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1.2 QUALITATIVE INORGANIC ANALYSIS The determination of the empirical formula of a compound can be made experimentally, by determining the percentage amounts of elements present in the substance using the methods of quantitative chemical analysis. At the same time the relative molecular mass of the compound has to be measured as well. From these data the empirical formula can be determined by a simple calcu- lation. If, for some reason, it is impossible to determine the relative molecular mass the simplest (assumed) formula only can be calculated from the results of chemical analysis; the true formula might contain multiples of the atoms given in the assumed formula. If the empirical formula of a compound is known, we can draw several con- clusions about the physical and chemical characteristics of the substance. These are as follows: (a) From the empirical formula of a compound we can see which elements the compound contains, and how many atoms of each element form the molecule of the compound. Thus, hydrochloric acid (HCI) contains hydrogen and chlorine; in its molecule one hydrogen and one chlorine atom are present. Sulphuric acid (H,SO,) consists of hydrogen, sulphur, and oxygen; in its molecule two hydrogen, one sulphur, and four oxygen atoms are present etc. (b) From the empirical formula the relative molecular mass (molecular weight) can be determined simply by adding up the relative atomic masses (atomic weights) of the elements which constitute the compound. In this summation care must be taken that the relative atomic mass of a particular element is multiplied by the figure which shows the number of its atoms in the molecule. Thus, the relative molecular mass of hydrochloric acid (HCI) is calculated as follows: M, = 1:0080+ 35-453 = 36-4610 and that of sulphuric acid (H,SO,) is M, = 2x 1-:0080+ 32:06 +4 x 15:9994 = 98-0736 and so on. (c) Based on the empirical formula one can easily calculate the relative amounts of the elements present in the compound or the percentage composition of the substance. For such calculations the relative atomic masses of the elements in question must be used. Thus, in hydrochloric acid (HCl) the relative amounts of the hydrogen and chlorine are H:Cl = 1-0080:35:453 = 1-0000: 35-172 and (as the relative molecular mass of hydrochloric acid is 36-461) it contains 1-008 100 x 36-461 = 2:76 per cent H and 35-453 : 100 x 36461 = 97:24 per cent Cl Similarly, the relative amounts of the elements in sulphuric acid (H,SO,) are H:S:O0 = 2x 1-0080:32:06:4 x 15-9994 = 2:016:32:06:63:9976 1: 15-903: 31-745THEORETICAL BASIS 13 and knowing that the relative molecular mass of sulphuric acid is 98-0763, we can calculate its percentage composition which is 2-0160 100 x 98-0736 = 2:06 per cent H 32:06 100 x 98-0736 = 32:69 per cent S and 63-9976 100 x 98-0736 = 65-25 per cent O and so on. (d) Finally, if the formula is known — which of course means that the telative molecular mass is available — we can calculate the volume of a known amount of a gaseous substance at a given temperature and pressure. If p is the pressure in atmospheres, T is the absolute temperature in degrees kelvins, M, is the relative molecular mass of the substance in g mol7! units and m is the weight of the gas in grams, the volume of the gas (¥) is mRT = mR PM, where R is the gas constant, 0:0823 £ atm K~! mol~!. (The gas here is con- sidered to be a perfect gas.) 1.3 VALENCY AND OXIDATION NUMBER In the understanding of the composition of compounds and the structure of their molecules the concept of valency plays an important role. When looking at the empirical formulae of various substances the question arises: are there any rules as to the number of atoms which can form stable molecules? To understand this let us examine some simple compounds containing hydrogen. Such compounds are, for example, hydrogen chloride (HCI), hydrogen bromide (HBr), hydrogen iodide (HI), water (H,O), hydrogen sulphide (H,S), ammonia (H3N), phosphine (H3P), methane (H,C), and silane (H,Si). By comparing these formulae one can see that one atom of some of the elements (like Cl, Br, and I) will bind one atom of hydrogen to form a stable compound, while others combine with two (O,S), three (N, P) or even four (C, Si). This number, which represents one of the most important chemical characteristics of the element, is called the valency. Thus, we can say that chlorine, bromine, and iodide are monovalent, oxygen and sulphur bivalent, nitrogen and phosphorus tervalent, carbon and silicon tetravalent elements and so on. Hydrogen itself is a monovalent element. From this it seems obvious that the valency of an element can be ascertained from the composition of its compound with hydrogen. Some of the elements, for example some of the metals, do not combine with hydrogen at all. The valency of such elements can therefore be determined only in an indirect way, by examining the composition of their compounds formed with chlorine or oxygen and finding out the number of hydrogen atoms these elements replace. Thus, from the formulae of magnesium oxide (MgO) and magnesium chloride (MgCl,) we can conclude that magnesium is a bivalent metal, similarly from the composition of aluminium chloride (AICI;) or aluminium oxide (Al;03) it is obvious that aluminium is a tervalent metal etc.14 QUALITATIVE INORGANIC ANALYSIS In conclusion we can say that the valency of an element is a number which expresses how many atoms of hydrogen or other atoms equivalent to hydrogen can unite with one atom of the element in question.* If necessary the valency of the element is denoted by a roman numeral following the symbol like Cl(I), Br(I), N(III) or as a superscript, like Cl’, Br', N", etc, Some elements, like hydrogen, oxygen, or the alkali metals, seem always to have the same valency in all of their compounds. Other elements however show different valencies; thus, for example, chlorine can be mono-, tri-, penta- or heptavalent in its compounds. It is true that compounds of the same element with different valencies show different physical and chemical characteristics. A deeper study of the composition of compounds and of the course of chemical reactions reveals that the classical concept of valency, as defined above, is not quite adequate to explain certain phenomena. Thus, for example, chlorine is monovalent both in hydrochloric acid (HCI) and in hypochlorous acid (HCIO), but the marked differences in the chemical behaviour of these two acids indicate that the status of chlorine in these substances is completely different. From the theory of chemical bondingt we know that when forming hydrochloric acid, a chlorine atom takes up an electron, thus acquiring one negative charge. On the other hand, if hypochlorous acid is formed, the chlorine atom releases an electron, becoming thus a species with one positive charge. As we know, the uptake or release of electrons corresponds to reduction or oxidation (cf. Section 1.35), we can therefore say that though chlorine is monovalent in these acids, its oxidation status is different. It is useful to define the concept of oxidation number and to use it instead of valency. The oxidation number is a number identical with the valency but with a sign, expressing the nature of the charge of the species in question when formed from the neutral atom. Thus, the oxidation number of chlorine in hydrochloric acid is —1, while it is +1 in hypochlorous acid. Similarly we can say that the oxidation number of chlorine in chlorous acid (HCIO,) is + 3, in chloric acid (HCIO3) is + 5, and in perchloric acid (HCIO,) +7. The concept of oxidation number will be used extensively in the present text. 1.4 STRUCTURAL FORMULAE Using the concept of valency the com- position of compounds can be expressed with structural formulae. Each valency of an element can be regarded as an arm or hook, through which chemical bonds are formed. Each valency can be represented by a single line drawn outwards from the symbol of the element, like H— Ck O= N= C= The structural formulae of compounds can be expressed with lines drawn between the atoms ¢ like * Cf. Mellor’s Modern Inorganic Chemistry, newly revised and edited by G. D. Parkes, Longman 1967, p. 99 et f. + Cf. Mellor op. cit., p. 155 et f. } There are no restrictions about the direction of these lines (unless differentiation has to be made between stereochemical isomers). Nor is there any restriction on the distances of atoms. Structural formulae must therefore be regarded only as a step in the approximation of the true structure. A three dimensional representation with true directions and proportional distances can most adequately be made with molecular model kits. 4THEORETICAL BASIS 15 ° 4 HCl H—O-H c \ H : ° I N H—C_H “oN | H H H Structural formulae will be used in this text only when necessary, mainly when dealing with organic reagents. A more detailed discussion of structural formulae will not be given here; beginners should study appropriate textbooks.* Readers should be reminded that the simple hexagon O (O- O} represents the benzene ring. Benzene (C,Hg) can namely be described with the (simplified) ring formula in which double and single bonds are alternating (so-called conjugate bonds): H I ei All the aromatic compounds contain the benzene ring. 15 CHEMICAL EQUATIONS Qualitative and quantitative relationships involved in a chemical reaction can most precisely be expressed in the form of chemical equations. These equations contain the formulae of the reacting substances on the left-hand side and the formulae of the products on the right- hand side. When writing chemical equations the following considerations must be kept in mind: (a) Because of the fact that the formulae of the reacting species are on the left-hand side and those of the products are on the right, the sides generally cannot be interchanged (in this sense chemical equations are not equivalent to mathematical equations). In the cases of equilibrium reactionst when the reaction may proceed in both directions, the double arrow (@) sign should be used instead of the equal (=) or single arrow (—) sign. (6) The individual formulae, used in the chemical reactions, must be written correctly. (c) If more molecules (atoms or ions) of the same substance are involved in the reaction, an appropriate stoichiometric number has to be written in front of the formula. This number is a multiplication factor, which applies to all atoms in the formula. (Thus, for example 2Ca;(PO,), means that we have 6 calcium, 4 phosphorus, and 16 oxygen atoms in the equation.) * Cf. Mellor’s Modern Inorganic Chemisiry, newly revised and edited by G. D. Parkes, Longman 1967, p. 155. + Theoretically speaking, all reactions lead to an equilibrium. This equilibrium however may be shifted completely towards the formation of the products.1.6 QUALITATIVE INORGANIC ANALYSIS (d) A chemical equation must be written in such a way that it fulfils the law of conservation of mass, which is strictly valid for all chemical reactions. This means, that the equation should be balanced by applying proper stoichio- metric numbers in such a way that the numbers of different individual atoms are the same on both sides. (e) If charged species (ions or electrons) are involved in the reaction, these charges must be clearly indicated (like Fe?* or Fe* * *)and properly balanced; the sum of charges on the left-hand side must be equal to the sum of charges on the right-hand side. The electron, as a charged particle, will be denoted by e~ in this text. As an example let us express the equation of the reaction between calcium hydroxide and phosphoric acid. Knowing that the products of such a reaction are calcium phosphate and water, we can write the formulae of the substances into the yet incomplete equation: Ca(OH), +H3PO, > Ca;(PO,),+H,0 _—_ (incomplete) (note that the sides of the equation cannot be interchanged, because the reaction will not proceed in the inverse direction). Now we try to balance the equation by applying suitable stoichiometric numbers: 3Ca(OH), +2H;PO, = Ca3(PO,),+6H,O It is advisable to check the equation by counting the numbers of individual atoms on both sides. Doing so we can see that there are 3 calcium, 2 phosphorus, 12 hydrogen and 14 oxygen atoms on both sides. It is useful to denote the physical state of the reaction partners. For this purpose the letters s, l, and g are applied for solid, liquid, and gaseous substances respectively, while the notation aq is used for species dissolved in water. These letters are used in parenthesis after the formula, e.g. AgCl(s), H,O(1), CO.(g), while the aq follows the formula simply, without parenthesis e.g. H;PO,aq. The systematic use of these notations is important only in thermodynamics, that is when the energetics of the reactions are examined. In the present text we shall use them in some cases. The formation of a precipitate will be denoted by a | Sign (indicating that the precipitate settles to the bottom of the solution) while the liberation of gases will be denoted by a f sign. If not otherwise stated, equations will refer to reactions proceeding in dilute aqueous solutions. Following those considerations discussed in Section I.2., relative masses, mass balances, and volumes (of gaseous substances only) can be calculated on the basis of chemical equations. Such calculations are involved in all kinds of quantitative analyses based on chemical reactions. B. AQUEOUS SOLUTIONS OF INORGANIC SUBSTANCES 16 ELECTROLYTES AND NON-ELECTROLYTES Quantitative in- organic analysis is based mainly on the observation of chemical reactions carried out in aqueous solutions. Other solvents are rarely employed except for special tests or operations. It is therefore important to have a general knowledge of the characteristics of aqueous solutions of inorganic substances. 6THEORETICAL BASIS 17 A solution is the homogeneous product obtained when a substance (the solute) is dissolved in the solvent (water). Substances can be classified into two important groups according to their behaviour when an electric current is passed through their solution. In the first class there are those which conduct electric current; the solutions undergo chemical changes thereby. The second class is composed of materials which, when dissolved in water, do not conduct electricity and which remain unchanged. The former substances are termed electrolytes, and these include, with few exceptions, all inorganic sub- stances (like acids, bases, and salts); the latter are designated non-electrolytes, and are exemplified by such organic materials as cane sugar, mannose, glucose, glycerine, ethanol, and urea. It must be pointed out that a substance which behaves as an electrolyte in water, e.g. sodium chloride, may not yield a con- ducting solution in another solvent such as ether or hexane. In the molten state most electrolytes will conduct electricity. 1.7 ELECTROLYSIS, THE NATURE OF ELECTROLYTIC CONDUC- TANCE,IONS Chemically pure water practically does not conduct electricity, if however, as already stated, acids, bases, or salts are dissolved in it, the result- ant solution not only conducts the electric current, but undergoes chemical changes as well. The whole process is called electrolysis. Phenomena occurring during electrolysis can be studied in the electrolysis cell shown in Fig. I.1. The electrolyte solution is placed in a vessel, into which Source of current (battery) ih ‘Cathode Fig L1 two solid conductors (e.g. metals), the so called electrodes, are immersed. With the aid of a battery (or another d.c. source) a potential difference is applied between the two electrodes. The electrode with the negative charge in the electrolysis cell is called the cathode, while that with the positive charge is termed the anode.* * It must be emphasized that the terms cathode and anode correspond to the negative and positive electrodes respectively only in electrolysis cells. According to Faraday's nomenclature, cathode is the electrode where cations lose their charge, while anions do the same on the anode. Consequently, in a battery (like the Daniell-cell) the anode is the negative and the cathode is the positive electrode.L7 QUALITATIVE INORGANIC ANALYSIS The chemical change occurring during the course of electrolysis is observable on or in the vicinity of the electrodes. In many cases such a change is a simple decomposition. If for example a dilute solution of hydrochloric acid is elec- trolysed (between platinum electrodes), hydrogen gas is liberated on the cathode and chlorine on the anode; the concentration of hydrochloric acid in the solution decreases. It is easy to demonstrate that electrolysis is always accompanied by the transport of material in an electrolysis cell. If for example the blue solution of copper sulphate and the orange solution of potassium dichromate are mixed in equimolar concentrations, a brownish solution is obtained. This solution can be placed in a U-shaped electrolysis cell and topped up with a colourless layer of dilute sulphuric acid on each side (Fig. 1.2). If this solution is then electrolysed, the hitherto colourless solution next to the cathode slowly becomes blue, while dec. lh’ Pt H,80, Orange (Cr,0,?") Brown (CuSO, +K Cr)07) Fig. 12 the solution next to the anode becomes orange. As the blue colour is associated with copper and the orange with dichromate, it can be said that copper moves towards the cathode and dichromate towards the anode during the electrolysis. As such a movement can be achieved solely by electrolysis, it is obvious that those particles which move towards one of the electrodes must be charged and that this charge must be opposite to that of the electrode towards which they move. The migration of such particles is a result of the electrostatic attraction force, which is created when switching on the current. Thus the particles of hydrogen or copper, which move towards the cathode, must be positively charged, while those of chlorine or dichromate must be negatively charged. Faraday termed the charged particles in the electrolyte ions; the positively and negatively charged ions were called cations and anions respectively. It can be stated generally that solutions of electrolytes do not contain neutral molecules dispersed among the molecules of the solvent, as solutions of non-electrolytes do, but they are composed of ions. Cations and anions are present in equivalent amounts and are dispersed evenly in the solution among the molecules of the solvent; macroscopic portions of the solution therefore appear to be electro- statically neutral in all cases. 8