TEXTBOOK OF QUANTITATIVE CHEMICAL ANALYSIS FIFTH EDITION G.H. JEFFERY * J.BASSETT + J.MENDHAM ° R.C.DENNEYVOGEL’s TEXTBOOK OF QUANTITATIVE CHEMICAL ANALYSIS FIFTH EDITION Revised by the following members of The School of Chemistry, Thames Polytechnic, London GH Jeffery, BSc, PhD, C Chem, FRSC Former Principal Lecturer and Deputy Head of the School of Chemistry J Bassett, MSc, C Chem, FRSC Former Senior Lecturer in Inorganic Chemistry J Mendham, M Sc, C Chem, MRSC Principal Lecturer in Analytical Chemistry RC Denney, BSc, PhD, C Chem, FRSC, MBIM Principal Lecturer in Organic Chemistry Longman Scientific & Technical 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 States with John Wiley and Sons Inc, 605 Third Avenue, New York NY 10158 © 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 WCE 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 titie 4 Text-book of Quantitative Inorganic Analysis Including Elementary Instrumental 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 Isract Vogel's textbook of quantitative chemical analysis, - 5th ed, 1. Quantitative analysis L Title IL. Jeffery, G. H. 545 ISBN O-S82-44b93-? Library of Congress Cataloguing in Publication Data Vogel, Arthur Israel [Textbook of quantitative chemical analysis] Vogel’s textbook of quantitative chemical analysis. ~ Sth ed./ revised by... G. H. Jeffery ... [et al.] Pp. ocm. Rev. ed. of: Vogel’s textbook of quantitative inorganic analysis. 4th ed. 1978. Includes bibliographies and index. ISBN 0-470-21517-8 1. Chemistry, Analytic-Quantitative. 2. Chemistry, Inorganic, I. Jeffery, G. H. 1909- TL. Vogel, Arthur Israel. Vogel's textbook of quantitative inorganic analysis. IIL. Title QD101.2.V63 1989 545~dc20 89-12296 CIP Set in 10/11pt 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 13 Sampling 4 1.4 Types of analysis 5 1.5 Use of literature 6 16 Common techniques 7 1.7 Instrumental methods 8 18 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 24 Electrolytic dissociation 19 25 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 cell 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 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 vi 72 78 89 92CONTENTS 3.20 Metal 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 104 3.26 Reagents 104 3.27 Purification of substances 105 3.28 Preparation and storage of standard solutions 107 SOME BASIC TECHNIQUES 109 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 115 3.33 Filtration 115 3.34 Filter papers 115 3.35 Crucibles with permanent porous plates 117 3.36 Washing precipitates 118 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 125 CHAPTER 4 ERRORS AND STATISTICS 127 4.1 Limitations of analytical methods 127 42 Classification of errors 127 4.3 Accuracy 128 44 Precision 129 45 Minimisation of errors 131 4.6 Significant figures and computations 132 47 The use of calculators and microcomputers 133 48 Mean and standard deviation 134 49 Distribution of random errors 136 4.10 Reliability of results 137 411 Confidence interval 138 412 Comparison of results 139 413 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conTet CHAPTER 5 SAMPLING 5.1 5.2 53 5.4 55 5.6 5.7 58 The basis of sampling 150 Sampling procedure 150 Sampling statistics 151 Sampling and physical state 153 Crushing and grinding 155 Hazards in sampling 155 References for Part B 156 Selected bibliography for Part B 156 PART C SEPARATIVE TECHNIQUES CHAPTER G SOLVENT EXTRACTION 6.1 62 63 64 65 6.6 67 General discussion 161 Factors favouring solvent extraction 163 Quantitative treatment of solvent extraction equilibria 165 Synergistic extraction 167 Ton-association complexes 168 Extraction reagents 169 Some practical considerations 172 SOME APPLICATIONS 68 69 6.10 6.11 6.12 6.13 6.14 6.15 6.16 6.17 6.18 Determination of beryllium as the acetylacetone complex 175 Determination of boron using ferroin 175 Determination of copper as the diethyldithiocarbamate complex 177 Determination of copper as the ‘neo-cuproin’ complex 178 Determination of iron as the 8-hydroxyquinolate 178 Determination of lead by the dithizone method 179 Determination of molybdenum by the thiocyanate method 180 Determination of nickel as the dimethylglyoxime complex 181 Determination of silver by extraction as its ion-association complex with 1,10-phenanthroline and bromopyrogallol red 182 Determination of nickel by synergistic extraction 183 Extraction and determination of lead, cadmium, and copper using ammonium pyrollidine dithiocarbamate 184 CHAPTER 7 ION EXCHANGE TA 72 73 14 15 716 viii General discussion 186 Action of ion exchange resins 189 Ion exchange chromatography 194 Ton chromatography 197 Ion exchange in organic and aqueous—organic solvents 201 Chelating ion exchange resins 202 159 161 175