BENTLEY AND DRIVER'S

QUALITATIVE
CHEM I CAL 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 3988 ISBN 962 209 212 8
Printed by Printing Unit, University of Hong Kong
PREFACE

THIS 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]. Miller and other members of the Chemistry staff of the University of
Hong Kong, and to them my best thanks are due.
I. E. D.
January, 1965CONTENTS
Section Page
I. General principles . . . . . . . . . . . . . . 5 II. Reactions of cations . . . . . . . . . . . . 9
III. Reactions of anions . . . . . . . . . . . 17 IV. Systematic qualitative
analysis . . . . . . . . 23 V. Special problems . . . . . . . . . . . . . 31 Index .. .. .. .. .. . ..
.. .. 34
I
GENERAL PRINCIPLES
THE 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 cquilibria, 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 efiort 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)
5QUALITATIVE CHEMICAL ANALYSIS
compounds. Briey, 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 as the
solubility product of the compound. In this particular example each ionic
concentration (i.e., [Ag+] and [Cl]) is 1-4 >: l0*5 gm.-ions per litre, so that the
solubility product of silver chloride is (1-4-><10'5) (1-4-X10), or 196 X 10' 1.
Clearly, addition of either silver or chloride ions will diminish the solubility of
the saltthat 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'' + S2
gives a sulphide-ion concentration, (S2), of about l><10. 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 4x 10* (for PbS) to 3 X 10-54 (for HgS). These
sulphides are the precipitates of Group II.

More strictly, solvated hydrogen ions, H,O+. 6

GENERAL PRINCIPLES
Passage of hydrqgen sulphide through a solution made alkaline with ammonia
gives, by issociation of ammonium hydrogen sulphide, NH,HS, a sulphide-ion
concentration of the order of 1xl0*. This is high enough to precipitate
manganese, zinc, cobalt, and nickel sulphides, with solubility products between
I'4XI015 and 2x1027. 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 II.

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 distinctly alkaline:
NH,+I-1,0 NH,,OH ?) NH,+ +0H'

This treatment precipitates aluminium, chromic, and ferric ions as hydroxides

(Group III). The main function of the ammonium chloride is to provide a high
concentration of ammonium ions, NI-I,+, and so to depress the above
dissociation 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 (Group IV), 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
asks 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
7QUALITATIVE 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 isadded 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 gases 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 cone: ntrated acids, concentrated
solutions of alkalis, and strong oxidizing agents. T est-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 added from droppers instead of being poured out
of bottles, and liquids in the small test-tubes are heated in a water-bath,
instead of over a ame, 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 and 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 The practice of semi-micro
techniques is useful in developing skill in dealing with small quantities, and in
inculcating habits of clean and careful working.
8II
REACTIONS OF CATIONS
THIS 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 Hg2Cl2 (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, PbCrO4, 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(NH3)2+. 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, NH2HgCl, with finely-
divided mercury:
Hg,Cl,+2NH3 > NH.,,HgCl+Hg+NH4Cl

Group IIa. Mercuric, lead, bismuth, copper, cadmium.In the presence of dilute
hydrochloric acid, hydrogen sulphide precipitates the sulphides HgS (black),
PbS (black), Bi2S3 (very dark brown), CuS (black), and CdS (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 high a con- centration of
hydrochloric acid may depress the concentration of sulphide
9QUALITATIVE CHEMICAL ANALYSIS
ions sufficiently 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 thertby converted by
oxidation into soluble nitrates and/or sulphates. Mercurie 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 HgCl42 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, Hg2Cl2, and, later, greyish globules of
mercury: 2HgCl,+ Sn > Hg2Cl,+ S114 +2Cl" Hg,Cl2+Sn2+ > 2Hg+Sn+
+2Cl' Separation of lead.Dilute sulphuric acid precipitates lead from solution
as the very sparingly soluble sulphate, PbSO4. 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)3, Cu(0H)2, and Cd(OH)2. The copper and cadmium precipitates dissolve
in excess of ammonia to form solutions which contain the complex ions
Cu(NH3)42+ (deep blue) and Cd(NH3)42+ (colourless). Bismuth hydroxide I
does not dissolve in ammonia, but dissolves in dilute hydrochloric acid with
formation of the chloride, BiCl3; when the solution is poured into a large
quantity of water the chloride is hydrolysed to the insoluble oxychloride, BiOCl,
which causes a white turbidity: _ BiCl3+H2O ti BiOCl+2HCl 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, 7 when a
precipitate of a brown copper ferrocyanide is formed. 7 Identification of
cadmium.-In the absence of copper, the ammoniacal solu- tion containing the
Cd(NH3)4+ ion may be treated directly with hydrogen . sulphide; a yellow
precipitate of CdS then shows the presence of cadmium. In group analysis,
when the cations of Groups IIA and H3 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 or 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
sulphide, but the less stable cadmium complex gives a yellow precipitate of
CdS.

Group Ilb. Arsenic, antimony, stannous, stannic.In the presence of dilute

hydrochloric acid, hydrogen sulphide precipitates the sulphides As,S3 (yellow),1
Sb,S3 (orange), SnS (dark brown), and SnS, (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,,),S,,], with formation of the
corresponding thioarsenate, (NH,,)3AsS,, thioantimonate, (NH,,)3SbS4, and
thiostannate, (NH4).,,SnS,,. The reactions (except in the formation of
thiostannate from SnS2) involve oxidation by the polysulphide, which is
represented in the equations below as Sf:
As,Sa+2S,, +S2 -> 2AsS,3
Sb,S3+2S._3 +S2 > 2SbS,3
SnS+S,2 > SnS32"
SnS3+S2' > SnS,,2"
On acidification of the solutions of the thio-salts, precipitates of the higher
sulphidesAs,S5, Sb,,S5, and SnS,are produced.

Separation and identification of arsem'c.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 arsenic
sulphide, 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 (Fleitmanns test).
Fleitmanns test serves to distinguish arsenic from antimony, since compounds
of antimony are not reduced to SbH,, in alkaline solution.

Separation of antimony.I-Iydrogen 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

See also under Arsenite and arsenate (pp. 21, 22).

' Sb,S. is converted into antimony trichloride, SbCl., with precipitation of

sulphur.
11QUALITATIVE CHEMICAL ANALYSIS

filtered and the filtrate tested with mercuric chloride, which gives with
stannous chloride a white or grey precipitate (see under Group IIA).

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 III. Aluminium, chromium, iron.--Ammonia precipitates the hydroxides

Al(OI-1),, (white), Cr(OH)3 (green), and Fe(OH)a (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)2, is not precipitated by ammonia in presence of the usual
concentration of ammonium chloride (its solubility product being relatively high
about l x 10' 14 compared with 1 >:10'33 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, NaAlO,. The aluminate is decomposed by excess of ammonium

, chloride, with precipitation of Al(OH),,.2

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.

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 paragraph). Thorough boiling is necessary in
order to decompose the excess of peroxide.

Sodium peroxide can be used instead of hydrogen peroxide, but is less

convenient.
12REACTIONS 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, Na,CrO,,:
2Cr(OI-I),,+4OH +3H.,,O,, > 2CrOf +8H,O
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 Turnbulls 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, IV,
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 liquid 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. The 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.

1 A solution of the precipitate in a small quantity of dilute hydrochloric acid

should be treated with ammonia until a precipitate 'ust begins to form, and
should then be cleared by addition of a few more drops of the dilute acid.
13QUALITATIVE CHEMICAL ANALYSIS

In the above method it is necessary to test for cations of Groups IV, V, and VI in
two separate solutionsthe 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(OI-I)2, 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, Na2ZnO2. 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, MnO4:
5PbO._.+2Mn2"' +4H+ > 5Pb2+ +2l\InO, +2H,O

Zinc is confirmed by dissolving the precipitattd 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
ame: the presence of zinc is demonstrated by the ash being coloured green
(Rinmans green).

Identification of cobalt and m'ckel.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 head. The
deep blue of the cobalt head is intense enough to enable cobalt to be detected,
even in presence of large proportions of nickel. As an alternative
14REACTIONS 01- 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.

Group V. Barium, strontium, calcium.Successive addition of am- monium

chloride, ammonia, and ammonium carbonate precipitates the car- bonates
BaCO,,, SrCO,,, 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, SrCrO4, 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.
REAKSI-REAKSI KATION
Uji tambahan, bagian dari residu dapat larut dalam sejumlah minimum air (di atas gelas
arloji) dan ditetesi sejumlah asam asetat dan larutan kalium nitrit menghasilkan endapan kalium
cobaltnitrit.
Sisa lainnya dari residu larut dalam air dan sisa asam klorida dinetralisasi dengan
penambahan amonia. Kemudian cairan diasamkan dengan asam asetat dan beberapa tetes larutan
yang telah ditetesi setetes larutan dimetilglioksim menghasilkan endapan merah kompleks jika
terdapat nikel di dalamnya.
Grup V. Barium, stronsium, kalsium. Penambahan berturut-turut amonium klorida,
amonia, dan amonium karbonat mengahsilkan endapan karbonat BaCO3, SrCO3, dan CaCO3 yang
seluruhnya berwarna putih dan mudah larut dalam asam asetat encer.
Pemisahan Barium. Barium dipisahkan dengan penambahn kalium kromat sehingga
terbentuk kromatnya, BaCrO4, yang dibedakan dari kromat stronsium dan kromat kalsium yang
tidak larut dalam asam asetat.
Identifikasi Stronsium dan Kalsium. Setelah pemisahan barium dalam bentuk kromatnya,
larutan dibagi ke dalam dua bagian. Stronsium diuji dengan larutan kalsium sulfat, yang
mengendapkan sulfat yang tidak larut, SrSO4. Kalsium sulfat dipilih sebagai pengendap karena
garamnya tidak terlalu larut. Cara alternatif, bagian larutan ini dibuat dari basa dengan amonia dan
alkohol menghasilkan endapan kuning stronsium kromat, SrCrO 4, yang demikian larut dalam asam
asetat encer, sedikit larut dalam air, dan kurang larut dalam larutan alkohol.
Dari cara lain pembuatan larutan stronsium dengan diendapkan menggunakan
asam sulfur ( banyak kalsium yang diendapkan dengan stronsium adalah tidak
perlu). Setelah filtrasi larutan dibuat alkaline dengan ammonia, dan kalsium
diuji untuk menambah ammonium oksalat yang menghasilkan oxalate hidrate
(CO2)2Ca.H2O

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.

Kelompok IV, Magnesium, sodium, potasium. Bagian filtrat dari grup

V magnesium diuji dengan menggunakan sodium fosfat, yang membentuk
endapan warna putih magnesium ammonium fosfat, Mg(NH4)PO4.6H2O. Pada
larutan yang encer, pengendapan berlangsung agak lambat.

Another part of the filtrate may be used for confirmation of magnesium by

adding 8-hydroxyquinoline reagent. This precipitates a yellow magnesium
complex.

Fungsi lain filtrat digunakan untuk menetapkan magnesium dengan

penambahan reagen hidroksiquinoline. Mengendap sebuah magnesium
kompleks kuning.

The rest of the filtrate is evaporated to dryness and examined for sodium and
potassium by the ame test (p. 24-).

Sisa dari filtrat di evaporasi untuk pengeringan dan diuji untuk sodium
dan potasium dengan uji nyala.

For the same reason, only a small precipitate of strontium sulphate can be
expected when calcium sulphate is used as precipitant.

Untuk alasan yang sama , hanya sebuah endapan kecil stronsium

sulfat yang dapat dimungkinkan kecuali ketika kalsium sulfat digunakan
dengan cepat.

' Many cations of earlier groups also form complexes with 8-hydroxyquinoline,
but these will of course not be present at this stage of the analysis.

Banyak kation yang dulu-dulu juga terbentuk kompleks dengan 8-

hydroxyquinoline, tapi ini tidak akan berjalan pada saat tahap analisis.
15QUALITATIVE 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 Na,H2Sb2O,,6H2O
(sodium pyroantimonate). (ii) Add zinc uranyl acetate reagent; sodium gives a
yellow precipitate of the composition [NaZn(UO,)3](CH3CO2),,9H.,O. (iii) Add
sodium hydrogen tartrate, and, _ if necessary, scratch with a glass rod;
potassium gives a white precipitate of potassium hydrogen tartrate,
KHC4H4Oo. (iv) Xdd a drop of acetic acid and two drops of a solution of sodium
cobaltinitrite, Na3Co(NO2),,; potas- sium gives a yellow precipitate of
potassium cobaltinitrite, K3Co(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: NI-I4++OH ->NH3+
H20 This is important, since ammonium salts give precipitates with potassium
antimonate, sodium hydrogen tartrate, and sodium cobaltinitrite. 16
III
REACTIONS OF ANIONS
Tms section deals with tests used in systematic analysis for anions (Section IV),
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(OI-I)2+ CO, > CaCO3+ I-1,0
With excess of carbon dioxide the turbidity disappears, as a result of conver-
sion of the calcium carbonate into the soluble bicarbonate, Ca(HCO3).,,; but if
the solution is boiled this is decomposed with reprecipitation of calcium
carbonate: CaC0,+ HaO+ CO, FE 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 bicarbonate: are soluble, but only those of sodium,
potassium, and ammonium are commonly met with. They arddistinguished
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,O
2NO+ O, -> 2N0,

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
17QUALITATIVE 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 the dry state sodium and potassium nitrates evolve
oxygen, and ammonium nitrate is decomposed into nitrous oxide and water:
ZKNO3 > 2KNO2+ O2
NH4NO, > N,O+2H.,,O
All other nitrates evolve oxygen and brown fumes of nitrogen dioxide; for
example: 2Pb(NO3), -> 2PbO+4-NO3+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+ _) Cu +2No,+2H,o S

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 Devardas alloy (Cu, Al,
Zn), nitrates are reduced with evolution of ammonia, recognizable by odour. If
ammonium salts are present the substance must be boiled with 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 confused by
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. _
18REACTIONS or 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,S5, 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,SO, \-- I-I,0+SO,
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 thlosulphuric acid decomposes with formation
of sulphur dioxide and a precipitate of sulphur:
H,S,0,, -> S0,+ S+I-1,0

Sulphate.Sulphates in solution give with barium chloride a white pre-

cipitate of barium sulphate, BaSO., insoluble in dilute acids.

The white precipitate of lead sulphate, PbS0,, 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 uoride, HF, a colourless, fuming gas. Some of the
hydrogen uoride attacks the glass with formation of gaseous silicon tetra-
uoride, SiF,. This can be detected by holding a moist rod in the escaping gas,
when a gelatinous deposit of silicic acid, H4SiO,, is produced on the rod:
3SiF,+4-H,O > I-I.SiO,+2H,SiF,

Barium chloride precipitates, from solutions of uorides, white barium uoride,

BaF,, which is insoluble in dilute acetic acid but soluble in stronger acids (e.g.
hydrochloric).
19QUALITATIVE 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 by warming the substance with
concentrated sulphuric acid and manganese dioxide, when chlorine is evolved
(yellowish-green gas which bleaclies moist litmus):
MnO2~54HCl -> MnCl2+ C12-t 2H2O

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 gas) together with some bromine vapour
(red) formed by oxidation of some of the hydrogen bromide:
2HBr+H2SO,, ~: Br2+ SO.,,+.1H2O
The proportion of bromine vapour is much increased by, adding manganese
dioxide as an oxidizing agent. Bromides can also be oxidized to bromine by 7
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.

Iodide.~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 0 violet vapour; some of the sulphuric acid
is reduced as far as hydrogen sulphide, which can usually be detected by smell.

Iodides 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, AgI,
insoluble in nitric acid and only sparingly soluble in ammonia solution.

Hypocl-ilorite.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.
20REACTIONS or ANIONS

Hypochlorites evolve chlorine when treated with dilute sulphuric or hydrochloric

acid, and the resulting solution bleaches litmus.

Chlorate.Concentrated sulphuric acid decomposes chlorates with libera- tion

of chlorine dioxide, C102, a yellow gas which gives an orange-yellow colour to
the acid and crackles explosively when warmed:
3ClO,, +2H+ > C104 +2ClO,+H2O
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.

All 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(BO2),. 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, C31-
I5OH, in a dry porcelain dish, and applying a light to the mixture; volatile ethyl
orthoborate, (C,,H,,),,B0,,, is formed, and gives a green tinge to the ame.

Phosphate.Silver nitrate, added to a neutral solution of an orthophos- phate,

gives a yellow precipitate of silver orthophosphate, Ag,,PO4, soluble both in
ammonia solution and in dilute nitric acid (metaphosphates 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, (NH4),,PMo,.,,O4,,. 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, Ag,,AsO,,, and
dark brown silver arsenate, Ag3AsO. 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. Precipitation by hydrogen
sulphide from solutions of arsenates is slow unless a fairly high concentration
21QUALITATIVE CHEMICAL ANALYSIS
_ of hydrochloric acid is present; the precipitate then consists of arsenic sul-
phide, AS255, arsenious sulphide, As2S,,, and sulphur in varying proportions.

Chromate and dicliromate.Chromates are yellow, and are converted by

acids into orange dichromates; dichromates arc orange, and are converted by
alkalis into yellow chromates:
2CrO,," +2H+ -> Cr2O,"" + H20
Cr,,O.,*'* +2OH > 2CrO4" +H._.O -

Solutions of chromates or dichromates acidified with acetic acid give with

barium chloride a yellow precipitate of barium chromate, BaCrO4, with silver
nitrate a brownish-red precipitate of silver chromate, Ag._,CrO4, 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:
Cr2O," +3H2S+8H+ -> 2Cr3+ .3S+7I-I20
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:
2MnO4 +SH2S+ 6H+ > 2Mn I +5S+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.

In qualitative analysis substances containing permanganate(easilyrecognized

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).

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,O,-+6Cl-+14-H+ > 2Cr'+ + 3Cl,+7H,O
2MnO4+ 10Cl+ 161-I+ > 2Mn'+ + 5Cl.+8H,O
I and the chlorine is expelled by boiling.
22SYSTEMATIC QUALITATIVE ANALYSIS
THE 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 . . . . Blue or green Cobalt salts . . . . . . Pink Iron salts . . . . Green
or brown Chromates . . . . . Yellow Chromium salts . . . . Green Dichromates . . . .
. Orange Manganese salts . . . . Pale pink Permanganates . . . Dark purple Nickel
salts . . . . . Green

The oxides and/or sulphides of the following metals are coloured: lead,
mercury, silver, copper, bismuth, cadmium, arsenic, antimony, tin, iron,
chromium, 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 all
bicarbonates.

There is little 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).
23QUALITATIVE CHEMICAL ANALYSIS 7
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 ame. The ame test may be done at this stage of the
analysis or reserved for use as a confirmatory test later. The ame colours are:
7 Grey or bluish-grey . . . . Lead, arsenic, antimony, tin. Bluish-green . . . . .
Copper. Apple green . . . . . Barium. Brick-red . . . . . . Calcium. Crimson . . . . . .
Strontium. Bright yellow (invisible through 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 ame; in the inner
(reducing) part of the ame 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. 7 7 Bright green bead . . . .
Chromium. Yellow bead . . . . . Iron. Deep amethyst bead . . . . Manganese.
Deep blue bead . . . . . 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. 7 Hydrogen sulphide (characteristic odour; blackens lead acetate
paper).- Sulphide. 24
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 uoride (colourless, fuming gas which attacks g1ass).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.2

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 needed 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

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.
25QUALITATIVE 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 To
the solution add dilute hydrochloric acid. Cool well, and filter. feridue. Filtrate.
Dilute, warm, and pass hydrogen sulphide. ead, _ __~__...j_
sllven Residue.-Wash well, Filtrate.Boil to expel hydrogen sulphide, menu
heat (but do not boil) ' add a few drops of concentrated nitric acid "5- _ with
yellow ammo- | (or more, if the solution darkens), and boil Examine nium
sulphide for a ', again. Add ammonium chloride and a small y) gble
fewminutes,and filter. but distinct ex: ess of ammonia. Filter. or roup _ - I
Residue. Filtrate. i Residue.- Filtrate.-Pass hydrogen sulphide;
Mercuric, May con- Alumin- filter. lead, tain: ium, - bismuth As,nl
l'mlm Re3iJue. Filtrate.-Add ammo- 0PP}' "m"V "" 3
Mangan- nium carbonate, boil, cadmium. tin. insoluble ese, and fine!-_ Examine
Examine Ph09' a zinc, :__ by table by table Ph3l5e- cobalt, Res,-due._ F,-
ltmte___ gar Group 0; Group Examine nickel. Barium May cn_ Ia I by table E
' ' ; l for Group bi.fiiLe i'ic?J3.T" iu'gne- I In for Group Examine
sium, ! IV by tame sodium, l for Gmup potassium. . V Examine '1 by table . for
Group 1 w A 1 See footnote, p. 10. 3 When lead is present a little is always
precipitated in this group, as 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. W3 the fillet Confirm
by heating to boiling again and Re.ridue.-- Filtrate.Acidify with :1l"3
"f?""_ h'' Black: nitric acid. White pre- Ye ' p"ep'tte' ' Mercurous
Ciplffitein Ld S vei- SEPARATION OF CATIONS OF GROUP IIA Vziish the
precipitate, boil with nitric acid (1 part conc. acid to 1 part water), and ter.

Res1z;dIue.Black. Fifi.'rate.-Addi dilutefsulphuric aciddagii, preferably,

alcohol, ercuric. a ow to stan for a ew minutes, an ter. Confirm by dis- . . .
solving in 8 mix_ I%i'}ziii:4ee: Filtrate.-Add excess of ammonia, warm, and
filter. '9 f ' L Residue.- Filtrate.-If blue, copper is pre- tmted hYd"'
on White. sent. Divide into two parts. chloricandnitric Bismuth acids, diluting
D. I . d. PartI.Acidify PartII.If cop- well, and adding 1 980 kvledlrn C; with
acetic acid per is present, stannous chlor- 1 -e Yd 5 and add potas- add
potassium ide. White or me Pct ban t sium ferrocy- cyanide until grey precipi-
Kl;.r m 19:3 mi, anide. the blue colour tate: water afhifie Bmwn med-
disappears.Pass Mercurlc . pitate or color- hY,l'8n "1" tum '5' ti n. phide.
Yellow Bismuth 8 gohper precipitate: Cadmium SEPARATION OF CATIONS OF
GROUP Ila 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, Fillrate.Divide into two parts. 23 Part I.
Mske slightly alka- Pm II.-Dilute somewhat, 1 . line with ammonia, add about
add iron wire, and heat for a ;,r,l,)-nue 50 u 1 gm. of solid oxalic acid, and
few minutes. Filter, and add ' boil. Pass hydrogen sulphide. mercuric chloride to
the filt- C fiiegicm ,t Orange precipitate: rate. White or grey precipi-
manonnliin tgst e(lp: A'"imy me: . 11),performed on _ . _T the original sub-
For distinction between stan- stance. nous and stannic, see p. 11. 27
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- Fi'ltrate.If yellovr,chromium is present. Divide

solve in dilute hydrochloric -I into two parts. acid, and add potassium ferro- r-
j-~_ cyanide, Prussian b]ue prec,'_ Part _I.Acidify with Part II._Add
excess of mate; acetic acid, and add ammonium chloride,
Iron lead'a_cetate. Yellow and boil. White pre-
:ttt
Test original substance for precgisztfni clplilminium

ferrous and ferric (p. 13). um ] C E 13 on rm as on p. .

TREATMENT OF GROUP III
PRECIPITATE WHEN PHOSPHATE IS PRESENT

E 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 precipitate
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.

Resz'due.-Consists of basic ferric acetate Fzltmte.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. I
SEPARATION OF CATIONS OF GROUP IV

Wash the precipitate, shake well with cold, very dilutehydrochloric acid, and
filter.

Residue.Dissolve in the least possible I F1'ltrate.Boil to expel hydrogen

sul- quantity of concentrated hydrochloric phide. Cool, add excess of sodium
acid (3 parts) and concfintrated nitric hydroxide, and filter. I

'dl t.E tt lt' t-------- ?.i.n2.)ri~eZ?i.{ii 0551.?

.Z'sl3.ii'fy Resid:;e.white.rapid1y nitrate.- the nitrite reaction (p. 15) or in a
borax turning bT_0W11,-"M3!18' P335 hYd}'' bead. Yellow precipitate or blue
bead: a't}s1- B011 _"1t% excess %$!fi_S\1lPh1de~
Cobalt ' (donc;2i:i'at2d0:itric atijd dirtife (iiirhite

Dissolve the rest of _the residue in a little dilute and 3110, a; precipitate;

water, add ammonia until the liquid is 5ett1e_ pmpie supema_ .

nodlonger acidf, acidify with acetic acid, tam iiqmd: _ zlllc

an add, to a ew drops of the solution, b

one drop .of_ dirnethylglyoxime solution. Manganese * S1oex(fiRi:1lmanys

Red precipitate. green: test (P, !
Nickel I 14). ,
See also the modification of this method of dealing with a phosphate (p. 13).
28
SYSTEMATIC QUALITATIVE ANALYSIS
SEPARATION OF CATIONS OF GROUP V
Wash the precipitate, dissolve it in dilute acetic acid, and test a small portion of
the solution with potassium chromate. If a precipitate is formed, add potassium
chromate to the main portion of the solution, and filter. Resz'due. Filtrale.
Divide into two parts. Yellow: -------_ , , Barium Part I.Add
calcium sul- Part II.Add dilute sulphuric 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. st,-omium 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 1II.
Evaporate to dryness, and shake well. White precipitate: apply the ame test to
the residue. Magnesium Bright yellow ame, invisible through Part II .Use for
confirmation ofmagne- b3l"'bl119 813331

sium (p. 15), particularly if the sodium Sodium

Ph3Ph3t test h SW9 3 dbtfl Lilac ame, crimson through cobalt-

r5lt- blue glass:

Potassium
If necessary conrm 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.
29QUALITATIVE 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: Filtra2e.-Add dilute_ammonia_ solution

Chloride:-White, readily soluble in drop by grep. until a precipitate is

ammon;a_ produced

Bromide.Pale yellow, less soluble in Ye"W P1 ecipimtei Ph9P_h3t-

ammonia_ Arsenite.

Iodide.-Yellow, very sparingly soluble Brown PT*3CiPit3te? A1'3em5-

in ammonia. Brownish-red precipitate: Chromate. PART II OF THE SOLUTION

Acidify with dilute hydrochloric acid, add excess of barium chloride, boil, and
filter. Residue.- Fi'ltrate.Cool, and add ammonia solution drop by drop. The
White: following may be precipitated? SUlPh3te- Borate (white)
lgiggggiiztfvgzfiige) } Solublc in dilute acetic acid. Arsenate (white _ Fluoride
(white) , . . . chromate (yellow) } Insoluble in dilute acetic acid. PART III 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 Devardas 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 cooled, 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.
30V
SPECIAL PROBLEMS
THE 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 uoride may cause

cations of later groups to be precipitated in Group III, although in the case of
borate the presence of a sufiicient 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 uoride
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 uoride 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 sulfi- 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, SiO2, 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 Devardas alloy after
expelling ammonia from the ammonium ions by
31QUALITATIVE 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 Devardas 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 oi 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 whi(h is based on reactions pre-

' viously described (p. 20).

DETECTION OF CHLORIDE, BROMIDE, AND
IODIDE VVI-IEN 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:
Iodide

l Boil until all iodine is expelled, adding more sodium nitrite if necessary. Cool,
add i dilute nitric acid, and divide into two parts.

Part I.-Add chlorine water, and shake Part II.- -Boil to expel all bromine, I the
solution with carbon tetrachloride. adding more nitric acid if necessary.
[ Orange lower layer: Add SiI\ er nitrate. White precipitate: 1 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 uoride.
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:
BaSO4 + Na2CO3 > BaCO3 + Na2SO4

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, Na2PbO2. 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.

The acid-insoluble part of a mixture should always be examined separately in

order that the examination of the insoluble material, difficult enough in itself,
shall not be complicated by the unnecessary presence of soluble ions.
33I N D E X '
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 F leitmanns test 11 Anions, interfering 31 Fluoride

19

Anions, reactions of 17 Fusion mixture 33

Antimony 11 :,
Aqa gin, 10 Groups, separation of cations into 6, 26 Arsenate 21
Arsenic 11 V
Arsenite 21 Hydrogen peroxide, use of 12, 13
Hydrogen sulphide, dissociation of 6
Barium 15 8-Hydroxyquinoline 15 ,
Bicarbonate 17 Hypochlorite 20 5
Bismuth 9 V
Bleaching powder 20 Insoluble substances 33
Borate 21 Interfering ions 31 :
Borax-bead test 24 Iodide 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, examination 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 Nlicrocosmic salt 31

Chromium 12
Cobalt 14 Nickel 14
Complexes 7, 9, 10, 12, 15 Nitrate 18
Copper 9 Nitrite 17
E Devardas alloy 18 Permanganate 22 -
Dichromate 22 Phosphate 21
_ Dimethylglyoxime 15 Phosphate separation 13, 14 Polysulphides 19 Ethyl
orthoborate 21 Potassium 15, 16 34
INDEX

Potassium antimonate 16 Solubility products 5 Potassium cobaltinitrite 16

Solution. D!P31'3tl0 Of 25 Preliminary tests 23 Stannic 11
Prussian blue 13 Stannous 11
Starinous and stannic, distinction
Quinalizarin 12 S between
trontium Rinmans green 14 glipzffie u p i e
Semi-micro methods 8 gugpgillte 31:
Silica 33 P
S 3" 33 _ Thio-salts 11
Silicon tetrauoride 19 Thiosulphate 19
Silver 9 Tin 11
Sdim 15 16 Turnbull's blue 13
Sodium cobaltinitrite 16
Sodium hydrogen tartrate 16 Zinc 14

Sodium peroxide, use of 12 Zinc uranyl acetate 16

35