BENTLEY AND DRIVER’S QUALITATIVE CHEMICAL ANALYSIS REVISED BY J. E. DRIVER M.A(Cantab.), Ph.D., M.Sc.(Lond.), F.R.I.C, Emeritus Professor University of Hong Kong SEVENTH EDITION HONG KONG UNIVERSITY PRESS© Hong Kong University Press, 1970 Reprinted 1988 ISBN 962 209 212 8 Printed by Printing Unit, University of Hong KongPREFACE ‘Tuts small book has been published in different forms and developed gradually over many years with the co-operation and criticism of my colleagues and friends in various Universities and schools, It is designed primarily for those working for the G.C.E. and examinations of similar standard, and has been used by many thousands of them; but it has been much used also as a general outline or aide memoire by advanced students in Universities and technological institutions. The methods given follow standard practice, and, where a choice has had to be made between available methods, any prejudice I may have had has been kept in check by the freely expressed comments of other users. Some parts of the book (in particular Section V on special problems) are not needed by the beginner, while the more senior student will no doubt wish to supplement the outline here given of these more difficult operations by reference to larger works. Many improvements in recent editions are the result of suggestions by Professor J. Miller and other members of the Chemistry staff of the University of Hong Kong, and to them my best thanks are due. J.E.D. January, 1965CONTENTS Section I. General principles .. II. Reactions of cations IIL Reactions of anions IV. Systematic qualitative analysis V. Special problems .. .. .. Index ww wee Page 17 34I GENERAL PRINCIPLES ‘Tus immediate objective in qualitative inorganic analysis is usually to identify a single substance, or to detect the cations and anions (basic and acidic radicals) in a mixture. Behind this lies much more. A student who works through a course in qualitative analysis and thinks about what he is doing will become familiar at first hand with the properties and reactions of a great variety of individual compounds and ions; and many of the operations which he carries out provide practical illustrations of important chemical concepts, particularly those concerned with ionic equilibria, and including solubility products, oxidation-reduction reactions, and the formation and stability of complexes. Qualitative analysis has to be done as a routine, but it should be a routine intelligently followed. It need be no less instructive because the procedure, if it is to lead to a successful result, must be somewhat stereotyped. Full value from a course in qualitative analysis can be obtained only if a serious effort is made to understand the reactions involved, and for this reason a text-book on general chemistry should always be kept at hand for reference. ‘The earlier part (Sections II and III) of this book gives an explanatory account of the reactions used in qualitative analysis, It is sugg..ted that the student should work through these reactions with known substances before going on to the systematic examination of unknown substances (Section IV), and should follow the reasoning behind each step taken. Section V deals with the special problems created by interfering ions and insoluble substances, and is needed only at a more advanced stage. For exercises in analysis the substances given are usually salts, either in the solid state or in solution; but it must be remembered that inorganic substances include also free elements (metals and non-metals), metallic oxides and hydroxides, and free acids, all of which can be identified by the application of the ordinary methods, A metal or simple alloy given for analysis sometimes puzzles the student, but only because it is unexpected, Metals and alloys, whether in masses or in powder form, are usually recognizable as such by inspection, and thereafter it is only necessary to make a solution and test it for cations. Electropositive metals like magnesium, zinc, iron, aluminium, and tin dissolve in hydrochloric acid with evolution of hydrogen which can be made to burn at the mouth of the tube. Concentrated nitric acid is necessary for dissolving metals like lead, copper, and silver. When concentrated nitric acid is used in making a solution from an alloy containing tin, the tin remains undissolved as a white powder (‘metastannic acid’, a hydrated stannic oxide). Substances are commonly said to ‘dissolve’ or be ‘soluble’ in reagents such as acids or alkalis; this usually means that the substance is converted into a water-soluble product by the action of the reagent. Solubility products.—The concept of solubility products is of particular importance in the operations of qualitative analysis, so many of which depend on the precipitation of ions as very sparingly soluble (in looser terms, ‘insoluble’) 5QUALITATIVE CHEMICAL ANALYSIS compounds, Briefly, in a saturated solution of a sparingly soluble electrolyte, such as silver chloride, where silver and chloride ions are in equilibrium with undissolved solid: AgCl (solid) = Ag+ +Cl- the product of the ionic concentrations, [Ag+] [Cl], is constant at constant temperature, and is known as the ‘solubility product constant’ or simply asthe ‘solubility product’ of the compound. In this particular example each ionic concentration (ie, [Ag+] and [Cl-]) is 1-4%10-5 gm.-ions per litre, so that the solubility product of silver chloride is (1-4x 10-5) (1-4x 10-8), or 1-96 x 10~2°, Clearly, addition of either silver or chloride ions will diminish the solubility of the salt—that is to say, will cause precipitation of silver chloride— in order to maintain constancy of the ionic product in the solution. Illustrations of this common-ion effect on the precipitation of sparingly soluble electrolytes will be given later. The system of qualitative analysis.—The examination of a substance of unknown nature involves the following steps: Preliminary examination.—The appearance of the substance and its reaction to litmus, followed by certain preliminary tests (p. 23), may give an indication of the possible presence of many ions, and ‘may prove con- clusively the presence of some. Examination for cations.—For systematic examination, groups of cations are precipitated successively from solution by group reagents (table, p. 26). The individual cations are then identified by further examination of the group precipitates. Examination for anions.—Many anions will already have revealed their presence in the preliminary examination. As a final stage in the analysis, anions are tested for or confirmed by precipitation or other reactions (p. 29). Particularly instructive is the procedure for the separation of cations into groups. The main feature of this (see table, p. 26) is the precipitation of two groups of cations as sulphides, the first in acid and the second in alkaline solution. In a saturated solution at room temperature the two-stage dissociation of hydrogen sulphide: H,S = H++HS- HS- = H++8?- gives a sulphide-ion concentration, (S*-), of about 1x 10-18, Addition of dilute acid (that is, of hydrogen ions!) depresses these dissociations and greatly reduces the sulphide-ion concentration: this remains high enough, however, to precipitate the very sparingly soluble mercuric, lead, bismuth, copper, cadmium, arsenious, antimony, stannous, and stannic sulphides, with solubi- lity products ranging from 4 x 10—* (for PbS) to 3 x 10-® (for HgS). These sulphides are the precipitates of Group II. 1 More strictly, solvated hydrogen ians, H,O+. 6GENERAL PRINCIPLES Passage of hydrogen sulphide through a solution made alkaline with ammonia gives, by dissociation of ammonium hydrogen sulphide, NH,HS, a sulphide-ion concentration of the order of 1x10~®, This is high enough to precipitate manganese, zinc, cobalt, and nickel sulphides, with solubility products between 1-4x10-*5 and 2x 10-7. These sulphides are the pre- cipitates of Group IV. The Group I precipitates consist of the almost insoluble silver and mer- curous chlorides, and also lead chloride which, though readily soluble in hot water, is only slightly soluble in cold. All chlorides other than these are freely soluble in water. The small amount of lead remaining in solution is precipi- tated as sulphide in Group I. After removal of Group I and II cations, hydrogen sulphide is expelled from the solution, any ferrous ions present are oxidized to ferric by means of nitric acid, and ammonium chloride is added followed by enough ammonia to make the solution distiactly alkaline: NH,+H,0 = NH,OH = NH,+ +OH- This treatment precipitates aluminium, chromic, and ferric ions as hydroxides (Group III). The main function of the ammonium chloride is to provide a igh concentration of ammonium ions, NH,*+, and so to depress the above issociation to such an extent that the concentration of OH — ions is insufficient to precipitate cations of later groups. After removal of cations of the second sulphide group (Grou TV), am- monium carbonate precipitates the very sparingly soluble carbonates. of barium, strontium, and calcium (Group V). Magnesium is not precipitated in this group because magnesium carbonate forms soluble complexes with ammonium salts, The cations remaining in solution (magnesium, sodium, and potassium) constitute Group VI. Points of technique.—In all tests the best results are obtained by working with small quantities of substances and solutions. Large vessels like beakers and flasks are rarely required for qualitative analysis, and apparatus should be used for its proper purpose (test-tubes for testing; boiling-tubes for prolonged boiling; evaporating dishes for concentrating solutions or evaporat- ing them to dryness, and for expelling volatile products). Precipitation tests should always be done in hot solution unless there is some reason to the contrary, and likewise precipitates and undissolved residues should be washed with hot water before being further examined. Not only is hot water more effective as a solvent than cold, but hot liquids filter more quickly than cold ones. Where it is stated that a reagent is to be added in excess, the meaning is that the amount to be added must be a little more than is necessary to complete the reaction involved. Excess of the reagent is always necessary when ions 7QUALITATIVE CHEMICAL ANALYSIS are being separated from one another by precipitation; to confirm that enough reagent has been used, a little more should be added to the clear solution after the precipitate has been filtered off. Whenever a reagent is added to a solution, the liquids should be thoroughly mixed by shaking or inverting the test-tube unless there is some reason to the contrary. It is important to learn to recognize common yases and vapours, such as chlorine, bromine, hydrogen chloride, hydrogen sulphide, sulphur dioxide, nitrogen dioxide, and ammonia, by appearance or odour. Due care should be exercised when using concentrated acids, concentrated solutions of alkalis, and strong oxidizing agents. ‘Cest-tubes which are being heated should not be pointed in the direction of other people. Semi-micro methods.—With suitable techniques qualitative analysis can be done successfully with about one-tenth of the amount of material traditionally used. Generally speaking the methods and tests described in this book are suitable for use on the semi-micro scale, though it is sometimes convenient to modify or replace some of them. The main difference in techni- que lies in the apparatus used. Small test-tubes and short (but wide) boiling. tubes replace the usual sizes, reagents are adde«! from droppers instead of being poured out of bottles, and liquids in the smull test-tubes are heated in a water-bath, instead of over a flame, in order to prevent spurting. When using small quantities it is usually more convenient to separate precipitates by means of a centrifuge than by filtration, though simple and convenient apparatus for micro filtration is available (e.g., Barber tubes anil funnels), Bunsen burners, wash-bottles, hydrogen sulphide generators, spatulas, and other apparatus are used in small sizes or modified designs. Semi-micro methods of qualitative analysis are not necessarily either more or less reliable than macro methods: their main advantages are some saving in time and considerable saving in materials ‘I'he practice of semi-micro techniques is useful in developing skill in dealing with small quantities, and in inculcating habits of clean and careful working.II REACTIONS OF CATIONS Tuts Section deals with the reactions used in the separation and identification of cations, and the sequence follows that in which these reactions appear in the tables (pp. 26-29). The general principles governing the separation of the cations into groups have already been outlined (p. 6). For practice with known substances, solutions of suitable salts should be used. For the Group I cations solutions of the nitrates are appropriate, but for practice with cations of later groups the most suitable salts are soluble chlorides or sulphates, The procedure should be to follow the directions in the tables, and to refer to the explanation in the present Section before each step. Group I. Lead, silver, mercurous.—Dilute hydrochloric acid preci- Pitates the chlorides PbCl, (white), AgCl (white), and Hg,Cl, (white). Separation and identification of lead—Lead chloride differs from silver and mercurous chlorides in being readily soluble in boiling water. When the solution is cooled most of the salt is deposited in small, needle-shaped crystals, but enough remains in solution to give a slight, black precipitate of lead sulphide, PbS, with hydrogen sulphide. With solutions of lead salts potassium chromate gives a yellow precipitate of lead chromate, PbCrO,, which is insoluble in boiling water and in dilute acetic acid. The formation of the precipitate is prevented by a high con- centration of a strong acid (e.g. nitric). Separation and identification of silver and mercury.—Silver chloride dis- solves freely in dilute ammonia solution with formation (under ordinary conditions) of the complex ion Ag(NHs),+. On acidification of the ammoniacal solution the complex is decomposed, with reprecipitation of silver chloride. Mercurous chloride is turned black, but not dissolved, by ammonia solution; the black substance is a mixture of the white compound, NH,HgCl, with finely-divided mercury: Hg,Cl,+2NH, > NH,HgCl+-Hg+NH,Cl Group IIa. Mercuric, lead, bismuth, copper, cadmium.—In the presence of dilute hydrochloric acid, hydrogen sulphide precipitates the sulphides HgS (black), PbS (black), Bi,Sy (very dark brown), CuS (black), and C8 (yellow), The mercuric precipitate may at first appear white, yellow, or brown, and the lead precipitate yellow or red, because of the formation of complexes of the metallic chloride and sulphide. The solutions from which these sulphides are precipitated should not contain more than the equivalent of about 1 part of ordinary dilute acid to 8 parts of water. Too hig a con- centration of hydrochloric acid may depress the concentration of sulphide 9QUALITATIVE CHEMICAL ANALYSIS ions ey to prevent, completely or in part, the precipitation of lead and cadmium.: Separation and identification of mercury.—All the sulphides, with the excep- tion of HgS, are decomposed readily by boiling, diluted nitric acid (1 part of concentrated acid to 1 part of water), being thereby converted by oxidation into soluble nitrates and/or sulphates, Mercuric sulphide is oxidized by ‘aqua regia’ (1 part of concentrated nitric acid to 3 parts of concentrated hydrochloric acid) to soluble mercuric chloride, HgCl, (or more correctly the soluble HgCl,?~ ion). If the solution so obtained is diluted and treated with stannous chloride, the mercuric salt becomes reduced, giving first a white precipitate of mercurous chloride, Hg,Cl,, and, later, greyish globules of mercury: 2HgCl,+Sn?+ -> Hg,Clp+Sn*~ +2Cl- Hg,Cl,+Sn®+ — 2Hg+Sn*+ +2Cl- Separation of lead.—Dilute sulphuric acid precipitates lead from solution as the very sparingly soluble sulphate, PbSO,, If desired, precipitation can be made almost complete by adding to the solution an equal volume of alcohol, Separation and identification of bismuth—Ammonia, added to solutions of bismuth, copper, and cadmium salts, precipitates respectively the hydroxides* Bi(OH),, Cu(OH),, and Cd(OH),. The copper and cadmium precipitates dissolve in excess of ammonia to form solutions which contain the complex ions Cu(NH,)2+ (deep blue) and Cd(NH,),2+ (colourless). Bismuth hydroxide does not dissolve in ammonia, but dissolves in dilute hydrochloric acid with formation of the chloride, BiCl,; when the solution is poured into a lai quantity of water the chloride is hydrolysed to the insoluble oxychloride, BiOCI, which causes a white turbidity: BiCl,+H,O = BiOC]+2HCI Confirmation of copper—The formation of the deep blue ammoniacal solu- tion described above is evidence of the presence of copper, which may be confirmed by acidifying with acetic acid and adding potassium ferrocyanide, when a precipitate of a brown copper ferrocyanide is formed, Identification of cadmium.—In the absence of copper, the ammoniacal solu- tion containing the Cd(NH,)2+ ion may be treated directly with hydrogen sulphide; a yellow precipitate of CdS then shows the presence of cadmium, 1 In group analysis, when the cations of Groups IIA and Llp are being tested for (see Separation of cations into groups, p. 26), it is best to boil a small portion of the filtrate from Group I, pass hydrogen sulphide into it, dilute it considerably, and again pass hydrogen sulphide, If a precipitate is produced under these conditions it is necessary to treat the main portion of the solution in a similar way; but if there is no precipitate the main portion of the solution need not be treated with hydrogen sulphide at all, * The traditional formulae for these precipitates are used here for simplicity, although they may not all be strictly correct. 10REACTIONS OF CATIONS If copper is present, excess of potassium cyanide should be added. This converts both copper and cadmium into soluble, colourless, complex cyanides; of these, the copper complex is too stable to give a precipitate with hydrogen eulphide, but the less stable cadmium complex gives a yellow precipitate of dS. Group IIb. Arsenic, antimony, stannous, stannic.—In the presence of dilute hydrochloric acid, hydrogen sulphide precipitates the sulphides As,S, (yellow) Sb,S, (orange), SnS (dark brown), and Sn, (yellow). These sulphides, unlike the sulphides of Group IIa, dissolve readily (though in the case of stannous sulphide, rather slowly) in hot, yellow ammonium sulphide [a solution containing various polysulphides, (NH,),5,], with formation of the corresponding thioarsenate, (NH,)sAsS,, thioantimonate, (NH,),SbS,, and thiostannate, (NH,),SnS,. The reactions (except in the formation of thiostannate from Sn involve oxidation by the polysulphide, which is represented in the equations below as S,2- : ‘AsySy-+2S,?~ +S?~ > 2As8,3- Sb,85+28,?- +S*~ > 2Sb8,~ $nS+5,!- + SnS,2- SnS,+S?- + SnS,?~ On acidification of the solutions of the thio-salts, precipitates of the higher sulphides—As,S,, Sb,S,, and SnS,—are produced. Separation and identification of arsenic.—The higher sulphides of antimony and tin are decomposed, and converted into soluble chlorides, by hot, concen- trated hydrochloric acid ;* whereas this reagent has no effect on arsenicsulphide, which remains as a yellow residue. Arsenic sulphide (but not the sulphides of antimony and tin) is dissolved by hot ammonium carbonate solution, being converted into soluble thio- and oxy-salts. Arsenic can be confirmed by reducing the original substance with zinc and boiling sodium hydroxide solution to the gaseous hydride, AsH,; this is de- tected by holding a piece of filter paper moistened with silver nitrate in the evolved gas, when a black stain of metallic silver is formed (Fleitmann’s test). Fleitmann’s test serves to distinguish arsenic from antimony, since compounds of antimony are not reduced to SbH, in alkaline solution. Separation of antimony.—Hydrogen sulphide precipitates antimonious sul- phide, but not stannic sulphide, from solutions made strongly acid with oxalic acid. Identification of tin.—Iron in presence of hydrochloric acid reduces stannic compounds to stannous chloride, SnCl, (soluble), and antimonious compounds to metallic antimony (black precipitate). After the reaction the liquid is 1 See also under Arsenite and arsenate (pp. 21, 22). * Sb,S, is converted into antimony trichloride, SbCl,, with precipitation of eulphur. uQUALITATIVE CHEMICAL ANALYSIS filtered and the filtrate tested with mercuric chloride, which gives with stannous chloride a white or grey precipitate (sec under Group Ila). Whether tin in the original substance was present as stannous or stannic is evident from the colour of the Group II precipitate, provided that this was not masked by the colour of other Group II sulphides and that no nitric acid was used in preparing the original solution. Also, stannous ions may be tested for by means of mercuric chloride in a solution of the original substance in dilute hydrochloric acid. Group Ill. Aluminium, chromium, iron.—-Ammonia precipitates the hydroxides Al(OH), (white), Cr(OH), (green), and Fe(OH), (reddish-brown). ‘These hydroxides! are precipitated even in presence of excess of ammonium chloride (distinction from cations of Group IV, and from magnesium). Ferrous hydroxide, Fe(OH),, is not precipitated by ammonia in presence of the usual concentration of ammonium chloride (:ts solubility product being relatively high—about 1 x 10-* compared with 1 x 10— for ferric hydroxide) although, in contact with air, partial oxidation gives incomplete precipitation of a dark green hydroxide, Because of these facts, ferrous ions must be oxidized to the ferric state by means of nitric acid before the precipitation of cations of Group III. Manganese hydroxide should not be precipitated in this group (its solubility product being comparable with that of ferrous hydroxide), but it may be unless the concentrations of ammonium chloride and ammonia are carefully con- trolled. Separation and identification of aluminium.—Aluminium hydroxide, unlike chromic and ferric hydroxides, has strongly marked amphoteric properties, and dissolves freely in aqueous sodium hydroxide to form sodium meta- aluminate, NaAIO,, The aluminate is decomposed by excess of ammonium chloride, with precipitation of Al(OH),.? Many organic reagents give coloured complexes with aluminium, and the formation of these can be used as confirmatory tests. The following is one example. The precipitate of aluminium hydroxide obtained in the above separation is dissolved in a little dilute hydrochloric acid, and dilute ammonia is added drop by drop until a precipitate begins to form. A few drops of a solution of quinalizarin in very dilute sodium hydroxide is added, and the mixture, after being boiled and cooled, is acidified with acetic acid. A reddish- violet colour confirms the presence of aluminium. 1 See p. 10, footnote 2. * In the actual group separation the precipitate is suspended in sodium hydroxide solution, treated with hydrogen peroxide, and boiled. This treatment converts aluminium hydroxide into the soluble aluminate by the action of sodium hydroxide and at the same time oxidizes chromic hydroxide to the soluble chromate (see P, 13, ; first P paragraph). Thorough boiling is necessary in order to decompose the excess of Sodium peroxide can be used instead of hydrogen peroxide, but is less convenient. 12REACTIONS OF CATIONS Separation and identification of chromium and iron—Chromic hydroxide is oxidized by hydrogen peroxide and sodium hydroxide, being converted into soluble, yellow, sodium chromate, NagCrO,: 2Cr(OH),+40H~ +3H,0, > 2Cr0,?- +8H,0 The chromate can be recognized by the colour of the solution, and confirmed by production of the previously mentioned lead salt (p. 9). Ferric hydroxide is not oxidized by hydrogen peroxide and alkali, and remains as a reddish-brown residue. If iron is present, a solution of the original substance in dilute hydrochloric acid should be tested for ferrous and ferric ions, Ferrous ions give with potassium ferricyanide, and ferric ions with potassium ferrocyanide, deep blue precipitates. The blue substances are known respectively as ‘Turnbull’s blue’ and ‘Prussian blue’. The reactions are far from simple. Soluble thiocyanates give a deep red colour with ferric, but not with ferrous, ions. Ferrous salts become oxidized on exposure to air, and any salt, originally ferrous, is likely to give some reaction for ferric as well. Treatment of phosphates in analysis,—In group analysis the presence of the phosphate ion causes precipitation as phosphates of cations of Groups III, 'V, and V, and of magnesium, when the solution is made alkaline with ammonia. This necessitates a special method for the treatment of the Group III precipitate when a phosphate is present. A solution of the precipitate in hydrochloric acid of as low concentration as possible is prepared, and (after moderate dilution) excess of ammonium acetate is added. The ammonium acetate acts as a buffer, and so reduces the hydrogen-ion concentration of the solution to a point at which the phosphates of iron, chromium, and aluminium are precipitated, although the cations of subsequent groups remain in solution. Any precipitation at this stage, therefore, indicates the presence of iron, chromium, or aluminium, Ferric chloride solution is now added, drop by drop, in order to precipitate, as buff-coloured ferric phosphate, any phosphate ion remaining in solution. Completion of precipitation is shown by the Higuid becoming dull red, owing to formation of ferric acetate in solution. The slight excess of iron is then precipitated by boiling the solution, which causes hydrolysis of the ferric acetate with formation of an insoluble basic acetate, The liquid is filtered, treated with ammonium chloride and excess of ammonia, filtered again if necessary to remove any trace of residual iron precipitated as hydroxide, and examined for cations of Groups IV, V, and Vi. Phe precipitate of ferric phosphate and basic acetate is examined for aluminium and chromium, if necessary, by the ordinary Group III separa- tion. Iron must, of course, be tested for separately. 2 A solution of the precipitate in a amall quantity of dilute hydrochloric acid should be treated with ammonia until a precipitate just begins to form, and should then be cleared by addition of a few more drops of the dilute acid. 13QUALITATIVE CHEMICAL ANALYSIS In the above method it is necessary to test for cations of Groups IV, V, and VI in two separate solutions—the filtrate from the Group III precipitate, and the filtrate from the phosphate separation. An alternative process is as follows. The filtrate from Group II is freed from hydrogen sulphide and boiled with nitric acid, and a few drops of it are tested for phosphate. If this is found, and if ammonia added after ammonium chloride to the main bulk of the solution causes a precipitate, this precipitate is just redissolved by adding dilute hydrochloric acid drop by drop, and the phosphate is then separated from the whole solution by treatment with ammonium acetate and ferric chloride as previously described. Group IV. Manganese, zinc, cobalt, nickel.—Addition of ammonium chloride and ammonia, and passage of hydrogen sulphide through the alkaline solution, precipitates the sulphides MnS (yellowish-pink), ZnS (white), CoS (black), and NiS (black). Separation and identification of manganese and zinc—The sulphides of these metals are separated from nickel and cobalt by taking advantage of the fact that they are decomposed and converted into soluble chlorides by the action of cold, very dilute hydrochloric acid (1 part of ordinary dilute acid to about 5 parts of water). Manganese and zinc are then separated from one another by first boiling to expel hydrogen sulphide, and then adding to the remaining solution of the chlorides excess of sodium hydroxide. This precipi- tates manganese as the white hydroxide, Mn(OH),, which rapidly becomes brown on exposure to air owing to oxidation; on the other hand, zinc hydr- oxide, which is at first precipitated, is amphoteric, and reacts with the excess of sodium hydroxide to form soluble sodium zincate, Na,ZnO,, After removal of the manganese hydroxide by filtration, the zinc can be reprecipitated from the alkaline solution as sulphide, Manganese is confirmed by boiling a small quantity of the precipitated hydroxide with excess of lead dioxide and concentrated nitric acid, when the supernatant liquid, after dilution, is seen to be purple, owing to oxidation to the permanganate ion, MnO,~: 5PbO,+2Mn?+ +4H+ — 5Pb*+ +2MnO,- +2H,O Zinc is confirmed by dissolving the precipitated sulphide in a few drops of concentrated nitric acid, adding 2-3 drops of cobalt nitrate solution, soaking a piece of filter paper in the solution, and then burning the paper in a hot Bunsen flame: the presence of zinc is demonstrated by the ash being coloured green (‘Rinman’s green’), Identification of cobalt and nickel—The sulphides are converted into soluble chlorides by being heated with a small quantity of a mixture of concentrated hydrochloric acid (3 parts) and concentrated nitric acid (1 part). After evaporation to dryness, a little of the residue is tested in a borax bead. The deep blue of the cobalt bead is intense enough to enable cobalt to be detected, even in presence of large proportions of nickel. As an alternative 4REACTIONS OF CATIONS or additional test, part of the residue may be dissolved in the minimum quan- tity of water (on a watch glass) and treated with drop quantities of acetic acid and potassium nitrite solution to give the characteristic potassium cobaltinitrite Precipitate (p. 16). The rest of the residue is dissolved in water, and any residual hydrochloric acid is neutralized by addition of ammonia. The liquid is then acidified with acetic acid, and a few drops of the solution are treated with one drop of a solution of dimethylglyoxime: this precipitates a characteristic red complex if nickel is present. V. Barium, strontium, calcium.—Successive addition of am- monium chloride, ammonia, and ammonium carbonate precipitates the car- bonates BaCO,, StCO,, and CaCO,, all of which are white and readily soluble in dilute acetic acid. Separation of barium.—Barium is separated by addition of potassium chromate as its chromate, BaCrO,, which differs from the chromates of strontium and calcium in being insoluble in dilute acetic acid. Identification of strontium and calcium.—After separation of barium as chromate, the solution is divided into two parts. Strontium is tested for in one part by means of calcium sulphate solution, which precipitates the almost insoluble sulphate, SrSO,. Calcium sulphate is chosen as precipitant be- cause this salt is itself not very soluble, and the use of a more soluble sulphate in higher concentration might result in the precipitation of some calcium.? Alternatively, this part of the solution is made alkaline with ammonia and treated with alcohol to precipitate yellow strontium chromate, SrCrO,, which though soluble in dilute acetic acid is only slightly soluble in water and still less soluble in aqueous alcohol. From the other part of the solution any strontium present is precipitated by means of dilute sulphuric acid (whether some calcium is precipitated with the strontium is immaterial). After filtration the solution is made alkaline with ammonia, and calcium is tested for by adding ammonium oxalate, which precipitates the hydrated oxalate, (CO,),Ca,H,O. Group VI. Magnesium, sodium, potassium.—Part of the filtrate from Group V is tested for magnesium by means of sodium phosphate, which gives a white precipitate of magnesium ammonium phosphate, Mg(NH,)PO,,6H,0. In dilute solutions, precipitation may be somewhat slow. Another part of the filtrate may be used for confirmation of magnesium by adding 8-hydroxyquinoline reagent. This precipitates a yellow magnesium complex.* ‘The rest of the filtrate is evaporated to dryness and examined for sodium and potassium by the flame test (p. 24). 1 For the same reason, only a small precipitate of strontium sulphate can be d when calcium sulphate is used as precipitant. * Many cations of earlier groupe also form complexes with 8-hydroxyquinoline, but these will of course not be present at thie stage of the analysis. 15QUALITATIVE CHEMICAL ANALYSIS Sodium and potassium can be detected also by precipitation tests, The residue, after evaporation to dryness of the Group V filtrate, should be heated strongly to volatilize all ammonium compounds, dissolved in very little water, and examined in separate portions as follows (these tests should be done on watch glasses, with drop quantities only): (i) Add potassium antimonate solution, and scratch with a glass rod; sodium gives a white precipitate which quickly becomes microcrystalline and then has the com- position NagH,Sb,0,,6H,O (sodium pyroantimonate). (ii) Add zine uranyl acetate reagent; sodium gives a yellow precipitate of the composition [NaZn(UO,),|(CHyCO,),,9H,0. (iii) Add sodium hydrogen tartrate, and, if necessary, scratch with a glass rod; potassium gives a white precipitate of potassium hydrogen tartrate, KHC,H,O,. (iv) Add a drop of acetic acid and two drops of a solution of sodium cobaltinitrite, NagCo(NO,),; potas- sium gives a yellow precipitate of potassium cobaltinitrite, KsCo(NO,),. Ammonium.—The ammonium ion is detected by the evolution of ammonia when the original substance is heated with sodium hydroxide or sodium carbonate solution: NH,+-+OH- — NH,+4,0 itates with potassium 1 "This is important, since ammonium salts give altinitrite. antimonate, sodium hydrogen tartrate, and sodium cobs 16III REACTIONS OF ANIONS Tus section deals with tests used in systematic analysis for anions (Section TV), and also describes some additional confirmatory tests. For practice with known substances, sodium or potassium salts of the acid concerned are usually the most suitable. Carbonate.—Normal and basic carbonates, and also bicarbonates, evolve carbon dioxide when treated with dilute acids. The gas can be identified by passing it into calcium hydroxide solution (‘lime water’), which becomes turbid owing to formation of insoluble calcium carbonate, CaCO: Ca(OH), + CO, > CaCO, +H,0 With excess of carbon dioxide the turbidity disappears, as a result of conver- sion of the calcium carbonate into the soluble bicarbonate, Ca(HCO,),; but if the solution is boiled this is decomposed with reprecipitation of calcium carbonate: CaCO, +H,0+CO, = Ca(HCO,), A simple way to test for carbon dioxide evolved in small quantities in these and other chemical reactions is to hold a clean glass rod, moistened with lime water, in the gas; the turbidity caused by precipitation of calcium carbonate can then easily be seen. All carbonates with the exception of those of alkali metals and ammonium are insoluble in water. All bicarbonates are soluble, but only those of sodium, potassium, and ammonium are commonly met with. They are distinguished from the normal carbonates by the fact that, in cold aqueous solution, they give no precipitate on addition of magnesium sulphate, since magnesium bicarbon- ate is soluble; when the solution is boiled, however, the bicarbonate is decom- posed, and a precipitate is formed. Soluble normal carbonates give with magnesium sulphate in the cold a white precipitate of a basic carbonate; but many other ions give precipitates under these conditions, and the formation of a white precipitate on addition of magnesium sulphate to a cold aqueous solu- tion is therefore in itself no proof of the presence of carbonate. Nitrite.—Nitrites evolve nitric oxide (colourless gas, which becomes brown in air) on treatment with dilute acids, owing to decomposition of the liberated nitrous acid: 3HNO, +> HNO,+2NO+H,0 2NO+0,->2NO, When a nitrite is added to ferrous sulphate solution, and the solution is then acidified with dilute sulphuric acid, a deep brown colour is produced. In this reaction some of the ferrous sulphate reduces the nitrous acid to nitric oxide, NO, which then combines with more ferrous sulphate to form a dark 17QUALITATIVE CHEMICAL ANALYSIS brown, unstable, additive compound (or mixture of compounds, since the composition appears to be indefinite), Nitrates do not give this reaction under these conditions, Nitrites, in presence of dilute acid, oxidize potassium iodide with libera- tion of iodine, and reduce potassium permanganate. Neither of these reac- tions is specific, Nitrate.—When heated in thedry state sodium and potassium nitrates evolve oxygen, and ammonium nitrate is decomposed into nitrous oxide and water: 2KNO, + 2KNO,+0, NH,NO,-> N,0-+2H,0 All other nitrates evolve oxygen and brown fumes of nitrogen dioxide; for example: 2Pb(NO,), > 2PLO+4NO, +O, Warm, concentrated sulphuric acid liberates, from nitrates, fumes of nitric acid which have a brown tinge owing to partial decomposition, When a nitrate is warmed with concentrated sulphuric acid and metallic copper, brown fumes are evolved owing to reduction of nitric acid: Cu+2NO,~+4H+ -> Cut +2NO,+2H,O Nitrate can be confirmed by the brown-ring test, Aqueous solutions of the substance and of ferrous sulphate are mixed and cooled well in a test- tube, and concentrated sulphuric acid is poured carefully down the inside of the tube. A brown ring appears at the junction of the two liquids, caused by formation of a compound of ferrous sulphate and nitric oxide; this de- composes if the tube is shaken, and the ring then disappears. In systematic analysis the brown-ring test is best carried out in a solution from which precipitable cations have been removed (see p. 30). By being boiled with sodium hydroxide solution and Devarda’s alloy (Cu, Al, Zn), nitrates are reduced with evolution of ammonia, recognizable b: odour. If ammonium salts are present the substance must be boiled wit sodium hydroxide solution, until no smell of ammonia is perceptible, before, addition of the alloy. This test for nitrate is also given by nitrite, but it is not ees the presence of bromide or iodide as the brown-ring test is (see p. 31). Sulphide.—Many sulphides evolve hydrogen sulphide when treated with dilute sulphuric or hydrochloric acid, The gas is identified by smell and confirmed by holding in it a piece of filter paper moistened with a solution of a lead salt, when a black stain of lead sulphide, PbS, is formed. 18REACTIONS OF ANIONS: Sulphides which do not dissolve in dilute sulphuric or hydrochloric acid are decomposed by boiling dilute or concentrated nitric acid (‘aqua regia’ [p. 10] in the case of mercuric sulphide). The solution so obtained always contains some sulphuric acid formed by oxidation of the sulphide, and this can be detected, after dilution, by means of barium chloride. Polysulphides (such as Na,S,, and the compounds present in yellow ammo- nium sulphide, p. 11) evolve hydrogen sulphide when treated with dilute acids, and give, at the same time, a copious precipitate of sulphur. Sulphite.—Sulphites are decomposed by dilute sulphuric or hydrochloric acid with evolution of sulphur dioxide, owing to decomposition of the liberated sulphurous acid: H,S0, = H,0+80, The gas is recognized by smell, and confirmed by means of a piece of filter paper moistened with potassium dichromate solution, which is changed from orange to green by sulphur dioxide owing to reduction to chromic sulphate. A solution of a sulphite acidified with dilute hydrochloric acid gives no precipitate with barium chloride (provided that the sulphite is free from sulphate), since barium sulphite is soluble in dilute acids, By adding nitric acid and boiling, however, a white precipitate of barium sulphate is produced, owing to oxidation of the sulphite. Thiosulphate.—When a thiosulphate is warmed with dilute sulphuric or hydrochloric acid, the liberated thiosulphuric acid decomposes with formation of sulphur dioxide and a precipitate of sulphur: H,8,0, > SO,+S+H,O Sulphate.—Sulphates in solution give with barium chloride a white pre- cipitate of barium sulphate, BaSQ,, insoluble in dilute acids. ‘The white precipitate of lead sulphate, PbSO,, formed when a solution of a lead salt is added to a sulphate solution, is not soluble in dilute acids, but dissolves in sodium hydroxide solution with formation of sodium plumbite, Na,PbO,. Fluoride.—Fluorides, heated with concentrated sulphuric acid in a glass tube, evolve hydrogen fluoride, HF, a colourless, fuming gas. Some of the hydr fluoride attacks the glass with formation of gaseot icon tetra- fluoride, SiF,. This can be detected by holding a moist rod in the escaping gas, when a gelatinous deposit of silicic acid, H,SiO,, is produced on the rod: 3SiF,+4H,0 -> H,Si0,+2H,SiF, Barium chloride precipitates, from solutions of fluorides, white barium fluoride, BaF, which is insoluble in dilute acetic acid but soluble in stronger acids (e.g. hydrochloric), 19QUALITATIVE CHEMICAL ANALYSIS Chloride.—Chlorides evolve hydrogen chloride on being warmed with concentrated sulphuric acid. The gas fumes in moist air, and gives dense fumes of ammonium chloride when a glass rod moistened with ammonia solution is held in it. Chloride can be confirmed hy warming the substance with concentrated sulphuric acid and manganese dioxide, when chlorine is evolved (yellowish-green gas which bleaches moist litmus): MnO,+-4HCl-> MnCl,+Cl,+ 2H,0 Chlorides give with silver nitrate solution a white precipitate of silver chloride, AgCl, which is insoluble in nitric acid but readily soluble in am- monia solution (see p. 9). Bromide.—Bromides when warmed with concentrated sulphuric acid evolve hydrogen bromide (colourless, fuming srs) together with some bromine vapour (red) formed by oxidation of some of the hydrogen bromide: 2HBr +H,SO, + Brp+SO,+2H,0 The proportion of bromine vapour is much increased by adding manganese dioxide as an oxidizing agent. Bromides can also le oxidized to bromine by the action of boiling, dilute nitric acid, Chlorine water liberates bromine from bromides. The bromine can be extracted by shaking the solution with carbon tetrachloride or carbon di- sulphide, in which bromine forms orange solutions, With silver nitrate solution bromides give a pale yellow precipitate of silver bromide, AgBr, which is insoluble in nitric acid and not so soluble as silver chloride in ammonia solution. Todide.—When an iodide is warmed with concentrated sulphuric acid the hydrogen iodide first produced is largely oxidized by the sulphuric acid to iodine, which is evolved in the form of violet vapour; some of the sulphuric acid i reduced as far a8 hydrogen sulphide, which'can usually be detected ry smell. Todides are readily oxidized, even by nitrous acid. If an iodide is heated with sodium nitrite and dilute sulphuric acid, the violet vapour of iodine is evolved. Chlorine water liberates iodine from iodides, ‘The iodine can be extracted by shaking the solution with carbon tetrachloride or carbon disulphide, in which iodine forms violet solutions. With silver nitrate solution iodides give a yellow precipitate of silver iodide, Agl, insoluble in nitric acid and only sparingly soluble in ammonia solution. Hypochlorite.—Sodium hypochlorite is well known in solution, but calcium hypochlorite is the only common solid hypochlorite. ‘Bleaching powder’ is an industrial product which gives hypochlorite reactions. 20REACTIONS OF ANIONS Hypochlorites evolve chlorine when treated with dilute sulphuric or hydrochloric acid, and the resulting solution bleaches litmus. Chiorate.—Concentrated sulphuric acid decomposes chlorates with libera- tion of chlorine dioxide, C1O,, a yellow gas which gives an orange-yellow colour to the acid and crackles explosively when warmed: 3C10,~ +2H+ + ClO,- +2C10,+-H,0 This test should be done cautiously and with small quantities, because of the risk of violent explosion. In the analysis of an unknown substance, the formation of an orange-yellow colour when cold concentrated sulphuric acid is added serves as a warning of the likely presence of chlorate. Alll chlorates lose oxygen when strongly heated, leaving eventually a residue of the chloride of the metal. This can then be dissolved in dilute nitric acid and tested with silver nitrate. Borate.—Borates give with barium chloride in neutral solution a white precipitate of barium metaborate, Ba(BO,),. The precipitate dissolves in ammonium chloride solution, and'in dilute acids, The most satisfactory test for a borate consists in mixing the substance with a little concentrated sulphuric acid and an equal volume of ethyl alcohol, C,H,OH, in a dry porcelain dish, and applying a light to the mixture; volatile ethyl orthoborate, (CyH,),BO,, is formed, and gives a green tinge to the flame. Phosphate.—Silver nitrate, added to a neutral solution of an orthophos- phate, gives a yellow precipitate of silver orthophosphate, Ag,PO,, soluble both in ammonia solution and in dilute nitric acid (elses and pyrophosphates give white precipitates with silver nitrate, but are rarely met with in qualitative analysis). A solution of a phosphate, gently warmed with nitric acid and ammonium molybdate, gives a canary yellow precipitate of ammonium phosphomolybd- ate, (NH,)sPMo,,049. In this test it is important to use sufficient nitric acid and an excess of ammonium molybdate. The method of separating a phosphate in the qualitative examination for the cations has already been described (p. 13). Arsenite and arsenate.—From neutral solutions of arsenites and arsen- ates, silver nitrate precipitates respectively yellow silver arsenite, AggAsO,, and dark brown silver arsenate, AgsAsO,. Both precipitates dissolve in am- monia solution, and in dilute nitric acid. When a solution of an arsenate is boiled with nitric acid and ammonium molybdate, a yellow precipitate of ammonium arsenomolybdate is formed (compare with the corresponding test for phosphate). Hydrogen sulphide readily precipitates arsenious sulphide, As,S,, from solu- tions of arsenites acidified with hydrochloric acid. Preci eae en by hydrogen sulphide from solutions of arsenates is slow unless a fairly high concentration 21QUALITATIVE CHEMICAL ANALYSIS of hydrochloric acid is present; the precipitate then consists of arsenic sul- phide, As,S,, arsenious sulphide, As,Ss, and sulphur in varying proportions. Chromate and dichromate.—Chromates are yellow, and are converted by acids into orange dichromates; dichromates arc orange, and are converted by alkalis into yellow chromates: 2Cr0,2~ +2H+ -> Cr,0,2- +H, Cr,0,?- +20H- — 2CrO,*- +H,0 Solutions of chromates or dichromates acidified with acetic acid give with barium chloride a yellow precipitate of barium chromate, BaCrO,, with silver nitrate a brownish-red precipitate of silver chromute, AgsCrO,, and with lead acetate a yellow precipitate of lead chromate, PbCrO,. All these precipitates are decomposed by dilute acids. Chromates and dichromates are reduced by most common reducing agents in acid solution, with formation of green solutions containing chromic ions; for example: Cr,0,?~ +3H,S+8H+ + 2Cr*+ --38-4-7H,0 Before the examination for cations, chromates and dichromates should be reduced by being boiled with concentrated hydrochloric acid before the systematic examination for the cations, From the resulting green solution the chromium is precipitated in Group III in the ordinary way.! Permanganate.—Permanganates form purple solutions in water or dilute hydrochloric acid. In acid solution they are decolorized by most common reducing agents, owing to reduction of permanganic ions to manganous ions which in dilute solution are almost colourless; for example: 2Mn0,~ +5H,S+4 6H+ > 2Mn*+ +58+8H,O Permanganates should be reduced by being boiled with concentrated hydro- chloric acid before the systematic examination for the cations, after which the manganese will be precipitated as usual in Group IV.1 In qualitative analysis substances containing permanganate(easily recognized by colour when treated with water or dilute acid) should not be heated with concentrated sulphuric acid, because of risk of explosion of the liberated permanganic anhydride, Mn,O>. Silicate—See Section V (p. 31). 3 Hydrochloric acid is chosen for reducing chromates, dichromates, and perman- ganates because it yields no products which would interfere with the course of cationic analysis, Hydrogen sulphide, for example, would cause precipitation of sulphur and sulphides of any Group II cations, Sulphur dioxide would be oxidized to sulphate, which would precipitate Group V cations and lead. With concentrated hydrochloric acid the reactions are: Cr,0,%+6CI-+ 14H + > 2Cr*+ +3Cl,+-7H,0 2MnO,-+10CI--+16H+ —> 2Mnt+ 4.5Cl,+8H,0 and the chlorine is expelled by boiling. 22IV SYSTEMATIC QUALITATIVE ANALYSIS ‘Tue colour and general appearance of the substance should be noted, and also its reaction towards moistened litmus paper. The following colours are general: Copper salts . . . . Blueorgreen Cobaltsalts . . . . . . Pink Tron salts. . . . Greenor brown Chromates . . . . . Yellow Chromium salts. . . . Green Dichromates . . . . . Orange Manganese salts . . . . Palepink © Permanganates . . . Dark purple Nickel salts . 9.0... Green ‘The oxides and/or sulphides of the following metals are coloured: lead, mercury, silver, copper, bismuth, cadmium, arsenic, antimony, tin, iron, chrorhium, manganese, nickel, and cobalt. The following turn blue litmus red: free acids; acid salts derived from strong acids (e.g. sodium hydrogen sulphate); many salts of weak bases. The following turn red litmus blue: ammonia solution; soluble metallic hydroxides and oxides; many salts of weak acids (e.g. carbonates, borates). Preliminary Tests Heat to redness in a dry ignition tube.—A few substances (mostly oxides) undergo temporary changes in colour, Many hydrated salts undergo changes in colour due to loss of water of crystallization. Ammonium salts, and most compounds of mercury and arsenic, sublime. ‘The following gases or vapours may be evolved: Water vapour.—Salts containing water of crystallization, and certain hydroxides and basic salts. Oxygen (rekindles a glowing splint).—Some oxides, also nitrates, chlorates, and certain other salts containing oxygen. Nitrous oxide (rekindles a glowing splint)—Ammonium nitrate. Nitrogen dioxide (brown fumes).—All nitrates and nitrites, except those of the alkali metals and ammonium. Carbon dioxide (gives a precipitate with lime water).—Many carbonates and alll bicarbonates.? £ There i litle to be gained by testing for carbon dioxide during this ignition-tube test, since any carbonate or bicarbonate will evolve carbon dioxide freely when treated with dilute acid (p. 24). 23QUALITATIVE CHEMICAL ANALYSIS Sulphur dioxide (characteristic odour; turns potassium dichromate paper green).—Some sulphates and sulphites. ‘Sulphur vapour —Thiosulphates and polysulphides. Ammonia (characteristic odour; alkaline to litmus).—Some ammonium salts, Flame test.—This is most easily done by taking up a little of the substance on a clean platinum wire moistened with concentrated hydrochloric acid (to form volatile metallic chlorides), and then heating the wire in the side of a Bunsen flame. The flame test may be done at this stage of the analysis or reserved for use as a confirmatory test later. The flame colours are: Grey or bluish-grey Lead, arsenic, antimony, tin. Bluish-green » 2 4... Copper. Apple green =...) .. Barium, Brick-red 2. ew. Calcium, Crimson. . Strontium. Bright yellow (invisible throug cobalt-blue glass). . . Sodium. Lilac (crimson through cobalt-blue glass) . . . . Potassium. Borax-bead test.—Introduce a trace of the substance into a fused borax bead on a platinum wire, and reheat the bead in the outer (oxidizing) part of a Bunsen flame; in the inner (reducing) part of the flame some cations give different colours. ‘This test need only be applied if the original substance is coloured, and even then is best reserved as a confirmatory test for use after the cations have been identified in the group analysis. Bluish-green bead Copper. Bright green bead Chromium. Yellow bead Iron. Deep amethyst bead : . Manganese. Deep blue bead . «Ss S- Cobalt. Brown bead » + + + Nickel. Action of sodium carbonate solution-—Ammonia liberated, and evolved freely when the solution is warmed.—Ammonium salt. Action of dilute sulphuric acid.—The following gases or vapours may be evolved: Carbon dioxide.—Carbonate or bicarbonate. Hydrogen sulphide (characteristic odour; blackens lead acetate paper).— Sulphide. 4SYSTEMATIC QUALITATIVE ANALYSIS Hydrogen sulphide, with precipitation of sulphur.—Polysulphide. Sulphur dioxide.—Sulphite. Sulphur dioxide, with precipitation of sulphur.—Thiosulphate. Nitric oxide (colourless gas which turns brown in air).—Nitrite, Chlorine (yellowish-green gas; characteristic odour; bleaches moist litmus paper).—Hypochlorite. Action of concentrated sulphuric acid.—This test should be done with small quantities, in a dry test-tube, and after addition of the acid to the substance the mixture should be very cautiously warmed.? The following gases or vapours may be evolved, in addition to those mentioned in the previous test: Hydrogen fluoride (colourless, fuming gas which attacks glass)—Fluoride. Hydrogen chloride (colourless, fuming gas).—Chloride. Confirm by adding manganese dioxide and warming, when chlorine will be evolved. Hydrogen bromide (colourless, fuming gas) and bromine vapour (brown).— Bromide? Iodine vapour (violet),—Iodide.? Nitric acid fumes.—Nitrate. Confirm by warming with metallic copper and concentrated sulphuric acid, when nitrogen dioxide will be evolved. Chlorine dioxide (explosive, yellow gas which crackles when the tube is warmed),—Chlorate, Examination for Cations Prepare a solution of the substance, trying the following solvents in turn: ‘Water. Dilute hydrochloric acid. Concentrated hydrochloric acid. Dilute nitric acid. Concentrated nitric acid. : A mixture of concentrated hydrochloric acid (3 parts) and concentrated nitric acid (1 part). A solvent should not be rejected as unsuitable unless a small quantity of the substance has been heated with it for some time, and has remained undissolved. The treatment of insoluble substances is discussed on p, 33, When concentrated acids are necded very little should be used, and the solution obtained should be suitably diluted before continuing with the analysis, Sulphuric acid is unsuitable as a solvent because it forms insoluble 1 See also the warnings given under chlorate (p. 21) and permanganate (p. 22). * Reduction products of the sulphuric acid (sulphur dioxide or hydrogen sulphide) are also evolved. 25QUALITATIVE CHEMICAL ANALYSIS or sparingly soluble sulphates with Group V cations, and with lead. Nitric acid oxidizes hydrogen sulphide (the Group II precipitant) with formation of colloidal or precipitated sulphur, and its use in preparing the solution for cation analysis should therefore be avoided if possible. If any nitric acid has been used it should be removed, before proceeding further, by evaporating the solution nearly to dryness, adding concentrated hydrochloric acid, evaporat- ing nearly to dryness again, and finally diluting with water. Examine the solution according to the following tables. SEPARATION OF CATIONS INTO GROUPS | Residue —] Fitrate—Ditte, warm, and pase hydrogen sulphide! silver, | Residue—Wash well, | Filtrate—Boil to expel hydrogen sulphide, Lanannnn heat (but do not boil) | add a few drops of concentrated nitric acid rous. | with yellow ammo- | (or more, if the solution darkens), and boil Examine | nium sulphide for a, again, Add ammonium chlorid by table | fewminutes,andfilter. | but distinct excess of ammonia, for Group Residue—| Filtrate.— | Residue— | Filtrate-—Pass hydrogen sulphide; Mercuric, | May con- | Alumin- filter. lead” | tain ium, bismuth, | Arsenic, | chromium,| Residue-— ‘copper, antimony, | iron, or an| Mangan- | nium carbonate, boil, cadmium. | un. insoluble | ese, tnd filter, Examine | Examine | Phos- | by table | by table | phate. cobalt, idue-— | Filtrate. for Group | for Group | Examine i Rene: Mae coal Ta 0 by table | Examine | strontium, | tain: for Group | by table | calcium. '| Magne- mi for Group | Examine | sium, Vv by table | sodium, for Group | Potassium, v Examine by table for Group VI 1 See footnote, p. 10. 2 When lead is present a little is always precipitated in this group, a3 lead chloride is slightly soluble in cold water. + Manganese is sometimes precipitated in this group (see p. 12), and should always be tested for in a small quantity of the precipitate by lead dioxide oxidation (p. 14) unless the precipitate is white. 26SYSTEMATIC QUALITATIVE ANALYSIS SEPARATION OF CATIONS OF GROUP I Wash the precipitate with cold water. Boil with water, and filter hot. Residue—Wash with boiling water, and | Filtrate—Small, needle-like crystals de- pour warm, dilute ammonia solution | posited on cooling.—Lead. |_over the filter. Confirm by heating to boiling again and Residue— | Filtrate—Acidify with | ,*4ding potassium chromate, Black: ic acid, White pre- | Y¢llow precipitate: Mercurous Le Silver SEPARATION OF CATIONS OF GROUP Ila Wash the precipitate, boil with nitric acid (I part cone. acid to 1 part water, and Iter, Residue.—Black. —Meercuric. Confirm by dis- solving in a mix- ture of concen- Filtrate—Add dilute eulphuric acid and, preferably, alcohol, allow to stand for a few minutes, and filter, Residue— | Filirate-—Add excess of ammonia, warm, and filter. White: Filtrate—If blue, copper is pre- trted hydro | Lead sent, Divide into two parts. acids, diluting " in die | PartI.—Acidify | Part II.—Ifcop- well and adding et heats with acetic acid | per is present, stannous chlor- fe hy and add potas- potassium ide. White or lorie acid, and | sium ferrocy-| cyanide until grey precipi- err iead staer anide. the blue colour tate: Nater, White | Brown preci- | disappears.Pass Mercuric turbidity: pitate or color- oesee'y = he Bismuth ticdpner precipitate: Ee Cadmium SEPARATION OF CATIONS OF GROUP IIe ‘Acidify the solution with dilute hydrochloric acid. A yellow or orange precipitate (other than sulphur, which is very pale yellow) shows the presence of arsenic, antimony, or tin. Boil the precipitate with concentrated hydrochloric acid, and filter. Residue—Yellow, | Filtrate.- ‘Divide into two parts. ee “Part T-—Make lightly elka- | Part 12-—Dilute somewhat, carbonate solu- | line with ammonia, add about add iron wire, and heat for a fon: Igor of solid oxalic acid, and | few minutes, Filter, and add pene Boll Pa hydrogen sulphide, | mercuric chloride tothe fit .. | Orange precipitate: rate. White or grey precipi- foe Antimony tate: 11),performed on Tin the original tube For distinction between stan- stance. nous and stannic, see p. 11.QUALITATIVE CHEMICAL ANALYSIS SEPARATION OF CATIONS OF GROUP III A small portion of the washed precipitate should be tested for phosphate by dissolv- ing it in dilute nitric acid, adding excess of ammonium molybdate solution, and warming. A canary-yellow precipitate shows the presence of phosphate. If phos- phate is present, examine the main portion of the precipitate by the next table, If phosphate is absent, suspend the main portion of the precipitate in sodium hydr- oxide solution, add hydrogen peroxide solution, boil well, and filter. Residue,—Brown.—Iron. _Dis- | Filtrate.—Ifyellow chromium is present, Divide solve in dilute hydrochloric | mto two parts. acid, and add potassium ferro- }——————--—-- —~ cyanide. Prussian blue preci- | Part J.—Acidify with tate: acetic acid, and add ae Iron lead acetate. Yellow Test iginal Ibstance fe precipitate: cipitate: ‘est original substance for ; ferrous and ferric (p. 13). Chromium Aluminium Confirm as on p. 13. TREATMENT OF GROUP III PRECIPITATE WHEN PHOSPHATE IS PRESENT* ; Test a small portion of the precipitate for iron by dissolving it in dilute hydrochloric acid and adding potassium ferrocyanide. A Prussian blue precipitate shows pre- sence of iron. Dissolve the remainder of the precipstate in the least possible quan- tity of dilute’ hydrochloric acid, dilute somewhat, and add excess of ammonium acetate, followed by ferric chloride solution, drop by drop, until the liquid is dull red, Boil well, and filter, Residue —Consists of basic ferric acetate | Filtrate—Add ammonium chloride and and ferric phosphate, with, possibly, | excess of ammonia, filter if necessary, aluminium and chromium, Examine | and examine the filtrate for cations of for aluminium and chromium by the | Groups IV, V, and VI. * previous table. | SEPARATION OF CATIONS OF GROUP IV Wash the precipitate, shake well with cold, very dilute hydrochloric acid, and filter. Residue —Dissolve in the least possible | Filtrate—-Ioil to expel hydrogen sul- quantity of concentrated hydrochloric | phide. Cool, add excess of sodium acid G Part) tnd concentrated nitric | hydroxide, and filter. acid (1 part). Evaporate the solution yust_ | ~~ todryness, Testa little of the residue by | Residve.—White, rapidly Filtrate— the nitrite reaction (p. 15) or ina borax | turning brown. ng- | Pass hydro- bead. Yellow precipitate or blue bead: | nese. Boil with excess | gen sulphide. ‘Cobalt of lead dioxide and ite or Dissolve the rest ofthe residue in a utle | Sfineenttated mitricacid, | disty | white water, add ammonia until the liquid is | Settle,’ Pur pl no longer acid, acidify with acetic acid, tent liquide tbe asta Zinc and add, to a fe few drops of the solution, ; one drop of dimethylglyoxime solution, Manganese pret Usieeet Red precipitate: green’ test (p. Nickel | 14). 1 See also the modification of this method of dealing with a phosphate (p. 13). 28SYSTEMATIC QUALITATIVE ANALYSIS SEPARATION OF CATIONS OF GROUP V solution with potassium chromate. If a ‘Wash the precipitate, dissolve it in dilute acetic a |, and test a small portion of the | precipitate is formed, add potassium. chromate to the main portion of the solution, and filter. Reridue— | Filtrate—Divide into evo parts llow: = Barium | Part I—Add calcium sul- | Part If—Add dilute eulphuric acid, phate solution, boil, and | warm, and allow to stand.! Filter, allow to. stand, Small | make the filtrate alkaline with am- white precipitate: monia, and add ammonium oxalate. Strontium White’ precipitate: Alternatively, precipitate Calcium strontium as chromate as described on p. 15, SEPARATION OF CATIONS OF GROUP VI ‘Use separate parts of the solution for each of the following tests. Part I.—Add sodium phosphate, and | Part IIf—Evaporate to dryness, and shake well. White precipitate: apply the flame test to the residue. Magnesium Bright yellow flame, invisible through Part II.—Use for confirmation ofmagne- | cobalt-blue glass: sium (p, 15), particularly if the sodium Sodium phosphste test has given a doubtful | Lilac flame, crimson through cobalt- result. blue glass: Potassium If necessary confirm these ions by the precipitation tests given on p. 15. Examination for Anions Many of the commoner anions are detected in the preliminary tests (p. 23), and confirmatory tests from Section III (pp. 17-22) can be applied where necessary, Chromate, dichromate, and permanganate are indicated by colour, and confirmed by reduction by hydrochloric acid and subsequent identification of chromic or manganous ions in the examination for cations (see p. 22). Arsenite and arsenate result in precipitation of sulphides of arsenic in Group II. Phosphate is tested for in the course of the examination for cations. Borate may be overlooked unless it is tested for separately by the sulphuric acid and alcohol test. 1 This is unnecessary if strontium is absent. * The cobaltinitrite test for potassium is conveniently done with the sodium carbonate solution prepared for anion analysis (p. 30). A small quantity of the solution should be boiled well to expel any ammonia, made just acid with acetic acid, and tested with sodium cobaltinitrite. 29QUALITATIVE CHEMICAL ANALYSIS Many anions are detected or confirmed by precipitation as their silver or barium salts. For this purpose, and for the brown-ring nitrate test, precipitable cations should first be removed. The procedure is as follows. Boil the original substance with sodium carbonate solution, and filter. Divide the filtrate into three parts and apply the following tests: PART I OF THE SOLUTION Acidify with dilute nitric acid, filter if necessary, add excess of silver nitrate, and filter cold. Residue.—May contain: Filtrate--Add dilute ammonia solution Chloride —White, readily soluble in | drop by drop, until a precipitate is ammonia, produced * Bromide.—Pale yellow, less soluble in | Yellow precipitate: Phosphate, ammonia, Arsenite. Iodide.—Yellow, very sparingly soluble | | Brown precipitate: Arsenate, an ammonia, Brownish-ted precipitate: Chromate. PART Il OF THE SOLUTION Acidify with dilute hydrochloric acid, add excess of barium chloride, boil, and filter. Residue— | Filtrate—Cool, and add ammonia solution drop by drop. The White: following may be precipitated:* Sulphate. Borate (white) _ Heer iink®) Soluble in dilute acetic acid. Arsenate (white Fluoride (white) Fees Cty} Insoluble in dilute acetic acid, PART II] OF THE SOLUTION Acidify with dilute sulphuric acid, heat to expel carbon dioxide, cool to room temperature, and apply the brown-ring test (p. 18) for nitrate. Alternatively, test the original substance for nitrate by Devarda’s alloy reduction (p. 18). ” If sulphide, sulphite, or thiosulphate have been found in preliminary tests, the solution should ‘be boiled after acidification in order to expel hydrogen sulphide or sulphur dioxide, and then filtered if necessary, and couled, before the silver nitrate is added. * A dark precipitate of silver oxide may be seen at an early stage, but this dissolves freely in a small excess of ammonia, * Precipitation of some of these may be prevented by too high a concentration of ammonium or barium ions. 30v SPECIAL PROBLEMS Tue following is an outline of some of the commoner problems that may be encountered in the analysis of more difficult substances. Interfering Ions Interference in tests for cations.—Phosphate, borate, and fluoride may cause cations of later groups to be precipitated in Group III, although in the case of borate the presence of a sufficient concentration of ammonium chloride will usually prevent this interference. The treatment of the Group III precipi- tate when a phosphate is present has already been described. Borate and fluoride can be eliminated before Group III by evaporating the filtrate from Group II to dryness, and then repeatedly evaporating the residue with concentrated hydrochloric acid. In this way boric acid (which is slowly volatile in steam) and hydrogen fluoride are expelled. The residue is finally extracted with dilute hydrochloric acid, and the filtered solution examined for cations of the later groups. Silicates pose various problems in analysis, Solutions of silicates, if suffi- ciently concentrated, give a silica gel when treated with hydrochloric acid: if not, they give a gel when ammonium chloride is added before Group III. Evaporation with concentrated hydrochloric acid, as described above, converts silicate into insoluble silica, SiO,, and the hydrochloric acid extract of the residue is then suitable for the examination for cations. Silica can be confirmed in the insoluble residue by fusing it in a bead of microcosmic salt (sodium ammonium hydrogen phosphate), when the silica is seen in the fused bead as an opaque skeleton. Interference in tests for anions.—Many anions interfere with or mask the reactions of others. The following are common and important examples. Carbonate may be overlooked in the presence of sulphide or sulphite, but the carbon dioxide evolved by the action of dilute acid can be detected, even in presence of hydrogen sulphide or sulphur dioxide, by the lime-water test. If sulphite is present the test is modified, because of the low solubility of calcium sulphite, by mixing the substance with powdered potassium dichrom- ate before addition of dilute sulphuric acid. By this means sulphite becomes oxidized to sulphate, and any carbon dioxide evolved can be detected by lime water, The brown-ring test for nitrate is interfered with by nitrite (because nitrites give a brown colour with ferrous sulphate and dilute acid) and by iodide and less markedly by bromide (because of the colour of the liberated iodine or bromine). To identify nitrate in presence of nitrite, the substance should be boiled with ammonium chloride solution. In this way the nitrite is decomposed with evolution of nitrogen, and, after the solution has been cooled, the nitrate can be detected by the brown-ring test (or by reduction with Devarda’s alloy after expelling ammonia from the ammonium ions by 31QUALITATIVE CHEMICAL ANALYSIS boiling with sodium hydroxide; see p. 18). To identify nitrate by the brown- ring test in presence of iodide or bromide, the interfering halogen should first be expelled by boiling the substance in an evaporating dish with chlorine water; but iodide and bromide do not interfere with the Devarda’s alloy reduction test for nitrate, The anions in a mixture of soluble sulphate, sulphite, and thiosulphate can be established by adding excess of barium chloride to the neutral, aqueous solution, This precipitates barium sulphate and sulphite, which are removed by filtration, Warming the filtrate with dilute hydrochloric acid gives a turbidity of sulphur and evolution of sulphur dioxide from the thiosulphate. ‘The precipitate of barium salts, after being washed, is warmed with dilute hydrochloric acid to give an evolution of sulphur dioxide from the sulphite, leaving the sulphate as an insoluble residue. Arsenate does not interfere with the detection of phosphate if the ammonium molybdate test is done, as here recommended (p. 28), after removal of Group II cations. Arsenate and arsenite can be detected together in solution by addition of ammonium chloride, ammonia, and magnesium chloride. This precipitates magnesium ammonium arsenate, leaving arsenite in solution; the presence of arsenic in the precipitate and filtrate (established by the use of hydrogen sulphide) then proves the presence in the original solution of both ions, The reactions of bromide are masked by iodide, and those of chloride are masked by either bromide or iodide, ‘These ions can be detected in presence of one another by the following procedure which is based on reactions pre- viously described (p. 20), DETECTION OF CHLORIDE, BROMIDE, AND IODIDE WHEN PRESENT ‘TOGETHER Boil with aqueous sodium carbonate, and filter; make the filtrate acid with dilute sulphuric acid, add sodium nitrite, and boil. Evolution of violet vapours: Todide Boil until all sodine 1s expelled, adding more sodium nitrite if necessary. Cool, add |_ dilute nitric acid, and divide into two parts, Part 1.—Add chlorine water, and shake | Part I/.-—Boil to expel all bromine, the solution with carbon tetrachloride. adding more nitric necessary. Orange lower layer: Add silver nitrate. White precipitate: Bromide Chloride 1 Water must be added if necessary during the boiling, in order to prevent the concentration of acid in the solution from becoming too high. 32SPECIAL PROBLEMS Insoluble Substances If a substance is insoluble in all the solvents given on p. 25, it is probably one of the following: Lead, barium, or strontium sulphate. Lead chromate made by a fusion process. Silver chloride, bromide, or iodide. Stannic oxide or sulphide (made by ignition or fusion processes). Ignited aluminium, chromium, or ferric oxide. Calcium fluoride. Silica or an insoluble silicate. Sulphur or carbon. A clue to the identity of many of these is given by colour or appearance, and they can be identified chemically by special methods. A common way of dealing with an insoluble substance is to fuse it in a crucible with about five times its weight of sodium carbonate or fusion mixture (sodium and potassium carbonates), allow to cool, boil the residue with water, and filter. During the fusion there may be an almost quantitative interchange of ions in reactions such as: BaSQ,+Na,CO,—> BaCO,+Na,SO, The filtrate is examined for anions, and the residue, after having been washed with water, is dissolved in dilute hydrochloric acid and examined for cations. Alkali fusion partly or wholly converts stannic oxide, aluminium oxide, and silica into soluble stannate, aluminate, and silicate, which are then found among the soluble anions, Stannic sulphide is converted into soluble stannate and thiostannate. Lead chromate (‘chrome yellow’) dissolves in hot sodium hydroxide solution to form sodium chromate and sodium plumbite, NagPbO,. Acidification of the cold solution with hydrochloric acid precipitates the lead as chloride. Silver halides are reduced to metallic silver (which can afterwards be dissolved in nitric acid and identified) by being heated by means of a blowpipe on charcoal with fusion mixture, and are distinguished from one another by colour and differing solubility in ammonia, Chromic oxide is dark green, and ferric oxide dark reddish-brown. Chrom- ic oxide is converted into yellow, soluble chromate by oxidizing fusion (with fusion mixture containing potassium nitrate). Sulphur and carbon are characteristic in appearance; they are combustible and (if pure) leave no residue when strongly heated on a crucible lid or piece of platinum foil. The odour of sulphur dioxide from burning sulphur is characteristic, 1 The acid-insoluble part of a mixture should always be examined separately in order that the examination of the insoluble materi ifficult enough in itself, shall not be complicated by the unnecessary presence of soluble ions. 33INDEX Alloys 5 Ferric 12 Aluminium 12 Ferrous 12 Ammonium 16 Ferrous and ferric, distinction between 13 Ammonium sulphides 7, 11 Flame test 24 Anions, examination for 29 Fleitmann’s test 11 Anions, interfering 31 Fluoride 19 Anions, reactions of 17 Fusion mixture 33 Antimony 11 “Aqua regia’ 10 Groups, separation of cations into 6, 26 Arsenate 21 Arsenic 11 Arsenite 21 Hydrogen peroxide, use of 12, 13 Hydrogen sulphide, dissociation of 6 Barium 15 8-Hydroxyquinoline 15 Bicarbonate 17 Hypochlorite 20 Bismuth 9 ‘Bleaching powder’ 20 Insoluble substances 33 Borate 21 Interfering ions 31 Borax-bead test 24 Todide 20, 32 Bromide 20, 32 Iron 12 Brown-ring test 18, 31 Lead 9 Cadmium 9 Lead chromate 9, 33 Calcium 15 Lead dioxide oxidation 14 Carbon 33 ‘Lime water 17 Carbonate 17 Cations, exarnination for 25 Magnesium 15 Cations, reactions of 9 Manganese 14 Chlorate 21 Mercuric 9 Chloride 20, 32 Mercurous 9 Chlorine dioxide 21 Metals 5 Chromate 22 “Metastannic acid’ 5 ‘Chrome yellow’ 33 Microcosmic salt 31 Chromium 12 Cobalt 14 Nickel 14 Complexes 7, 9, 10, 12, 15 Nitrate 18 Copper 9 Nitrite 17 Devarda's alloy 18 Permangunate 22 Dichromate 22 Phosphate 21 Dimethylglyoxime 15 Phosphate separation 13, 14 Polysulphides 19 Ethyl orthoborate 21 Potassium 15, 16 34Potassium antimonate 16 Potassium cobaltinitrite 16 Preliminary teste 23 Prussian blue 13 Quinalizarin 12 Rinman’s green 14 Semi-micro methods 8 Silica 33 cates 31, 33 Silicon tetrafluoride 19 Silver 9 Sodium 15, 16 Sodium cobaltinitrite 16 Sodium hydrogen tartrate 16 Sodium peroxide, use of 12 INDEX Solubility products 5 Solution, preparation of 25 Stannic 11 Stannous 11 Stannous and stannic, distinction between 12 Strontium 15 Sulphate 19 Sulphide 18 Sulphite 19 Sulphur 33 Thio-salts 11 ‘Thiosulphate 19 Tin 11 Turnbull's blue 13 Zine 14 Zinc uranyl acetate 16 35