VOGEL'S TEXTBOOK OF MACRO AND SEMIMICRO QUALITATIVE INORGANIC ANALYSIS FIFTH EDITION Revised by _ G.SVEHLAVOGEL'S| TEXTBOOK OF MACRO AND SEMIMICRO QUALITATIVE INORGANIC ANALYSIS Fifth Edition Revised by G. Svehla, Ph.D., D.Sc., F.R.LC. Reader in Analytical Chemistry, Queen’s University, Belfast Elly mun ERY —_7y Longman London and New YorkLongman Group Limited London Associated companies, branches and representatives throughout the world Published in the United States of America by Longman Inc., New York © Longman Group Limited 1979 All rights reserved. No part of this 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 permission of the Copyright owner. First Published under the title ‘A Text-book of Qualitative Chemical Analysis’ 1937 Second Edition 1941 Reissue with Appendix 1943 Third Edition under the title ‘A Text-book of Qualitative Chemical Analysis including Semimicro Qualitative Analysis’ 1945 Fourth Edition under the title ‘A Text-book of Macro and Semimicro Qualitative Inorganic Analysis’ 1954 New Impression (with minor corrections) 1955 New Impression 1976 Fifth edition 1979 Library of Congress Cataloging in Publication Data Vogel, Arthur I. Vogel’s Macro and semimicro qualitative inorganic analysis. First-3d ed. published under title: A text-book of qualitative chemical analysis; 4th ed. published under title: A text-book of macro and semimicro qualitative inorganic analysis. Includes index. 1. Chemistry, Analytic-Qualitative. 2. Chemistry, Inorganic. I. Svehla, G. II. Title. III. Title: Macro and semimicro qualitative inorganic analysis. QD81.V6 1978 544 77-8290 ISBN 0-582-44367-9 Printed in Great Britain by Richard Clay (The Chaucer Press) Ltd, Bungay, Suffolk ivCONTENTS CHAPTER | THE THEORETICAL BASIS OF QUALITATIVE ANALYSIS A. Chemical formulae and equations Il 12 13 14 Ls Symbols of elements Empirical formulae Valency and oxidation number Structural formulae Chemical equations B. Aqueous solutions of inorganic substances 16 17 18 19 110 Ll 1.12 1.13 114 Electrolytes and non-electrolytes Electrolysis, the nature of electrolytic conductance, ions Some properties of aqueous solutions The theory of electrolytic dissociation Degree of dissociation. Strong and weak electrolytes The independent migration of ions. Calculation of conductivities from ionic mobilities Modern theory of strong electrolytes Chemical equilibrium; the law of mass action Activity and activity coefficients C. Classical theory of acid-base reactions 115 116 117 118 119 1.20 1.21 1.22 Acids, bases, and salts Acid-base dissociation equilibria. Strength of acids and bases Experimental determination of the dissociation equilibrium constant. Ostwald’s dilution law The dissociation and ionic product of water The hydrogen-ion exponent (pH) Hydrolysis Buffer solutions The experimental determination of pH D. The Brgnsted—Lowry theory of acids and bases 1.23 Definition of acids and bases v Soon an vaw—-— 17 19 22 25 28 33 35 39 53 611.24 Protolysis of acids. Strength of acids and bases 64 1.25 _ Interpretation of other acid-base reactions with the Brensted-Lowry theory 66 E. Precipitation reactions 67 1.26 Solubility of precipitates 67 127 Solubility product 68 1.28 Applications of the solubility product relation 75 1.29 Morphological structure and purity of precipitates 83 1.30 The colloidal state 85 F. Complexation reactions 89 1.31 The formation of complexes 89 1.32 The stability of complexes 92 1.33. The application of complexes in qualitative inorganic analysis 96 1.34 The most important types of complexes applied in qualitative analysis 97 G. Oxidation-reduction reactions 100 1.35 Oxidation and reduction 100 1.36 Redox systems (half-cells) 101 1.37 _ Balancing oxidation-reduction equations 104 1.38 Important oxidizing and reducing agents 108 1.39 Redox reactions in galvanic cells 112 1.40 _ Electrode potentials 1S 141 Oxidation-reduction potentials 119 1.42 Calculations based on the Nernst equation 124 1.43 Conclusionsdrawn from thetables of oxidation-reduction potentials 126 1.44 Equilibrium constant of oxidation-reduction reactions 128 H. Solvent extraction 130 1.45 The distribution or partition law 130 1.46 The application of solvent extraction in qualitative analysis 131 CHAPTER Il EXPERIMENTAL TECHNIQUES OF QUALITATIVE INORGANIC ANALYSIS 135 IL Introduction 135 IL.2 Dry reactions 136 113 Wet reactions 145 IL4 Semimicro apparatus and semimicro analytical operations 153 ILS Micro apparatus and microanalytical operations 173 IL6 Spot test analysis 180 CHAPTER Ill REACTIONS OF THE CATIONS 191 IIL1 Classification of cations (metal ions) into analytical groups 191 III.2___ Notes on the study of the reactions of ions 192 viHIL3 First group of cations: lead(1I), mercury(I) and silver(I) 193 IIL4 — Lead, Pb (A,: 207-2) 194 IILS Mercury, Hg (A,: 200°59) — Mercury(I) 199 IIL.6 Silver, Ag (4,: 107-9) 204 IIL.7 Second group of cations: mercury(II), lead(II), bismuth(II]), copper(II), cadmium(II), arsenic(III) and (V), antimony(III) and (V), tin(II) and (IV) 208 IIL8 Mercury, Hg (4,: 200-59) — Mereury(II) 209 IIL.9 Bismuth, Bi (4,: 208-98) 212 IIL.10 Copper, Cu (A,: 63°55) 215 IIL.11 Cadmium, Cd (4,: 112-90) 221 TIL.12 Arsenic, As (A,: 74-92) — Arsenic(III) 223 TIL13 Arsenic, As (A,: 74-92) — Arsenic(V) 225 II1.14 Special tests for small amounts of arsenic 228 111.15 Antimony, Sb (A,: 121-75) — Antimony(III) 231 IIL.16 Antimony, Sb (A,: 121-75) — Antimony(V) 234 II1.17 Special tests for small amounts of antimony 236 TIL18 Tin, Sn (4,: 118-69) — Tin(II) 237 HL19 Tin, Sn (4,: 118-69) — Tin(IV) 240 111.20 Third group of cations: iron(II) and (III), aluminium, chromium(III), nickel, cobalt, manganese(II) and zinc 241 I1.21 Iron, Fe (4,: 55°85) — Iron(II) 241 III.22 Iron, Fe (A,: 55°85) - Iron(III) 245 111.23 Aluminium, Al (4,: 26-98) 250 111.24 Chromium, Cr (4,: 51-996) — Chromium(III) 254 111.25 Oxianions of group III metals: chromate and permanganate 259 111.26 Cobalt, Co (4,: 58-93) 259 T1127 Nickel, Ni (4,: 58.71) 264 111.28 Manganese, Mn (4,: 54-938) —- Manganese(II) 268 111.29 Zine, Zn (A,: 63:58) 272 111.30 Fourth group of cations: barium, strontium, and calcium 2717 111.31 Barium, Ba (A,: 137-34) 278 111.32 Strontium, Sr (A,: 87°62) 281 111.33 Calcium, Ca (A,: 40-08) 282 111.34 Fifth group of cations: magnesium, sodium, potassium, and ammonium 285 II1.35 Magnesium, Mg (4,: 24-305) 285 111.36 Potassium, K (A,: 39-098) 289 II1.37 Sodium, Na (4,: 22:99) 291 I1.38 Ammonium, NH, (M,: 18-038) 293 CHAPTER IV REACTIONS OF THE ANIONS 297 Iv.1 Scheme of classification 297 IV.2_ Carbonates, CO3- 298 IV.3 Hydrogen carbonates, HCO; 300 viiIv.4 IV.5 IV.6 IV.7 IV.8 Iv.9 IV.10 IV.11 IV.12 IV.13 Iv.14 IV.15 IV.16 IV.17 IV.18 IV.19 IV.20 IV.21 IV.22 IV.23 TV.24 IV.25 IV.26 IV.27 IV.28 IV.29 IV.30 IV.31 IV.32 IV.33 IV.34 IV.35 1V.36 IV.37 IV.38 IV.39 IV.40 IV.41 IV.42 IV.43 IV.44 IV.45 Sulphites, SO3~ Thiosulphates, S,03~ Sulphides, S?~ Nitrites, NOz Cyanides, CN™ Cyanates, CNO- Thiocyanates, SCN~ Hexacyanoferrate(II) ions, [Fe(CN),]*~ Hexacyanoferrate(III) ions, [Fe(CN),]*~ Hypochlorites, OCI~ Chlorides, Cl~ Bromides, Br~ lodides, I~ Fluorides, F~ Nitrates, NOZ Chlorates, CIOS Bromates, BrOz lodates, 105 Perchlorates, ClOz Borates, BO3~, B,O?~, BO Sulphates, SO2~ Peroxodisulphates, $037 Silicates, Si03~ Hexafluorosilicates (silicofluorides), [SiF,]?~ Orthophosphates, PO2~ Pyrophosphates, P,03”, and metaphosphates, PO; Phosphites, HPO3~ Hypophosphites, H, POz Arsenites, AsO3~, and arsenates, AsO}7 Chromates, CrO3~, and dichromates, Cr,03~ Permanganates, MnOz Acetates, CH,COO7~ Formates, HCOO™ Oxalates, (COO)3~ Tartrates, C§H,02- Citrates, CsH;03- Salicylates, CsH4(OH)COO™ or C,H;03 Benzoates, CsH,COO~ or C,H,O7 Succinates, C,H,O3- Hydrogen peroxide, H,O2 Dithionites, $,03~ Special tests for mixtures of anions 301 305 308 310 313 316 317 319 322 323 325 327 329 332 334 337 339 340 342 343 346 349 350 353 354 358 358 360 361 361 364 366 368 369 371 374 376 377 378 379 382 383 viii