Vogel's Textbook of Quantitative Chemical Analysis

906 Pages·2005·33.67 MB·English

TEXTBOOK OF
QUANTITATIVE
CHEMICAL
G. H. JEFFERY J. BASSETT J. MENDHAM R C. DENNEY
TEXTBOOK OF
QUANTITATIVE CHEMICAL ANALYSIS
FIFTH EDITION
Revised by the following members of
The School of Chemistry,
Thames Polytechnic, London
G H Jeffery, B Sc, Ph D, C Chem, F R S C
Former Principal Lecturer and Deputy Head of the School of Chemistry
J Bassett, M Sc, C Chem, F R S C
Former Senior Lecturer in Inorganic Chemistry
J Mendham, M Sc, C Chem, M R S C
Principal Lecturer in Analytical Chemistry
R C Denney, B Sc, Ph D, C Chem, F R S C, M B 1 M
Principal Lecturer in Organic Chemistry
.
.n Longman
iii Scientific &
Technical
w
Copublished in the United States with
John Wiley & Sons, Inc., New York
Longman Scientific & Technical
Longman Group UK Limited
Longman House, Burnt Mill, Harlow
Essex CM20 2JE, England
and Associated Companies throughout the world
Copublished in the United Srates with
John Wiley and Sons Inc, 605 Third Avenue, New York NY 10158
O Longman Group UK Limited 1978, 1989
All rights reserved; no part of the publication
may be reproduced, stored in a retrieval system,
or transmitted in any form or by any means, electronic,
mechanical, photocopying, recording, or otherwise,
without the prior written permission of the Publishers, or a
licence permitting restricted copying in the United Kingdom issued by
the Copyright Licensing Agency Ltd, 33-34 Alfred Place, London WClE 7DP.
First published in 1939
New impressions 1941, 1942, 1943, 1944, 1945, 1946, 1947, 1948
Second edition 1951
New impressions 1953, 1955, 1957, 1958, 1959, 1960
Third edition 1961 (published under the title A Text-book of Quantitative lnorganic Analysis
lncluding Elementary Instrumrntal Analysis)
New impressions 1962, 1964, 1968, 1969, 1971, 1974, 1975
Fourth edition 1978
New impressions 1979, 1981, 1983, 1985, 1986, 1987
Fifth edition 1989
British Library Cataloguing in Publication Data
Vogel, Arthur Israel
Vogel's textbook of quantitative chemical
analysis. - 5th ed.
1. Quantitative analysis
1. Title II. Jeffery, G. H.
545
ISBN 0-582-Wb93-?
Library of Congress Cataloguing in Publication Data
Vogel, Arthur Israel
[Textbook of quantitative chemical analysis]
Vogel's textbook of quantitative chemical analysis. - 5th ed./
revised by ... G. H. Jeffery ... [et al.]
p. cm.
Rev. ed. of: Vogel's textbook of quantitative inorganic analysis.
4th ed. 1978.
Includes bibliographies and index.
ISBN 0-470-2151 7-8
1. Chemistry, Analytic-Quantitative. 2. Chemistry, Inorganic.
1. Jeffery, G. H. 1909- . II. Vogel, Arthur Israel. Vogel's
textbook of quantitative inorganic analysis. III. Title.
QD101.2.V63 1989
545-dc20 89- 12296
CIP
Set in 1011 1p t Lasercomp Times New Roman
Printed in Great Britain
by Bath Press, Avon
CONTENTS
PART A FUNDAMENTALS OF QUANTITATIVE CHEMICAL
ANALYSIS 1
CHAPTER 1 INTRODUCTION 3
1.1 Chemical analysis 3
1.2 Applications of chemical analysis 3
1.3 Sampling 4
1.4 Types of analysis 5
1.5 Use of literature 6
1.6 Common techniques 7
1.7 Instrumental methods 8
1.8 Other techniques 9
1.9 Factors affecting the choice of analytical methods 10
1.10 Interferences 12
1.11 Data acquisition and treatment 13
1.12 Summary 14
CHAPTER 2 FUNDAMENTAL THEORETICAL PRINCIPLES OF
REACTIONS IN SOLUTION 15
2.1 Chemical equilibrium 15
2.2 The law of mass action 16
2.3 Factors affecting chemical reactions in solution 18
2.4 Electrolytic dissociation 19
2.5 Activity and activity coefficient 23
2.6 Solubility product 24
2.7 Quantitative effects of a common ion 26
2.8 Fractional precipitation 28
2.9 Effect of acids on the solubility of a precipitate 29
2.10 Effect of temperature on the solubility of a precipitate 30
2.11 Effect of the solvent on the solubility of a precipitate 30
2.12 Acid-base equilibria in water 31
2.13 Strengths of acids and bases 31
CONTENTS
2.14 Dissociation of polyprotic acids 33
2.15 Common-ion effect 34
2.16 The ionic product of water 36
2.17 The hydrogen ion exponent 38
2.18 The hydrolysis of salts 40
2.19 Hydrolysis constant and degree of hydrolysis 42
2.20 Buffer solutions 46
2.21 Complex ions 49
2.22 Complexation 51
2.23 Stability of complexes 52
2.24 Metal ion buffers 53
2.25 Factors influencing the stability of complexes 53
2.26 Complexones 55
2.27 Stability constants of EDTA complexes 58
2.28 Electrode potentials 60
2.29 Concentration cells 63
2.30 Calculation of the e.m.f. of a voltaic ce11 64
2.31 Oxidation-reduction cells 64
2.32 Calculation of the standard reduction potential 65
2.33 Equilibrium constants of oxidation-reduction reactions 67
CHAPTER 3 COMMON APPARATUS AND BASIC TECHNIQUES 71
3.1 Introduction 71
BALANCES
3.2 The analytical balance 72
3.3 Other balances 74
3.4 Weights, reference masses 75
3.5 Care and use of analytical balances 75
3.6 Errors in weighing 76
GRADUATED GLASSWARE
3.7 Units of volume 78
3.8 Graduated apparatus 79
3.9 Temperature standard 80
3.10 Graduated flasks 81
3.11 Pipettes 81
3.12 Burettes 84
3.13 Weight burettes 86
3.14 Piston burettes 87
3.15 Graduated (measuring) cylinders 87
3.16 Calibration of volumetric apparatus 87
WATER FOR LABORATORY USE
3.17 Purified water 89
3.18 Wash bottles 91
GENERAL APPARATUS
3.19 Glassware, ceramics, plastic ware 92
CONTENTS
3.20 Meta1 apparatus 93
3.21 Heating apparatus 97
3.22 Desiccators and dry boxes 98
3.23 Stirring apparatus 101
3.24 Filtration apparatus 102
3.25 Weighing bottles 104
REAGENTS AND STANDARD SOLUTIONS
3.26 Reagents 104
3.27 Purification of substances 105
3.28 Preparation and storage of standard solutions 107
SOME BASIC TECHNIQUES
3.29 Preparation of the substance for analysis 109
3.30 Weighing the sample 110
3.31 Solution of the sample 110
3.32 Precipitation 11 5
3.33 Filtration 115
3.34 Filter papers 115
3.35 Crucibles with permanent porous plates 117
3.36 Washing precipitates 11 8
3.37 Drying and igniting precipitates 119
3.38 References for Part A 122
3.39 Selected bibliography for Part A 122
PART B ERRORS, STATISTICS, AND SAMPLING
CHAPTER 4 ERRORS AND STATISTICS
4.1 Limitations of analytical methods 127
4.2 Classification of errors 127
4.3 Accuracy 128
4.4 Precision 129
4.5 Minimisation of errors 131
4.6 Significant figures and computations 132
4.7 The use of calculators and microcomputers 133
4.8 Mean and standard deviation 134
4.9 Distribution of random errors 136
4.10 Reliability of results 137
4.1 1 Confidence interval 138
4.12 Comparison of results 139
4.13 Comparison of the means of two samples 140
4.14 Paired t-test 142
4.15 The number of replicate determinations 142
4.16 Correlation and regression 144
4.17 Linear regression 145
4.18 Comparison of more than two means (analysis of variance) 146
4.19 The value of statistics 149
vii
CONTENTS
CHAPTER 5 SAMPLING 150
5.1 The basis of sampling 150
5.2 Sampling procedure 150
5.3 Sampling statistics 151
5.4 Sampling and physical state 153
5.5 Crushing and grinding 155
5.6 Hazards in sampling 155
5.7 References for Part B 156
5.8 Selected bibliography for Part B 156
PART C SEPARATIVE TECHNIQUES
CHAPTER 6 SOLVENT EXTRACTION
6.1 General discussion 161
6.2 Factors favouring solvent extraction 163
6.3 Quantitative treatment of solvent extraction equilibria 165
6.4 Synergistic extraction 167
6.5 Ion-association complexes 168
6.6 Extraction reagents 169
6.7 Some practical considerations 172
SOME APPLICATIONS 175
6.8 Determination of beryllium as the acetylacetone complex 175
6.9 Determination of boron using ferroin 175
6.10 Determination of copper as the diethyldithiocarbamate
complex 177
6.11 Determination of copper as the 'neo-cuproin' complex 178
6.12 Determination of iron as the 8-hydroxyquinolate 178
6.13 Determination of lead by the dithizone method 179
6.14 Determination of molybdenum by the thiocyanate method 180
6.15 Determination of nickel as the dimethylglyoxime complex 181
6.16 Determination of silver by extraction as its ion-association
complex with 1,lO-phenanthroline and bromopyrogallol red 182
6.17 Determination of nickel by synergistic extraction 183
6.18 Extraction and determination of lead, cadmium, and copper
using ammonium pyrollidine dithiocarbamate 184
CHAPTER 7 ION EXCHANGE
7.1 General discussion 186
7.2 Action of ion exchange resins 189
7.3 Ion exchange chromatography 194
7.4 Ion chromatography 197
7.5 Ion exchange in organic and aqueous-organic solvents 201
7.6 Chelating ion exchange resins 202
CONTENTS
7.7 Liquid ion exchangers 204
APPLICATIONS IN ANALYTICAL CHEMISTRY 205
7.8 Experimental techniques 205
7.9 Determination of the capacity of an ion exchange resin (column
method) 207
7.10 Separation of zinc and magnesium on an anion exchanger 208
7.11 Separation of chloride and bromide on an anion exchanger 209
7.12 Determination of the total cation concentration in water 210
7.13 Separation of cadmium and zinc on an anion exchanger 210
7.14 Concentration of copper(I1) ions from a brine solution using a
chelating ion exchange resin 212
7.15 Determination of anions using ion chromatography 213
CHAPTER 8 COLUMN AND THIN-LAYER LlQUlD
CHROMATOGRAPHY
8.1 Introduction 216
8.2 Types of liquid chromatography 216
8.3 Equipment for HPLC 220
8.4 Derivatisation 228
8.5 Quantitative analysis 229
8.6 Thin-layer chromatography 229
8.7 High performance thin-layer chromatography (HPTLC) 232
8.8 Determination of aspirin, phenacetin and caffeine in a mixture 233
8.9 Thin-layer chromatography - The recovery of separated
substances by elution techniques 233
CHAPTER 9 CAS CHROMATOGRAPHY
9.1 Introduction 235
9.2 Apparatus 235
9.3 Programmed-temperature gas chromatography 244
9.4 Quantitative analysis by GLC 245
9.5 Elemental analysis using gas chromatography 247
9.6 Determination of aluminium by gas chromatographic analysis of
its tris(acety1acetonato) complex 248
9.7 Analysis of a mixture using the interna1 normalisation
method 249
9.8 Determination of sucrose as its trimethylsilyl derivative using
gas-liquid chromatography 250
9.9 References for Part C 251
9.10 Selected bibliography for Part C 253
CONTENTS
PART D TITRIMETRY AND GRAVIMETRY 255
CHAPTER 10 TlTRlMETRlC ANALYSIS
10.1 Titrimetric analysis 257
10.2 Classification of reactions in titrimetric analysis 258
10.3 Standard solutions 259
10.4 Equivalents, normalities and oxidation numbers 260
10.5 Preparation of standard solutions 260
10.6 Primary and secondary standards 260
NEUTRALISATION TlTRATlONS
10.7 Neutralisation indicators 262
10.8 Preparation of indicator solutions 266
10.9 Mixed indicators 267
10.10 Universal or multiple range indicators 268
10.1 1 Neutralisation curves 269
10.12 Neutralisation of a strong acid with a strong base 269
10.13 Neutralisation of a weak acid with a strong base 272
10.14 Neutralisation of a weak base with a strong acid 274
10.15 Neutralisation of a weak acid with a weak base 275
10.16 Neutralisation of a polyprotic acid with a strong base 276
10.17 Titration of anions of weak acids with strong acids:
'displacement titrations' 277
10.18 Choice of indicators in neutralisation reactions 280
10.19 Titrations in non-aqueous solvents 281
10.20 Solvents for non-aqueous titrations 283
10.21 Indicators for non-aqueous titrations 283
10.22 Preparation of a standard acid 284
10.23 Preparation of constant boiling point hydrochloric acid 285
10.24 Direct preparation of 0.1M hydrochloric acid from the
constant boiling point acid 285
10.25 Preparation of approximately 0.1M hydrochloric acid and
standardisation 286
10.26 Preparation of standard alkali 289
10.27 Standardisation of approximately 0.1M sodium hydroxide 292
10.28 Other standard substances for acidimetry and alkalimetry 293
10.29 Standard barium hydroxide solution 294
10.30 Determination of the Na2C0, content of washing soda 295
10.31 Determination of the strength of concentrated acids 296
10.32 Determination of a mixture of carbonate and hydroxide
(analysis of commercial caustic soda) 297
10.33 Determination of a mixture of carbonate and
hydrogencarbonate 299
10.34 Determination of boric acid 299
10.35 Determination of ammonia in an ammonium salt 300
10.36 Determination of organic nitrogen (the Kjeldahl procedure) 302
10.37 Determination of nitrates 303
CONTENTS
10.38 Determination of phosphate (precipitation as quinoline
molybdophosphate) 304
10.39 Determination of the relative molecular mass of an organic
acid 305
10.40 Determination of hydroxyl groups in carbohydrates 306
10.41 Determination of a mixture of aniline and ethanolamine using
a non-aqueous titration 307
10.42 Determination of the saponification value of oils and fats 308
COMPLEXATION TlTRATlONS
10.43 Introduction 309
10.44 A simple complexation titration 309
10.45 Titration curves 310
10.46 Types of EDTA titrations 311
10.47 Titration of mixtures, selectivity, masking and demasking
agents 312
10.48 Meta1 ion indicators 314
10.49 Standard EDTA solutions 321
10.50 Some practical considerations 322
DETERMINATION OF INDIVIDUAL CATIONS
10.51 Determination of aluminium: back-titration 324
10.52 Determination of barium: direct titration 324
10.53 Determination of bismuth: direct titration 324
10.54 Determination of calcium: substitution titration 325
10.55 Determination of copper: direct titration 326
10.56 Determination of iron(II1): direct titration 326
10.57 Determination of nickel: direct titrations 327
10.58 Determination of silver: indirect method 327
10.59 Details for the determination of a selection of metal ions by
EDTA titration 328
ANALYSIS OF MIXTURES OF CATIONS
10.60 Determination of calcium and magnesium 328
10.61 Determination of calcium in the presence of magnesium using
EGTA as titrant 331
10.62 Determination of the total hardness (permanent and
temporary) of water 332
10.63 Determination of calcium in the presence of barium using
CDTA as titrant 333
10.64 Determination of calcium and lead in a mixture 333
10.65 Determination of magnesium, manganese and zinc in a
mixture: use of fluoride ion as a demasking agent 334
10.66 Determination of chromium(II1) and iron(II1) in a mixture:
an example of kinetic masking 335
10.67 Determination of manganese in presence of iron: analysis of
ferro-manganese 336
10.68 Determination of nickel in presence of iron: analysis of nickel
steel 336