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CHAPTER V SYSTEMATIC QUALITATIVE INORGANIC ANALYSIS 395 Vv. Introduction 395 V2 Preliminary tests on non-metallic solid samples 395 V.3 Preliminary tests on metal samples 405 V.4 Preliminary tests on liquid samples (samples in solution) 406 VS Preliminary tests on insoluble substances 407 V6 Dissolution of the sample 4i1 V7 Examination of the insoluble residue 4ll V8 Separation of cations into groups 413 v9 Separation and identification of the Group I cations (silver group) 420 V.10 Separation of Group Il cations into Groups ITA and IIB 421 V.I1 Separation and identification of Group IIA cations 424 V.12__ Separation and identification of Group IIB cations 428 V.13 Removal of interfering ions before the precipitation of the Group III cations 431 V.14 — Separation and identification of Group IIIA cations 436 V.15 Separation and identification of Group IIIB cations 437 V.16 Separation and identification of Group IV cations 441 V.17 Identification of Group V cations 444 V.18 Preliminary tests for and separation of certain anions 446 v.19 Confirmatory tests for anions 458 CHAPTER VI SEMIMICRO QUALITATIVE INORGANIC ANALYSIS 461 VII Introduction 461 VI2 The study of reactions of cations and anions on the semimicro scale 461 VL3 Systematic analysis on the semimicro scale. General considerations 463 VI.4 Preliminary tests on the semimicro scale 464 VL5 Testing for anions in solution on the semimicro scale 470 VIL.6 — Confirmatory tests for anions on the semimicro scale 473 VIL7 Special tests for mixtures of anions on the semimicro scale 476 VL8 Preparation of solution for cation testing on the semimicro scale 479 VI.9 Separation of cations into groups on the semimicro scale 480 VI.10 Separation and identification of Group I cations on the semimicro scale 485 VI.11 Separation of Groups IJA and IIB and separation and identification of Group IIA cations on the semimicro scale 485, VI.12 Separation and identification of Group IIB cations on the semimicro scale 487VI.13 Separation and identification of Group IIIA cations on the semimicro scale 488 VI.14 Separation and identification of Group IIIB cations on the semimicro scale 489 VI.15 Separation and identification of Group IV cations on the semimicro scale 490 VI.16 Identification of Group V cations on the semimicro scale 492 VI.17 Modifications of separation procedures in the presence of interfering anions 493 VI.18 Separations by paper and thin layer chromatography. General introduction 495 VI.19 Apparatus and technique for chromatographic separations 497 VI.20 Procedures for selected chromatographic separations 500 CHAPTER VII REACTIONS OF SOME LESS GOMMON IONS 507 VIL Introduction 507 VIL.2 — Thallium, TI (4,: 204-34) — Thallium(1) 507 VII.3 Thallium, Tl (4,: 204-34) — Thallium(III) 509 VII.4 = Tungsten, W (4,: 183-85) — Tungstate 509 VII.5 Separation and identification of Group I cations in the presence of thallium and tungsten Sil VII.6 Molybdenum, Mo (4,: 95-94) — Molybdate Sil VII7 Gold, Au (A,: 196-97) — Gold(III) 514 VII.8 — Platinum, Pt (4,: 195-09) 516 VIL.9 — Palladium, Pd (4,: 106-4) 518 VII.10 Selenium, Se (4,: 78-96) — Selenites, SeCO}~ 520 VIL11 Selenium, Se (A,: 78-96) — Selenates, SeO3~ 521 VIL.12 Tellurium, Te (A,: 127-60) — Tellurites, TeO3~ $22 VII.13 Tellurium, Te (4,: 127-60) - Tellurates, TeO?- 523 VII.14 Separation and identification of Group II cations in the presence of molybdenum, gold, platinum, palladium, selenium, and tellurium 524 VIL.I5 Vanadium, V (4,: 50-94) — Vanadate 527 VII.16 Beryllium, Be (4,: 9:01) 530 VII.17 Titanium, Ti (4,: 47-90) — Titanium(IV) 532 VII.18 Zirconium, Zr (A,: 91:22) 535 VII.19 Uranium, U (4,: 238-03) 538 VII.20 Thorium, Th (4,: 232-04) 540 VIL.21 Cerium, Ce (4,: 140-12) - Cerium(III) 541 VIL22 Cerium, Ce (4,: 140-12) — Cerium(IV) 542 VII.23 Separation of Group III cations in the presence of titanium, zirconium, thorium, uranium, cerium, vanadium, thallium, and molybdenum 544 VII.24 Lithium, Li (4,: 6-94) 546 VII.25 The borax bead test in the presence of less common cations 548, xCHAPTER Vill AN ABBREVIATED COURSE OF QUALITATIVE INORGANIC ANALYSIS 550 VIIL1 Introduction 550 VIII.2_ Reactions of cations and anions 550 VIII.3 Systematic analysis. General considerations 551 VIII.4 Preliminary tests on solutions 552 VIII.S Testing for anions in solution 553 VIIL6 Confirmatory tests for anions 556 VIII.7 Special tests for mixtures of anions 557 VIIL.8 Separation and identification of cations in solution 560 VIII.9 Modifications in the presence of anions of organic acids, fluoride, and phosphate 564 IX APPENDIX 566 Ix. Relative atomic masses of the elements 566 1X.2 Reagent solutions and gases 568 1X.3 Solid reagents 589 IX.4 _ Solubilities of salts and bases in water at 18°C 592 IX.5 Logarithms 593 IX.6 — Antilogarithms 595 IX.7_ Concentrated acids and bases 597 IX.8 Periodic table of the elements 598 INDEX 599FROM PREFACE TO THE FIRST EDITION Experience of teaching qualitative analysis over a number of years to large numbers of students has provided the nucleus around which this book has been written. The ultimate object was to provide a text-book at moderate cost which can be employed by the student continuously throughout his study of the subject. It is the author’s opinion that the theoretical basis of qualitative analysis, often neglected or very sparsely dealt with in the smaller texts, merits equally detailed treatment with the purely practical side; only in this way can the true spirit of qualitative analysis be acquired. The book accordingly opens with a long Chapter entitled ‘The Theoretical Basis of Qualitative Analysis’, in which most of the theoretical principles which find application in the science are discussed. The writer would be glad to hear from teachers and others of any errors which may have escaped his notice: any suggestions whereby the book can be improved will be welcomed. A. 1. Vogel Woolwich Polytechnic London S.E.18 xiiiTHE THEORETICAL BASIS OF CHAPTER | QUALITATIVE ANALYSIS A. CHEMICAL FORMULAE AND EQUATIONS 1.1 SYMBOLS OF THE ELEMENTS To express the composition of substances and to describe the qualitative and quantitative changes, which occur during chemical reactions in a precise, short, and straightforward way we use chemical symbols and formulae. Following the recommendations of Berzelius (1811), the symbols of chemical elements are constructed by the first letter of their international (Latin) names with, in most cases, a second letter which occurs in the same name. The first letter is a capital one. Such symbols are: O (oxygen, oxygenium) H (hydrogen, hydrogenium), C (carbon, carbonium), Ca (calcium), Cd (cadmium), Cl (chlorine, chlorinum), Cr (chromium), Cu (copper, cuprum), N (nitrogen, nitrogenium), Na (sodium, natrium), K (potas- sium, kalium), etc. As well as being a qualitative reference to the element, the symbol is most useful in a quantitative context. It is generally accepted that the symbol of the element represents | atom of the element, or, in some more specific cases, | grammatom. Thus C represents | atom of the element carbon or may represent | grammatom (12-011 g) of carbon. In a similar way, O represents one atom of oxygen or one grammatom (15-9994 g) of oxygen, H represents one atom of hydrogen or | grammatom (1-0080 g) of hydrogen etc. Names, symbols, and relative atomic masses of the elements are given in Section IX.1. 1.2 EMPIRICAL FORMULAE To express the composition of materials whose molecules are made up of more atoms, empirical formulae are used. These are made up of the symbols of the elements of which the substance is formed. The number of atoms of a particular element in the molecule is written asa subscript after the symbol of the element (but | is never written asa subscript as the symbol of the element on its own represents one atom). Thus, the molecules of carbon dioxide is formed by one carbon atom and two oxygen atoms, therefore its empirical formula is CO. In the molecule of water two hydrogen atoms and one oxygen atom are present, therefore the empirical formula of water is HO. In the molecule of hydrogen peroxide on the other hand there are two hydrogen and two oxygen atoms present, its empirical formula is therefore H,0,. Although there are no strict rules as to the order of symbols appearing in a formula, in the case of inorganic substances the symbol of the metal or that of hydrogen is generally written first followed by non-metals and finishing with oxygen. In the formulae of organic substances the generally accepted order is C,H, O,N, S, P. 1