bot>k, the author had as his primary object the
proyision of a complete up-to-date text book of quantitative'
inorganic analysis, both theory and practice, at a moderate
price to i>meet the requirements of
University and College
students of all grades. It is believed that the material con-
tained thereiq. is sufficiently comprehensive to cover the
syllapuses of all exa~inations in which quantitative, inorganic
analy:;is plays a part. The elementary student has been
provided for, and those sections devoted to his needs have
been'" treated in considerable detail.' The volume should
therefore be of value to the §tudent throughout the whole'
of his career. The book will be suitable inter alia for
students preparing for the various Intermediate B.sc. and
Higher School Certificate Examinations, the Ordinary and
Higher National. Certificates in Chemistry, the Honours and
Special B.Sc. of the Universities, the. Associateship of the
Institute of Chemistry, and other Examinations of equivalent
standard. It is. hoped, also, that the wide range of subjects
discussed within its covers will result in the v~lume having'a
special appeal to practising .analytical chemists and to all
those workers in industry-and research who have occasion to
utilise methods of inorganic quantitative analysis.
The kind reception accorded to the author's .Text Book of
Qualitative
Chemical Analysts by teachers and' reviewers
seems to indicate that the general. arrangement of that
book has met with approval: The companion volume on
Quantitative
Inorganic
Analysis tallows essentially similar
lines. Chapter I is devoted to .the theoretical basis of
quantitative inorganic analysis, Chapter II to the experi-
mental technique of quantitative analysis, Chapter III to
volumetric analysis, Chapter IV to gravimetric analysis
(including electro-analysis), Challter V to colorimetric analysis
and Chapter VI to gas analysis; a-comprehensive Appendix
has been added, which contains much useful matter for the
practising a.nalytical chemist. The experimental side is based
.
,
vi Preface esseI1tially upon the writer's experience with large classes of students of various grades.
vi
Preface
esseI1tially upon the writer's experience with large classes of
students of various grades. Most of the determinations have
been tested out in the laboratory in collaboration with the
author's colleagues and senior students, and in some cases
this has resulted in slight modifications of the details given by
the original authors. Particular emphasis has been laid upon
recent developments in experimt-mtaJ technique: Frequently
the source of certain apparatus 'Or chemicals has.been given in
the text: this is not intended to convey tbe impression that
these materials cannot be obtained from other'sources, but
merely- to indicate that the author's own experience is con-
fined to the particular products mentioned.
The ground covered by the book can best be j~dged by
perusal of the Table of Contents. An attempt has been.made
to strike a balance between the classical and modern prgce-
dures, and to present the subject of analytical chemistry as it
is to-day. The theoretical aspect has been stressed thr.ough-
out, and numerous cJ.;oss-references are given to Chapter I
(the theoretical basis of quantitative inorganic an~lysis)
No references to the original literature are given in-the text.
This ts because the introduction of such references would
have
considerably increased the size and therefore the price of the
book. However, a discussion on the literature of 'analytical
chemistry is given in the Appendix (Section A. 3). With the
aid of the various volumes mentioned therein-which should
-be available in all libraries of analytical chemistry-and the
Collective Indexes of Chemical Abstracts or of British
Chemical Abstracts, little difficulty will, in general, be
experienced in finding the original sources of most of the
determinations described in the book. "
In the preparation of this volume, the author has utilised
pertinent material wherever it was to be found. While' it is
impossible to acknowledge every source indi~idually (see, for
example, Section A. 3), mention must, however, be made of
Hillebrand and Lundell's ,Applied Inorganic Analysis (1929)
and of Mitchell and Ward's Modern Methods in Quantitative
Chemical Analysis (1932): In conclusion, the writer wishes
to express his thanks: to Dr. G. H. Jeffery, A.I:C., for
reading the galley proofs and making numerous helpful sug-
gestions; to Mr. A. S. Nic~elson, B.Sc., for reading some
of th~ g~lley proofs; to his laboratory steward, Mr. F. Mathie,
for preparing a numbet of the diagrams. including most
of those in Chapter VI, and for his assistance in other way~;
to Messrs. A. Gallenkamp.and Co., Ltd., oj London, E.C.2, arid
Preface V'll to Messrs. Fisher Scientific Co., of Pittsburgh, Pa., for provid- ing a number
Preface
V'll
to Messrs. Fisher Scientific Co., of Pittsburgh, Pa., for provid-
ing a number of diagrams and blocks;* and 'to Mr. F. W.
Clifford, F.L.A., Librarian to the Chemical Society, and his
able assistants for their help in the task of searching the
extensive literature.
A~y suggestions for improving the book will, be gratefully
receIved by the author.
Woolwich Polytechnic, London, S.E.lS.
June 1939.
• Acknowledgement to other firms and individuals is made in the body of
the text.
CONTENTS CHAPTER I mE THEORETICAL BASIS OF QUANTITATIVE. CHEMIC~ ~ANALYSIS PAGE 1, 1. Electrolytic dissociation
CONTENTS
CHAPTER I
mE
THEORETICAL
BASIS
OF QUANTITATIVE. CHEMIC~
~ANALYSIS
PAGE
1, 1. Electrolytic dissociation
J:, -2. The law of mass action
1
4
1,
3. Application of the
law ot mass action
to solutions
of
electrolytes
,
5
1,
I,
4. Strengths of acids and bases .
5. Activity and activity coefficient
ij
8
I,
6.
Ionisation of polyba~ic acids .
9~
I,
7. Common ion effect
8. Solubility product
II
I,
13
I, .9. Completeness of precipitation. Quantitative effects of a
common ion
17
I, 10. Limitations of the solubility product principle
19
I,
11.
Fractional precipitation
Complex ions
.
.
.'
21
.
I, 13. Effect of acids upon the solubility of a precipitate
I,
12.
.
.
22
25
I, 14. Effect of .temperature upon the solubility of a precipitate
I, 15. Effect of the solvent upon the solubility of a precipitate
I, 16. The ionic product of water
I, 17. The hydrogen ion exponent, pH
26
26
26
28
1,
18.
The hydrolysis of salts .
:
30
1, 19. Hydrolysis constant and degree of hydrolysis
.-
33
1, 20. Buffer solutions .
38
VOLUMETRIC
ANALYSIS
I,
21.
Volumetric analysis .
.
.
.
.
43
I, 22. Classification of reactions in volulltetric analysis
44
"1, 23. Equivalent weights.
Normal solutions
.
45
I, 24. Advantages of the use of the equivalent svstem for the
preparation of standard solutipns
I, 25. Preparation of standard solutions
1, 26. Primary standard substances
I, 27. Neutralisation indicators
.-
53
5U
56
58
1, 28. Preparation of indicator solutiovs
67
1.
29.
Mixed indicators
.
.
.
(jS
I, 30. Universal or multiple-range indicators
70
.
I, 32. Neutralisation of a strong acid and a strong base
I,
31. Neutralisation curves.
,
,
,
70
V
I, 33. Neutralisation of a weak acid with a strong base
I, 34. Neutralisation of a weak base with a strong acid
I, 35. Neutralisation of a weak acid with a weak base,
7.t
77
78
I, 36.
Neutralisation of a polybasic acid with a strong base.
SO
I, 37. Titration of solutions of hydrolysed s~lts.
Displacement
,
I, 3S. Choice of iItdicators in neutralisation reactions
titrations
,
.
,
.,
.
'&2
84
ix
x Contents THEORY OF PRECIPITATION AND COMPLEX-FORMATION . PROCESSES PAGE I. 39. Precipitation reactions. 86
x
Contents
THEORY
OF
PRECIPITATION
AND
COMPLEX-FORMATION
.
PROCESSES
PAGE
I. 39. Precipitation reactions.
86
I. 40. COplplex-formation reactiolls
89
I. 41. Determination of end points
complex-formation reactions
in
precipitation
and
in
90
1,42.
THEORY OF OXIDATION-REDUCTION. REACTIONS
9.6.
I, 43.
98
1,44.
101
1,45.
101
1,46.
102
I, 47.
103
'1,48.
104
·1, 49.
109
1,50.
ll2
1,51.
116
1,52.
.
.
.
.
llB.
I, 53.
Electrode potentials
Concentration cells
Calculation of the e.m.f. of a voltaic cell
Oxidation-reduction cells .
Calculation of the oxidation potential
Equili"brium constants of oxidation-reduction reactions
Change of the electrode potential during the titration of an
oxidant and a reductant. Oxidation-reduction curve
Indicators for the determination of end points in oxidation-
reduction titrations
Potentiometric titration
Determination of pH
Experime:ntal details concerning potentiometric titrations.
Recent developments in the tec;Imique oLpotentiometric
titration and of other physical methods of a~alysis
129
THEORY
OF
GRAVIMETRIC
ANALYSIS
I, 54. Gravimetric analysis
I, 55. Precipitation methods
I. 56. The colloidal state
I, 57. Supersaturation and precipitate formation
136
.
136
140
145
I, 58. The purity of the precipitate.
I, 59. Conditions of precipitation
I, 60. Washing of the precipitate
I, 61. Fractional precipitatiort'
Cbprecipitation
147
149
150
152
I.
62.
Organic precipitants
.
158
I. 63. Volatilisation or evolution methods
169
ELECTRO-ANALYTICAL METHODS
I, 64. Theory of electro-analysis
I, 65. Decomposition potentials
I, 66. Electrode reactions
I, 67. Overvoltage
171
172
171>
176
I. 68. Completeness of deposition
177
I
69. Electrolytic separation of metals
179
r: 70.
Character of the deposit
.
ISO
I. 71. Separation by miscellaneous physical methods.
lSI
I. 72. Errors in quantitative analysis
IS5
I. 73. Classification of errors
lS7
I.
.
r. 7S. Significant figures and ~omputations
74. Minimisation of errors.
.
190
192
Contents Xl CHAPTER II EXPERIMENTAL TECHNIQUE OF QUANTITATIVE ANALYSIS PAGE n, 1. Balance, weights, and
Contents
Xl
CHAPTER
II
EXPERIMENTAL TECHNIQUE OF QUANTITATIVE ANALYSIS
PAGE
n,
1. Balance, weights, and weighing
194-
n,
2. Description of a typical analytical balance
195
n.
3. The requirements of a good balance
197
n,
4. Weights.
Reference masses
198
n.
200
n.
201
n,
n.
n,
5. Care and use of the balance
6. Methods of weighing
7. Errors in weighing
8. Calibration of weights
9. Other types of balances
208
212
216
GENERAL APPARATUS,
REAGENTS AND OPERATIONS
n; 10. General apparatus
n, 11. Reagents
218
226
n,
12.
.
Purificatio~ Qf substances
228
n.
230
n.
13. Heating apparatus
~4. Sampling of solids .
233
n, 15. Crushing and grinding.
n, 16. Solution of the sample
234-
235
TECHNIQUE
OF
VOLUMETRIC
ANALYSIS
n,
17.
Unit of volume.
.•
238
fi, 18. Standard temperature
n, 19. Volumetric apparatus
n, 20. Measuring flasks
239
239
24()
n, 21. Pipettes .
n, 22. Burettes .
n, 23. Weight burettes
243
246
253
n,
24.
Graduated cylinders
.
254
n, 25. Storage
and
preservation.
of
solutions
in
volumetric
analysis.
'
254
TECHNIQUE
OF
GRAVIMETRIC
ANALYSIS
D, 26. Precipitation
258
n, 27. Filtration .
D, 28. Filter papers
259
29.
.
Macerated filter paper
259
D,
.
262
D, 30. Filter mats.
Gooch crucibles
263
n. 31. Preparation of a Gooch crucible
26a
n, 32. Munroe crucibles
.
.
.
.
.
266
n, 33. Crucibles fitted with pertnanent porous plates
266
>
n,
34.
Washing of precipitates
Technique of filtration
.
.
.
.
267
D,
35.
.
.
269
n, 36. Drying and ignition of precipitates
D, 37. The care and use of platinum vessels
270
274
n, 38. Perforated screens for cruci.bles
.
277
xii Contents CHAPTER III VOLUMETRIC ANALYSIS ACIDIMETRY AND ALKALIMETRY PAGE m, 1. Preparation of a
xii
Contents
CHAPTER
III
VOLUMETRIC
ANALYSIS
ACIDIMETRY
AND
ALKALIMETRY
PAGE
m,
1. Preparation of a standard acid.
.
.
.
278
m,
279
m.
280
m,
281
m.
286
Ill,
.
2. Preparation of constant boiling point hydrochloric acid
3. Direct preparation of O.lN hydrochloric acid from the
constant boiling point acid
4. Preparation of O.lN hydrochloric acid ann standardisa-
tion
5. Preparation of standard alkali
6. Standardisation of approx. O.lN sodium hydroxide
7. Other standard substances for acidimetry and alkali-
metry
289
m,'
291
m.
8.
Standgrd barium hydroxide (baryta) solution
295
m,
9.
D. * of the Na 2 C0 3 content of washing soda
295
In,
10.
D.
m.
11.
297
m,
12.
D.
of the strength of glacial acetic acid
of sulphuric acid in the concentrated acid
of sulphuric acid in the fuming acid
of carbon dioxide in the atmosphere
297
D.
298
m,
13.
D.
298
m,
14. D. of a mixture of carbonate and hydroxide. Analy~is
of commercial caustic soda
299
m.
15.
D.
of a mixture of carbonate and bicarbornlte
301
m.
16.
D.' of
phosphoric acid in commercial
orthophosphoric
acid
302
m.
17.
m.
18.
305
ill,
19.
D. of boric acid and borax,
D. of ammonia in an ammonium salt.
D. of nitrates (sodium nitrate in Chile saltpetre)
303
306
m.
·20.
D.
of nitrogen by Kjeldahl's methoa.
307
PRECIPITATION ~ND COMPLEX FORMATION REAC1'IONS
m,
21.
General d~scussion
310
m.
22.
Preparation of O.lN silver nitrate
310
m.
23.
Standardisation of the silver nitrat~ solution
311
m.
24.
D. of chlorides
313
m.
25.
D. of bromides
313
m.
26. D. of chlorides and bromides with
standard mercurous
315
m,
27.
perchlorate solution
D. of iodides .
316
m,
28.
D.
of thiocyanates.
.
.
317
m.
29. D. of mixtures of haltdes with absorption indicators
317
m.
30.
D.
of mixtures of halides by an indirect method 317-
m,
31. Preparation and
thiocyanate.
use of O.IN
ammonium or potassium
Titrations according to Volhard's
method
318
m.
32:
D.
of silver in a silver alloy
320
m.
33.
D.
of chlorides (Volhard's method)
321
m.
34.
D. of bromides (Volhard's method)
322
m.
35.
D.
of iodides (Volbard's method)
322
*D. =
Determination.
Contents Xlll PAGE m. 36. D. of hyposulphites 322 m. 37. D. of cobalt 323
Contents
Xlll
PAGE
m.
36. D. of hyposulphites
322
m.
37. D. of cobalt
323
m.
38. D. of nickel
324
m.
39. D. of fluoride as lead chlorofluoride
324
m.
40: D. of arsenic as silver arsenate
.
326
m.
41.
D. of cyanides
'!327
m.
42.
D. of nickel b)' potassium cyanide
328
m.
43. D. of thiocyanates
330
m.
44. D. of barium and of sulphates
.
332
OXIDATION-REDUCTION
TITRATIONS.
OXIDIMETRY
AND
REDUCTIMETRY
m.
45. General discussion
334
OXIDATIONS
WITH
POTASSIUM
PERl'vIANGANATE
m.
46.
Discussion
334
m.
47. Preparation of O.lN potassium permanganate
338
ill,
48. Standardisation- of permanganate solutions.
339
m.
49.
Permanence of potassium permanganate solutions
343
m.
50. D. of ferrous iron
344
m.
51. Reduction of ferric to ferrous iron
344
III,.-
52.
D. of iron in ferric ammonium sulphate
351
m.
53.
D. of total iron in an iron ore
352
m.
54.
D. of calcium in calcium carbonate
352
m.
55.
Analysis o~ hydrogen peroxide .
354
ill,
56.
Analysis of sodium peroxide .
355
m.
57.
D. of manganese dioxide in pyrolusite
355
m.
58.
D.
of nitrites
.
357
m.
59.
D: of
persulphates
358
m.
60.
D. of manganese in steel (bismuthate method)
358
m.
61.
D. of formates an,d of formic acid
361
m.
62.
D. of selenium
362
OXIDATIONS WITH
POTASSIUM DICHROMATE
m.
63.
General discussion
364
m.
64. Preparation of 0.1N potassium dichromate
366
m.
65.
Standardisation
of
potassium dichromate solution
against iron
367
m.
66.
D.
of ferrous iron
368
m,
67. D. of ferric iron (iron in ferric ammonium sulphate)
369
m.
68. D.
of total iron in an
iron ore
369
m.
69. D. of ferrous and ferric iron in an iron ore
.
370
m.
70. D. of chromium in a chromic salt
370
m.
71. D.
of chromium in chromite
371
m.
72. D. of manganese in steel or in manganese 'ore (Pattin-
son's methoq)
373
OXIDATIONS
WITH
CERIC
SULPHATE
m,
375
m,
73. General discussion
74. Preparation of 0.1N eerie sulphate
378
m.
75. Standardisation of eerie sulphate solution
379
XIV Contents PAGE" m, 382 m, 383 ill, .76. D. of oxalates 77. D. of
XIV
Contents
PAGE"
m,
382
m,
383
ill,
.76. D. of oxalates
77. D. of iron in an iron ore
78. D. of ferrocyanides
383-
m,
79.
D.
of nitrites.
.
384
m,
"
80. D. of tellurium
81. D. of thallium.
82. D. of cerium
385
m,
385
ill,
386
OXIDATIONS WITH MANGANIC SULPHATE
m,
83.
General discussion
387
m.
84. Preparation and standardisation of manganic sulphate
solutions
387
m,
85. Applications of manganic sulphate solutions
388
REDUCTIOXS
WITH
TITANOUS
SALTS
m,
m,
m,
m,
86. Genetpl discussion
87. Preparation of titanous solutions
88. Standardisation of titanous solutions
89• .D. of iron in an ore
389
390
391
392
REDUCTIONS
WITH
AMALGAMATED
ZINC
AND
WITH
LIQUID
AMALGAMS
m, 90. General discussion
393
m,
394
m.
394
ru,
395
m,
395
ru,
91. D. of uranium.
92. D. of titanium
93. D. of molybdenum
94. D. of vanadium
95. D, of titanium (zinc amalgam method)
396'
m.
96. D. of tungsten
398
m,
399
m,
97. Reductions with chromous salts
98. Reductions with vanadous salts
400.
OXIDATION
AND
REDUCTION
PROCESSES
INVOLVING
lODINE
IODIMETRY AND IODOMETRY
ru.
99.
401
m, 100.
General discussion
~etection of the end point , .
Preparation of O.IN sodium thiosulphate
403
ru,101.
405
m.
102. Standardisation of sodium thiosulphate solutions
407
m.103.
m, 104.
Preparation of O.IN iodine
Standardisation of iodine solutions
414
.
415
m.
105.
D.
of -copper in -crystallised copper sulphate
418
m.
106.
D.
of copper in an ore
419
m.107.
D. of manganese dioxide in pyrolusite
421
m, 108.
423
m.109.
D. of cblorates and of bromates
Volumetric D. of lead
424
.,
m, 111. D.d the avaibi.ble chlorine in bleaching powder
m, 110. Analysis of hydrogen peroxide.
425
426
Contents xv PAGE m, 112. D. m, 113.- D. of hypochlorites . 428 of antimony
Contents
xv
PAGE
m, 112. D.
m, 113.- D.
of hypochlorites
.
428
of antimony
428
m, 114. D. of antimony in antimonic oxide and in antimonates
429
m,115.
:B.
of arsenic in arsenic oxide and in arsenates
430
m, 116. D. of tin
.
.
430
m, 117. D.
of antimony and tin in type
metal
432
m,118. D.
of sulphurous acid and of sulphites
of hydrogen sulphides and of sulphides
433
m,119.
D.
434
m,
120.
D.
.
of ferric iron (iodometric method)
of ferricyanides
'.
.
.
435
m, 121. D.
.
436
OXIDATIONS WITH POTASSIUM IODATE
m, 122. General discussion
m,l23. Preparation of O.IN (0.025M)'potassium iodate
428
440
.
m,l25. D. of arsenic or of antimony
m,l24. D. of iodides
441
442
m,126.
D.
of copper.
.
.
442
m,l27. D. of mercury
m, 128. D. of tin
m,129. D. of peroxides (lead, barium and manganese dioxides)
443
444
445
m, 130. D. of hydrogen peroxide .
m, 131. D. of hydrazine
446
"
447
m,132.
D.
of thallium.
.'
447
m,133. D. of iodides by ceric sulphate
447
m,lM. D. of vanadium
448
OXIDATIONS WITH POTASSIUM BROMATE
m, 135.
m,136.
General discussion
Preparation of O.IN potassium bromate
D. of antimony or of arsenic
450
451
m,137.
451
m, 138.
D. of metals by means of 8-hydroxyquinoline (" oxine")
452
m
139.
D. of hydroxylamine
.
.
.
.
.
458
OXIDATIONS WITH CHLORAMINE-T
m, 140. General discussion.
m, 141. D. of antimony
Preparation of ()o.IN solution
459
460
m, lA2.
D.
of nitrites
.
460
.
m, 144. D. of ferrocyanides
m, 143.
D. of tin
461
462
MISCELLANEOUS VOLUMETRIC DETERMINATIONS
m,145. D.
of
zinc
with
standard
potassium
ferrocyanide
solution
463
m,l46.
D.
of phosphorus
'.
464
m.
147. D. of temporary and permanent hardness of water
466
m. 148.
D. of sodium
m,149.
m,l50.
.
D. of potassium
D. of cadmium
472
472
472
xvi Contents CHAPTER IV GRAVIMETRIC ANALYSIS PAGE IV, 1. General discussion 473 IV. 2. Note
xvi
Contents
CHAPTER
IV
GRAVIMETRIC
ANALYSIS
PAGE
IV,
1. General discussion
473
IV.
2. Note book entries, and calculations
473
IV, 3. Calculations of gravimetric analysis.
Chemical factors
473
SIMPLE
qRAVIMETRIC
DETERM,INATIONS
IV, -4. D. of watex; of hydration in crystallised barium chloride
474
IV,
5.
D.
475
IV,
6.
D.
478
IY,
7.
D.
482
IV,
8.
D.
of chloride as silver chloride
of sulphate as barium sulphate
of sulphur in iron pyrites
of iron as ferric oxide
484
IV,
9.
D. of aluminiqm as aluminium oxide
IV, 10.
D.
IV,I1. D.
IV,I2. D.
.
of calCium as oxalate, carbonate or oxide
of magnesium as pyrophosphate
of nickel as the dimethylglyoxime complex
488
490
494
",
497
SYSTEMATIC
GRAVIMETRIC
ANALYSIS
IV, 13. General discussion
500
IV.
14. Lead
501
IV, 15. Silver
503
IV, 16. Mercury
504
IV.
17. Bismuth
506
IV,18. Cadmium
508
IV, 19. Copper
512
IV.
'20. Arsenic'
515
IV.
21. Antimony
517
IV,22. Tin
519
.
IV, 24. Selenium and tellurium
IV,25. Platinum
IV, 26. Palladium .
IV, 27. Gold
IV, 28. Aluminium
IV, 29. Beryllium
IV, 30. Chromium
IV, 23.
Molybdenum
,_
522
.525
527
529
531
533
536
539
"
·IV,31. Iron
."
542
IV, 32. Nickel
545
IV, 33. Cobalt
IV,34. Zinc
546
549
IV.
35. Manganese
553
IV, 36. Vanadium
IV, 37. Uranium .
IV,38. Thorium .
555
556
557
IV,39. Cerium
558
IV, 40. Titanium-
559
IV, 41
Zirconium.
561
IV. 42. Thallium
563
IV, 43. Calcium
564
Contents xvii PAGE IV. 44. Strontium . IV. 45. Barium 564 565 IV. 46. Magnesium
Contents
xvii
PAGE
IV. 44. Strontium .
IV. 45. Barium
564
565
IV.
46. Magnesium
567
IV.
47. Sodium
567
IV. 48. Potassium
570
IV.
49. Lithium
574.
IV. 50. Ammonium
574-
IV.
51. Tungsten
575
IV.
52. Chloride
576
IV.
53. Bromiqe
566
IV. 54. Iodide
IV. 55. Thioc-yanate
576
577
IV.
56. Cyanide
578
IV.
57. Fluoride
"578
IV.
58. Chlorate
580
IV.
59. Perchlorate
581
IV.
60. Iodate
582
-IV.
61. Sulphate
.
582
IV.
62. Sulphide
583
IV.
63. Sulphite
583
IV.
64. Thiosulphate
584
IV. 65. Phosphate
584
IV.
66. Phosphite
586
IV.
67. Hypophosphite
587
IV. 68.
Oxalate
•.
587
IV.
69. Borate
588
IV.
70. Silicate
588
IV.
71. Fluosilicate
591
IV.
72. Ferrocyanide
.'
591
IV, 73. Ferri~yanide
592;
IV.
74. Nitrite
592
IV.
75. Nitrate
592
IV.
76. Carbonate .
592
ELECTROLYTIC
DETERMINATIONS
IV, 77.
Apparatus
596
IV, 78.
Copper
606
IV.
79. Lead
610
IV. 80.
Cadmium
611
IV, 81.
Nickel
612
IV,
82• .,Cobalt
61:l
IV. 83.
Silver
614.
IV, 84.
Zinc
.
614.
IV. 85. Electrolytic separation and
nickel.
.
.
determination of copper and
.'.
.
.
.
615
IV.
86. SIMPLE GRAVIMETRIC SEPARATIONS
617
ANALYSIS
OF
COMPLEX
MATERIALS
IV. 87. Analysis of brass
IV. 88. Analysis of bronze
625
.
.
.
.
631
IV.
89. Analysis of German silver (nickel silver)
634
Contents KVlll .l'A(iE . lV, 91. Analysis of a silver-coinage alloy ·IV,92. Analysis of steel
Contents
KVlll
.l'A(iE
.
lV, 91. Analysis of a silver-coinage alloy
·IV,92. Analysis of steel
IV, 93. Analysis of an aluminium alloy
iV, 90.
Analysis of solder
636
638
639
.
IV, 94. Analysis of a limestone or dolomite
652
• 654
lV, 95. Analysis of 'a felspar
IV, 96.
.
Analysis of portland cement
661
.'
666
CHAPTER
V
COLORIMETRIC
ANALYSIS
V,
1.
General discussion
670
V,
761
V,
2. Theory of spectrophotometry and colorimetry .
3. Classification 'of m.ethods of "colour" measurement or
V,
4.
comparison
A. Standard series method
B. Duplication method
675
.
678
68'2
D. Balancing method
.
683
E. Gradation or step-photometer method
687
V,
5.
F. Photo-electric photometer method
Turbidimetry and nephelometry
689
.
.
692
V.
6.
D. of th(l. pH of solutions by colorimetric methods .
693
V,
7. Some general remarks upon colorimetric determinations
697
V,
8.
D.
of ammonia
".
699
V,
9. D. of nitrites
700
V, 10.
D. of iron
701.
V,11. Manganese
V, 12. Titanium
V,13. Vanadium
V, 14. Chromium
V, 15. Aluminium
V, 16. Molybdenum
V, 17. Nickel
V, 18. Cobalt
V.19. Arsenic
V, 20. Antimony
703
705
708
709
710
711
713
714
714
721
V,21. Tin
723
V,22. Lead
724
V,23. Copper •
V.24. Bismuth
V, 25. Silver
726
727
728
.
'V,27. D. of other elements and radicals
V. 26.
Silicate
729
739
CHAPTER
VI
GAS
4NALYSIs
VI,
1. General discussion
2. Sampling
3. Purification of mercury
732
VI,
733
VI,
734
Contents xix PAGE VI, 4. Correction of volume of gas for temperature and pressure 736
Contents
xix
PAGE
VI,
4. Correction of volume of gas for temperature and pressure
736
VI,
5. Calibration of gas measuring vessels
739
VI,
6. Apparatus employed in- gas analysis
740
VI,
7. Absorbents for the various gases
.
762
VI,
8. D. by explosion and combustion methods
767
VI,
9.
Exercises in gas analysis
770
GAS-VOLUMETRIC METHODS OF ANALYSIS FOR SOLIDS AND
LIQUIDS
VI, 10. The Lunge nitrometer
VI, 11. D. of nitrates
771
772
VI.
12. D. of hydrogen peroxide
774
VI.
13. Evaluation of pyrolusite
775
VI.
14. D. of available clj.lorine in bleaching powder
776
VI.
15. Evaluation of zinc dust
776
VI.
16. D. of ammonium salts
776
APPENDIX
A,
1.
International atomic weights, 1939
778
A.
2.
779
A,
3.
Chemical factors
The literature of analytical chemistry
783
A,
4.
Densities of acids at
20°C
788
A,
5.
Densities of alkaline solutions at
20°C
790
A,
6. Data on the strength of aqueous solutions of the common
acids and ammonium hydroxide
790
A,
7.
791
A,
8.
792
A,
9.
798
A, 13.
A, 11.
A, 12.
A,13.
Samples and solutions for elementary analysis
Analysed samples
Analytical reagents
Buffer solutions .
Comparison of metric and other units
Decimals of an inch, 1.S.W.G., and millimetres
The Greek
808
813
815
815
A, 14. Suggested scheme of study for Intermediate Science and
Engineering, Higher School Certificate, and Ordinary
National Certificates in Chemistry, and Examinations of
similar character
816
A, 15. Suggested scheme of study for RSc. Special Chemistry,
Honours B.Sc., Chemistry, Associateship of the Institute
of Chemistry, and Examinations of similar scope
817
A, 16.
822
At 17.
Four-figure logarithms
Five-figure logarithms.
824
Index
843
LIST OF PLATES
To face page
PLATE
1. Cambridge pH meter,
electrical circuit Of latter,
and electrodes for use with this instrument
131
PLATE II.
R
D.
H.
Lovibond
nesslerimeter
682
PLATE III.
684
PLATE IV.
Bausch and Lomb Duboscq colorimeter
"Spekker" photo-electric absorptiometer
689
CHAPTER I THE THEORETICAL BASIS OF QUANTITATivE CHEMICAL ANALYSIS I, 1. Electrolytic diSsociation.-Many of t.he
CHAPTER
I
THE THEORETICAL
BASIS OF QUANTITATivE
CHEMICAL ANALYSIS
I, 1. Electrolytic diSsociation.-Many of t.he reactions of
qualitative and quantitative analysis take place in aqueous
solution. It is therefore necessary to have a general know-
ledge of the conditions which exist in such solutions. It is
assumed
that the reader is familiar with the broad concepts
of Arrhenius's theory of ,electrolytic dissociation.*
Ionisation of acids and bases in solution.-An acid may be
defined as a substance which, when dissolved in water,
under-
goes dissociation with the formation of hydrogen ions as the
only positive ion: HCl ~ H+ + Cl- ;
.HNO s
~
H+
+
NO s -.
Actually the free hydrogen ions H + (or protons) do not exist
in the free st~te in aqueous solution; each hydrogen ion
combines with one molecule of water to form the hydroxonium
ion HaO+. The hydroxonium ion is a hydrated proton. The
above equations are therefore more accurately written:
'
HCI
+
H 2 0
~
HaO+
HNO a + H 2 0
~ HaO+
+ Cl-;
+ NOs- .
The ionisation may be attributed to the great tendency of the
free hydrogen ions H+ or protons to combine with water
molecules to form hydroxonium ions. Hydrochloric and
nitric acids are almost completely dissociated in aqueous
solution in accordance with the above equations; this is
readily detected by freezing point measurements and by other
methods.
Polybasic acids ionise in stages.
In sulphuric acid,
the
first hydrogen atom is almost completely ionised:
or
H 2 SO, ~
H 2 SO, + H 2 0
~
H+ + HSO,- ,
HaO+ + HSO,-.
• 'A short account will be found in the author's Text Book of Qualitati",
Chemical Analysis, 1937 (Longmans, Green and Co,).
B
1
2 Quantitat~ve Inorganic Analysis The second hydrogen ~tom is only partially ionised, except in very
2 Quantitat~ve Inorganic Analysis
The second hydrogen ~tom is only partially ionised, except in
very dilute
solution:
H+
+ S04--'
or
HS0 4 -
HS0 4 -
+ H 2 0
~
~
HaO-f' + SO(--.
Phosphoric acid also ionises in stages :
H a P0 4 ~H+ + H 2 P0 4 -
~H+ + HP0 4 -- ~H+
+ P0 4 ---;
or
H a P0 4
H 2 P0 4 -
+
HP
~
HaO+
,
4 -
+ H 2 0
~
H30+
,
HP0 4 --" + H 2 0
~
HaO+
+ H 2 P0
+ HP0 4 --
+ PO"---.
The successive stages of ionisation are known as the primary,
secondary and tertiary ionisatibps respectively. As already
mentioned, these do not take place to the same degree. The
primary ionisation is. always greater than the secondary, and
the secondary very much greater than the tertiary.
Acids of the type of acetic acid H.C2Ha02 give an almost
normal freezing point depression in aqueous sol~tion; th,e
extent of dissociation is accordingly small. It is usual,
therefore, to distinguish between acids which are completely
or almost completely ionised in solution and those which are
only slightly ionised. The former are termed strong acids
(examples: hydrochloric, hydrobromic, hydriodic, iodic,
nitric and perchloric acids, primary ionisation of sulphuric
acid) and the latter are called weak acids (examples:
nitrous acid, acetic acid, carbonic acid, boric acid, phosphor-
ous acid, phosphoric acid, hydrocyanic acid, and lfydrogen
sulphide). There is, however, no sharp division between the
two classes. Methods for the measurement of the relative'
strengths of acids are described in Section I, 4.
A base may be defined as a substance which, when dis-
solved iI1 water, undergoes dissociation with the formation
of hydroxyl ions OH- as the only negative ions·. Thus
sodium hydroxide, potassium hydroxide and the hydroxides
of the alkaline earth metals a:J;e almost completely dissociated
in aqueous solution:
NaOH
~
Na+
+ OH-;
Ba(OHh
~
Ba++
+ 20H-.
• A more general eoncept of acids and bases is due to Bronsted; this is now
generally accepted. He defines an acid as a substance which ionises to yield
hydrogen ions or prbtons, and a base as a substance which combines with
hydrogen ions. An acid is accordingly a proton donor and a base a protor
acceptor. Both can be defined by the expression:
A
~H+ + B.
where A is the acid and B is the base.
The Theoretical Basis of Quantitative Analysis 3 These are strong bases. Ammonium hydroxide solution, however,
The Theoretical Basis of Quantitative Analysis 3
These are strong bases. Ammonium hydroxide solution,
however, is 'a weak base. Only a small concentration of
hydroxyl ions is produced in aqueous solution:
NH 4 0H ~ NH4+ + OH-,
,
or
Salts. The structure pf numerous salts in the solid state
has been investigated by means of X-rays and by other
methods, and it has been shown that they are composed of
charged atoms or groups of atoms held together in a crystal
lattice. When thes,e salts are dissolved in a solvent of high
dielectric constant such as water, or are hectted to the melting
point, the orystal forces are weakened and the substances
dissociate into the pre-existing charged particles Of" ions, so
that the resultant liquids ar,e good conductDrs of electricity.
The complete dissociation of salts in aqueous solution is the
modern view and is now almost universally accepted. There
are, however, some exceptions, and these have, in some cases,
been supported by X-ray measurements. Feebly ionised
salts (weak electrolytes) are exemplified by the cyanides,
thiocyanates and halides of mercury and cadmium, and by
lead acetate.
The theoretical implications of the theory of complete
ionisation, due to Debye, Hiickel and Onsager, have been
fully worked out by these authors. In particular, they have
been able to account for the increasing equivalent conductance
with decreasing concentration over the concentration range
O-O·002N. For full details the reader must be referred to
text-books of physical ,chemistry ; a short account will be
found in the author's Text Book of Qualitative Chemical
Analysis.
It is important to realise that whilst complete ionisation
occurs with strong electrolytes, this does not mean that the
effective concentrations of the ions are the same at all con-
centrations, for if this were the case, the osmotic properties
of aqueous solutions could not be accounted for. The varia-
tion of osmotic properties is ascribed to changes of the
" activity 11 of the ions; these are dependent upon the elec-
trical forces between the ions. Expressions for the varia!ions
of the II activity" or of related quantities, applicable to dilute
solutions, have also been deduced by the Debye-Hiickel-
Onsager theory. Further consideration of the conception of
" activity 11 will be found in Section I, 5.
4 Quantitative Inorganic Analysis I, 2. THE LAW OF MASS ACTION Guldberg and Waage in
4 Quantitative Inorganic Analysis
I, 2. THE LAW OF MASS ACTION
Guldberg and Waage in 1'867 clearly state<:]. the law of mass
action (sometimes termed the law of chemical equilibrium)
in the form: the velocity of a <:hemical reaction is propor-
tional to the product of the active masses of the reacting
substances. For the present we shall. interpret "active
mass" by concentration and express it in gram molecules
(or mols) per litre. By applying the law to homogeneous
systems, i.e., to systems in which all the reacting molecules
are present in one phase, for example in solution, we can
arrive at a mathematical expression for the condition of
equilibrium in a reversible reaction.
Let us consider first the simple reversible reaction at
constant temperature:
A+B
~C +D.
The velocity with which A and B react is proportional to their
concentrations, or
VI
=
kl
X rA]
X [B],
where ki is a constant known as the velocity coefficient, and
the square lJrackets in he<1vy type denote the molecular
concentrations of the substances enclosed within. the brackets.
Similarly, the velocity with which the reverse reaction occurs
is given by:
v 2 =
k2
X
[C]
X
[D].
At equilibrium, the velocities of the reverse and the forward
reactions will be equal (the equilibrium is a dynamic and not a
static one) and tHerefore VI = v 2 ,
or kl X [A] X [B] = R2 X [C] X [DJ,
or
[C]
X
[D] =
kll
=
K.
[A]
X [B]
kl
K
is
the equilibrium: constant of
the reaction
at the
given
temperature.
.
The
expression
may
be
generalised.
For
a
reversible
reaction represented by:
-
.
PIAl + P2 A 2 + PaAa +
~ q1B 1 + q2 B lI + q3 B a +
,
where PI' P2' P3 and q}l Q2' qa are the number of molecules of
reacting substances, the condition for equilibrium is given by
the expression :
[Bllql
K.
• The Theoretical Basis 0/ Quantitative Analysis 5 This result may be expressed in words:
• The Theoretical Basis 0/ Quantitative Analysis
5
This result may be expressed in words: When equilibrium is
reached in a reversible reaction, at constant temperature, the
product, of the molecular concentrations of the resultants
(the substances on the right hand side of the equation)
divided by the product of the molecular concentn!.tions of the
reactants (the substances on the left·hand side of the equation),
each concentration being raised to a power equal to the num-
. ber of molecules of that substance taking part in the reaction,
is constant.
It must be pointed out that there is no relation between the
velocity at which .a reaction attains equilibrium and the
equilibrium constant. The velocity of a reaction increases
rapidly with rise of temperature, and is also affected by
certain substances. Those substances which increase the
rate of reaction are termed positive catalysts, whilst those
which decrease it are called negative catalysts.
I,
3.
Application of the Jaw of mass action to solutions of
electrolytes.-Weak (or slightly dissociated) electrolytes, such
as acetic. acid and ammonium hydroxide, undergo reversible
dissociation when dissolved in water, The equilibrium be-
tween the undissociated molecules and the ions f-or such
electrolytes can be investigated by the law of mass action.
The law cannot be applied to strong electrolytes, such as
salts, since dissociation is complete, or virtually complete.
The equilibrium 'which exists in a dilute sol~tion of acetic
acid at constant temperature is :
H.C2Ha02 ~ H+
+
C 2 H a 0 2 -
*.
Applying the law of mass action, we have:
[C 2 H a 0 2 -]
X [H+] / [H.C 2 H a 0 2 ]
=
K.
K is the ionisation constant or dissociation constant at constant
temperature. The term affinity constant is 'sometimes em-
ployed for acids and bases. If one gram equivalent of the
electrolyte is dissolved in V litres of solution (V = lie, where
c is the concentration in gram equivalents per litre), and if a
is the degree of ionisation at equilibrium, then the amount of
unionised electrolyte will be (1 - a) gram equivalents, ~nd
the amount of each of the ions will be a gram equivalents.
The concentration (gram equivalents per litre) of unionised
• Strictly speaking the equilibrium should be written:
H.C,HaC. + H 2 0 .p H.O+ + C.H.O.-
no free protons (H+) exist in aqueous solution. The older form will. however,
be retained for the sake of simplicity.
6 Quantitative Inorganic Analysis acetic acid will therefore be (1 - a);V, and the concentration
6 Quantitative Inorganic Analysis
acetic acid will therefore be (1 - a);V, and the concentration
of each of the ions a/V. Substituting in the equilibrium
equation, we obtain the expression:
a 2
(1
-
a)V =
K
or a 2 c / (1
-
a)
=
K.
/
This is known as Ostwald's dilution law. The agreement of
the" la'Y" with experiment is illustrated by the following
results for acetic acid (Table I).
TABLE I.
EQUIVALENT CoNDUCTANCE AND DISSOCIATION CoNSTANT OF
ACETIC
ACID
AT 25°C.
Concn
x
10 4
A,
a
K
X
10 5
1·873
102·5
0·264
1·78
5'160
65·95
0·170
1·76
9·400
50·60
0·130'
1·83
24·78
31·94
0·080
1·82
38'86
25·78
0·066
1·83
56·74
21·48
0·055
1·84
,
68·71
19·58
0·050
1·84
92'16
16-99-
0·044
1·84
112·2
15·41
0.040
1·84
0
388·6
The mean classicai or Ostwald dissociation constant of"acetic
acid at 25°C is 1·82 X 10- 5 , Similar results-the individual
variations may sometimes be slightly greater-are obtained
for other weak electrolytes.
It 4. Strengths of acids and bases.-It has already been
stated (Section It 1) that the properties of acids are the pro-
pertie~ of the hydrogen ion H+ (or, more correctly, the
hydroxonium ion HaO+). For any given total concentration
of acid, the concentration of hydrogen ions will depend upon
the degree of dissociation a; the strength of an acid will thus
depend .upon the value 6f a at a given concentration. The
dissociation constant gives a relationship between a and the
concentration, and it accordingly also represents a measure
of the strength of the acid or a measure of its tendency to
undergo dissociation.
The properties of bases, according to the roost elementary
view, depend upon the hydroxyl ion* and the ionisation
* See footnote, Section I, 1.
The Theore!ical Basis of Quantitative Analysis 7 . TABLE II. DISSOCIATION' CoNSTANTS AT 25 o
The Theore!ical Basis of Quantitative Analysis
7
.
TABLE II.
DISSOCIATION' CoNSTANTS AT 25 o c.
Acid.
Formula
K.
pK. =
-
log K.
-
Acetic
H.C.H.O.
1·82 X 10-·
4·75
,
1·76
X
10- 5
t
4·75
Benzoic
Formic
H.C 7 H.O.
H.C,H.ozCI
H.CHO z
H.C.HaO.
H.CN
H.NO.
H.C 7 H.O•. NO z
6·37
o-Chlorobenzoic
1·20
1·77
X 1O- s
X 1'0-·
X 10-'
t
4·20
t
2·92
t
3·75
Furoic
.
6·78
X
10- 5
t
4·17
Hydrocyanic
7·2
X 10- 10
9·14
Nitrous
4·6
X 10- 4
3·33
o-Nitrobenzoic
t
:l·22
Phenylacetic
.
H,C s H 70.
6·00 X 10-'
4·88.x 10- 5
t
4·31
-
Adipic
H
•.C.HsO,
}(13'72 X
10- 5
t
4·43
K.
3·86 X 10-"
t
5·41
Carbonic
H
•.CO.
K
1 4·31
X 10-'
t
6·37
K.
5·61
X
1O- 11
t
10·25
Hydrogen
H
•.S
K
1 9·1
X 10-'
7·04
Sulphide
K.l·2
x.I0- IS
14·92
Malonic
Hz.c.H.O,
Kl 1·40
X 10- 3
t
2·85
K.
2·20 x 10-"
t
5·66
Oxalic
H
•.CzO,
K
1 5'9
X 10-'
t
1·23
K.6·4
X 10-·
t
4·19
Phthalic
H
•. CsH,O,
K
l·2
X 10-'
2·92
l
K.l
X 10-·
5'00
Succinic
H
2 .C,H,O,
KI 6·63
X 10-·
t
4·18
K.
2·54
X
10- 8
t
5·60
Sulphuric
Hz·SO,
K.
1·15
X
10- 2
t
1·94
Sulphurous
Hz·SO.
K
l'7
X 10-'
1·77
l
K
z 1·0
X 10- 7
7·00
d-Tartaric
H
•.C,H,O.
K
1 1·04
X 10- 3
t
2·98
K
4·55 X
10- 5
4·34
z
t
Boric
H.H.BO.
Kl
5·80 X
10- 10
t
9·24
Citric
H
•. C.H.O,
Kl 9·20
X 10-'
t
3·04
K.
2·69
X
10- 5
t
4·57
K.
1·34
X
10- 6
t
5·87
Phosphoric
H
•.PO.
.
K
I 7'52
X 10-'
t
2·12
K.
6·23
X 10-'
X 10- 13
t
7·21
K.5
t
12·30
Base
K.
pK. =
-
log K
Ammonium
NH,OH
}·8
X 10
S
4·74
hydroxide
1·79 X
10- 5
t
4·75
Aniline
C.HsNH.
4·0
X 10- 10
9·40
Ethylamine
C.H.NH.
*
*
*
* * *
*
4·6
X 10-'
3·34
Dimethylamine
(CH.)zNH
5·20 X 10-'
t
3·28
Methylamine
CH.NH.
4·38
X 10-'
t
3·36
Piperidine
C.HllN
1·3
X 10-"
2·88
Quinoline
CoH,N
6·0
X
10- 10
9·22
Trimethylamine
(CH')3 N
5·45
X 10-'
t
3·26
Calcium
Ca(OH).
K.3·1
X 10-'
t
1'51
hydroxide
Barium
Ba(OH),
K.2·3
X 10- 1
t
0·64
hydroxide
* All compounds marked with an asterisk are of the ammonium type, e.g.,
aniline is really anilinium hydroxide:
(C.N.NH.)OH ~ (C.H.NHa)++ OH-.
t Figures marked with a
t
are
the true or thermodynamic dissociation
constants.
(See Section I, 5.)
8 Qltantitative Inorganic Analysis constant will likewise be a measure of the strength of the
8 Qltantitative Inorganic Analysis
constant will likewise be a measure of the strength of the base.
For very weak or slightly ionised electrolytes, the expression
0. 2 /(1 - o.)V = K reduces to 0. 2 = KV or a. = V1{V, since 0.
may be neglected in comparison with unity.
Rence for any
two weak acids or bases at a given dilution V (in litres), we
have 0.1 = VK;V and 0. 2 =
vK 2 V, or 0.1/0.2 ~ vKdvK2'
Expressed in words, for any two weak or slightly dissociated
electrolytes at equal dilutions, the degrees of dissociation are
proportional to the square 'roots of their ionisation constants
Some values for the dissociation constants at 25°C jor weak
acids and bases are collected in Table II.
I, 5. Activity and activity coefficient.-In our deduction
of the law of mass action it was assumed that the effective
concentrations or active masses of the components could be
expressed by the stoichiometric concentrations. According
to modern thermodynamics, this is not strictly true. The
rigid equilibrium equation for, say, a binary electrolyte:
AB
~
A+
+ B-,
is
aA+
X
aB-
/ aAB
=
Ka,
where aA+, aB- and aAB represent the activities of A+, B-
and AB respectively, and Ka is the true or thermodynamic
dissociation constant. The concept of acti,vity. a thermody-
namic quantity, is due to G. N. Lewis. The quantity is
related to the concentration by a factor, termed the activity
coefficient :
activity =
concentration X activity coefficient.
Thus at any molar concentration
aA+ = lA+' [A+], aB- =lB-' [B-], and a AB =
lAB' [AB],
where 1 refers to the activity coefficients, and the square
brackets to the molar concentrations. Substituting in the
above equation, we obtain:
1 A+' [A+]
xl B-' [B-]
=
[A+].[B-] X
f A+ XfB-
=
K
fAB . [AB)
[AB]
lAB
a'
This is the rigorously correct expression for the law of mass
action as applied to weak electrolytes.
The activity coefficient varies with the concentration. For
ions, it varies with the valency, and is the same for all dilute
solutions having the same ionic
strength, the latter being a
measure of the electrical field existing in the solution. The
term ionic strength, designated by the symbol !-'-' was intrQ-
The Theoretical Bast's of Quantitative Analysis 9 duced by Lewis and Randall in 1921, and
The Theoretical Bast's of Quantitative Analysis 9
duced by Lewis and Randall in 1921, and is defined as equal
to one half of the sum of the products of the concentration of
each ion ml)ltiplied by the square of its valency, or f-I- =
0·5.Ec,~, where c. is the ionic
concentration in gram mols per
litre of solution and z, is the val_ency of the ion concerned.
An example will make this clear. The ionic strength of 0,]
molar HNO a solution containing 0·2 molar
by:
Ba(NO a )2 is given
0'5{ 0·1 (for H+) + 0·1 (for NO a -) + 0·2
X 22 (for Ba++)
+ 0·2
X 2 (for NO a -) }
=
0·5 {l'4}
=
0·7.
The activity coefficient depen~s upon the total ionic strength
of the solution in a manner whic'll is discussed in Section I, 10.
Generally speaking, it is comparatively difficult to determine
activity coefficients experim~ntally, partic~larly in concen-
trated solutions and in mixtures of ions of several valency
types. The activity coefficients of unionised mole«ules do
not differ considerably from unity. For weak electrolytes in
which the ionic concentration and therefore the ionic strength
is small, the error introduced by neglecting the difference
between the actual values of the activity coefficients of the
ions, fA+ and fB-" and unity is small « 5 per cent.). Hence
for weak electrolytes, the true or therplOdynamic expression
reduces to [A+] X [B-] / [AB] = K; the constants obtained
by the use of simple concentrations will be accurate to 2-6
per cent. Such values are sufficiently precise for purposes 0f
calculation in quantitative analysis. It must, however, be
pointed out that precisioR values for the dissociation constants
of weak electrolytes 'can be obtained by the use of special
methods; the discussion of these is outside the scope of this
volume.
Strong electrolytes will be assumed to be completely
dissociated, and no correction for activity coefficients will be
made for 'dilute solutions.
I, 6. Ionisation of polybasic acids.-When a polybasic
acid is dissolved in water, the various hydrogen atoms undergo
ionisation to different extents. For a dibasic acid H2A, the
primary and secondary ionisations can be represented by the
equations:
H2A ~H+
+ HA-
(1)
HA-
H+
+ A--
~
(2).
B
10 Quantitative Inorganic Analysis If the dibasic acid is a weak electrolyte, the 1aw of
10 Quantitative Inorganic Analysis
If the dibasic acid is a weak electrolyte, the 1aw of mass action
may be applied, and the following expressions obtained:
[H+]
X
[HA-] / [H2A] = KI
(IA),
[H+]
X
[A--] I [HA-]
=
K2
(2A).
K I.and K 2 are known as the primary and 'SeCOndary dissociation
constants respectively. Each stage of the dissociation
process has its own ionisation c~mstant, and the magnitudes
of these constants give a measure of the extent to which each
ionisation has proceeded at any given concentration. The
greater the value of Kl relative to K 2 , the smaller will be the
secondary di~sociation, and the. greater must be the dilution
before the latter becomes appreciabte. It is therefore possible
that a dibasic (or polybasic) acid may behave, so far as
dissociation is concerned, as a monobasic acid. This is
indeed characteci.stic of many polybasic acids (see Table II). '
A tribasic acid H3A (e.g., orthophosphoric acid) will simi-
larly yield
three dissociation constants, Kv K2 and K 3 ,
which may be computed in an analogous manner:
+
H3A
~
H+
H 2 A-
(3) ;
H 2 A
·
~
H+
+ HA--
(4);
HA-- ~
H+
+ A---
(5).
We can now apply some of the theoretical considerations to
actual examples encountered in analysis.
. Example 1. To calculate the concentrations of HS- and S~- in a
saturated solution of hydrogen sulphide.
A saturated aqueous solution of hydrogen sulphide at 25°C, at
atmospheric pressure, is approximately O'~1 molar. The primary aqd
to
secondary dissociation constants
respectively.
are 9·1 X lO-8 and 1·2 X 10- 15
Thus
[H+] X
[HS-]
=
9·1
X
lV-a
(i),
and
[H+] X
[S--]
/ [H 2 S]
/ [HS-]
=
1·2
X
10- 15
(ii).
The very much smaller value of. K2 indicates that the secondary
dissociation and consequently [S--] , is exceedingly small. It follows,
therefore, that only the primary ionisation is of importance, and
[H+] and [HS-] are pra.ctically equal in value. Substituting in
equation (i) :
[H+] =
[HS-]
and [H 2 S] = 0·1, we obtain
[H+l = [HS-] =
y!9·1
X
10- 8 X 0·1
=
9·5 X 10- 6 •
Both the eqUilibrium equations must be satisfied simultaneously;
by substitution of these values for [H+] and [HS-] in equation (ii),
The Theoretical Basis of Quantitative Analysis 11 we obtain 9·5 X IO- a X [S--]
The Theoretical Basis of Quantitative Analysis
11
we obtain 9·5 X
IO- a X [S--] =,1,2
X
10- 16 X 9·5
X
10- 5 , or
[5--1 = 1·2 X 10- 15 , which is the value for K 2 •
If we multiply equations (i) and (ii) together and t~anspose :
[S--] = 1·1 X 1O- 23 /[H+p.
Thus the concentration of the sulphide ion is inversely proportional
to the square of the hydrogen ion concentration, i.e., if we, say,
double [H+] by.the addition of a strong acid, the [S--] would be
reduced to 1/22. or 1/4 of its original
i,7. Common ion effect.-The concentration of.a particu-
lar ion in an ionic reaction can be increased by the addition
of a compound which produces that ion upon dissociation.
The particular ion is thus derived from the compound already
in solution aItd from the added reagent, hence the name
common ion. We shall confine our attention to the case in
which the original compound is a weak -electrolyte in order
that the law of mass action may be applicable. The result is
usually that there is a higher concentration of" this ion in
solution than that derived from the original compound alone, •
and new equilibrium' conditions will be produced. Examples
of the calculation of the common ion effect are given below.
In general, it may be stated. that if the total concentration of
the common ion is only slightly greater than that which the
original compound alone would furnish, the effect is small ;
if, however, 'the concentration of the common ion is very
much increased (e.g., by the addition of a completely disso-
ciated salt), the effect is very great and may be of considerable
practical importance. Indeed, the common ion effect pro-
vides a valuable method for controlling the concentration ,of
the ions furnished by a weak electrolyte.
Example 2. To calculate the sulphide ion concentration in a 0·25
molar hy,drochloric acid solution saturated with hydrogen sulphide.
This concentration has been chosen since it is that at which the
sulphides of the metals of Group II are precipitated. The total
concentration of hydrogen sulphide will be approximately the same
as in aqueous solution, i.e., O·IM; the [H+] will be equiJ) to that of
the completely dissociated Hel, i.e" 0·25M, but the [S--] will be
reduced below 1·2 X 10- 15
Substituting in equations (i) and (ii) (Section I. 6). we find:
9·1
X 10- 8 X [H S]'
9·1
X 10- 8 X 0·1
2
[HS-] =
[H+)
0.25
=
3·6 X 10- 8 ,
1·2 X 10- 15 X [HS-]
1·2
X lO- rs X 3·6 X 10-8
[S
)=
[H+]
-
0.25
=
1·7
X
10- 22 •
12 QuantitaHve Inorganic Analysis Thus by changing the acidity from 9·5 X 10- 5 M
12 QuantitaHve Inorganic Analysis
Thus by changing the acidity from 9·5 X 10- 5 M
(that present in
saturated H 2 S water) to 0·25M, the sulphide ion concentration is
reduced from 1·2 X 10- 15 to 1·7 X 10- 22 •
Example 3. What effect has the addition of 0·1 gram molecule
(8·20 g.) of anhydrous sodium acetate to I litre of 0·1 molar acetic
acid upon the degree" of dissociation of the acid?
The dissociation constant of acetic acid
at 25°C is
1·82 X 10- 5 •
The degree of ionisation a in O·IM solution (e = 0'1) may be com-
puted by solving the quadratic equation:
[H+] X [C2H a0 2-] =
[H.C 2 H a 0 2 ]
~
=
1.82 X 10-5.
(I -
a)
-
.'. a = "'I/Ke - V~I-'8~2-X-'-1-0-- 4 = 0·0135.
Hence in O'IM acetic acid,
[H+] = 0-00135, [C 2 H a 0 2 -] = 0'00135, and [H.C 2 H a 0 2 ] = 0·0986.
The concentrations of sodium and acetate ions produced by the
addition of the completely dissociated sodium acetate are:
For our purpose it is suffiGiently accurate to neglect a in (I -
since a is small:
q.)
[Na+] = 0·1, and [C 2 H a 0 2 -] = 0·1 gram molecule respectively.
The acetate ions from the salt will tend to decrease the ionisation of
the acetic acid since K is constant, and consequently the acetate ion
concentration derived from it. Hence w,e may write [C 2 H a 0 2 -] =
0·1 for the solution, and if a' is the new degree of ionisation, [H+] =
a'e = O'la', and [H.C 2 H a 0 2 ] = (1 - a')e = 0-1, since a' is negli-
gibly small.
Substituting in the mass action equation:
[H~ X
{C 2H a0 2-]
=
O·la'
0·1
=
X
1.82
X
10- 5 ,
[H.C 2 H 3 0 2 ]
0·1
or
a' =
1·8 X 10-4.
[H+]
=
a'e = 1·8 X 10- 5 •
The addition of a tenth of an equivalent weight of sodium acetate
to a 0·1 molar solution of acetic acid has decreased the degree of
ionisation from 1'35% to 0 ·018%, and the hydrogen ion concentration
from 0·0135 to 0·000018.
I Example 4.
What effect has the addition of 0·5 gram molecule
(26-75 g.) of ammonium chloride to I litre of 0·1 molar ammonium
hydroxide solution. upon
the degree 'of dissociation of the base?
(Dissociation constant of NH 4 0H = 1·8 X 10- 5 .)
.
In O·IM ammonia solution a = Vl·8 X 10- 1i X 0·1 = 0·013.
Hence [OH-] = 0'0013, [NH,+] = 0'0013, and [NH,OH] = 0·0987.
Let a' be the degree of ionisation in the presence of the added
The Theoretical Basis of Quantitative Analysis 13 ammonium chloride. Then [OH-] = a'e = 0·10.',
The Theoretical Basis of Quantitative Analysis 13
ammonium chloride. Then [OH-] = a'e = 0·10.', and [NHPH] =
(1 - a')e = 0·1, since a' may be taken as negligibly small. The
addition of the completely ionised ammonium chloride will of
necessity decrease the [NH,+] derived from the base and increase
[NH"OH], since K is constant under all conditions, Now [NH,,+] =
0·5, as a first approximation.
Substituting in the equation:
[NH/] X [OH-] _
[NH"OH]
0·5 X 0·10.'
=
1'~ X
10- 5 ,
0·1
or
a' -= 3·6
X
10- 5 and [OH-] =
3·6 X
10.- 6 •
The addition of half an equivalent weight of ammonium
chloride to a 0·1 molar s6lution of ammonium hydroxide has
decreased the degree of. ionisation from 1'35% to 0'0036%,
and the hydroxyl ion concentration from 0·0013 to 0'0000036.
1, 8. Solubility product.-For sparingly soluble §alts (i.e.)
those of which the solubility is less than 0·01 g-ram molecules
per litre) it is an experimental fact that the product of' the
total molecular concentrations of the ions is a constant at
constant temperature. This product S is termed the
solubility product. For a binary electrolyte:
AB
,.: A+
+ B-,
[A+]
[B-].
SAB
=
X
In general, for an electrolyte ApBg, which ionises into PA+,
and qB- •• ions:
ApBg": pA.+'
+ qB-'
,
[A+'
SAliBI =
']P
X [B-
.]g,
A plausible deduction of the sol~bility product relation is
the following. When exc~ss of a sparingly soluble electrolyte,
,say silver chloride, is shaken up with water, some of it passes
into solution to form a saturated solution of the salt and the
reaction appears to cease. The following equilibrium is
.actually present (the silver chloride is completely ionised in
solution) :
AgCl (solid) ,.: Ag+ + CC
The velocity of the forward reaction depends only upon the
temperature, and at any given temperature:
VI
=
kr'
where kI is a constant.
The velocity of the reverse reaction is
14 Quantitative Inorganic Analysis proportional to the concentrations of each of the reacting substances; hence
14 Quantitative Inorganic Analysis
proportional to the concentrations of each of the reacting
substances; hence at any given temperature:
V 2 =
k2
X [Ag+]
X [cq,
where K'1, is another constant. At equilibrium the two
velocities are equal,
i.e., kl
=
k2 X [Ag+]
X [Cl-],
or
[Ag+] X
[Cl-] =
kl/k2 =
SAgel'
A more rigid deduction of the solubility product pril}ciple
can be obtained along the following.lines. For simplicity, we
shall again consider a binary electrolyte:
AB
~
A+
+ B-.
The solid is completely dissociated in dilute solution; no
undissociated molecules will therefore be present. It can be
shown by thermodynamics that in.a saturated solution of any
salt containing varying amounts of a more soluble .salt with a
common ion, the products of the activities of the two ions in
the various saturated solutions are the same:
i.e., aA+
X
aB- =
constant (activity product).
In the very dilute solutions with which yve are at present
concerned, the activities may be taken as practically equal to
the concentrations,* so that [A+] X [B-] =
Some experimental results, due to ]ahn (190f), illustrating
the approximate consta"'ncy of the solubility product of silver
chloride in the presence of varying concentrations of chloride
ion (from potassium chloride) are collected in Table III.
TABLE III.
EFFECT OF CHLORIDE IONS UPON THE SOLUBILITY PRODUCT
OJ AgCl.
[KCl]
I[Cl-] X 10_ 3 I[Ag+] X 10 8 SAgCl= [~g+].[CqXI010
0·00670
6·4
1·75
1·12
0·00833
7·9
1·39
1·10
0·01114
10·5
1·07
1·12
0·01669
15·5
0·74
1·14
0·03349
30·3
0·39
1·14
* Activity =
activity coefficient X concentration, i.e., a = fr
The activity
product may therefore be written:
fA+[A+] X jB-[B-) = constant.
In very dilute solution j is proportional to (1 -
quantity is approximately unity.
k -vc). and if c is small, this
The Theoretical Basis of Quantitative Analysis 15 It is important to note that tb,e solubility
The Theoretical Basis of Quantitative Analysis 15
It is important to note that tb,e solubility product relation
applies with sufficient accuracy for purposes of quantitative
analysis only to saturated solutions of slightly soluble elec-
trolytes
and with small additions of other salts. In the
presence 6f.large concentrations of salts, the ionic concentra-
tion, and therefore the ionic strength of the solution, will
increase. This will, in general, lower the activity coefficients
of both ions, and consequently the ionic concentrations (and
therefore the solubility) must increase in order to maintain the
solubility product constant (see Section I, 10 for a more
detailed discussion).
The great importance of the conception of solubility product
lies in its bearing upon precipitation from solution, which is,
of course, one of the principal operations of quantitative
analysis
The solubility product is the ultimate value which
is attained by the ionic product when equilibrium has been
established between the solid phase of a difficultly soluble salt
and the solution. If the experimental conditions :j.re such
that the ionic product is different from the solubility product,
then the system will attempt to adjust itself in such a manner
that the ionic and solubility products are equal in value.
Thus, if, for a given electrolyte, the product of the concen-
trations of the ions in solution is arbitrarily made to exceed
the solubility product, as, for example, .by the addition of a
salt with a common ion, the adjustment of the system to
equilibrium results in the precipitation of the solid salt,
provided supersaturation conditions are excluqed. If the
ionic product is less than the solubility product or can
arbitrarily be made so, as, for example, by complex salt
formation or by the formation of weak electrolytes, then a
furth()r
quantity of solute can pass into solution until the
solubility product is attained, or,. if this is not possible, until
all the solute has dissolved.
Table IV contains the solubility products (S) a.t the labora-
tory temperature (ca. 20°C) of some common sparingly soluble
substances. Values for
pS = -loglo S are given in the
last column. The student is referred to text-books of
physical chemistry for a· description of the methods for
determining solubility
products.
.It must, however, be
pointed out that the various methods do not always yield
consistent results, and what appear to be the best representa-
tive figures 'are given in the Table.
16 Quantitative Inorganic Analysis TABLE IV. SOLUBILITY PRODUCTS AT THE LABORATORY TEMPERATURE. Solubility Solubility
16 Quantitative Inorganic Analysis
TABLE IV.
SOLUBILITY PRODUCTS AT THE LABORATORY
TEMPERATURE.
Solubility
Solubility
Substance
pS
Substance
pS
Product
Product
-
AgBr
3'5
X 10- 11
12·46
-18·82
AgCNS
7·1
X
1O- 1a
12·15
17·89
AgC1
Ag,CrO,
1·2 X 10- 10
1·7 X 10- 12
9·92
1'5 X 10- 11
1·3 X 10- 18
2·0 X 10- 11
20'70
11'77
1·2
X
10- 28
27·92
AgI
1·7
X 10- 18
15·77
4
X
IO- A
52·4
Ag.PO,
1·8 X 10- 18
17:74
3·0 X 10-'
3·52
Ag,S
1·6 X 10-"
8·5 X 10- 28
1·9 X 10-·
48·80
4·9
X
10- 5
4·31
AI(OH).
22·07
2·6
X
10- 6
4'58
BaCO.
8·72
8·6
X
10- 6
4·07
BaC,O,
1·7
X
10- 7
6·77
8·15
BaCrO,
2·3 X 10- 10
• 9·64
12·60
BaSO,
1·2
X
10- 1 •
9·92
10·82
CaCO.
1·7
X 10- 8
7·77
13·40
CaC,O,
3·8
X
10- 9
8·42
7·0 X 10-'
2·5 X 10- 18
1·5 X 10- 11
4·0 X 10-1<
1·4 X 10- 16
14'85
Ca.C.R,O.
7·7 X lO-7
6·11
8·7 X 10- 19
1·4 x-10-2&
18·06
(tartrate)
23·85
CaF.
10·49
7·9
X
10- 5
4·10
CaSO,
3·64
3·62
CdS
28·44
10'77
Co(OR)s
17·80
13·74
CoS
26·72
8·15
Cr(OR)a
3·2 X 10- 11
2·3 X lO-'
3·6 X lO-"
1·6 X 10- 18
1·9 X 10-'7
2·9 X lO-2I
1'7 X 10- 11
28·54
2·4 X ~o-'
1·7 X 10- 11
1·8 X 10-1&
7·0 X lO-1
-1'4 X 10- 8
7·85
Cu,(CNS),
10·77
4·2
X
10- 29
27·38
Cu,Br,
4·1
X 10- 8
7·39
2·3 X ~0-8
7·64
Cu,Cl.
1·4 X 10-'
5·85
8·34
Cu,I,
2·6 X 10- 12
8·5 X lO-46
11·58
4·6 X 10- 8
1·4 X 10-"-
6·85
CuS
44'07
3·6
X
10- 7
6·44
Fe(OR).
1~6 X
10-1&
13·80
1·0 X 10- 18
18·00
Fe(OH).
1·1 X lO-88
35·96
FeS
Hg,Br.
Hg,C1 a
Hg,I.
HgS
KH.C,H,O.
K 2 PtCl.
MgCO a
MgC.o,
MgF.
Mg(NH,)PO.
,Mg(OR),
Mn(OR),
MnS
Ni(OH).
NiS
PbBr.
PbCl.
PbCO.
PbCrO,
PbF.
PbI.
PbS
PbSO,
srCO.
srC.O,
SrSO,
Zn(OR).
ZnS
ca. 1
X 10-zo
20·0
A few examples may help the reader to fully understand the
subject. The concentrations are expressed in gram mols,per
litre for the calculation of solubility products.
Example 5. The solubility of silver chloride is 0·0015 grams per
litre. Calculate the solubility product.
The molecular weight of silver chloride is 143·5. The solubility is
therefore 0·0015/143'5 = 1·05 X 10- 5 mols per litre. In a satur-·
ated solution the dissociation, AgCI ~ Ag+ + CC is complete; 1
mol of AgCI will give 1 mol each of Ag+ and Cl-. Hence [Ag+] =
1·05 X 10- 5 and [cq'= 1·05 X 10:- 5 •
[Ag+] X. [cq =
SAgCl
=
(1'05 X 10- 5 )
X (1'05
X 10- 5 )
=
1·1
X
10- 10 •
'
Example 6.
Calculate the solubility product of silver chromate,
given that its
sqlubility is 2·5
X 10- 2 grams per litre.
Ag 2 Cr0 4 ~ 2Ag+ + Cr0 4 --.
The Theoretical Basis of Quantitative Analysis 17 The molecular weight of Ag 2 Cr0 4
The Theoretical Basis of Quantitative Analysis
17
The molecular weight of Ag 2 Cr0 4 is
= 2·5
X
10 -2 /332 =
7·5
X
10 -5 mols
332, hence the solubility
per litre.
Now 1 mol of Ag 2 Cr0 4 gives two mols of Ag+ and 1 mol of Cr0 4 --,
therefore SAg2 Cr O( = [Ag+p X [Cr0 4 --]
= (2
X 7·5
X 10- 5 )2
X
(7·5
X 10- 5 )
= 1·7 X
10- 12 •
Example '7.
3·4
X
10- 11 .
The solubility product of magnesium hydroxide is
Calculate its solubility in grams per litre.
Mg(OH)2 (solid) ~ Mg++ + 20H-.
[Mg++] X [OH-P = 3·4 X iO-11.
The molecular weight of magnesium hydroxide is 58. Each mol of
magnesium hydroxide, when dissolved, yields one mol of magnesium
ions and two mols of hydroxyl ions. If the solubility is -x gram
mols per litre, [Mg+j] = x and [OH-] = 2x. Substituting these
values in the solubility product expression:
x
X
(2X)2 =
3·4:
X 10- 11
or
x =
2·0
X 10- 4 g. mols per litre
=
2·0
X 10- 4
X 58 =
1·2 X 10- s ·g. per litre.
I, 9. Completeness of precipitation. Quantitative effects
of a conu,non ~on.-An important' application of the solubility
product principle is to the calculation of the solubility of
sparingly soluble salts in solution of salts with a common ion.
Thus the solubility of a salt MA in the presence of a relatively
large amount of the common M+ ions,* supplied by a second
salt MB, follows from the definition of solubility product:
[M+] X
[A-] =
SMA
or
[A-]
=
SMA I [M+]
(i).
The solubility of the salt is represented by the [A-] which it
furnishes in solution. It is. clear that the addition of
'mon ion will decrease the solubility of the salt.
a com-
,
"
Example 8.
Calculate the solubility of silver chloride in O·OOIM
and O'OIM sodium chloride solutions n:spectively (SAgCI = 1·1 X
10- 10 ).
In a saturated solution of silver chloride
[cq = 1·1 ·x 10- 10 = 1·05 X 10- 5 g. m'oI per litre; this may be
neglected in comparison with the excess of Cl- ions added.
• This ena~les us to neglect the concentration of M+ ions supplied by the
sparingly soluble salt itself, and thus to simplify the calculati?n.
18 Quantitative Inorganic Analysis For [cq = 1 X 10- 3 , [Ag+] = 1·1
18 Quantitative Inorganic Analysis
For [cq =
1
X 10- 3 , [Ag+]
=
1·1
X 10- 10 /1
X 10- 3
= 1·1 X 10- 7 g. mol per litre.
For[Cq =
1 X 10-',
[Ag+] = 1·1
X 10- 1 °/1
X 10- 2
• =
1·1
X
10- 8 g. mol per litre.
Thus the solubility is decreased 100 times in O'OOlM'sodium chloride
and 1000 times in O'OlM sodium chloride. SImilar results are
obtained for O'OOlM and O'OlM silver nitrate solution.
Example 9. Calculate the solubilities of silver chromate in
O'OOIM and O·OlM silver nitrate solutions, and in O'OOlM and O'OIM
potassium chromate solutions (Ag 2 Cr0 4 : S.P. = 1·7 X 10- 12 ,
solubility =
7·5 X 10- 5 mols per litre).
[Ag+]2 X [Cr0 4 --] =
1·7
X
or
[CrO,--] = 1·7
10- 12 ,
X 10- 12 / [Ag+)2.
For O·OOlM silver nitrate solution: [Ag+] =
1
X
10- 3 ,
.'. [Cr0 4 --] =
1·7 X 10- 12 /1
X 10- 6 =
1·7 X
10- 6 mols perlitre.
For 0'01M silver nitrate solution:
[Cr0 4 --] = 1·7 X 10- 12 /1
X
10- 4 =
1·7 X
10- 8 mols
per litre
The solubility product equation gives:
[Ag+] =
y'C:-
1 '-=-7-x--'1=-=0---'1-;;2'-;/-;;'[C""'r"""'O""',===-].
For [CrO,--] =
0'001,
[Ag+] =
y'1'7 X 10",,12 /1
X 10- 3
= 4·1
X
10- 5 mols per litre.
For [Cr0 4 --] =
0·01, [Ag+] = y''-:;-I---::'7'-x~I'''''0---;1=2-'/~1-x"-710''---':2
= 1·3 X 10- 5 mols per litre.
This decrease in solubility by the common ion effect is of
fundamental importance in gravimetric analysis. By the
addition of a suitable excess of a precipitating agent, the
solubility of a precipitate is usually decreased to so small a
value that the loss by washing is negligible. Let us consider
a specific case-the determination of silver as silver- chloride.
Here the chloride solution is added to the solution of the silver
salt. If an exactly equivalent amount is added, the resultant
saturated solution, of silver chloride will contain 0·0015 g.
perlitre (Example 5). If 0·2 g. of silver chloride is produced
and the volume of the solution and washings is 500 ml, the
loss, owing to solubility, will be 0·00075 g. or 0·33 per cent.
of the weight of the salt; the analysis would then be 0·33 per
cent. too low. By using an excess of the precipitant, say, to a
concentration of O·OIM, the solubility of the silver chloride is
reduced to 1·5 X 10- 5 g. per litre (Example 8), and the loss
The Theoretical Basis of Quantitative Analysis 19 will be 1·5 X 10- Ii X.0·5 X
The Theoretical Basis of Quantitative Analysis
19
will be 1·5 X 10- Ii X.0·5 X 100/0'2 = 0·0033 per cent.
Spver chloride is therefore very suitable for the quantitative
determination of silver with high a~curacy.
1,10.
Limitations of the solubility product principle.-for a
binary electrolyte MA, thermodynamical considerations lead
to the result that the product of the activities of the two ions
is constant at constant temperature: .
i.e.,
aM+ X
aA- = constant (activity product = f5 MA ) (1).
Now activity = concentration X activity coefficient, or a =.
cJ. Substituting in (1), we obtain:
[M+]fM+ X [A-]fA- =
fSMA
(2).
in which fM+ and fA- denote the activity coefficients of M+
and A-respectively. For a saturated solution of a sparingly
soluble salt in water, the ionic concentration is so small'that
!M+ and fA- are not far removed from unity p.nd the expres-
sion (1) reduces to the classical solubility product equation.
Numerous experiments
80
----------,
have been carried out to
.,
,. determine the accuracy
MI(NO s
£:
70
KNO, with which the'solubility
x
product principle applies.
Some results of Bray and
Winninghoff (1911) upon
the solubility of thallous
chloride in the presence
""
of various salts are shown
".
SO'- added·
.
m FIg. 1-1.
The d6tted
• (Cak.'
line represents the effect
of a simple uni-univalent
", Ag+ added
salt with a common ion,
calculated by assuming
100~~O~.O::-:2~O~,04~O~.':"06~0~.0::-:8~0010
(Calc.)
Normolitv of added salt
complete dissociation of
the salt. The salts with
FIG. ,I·I.-Influence of various salts
on the solubility of TICI.
a common ion decrease
the solubility to nearly
the same extent, and are in approximate agreement with the
values computed on the basis of the simple solubility product
principle. Fig. 1-2 shows graphically some selected results for
silver sulphate. The addition, in moderate concentrations,
of a common univalent ion, like Ag+, is in approximate
agreement with the simple theory, but no such agreement is
obtained by the addition of a common divalent ion, like
50 40 --, A striking fact that emerges from these studies is,
20 Quantitative Inorganic Analysis .that the solubility increases in most cases upon the addition of
20
Quantitative Inorganic Analysis
.that the solubility increases in most cases upon the addition
of electrolytes with no common ion;
we may term this influ-
ence the salt effect. Furt,hermore, it was found that the salt
,
~
x ~o
~
;::;:
~8
§'
TlNO.
~
4
"
~
BaCI 2
~
Calc: •••• _ ••
: •••••
I
00
0.02
0·04
0·06
0'06
0·10
0·12
0·14
0·16
Normaldy 0/ added salt
FIG. 1-2.-Influence of various salts on the solubility of Ag.SO,.
effect depends upon the valency of the ions of the precipitate
and upon the nature of the added electrolyte; usually it
increases markedly with increasing valency of the ions of the
precipitate. The addition of a salt with no common ion will.
increase the ionic strength of the solution and hence decrease
the activity coefficients of both ions of the sparingly soluble
salt; the solubility of the latter must increase in order that
the .activity product, [M+]. [A-] . fM+ . fA-, may be kept
constant. It can be shown on the basis of the Debye-
Huckel-Onsager theory that for aqueous solutions at 25°C:
0·505z,2· ft °.5
log f,. -
-
----
:
---
• -
1
+ 3'3
X
107a. ft°'s '
where!. is the activity coefficient of the ion, z. is the valency
of the ion concerned, p. is the ionic strength of the solution
(Section I, 5), and a is the average" effective diameter" of all
the ions in the solution. For very dilute solutions (ft 0.5 < 0·1)
the second term. of the denominator is negligible and the
equation reduces to :
log!. =
~ 0·505 Z,2. ft °.5.
For more concentrated solutions (ft°' s > 0'3) a.n additional
term Bp. is added to the equation; B is an empirical constant.
For a more detailed treatment of the influence of salts upon
The Theoretical Basis of Q1tantitative Analysis 21 solubility and solubility product, particularly of the work
The Theoretical Basis of Q1tantitative Analysis 21
solubility and solubility product, particularly of the work of
Bronsted and of La Mer, the reader. is referred to text-books
of electrochemistry.*
I
It will be clear from the above short discussion that two
factors may come into play wpen a solution of a salt containing
a common ion is added to a saturated solution of a slightly
soluble salt. At moderate concentrations of the added salt,
the solubility will generally decrease, but with higher con-
centrations when the ionic strength of the solution increases
considerably and the activity coefficients of the ions decrease,
t]J.e solubility may actually increase. This is one of the
reasons, provided complex ion formation. is absent,
why a
very large excess of the precipitating agent is avoided in
quantitative analysis.
:t
11.
Fractional precipitation.-We have thus far con-
sidered the solubility product principle in connexion with the
precipitation of one sparingly soluble salt. We shall now
extend our studies to the case where two slightly soluble salts
may be formed. For simplicity, we shall study the situation
which arises when a precipitating agent is added to a solution
containing two anions, both of which form slightly soluble
salts with the sam~ cation, e.g., when silver nitrate solution is
added to a solution containing both chloride and iodide ions.
The questions which arise are: which salt will be precipitated
first, and how completely' will the first salt be precipitated
before the second ion begins to react with the reagent?
The solubility products of silver chloride and silver iodide
are respectively
1·2
X
10- 10 and 1·7
X 10.;-16;
i.e.,
[Ag+]
[cq
-
X
1·2 X
10-
10
(i),
[Ag+]
X
[r]
=
1·7
X
10- 16
(ii).
It is evident that silver iodide being less soluble will be
precipitated first since its solubility proauct will be first
exceeded. Silver chloride will be precipitated when the Ag+
ion concentration is greater than
SAgCI
1·2 X '10- 10
[Cr] =
[CI
]
and then both salts will be precipitated simultaneously.
When silver chloride commences to precipitate, silver ions
* See, for example, S. Glasstone, The Electrochemistry of Solutions.
1937.
p. 127 (Methuen and Co.).
22 Quantitative Inorganic Analysis will be in equilibrium with both salts and equations (i) and
22 Quantitative Inorganic Analysis
will be in equilibrium with both salts and equations (i) and (ii)
will be simultapeously satisfied, or
+] _
SAgI
_
SAgel
[ A
(iii) ,
g
-
[r)
-
[Cl-)
[rl
SAgI
1·7
and
[CI-l =
SAgel
-
1·2
X 10- 18
X 10-10 -
1
7:1
X
107
(iv).
Hence when the concentration of the iodide ion is about one
millionth part of the chloride ion concentration, silver chloride
will be precipitated. If the initial concentration of both
chloride and iodide ions is O·lN, then silver chloride will be
precipitated when
[r] =
0·1/7·1X10 7 =
1·4x10- 7 N =
1·SxlO- 6 g. per litre.
Thus'an ahn.ost complete separation is theoretically possible.
The separation is feasible in practice if the point at which the
iodide precipitation is complete can be detected. This may
be done: (a) by the use of an absorption indicator (see
Section 1, 41C), or (b) by a potentiometric method with a silver
electrode (see Section I, 53).
For a mixture of bromide and iodide:
[C] SAgi
1·7
X
10-
18
1
===---p
[Br-]
SAgBr
3·5
X
10-
13
2·0 X lOS
Precipitation of silver bromide will Occur when the concentra-
tion of the 'bromide ion in the solution is 2·0 X 10 3 times that
of the iodide concentration. The separation is therefore not
quite so complete as in the case of chloride and iodide, but
can nevertheless be effected with fair accuracy with the aid
of adsorption indicators (Sections I, 41C and m, 29).
1, 12. Complex ions.-The' increase in solubility of a pre-
cipitate upon the addition of excess of.the precipitating agent
is frequently due to the formation of a complex ion. A
complex ion is formed by the union of a simple ion with either
other ions of opposite charge or with neutral molecules. Let
us examine a few examples in detail.
When putassium cyanide solution is added to a solution of
silver nitrate, a white precipitate of silver cyanide is first
formed because the solubility product of silver cyanide,
[Ag+] X
[CN-] =
SAgeN
(i),
is exceeded.
The reaction is expressed:
K+
+ CN-
+ Ag+
or
CN-
+ NO a -
+ Ag+
=
AgCN
+ ~+
+ N0 3 -,
=
AgCN.
The Theoretical Basis of Quantitative Analysis 23 The precipitate dissolves upon the addition of excess
The Theoretical Basis of Quantitative Analysis
23
The precipitate dissolves upon
the
addition
of
excess
of
potassium cyanide, the complex ion [Ag(CN)2r being pro-
duced: AgCN (s01id)
(or AgCN + KCN =
+ CN- (excess)
~ [Ag(CN)2r*
K[Ag(CN)2]-a soluble complex salt).
This complex ion -dissociates to give silver ions, since the
addition of sulphide ions yields a precipitate of silver s)llphide
(solubility product 1·6 X 10-49), and also silver is precipi-
tated from the complex cyanide solution upon electrolysis.
The complex ion thus dissociates in accordance with the
equation: [Ag(CNhr ~ Ag+ + 2CN-
(ii).
By applying the law of mass action to (ii), we obtain the
dissociation constant or instability constant of the complex
ion:
[Ag+]
X
[CN-P _
K
(iii).
. £{Ag(CN)d I
-
The constant has a value of 1·0 X 10- 21 at the ordinary
temperature. By inspection of this expression, and bearing
in mind that excess of cyanide ion is present, it should be
evident that the silver ion concentration must be very small,
so small in fact that the solubility product of silver cyanide
is not exceeded.
Consider now a somewhat different type' of complex 'ion
formation, viz., the production of a complex ion with con-
stituents other than the common ion present in the solution.
This is exemplified by the solu""ility of silver chloride in
ammonia solution. The reactions are: .
Ag+ + Cl-
~
AgCl ;
AgCl
(solid)
~
Ag+
+ Cl-
+ 2NHa
~ [Ag(NHa)2]+
+ Cl-
(or AgCI + 2NHa =
[Ag(NH 3 hJct).
'
Here again, for reasons similar to those already given, silver
ions are pI~sent in solution~ The dissociation of the complex
ion is represented by :
[Ag(NHah]+ ~ Ag+ + 2NH a ,
and the instability const~nt is given by :
[Ag+] X [NHaP _
-8
[fAg( NH a)2}+] , -
K
-
6
8
X
10
.
• It is usual to employ square brackets to include the whole of a complex
ion. In order to avoid confusion with concentrations for which square brackets .
are also widely used, concentrations will be represented in heavy type and
complex ions either in lighter type or between curly brackets.
24 Qttantitative I norgant'c Analyst's The magnitude of the instabiiity constant clearly shows that only
24 Qttantitative I norgant'c Analyst's
The magnitude of the instabiiity constant clearly shows that
only a very small silver ion concentration is produced by the
dissociation of the complex ion.
The stability of complex ions varies within very wide limits.
It is quantitatively expressed by means of the dissociation
or instability constant. The more stable the complex, the
smaller is the instability constant, i.e., the smaller is the
tendency of the complex ion to dissociate into its constituent
ions: When the complex ion is very stable, e.g., the ferro-
cyanide ion [Fe(CN)6r---, the ordinary ionic reactions of the
components are not shown. A few selected values of these
constants at the ordinary temperature, determined by
methods involving potentiometric titr~tion (Sectiqns 1,51-53),
are collected iIi Table V; this is instructive and also useful for
reference purposes.
TABLE V.
INSTABILiTY CONSTANTS OF COMPLEX
IONS
[Ag+J X [NH3]1
[{Ag(NH.l.}+ ]
[Cd++] x rCN-]·
= 6·8
X
lO-8
=
-"---,--'::"_-=---=-
1·4 X lO-17
[{Cd[CNl.}- ]
[ A
+J
[5 0
--J3
[Hg++] X [(,;:'-]4
g X
lO-18
3
=
1.0
= 6·0
X lO-17
[{Ag(5.0.l.}---J
X
({HgCl,}
]
[Ag+] X [CN-J 1
[Hg++] x [r]'
=
1·0 X lO-21
= 5·0
X
lO-11
.[{Ag(CNltn
[{HgI.}
]
[Cu+J x [CN-J'
[Hg++] x [CN-]'
=
5·0 X lO-28
[{Hg(CNl.}
]
= 4·0
x
lO-(I
[{Cu(CNJJ ]
The application of complex ion formation in chemical separa-
tions depends upon the fact that one component may be
transformed into a complex ion which is no longer precipitable
with the precipitating agent, whereas another component is
precipitated. One example may be mentioned here. This
is concerned with the _separatioh of cadmium and copper.
Excess of potassium cyanide solution is added to the solution
containing the two salts when the complex ions [(Cd(CN)J--
and [CU(CN)4r-- respectively ar~ formed. Upon passing
hydrogen sulphide into the solution containing excess of
CN- ions, a precipitate of cadmium sulphide is produced.
Despite the higher solubility product of CdS _(3'6 X 10- 28
as against 8·5 X 10- 45 for copper sulphide), the former is
precipitated because the complex cadmium cyanide ion
has a greater instability constant (see Table V).
The Theoretical Basis of Quantitative Analysis 25 I, 13. Effect of acids upon the solubility
The Theoretical Basis of Quantitative Analysis 25
I, 13. Effect of acids upon the solubility of a precipitate.-
For sparingly soluble salts of a strong acid the effect of the
addition of an acid will b~ similar to that of any other indiffer-
ent electrolyte (compare salt effect in Section I, 10). If the
sparingly soluble salt MA is the salt of a weak acid HA, then
acids will, in general, have a solvent effect upon it. Let us
suppose that hydrochloric acid is added to an aqueous sus-
pension of such a salt. The following equilibrium will be
established:
M+
+ A-
+ H+
+ Cl-
~
HA
+ M+
+ CC.
lf the dissociation constant of the acid HA is very small, the
anion A- will be removed from the solution to form the undis-
sociateq acid HA. Consequently more of the salt will pass
into solution to replace the anions removed in this way and
this process will continue until equilibrium is es1:ablished (i.e.,
until [M-t] X [A-] has become equal to the solubility product
of MA) or, if sufficient hydrochloric acid is present, until the
sparingly soluble salt has dissolved completely. Similar
reasoning may be applied to salts of polybasic acids, such as
phosphoric acid (KI = 7·5 X 10- 3 ; K2 = 6·2 X 10- 8 ;
Ka = 5 X 10- 13 ), oxalic acid (Kl = 5·9 X 10- 2 ; K2 =
6·4 X 10- 5 ), and arsenic acid. Thus the solubility of, say,
silver orthophosphate is due to the removal of the P9,---
ion as HPO,-- and/or H 2 P0 4 -:
+
H+
P0 4 ---
~
HP0 4 --
+
H+
HPO,-- ;
H 2 PO,-.
~
With weak acids, such as carbonic (KI = 4·3 X 10- 7 ;
Kz = 5·6 X 10- 11 ), sulphurous (Kl = 1·7 X 10- 2 ; K z =
1·0 X 10- 7 ), and nitrous (Kl
= 4·6 X 10- 4 ) acids, an addi-
tional factor contributing to the increased solubility is the
actual disappearance of the acid from solution either spon-
ta.neously or on gentle warming. An explanation is thus
provided for the well-known solubility of the sparingly soluble
sulphites, carbonates, oxalates, phosphates, arsenites, arse-
nates, acetates, cyanides (with the exception of silver cyanide,
which is actually a salt of the strong acid H[Ag(CNhJ),
fluorides, and salts of other organic acids in strong acids.
The sparingly soluble sulphates (e.g., those of barium,
strontium, and lead) also exhibit increased solubility in acids
as a consequence of the weakness of the second ~tage of
ionisation of sulphuric acid (K2 = 1·2 X 10- 2 ); .tfie first
stage is completely ionised:
Ba++ + S04--
+ H+ + Cl-
~
HS0 4 -
+ Ba++ + Cr-.
26 Quantitative Inorganic Analysis Since K2 is comparatively large, the solvent effect is relatively small.
26 Quantitative Inorganic Analysis
Since K2 is comparatively large, the solvent effect is relatively
small. However, in the quantitative separation of barium
sulphate, precipitation is usually carried out in slightly acid
solution in order to obtain a more easily filterable precipitate
and to reduce coprecipitation (Section I, 58).
The precipitation of substances within a controlled range of
pH is discussed in Section I, 61B.
I,
14.
Effect
of
temperature
upon
the
solubility
of
a
precipitate.-The solubility of the precipitates encountered
in quantitative analysis increases with rise of temperature.
With some substances the infruence of temperature is small,
but with others it is quite appreciable. Thus the solubility
of silver chloride at 10° and 100°C is 1·72 and 21·1 mg. per
litre respectively, whilst that of barium sulphate at these two
temperatures.is 2·2 and 3·9 mg. per litre respectively. In
many instances, the common ion effect reduces the solubility
to so small a value that the temperature effect, which ,is
otherwise appreciable, becomes very small. Wherever pos-
sible it is advantageous to filter while the solution is hot;
the rate of filtration is increased as is also the SOlubility of
f9reign substances, thus rendering their removal from the
precipitate more complete. The double phosphates of
ammonium with magnesium, manganese or zinc as well as
lead SUlphate and silver chloride are usually filtered at the
laboratory Femperature to avoid solubility losses.
I, 15.
EHect of the solvent upon the solubility of a precipi-
tate.-The solubility of most inorganic compounds is reduced
by the addition of organic solvents, such as methyl, ethyl and
n-propyl alcohols, acetone, etc. For example, the addition
of about 20 per cent. by volume.of ethyl alcohol renders the
solubility of lead sulphate practically negligible, thus permit-
ting quantitative separation. Similarly calcium sulphate
separates quantitatively from 50 per cent. ethyl alcohoL
Other examples of the influence of solvent will be found in
Chapter IV.
I, 16. The ionic product of water.-K@hlrausch and Hey-
dweiller (1894) found that the most highly purified water
that can be obtained possesses a small but definite conduc-
tivity. Water must therefore be ~lightlyionised in accordance
with the equation: H 2 0 ~ H+ + OH-*.
• Strictly"
ion HaO+.
speaking the hydrogen ion H+ exists in water as the hydroxonium
The electrolytic dissociation of water should therefore be written:
2H.O "" HaO+ + OH-.
For the sake of simplicity, the more familiar symbol H+ will be retained.
The Theoretical Basts of Q1tantita!ive Analysis 27 Applying the law of mass action to this
The Theoretical Basts of Q1tantita!ive Analysis
27
Applying the law of mass action to this equation, we obtain,.
for any given temperature:
aH+ X
[H+J . [OH-]
/H+' /OH-
t
aOH-
=
X
=
a constan ,
[HPJ
.
.
aH20
/HsO
where a"" [xl. andj", refer to the activity, concentration and
activity coefficient of the species x. Since water is only
slightly ionised, the ionic concenttations will be small and
their activity coefficients may be regarded as unity; the
activity of the unionised molecules may also be taken as
unity. The expression thus becomes:
[H+] X [OH-]
[HPJ
=
a constant.
.
In pure water or in dilute aqueous solutions, the concentration
of the undissociated water may be considered constant.
Hence: [H+J x· [OH-J = K w ,
where Kw is the ionic product of water. It must be pointed
out that ,the assumption that the activity coefficients of the
ions are unity and that the activity coefficient of water is
constant applies strictly to pure water and to very dilute
solutions (ionic strength < 0'01); in more concentrated
solutions, i.e., in solutions of appreciable ionic strength, the
electrical environment affects the activity coefficients of the
.ions (compare Section I, 10) and also the activity of the
unionised water. The ionic product of water will then not
be constant, but will depend upon the ionic environment.
It is, however, difficult to determine the" activity coefficients,
except under specially selected conditions, so that in practice
the ionic product K w , although not strictly constant, is
employed.
The ionic product varies with the temperature, but under
ordinary experimental conditions (at about 25°C) its value
may be taken as 1 X 10- 14 with concentrations expressed in
gram ions per litre. This is sensibly constant in dilute
aqueous solutions. If the product of [H+J and [OH-l in
aqueous solution momentarily exceeds this value, the excess
ions will immediately combine to form water. Similarly if
the product of the two ionic concentrations is momentarily
less than 10- 14 , more water molecules will dissociate until the
eqUilibrium value is attained.
28 QuantitaHve Inorganic Analysis • The hydrogen and hydroxyl ion cqncentrations are equal in pure
28
QuantitaHve Inorganic Analysis
The hydrogen and hydroxyl ion cqncentrations are equal in
pure water; therefore [H+] = [OH-] = vKw = 10- 7 gram
ions per litre at about 25°C. A solution in whiCh the hydro-
gen and hydroxyl ion concentrations are equal is termed an
exactly neutral solution. If [R+1 is greater than 10- 7 , the
solution is acid, and if less than 10- 7 , the solution is alkaline
(or basic). It follows that at ordinary temperatures [OH-]
is greater than 10- 7 in alkaline solution and less
than
this
value in acid solution.
In all cases the reaction of the solution can be quantita-
tively expressed by the magnitude of the hydrogen ion (or
hydroxonium ion) concentration, or, less frequently, of the
hydroxyl -ion concentration, since the following simple rela-
tions between [H+1 and [OH-] exist:
[H+] _:_ [O~-]'and [OH-] ='[~:r
The variation oj K", with temperature is shown in Table VI.
TABLE VI. IONIC PRODUCT OF WATER AT VARIOUS TEMPERATURES.
Temp. (0C)
I
K
X 1014
Temp. (0C)
I
K.,
X IOU
0·12
35°
2·09
0·19
40°
2··92
10·
0·29
45
Q
4·02
15°
0·45
50·
5·48
20·
0·68
55°
7·30
25·
1·01
60·
I
9·62
30°
1·47
I, 17.
The hydrogen ion exponent, pR.-For many pur-
poses, especially when dealing with small concentrations, it is
cumbersome to express concentrations of hydrogen and
hydroxyl ions in terms of gram equivalents per litre. A very
convenient method was proposed by S. P. L. Sorensen (1909).
He introduced the hydrogen ion exponent pH defined by the
relationships:
pH =
-
loglo [H+] =
loglo 1/[H+], or [H+] =
lo-pH.
The quantity pH is thus the logarithm (to the base 10) of the
reciprocal of the hydrogen ion concentration, or is equal to the
logarithm of the hydrogen ion concentration with negative
sign. This method has the advantage that all states of
acidity and ·alkalinity between those of solutions molar (or
normal) with respect to hydrogen and hydroxyl ions can be
The Theoretical Basis of Quantitative Analysis 29 expressed by a series of positive numbers between
The Theoretical Basis of Quantitative Analysis
29
expressed by a series of positive numbers between 0 and 14.
Thus a neutral solution with [H+] = 10- 7 has a pH of 7; a
solution with molar (or normal) concentration of hydrogen
ions has a pH of 0 (= 10°); and a solution ,molar with
respect to hydroxyl ions has [H+] = K", / [OH-] = 10- 14 /10°
= 10- 14 , and possesses a pH of 14. A neutral solution is
therefore one in which pH = 7, an acid solution one in which
pH .< 7, and an, alkaline solution one in which PH > 7.
An alternative definition for a neutral solution, applicable to
all tempe!atures, is one in which the hydrogen ion and
hydroxyl ion .(:oncentrations are equal. In an acid solution
the hydrogen ion concentration exceeds the hydroxyl ion
concentration, whilst in an alkaline or basic solution, the
hydroxyl ,ion concentration is greater,
Example 10.
(i) Find the
pH
of
a
solution
of
which
[H+]
= 4·0
X
10- 6 •
Log
4·0 =
0·602, hence
log
4-0 X
10- 6 is
5·602 = 0·602 -
5
=
-4:398
(the decimal part or mantissa of the logarithm is alway~ positive).
pH =
-log [H+] =
-
(- 4·398) =
4·398.
(ii)
Find
the
hydrogen ion
concentration
corresponding
to
:.;H = 5·643.
PH =
-log [H+] = 5·643; . '. log [H+] =
-
5·643.
This must be written in the usual form containing a negative
characteristic and a positive mantissa:
Jog [H+] =
-
5·643 =
6·357.
Referring to a table of ~ntilogarithms, the number corresponding to
the logarithm of 0·357 is 2·28;
the number corresponding to the
logarithm 6·357 is accordingly 2·28 X 10- 6 •
[H+J is therefore 2·28 X
10- 6 •
(iii) Calculate the pH of a 0·01 molar solution of acetic acid (the
degree of dissociation is 12'5%),
The hydrogen ion concentration is 0·125
Now log 1·25 = 0·097 ;
X 0·01 =
1·25
.
X 10- 1 •
pH =
-
(
-
3 + 0'097) = 2·903.
The hydroxyl ion concentration may be expressed
similar way:
m
a
POH =
-loglo [OH-] = loglo i/[OH-1, or [OH-] =
10- OR.
30 Quantitative Inorganic Analysis If we write the equation: [H+] X {OR'1 = Kw =
30
Quantitative Inorganic Analysis
If we write the equation:
[H+] X
{OR'1 =
Kw =
10- 14 ,
in the form:
log [H+]
+ log [OH-1
=
log Kw =
-14,
then pH + pOH = pK", =
14.
This relationship should hold for all dilute solutions at about
25°C.
Fig. 1-3 will serve.as a useful mnemonic for.the relation be-
tween [H+], pH, [OH-] and pOH in acid and alkaline solution.
I
pH
pOH
876643210
~
~
~
"
W
9
[OH-]10'4 1()'3 10'2 lOU 16 10 10 9
10 8
16 7
10 8
lOll
16 4
16 3
16 2
16'
1 (1d')
--------A-C-id-------+t~.-------AI-ka-li-n.------­
Neutral
FIG. 1-3.
The logarithmic or exponential method has also been fou¥>-
useful for expressing other small quantities which arise in
quantitative analysis. These include (i) dissociation con-'
stants (Section I, 4), (ii) other ionic concentrations, and (iii)
solubility products (Section I, 8).
(i) For any acid with a dissociation constant of K,. :
pK,. =
-
log K,.
=
IJlog Ka.
Similarly for any base with dissociation constant Kb :
PKb =
-
log Kb =
1 jlog K b .
(ii) For any ion I of concentration [Il :
pI =
-
log [I]
=
Ijlog [I].,
J:hus for [Na+] =
8
X
10- 5 , pI _= 4·1.
(iii) For a salt with a solubility product 5 :
ps =
-
log 5
=
1Jlog S.
I, 18.
The hydrolysis of salts.-Salts may be divided into
four main groups:
I. those derived from the strong acids and strong bases,
e.g., potassium chloride;
,
The Theoretical Basis of Quantitative Analysis 31 II, those derived from weak acids and strong
The Theoretical Basis of Quantitative Analysis 31
II, those derived from weak acids and strong bases, e.g.,
sodium acetate;
III, those derived from strong acids and weak bases, e.g.,
ammonium chloride; and
IV, those derived from weak acids and weak bases, e.g.,
ammonium formate or aluminium acetate.
When any of these is dissolved in water, the solution, as is
well known, is not always neutral in reaction. Interaction
occurs with the ions of water and the resulting solution may be
neutral, acid or alkaline according to the nature of the salt.
With an aqueous solution of a salt of group I, neither the
anions have any tend'ency to combine with the hydrogen
ions nor the cations with the hydroxyl ions of water since the
rel~ted acids and bases are strong electrolytes. The equili-
brium between the hydrogen and hydroxyl ions in water:
H 2 0
~ H+
+ OH-
(i),
is therefore not disturbed and the solution remains neutral.
Consider, however, a salt MA derived from a weak acid
HA and a strong base BOH (group II). The salt is completely
dissociated in aqueous solution:
MA ~M+ +A-.
A very small concentration of hydrogen and hydroxyl ions,
originating ftom the small but finite ionisation of water, will
be initially present. HA is a weak acid, that is, it is disso-
ciated only to a small degree; the conceI}tration of A-ions
which can exist in equilibrium with H+ ions is accordingly
small. In order to maintain the equilibrium, the large
initial concentration of A- -ions must be reduced by combina-
tion with H+ ions to form undissociated HA:
H+ + A-
HA
~
(ii) .
The hydrogen ions required for this reaction can be obtained
only from the further dissociation of the water; this dissocia-
tion produces simultaneously ah equivalent quantity of
hydroxyl ions. The hydrogen ions are utilised in. the forma-
tion of HA, consequently the hydroxyl ion concentration of
the solution will increase and the solution will react alkaline.
The net result is that the anions of the salt react with t~e
hydrogen ions of the water yielding the weak acid HA, and
there is an increase in the concentration of hydroxyl ions over
that present in water.
32 Quan}itative Inorganic Analysis It is usual in writing equations involving equilibria ,between completely dissociated
32 Quan}itative Inorganic Analysis
It is usual in writing equations involving equilibria ,between
completely dissociated and slightly dissociated or sparing1y
soluble substances to employ the ions of the former and the
molecules .of the latter. The reaction is therefore written:
(iii) .
This equation can also be obtained by combining (i) and (ii)
since both equilibria must coexist.
This interaction between the ion (or ions) of a salt and the
ions of water is called hydro~sis. Formerly the chemical.
reaction was written:
MA
+
H 2 0
MOH
+
~
HA,
or as:.
Salt
+
Water
~ Base
+
Acid.
The reaction of the solution was clearly dependent upon the
relative strengths of MOH and HA. This led to th~ definititm
of hydrolysis as the decompdsition of a salt 'into an acid and
a base.
Let us now study the salt of a strong acid and a weak base
(group III). Here the initial high concentration of cations
M+ will be reduced by combination with the hyqroxyl ions of
water to form the littlfT dissociate<;l base MOH until the
equilibrium:
(iv),'
is attained. The hydrogen ion concentration of the solution
will thus be increased and the solution will rea:ct acid. The
hydrolysis is here represented by :
M+
+
H 2 0
~
MOH
+ H+
(v).
For salts of group IV in which both the acid and the base
are weak, two reactions will occur simultaneously:
M+
+
H 2 0
~
MOH + H+
(vi),
A-
+
H 2 0
~
ItA
+ OH-
(vii).
The reaction of the solution, will clearly depend upon the
relative dissociation constants of the acid and the base. If
they are equal in strength, the solution will be neutral; if
K" > Kb, it. will be acid, and if Kb > K", it will
-be alkaline.
Having considered all the possible cases, we are now in a
position to give a more general definition of hydrolysis.
Hydrolysis is the interaction between the ion (or ions)' of a
salt and the ions of water with the production of (a) a weak
acid or a weak base, or (b) of both a weak acid and a weak
base.
The Theoretical Basis of Quan,titative Analysis 33 I, 1~. Hydrolysis constant and degree of hydrolysis.-
The Theoretical Basis of Quan,titative Analysis
33
I, 1~.
Hydrolysis
constant and degree
of hydrolysis.-
Case I.
Salt of
a
weak
acid and a strong
base.
The equili-
brium in a solution of a salt MA may be represented hy :
M+
+
A-
+
H 2 0
M+
+
~
OH- + HA,
or by
A-
+ HIP
~
OH-
+ H~
(i).
Applying the law of mass action, we obtain:
aOH- X aHA'
[OH-]. [HA]
fOH-' fHA
= X
=
KL
(ii)
.,
~
~]
~
"there a, f, and [ ] refer to activiti::!s, activity coefficients
and
concentrations
respectively,
and
K"
is
the
hydrolysis
constant. The solution is ,assumed to be dilute; the activity
of the unionised water may be taken as constant. In dilute
solutions, the ionic strength is small, and the approximation
that the activity coefficient of the unionised acid is unity and
that both ions have the same activity coefficient may be
introduced. Equation (ii) then reauces to :
K
_ [OH-] X [HAJ
(iii).
"
-
[A]
This is often written in the form:
K"
=
[Base1 X [Acid]
[Unhydrolysed salt]
(iv) ;
the free strong base and the unhydrolysed salt are completely
dissociated and the acid is very little dissociated.
The degree of hydrolysis is the fraction of each gram mole-
cule hydrolysed at equilibrium.
Let 1 gram 'mol of sals be
dissolved in V Htres of solution and let x be the degree of
hydrolysis.
per litre are:
The concentrations in gram mols OF gram ions
A-
+
H
0
OH-
+
HA
2 ~
(I-x )tV
~/V
xW
Substituting these values, in (iii) : •
K _ [OH-]
X
[HAl _ xjV
X
xjV _
X2
(
)
[A-]
-
(1 -x)/V
-
(l-x)V
v.
II
-
This expression enables us to calculate the degree of hydrolysis
from the value
of
the )lydrolysis constant at
the dilution V.
It is eviden~ that as V increases, the degree of hydrolysis x
must increase.
c
34 Quantitative Inorganic Analysis The two equilibria :. H 2 0 ~ H+ + OR-,
34 Quantitative Inorganic Analysis
The two equilibria :.
H 2 0
~
H+
+ OR-,
and ~
'HA
~
H+
+ A-,
must coexist with the hydrolytic equilibrium:
A-
+ H 2 0
~
HA
+ OH-.
Hence the two relationships:
[H+]
X [OH-]
K",
and
[H+] X [A-]
j [HAl
-
Ka.
must hold in the same solution as :
[OH-] X
[HA] j [A-] =
Kil.
K", _
[H+] X [OH-]
X
[HA] _
[OH-]
X
[HA] _
K
But
Ka
-
[H+]
X
[A-]
-
[A
]
-
h,
therefore
K",jK a =,K h
(vi),
or
pK" =
pK",
-
pK a
(vii).
The hydrolysis constant is thus related to the ionic product of
the water and the ionisation constant of the acid. Since Ka
varies slightly and K", varies considerably with temperature,
KI> and consequently the degree of hydrolysis will be largely
influenced by changes of temperature,
Example II.
Calculate (i) the hydrolysis constant, (ii) the degree
of hydrolysis" and (iii) the hydrogen ion ~oncentration of a 0·01
molar solution of sodium acetate at the laboratory temperature.
K"
1·0 X 10-
14
Kb = Ka = 1.82 ><10-
5·5 X 10- 1 °.
5
=
The degre£ of hydrolysis x is given by :
x 2
K" =
(1 -x)V
Substituting for K" and V (= lIe), we' obtain:
x 2
X
0·01
5·5 X 10-
10 =
.
• (1 -x)
Solving this quadratic equation for x, x = 0·000235 or 0'0235%.
C 2 H a 0 2 -
+ H 2 0
~ H.C 2 H a 0 2
+ OH-.
-
If the solution were completely hydrolysed, the concentration of
acetic acid produced would be O·OIM. But the degree of hydrolysis
is 0·0235%, therefore the concentration of acetic acid is 2';35 X 10- 8
(1
x) mols
x mols
x mols
The Theoretical Basis oj Quantitative Analysis 35 M. This is also equal to the hydroxyl
The Theoretical Basis oj Quantitative Analysis
35
M. This is also equal to the hydroxyl ion concentntion produced,
i.e., POH = 5·63.
pH = 14·0 -
5·63 = 8·37.
The pH may also be computed from equation (ix) below:
pH =
1/2 pKw + 1/2 PK" + 1/2 log c,
= 7·0
+ 2·37
+ 1/2
(- 2)
=
8·37.
The hydrogen ion concentration of a solution of a hydrolysed
salt can be readily computed. The amounts of HA and OH-
ions formed as a result of hydrolysis are equal, th~refore in a
solution of the ~ure salt in water [HA] = [OH-]. If the
concentration of the salt is c gram mols per litre, then:
[HA] X [OH-] _
_
K."
[A
]
-
[OH-P _ K
c
-
~- K,,'
and
[OH-] =
yc.
Kw I K"
(vii),
or
[H+] =
vK.". ~a / c, since [Ji+] =
K", I [OH-]
(viii);
PH =
If2pK w + 1/2pK a + 1/2logc *
(ix).
Equation (ix) can be employed for the cal~ulation of the
pH of a solution of a salt of a weak acid and a strong base.
Thus the pH of a O'05N solution of sodium benzoate is given
by: pH = 7·0 + 2·10 + 1/2( - 1·30) = 8'45.
(Benzoic acid: Ka:- 6·37 X 10- 5 ; pK" =
4·20.)
Such a calculation will provide useful information as to the
indicator whiCh should be employed in the titration of a weak
acid and a strong base (see Section I, 33).
case 2.
Salt of a strong acid a.nd a weak base.
The hydro-
lytic equilibrium is represented by :
M+
+ H 2 0
~ MOH
+ H+
(x).
the following equations
By apply~ng the law of mass action along the lines of Case 1.
are obt~ined :
K" =
[H+] X [MOI{] =
[M+]
[Acid] X [Base]
[Unhydrolysed Salt] =
K",
Kb
(xi),
(xii).
(1 -
x)V
• :ro be consistent we should write pc =
-
log c.
36 Quantitative Inorganic Analysis Kb is the dissociation constant of the base. Furthermore, since [MOH)
36 Quantitative Inorganic Analysis
Kb is the dissociation constant of the base. Furthermore,
since [MOH) and. [H+) are equal (equation (x),
K
_
[H+) X [MOH] _
-
[H+)2 _
K
"
-
[M+]
-c- -
Kb
'
[H:'-} =
v'c.K", I K b , •
()r
pH =
1/2PKfII _
1/2 PKb -
1/2 log
c
(xiii) •
Equation (xiii) may be applied to the caloulation of the
pH of solutions of salt>s of strong acids and weak bases. Thus
the. PH of a O·02N solution of ammonium chlQride is :
pH =
7·0 _
2·37 _
1/2 (-0'70)
4: 98.
(Ammonium·hydroxide:
Kb =
1·85 X
10- 0 ;
PKb =
4'74.)
. Case 3, Salt of a weak acid and a weak base. The hydro-
lytic equilibrium is expressed by the equation:
M+ + A-
+ H 2 0
~ MOH
+ HA
(xiv) .
.
Applying the law of mass action and taking the activity.of
unionised water as u~ity, we have:
K" =
[MOH]. [HAl X /MOH • /HA
aMOH
X
aHA =
aM+
X
aA-
[M+] . [A
]
/M+
. f A-
(xv).
By the usual approximations, that is, by assuming that the
activity coefficients of the unioni'sed molecules and, less
justifiably, of the ions are unity, the following approximate
equation is obtained:
K
_ [MOH1 x {HAl
(xvi),
,,- [M+] X
[A
]
[Base] X [Acid]
_--~--~~--~-
(xvir)~
[Unhydrolysed
Saltp
If x. is the degree of •hydrolysis of 1 gram mol of the salt
dissolved in V litres of solution, then the individual concen-
trations are:
[MOR] = .JHA] = xiV; [M+] =
[A -1 =
(I
-
x)/Y.
Substituting these values in (xvi) :
K,,= _
xIV. xIV
_
(xviii) .
(1
x)/V.(l -
x)/V
_
(1 _" X)2
X_2_
-
The Theoretical Basis of Quantitative Analysis 37 The degree of hydrolysis and consequently the pH
The Theoretical Basis of Quantitative Analysis
37
The degree of hydrolysis and consequently the pH is inde-
pendent of concentration the of the solution.*
As in Case 1 the expressions :
Kw =
[H+] X [OH-],
K -
[H+] X [A-]
[HA
d K
,. -
,.an
_ [M+]X [OH-]
[MOH]
,
b
-
hold simultaneously with equation (xiv) for the hydrolytic
equilibrium. By substitution in ·the last-named equation,
it can be readily shown that:
K"
=
Kw / K,.
X Kb
(xix),
or
pK" = pKw - PK"
PKb
(xx).
This expression enables us to compute the value of the degree
of hydrolysis x from the dissociation constants of the acid and
the base.
The hydrogen ion concentration of the hydrolysed solution
is calculated in the following manner~: -
+
_
[HAl _
xIV
_
x
[H
]
-
K
X
[A-] -
K,.
X
(I
_
x) IV
-
KtJ X
(1
_
x)·
But x/{1 -
x)
=
IYK; (by equation (xviii) ),
hence
[H+] =
K,
vK" =
vKw X
K,. f Kb
. (xxi),
or
,
pH.
If2pK w + IJ2pK,.·- I/2PK b
(xxii).
If the ionisation constants of the acid and the base are equal,
that is, K,. = K b , pH = 1/2 pKw = 7·0; and the solution is
neutral although hydrolysis may' be. considerable. If
1(. > K b , pH < 7 and the solution is acid, but when
K. > K,. , pH > 7 and the solution reacts alkaline.
The pH of a solution of ammonium acetate is given by :
-
i.e., the solution is approximately neutral. On the other
hand, for a dilute solution of ammonium formate:
pH =
7·0
+ 2·37
2·37 =
7·0,
pH =
7·0 + 1·88
-
2·37 =
6·51,
(Formic acid: 1}
=
1·77 X 10-4; PK
=
3·75.)
i.e., the solution reacts slightly acid.
•• This applies only 'f the original assumptions as to activity coefficients are
justified.
In solutions crf appreciable ionic strength, the activity coefficients
of the ions will vary with the total ionic strength.
38 Quantitative lnorgimic Analysis I, 20. Buffer solutions.-A solution of 0, oo()1N hydro- chloric acid
38 Quantitative lnorgimic Analysis
I,
20.
Buffer solutions.-A solution of 0, oo()1N hydro-
chloric acid should have a pH equal to 4, but the solution is
extremely sensitive to traces of alkali from the glass of the
containing vessel and to ammonia from the air. Likewise a
O·OOOIN solution of sodium hydroxide, which should have a
pH of 10, is sensitive to traces of carbon dioxide from the
atmosphere. Aqueous solutions of potassium chloride and
of ammopium acetate have a pH of about 7. The addition of
I m!. of normal hydrochloric acid to I litre of the solution
results in a change of pHOto 3 in the former case and in very
little change in the latter. The resistance ,of a solution to
changes in hydrogen ion concentration upon the addition of,
small amounts of acid or alkali is termed buffer action; a
solutipn which possesses such properties is known as a buHer
solution. It is said to possess" reserve acidity" and" reserve
alkalinity." Solutions of which the PH values (determined
by reference to the hydrogen electrode) are known, which can
be readily prepared, and which are unaffected by small
additions of alkali or acid, are required for the colorimetric
determination of hydrogen ion concentration (see Section
V, 6) and for other purposes.
Buffer solutions usually consist of solutions containing a
mixt\lre of a weak acid or base and its salt. In' order to
understand buffer action, let us study first the equilibrium
between a weak acid and its salt. The dissociation of a weak
acid is given by :
'
HA
~
H+
+ A-,
and its magnitUde is controlled by the value of the dissociation
constant Ka :
(i),
where a" refers to the activity of the species x. The expres-
sion may be approximated by writing concentrations for
activities (strictly speaking, it will be recalled (Section I, 5),
activity = co;ncentration X activity coefficient) :
[ H+J =
[HAJ
K
(ii) .
[A-] X
a
This equilibrium applies to a mixture of an acid HA arid its
salt, say, MA. If the concentratiori of the acid be C a and that
of the salt be c., then the conc,entration of the undissociated
portion of the acid is C a - [H+]. The solution is electrically
The Theoretical Basis of Quantitative Analysis 39 neutral, hence [A-] = c. + [H+] (the
The Theoretical Basis of Quantitative Analysis
39
neutral, hence [A-] = c. + [H+] (the salt is completely dis-
sociated).
Substituting
these
values
in
the
equilibrium
equation (ii), we have:
c
-
[H+]
[H+] =
K
(iii).
a
X
c.
+ [H+]
a
This is a quadratic equation for [H+] and may be solved in the
usual manner. It can, however, he simplified by introducing
the following further approximations. In a mixture of a
weak acid and its salt, the dissociation of the acid is repressed
by the common ion effect, and [H+] may be taken as ~egli­
gibly small by comparison with C a and c Equation (iii)
then' reduces to :
[ H+
= ~
K
[H+] = [Acid] [Salt)
K
(iv),
.]
'
or
a,
X
a
C s
or
pH =
[Salt]
pK a + log [Acid)
(v).
Similarly for
a
mixture
of a weak base of dissociation
constant Kb and its salt with a strong acid:
[ OH-] =
[Base]
X
K
(vi)
[Salt]
b
or
POH = PKb + log [~::?]
(vii).
Let us confine our attention to the case in which the con-
centrations of the acid and its salt are equal, i.e., of a half
neutralised acid. Then pH = pK a .
Thus
the pH
of
a_
half neutralised solution of a weak acid is equal to the nega-
tive logarithm of the dissociation constant of the acid.
For
acetic acid, Ka = 1·82 X 10- 5 , PK a = 4'74; a half neu-
tralised solution of, say, O'lN acetic acid will have a pH of
4·74. If we add a small conc~ntration of H+ ions to such a
solution, the former will
combine
with
form undissociated acetic acid:
the acetate ions to
.
':to
H+
+ C 2 H 3 0 2 -
~
H.C 2 H a 0 2 •
Similarly, if a small concentration of hydroxyl iQns be added,
the
latter will combine with the hydrogen ions arising from
the dissociation of the acetic acid and form unionised water;
the equilijJrium will be disturbed. and more acetic acid will
dissociate to replace the hydrogen ions removed in th}s' way.
In either case, the' concentration of
the acetic acid and acetate
ion (or salt) 'will not be appreciably changed. It follows
40 Quantitative Inorganic Analysis from equation (v) that the pH of the solution will not
40 Quantitative Inorganic Analysis
from equation (v) that the pH of the solution will not be
materially affected.
The solution containing equal concentrations of acid and
its salt, or a half neutralised solution of the acid, has the
maximum buffer capacity. Other mixtures also possess
considerable buffer
capacity, but the pH will differ slightly
from the half neutralised acid. Thus in a.quarter neutralised
solution of acid, [Acid] =.3 [Salt]: -
pH =
PK"
+ log 1/3 =
pK" + 1'52,
=pK" - 0·48.
For a three-quarter neutralised acid, [Salt] =
3
[Acid] :
pH = pK" + log 3,
=pK" + 0·48.
In general, we may 'state that the: buffering capa~ity is main-
tained for mixtures within the range I acid: 10 salt and 10
acid: .1 salt. The approximate pH range of a weak acid
buffer is: •
pH =
pK" ±
1.
The conGentration of the acid is usually of the order 0·05 -;- 0·2
molar. Similar remarks apply to weak
The preparation of a buffer solution of a definite PH is a
simple process if the acid (or base) of appropriate dissociation
constant is
found: small variations in pH are obtained by
variations in the ratio of the aci$l to the salt concentration.
One example is given in Table VII,
TABLE vn. pH OF ACETIC ACID-SODIUM ACETATE BUFFER MIXTURES.-
l~ ml. mixtures of x ml. of O·2M acetic acid and y m!. of O·2M sodium acetate .
Acetic Acid (x ml.)
.
.$odi~m Acetate (y ml.)
.PH
9·5
0'0
3·42
3·72
.
9·0
1·0
-g·0
2·0
4·05
7·0
3·0
4·27
6·0
4·0
4·45
5·0
5·0
4·63
4·0
6·0
4·80
3·0
,7·0
4'99
2·0
8·0
5·23
1·0
9·0
5·57
• 0·5
9·5
5·89
-. See
(\ppendix,
Section A, 10.
The Theoretical Basis of Quantitative A.nalysis 41 BeJore leaving the subject of buffer solutions, it
The Theoretical Basis of Quantitative A.nalysis
41
BeJore leaving the subject of buffer solutions, it is neces-
sary to draw attention to e. pos&ible ~rroneous deduction from
equation ~v), 'namely, that the hydrogeh ion concentration
of a buffer solution is depeQlient only 'upon the ratio of the
concentrations of acid.and salt and upon K a , and not upon
the actual concentration~; otherwise expressed, that the
pH of such a buffer mixture should not change upon dilution
with water. This is approximately although not strictly
true. In deducing equation (ii), concentrations have been
substituted for activities\ a step which is not entirely justi-
fiable except in dilute solutions. Theoretically,.the expression
controlling buffer action is :
aHA
c
f"
-
X K" = -_
aH+ =
X
K"
(viii)
aA-
Cs.fA-'·
where a and f refer to activities and act,ivity coefficients
respectively of the species indicated in the subscript. The
,activity coefficient: fa of the undissociated -acid is approxi-
mately unity in dilute aqueous solu~ion. Expression (viii)
thus becomes :
[Acid]
[Salt] X fA-
X K
(ix),
aH+ =
a
or
pH
PK
=
+"log [Salt]/[Acid] + log !A-
(x).
According to the Debye-Hiickel-Onsager theory, the activity
coefficirnt ot an ionfi in aqueous solution at 25°C is given by :
0'505z,2
0·&
1L
log/. =
-
.
+ BIL,
1 + A1L 0 • 5
where Z; is the valency of the ion, IL is the ionic strength of the
solution, and A and B are constants. This may be written
in the
form:
log!; =
-
0·505 Z;2 IL O.5 + CIL,
where C is another constant approximately equal to 0·505 z;2A
+ Band usu<,\lly has a value varying between 0'2 and
1'5. Substituting for J~- in (v), we obtain:
pH = PK a + log [Salt] I [Acid] - 0·505z;2 1L 0.5 + CIL (xi).
The activity coefficient of the ion fA- generally iijcreases
with decrease of concentration, so that when a buffer solution
is diluted, fA- increase§ and consequently aH+ will increase
(equation (ix) )
For most pr!lctical purposes the change is
small, but for exact work the change must be taken into
account. The addition of salts to buffer m.ixtures results in
c*
42 Quantitative Inorganic Analysis a change of the ionic strength of the solution; this will
42 Quantitative Inorganic Analysis
a change of the ionic strength of the solution; this will affect
the pH of the solution (~quation (xi)). Indeed, in all buffer
solutions a correction should, strictly speaking; be applied for
the ionic strength of 'the solution.
Buffer mixtures are not ctmfined to mixtures of monobasic
acids or monoacid base:; and their salts. We may employ a
mixture of salts oL a polybasic acia, e.g., NaH 2 P0 4 and
Na 2 HP0 4 • The salt
NaH 2 P0 4 is completely dissociated:
NaH 2 P0 4 .= Na+ + H 2 P0 4 -.
The ion H 2 PO4- acts as a monobasic acid:
H 2 P0 4 -
.=
H+
+ HP.0 4 --,
for'"Which K (sK 2 for
phosphoric aeid) is 6·2 X 10- 8 • The
addition of the salt
Na 2 HP0 4
is analogous to the addition of,
say,
acetate ions to a solution of acetic acid, since the tertiary
ionisation of phosphoric acid (HP0 4 -- .= H+ + P0 4 ---)
is small (K3 = 5 X 10- 13 ). The .mixture of NaH P0 4 and
2
Na 2 HP0 4
is Ltherefore an effective buffer over the range pH
7·2 ±
1'0 (:
PK±l).
.
Buffer solutions find mahy applications in quantitative
analysis. Many precipitations are made in certain ranges of
pH values. Examples are given in Sec1ion I, 61 under
Separations; many others will b~ found scattereq. throughout
the text. Buffer solutions are ~lso employed in the colori-
metric determination:of pH with the aid of indicators CSection
V,6).
VOLUMETRIC ANALYSIS In the foregoing pages we have studied some general theory, a knqwledge of
VOLUMETRIC ANALYSIS
In the foregoing pages we have studied some general theory,
a knqwledge of which is indispensable for the comprehension
of the processes of quantitative analysis, both gravimetric
and volumetric. We will now confine our attention to the
principles of vQlum~tric analysis and postpone the parallel
study of gravimetric analysis to a later stage (Section 1,54).
I, 21. Volumetric analysis, or quantitative chemical
analysis by measure, consists essentially in determining the
volume of a solution of accurately known cQncentratism which
is required to react quantitatively with the solution of the
substance being determined. The solution of accurately
known 1;_trength is called the standard Bolution; it contains a
definite ·number of gram
equivalents (see Section I, 23) per
litre. The weight qf the substance to be determined is then
calculated from the volume of the standard solution and the
known laws of chemical equivalence.
The standard solution is usually added from a graduated
vessel, called a burette. The process of. adding the standard
solution until the reaction is just comp~ete is tfirmed a
titration, and the substance to be determined is titrated. The
point at which this occurs is called the equivalence point or the
theoretical
(or
stoichiometric)
end
pOint.
The completion of
the titration should, as a rule, be detectable by some change
unmistakC1ble to the eye produced by tlie standard solution
its~lf (e.g., potassium permanganate) or, more usually,_by the
adaition of an auxiliary reagent, known as an indicator.
After the reaction between the substance and the standard
solution is practically complete, the indicator should give a
clear visual change (either a colour change or, the forlV-ation
of a turbidity) in the liquid being titrated. The pomt' at
which this occurs is called the end point of the titration. In
the ideal titration the visible end point will coincide with the
stoichiometric or theoretical end point. In practice, how-
ever, a very small difference usually occurs; this represents
the titration error. We should always endeavour to select an
indic.ator and also the experimental conditions such that the
difference between the visible end point and the equiV'alence
point is as small as possible.
For use in volumetric analysis a reaction must fulfil the
following conditions:
43
44 Quantitative Inorganic Analysis 1. There must be a simple reaction which can be expressed
44 Quantitative Inorganic Analysis
1. There must be a simple reaction which can be expressed
by a chemical equation; the substance to be determined
should react completely with the reagent in stoichiometric
or equivalent proportions.
2. The reaction should be practically instantaneous or
proceed with very great speed. "(Most ionic reactions satisfy
this condition.) In some cases the additiQn of a catalyst
increases the speed of a reaction.
3. There must be a marked change .in some physical or
chemical property of the solution at the equivalence point.
4. An indicator should be available which, by a change in
physical properties (colour or formation of a precipitate),
should sharply define the end point of the reaction. [If no
visible indicator. is available for the'detection of the equiva-
lence point, the latter can often be determined by fpllowing
during the course of the titration (a) the change of the
potential of a suitable electrode (potentiometric titration, see
Sections I, 53), or (b) the change of the electrical conductance
of the solution (conductometric titration).]
Volumetric methods are, as a rule, susceptible of high
accuracy (1 part in 1000) and possess several advantages,
wherever applicable, over gravimetric methods. They need
simpler apparatus, tedious and difficult separations can often
be avoided, and are, generally, quickly performed. The
following are required for volumetric analysis: (i) Calibrated
measuring vessels including burettes, pipettes and measuring
flasks (see Sections n, 20-22). (ii) Substances of known purity
for the pJ;eparation of standard solutions. (iii) An indicator
or other device (see Section I, 53) for detecting the complete-
ness of the reaction.
I, 22.
Classification of reactions in volumetric analysis.-
The reactions employed in volumetric analysis fall into two
m:Hn Classes:
(a) Those in which no change in valency occurs; these are
dependent upon the combination of ions.
(b) Oxidation-reduction reactions; these involve a change
of valency'or, otherwise expressed, a transfer of electrons
For purposes of convenience, however, these two types gf
reactions are divided into three main classes :'
1. Neutralisation reactions.- or acidimetry and alkalimetry.
These include the titration of free bases or those formed from
salts of weak acids by hydrolysis with a standard acid (acidi-
metry), and the titration of free acids or those formed by the
The Theoretical Basis of 9uantitative. Analysis 45 hydrolysis of salts of weak bases with a
The Theoretical Basis of 9uantitative. Analysis
45
hydrolysis of salts of weak bases with a standard base (alkali-
metry). These reactions involve the combinat'ion of hydrogen.
and hydroxyl ions to form water. • -
2. Precipitation reactions. These depend upon the com-
bination of ions, other than hydrogen and hydroxyl ions, to
form either. a simple precipitate, as in the titration of silver
with a solution oJ a chloride (Section m. 24). or a complex
ion, as in the titration of a cyanide with silver nitrate ~olution
(Section m. 41; 2CN- + Ag+ ~ [Ag(CN)zr).
3. Oxidation-reduction reactions. Under this heading are
included all reactions involving change in oxidation number
(Section I. 23) or transfer of electrons (Section I. 23) among the
reacting substances. The standard solutions are either
oxidising or reducing agents. The principal oxidising agents
are potassium permanganate, potassium dichromate, ceric
.sulphate, manganic sulphate, iodine, potassium iodate, potas-
sium bromate and chloramine-To Frequently used reducing
agents aret'ferrous and stannous compounds, sodium thiosul-
phate, arsenious oxide and titanous chloride or sulphate.
I
1.23. Equivalent weights.
Normal solutions.-A-standard
solution is one-which contains a known weight of the reagent
in' a definite volume of the solution. ·A molar solution is one
which contains'one gram molecular weight of the reagent per
litre of solution. A normal solution of a reagent is one that
contains one gram. equivalent weight* per litre of solution.
It is designated by N. Semi-normal, .penti-normal, deci-
nprmal and centi-normal solutions are often required; these
are shortly written·N/2 or 0·5N, N (5 or, 0·2N, N /10 or O'lN,
and N {100 or O·OlN respectively.
.
The above definition of normal solution utilises the term
" equivalent weight." This quantity varies with the type of
reaction, and, since it is difficult to give a clear definition of
"equivalent weight" which will cover all reactions, it is
proposed to discuss this subject in some detail below. It often
happens that the same compound: possesses different equiva-