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Introduction
You know that the qualitative analysis involves the detection of the anions and the cations
present in an inorganic mixture. Sometimes the knowledge of anions present in a mixture provide
important clues about the cations which may be present in a mixture and the scheme of analysis
to be followed. Therefore, it is desirable to first detect the presence of anions and after that the
cations. In this unit, we will discuss the scheme of detection of anions which will be followed by
the scheme of analysis of cations.

Classification of the Anions

For the systematic identification of the anions present in any mixture, the anions are divided into
following three classes:

Anions of Class I: The anions of Class I evolve gases or vapours on treatment with dil. HCl or
dil. H2SO4. These anions are carbonate, sulphite, sulphide, thiosulphate, nitrite and oxalate.

Anions of Class II: The anions of Class II evolve gases or vapours on treatment with conc.
HCl or conc. H2SO4. These anions are fluoride, chloride, bromide, iodide, nitrate and oxalate.

Anions of Class III: The anions of this class do not evolve any gas on treatment with acids.
These are identified by formation of precipitate on treatment with certain reagents. Sulphate,
borate and phosphate ions are the anions of Class III.

Here we would like to emphasise the unlike scheme of classification of cations, the scheme of
classification of anions is not a rigid one since some of the anions belong to more than one of the
classes, e.g., acetate. Also, it is not always necessary to test for the presence of anions of Class I
before testing for the presence of anions of Class II or Class III in any mixture.

Preliminary Tests for the Anions

In this unit the tests for all these anions will be systematically discussed. We shall first discuss
the preliminary tests for detecting the presence of anions of Class I and Class II, which will be
followed by their confirmatory tests. As there are no preliminary tests for the anions of Class III
only their confirmatory tests will be discussed.

Preliminary Tests for the Anions of Class I: Take about 0.2g of dry mixture in a test
tube. Add 2 cm3 of dilute hydrochloric or sulphuric acid. If a gas is evolved, note its colour and
odour and draw inference with the help of Table 1. Heat the test tube if necessary. If no gas is
evolved, anions of this class are absent in the mixture.
Table 1: Preliminary Tests for the Anions of Class I

Sl. No. Observation Inference Explanation / Reaction

1 Colourless, suffocating gas with SO32 − may be SO32–(aq) + 2H+(aq) → H2O(l) + SO2(g)
smell of burning sulphur; the 2−
present Cr2 O7(aq) + 2H+(aq) + 3SO2(g)
gas turns acidified K2Cr2O7
paper green.

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3+ −
→ 2Cr(aq) + 3SO 24(aq) + H 2O (l)
green

2 Colourless gas which turns KI S2– may be S2–(aq) + 2H+(aq) → H2S(g)

starch paper blue. present Pb2+(aq) + H2S(g) → PbS(s) + 2H+(aq) Comment [AKG1]:
Black

3. Light brown gas which turns KI NO −2 may be 2NO −2(aq) + 2H+(aq) → H2O(l) + NO(g) + NO2(g)
starch paper blue.
present

4. Colourless vapours with smell CH3COO– may CH3COO–(aq) + H+(aq) → CH3COOH(g)

of vinegar on warming the test be present
tube

When salts of the anions of Class I are treated with strong, non-oxidising acids, corresponding
acids are generated in the solution.
2− +
SO3(aq) + 2H (aq) 
→ H 2SO3(aq)
NO −2(aq) + H (aq)
+

→ HNO 2(aq)
2− +
S(aq) + 2H (aq) 
→ H 2S(aq)

Out of these H2CO3, H2SO3 and HNO2 are thermally unstable and decompose into gaseous
products, whereas H2S and CH3COOH are evolved as vapours on warming:

H 2SO3(aq) 
→ SO 2(g) + H 2 O(l)
2HNO 2(aq) 
→ NO (g) + NO 2(g) + H 2 O(l)

Preliminary Tests for the Anions of Class II: Take 0.2 to 0.3g of the mixture in a dry test
tube and add 2-3 cm3 of conc. sulphuric acid drop-wise. Observe the reaction at room
temperature and then warm the test tube gently. If no gas or vapours are evolved, the anions of
this class are absent. Draw inference with the help of Table 2.

Table 2: Preliminary Tests for the Anions of Class I

Sl. No. Observation Inference Explanation / Reaction
1 Colourless, pungent smelling –
Cl may be –
H+(aq)
Cl (aq) + → HCl(g)
gas is evolved, which gives present HCl(g) + NH3(g) → NH4Cl(g)
white dense fumes of NH4Cl
when a glass rod dipped in
aqueous ammonia is placed in
the evolved gas.
2 Reddish brown gas is evolved Br– may be Br–(aq) + 6H+(aq) + 3SO42–(aq) →
and the solution in the test tube present 2HSO4–(aq) + Br2(g) + 2H2O(l)
acquires a yellow-red colour.
3. Violet vapours of I2 are I–may be 2I–(aq) + 6H+(aq) + 3SO42–(aq) →
evolved, which turn the moist present 2HSO42–(aq) + SO2(g) + I2(g) + 2H2O(l)
starch paper blue.
4. Pungent smelling, brown fumes NO3– may be NO–3(aq) + H+(aq) → HNO3(aq)
of NO2 are evolved. The present

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evolution of NO2 increases on 4HNO3(aq) → 4NO2(g) + O2(g) + 2H2O(l)

heating the reaction mixture Cu(s) + 4HNO3(aq) →
with copper turnings. Cu(NO3)2(aq) + 2NO2(g) + 2H2O(l)

Preparation of Solution for Identification of the Anions

The preliminary tests described in the preceding section do not always offer very conclusive
evidence for the presence of anions in a mixture. Therefore, further tests have to be performed for
confirmation of those anions which are indicated by the preliminary tests and for the detection
and confirmation of the anions of Class III which have no preliminary tests. These tests are called
confirmatory tests and are performed on the solution of anions which is prepared as described
below.

Preparation of Water Extract (W.E.): All common acetates, nitrites, nitrates and
thiosulphates are soluble in water. Confirmatory tests for these anions can be performed with the
water extract of the mixture. Water extract can be prepared by boiling 1-2g of the mixture with
10-15 cm3 distilled water in a boiling tube for a minute or two. Residue, if any, is filtered. The
filtrate is called water extract (W.E.).

Preparation of Sodium Carbonate Extract (S.E.): If the mixture is found to be partially

or wholly insoluble in water, it is boiled with saturated sodium carbonate solution. This treatment
converts the anions present in mixture into soluble sodium salts as a result of double
decomposition e.g.,
BaSO 4(s) + Na 2 CO3(aq) 
H 2O
→ BaCO3(s) + Na 2SO 4(aq)
PbCl 2(s) + Na 2 CO3(aq) 
H2O
→ PbCO3(s) + 2NaCl(aq)

For preparing sodium carbonate extract, take 0.5-1.0g of powdered mixture, 1.0-2.0g of sodium
carbonate and 5-10 cm3 of distilled water in a boiling tube or a 50 ml beaker. Heat with stirring
for 5-10 minutes. Cool the contents and filter. The filtrate is called sodium carbonate extract
(S.E.). This extract is used for confirming the presence of most anions except for carbonate since
sodium carbonate has been added during its preparation.

Confirmatory Tests for the Anions

After preparation of the water extract or the sodium carbonate extract, the following tests are
performed to confirm the presence of various anions in the mixture.

Tests for the Sulphide Ions

1. Take 1 ml of sodium carbonate extract in a test tube and add 1 – 2 ml of sodium

nitroprusside solution. A purple or violet colour confirms sulphide ions:
2− 2− 4−
S(aq) + [Fe(CN)5 NO](aq) 
→ [Fe(CN)5 NOS]aq
purple or violet colour

2. Take 1 – 2 ml of S.E. in a test tube, acidify it with acetic acid and boil to remove CO2.
Then add 1 – 2 ml of lead acetate solution. Formation of black precipitate confirms
sulphide ions:
2−
S(aq) + Pb 2 + 
→ PbS(s)

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Tests for Sulphite Ions: Take 2 – 3 ml of S.E. and add 2 – 3 cm3 of BaCl2 solution to it. A
white precipitate may appear due to the presence of SO32 − , SO 42- or excess of CO32 − ions present
in the solution. Filter the precipitate and divide into three parts.

1. To the first part, add dil. HCl. Evolution of SO2 gas which turns acidified dichromate
paper green confirms the presence of SO32 − ions

+ 2+
BaSO3(s) + 2H (aq) + 5e 
→ Ba (aa ) + SO 2(g) + H 2 O (l)

2. To the second part, add a few drops of KMnO4 solution and acidify with dil. H2SO4. If the
pink colour of KMnO4 is discharged, the presence of SO32 − ions is confirmed.

+
BaSO3(s) + H 2 O (l) 
→ BaSO 4(s) + 2H (aq) + 2e] × 5
− + 2+
MnO 4(aq) + 8H (aq) + 5e 
→ Mn (aq) + 4H 2 O (l) ] × 2
–––––––––––––––––––––––––––––––––––––––––––––––––
5BaSO3(s) + 2MnO −4(aq) + 6H (aq)
+
 2+
→ 5BaSO 4(s) + 2Mn (aq) + 3H 2 O(l)

3. To the third part, add I2 solution. If colour of iodine is discharged, SO32− is confirmed.

BaSO3(s) + I 2(aq) + H 2 O(l) 

→ BaSO 4(s) + 2HI(aq)

Tests for the Nitrite Ions

1. Take 5 drops of W.E. in a test tube. Dilute with 5 drops of distilled water. Add 5M acetic
acid until the solution is just acidic. Cool the test tube in a cold water bath. Add 2-3 drops
of freshly prepared 0.2M FeSO4 solution to the cooled solution. Appearance of a brown
colour throughout the solution confirms the presence of nitrite ions.

NO −2(aq) + CH 3COOH (aq) 

→ HNO 2(aq) + CH 3COO −(aq)
3HNO 2(aq) 
→ HNO3(aq) + H 2 O(l) + 2NO(g)
2− 2+
[Fe(H 2 O)6 ](aq) + NO(g) 
→[Fe(H 2 O)5 NO](aq) + H 2 O (l)

2. To 1 cm3 of W.E. add 5 drops of KI solution, 1 cm3 of starch solution and 1 cm3 of dil.
H2SO4. Appearance of a deep blue colour confirms the presence of nitrite ions.

2NO −2(aq) + 4H (aq)

+ −
+ 2I(aq) 
→ 2NO(g) + I 2(aq) + 2H 2 O(l)
I2(aq) + Starch → Blue coloured complex

3. Take 5 drops of W.E. in a test tube, acidify with 6 M acetic acid. Add a pinch of thiourea
and stirr well. Add 2 drops of FeCl3 solution. A blood red colur confirms nitrite ions.

NO −2(aq) + H 2 NSCNH 2(s)  −

→ N 2(g) + CNS(aq) + 2H 2 O(l)

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+ −
Fe3(aq) + 3CNS(aq) 
→ Fe(SCN)3(aq)
(Blood red colour)

You should note that the nitrite ion is a moderately strong oxidizing agent in acidic
medium. It oxidizes S2 − ,SO32 − ,S2 O32 − and I– ions to S, SO 2-4 , S and I2 respectively.
Therefore, these anions cannot be present if NO2– ions are present in the mixture.
2− − +
S(aq) + NO 2(aq) + 2H (aq) 
→ S(s) + NO(g) + H 2 O(l)
2−
SO3(aq) + 2NO −2(aq) + 2H (aq)
+
 2−
→ SO 4(aq) + 2NO (g) + H 2 O(l)
2− − +
S2 O3(aq) + 2NO 2(aq) + 2H (aq) 
→ SO 4(aq)
2
+ S(s) + 2NO (g) + H 2 O(l)
2I−(aq) + 2NO −2(aq) + 4H (aq)
+

→ I 2(s) + 2NO(g) + 2H 2 O(l)

Test for the Nitrate Ions: Take 2 cm3 W.E. in a test tube. Add 4 cm3 concentrated sulphuric
acid, mix two liquids thoroughly and cool the mixture under a stream of cold water from the tap.
Pour few cc of saturated solution of FeSO4 slowly down the side of the test tube so that it forms a
separate layer on top of the solution in the test tube. A brown ring will be formed at the zone of
contact of the two liquids.
− + 2+ +
NO3(aq) + 4H (aq) + 3Fe(aq) 
→ 3Fe3(aq) + NO(g) + 2H 2 O (l)
2+ 2+
[Fe(H 2 O)6 ](aq) + NO(g) 
→[Fe(H 2 O)5 NO](aq) + H 2 O (l)

This test for nitrate ion is based on its ability to oxidize Fe2+ to Fe3+ in acidic solution with the
product of NO gas. Since NO is more soluble in water at low temperature, in well cooled solution
it reacts with excess Fe2+ present in solution to form brown nitrosyliron (II) complex ion,
[Fe(H2O)NO]2+. Nitrite, bromide and iodide ions interfere in this test.

Test for the Chloride Ions

1. Acidify 2 – 3 cm3 of S.E. with dil. HNO3. Boil off CO2. Then add AgNO3 solution.
Formation of a curdy white precipitate, which is soluble in aqueous ammonia, confirms
the presence of chloride ions in the mixture.
− +
Cl(aq) + Ag (aq) 
→ AgCl(s)
+ −
AgCl(s) + 2NH 3(aq) 
→[Ag(NH 3 )2 ](aq) + Cl(aq)

2. Heat 0.5g of dry mixture with 0.5g of K2Cr2O7 and 2 ml of conc. H2SO4 in a dry test tube,
red vapours of chromyl chloride will be evolved. Pass the vapours in dil. NaOH solution,
a yellow solution will be obtained. Acidify the solution with acetic acid and then add lead
acetate solution. Formation of a yellow precipitate of lead chromate, which is soluble in
NaOH, confirms the presence of chloride ions.

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4NaCl(s) + K 2 Cr2 O7(s) + 3H 2SO 4(l) 

→ K 2SO 4(s) + 2Na 2SO 4(s) + CrO 2 Cl 2(g) + 3H 2 O(l)
Chromyl chloride gas

CrO 2 Cl 2(g) + 4NaOH (aq) 

→ Na 2 CrO 4(aq) + 2NaCl(aq) + 2H 2 O (l)
Na 2 CrO 4(aq) + Pb(CH 3COO) 2(aq) 
→ PbCrO 4(s) + 2CH 3COONa (aq)

Due to the formation of chromyl chloride gas, this test is called chromyl chloride test. The
test fails if the mixture contains chlorides of Hg2+, Sn2+, Pb2+ or Ag+.

Test for the Bromide Ions

1. Acidify 2-3 ml of S.E. with dil. HNO3 and boil off CO2. Add AgNO3 solution. Formation
of a light yellow precipitate which is partially soluble in aqueous ammonia solution,
confirms the presence of bromide ions.
− +
Br(aq) + Ag (aq) 
→ AgBr(s)
Light yellow ppt.

2. Take 2 cm3 of S.E. acidify it with dil. HCl and boil off CO2. Add 2 cm3 of carbon
disulphide, dichloromethane or carbon tetrachloride. Then add chlorine water drop-wise
and shake. Bromide ions are oxidized to bromine, which imparts an orange colour to the
organic layer. This confirms the presence of bromide ions in the mixture.
− −
2Br(aq) + Cl2(aq) 
→ 2Cl(aq) + Br2(l)
Br2(l) + CS2(l) 
→ Orange colour

Tests for the Iodide Ions

1. Acidify 2 – 3 cm3 of S.E., with dil. HNO3 and boil off CO2. Add AgNO3 solution.
Formation of a pale yellow precipitate insoluble in aqueous ammonia confirms the
presence of iodide ions in the mixture.
− +
I(aq) + Ag (aq) 
→ AgI(s)
Pale yellow ppt.

2. Take 2 cm3 of S.E. in a test tube. Acidify it with dil. HCl and boil off CO2. Add 2 cm3
carbon disulphide, dichloromethane or carbon tetrachloride. Then add chlorine water
drop-wise and shake. Iodide ions are oxidized to iodine, which imparts a violet colour to
the organic layer.

2I−(aq) + Cl2(aq) 
→ I2(s) + 2Cl−(aq)
CS2(l) + I2(s) 
→ Violet colour

The violet colour disappears on addition of excess of chlorine water. This confirms the
presence of iodide ions in the mixture.

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I 2(s) + Cl2(aq) 
→ 2ICl (aq)
Iodine monochloride (colourless)

Test for the Sulphate Ions: Take 1 – 2 cm3 of S.E. in a test tube. Acidifiy it with dil. HCl
and boil off CO2. Add BaCl2 solution. Appearance of a white precipitate, which is insoluble in
conc. HCl and conc. HNO3, confirms the presence of sulphate ions.
− 2+
SO 24(aq) + Ba (aq) 
→ BaSO 4(s)

Test for Nitrate Ions in Presence of Nitrite Ions: In presence of nitrite, nitrate cannot be
tested either by heating with conc.H2SO4 or by the ring test because both liberate NO2. Therefore,
nitrite must be destroyed completely before testing for the nitrate. Nitrite ions can be destroyed
by any one of the following methods:

1. Add sulphamic acid, H2NSO3H, to the water extract containing NO −2 and NO3− ions.
Acidify the solution with dilute H2SO4. Nitrite will be decomposed and nitrogen gas will
be evolved.
− −
H 2 NSO3 H (aq) + NO 2(aq) 
→ HNO 2(aq) + H 2 NSO3(aq)
− + 2−
H 2 NSO3(aq) + HNO 2(aq) 
→ N 2(g) + H (aq) + SO 4(aq) + H 2 O(l)

2. Take 2 – 3 ml of water extract, add 1g solid NH4Cl and boil till effervescence ceases.

NO −2(aq) + NH 4 Cl(aq)  −
→ N 2(g) + 2H 2 O(l) + Cl(aq)

3. Take 2 – 3 ml of water extract, add urea and acidify with dil. H2SO4. Boil the solution till
evolution of gases ceases.
− +
NH 2 CONH 2(aq) + 2NO 2(aq) + 2H (aq) 
→ 2N 2(g) + CO 2(g) + 3H 2 O(l)

Now divide the nitrite free solution thus obtained in two parts.

a) Perform ring test with one part to confirm the presence of nitrate ions.

b) Acidify the other part with dil. H2SO4. Add a little KI and 1 cm3 starch solution.
Absence of any blue colour indicates the complete removal of nitrite ions. Now add a
piece of granulated zinc to the solution. Appearance of a blue colour confirms the
presence of nitrate ions.
+ +2
Zn (s) + 2H (aq) 
→ Zn (aq) + 2H (g)
− −
NO3(aq) + H 2(g) 
→ NO 2(aq) + H 2 O (l)
2I−(aq) + 2NO −2(aq) + 4H (aq)
+

→ 2NO(g) + I 2(s) + 2H 2 O(l)
I 2(s) + Starch 
→ Blue coloured complex

Tests for Nitrate Ions in Presence of Bromide and/or Iodide Ions

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1. Bromide and iodide interfere in the ring test of nitrate because of the colour of liberated
bromine and iodine. In order to identify nitrate in presence of iodide and/or bromide, the
interfering halide should be expelled before performing the ring test. This can be done by
boiling 2 – 3 cm3 of water extract or sodium carbonate extract with excess of chlorine
water in a china dish, till no more vapours of Br2 or I2 evolve.
− −
2Br(aq) + Cl 2(aq) 
→ 2Cl(aq) + Br2(g)
2I−(aq) + Cl2(aq)  −
→ 2Cl(aq) + I 2(aq)

Now perform the ring test on the halide free solution to identify the nitrate ion in the
mixture.

2. Alternatively, take 2 – 3 cm3 of water extract in a test tube. Acidify with dil.H2SO4. Now
add 1 cm3 of KI solution, 1 cm3 of starch solution and a few granules of zinc. Appearance
of a blue colour confirms the presence of nitrate ions in the mixture.
+ 2+
Zn (s) + 2H (aq) 
→ Zn (aq) + H 2(g)
− −
NO3(aq) + H 2(g) 
→ NO 2(aq) + H 2 O (l)
2I−(aq) + 2NO −2(aq) + 4H +(aq) 
→ 2NO(g) + I2(g) + 2H 2 O(l)
I 2 + Starch 
→ Blue coloured complex

Test for Chloride, Bromide and Iodide Ions in Presence of Each Other: As you
know that chloride, and iodide ions react with AgNO3 solution to form a precipitate, special tests
are required to identify if more than one of them are present in the mixture. These anions can be
detected in presence of one another by any one of the following methods.

1. Acidify 2 – 3 cm3 of S.E., with excess dil. H2SO4 in a china dish. Add 0.5g of potassium
persulphate and heat gently. Add distilled water if necessary to prevent dryness.
Evolution of violet vapours of I2 will confirm the presence of I– ions.
− 2− −
2I(aq) + S2 O8(aq) 
→ 2SO 24(aq) + I 2(g)

Boil till evolution of I2 ceases. If the solution after elimination of I2 is brown, it indicates
the presence of Br– ions. Continue boiling, brown vapours of Br2 will be evolved.
− 2− 2−
2Br(aq) + S2 O8(aq) 
→ 2SO 4(aq) + Br2(g)

Add more K2S2O8 if required. Continue boiling till the residual solution becomes
colourless. Cool the solution, add dil. HNO3 and AgNO3 solution. A curdy white
precipitate soluble in ammonia confirms the presence of Cl– ions in the mixture.
− +
Cl(aq) + Ag (aq) 
→ AgCl(s)
+
AgCl(s) + 2NH 3(aq) 
→[Ag(NH 3 )2 ](aq) + Cl−(aq)

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2. Acidify 2 – 3 cm3 of S.E. with dil. H2SO4 in a china dish. Boil off CO2. Add solid sodium
nitrite and boil. Evolution of violet vapours of I2 confirms the presence of iodide ions.

2NO −2(aq) + 2I−(aq) + 4H +(aq) 

→ 2NO(g) + I2(g) + 2H 2 O(l)

Add distilled water if necessary to prevent dryness. Continue boiling till all iodine is
expelled. Cool the solution and divide into 2 parts.

To 1st part add 1 cm3 CS2 (or CH2Cl2 or CCl4), 2 cm3 chlorine water and shake.
Appearance of an orange colour in organic layer confirms the presence of bromide ions.
− −
2Br(aq) + Cl2(aq) 
→ 2Cl(aq) + Br2(l)
CS2(l) + Br2(l) 
→ Orange colour

If Br– is present, boil the 2nd part with 1 cm3 of conc. HNO3 to expel Br2 gas. This
treatment can be avoided if Br– ion is absent. Then add AgNO3 solution. Formation of a
curdy white precipitate confirms the presence of Cl– ions.
− − +
2Br(aq) + 2NO3(aq) + 4H (aq) 
→ 2NO 2(g) + Br2g) + 2H 2 O(l)
− +
Cl(aq) + Ag (aq) 
→ AgCl(s)

Test of Cations
Flame Test on Dry Samples
Bunsen Flame: A Luminous Bunsen flame (air holes completely closed), about 5 cm long, is
employed for conducting blowpipe test. A reducing flame is produced by placing the nozzle of a
mouth pipe just outside the flame, and blowing gently, so as to cause the inner cone to play on
the substance under examination. An oxidizing flame is obtained by holding the nozzle of the
blowpipe about one third within the flame and blowing somewhat more vigorously in a direction
parallel with the burner top, the extreme, tip of the flame is allowed to play upon the substance.

Charcoal Cavity Test: The test are carried out upon a clean charcoal block in which a small
cavity has been made. A little of the substance is placed in the cavity and heated in the oxidizing
flame, crystalline salts break into smaller pieces: burning indicates the presence of an oxidizing
agent (nitrate, chlorate etc.). More frequently the powdered substance is mixed with twice its
bulk of anhydrous Na2CO3 or preferably with fusion mixture (an equimolar mixture of together
Na2CO3 and K2CO3; this has a lower mp than Na2CO3) in a reducing flame. The initial reaction
consists of the formation of the carbonates of the cations present and the alkali salts of anions.
The alkali salts are largely adsorbed by the porous charcoal, and the carbonates are, for the most
part, decomposed into oxides and CO2. The oxides of the metal may further decompose, or be
reduced to the metals, or they may remain unchanged. The final products of the reaction are,
therefore, either the metals alone, metals and their oxides, or oxides. The oxides of the noble
metals (Ag and Au) are decomposed without the aid of the charcoal, to the metal, which is often
obtained as a globule and oxygen. The oxides of Pb, Cu, Bi, Sb, Sn, Fe, Ni and Co are reduced
either to a fused metallic globule (lead, bismuth, tin and antimony) or to a sintered mass (copper)
or to a glistening metallic fragments (iron, nickel and cobalt). The oxides of cadmium, arsenic

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and zinc are readily reduced to the metal but these are so volatile that they vapourise and are
carried from the reducing to the oxidizing flame zone, where they are converted into sparingly
volatile oxides. The oxides thus formed are deposited as an incrustation round the cavity of the
charcoal block, zinc yields an incrustation which is yellow while hot and white when cold.

Incrustation of cadmium is brown and is moderately volatile, that of arsenic is white and is
accompanied by a garlic odour due to the volatilization of the arsenic. A characteristic
incrustation accompanies the globules of lead, bismuth and antimony.

The oxides of Al, Ca, Sr, Ba and Mg are not reduced by charcoal; they are infusible and glow
brightly when strongly heated. If the white residue or white incrustation left on a charcoal block
is treated with cobalt nitrate solution and again heated, a bright blue colour, which probably
consists of either a compound or a solid solution of cobalt (II) and aluminium oxide (Thenard’s
blue) indicates the presence of aluminium; a pale green colour, probably of similar composition
(Rinmann’s green), is indicative of zinc oxide; and pale zinc mass is formed when magnesium
oxide is present.

Principle of Charcoal Cavity Test

ZnSO 4 + Na 2 CO3 
→ ZnCO3 + Na 2SO 4
(1:3)

ZnCO3 
→ ZnO + CO 2
ZnO + C 
→ Zn + CO

Colour of bead, residue or incrustation will be used to diagnose the metal.

Colour of Bead Colour of Residue or Incrustation Inference
White bright bead which Incrustation does not form Ag +
does not impart mark on
paper on rubbing
White brittle bead White Incrustation Sb3+
Red bead Reddish brown incrustation Cu 2+
Brittle bead Violet Red when hot and yellow Bi 3+
incrustation when cold
White soft ball which mark Brown incrustation when hot and yellow Pb 2 +
on paper when cold
Bead does not from Yellow incrustation when hot while white Zn 2+
when cold
–– Garlic smell like fumes As3+
–– Yellow incrustation on hot while on cold Sn
dirty white incrustation
–– Reddish brown incrustation Cd 2 +
–– Incrustation does not form but black Fe, CO, Ni, Mn
residue is left in the cavity

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Cobalt Nitrate Bead Test: This is also like charcoal cavity test. This test is performed in
oxidizing flame rather than in reducing flame.

The oxides of Al, Ca, Sr, Ba and Mg are not reduced by charcoal; they are infusible and glow
brightly when strongly heated. If the white residue or white incrustation left on a charcoal block
is treated with a drop of cobalt nitrate solution and again heated, a bright blue colour, which
probably consists of either a compound or a solid solution of cobalt II and aluminium oxide
indicates the presence of aluminium. Other colours are listed in Table.

Principle Colour of Residue Inference

Green Zn2+
ZnSO 4 + Na 2 CO3 
→ ZnCO3 + Na 2SO 4
Blue Al3+
ZnCO3 
→ ZnO + CO 2 Light Pink Mg2+
2Co(NO3 )2 
→ 2CoO + 4NO 2 + O 2 Bluish Pink PO −4 , AsO34− , silicates borates

CoO + ZnO 
→ CoZnO 2
Cobalt zincate
(green residue)
C
1. Inner blue cone ADB consisting largely of Upper oxidizing zone
unburnt gas.
D
2. A luminous tip at D (this is only visible Hottest portion of the flame ( 1 / 3 of L)
Upper reducing zone
when the air holes are slightly closed). Lower oxidizing zone
Lower reducing zone
Lower temperature zone
A B
3. An outer mantle ACBD in which complete
combustion of gas occurs.

(Luminous flame is obtained when air holes are

completely closed)

(Non luminous flame is obtained when air holes are completely opened)

Borax Bead Test: A point wire is used for borax bead test. The free end of the point wire is
coiled into small loop through which ordinary match will barely pass. The loop is heated in
Bunsen flame until it is red hot and then quickly dipped into powdered borax Na2B4O7⋅10H2O.
The adhering solid is held in the hottest part of the flame, the salt swells up as it loses its water of
crystallization and shrinks upon the loop forming a colourless, transparent, glass like bead
consisting of a mixture of sodium metaborate and boric anhydride.

Na 2 B4 O7 
→ 2NaBO 2 + B2 O3

the head is moistened and dipped into the finely powdered substance so that a minute amount of
it adheres to the bead. It is important to employ a minute amount of substance as otherwise the
bead will become dark and opaque in the subsequent heating. The head and adhering substance
are first heated in the lower reducing flame, allowed to cool and the colour is observed again.

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Characteristic coloured beads are produced with salts of Cu, Fe, Cr, Mn, Co and Ni. Carry out
borax bead test with salts of these metals and compare results with those given below:

The coloured borax beads are due to the formation of colour borates; in those cases when
different coloured beads are obtained in the oxidizing and the reducing flames, borates
corresponding to varying stages of oxidation of the metal are produced. Thus, with the copper
salts in the oxidizing flame, one has.

Na 2 B4 O7 
→ 2NaBO 2 + B2 O3
CuO + B2O3 
→ Cu(BO)2
Copper(II)metaborate

The reaction
CuO + NaBO 2 
→ NaCuBO3
Orthoborate

probably also occurs. In the reducing flame (i.e. in the presence of carbon), two reactions may
take place.

1. The coloured copper (II) is reducing to colourless copper (I) metaborate.

2Cu(BO 2 )2 + 2NaBO 2 + C 
→ 2CuBO 2 + Na 2 B4 O7 + CO ↑

2. The copper (II) borate is reduced to metallic copper, that the bead appears red and
opaque.

2Cu(BO 2 )2 + 4NaBO 2 + 2C 
→ 2Cu + 2Na 2 B4 O 7 + 2CO ↑

With iron salts Fe(BO2)2 and Fe(BO2)3 are formed in reducing and oxidizing flames
respectively.

Colours of Borax Beads

Oxidizing Flame Reducing Flame
Metal
Hot Cold Hot Cold
Opaque Red
Green Blue Colourless Copper
brown
Yellowish
Yellow Green Green Iron
green
Yellow Green Green Green Chromium
Violet Amethyst Colourless Colourless Manganese
Blue Blue Blue Blue Cobalt
Violet Reddish Brown Green Grey Nickel
Yellow Colourless Brown Brown Molybdenum
Rose Violet Rose Violet Red Violet Gold

[Type text]
[Type text]

Yellow Colourless Yellow Yellowish brown Tungeston

Yellow Pale Yellow Green Bottle green Uranium
Yellow Greenish Yellow Brownish Green Vanadium
Yellow Colourless Grey Pale violet Titanium
Orange Red Colourless Colourless Colourless Cerium

Group I: Radicals

Pb2+, Hg 22+ , Ag+

Group Reagent – dil. HCl
Precipitates as – Chlorides

Since PbCl2 is not completely precipitated in group I as chloride because of its solubility in hot
water is 33.4g/litre of solvent. So Pb2+ has been placed in both the groups.

Reactions of Pb2+ ion

1. Dilute HCl: A white ppt. in cold solution of the acid is not too dilute.

Pb 2 + + 2Cl− PbCl2 ↓
White
Soluble in hot water (33.4g/L at 100°C, 9.9 g/L at 20°C)

It is also soluble in conc. HCl or conc. KCl when the tetrachloroplumbate (II) ion is
formed.

PbCl 2 ↓ +2Cl− 
→[PbCl 4 ]2 −

If the ppt is washed and dil. NH3 is added, no visible change occurs (difference from
Hg22+ or Ag+ ions), through a ppt. exchange reaction takes place and lead hydroxide is
formed.

2. H2S (gas or saturated aqueous solution) in neutral or dilute acid medium, black ppt. of
lead sulphide is obtained

Pb 2 + + H 2S 
→ PbS ↓ +2H +

When H2S gas is introduced into a mixture which contains a ppt. of white lead chloride,
the latter is converted into lead sulphide (black) in a precipitate exchange reaction.

→ PbS ↓ +2H + + 2Cl −

PbCl 2 ↓ + H 2S 

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If the test is carried out in the presence of larger amounts of Cl– (KCl saturated), initially
a red ppt. of lead sulphochloride is formed when introducing H2S↑.

2Pb 2+ + H 2S + 2Cl− 
→ Pb 2SCl 2 ↓ +2H +

This, however, decomposes on dilution or on further addition of H2S and a black ppt. of
PbS is formed.

Pb 2SCl 2 ↓ 
→ PbS ↓ + PbCl 2 ↓
→ 2PbS + 2Cl − + 2H +
PbSCl 2 + H 2S 

3. NH3 solution: White ppt of Pb(OH)2 is obtained

Pb 2 + + 2NH 3 + 2H 2 O 
→ Pb(OH) 2 ↓ +2H +

Pb(OH)2 is insoluble in NH3 solution excess.

4. NaOH: White ppt. of Pb(OH)2

Pb 2 + + 2OH − 
→ Pb(OH) 2 ↓

The ppt. is dissolved in excess of NaOH, when tetrahydroxoplumbate (II) ions are
formed.

Pb(OH)2 ↓ + 2OH − 
→[Pb(OH)4 ]2−

thus, lead hydroxide has an amphoteric character.

5. H2SO4 (or soluble sulphate) white ppt. of PbSO4 is obtained

Pb 2 + + SO 24− 
→ PbSO 4 ↓
(white)

6. K2CrO4: Potassium chromate in neutral, acetic acid or ammonium solution yellow ppt of
lead chromate is obtained.

Pb 2 + + CrO 42− 
→ PbCrO 4 ↓ (yellow)

7. KI: yellow ppt of lead iodide is formed.

Pb 2 + + 2I − 
→ PbI 2 ↓
yellow ppt.

The ppt. is moderately soluble in boiling water to yield a colourless solution, from which
it separates as golden yellow plates on cooling.

[Type text]
[Type text]

An excess of a more conc.(6M) solution of the reagent dissolves the ppt. and
tetraiodoplumbate (II) ions are formed

PbI 2 ↓ +2I− [PbI 4 ]2 −

The reaction is reversible, on cooling ppt. reappears.

Reactions of Hg22+ ions

1. Dilute Hydrochloric acid or Soluble Chlorides: White precipitate of Hg2Cl2

(calomel)_ is obtained.

Hg 22 + + 2Cl − 
→ Hg Cl ↓
2 2
(white)
Insoluble in dilute acids

Ammonia solution converts the ppt. into a mixture of mercury (II) amidochloride and
mercury metal, which are both insoluble.

→ Hg ↓+ Hg(NH 2 )Cl ↓+ NH 4+ + Cl −
Hg 2Cl 2 + 2NH 3 
Black White

Shiny back
Mercury (II) chloride dissolves in aqua-regia, forming undissociated but soluble mercury
(II) chloride.

2. Hydrogen Sulphide (Gas or Saturated Aqueous Solution): In neutral or dilute

acid medium black precipitate is obtained which is a mixture of Hg(II) sulphide and
mercury metal.

Hg 22 + + H 2S 
→ Hg ↓+ HgS ↓+ 2H +
Black Black

Sodium sulphide (colourless) dissolves the mercury (II) sulphide (but leaves mercury
metal) and a disulphomercurate (II) complex is formed.

HgS ↓ +S2 − 
→[HgS2 ]2 −

After removing the mercury metal by filtration black HgS can again be precipitated by
acidification with dilute mineral acid.

[HgS2 ]2 − + 2H + 
→ HgS ↓+ H 2S ↑
Black

Sodium disulphate (yellow) dissolves both mercury and mercury (II) sulphide.

HgS ↓ + Hg ↓ +3SO 24− 

→ 2[HgS2 ]2 − + S32 −

[Type text]
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Aqua-regia dissolves the precipitate, yielding undissociated mercury (II) chloride and
sulphur.

12HCl + 4HNO3 + 3Hg ↓ 

→ 6HgCl2 + 3S ↓+ 4NO ↑ +8H 2 O
White

When heated with aqua-regia, sulphur is oxidized to H2SO4 and the solution becomes
clear.

→ SO 24 − + 8H + + 6Cl − + 2NO ↑
S ↓ +6HCl + 2HNO3 

3. Ammonia Solution: Black ppt. which is a mixture of Hg metal and basic mercury (I)
amidonitrate (white ppt.)

NH2
2+ −
2Hg + NO + 4NH3 + H 2O 
2 3 → HgO.Hg ↓ + 2Hg ↓+ 3NH +4
Black
NO 3
white

This reaction can be used to differentiate between Hg 22+ and Hg2+ ions.

4. Sodium Hydroxide: Black ppt. of mercury (I) oxide.

Hg 2 + + 2OH − 
→ Hg 2 O + H 2 O
Black
Insoluble in excess NaOH.But
soluble in dil. HNO3

When boiling, the colour of the ppt. turns to grey, owing to disproportionation, when
HgO and Hg are formed.

Hg 2O ↓ →
Boil
HgO ↓ + Hg
grey

5. Potassium Chromate: In hot solution a red crystalline ppt. of Hg2CrO4 is obtained.

Hg 22 + + CrO 24 − 
→ Hg 2 CrO 4 ↓
Red Crystalline (in put)

If the test is carried out in cold, a brown amorphous ppt. with an undefined composition is
obtained, when heated the ppt. turns to red crystalline HgCrO4.

Sodium hydroxide turns into black mercury (I) oxide.

Hg 2 CrO 4 ↓+ 2OH − 
→ Hg 2 O+ CrO 42 − + H 2 O
Red Black

6. KI Solution: Added slowly in cold solution, green ppt. of mercury (I) iodide.

[Type text]
[Type text]

Hg +2 + 2I− 
→ Hg 2 I2 ↓
Green

If excess of reagent is added disproportionation takes place, soluble tetraiodomercurate

(II))ions and a black ppt. of finely divided mercury being formed.

Hg 2 I2 ↓+ 2I − 
→[HgI 4 ]2 − + Hg ↓
Green Black

Produces a mercury (II) cyanide solution and black ppt. of Hg metal Is obtained.

Hg 22 + + 2CN − 
→ Hg ↓ +[Hg(CN)2 ]

Hg(I) ions to mercury metal (grayish black ppt)

Hg 22 + + Sn 2 + 
→ 2Hg ↓ + Sn 4 +
Greyish-Black

Hg (II) ions react in a similar way.

[Type text]
[Type text]

Reactions of Silver (I) Ions

1. Dilute Hydrochloric Acid (or Soluble Chlorides): White ppt. of AgCl is obtained.

Ag + + Cl− 
→ AgCl ↓
White

With conc. HCl precipitation does not occur. After decanting the ppt., it can be dissolved
in conc. HCl, when dichloroargentate complex is formed.

AgCl ↓ + Cl − [AgCl 2 ]−
On dilution with H2O, the equilibrium shifts back to the left and the ppt. reappears.
Dilute NH3 solution dissolves the ppt., to form the diamine silver ion.
AgCl ↓ +2NH 3 [Ag(NH 3 ) 2 ]− + Cl −
Dilute HNO3 or HCl neutralizes the excess of NH3, and the ppt. reappears because the
equilibrium is shifted back towards the left.

KCN dissolves the ppt. with formation of the dicyanoargentate complex.

AgCl + 2CN − 
→[Ag(CN) 2 ]− + Cl−

Na2S2O3 dissolved the ppt. with the formation of a dithiosulphatoargentate complex.

AgCl + 2S2 O32 − 

→[Ag(S2 O3 )2 ]3− + Cl−
Sunlight or ultraviolet light decomposes the AgCl precipitates, which turns to grayish or
black owing to the formation of the metal.
hν
2AgCl ↓  → 2Ag ↓ + Cl 2 ↑

2. H2S (Gas or Saturated aqueous Solution): Black ppt. of Ag2S is formed.

2Ag + + H 2S 
→ Ag 2S ↓+ 2H +
Black

Hot conc.HNO3 decomposes the Ag2S, and sulphur remains in the form of a white ppt.

→ 3S ↓+ 2NO ↑ +6Ag + + 6NO3− + 4H 2 O

3Ag 2S ↓ +8HNO3 
white

If the mixture is heated with conc. HNO3 for a considerable time, sulphur is oxidized to
SO 24 − and the precipitate disappears.

3. Ammonia Solution: Brown ppt. of Ag2O is obtained.

2Ag + + 2NH 3 + H 2 O 
→ Ag 2 O ↓+ 2NH 4+
Brown

[Type text]
[Type text]

The reaction reaches an equilibrium and therefore precipitation is incomplete at any stage
(if the NH4NO3 is present in the original solution or the solution is strongly acidic, no
precipitation occurs). The ppt dissolves in excess of NH3 solution, and diammine silver
(I) complex is formed.

→ 2[Ag(NH 3 ) 2 ]+ + 2OH −
Ag 2 O ↓ +4NH 3 + H 2 O 

4. Sodium Hydroxide: Brown ppt. of AgO is obtained.

2Ag + + 2OH − 
→ Ag 2 O ↓+ H 2 O
Brown

A well washed suspension of the ppt. shows a slight alkaline reaction owing to the
hydrolysis reaction.

Ag 2 O + H 2 O 2Ag(OH)2 ↓ 2Ag + + 2OH −

The ppt. is insoluble in excess of NaOH. The ppt. dissolves in NH3 solution and in HNO3.

Ag 2 O ↓ + H 2 O 2Ag(OH)2 ↓ 2Ag + + 2OH −

The ppt. is insoluble in excess of NaOH. The ppt. dissolves in NH3 solution and in HNO3.

→ 2[Ag(NH 3 ) 2 ]+ + 2OH −
Ag 2 O ↓ +4NH 3 + H 2 O 
Ag 2 O ↓ +2H + 
→ 2Ag + + H 2 O

5. Potassium Iodide: Yellow ppt.. of AgI is obtained.

Ag + + I − 
→ AgI ↓

The ppt. is insoluble in dil. or conc. NH3 solution, but dissolves readily in KCN and in
Na2S2O3.

AgI ↓ +2CN − 
→[Ag(CN)2 ]− + I −
AgI ↓ +2S2 O32 − 
→[Ag(S2 O3 ) 2 ]3− + I −

6. Potassium Chromate: Red ppt. of Ag2CrO4 is obtained.

2Ag + + CrO 24 − 
→ Ag 2 CrO 4 ↓
Re d
The ppt. is soluble in diluted HNO3 acid and NH3 solution.

Ag 2 CrO 4 ↓ +2H + 2Ag + + Cr2 O72− + H 2 O

Orange

→ 2[Ag(NH 3 )2 ]+ + CrO 42 −
Ag 2 CrO 4 ↓ +4NH 3 

[Type text]
[Type text]

7. Potassium Cyanide: When added drop wise to a neutral solution of AgNO3; white ppt.
of AgCN is obtained.
Ag + + CN − 
→ AgCN ↓
White
When KCN is added in excess, ppt. dissolves owing to formation of dicyanoargentate (I)
ion.
AgCN ↓ + CN −  →[Ag(CN) 2 ]−

Second Group of Cations

Group Reagent H2S in presence of dil. HCl
IIA Cu2+, Pb2+, Bi3+, Cd2+, Hg-2+
IIB As3+, As5+, Sb3+, Sb5+, Sn2+, Sn4+
Precipitates as Sulphides
Black PbS, CuS, HgS
Yellow CdS, As2S3, As2S5, SnS2
Orange Sb2S3, Sb2S5
Brown Bi2S3, SnS

Cations of IInd group are traditionally divided into two sub-groups the copper sub group and
arsenic group. The basis of this division is the solubility of the precipitates in
ammoniumpolysulphide. White sulphides of the copper sub-groups are insoluble in this reagent,
those of the arsenic sub-group are soluble in this reagent with the formation of thiosalts.

Copper Sub-Groups: The copper sub-group consists of Hg(II), Pb(II), Bi(III), Cu(II) and
Cd(II). Although the bulk of the lead ions are precipitated with dil. HCl together with other ions
of the group –I, this precipitation is rather incomplete owing to relatively high solubility of
PbCl2. In the course of systematic analysis therefore, lead ions will still be present when the
precipitation of the second group of the cations is the task.

The chlorides, nitrates and sulphates of the cations of the copper sub-group are quite soluble in
water. The sulphides,. Hydroxides and carbonates are insoluble. Some of the ions of copper sub-
group (Hg2+, Cu2+ and Cd2+) tend to form complexes (NH3, RCOO–, etc.)

Arsenic Sub-Group: The arsenic sub-group consists of As3+, As5+, Sb3+, Sb5+ and Sn4+ ions.
These ions both acids and bases. Thus As(III) oxide can be dissolved in HCl (6M) and As(III)
cations are formed.

→ 2As 3+ + 6Cl − + 3H 2 O
As 2 O3 + 6HCl 
(Basic)

The same time As2O3 dissolves in NaOH (2M) forming arsenite anions.

As 2 O3 + 6OH − 
→ 2AsO33− + 3H 2 O
The dissolution of sulphides in ammonium polysulphide can be regarded as the formation of
thiosalts from anhydrous thioacids. Thus the dissolution of As2S3 (anhydrous thioacid) in
ammonium sulphide (anhydrous thiobase) yield the formation of ammonium and thioaresenite
ions (a thiosalt)

[Type text]
[Type text]

As 2S3 ↓ +3S2− 
→ 2AsS33−
All the sulphides of the arsenic sub-group dissolve in ammonia sulphide except tin (II) sulphide
(SnS); to dissolve latter, ammonium polysulphide is needed, which acts partly as an oxidizing
agent, thiostannate ions being formed:

SnS ↓ +S22 −  → SnS32−

Note that while tin is bivalent in the tin (II) sulphide ppt., it is tetravalent in the thiostannate ion.

As3+, Sb3+ and Sn2+ ions can be oxidized to As5+, Sb5+ and Sn4+ ions respectively. On the other
hand, the latter three can be reduced by proper reducing agents. The oxidation reduction
potentials of the arsenic (V), arsenic (III) and Sb (V) – Sb(III) systems vary with pH, therefore
the oxidation or reduction of the relevant ions can be assisted by choosing an appropriate pH of
the reaction.

Reactions of Mercury (II) Ions: (HgNO3)

1. Hydrogen Sulphide (Gas or Saturated Aqueous Solutions): In the presence of

dilute (1M) HCl, initially a white ppt of mercury (II) chlorosulphide forms, which reacts
with further amounts of H2S and finally a black ppt. of HgS is formed.

3Hg 2+ + 2Cl − 
→ Hg 3S2 Cl 2 ↓+ 4H +
White

→ HgS ↓+ 2H + + 2Cl−
Hg 3S2 Cl ↓ + H 2S 
Black

HgS is one of the least soluble precipitates known (Ksp = 4 × 10–54).

HgS is insoluble in water, hot dilute HNO3, alkali hydroxides or coloulress ammonium
sulphide.
Sodium sulphides (2M) dissolves the precipitate when the disulphomercurate (II)
complex ion is formed:

HgS ↓+ S−2 
→[HgS2 ]2−
Black

Adding NH4Cl to the solution, HgS precipitates again aqua-regia dissolves the precipitate.

3HgS ↓ +6HCl + 2HNO3 

→ 3HgCl2 + 3S ↓ +2NO ↑ +4H 2 O

HgCl2 is practically undissociated under these circumstances. Sulphur remains as a white

ppt., which however dissolves readily if the solution is heated, to form H2SO4.

→ SO 24 − + 2H + + 2NO ↑
2HNO3 + S ↓ 
White

2. Ammonia Solution: White precipitate with a mixed composition is obtained,

essentially it consists of HgO and mercuryamidonitrate.

[Type text]
[Type text]

2Hg 2+ + NO3− + 4NH 3 + H 2 O 

→ HgO ⋅ Hg(NH 2 )NO3 ↓+ 3NH 4+
White

The salt like most of the mercury compounds, sublimes at atmospheric pressure.

3. Sodium Hydroxide: When added in small amounts, brownish-red precipitate with

varying composition is obtained; if added in stoichiometric amounts, the precipitate turns
to yellow when HgO is formed.

Hg 2+ + 2OH − 
→ HgO ↓+ H 2O
Yellow
Insoluble in excess NaOH soluble in acids.

4. Potassium Iodide: When added slowly to the solution, red precipitate of HgI2 is
obtained.

Hg 2 + + 2I − 
→ HgI 2 (Re d)

The precipitate dissolves in excess reagent, when colourless tetraiodomercurate (II) ions
are formed

HgI2 ↓+ 2I − 
→[HgI4 ]2 −
Red

An alkaline solution of K2[HgI4] serves as a selective and sensitive reagent for NH +4 ion
(Nessler’s Reagent).

5. Potassium Cyanide: Does not cause any change in dilute solutions (difference from
other ions of the copper sub-group).

6. Tin (II) Chloride: When added in moderate amounts, white, silky precipitate of Hg2Cl2
(calomel)

2Hg 2+ + Sn 2 + + 2Cl − 
→ Hg 2 Cl2 ↓ +Sn 4 +

This reaction is widely used to remove the excess of Sn (II) ions, used for prior reduction,
in oxidation-reduction titrations.

If more reagent is added, mercury (I) chloride is further reduced and black precipitate of
mercury is formed.

HgCl2 ↓ +Sn 2 + 
→ 2Hg ↓ +Sn 4+ + 2Cl −

7. Cobalt (II) Thiocyanate Test: To the test solution add an equal volume of Co(SCN)2
(about 10% freshly prepared), and stirr the wall of the vessel with a glass rod. A deep
blue crystalline precipitate of cobalt tetrathiocyanatomercurate (II) is formed.

Hg 2 + + Co 2 + + 4SCN − 
→ Co[Hg(SCN)4 ] ↓
Deep blue crystalline

[Type text]
[Type text]

Reactions of Copper (II) Ions

1. Hydrogen Sulphide (Gas or Saturated aqueous solution): Black precipitate of

CuS is formed.

Cu 2 + + H 2S 
→ CuS ↓ +2H +
–44
Ksp (CuS) = 10

The solution must be acidic (1M in HCl) in order to obtain a crystalline, easily filterable
precipitate. In the absence of acid, or in very slightly acid solutions a colloidal, brownish
black precipitate or colouration is obtained. By adding some acid and boiling, coagulation
can be achieved.

The precipitate is insoluble in boiling dilute (1M) H2SO4 (distinction from Cd), in sodium
hyodrixide, Na2S and (NH4)2S. It is only very slightly soluble in polysulphides.

Hot conc. HNO3 dissolves the CuS, leaving behind sulphur as a white precipitate.

→ 3Cu 2 + + 6NO3− + 3S ↓+ 2NO ↑ +4H 2 O

3CuS ↓ +8HNO3 
White
When boiled for longer, sulphur is oxidized to H2SO4 and a clear solution is obtained.

→ SO 24− + 2NO ↑ +2H +

S + 2HNO3 

KCN dissolves the ppt., when colourless tetra cyano cuprate (I) ions and disulphide ions
are formed.

2CuS ↓ +8CN − 
→ 2[Cu(CN)4 ]3− + S22−

This is an oxidation and reduction reaction (cooper is reduced and sulphur is oxidized)
coupled with a formation of a complex.

When exposed to air, in the moist state, CuS tends to oxidize to CuSO4.

CuS + 2O 2 
→ CuSO 4

and therefore becomes water soluble. A considerable amount of heat is liberated during
this process. A filter paper with CuS precipitate on it should never be thrown into a waste
container, with paper or other inflammable substances in it. Instead the precipitate should
be washed away first with running water.

2. Ammonia Solution: When added slowly blue precipitate of basic copper sulphate is
formed.

2Cu 2+ + SO 24 − + 2NH3 + 2H 2 O 
→ Cu(OH)2 CuSO 4 ↓+ 2NH +4
Blue

[Type text]
[Type text]

Which is soluble in excess reagent, when a deep blue colouration is obtained owing to the
formation of tetrammine copper (II) complex ion.

→ 2[Cu(NH3 ) 4 ]2+ + SO24− + 2OH −

Cu(OH) 2 ⋅ CuSO4 ↓ +8NH3 
Blue

If the solution contains NH +4 salt (or it was highly acidic larger amounts of NH3 were
used up for its neutralization) precipitation does not occur at all, but the blue colour
appears right away.

The reaction is characteristic for Cu2+ ions in the absence of Nickel.

3. NaOH: In cold solution blue precipitate of Cu(OH)2 is formed.

Cu 2+ + 2OH − 
→ Cu(OH) 2 ↓
Blue

The precipitate is insoluble in excess reagent. When heated, the precipitate is converted to
black CuO by dehydration.

Cu(OH)2 ↓ 
→ CuO ↓+ H 2O
Blue Black

In the presence of a solution of tartaric acid or of nitric acid, copper (II) hydroxide is not
precipitated by solutions of caustic alkalis but the solution is coloured, an intense blue . If
the alkaline solution is treated with certain reducing agents, such as hydroxyl amine,
hydrazine, glucose and acetaldehyde, yellow copper (I) hydroxide precipitated from the
warm solution. It is converted into red copper (I) oxide (Cu2O) on boiling. The alkaline
solution of Cu(II) salt containing tartaric acid is usually known as Fehling solution; it
contains the complex ion [Cu(C4H2O6)2]2–.

4. Potassium Iodide: Precipitates copper (I) iodide, which is white, but the solution is
intensely brown because of formation of triiodide ions.

2Cu 2+ + 5I− 
→ 2CuI ↓ + I3−

Adding an excess of Na2S2O3 to the solution triioide ions are reduced to colourless iodide
ions and the white colour of ppt. becomes visible. These reactions are used in quantitative
analysis for the iodometric determination of copper.

5. KCN: When added sparingly forms first a yellow precipitate of copper (II) cyanide.

Cu 2+ + 2CN − 
→ Cu(CN) 2 ↓
Yellow

The precipitate quickly decomposes into copper (II) cyanide and cyanogens (highly
poisonous gas) is liberated.

2Cu(CN) 2 ↓ 
→ 2CuCN ↓ + (CN)2 ↑

[Type text]
[Type text]

Excess of KCN dissolves the precipitate and the colourless tetracyanocuprate (I) complex
is formed.

CuCN + 3CN − 
→ [Cu(CN) 4 ]3−
Colourless

The complex is so stable that H2S cannot precipitate copper I sulphide from this solution
(distinction from Cd).

6. Potassium Thiocyanate (KSCN): Black precipitate of copper (II) thiocyanate is

obtained.
Cu 2+ + 2SCN − 
→ Cu(SCN)2 ↓
Colourless
The precipitate decomposes slowly to form white copper (I) thiocyanate and thocyanogen
is obtained.

2Cu(SCN) 2 ↓ 
→ 2CuSCN ↓+ (SCN)2 ↑
White
Thiocyanogen rapidly decomposes in aqueous solution.

Reactions of Bi3+ Ions

1. With H2S (Gas or saturated aqueous solution): Blackish brown precipitate of

Bi2S3 is obtained.
2Bi3+ + 3H 2S 
→ Bi 2S3 ↓+ 6H +
Black
Insoluble in cold. Dilute acid in (NH4)2S

Boiling conc. HCl dissolves the precipitate when H2S gas is evolved.

→ 2Bi3+ + 6Cl − + 3H 2S ↑
Bi 2S3 ↓ +6HCl 

Hot dil. HNO3 dissolves Bi2S3, leaving behind sulphur in the form of a white precipitate.

Bi 2S3 ↓ +8H + + 2NO3− 

→ 2Bi3+ + 3S ↓ +2NO ↑ +4H 2 O

2. With NH3 Solution: White basic salt of variable composition. The approximate
chemical reaction is

Bi 2S3 ↓ + NO3− + 2NH 3 + 2H 2O 

→ Bi(OH) 2 NO3 ↓ + 2NH +4
white
Bi(OH)2NO3 does not dissolve in excess NH3 (distinction from Cu and Cd)

3. With NaOH: White precipitate of Bi(OH)3 is obtained.

Bi 3+ + 3OH − 
→ Bi(OH)3 ↓
White
Slightly soluble in excess NaOH
Soluble in acid

[Type text]
[Type text]

Bi(OH)3 ↓ +3H + 
→ Bi3+ + 3H 2O

When boiled precipitate loses water and turns yellowish white

Bi(OH)3 ↓ 
→ BiO ⋅ OH ↓+ H 2O
Yellowish white

Both the hydrated and the dehydrated precipitate can be oxidised by 4-6 drops of conc.
H2O2 when yellowish brown bismuthate ions are formed.
→ BiO3− + H + + H 2 O
BiO ⋅ OH ↓ + H 2 O 2 

4. Potassium Iodide: When added drop-wise black precipitate of BiI3 is obtained.

Bi 3+ + 3I− 
→ BiI3 ↓
Black
The precipitate dissolves readily in excess reagent when orange coloured
tetraiodobismuthate ions are formed.
BiI3 + I − [BiI 4 ]−
When diluted with H2O, the above reaction is reversed and black precipitates of BiI3
reappear.

Reactions of Cadmium (II) Ions [Cd2+]

1. Reaction with H2S (Gas or saturated aqueous solution): Yellow precipitate of CdS is
obtained.
Cd 2+ + H 2S CdS ↓+ 2H +
Yellow

The reaction is reversible, if the conc. of strong acid in the solution is above 0.5M,
precipitation is incomplete. Conc. acids dissolve the precipitate for the same reason. The
ppt is insoluble in KCN: this distinguishes Cd2+ ions from Cu2+.

2. Ammonia Solution: When added drop wise white precipitate of Cd(OH)2 is formed.

Cd 2+ + 2NH 3 + 2H 2 O Cd(OH) 2 ↓+ 2NH 4+

white

The precipitate dissolves in acid when the equilibrium shifts towards the left.

An excess of NH3 dissolves the precipitate, when tetraammine cadmiate (II) ions are
formed.

→ [Cd(NH 3 )4 ]2+ + 2OH −

Cd(OH) 2 ↓+ 4NH 3 
White Colourless

3. NaOH: White precipitate of Cd(OH)2

[Type text]
[Type text]

Cd 2 + + 2OH − 
→ Cd(OH) 2 ↓
White
insoluble in excess NaOH

White precipitate dissolves in dilute acids when equilibrium shifts in the backward
direction.

4. KCN: White precipitate of Cd(CN)2 is obtained when KCN is added slowly to Cd2+ ions.

Cd 2+ + 2CN − 
→ Cd(CN)2 ↓
white

An excess of reagent (KCN) dissolves the precipitate with the formation of

tetracyanocadmiate ions.

Cd(CN)2 ↓ +2CN − 
→[Cd(CN) 4 ]2 −

The colourless complex is not very stable; when H2S gas is introduced, CdS is
precipitated

[Cd(CN) 4 ]2 − + H 2S 
→ CdS ↓+ 2H + + 4CN −
yellow

(Difference from copper)

5. KI: KI forms no precipitate (distinction from copper). Heating the precipitate with H2O,
BiI3 turns orange owing to the formation of bismuthyl iodide.

→ BiOI ↓ + 2H + + 2I −
BiI3 ↓ + H 2 O 
Orange
Bismuthyl iodide

6. Sodium Tetrahydroxostannate (II) (0.125M freshly prepared): In cold

solution, Bi3+ ions are reduced to Bismuth metal which separates in the form of a black
precipitate. First the sodium hydroxide present in the reagent reacts with Bi3+ ions,
Bi(OH)3 is then reduced by tetrahydroxostannate (II) ions to form Bi metal and
hexahydroxostannate is formed.

Bi 3+ + 3OH − 
→ Bi(OH)3 ↓
Black

2Bi(OH)3 ↓ +3[Sn(OH)4 ]2− 

→ 2Bi ↓ +3[Sn(OH)6 ]2 −

Reactions of Sn2+ Ions

1. H2S (Gas or Saturated Solution): Brown precipitate of SnS, from mildy acidic
solutions. The precipitate is soluble in conc. HCl. It is also soluble in yellow (NH4)2Sn
(but not in colourless (NH4)2S) to form a thiostannate treatment of the solution of
ammonium thiostannate with an acid yields a yellow precipitate of SnS2.

Sn 2+ + H 2S 
→ SnS ↓ +2H +

[Type text]
[Type text]

SnS + S22− 
→ SnS32−
SnS32 − + 2H + 
→ SnS2 ↓ + H 2S ↑

2. NaOH Solution: White precipitate of Sn(OH)2, soluble in excess alkali.

Sn 2 + + 2OH − Sn(OH)2 ↓
White

Sn(OH) 2 + 2OH − [Sn(OH) 4 ]2 −

With NH3 solution, white Sn(OH)2 is precipitated which cannot be dissolved in excess
NH3.

3. HgCl2 Solution: White precipitate of Hg2Cl2 and finally Hg metal (black)

HgCl2 + Sn 2+ 
→ Sn 4+ + Hg 2Cl 2 ↓
White

Hg 2Cl 2 + Sn 2+ 
→ Sn 4+ + 2Hg ↓+ 2Cl −
Black

Reactions of Sn4+ Ions

1. Hydrogen Sulphide: Yellow precipitate of Sn(IV) sulphide SnS2 from dil. Acid
solution. The precipitate is soluble in conc. HCl in solution of alkali hydroxide and also in
(NH4)S and (NH4)2Sn. Yellow SnS2 is precipitate upon acidification.

Sn 4+ + 2H 2S 
→ SnS2 ↓ +4H +
SnS2 ↓ +S2− 
→ SnS32−
SnS2 ↓ +2S22 − 
→ SnS32 − + S32 −
SnS32− + 2H + 
→ SnS2 ↓ + H 2S ↑

2 NaOH: NaOH solution → gelatinous precipitation (white) of Sn(OH)4 soluble in excess

of the precipitant forming hexahydroxostannate (VI).

Sn 4 + + 4OH − 
→ Sn(OH)4 ↓
Sn(OH) 4 ↓ +2OH − [Sn(OH)6 ]2−

3. With HgCl2: No precipitate (difference from Sn(II))

4. Metallic Iron: Reduces Sn4+ ions to Sn2+

Sn 4 + + Fe 
→ Fe 2+ + Sn 2 +

Third Group of Cations: Fe2+, Fe3+, Al3+, Cr3+, Cr6+

Group Reagent NH4OH in presence of NH4Cl

[Type text]
[Type text]

Fe(OH)3 Red Brown

Al(OH)3 Gelatinous white
Cr(OH)3 Green (cotton like)

Reactions of Fe3+ ions

1. NH3 Solution: Reddish brown, gelatinous precipitate of Fe(OH)3 insoluble in excess of

the reagent, but soluble in acids.

Fe3+ + 2NH 3 + 3H 2O 
→ Fe(OH)3 ↓+ 3NH +4
(K sp =3.8×10−38 )

Iron (III) hydroxide is converted during strong heating into Fe2O3 the ignited oxide is
soluble with difficulty in dilute acids, but dissolves in vigorous boiling with conc. HCl.

2Fe(OH)3 ↓ 
→ Fe2 O3 + 3H 2 O
Fe 2O3 + 6H + 
→ 2Fe3+ + 3H 2O

2. NaOH Solution: Reddish brown precipitate of Fe(OH)3 in solute in excess of NaOH.

Fe3+ + 3OH − 
→ Fe(OH)3 ↓
Reddish brown

3. Hydrogen Sulphide: In acidic solution reduces Fe3+ to Fe2+ and sulphur is formed as a
milky white precipitate.

2Fe3+ + H 2S 
→ 2Fe3+ + 2H + + S ↓
White

If a neutral solution of FeCl3 is to a freshly prepared, saturated solution of H2S, a bluish

colouration appear first, followed by the precipitation of sulphur. The blue colour is due
to a colloidal solution of sulphur of extremely small particle size.

4. Ammonium Sulphide: A black precipitate, consisting of Fe and sulphur is formed.

2Fe3+ + 2S2 − 
→ 2FeS ↓ +S ↓

In HCl and black FeS precipitate dissolves and white colour of sulphur becomes visible.

FeS ↓ +2H + 
→ H 2S ↑ + Fe 2+

From alkaline solution black iron (II) sulphide is obtained.

2Fe3+ + 3S− 
→ Fe 2S3 ↓

On acidification with HCl, Fe3+ ions are reduced to Fe2+ and sulphur is formed.

Fe 2S3 ↓ +4H + 
→ 2Fe3+ + 2H 2S ↑ +S ↓

[Type text]
[Type text]

The damp iron (II) sulphide precipitate, when exposed to air, is slowly oxidized to brown
Fe(OH)3.

4FeS ↓ +6H 2 O + 3O 2 
→ 4Fe(OH)3 ↓+ 4S
Reddish brown

5. KCN: When added slowly, produces a reddish brown precipitate of Fe(CN)3.

Fe3+ + 3CN − 
→ Fe(CN)3 ↓
Reddish brown

In excess, reagent dissolves giving a yellow solution, when hexacyanoferrate (III) ions are
formed.

Fe(CN)3 + 3CN − 
→[Fe(CN)6 ]3−

6. K4[Fe(CN)6]: Solution intense blue precipitate of Fe(III) hexaycnoferrate (Prussian blue)

4Fe3+ + 3[Fe(CN)6 ]4 − 
→ Fe4 [Fe(CN)6 ]3 ↓
Iron(III)hexcyanoferrate(II)
(Prussian blue)

The precipitate is insoluble in dilute acids, but decomposes in conc. HCl. A large excess
of the reagent dissolves it partly or entirely, when an intense blue solution is obtained.
NaOH turns the precipitate red as Fe2O3 and [Fe(CN)6]4– ions are formed.

Fe 4 [Fe(CN)6 ]3 + 12OH − 
→ 4Fe(OH)3 ↓ +3[Fe(CN)6 ]4 −

7. K3[Fe(CN)6]: A brown colouration is produced due to the formation of an undissociated

complex, Iron (III) hexacyanoferrate (III).

Fe3+ + [Fe(CN)6 ]3− 

→ Fe[Fe(CN)6 ]
Brown

Reactions of Al3+ Ions

1. Ammonia Solution: White gelatinous precipitate of Al(OH)3, slightly soluble in

excess of reagent. The solubility is decreased in presence of NH4+ ions. A small
proportion of the precipitate passes into the solution as colloidal Al(OH)3
(Al(OH)3 solution), the solution is coagulated on boiling the solution or upon the addition
of soluble salts (e.g. NH4Cl) yielding a precipitate of Al(OH)3, known as Al(OH)3 gel. To
ensure complete precipitation NH3 solution is added in slight excess and the mixture is
boiled until the liquid has a slight odour of NH3. When freshly precipitated, it dissolves
readily in strong acids and bases, but after boiling it becomes sparingly soluble.

Al3+ + 3NH3 + 3H 2 O 
→ Al(OH)3 ↓ +3NH +4

2. Sodium Hydroxide: White precipitate of Al(OH)3 is obtained.

[Type text]
[Type text]

Al3+ + 3OH − 
→ Al(OH)3 ↓
White

The precipitate dissolves in excess NaOH forming tetrahydroxoaluminate (III) iron.

Al(OH)3 ↓ + OH − [Al(OH) 4 ]−

The reaction is a reversible one, and any reagent which will reduce the OH– concentration
sufficiently should cause the reaction to proceed from sight to left with the consequently
precipitation of Al(OH)3↓. This may be effected by AlCl3 or by adding the acid; in the
latter case, a large excess of acid causes the precipitated hydroxide to redissolve.

[Al(OH)4 ]− + NH 4+ 
→ Al(OH)3 ↓ + NH 3 ↑ + H 2 O

[Al(OH)4 ]− + H + Al(OH)3 ↓ + H 2 O
+
Al(OH)3 ↓ +3H Al3+ + 3H 2 O

The precipitation of Al(OH)3 by solutions of NaOH and NH3 does not take place in the
presence of tartaric acid, citric acid because of the formation of soluble complex salt.

3. Ammonium Sulphide Solution: A white precipitate Al(OH)3 is obtained.

2Al3+ + 3S2− + 6H 2 O 
→ 2Al(OH)3 ↓ +3H 2S ↑

4. Sodium Acetate Solution: No precipitate is obtained in cold, neutral solution, but on

boiling with excess reagent, a voluminous precipitate of basic aluminium acetate
Al(OH)2(CH3COO) is formed

Al3+ + 3CH 3COO − + 2H 2 O 

→ Al(OH)2 (CH 3COO) ↓+ 2CH 3COOH
White

Reactions of Cr3+ Ions

1. Ammonia Solution: Green-grey or grey-blue gelatinous precipitate of Cr(OH)3,

slightly soluble in excess of reagent in cold forming a violet or pink solution containing
complex hexamine chromium (III) ion; upon boiling the solution, Cr(OH)3 is precipitated.
Hence for complete precipitation of chromium as the hydroxide, it is essential that the
solution be boiling and excess aqueous ammonia solution be avoided.

Cr 3+ + 3NH 3 + 3H 2O 
→ Cr(OH)3 ↓ +3NH +4
→[Cr(NH 3 )6 ]3+ + 3OH −
Cr(OH)3 ↓ +6NH 3 
In the presence of acetate ions and the absence of other trivalent metal ions, Cr(OH)3 is
not precipitated. The precipitation of Cr(OH)3↓ is also prevented by tartarates and
citrates.

[Type text]
[Type text]

2. Sodium Hydroxide Solution: The green-grey or grey blue precipitates of Cr(OH)3 is

obtained.
Cr 3+ + 3OH − 
→ Cr(OH)3 ↓
The reaction is reversible; the addition of the acids, the precipitates readily,
tetrahydroxochromate (III) ions are formed

Cr(OH)3 ↓ + OH − [Cr(OH) 4 ]−
Green

The solution is green. The reaction is reversible on (slight) acidification and also on
boiling Cr(OH)3 precipitates again.

On adding H2O2 to alkaline solution of [Cr(OH)4]–, a yellow solution is obtained, owing

to the oxidation of Cr3+ to CrO42-.

2[Cr(OH) 4 ]− + 2H 2 O 2 + 2OH − 
→ 2CrO 42− + 8H 2O
Yellow

3. Sodium Carbonate Solution: Precipitate of Cr(OH)3 is obtained.

2Cr 3+ + 3CO32− + 3H 2O 
→ 2Cr(OH)3 ↓ +3CO 2 ↑

4. Ammonium Sulphate Solution: Precipitate of Cr(OH)3 is obtained.

2Cr 3+ + 3S2 − + 6H 2 O 
→ 2Cr(OH)3 ↓ +3H 2S ↑
2Cr 3+ + 3S2− + 6H 2O 
→ 2Cr(OH)3 ↓ +3H 2S ↑
3+
5. Chromate Test: Cr ions can be oxidized to CrO42– in several ways
a) Adding an excess of NaOH to a Cr3+ salt followed by a few ml of 10% H2O2. The
excess of H2O2 can be removed by boiling the solution for few minutes.

2[Cr(OH) 4 ]− + 3H 2O 2 + 2OH − 
→ 2CrO 24− + 8H 2 O
Yellow

b) Oxidation can be carried out by Br2/H2O in alkaline solution (i.e. by OBr–).

2Cr 3+ + 3OBr − + 10OH − 

→ 2CrO 24 − + 3Br − + 5H 2 O

c) In acid solution Cr3+ ions can be oxidized by potassium (or ammonium)

peroxodisulphate.
2Cr 3+ + 3S2 O82− + 8H 2 O 
→ 2CrO 24− + 16H + + 6SO 24−

Identification of CrO42–: Having carried out the oxidation with one of the methods
described above, CrO42– ions can be identified by anyone of the following methods.

a) BaCl2 Test: After acidifying the solution with CH3COOH and adding BaCl2, a yellow
precipitate of BaCrO4 is formed.

[Type text]
[Type text]

Ba 2+ + CrO 42− 
→ BaCrO 4 ↓
Yellow

b) Chromium Pentoxide (or Peroxide) Test: On acidifying the solution with dil.
H2SO4 adding 2 to 3 ml of ether or amyl alcohol to the mixture and finally adding some
H2O2, a blue coloration is formed . During the reaction CrO5 is formed.

CrO 24− + 2H + + 2H 2O 2 
→ CrO5 + 3H 2 O
Blue colour

In aqueous solution blue colour fades speedily, because CrO5 decomposes to Cr3+ and
oxygen.
4CrO5 + 12H +  → 4Cr 3+ + 7O 2 ↑ +6H 2 O

Radicals of Group IV
Radicals Co2+, Ni2+, Zn2+, Mn2+
Group Reagent H2S in presence of NH4OH and NH4Cl
Black CoS, NiS
Pink MnS
White ZnS

Group V of Cations

Radicals Ba2+, Sr2+, Ca2+

Group Reagent (NH4)2CO3 in presence of NH4OH
Precipitates as Carbonates
White BaCO3, SrCO3, CaCO3

Reactions of Ba2+ ions

1. Reactions with NH3 Solution: No precipitate OF Ba(OH)2 is obtained because of its

relatively high solubility. If the alkaline solution is exposed to the atmosphere some CO2
gas is absorbed and a turbidity due to BaCO3 is produced.

2. (NH4)2CO3 Solution: White precipitate of BaCO3, soluble in acetic acid and dilute
mineral acids
Ba 2+ + CO32− 
→ BaCO3 ↓
White
The precipitate is slightly soluble in ammonium salts of strong acids.

3. (NH4)2C2O4 Solution: A white precipitate of Ba(C2O4) is obtained slightly soluble in

water (0.09 g L–1) but readily dissolved by hot dilute acetic acid (distinction from Ca2+)
and by mineral acid.

Ba 2 + + C2 O 42− Ba(COO) 2 ↓

[Type text]
[Type text]

4. Dilute Sulphuric Acid: Heavy, white, finely divided precipitate of BaSO4, practically
insoluble in water (2.5 × 10–3 g/L), almost insoluble in dilute acids and in (NH4)2SO4
solution, but appreciably soluble in boiling conc. H2SO4. By precipitation in boiling
solution, or preferably in the presence of NH4OOCCH3, a more readily filterable form is
obtained.

Ba 2+ + SO 42− 
→ BaSO 4 ↓
→ Ba 2+ + 2HSO −4
BaSO 4 + H 2SO 4 

If BaSO4 is boiled with a conc. solution of Na2CO3 partial transformation into the less
soluble BaCO3 occurs in accordance with the equation.

BaSO 4 ↓ +CO32− BaCO3 ↓ +SO 24−

Owing to the reversibly of the reaction, the transformation is incomplete. BaSO4

precipitate may also be dissolved in a hot 5% solution disodium ethylene diammine
tetracetae (Na2EDTA] in the presence of NH3.

5. Saturated CaSO4 Solution: Immediate white precipitate of BaSO4. A similar

phenomenon occurs if saturated SrSO4 is used.

This is because of the three alkaline earth metal sulphates, BaSO4 is the least soluble. In
the solutions of saturated CaSO4 or SrSO4 the concentration of SO42– ion is high enough
to cause precipitation with larger amounts of Ba2+, because the product of ionic
concentrations exceeds the value of the solubility product.

SO 24 − + Ba 2 + BaSO 4 ↓

6. K2CrO4 Solution: A yellow precipitate of BaCrO4, practically insoluble in water

(3.2 mg L–1)

Ba 2+ + CrO 42− 
→ BaCrO 4 ↓
Yellow

The precipitate is insoluble in dilute CH3COOH (distinction from Ca2+ and Sr2+ ions), but
readily soluble in mineral acids.

The addition of acid to K2CrO4 solution causes the yellow colour of the solution to
change to reddish orange, owing to the formation of dichromate.

2CrO 24− + 2H + Cr2 O72− + H 2 O

The solubility products for SrCrO4 and CaCrO4 are much larger than for BaCrO4 and
hence they require a larger CrO42– ion concentration to precipitate them. The addition of
acetic acid to the K2CrO4 solution lowers the CrO42– ion concentration sufficiently to

[Type text]
[Type text]

prevent the precipitation of SrCrO4 and CaCrO4 but it is maintained high enough to
precipitate BaCrO4.

Reactions of Ca2+ Ions

1. Ammonia Solution: No precipitate as Ca(OH)2 is fairly soluble. With an aged

precipitant a turbidity may occur owing to the formation of CaCO3.

2. (NH4)2CO3 Solution: White amorphours precipitate of CaCO3 is obtained.

Ca 2+ + CO32− 
→ CaCO3 ↓

On boiling the precipitate becomes crystalline. The precipitate is soluble in water which
contains excess carbonic acid (freshly prepared soda water) because of the formation of
soluble Ca(HCO3)2.

CaCO3 ↓ + H 2 O + CO 2 Ca 2 + + 2HCO32 −

On boiling, precipitate appears again, because CO2 is removed during the process and the
reaction proceeds towards the left. Ba2+ and Sr2+ ions reacts in a similar way.

The precipitate is soluble in acids, even in CH3COOH.

3. Dilute Sulphuric Acid: White precipitate of CaSO4 is obtained.

Ca 2 + + SO 24− 
→ CaSO 4 ↓

The precipitate is appreciably soluble in water, i.e., more soluble than BaSO4 and SrSO4.
In the presence of C2H5OH solubility is much less.

CaSO 4 + H 2SO 4 2H + + [Ca(SO 4 )2 ]2−

The same complex is formed if a precipitate is heated with a 10% of (NH4)2SO4, leading
to partial dissolution.

4. (NH4)2C2O4 Solution: White precipitate of CaC2O4, immediately from concentrated and

slowly from dilute solution.

Ca 2+ + C2O 42− 
→ Ca(C2 O 4 ) ↓

Precipitation is facilitated by making the solution alkaline by NH3. The precipitate is

practically insoluble in H2O and CH3COH but readily soluble in mineral acids.

5. K2CrO4 Solution: No precipitate from dilute solution nor from conc. solution in the
presence of CH3COOH.

6. K4[Fe(CN)6] Solution: White precipitate of a mixed salt is obtained.

[Type text]
[Type text]

Ca 2+ + 2K + + [Fe(CN)6 ]4− 
→ K 2 Ca[Fe(CN)6 ] ↓

In the presence of NH4Cl the test is more sensitive. In this case potassium is replaced by
ammonium ions in the precipitate. The tests can be used to distinguish calcium from
strontium, barium and Mg2+ ions however interfere.

Sixth Group of Cations: Mg2+, Na+, K+

Group Reagent No common group reagent

Reaction of Mg2+ ions

1. Ammonium Solution: Partial precipitation of white gelatinous Mg(OH)2.

Mg 2+ + 2NH 3 + 2H 2O  → Mg(OH)2 ↓ +2NH 4+

The precipitate is very sparingly soluble in water (1.2 × 10–2g/L) but readily soluble in
ammonium salts.

2. NaOH Solution: White precipitate of Mg(OH)2, insoluble in excess NaOH, but readily
soluble in NH4+ salts.
Mg 2+ + 2OH − 
→ Mg(OH) 2 ↓

3. (NH4)2CO3 Solution: In the absence of NH4+ salts, a white precipitate of basic

magnesium carbonate is obtained.

5Mg 2+ + 6CO32 − + 7H 2 O 
→ 4MgCO3 ⋅ Mg(OH) 2 ⋅ 5H 2 O ↓ +2HCO3−
+
In the presence of NH4 salts, no precipitation occurs, because the equilibrium is shifted
to left
NH +4 + CO32 − NH 3 + HCO3−

4. Na2CO3 Solution: White voluminous precipitate of basic carbonate as above is formed,

insoluble in bases but readily soluble in acids and in solutions of NH4+ ions.

5. Na2HPO4 Solution: White crystalline precipitate of Mg(OH)4PO4⋅6H2O in the presence

of NH4Cl (to prevent precipitation of Mg(OH)2) and NH3 solution).

Mg 2+ + NH 3 + HPO 24−  → MgNH 4 PO 4 ↓

The precipitate is sparingly soluble in water, soluble in CH3COOH and in mineral acids.
The precipitate separates slowly from dilute solutions because of its tendency, to form
supersaturated solutions, this may usually be overcome by cooling and by rubbing the test
tube or beaker beneath the surface of the liquid with a glass rod.

A white flocculants precipitate of MgHPO4 is produced in neutral solutions.

Mg 2+ + HPO 42− 
→ MgHPO 4 ↓

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Solved Problems
Objective

Problem 2: An inorganic salt, when treated with conc. H2SO4 produced oily drops. The
probable salt is
(a) an oxalate (b) a fluoride
(c) a nitrite (d) an iodide

Solution: (b) When a fluoride is heated with conc. H2SO4 corrosive HF gas is evolved.
This gas reacts with silica of glass to form SiF4 and due to corrosive action
of HF, the test tube becomes greasy (oily)
NaF + H2SO4 → NaHSO4 + HF
SiO2 + 4HF → SiF4 + 2H2O

Problem 3: Which of the following gives foul smelling gas with smell of rotten eggs with
dil H2SO4 ?
(a) CO32− (b) SO32−
(c) S2- (d) NO −2

Solution: (c) S2- + H2SO4  → H2S + SO 24−

H2S is foul smelling gas with smell of rotten eggs.

Problem 4: Mn2+ + PbO2 + conc. HNO3 → Pink colour is due to

(a) HMnO4 (b) Pb(NO3)2
(c) Mn(NO3)2 (d) H2MnO4

Solution : (a) HMnO4 permanganic acid is formed (b), (c) and (d) are not formed.

Problem 5: Pure silver jewwellary turns black due to the formation of

(a) Ag2O (b) Ag(OH)
(c) Ag2S (d) AgCl

Solution : (c) is correct Q 4Ag + H2S + O2  → 2AgS + 2H2O (a), (b) and (d) are
ruled out because they are not black.

Problem 6: Na2CO3 cannot be used in place of (NH4)2CO3 for the precipitation of fifth
group radicals, since:
(a) magnesium will be precipitated
(b) concentration of carbonate ions is very low
(c) sodium ions will react with acidic radicals
(d) Na+ ions interfere with the detection of fifth group

Solution: (a) Na2CO3 will yield large concentration of CO32 − ions to exceed the
solubility product of MgCO3 and it will be precipitated along with

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carbonates of Ca2+, Sr2+ and Ba2+ in fifth group. Further, in absence of

common ion NH4OH will ionize more to give sufficient [OH–] to exceed
the solubility product of Mg(OH)2 and its ppt.

Problem 7: Which of the following can be used to prepare chlorine water ?

(a) KMnO4 + conc. HCl (b) KMnO4 + dil HCl
(c) KMnO4 + KCl (d) KMnO4 (s) + NaCl(aq)

Solution : (a) is correct

2KMnO4 + 16HCl  → 2KCl + 2MnCl2 + 5Cl2 + 8H2O
(b), (c) and (d) are not possible.

Problem 8: Which of the following does not respond to chromyl chloride test ?
(a) HgCl2 (b) CuCl2
(c) NiCl2 (d) MnCl2

Solution : (a) HgCl2 does ionised easily, therefore does not respond to chromyl chloride
test. (b), (c) and (d) respond to chromyl chloride test.

Problem 9: An inorganic salt in its aqueous solution produced a white ppt. with NaOH
which dissolves in excess of NaOH. Also its aqueous solution produced light
yellow ppt., with AgNO3 sparingly soluble in NH4OH. The probable salt is
(a) AlBr3 (b) AlI3
(c) AlCl3 (d) ZnCl2

Solution: (a) AlBr3 + 3NaOH 

→ Al(OH)3 + 3NaBr
white ppt.

Al(OH)3 + NaOH 
→ NaAlO 2 + 2H 2O
soluble

3AgNO3 + AlBr3 
→ 3AgBr + Al(NO3 ) 3
light yellow ppt.

Problem 10: A compound (A) forms a unstable pale blue colour solution in water. The
solution decolourised Br3 water and an acidified solution of KMnO4. The
possible compound (A) is:
(a) HNO2 (b) HNO3
(c) N2O5 (d) None of these

Solution: (a) HNO2 is pale blue in colour due to dissolution of N2O3. In concentrated
solution it decomposes as:
2HNO 2  → NO +NO 2 + H 2 O
and in dilute solution is
3HNO3  → HNO3 + H 2 O + 2NO
Reaction with:
a) Br2 water
HNO 2 + H 2 O + Br2  → HNO3 + 2HBr

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b) KMnO4
2KMnO 4 + 3H 2SO 4 + 5HNO 2 
→
K 2SO 4 + 2MnSO 4 + 3H 2O + 5HNO3
Problem 11: Which of the following gives black pricipitate when H2S gas is passed
through the its solution
(a) Acidic AgNO3 (b) Mg(NO3)2
(c) Ammonical BaCl2 (d) All of them
[CPMT 1984]
Solution: (a) 2 AgNO3 + H2S → Ag2S + 2HNO2

Problem 12: Which of the following combines with Fe (III) ions to form a brown
complex
(a) N2O (b) NO
(c) N2O3 (d) N2O5
[AIIMS 1982; AFMC 1988; MP PET 2000, 01]

Solution: (b) Brown ring test with (FeSO4. NO)

Problem 13: Sodium nitroprusside, when added to an alkaline solution of sulphide ions,
produces surple colour ion due to the formation of
(a) Na[Fe(H2O)5NOS] (b) Na2[Fe(H2O)5NOS]
(c) Na3[Fe(CN)5NOS] (d) Na4[Fe(CN)5NOS]
[IIT 1995]

Solution: (d) Na4[Fe(CN)5NO] + S2− → Na4 [Fe(CN)5NOS]

Sodium thio-nitroprusside (violet)]

Problem 14: In the chromyl chloride test, the reagent used is

(a) K2CrO4 (b) CrO3
(c) K2Cr2O7 (d) (NH4)2Cr2O7
[AMU 1983]

Solution: (c)

Problem 15: Aqueous solution of a salt when treated with AgNO3 solution gives a white
precipitate, which dissolves in NH4OH. Radical present in the salt is
(a) Cl− (b) Br−
−
(c) I (d) NO3−
[RPET 2001]

Solution: (a) When Cl−, Br− and F− are treated with AgNO3 solution in presence of
dilute HNO3, corresponding silver halide is obtained which is soluble in
NH4OH, NaCN, and Na2S2O3.
AgNO3 + NaCl  → AgCl ↓ + NaNO3
white

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AgCl + dil. 2NH4OH  → [Ag(NH3)2]Cl + 2H2O

complex
Problem 16: A substance on treatment with dil H2SO4 liberates a colourless gas which
produces (i) turbidity with baryta water and (ii) turns acidified dichromate
solution green. The reaction indicates the presence of
(a) CO32− (b) S2−
(c) SO32− (d) NO −2
[IIT Screening 1992]

Solution: (c) Na2SO3 + 2HCl (dil.) → 2NaCl + H2O + SO2

K2Cr2O2 + H2SO4 + 3SO4 → K2SO4 + Cr2(SO4)3 + H2O

Problem 17: A solution of a salt in dilute sulphuric acid imparts deep blue colour with
starch iodine solution it confirms the presence of which of the following :
(a) NO −2 (b) I−
(c) NO3− (d) CH3COO−
[MP PET 2003; CPMT 1977]
Solution: (a)

Problem 18: Gas A is bubbled through slaked lime when a white precipitate is formed.
On prolonged bubbling, the precipitate is dissolved, on heating the resultant
solution, the white precipitate reappears with the evolution of gas B. The
gases A and B respectively are
(a) CO2 and CO (b) CO and CO2
(c) CO and CO (d) CO2 and CO2
[DPMT 2004

Solution: (d) According to the equation,

∆
Ca(OH)2 + CO2  → CaCO3 + H2O
CaCO3 + H2O + CO2  → Ca(HCO3)2
∆
Ca(HCO3)2  → CaO + H2O + 2CO2
Hence, the gas A and B are CO2 and CO2 respectively

Problem 19: [X] + H2SO4 → [Y] a colourless gas with irritating smell
[Y] + K2Cr2O7 + H2SO4 → green solution
[X] and [Y] is
(a) SO32− , SO2 (b) Cl−, HCl
(c) S2−, H2S (d) CO32− , CO2
[IIT-JEE Screening 2003]
Solution: (c)

Problem 20: Al3+, Fe3+, Zn2+ and Ni2+ ions are present in an acidic solution. Excess of
ammonium chloride solution is added followed by addition of ammonium
hydroxide solution. The available precipitate will contain

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(a) Zn(OH)2 and Ni(OH)2 (b) Al(OH)3 and Fe(OH)3

(c) Zn(OH)2 and Al(OH)3 (d) Ni(OH)2 and Fe(OH)3
[MP PMT 1996]

Solution: (a) As the concentration of OH− ions is less due to common ion effect but
enough to precipitate the IIIrd group radicals as hydroxides, as the solubility
product of III group hydroxides is lower than IV, V and VI group hydroxides.

Problem 21: Which of the following change the colour of the aqueous solution of FeCl3
(a) K4[Fe(CN)6] (b) H2S
(c) NH4CNS (d) KCNS

Solution: (a, b, c, d)
FeCl3 + K4[Fe(CN)6] → Fe4[Fe(CN)6]3
Ferri ferrocyanide (Blue)
2FeCl3 + 3H2S → Fe2S3 + 6HCl
3NH4CNS + FeCl3 → Fe(CNS)3 + 3NH4Cl
(Blood red)
FeCl3 + 3KCNS → Fe(CNS)3 + 3KCl
(Blood red)

Problem 22: Which of the following substances are soluble in concentrated HNO3
(a) BaSO4 (b) CuS
(c) PbS (d) HgS

Solution: (b, c, d)

Problem 23: Which of the following statement (s) is (are) correct when a mixture of NaCl
and K2Cr2O7 is gently warmed with conc. H2SO4.
(a) A deep red vapour is evolved
(b) The vapour when passed into NaOH solution gives a yellow solution of
Na2CrO4
(c) Chlorine gas is evolved
(d) Chromyl chloride is formed

Solution: (a, b, d)
Chromyl chloride test
4NaCl + K2Cr2O7 + 3H2SO4  
heat
→ K2SO4 + 2Na2SO4
+ 2CrO2Cl2 + 3H2O
chromyl chloride (orange red)
4NaOH + CrO2Cl2 → 2NaCl + Na2CrO4 + 2H2O
sod. Chromate (yellow)
Na2CrO4 + (CH3COO)2Pb → 2CH3COONa + PbCrO4↓
(Lead chromate yellow ppt. )

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Problem 24: Which of the following are soluble in aqua regia ?

(a) HgS (b) NiS
(c) CoS (d) MnS

Solution: (a), (b) and (c)

Hg, NiS and CoS are soluble in aqua regia.

Problem 25: Mg2+ forms precipiate in presence of NH4OH and NH4Cl, on adding
disodium hydrogenphosphate due to the formation of
(a) White ppt. (b) Pink ppt.
(c) Mg(NH4)PO4 (d) Mg(NH4)HPO4

Solution: (a), (c)

Mg2+ from white coloured ppt. of Mg(NH4)PO4.

Problem 26: Which of the following sulphides are soluble in yellow ammonium
sulphide ?
(a) As2S3 (b) Bi2S3
(c) Sb2S3 (d) SnS

Solution: (a), (c) and (d)

(a) is correct As2S3 + 2(NH4)2S2  → 2(NH4)2S + As2S5
As2S5 + 3(NH4)2S  → 2(NH 4 3AsS4
)
Soluble complex
(ammonium thioarsenate)
(c) is correct as Sb2S3 forms 2(NH4)3SbS4
Soluble complex
(Ammonium thioantimonate)
(d) is also correct as SnS forms (NH4)2SnS3
Soluble complex
(Ammonium thioantimonate)
(b) is incorrect as it does not form any compelx.

Problem 27: Match the following :

List – I (Compounds) List – II (Precipitate colour)

(A) Bi2S3 (p) yellow
(B) ZnS (q) white
(C) CdS (r) Brown
(D) CuS (s) Black

Solution: (a – r), (b – q), (c – p), (d – s)

Write-up I

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Colourless salt (A) on heating with NaOH gives gas (B). When reaction of (A) with
NaOH was complete, solution obtained on reacting FeSO4 and conc. H2SO4 gave a brown
coloured ring (C) between two layers. (A) on heating strongly forms (D) and (E).
Compound (E) is neutral oxide of a dibasic acid (F).

1. What is compound (A)

(a) NH4NO3 (b) NaNO3
(c) KNO3 (d) None of these

2. What is compound (C)

(a) [Fe(H2O)4.NO]SO4 (b) [Fe(H2O)5NO]SO4
(c) [Fe(H2O)4]SO4 (d) None of these

3. Compound (F) is what

(a) HNO2 (b) cis N2H2O2
(c) trans N2H2O2 (d) both (b) and (c)

4. What is compound (D)

(a) NO2 (b) NO
(c) N2O (d) None of these

Solution :

1. (a) 2. (b) 3. (d) 4. (c)

∆
NH4NO3 + NaOH  → NH3 + NaNO3 + H2O
(A) (B)
NO3− + FeSO4 + H2SO4  → [Fe(H2O)5NO]SO4
Brown ring
.. ..
∆
HO − N = N − OH  → N 2O + H 2O
(F) (E)
∆
NH4NO3  → N2O + 2H2O
(A) (D) (E)

Write-up II

i) A black mineral (A) on treatment with dilute sodium cyanide solution in presence of
air gives a clear solution of (B) and (C).
ii) The solution of (B) on reaction with zinc gives precipitate of a metal (D).
iii) (D) is dissolved in dil. HNO3 and the resulting solution gives a white precipitate (E)
with dil. HCl.
iv) (E) on fusion with sodium carbonate gives (D). (v) (E) dissolves in aqueous solution
ammonia giving a colourless solution (F).

1. The black mineral (A) is

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(a) Ag2S (b) PbS

(c) CuS (d) HgS′

2. The solution (B) is of

(a) NaCN (b) Na[Ag(CN)2]
(c) Ag(CN )4
3−
(d) Na2Zn(CN)4

3. The colourless solution of (F) is

(a) Ag(NH3)Cl (b) AgCl.2NH3
(c) [Ag(NH3)2 ]+ (d) Ag(NH3)4Cl

4. White ppt (E) is of

(a) CuCl (b) MnCl2
(c) AgCl (d) ZnCl2

Solution :
1. (a) 2. (b) 3. (c) 4. (c)

Ag2S + NaCN  air

→ Na[Ag(CN)2] + Na2SO4
(A) dilute solution (B) (C)
2Na[Ag(CN)2] + Zn  → Na2[Zn(CN)4] + 2Ag ↓
(D)
Ag + dil HNO3  → Ag+ + NO3−  dil HCl
→ AgCl (s)
(D) (E)
∆
2AgCl (s) + Na2CO3  fuse
→ 2Ag + CO2 + 2NaCl + O2↑
(D)
AgCl (s) + 2NH3 
→ [Ag(NH3)2]Cl

Subjective

Problem 1: i) An ore (A) on roasting with sodium carbonate and lime in the presence of
air gives two compounds, (B) and (C).
ii) The solution of (B) in conc. HCl on treatment with potassium ferrocyanide
gives a blue colour or precipitate of compound (D).
iii) The aqueous solution of (C) on treatment with conc. H2SO4 gives a yellow
coloured compound (E).
iv) Compound (E) when treated with KCl gives an orange-red compound (F)
which is used as an oxidizing reagent.
v) The solution of (F) on treatment with oxalic acid and then with an excess
of potassium oxalate gives blue crystals of compound (G).
Identify (A) to (G) and give balanced chemical equations for reactions at steps
(i) to (v)

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Solution: a) Reaction (i) suggests that the ore contains Fe.

b) Reaction (ii) and (iv) suggest that the ore also contains chromium.
In fact, if we review our memory, we will remember that the reaction
sequence (i), (iii) and (iv) are involved in the preparation of K2Cr2O7 from
chromite ore, FeO⋅Cr2O3.
Hence the given reactions can be written as below
i) 4FeO ⋅ Cr2O3 + 8Na 2 CO3 + 7O 2  lime
(Roasting)
→ 2Fe2 O3 ↓+ 8Na 2 CrO 4 + 8CO 2 ↑
Chromite ore (A) (B) (C)

ii) Fe 2 O3 + 6HCl 
→ 2FeCl3 + 3H 2 O
4FeCl3 + 3K 4 [Fe(CN)6 ] 
→ Fe4 [Fe(CN)6 ]3 + 12KCl
Blue (D)

iii) 2Na 2 CrO 4 + H 2SO 4 

→ Na 2 Cr2 O7 + Na 2SO 4 + H 2 O
So lub le (C) Yellow colour (E)

iv) Na 2Cr2O7 + 2KCl 

→ K 2Cr2O7 + 2NaCl
(E) (F)

K2Cr2O7 (F) is well known oxidizing agent

v) K 2Cr2 O7 + 7H 2C2 O 4 
→ K 2 C2O 4 + Cr2 (C2O 4 )3 + 6CO 2 + 7H 2O
oxalic acid

Cr2 (C2 O 4 )3 + 3K 2 C2 O 4 
→ 2K 3 [Cr(C2 O 4 )3 ]
Potassium oxalate Potassium trioxalatochromium
Blue crystals (G)

Problem 2: i) A black mineral (A) on heating in presence of air gives a gas (B).
ii) The mineral (A) on reaction with dilute H2SO4 gives a gas (C) and solution
of a compound (D).
iii) On passing gas (C) into an aqueous solution of (B) a white turbidity is
obtained.
iv) The aqueous solution of compound (D) on reaction with potassium
ferricyanide gives a blue compound (E).
Identify (A) to (E) and give chemical equations for reactions at steps
(i) to (iv).

Solution: Let us summarise the given statements.

Gas C +Solution of D ←
dil. H 2SO 4
→ Black mineral A 
O2
→ Gas B 
i) H 2 O
ii) gas C

→ White turbidity
K 3 [Fe(CN)6 ]

Blue compound E
Formation of blue coloured compound E by treating solution of compound D
with potassium ferricyanide indicates that compound D contains Fe2+ ion
which is also the constituent ion of the compound A. Further A, is a black
mineral of Fe2+ion, it should be ferrous sulphide (FeS) which is confirmed by
the various given reactions.
i) 4FeS+ 7O 2  → 2Fe2 O3 + 4SO 2
(A) (B)

ii) FeS + H 2SO 4 

→ FeSO 4 + H 2S+ S
(A) (D) (C)

iii) a) SO 2 + H 2O 
→ H 2SO3

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b) 2H 2S+ H 2SO3 
→ 3S + 3H 2O
(C) Turbidity

iv) FeSO 4 + K 3 [Fe(CN)6 ] 

→ KFe[Fe(CN)6 ]+ K 2SO 4
(D) (E)

Problem 3: A white substance A reacts with dilute H2SO4 to produce a colourless gas B
and a colourless solution C. The reaction between B and acidified K2Cr2O7
solution produces a green solution and a slightly coloured precipitate D. The
substance D burns in air to produce a gas E which reacts with B to yield D and
a colourless liquid. Anhydrous copper sulphate is turned blue on addition of
this colourless liquid. Addition of aqueous NH3 or NaOH to C produces first a
precipitate which dissolves in the excess of the respective reagent to produce a
clear solution in each case. Identify A, B, C, D and E. Write the equation of
the reactions involved.

Solution: A 
dil. H2SO4
→ B↑ + C
(white) (colourless) (colourless solution)

K 2 Cr2 O7 / H +

Green solution + D ↓ (burns in air to form E)

(coloured)

E ↑ + B ↑ 
→ D + colourless liquid 
anhy. CuSO4
→ Blue
C 
aq. NH3
or NaOH
→ Precipitate 
excess of
reagent
→ Clear solution
The above set leads to following conclusions.
i) Since the gas (B) is colourless and turns acidified K2Cr2O7 solution green,
it should be H2S.
ii) Since H2S gas is obtained by the reaction of dil. H2SO4 on A, the latter
must be sulphide.
iii) The white colour of the sulphide (A) points out towards ZnS.
Thus the various reactions can be written as below.
ZnS+ H 2SO 4 (dil)  → ZnSO 4 + H 2S ↑
(A) (C) (B)

3H 2S+ K 2 Cr2 O7 + 4H 2SO 4 

→ K 2SO 4 + Cr2 (SO 4 )3 + 7H 2 O + 3S
(B) (green) (D)

S + O 2 
→ SO 2 ↑ 
→ 2H 2 O + 3S ↓
2H 2S(B)
(D) (E) (colourless liq) (D)

CuSO 4 (white)
CuSO 4 ⋅ 5H 2 O
(blue)

ZnSO 4 + 2NaOH 
→ Zn(OH) 2 ↓ 
2NaOH
→ Na 2 ZnO 2 + 2H 2 O
(C) (solub le0)

Problem 4: A black coloured compound (A) on reaction with dilute sulphuric acid gives a
gas (B) which on passing in a solution of an acid (C) gives a white turbidity
(D). Gas (B) when passed in acidified solution of a compound (E) gives a

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precipitate (F) soluble in dilute nitric aid. After boiling this solution when an
excess of ammonium hydroxide is added, a blue coloured compound (G) is
formed. To this solution on addition of acetic acid and aqueous potassium
ferrocyanide a chocolate precipitate (H) is obtained. On addition of an aqueous
solution of barium chloride to an aqueous solution (E), a white precipitate
insoluble in HNO3 is obtained. Identify from (A) to (H).
Solution: Black compound  dil. H 2SO 4
→ Gas →
acid (C)
White turbidity
(A) (B) (D)

(E) + Acid

Solution ← dil

HNO 3
 Precipitate (soluble in dil. HNO3 )
(F)
i) boil
ii) NH 4OH
Blue compound 
CH3COOH
aq. K 4 [Fe(CN)6 ]
→ Chocolate ppt.
(G) (H)

E (aq. solution)  BaCl2

→ White precipitate (insouble in HNO3 )
Let us draw important conclusion from the given summary
i) Reaction in aqueous solution of the compound E with BaCl2 to give white
precipitate insoluble in nitric acid indicates that the salt (E) contains SO42–
ion.
ii) Reaction of compound (G) with potassium ferrocyanide in presence of
acetic acid to give chcoclate precipitate (H) indicates that (G) must contain
Cu2+ and hence (H) must be cupric ferrocyanide, Cu2[Fe(CN)6].
iii) Since compound (G) is derived from (F), compound (F) also contains
Cu2+. Further since (F) is derived from the reaction of the gas (B) and
compound (E), (E) must contain Cu2 ion. Precipitate of Cu2+ ion soluble in
dil. nitric acid should be CuS; hence (F) must be CuS and thus (B) is H2S.
iv) According to point (i), compound (E) contains SO42– hence (E) must be
CuSO4.
v) Gas (B) which has now been identified as H2S is obtained by the
decomposition of black coloured compound (A) with dil. H2SO4. Hence
(A) must be sulphide of Cu, Pb, Hg, Fe, Co, Ni, etc.
Thus the various compounds from (A) to (H) and their reactions can be written
as below.
FeS + H 2SO 4 (dil)  → FeSO 4 + H 2S ↑
Ferrous sulphide (A) Hydrogen sulphide (B)

H 2S + HNO3 
→ 2H 2 O + 2NO 2 + S↓
Hydrogen sulphide (B) Nitric acid (C) Sulphur (turbidity, D)

CuSO 4 + H 2S 
in presence
of dil. HCl
→ CuS ↓ + H 2SO 4
Copper sulphide (E) (B) Copper sulphide (F)

3CuS+ 8HNO3 
→ 3Cu(NO3 ) 2 + 2NO + 3S + 4H 2 O
(F)

Cu(NO3 )2 + H 2SO 4 
→ CuSO 4 + 2HNO3
CuSO 4 + 4NH 4 OH 
→ [Cu(NH 3 )4 ]SO 4 + 4H 2 O
Solution Cupric ammonium sulphate
(blue compound (G))

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[Cu(NH 3 ) 4 ]SO 4 + 4CH 3COOH 

→ CuSO 4 + 4CH 3COONH 4
(G )

2CuSO 4 + K 4 [Fe(CN)6 ] 
→ Cu 2 [Fe(C)6 ] ↓ + 2K 2SO 4
Potassium ferrocyanide Cupric ferrocyanide
(Chocolate precipitate, H)

CuSO 4 + BaCl2 
→ BaSO 4 ↓ + CuCl2
(E) Barium sulphate
(insoluble in HNO3 )

Thus the compounds (A) to (H) are

A = Ferrous sulphide, FeS, B = Hydrogen sulphide, H2S, C = Nitric acid,
HNO3, D = Sulphur S, E = Copper sulphate, CuSO4, F = Copper sulphide,
CuS, G = Cupric ammonium sulphate, [Cu(NH3)4]SO4, H = Cupric
ferrocyanide, Cu2[Fe(CN)6].

Problem 5: i) A black coloured compound (B) is formed on passing hydrogen sulphide

through the solution of a compound (A) in NH4OH.
ii) (B) on treatment with hydrochloric acid and potassium chlorate gives (A).
iii) (A) on treatment with potassium cyanide gives a buff coloured precipitate
which dissolves in excess of this reagent forming a compound (C).
iv) The compound (C) is changed into a compound (D) when its aqueous
solution is boiled.
v) The solution of (A) was treated with excess of sodium bicarbonate and
then with bromine water. On cooling and shaking for some time, a green
colour of compound (E) is formed. No change is observed on heating.
Identify (A) to (E) and give chemical equations for the reactions at steps
(i) to (v).

Solution: The formation of black coloured compound (B) by passing H2S through the
alkaline solution of the compound (A) indicate that (A) is a salt of the IV
group radicals (Co2+, Ni2+ or Zn2+). However, the given reactions especially
reaction (iii) indicates what compound (A) is a cobalt salt (CoCl2) which
explains all the given reactions.
i) CoCl2 + 2NH 4 OH + H 2S  → CoS+ 2NH 4 Cl + 2H 2 O
(A) (B)

ii) CoS + 2HCl + O → CoCl2 + H 2 O + S

(B)
(from KClO3 )

2KClO3 
→ 2KCl + 3O 2
iii) CoCl2 + 2KCN 
→ Co(CN)2 ↓+ 2KCl
buff coloured

Co(CN) 2 + 4KCN 
→ K 4 [Co(CN)6 ]
iv) 2K 4 [Co(CN)6 ] + O + H 2 O 
→ 2K 3 [Co(CN)6 ]+ 2KOH
(D)

v) CoCl2 + 6NaHCO3 
→ Na 4 [Co(CO3 )3 ] + 2NaCl + 3CO 2 + 3H 2 O

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2Na 4 [Co(CO3 )3 ] + 2NaHCO3 + O 

→ 2Na 3 [Co(CO3 )3 ]+ 2Na 2 CO3 + H 2 O
(E)

Problem 6: A substance X dissolves in hot conc. HCl to give solution which when treated
with caustic soda solution gives a white precipitate which however dissolves
in excess of caustic soda solution giving a strongly solution.

On heating X with sulphur, a brown powder Y is formed which dissolved on

warming with yellow ammonium sulphide solution. The solution gives a grey
precipitate with HCl.
When Xis heated in air, a white powder Z is obtained which can be dissolved
only in conc. H2SO4. When Z is fused with NaOH, extracted with hot water,
then treated with mineral acid, white gelatinous precipitate is obtained.
Identify X, Y, Z and give the reactions involved.

Solution: X 
conc. HCl
→ Solution 
NaOH
→ White ppt. 
NaOH
→ Solution
(Strongly reducing)

X 
S
→ Brown powder 
(NH 4 )2 Sx
→ Solution →
HCl
Grey ppt.
Y

X →
air
heat
White powder 
i) NaOH fuse

ii) Hot water
→ Solution →
HCl
Gelatinous ↓
Z (White)
(soluble only in
conc. H 2SO4 )

i) Reaction of the HCl solution of X with NaOH first forms white ppt. which
dissolves in excess of NaOH to give solution. The strongly reducing
properties of this solution points out that the solution might be containing
sodium stannite and hence X must be tin which explains all the given
reactions of this step.
ii) The nature of X as tin is confirmed by its reaction with S forming SnS2
which dissolves in yellow ammonium sulphide but regenerates in presence
of HCl.
Thus the various reactions and nature of X, Y and Z can be written as below.
i) Sn + 2HCl  → SnCl2 + H 2
(X)

SnCl 2 + 2NaOH 
→ Sn(OH) 2 + 2NaCl
Sn(OH) 2 + 2NaOH 
→ Na 2SnO 2 + 2H 2 O
Sodium stannite
(strongly reducing)

ii) Sn + 2S 
→ SnS2
SnS2 + (NH 4 ) 2 S 
→(NH 4 )2 SnS3
(NH 4 ) 2 SnS3 + 2HCl 
→ SnS2 + 2NH 4 Cl + H 2S
iii) Sn + O 2 
→ SnO 2 (soluble only in conc. H 2SO 4 )
(Z)

SnO 2 + 2NaOH 
→ Na 2SnO3 + H 2 O
Na 2SnO3 + 2HCl 
→ H 2SnO3 ↓+ 2NaCl
Stannic acid

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Problem 7: A coloulress solid A on heating gives a white solid B and a coloulress gas, C;
B gives off reddish brown fumes on treatment with dilute acids. On heating
with NH4Cl, B gives a colourless gas D and a residue E.

The compound a also gives a coloulress gas F on heating with ammonium

sulphide and white residue G. Both E and G impart bright yellow colour to
Bunsen fumes. The gas C forms white powder with strongly heated
magnesium metal. The white powder forms magnesium hydroxide with water.
The gas D, on the other hand, is absorbed by heated calcium which gives off
ammonia on hydrolysis.

Identify the substance A to G and gives reactions for the changes involved.

Solution: It is advisable to summarise the given facts in the form of a chart.

G + F ←
( NH 4 )2 SO 4
heat
A →heat
B + C
colourless residue colourless gas colourless solid colourless solid colourless gas

D + E ←
NH 4Cl
heat
 B 
dil
solid
→ Reddish brown fumes
colourless residue residue

C + Mg 
→ White powder 
H2O
→ Mg(OH) 2
colourless residue

D + Ca(heated) 
H2O
→ NH 3
colourless residue

The above reactions lead to the following conclusions.

(A) and (D) reacts with calcium forming a compound which on hydrolysis
gives ammonia indicating that D must be nitrogen.
(B) Residues E and G give yellow flame on burning indicating that these are
sodium salts. Hence compounds B (which give E) and A (which give G) must
be sodium salts.
(C) The colourless solid B gives reddish brown fumes with dilute acids, the
reddish brown fumes are probably of NO2. Hence compound B must be nitrite
(recall that NO3– ions are not attacked by dil. Acids). Consequently, A must be
NO3– which can give NO2– (B) on heating.
Thus compound A is NaNO3 which explains all the given reactions as below.
i) 2NaNO3  → 2NaNO 2 + O 2 ↑
(A) (B) (C)

ii) 2NaNO 2 + H 2SO 4 (dil.) 

→ NaSO 4 + 2HNO 2
(A)

3HNO 2 
→ HNO3 + H 2 O + 2NO
2NO + O 2 
→ 2NO ↑ 2
Reddish brown fumes

iii) NaNO 2 + NH 4 Cl →

heat
NaCl+ N 2 ↑+ 2H 2 O
(A) (E) (D)

iv) 2NaNO3 + (NH 4 ) 2 SO 4 

→ Na 2SO 4 + 2NH 3 ↑+ 2HNO3
(A) (G ) (F)

v) 2Mg + O 2 
→ 2MgO
(C) white powder

MgO + H 2 O 
→ Mg(OH) 2

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vi) 3Ca + N 2 
→ Ca 3 N 2
(D)

Ca 3 N 2 + 6H 2 O 
→ 3Ca(OH)2 + 2NH 3 ↑
Thus substance (A) to (G) can be represented as
(A) NaNO3 (B) NaNO2
(C) O2 (D) N2
(E) NaCl (F) NH3 (G) Na2SO4

Problem 8: An inorganic compound (A) shows the following reactions.

i) It is white solid and exists as dimmer; gives fumes of (B) with wet air.
ii) It sublimes on 180°C and forms monomer if heated to 400°C.
iii) Its aqueous solution turns blue litmus to red.
iv) Addition of NH4OH and NaOH separately to a solution of (A) gives white
precipitate which is however soluble in excess of NaOH.
Solution: i) (A) is a characteristic dimerized compound which sublimes on 180°C and
forms monomer if heated to 400°C and thus, (A) is (AlCl3)2 or Al2Cl6.
180° C 400° C
Al 2 Cl6(s)  → Al 2 Cl6(v)  → 2AlCl3
ii) It fumes with wet air
Al 2 Cl6 + 6H 2 O  → 2Al(OH)3 + 6HCl ↑
Fumes (B)

iii) Its solution in water is acidic due to hydrolysis

2AlCl3 + 6H 2 O  → 2Al(OH)3 + 6HCl(aq)
iv) (A) gives white ppt. with NH4OH and NaOH, soluble in excess of NaOH.
Al 2 Cl6 + 6NH 4 OH  → 2Al(OH)3 + 6NH 4 Cl
Al2 Cl6 + 6NaOH 
→ 2AlOH + 6NaCl
Excess of NaOH

2NaAlO 2 + 2H 2 O

Problem 9: i) Solution salt of an acid (A) is formed on boiling white phosphorus with
NaOH solution.
ii) On passing chlorine through phosphorus kept fused under water, another
acid (B) is formed which on strong heating gives metaphosphorus acid.
iii) Phosphorus on treatment with conc. HNO3 gives an acid (C) which is also
formed by the action of dilute H2SO4 on powdered phosphorite rock.
iv) (A) on treatment with a solution of HgCl2 first gives a white precipitate of
compound (D) and then a grey precipitate (E).
Identify (A) to (E) and write balanced chemical equations for the reactions at
step (i) to (iv)

Solution: i) P4 + 3NaOH + 3H 2 O 
→ 3NaH 2 PO 2 + PH 3
(sodium hypophosphate)

Thus, acid (A) is H3PO2, i.e., hypophosphorus acid

ii) 2P + 3Cl2 + 6H 2 O → 2H 3 PO3 + 6HCl
(Phosphorus acid)

Thus, acid (B) is H3PO3

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H 3 PO3 + HPO 2 + H 2 O
iii) P4 + 20HNO3 
→ 4H 3 PO 4 + 20NO 2 + 4H 2 O
(C)

P4 + 10HNO3 
→ 4H 3 PO 4 + 10NO 2 + 4H 2 O
Phosphoric acid (C)

Thus, acid (C) is H3PO4

iv) H 3 PO 2 + 2H 2 O 
→ H 3 PO 4 + 4H
HgCl2 + 2H 
→ Hg 2 Cl 2 + 2HCl
(white)(D)

Hg 2 Cl2 + 2H 
→ 2Hg + 2HCl
(Grey)(E)

Problem 10: A gaseous mixture containing (X), (Y) and (Z) gases, when passed into
acidified K2Cr2O7 solution, gas (X) was absorbed and the solution was turned
green. The remainder gas mixture was then pass through lime water, which
turns milky by absorbing gas (Y). The residual gas when passed through
alkaline pyrogallol solution, it turned black. Identify gas (X), (Y) and (Z) and
explain the reaction involved.

Solution: i) Gas (X) is absorbed in acidified K2Cr2O7 and the solution turns green. So
(X) is SO2.
ii) Gas (Y) is absorbed in lime water turning it white so (Y) is CO2.
iii) Gas (Z) is absorbed in pyrogallol so (Z) is O2.
Reactions
i) 3SO 2 + K 2 Cr2 O7 + H 2SO 4 
→ H 2SO 4 + Cr2 (SO 4 )3 + H 2 O
(X) Green

ii) Ca(OH)2 + CO 2 
→ CaCO3 ↓+ H 2 O
(Y) White

iii) O 2 + Pyrogallol 
→ Absorbed
(Z)

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KVPY
1. A hydrated salt of a bivalent metal when heated strongly produces a mixture of gases which when
2
bubbled
through Ba(OH) solution produces a white solid. This solid on treatment with dilute HCl dissolves a
part of
the solid leaving another part insoluble which is filtered. The filtrate on treatment with Br2 water slowly
2
precipitates another white solid, which is not soluble in HCl. The gas mixtures are (2007)
(A) CO2 and CO (B) SO3 and SO2 (C) SO2 3 and CO 2 (D)
SO2 and CO

Answer Key

1:B

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[Type text]

Assignments
SECTION – I Single Choice Questions

LEVEL - I

1. Two test tubes containing a nitrate and a bromides are treated separately with H2SO4 ;
brown fumes evolved are passed in water. The water will be coloured by vapours
evolved from the test tube containing.
(a) Nitrate (b) Bromide
(c) both (a) and (b) (d) none of these

2. A white salt is insoluble in cold water but soluble in boiling water. Its solution when
treated with potassium chromate solution gives yellow precipitate. The salt may be :
(a) BaCl2 (b) SrCl2
(c) PbCl2 (d) Hg(NO3)2

3. A white powder when strongly heated gives off brown fumes. a solution of this powder
gives as yellow precipitate with a solution of KI. When a solution of barium chloride is
added to a solution of powder, a white precipitate results. This white powder may be :
(a) A soluble sulphate (b) KBr and NaBr
(c) Ba(NO3)2 (d) AgNO3

4. A reddish-pink substance on heating gives off a vapour which condenses on the sides of
the test tube and the substance turns blue. If on cooling water is added to the residue it
turns to its original colour. The substance is :
(a) Iodine crystals (b) Copper sulphate crystals
(c) Cobalt chloride crystals (d) Zinc oxide

5. A solution of white crystals gives a precipitate with AgNO3 but no precipitate with
solution of Na2CO3. The action of conc. H2SO4 on the crystal yields a brown gas. The
crystals are of :
(a) NaNO3 (b) KCl
(c) Ca(NO3)2 (d) NaBr

6. The solution of a chemical compound X reacts with AgNO3 solution to from a white
precipitate of Y which dissolves in NH4OH to give a complex Z. When Z is treated with
dilute HNO3, Y reappears. The chemical compound X can be :
(a) NaCl (b) CH3Cl
(c) NaBr (d) NaI

7. A mixture when heated with dil. H2SO4 does not evolve brown vapours but when heated
with conc. H2SO4, brown vapours are obtained. The vapours when brought in contact
with silver nitrate solution do not give any precipitate. The mixture contains
(a) NO −2 (b) NO 3−
(c) Cr (d) Br–

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[Type text]

8. Ammonium dichromate is used in some fireworks. The green coloured powder blown in
air is due to
(a) CrO3 (b) Cr2O3
(c) Cr (D) CrO(O2)

9. A mixture, on heating with conc. H2SO4 and MnO2, liberates brown vapours of
(a) Br2 (b) NO2
(c) HBr (d) I2

10. A white solid is first heated with dil. H2SO4 and then with conc.H2SO4. No action was
observed in either case. The solid salt contains
(a) sulphide (b) sulphite
(c) thiosulphate (d) sulphate
11. Which of the following metal oxides is white in colour but becomes yellow in heating?
(a) AgO (b) Ag2O
(c) FeO (d) ZnO

12. A white precipitate obtained in the analysis of a mixture becomes black on treatment with
NH4OH. It may be
(a) PbCl2 (b) AgCl
(c) HgCl2 (d) Hg2Cl2

13. Which one among the following pairs of ions cannot be separated by H2S in dilute
hydrochloric acid?
(a) Bi3+, Sn4+ (b) Al3+, Hg2+
2+ 2+
(c) Zn , Cu (d) Ni2+, Cu2+

14. The best explanation for the solubility of MnS in dil. HCl in salt
(a) solubility product of MnCl2 is less than that of MnS
(b) concentration of Mn2+ is lowered by the formation of complex ions with chloride ions.
(c) concentration of sulphide ions is lowered by oxidation to free sulphur.
(d) concentration of sulphide ions is lowered by formation of the weak acid H2S.
15. Potassium ferricyanide [potassium hexacyanoferrate (III)] has
(a) Fe (II)_ (b) Fe(III)
(c) Cu(II) (d) Cd(II)
16. Calcium burns in nitrogen to produce a white powder which dissolves in sufficient water
to produce a gas (A) and an alkaline solution. The solution on exposure to air produces a
thin solid layer of (B) on the surface. Identify the compounds A and B.
(a) C2H2, CaCO3 (b) NH3, CaCO3
(c) NH3, Ca(OH)2 (d) CH4, CaCO3
17. A gas ‘X’ is passed through water to form a saturated solution. The aqueous solution on
treatment with silver nitrate gives a white precipitate. The saturated aqueous solution also
dissolves magnesium ribbon with the evolution of a colourless gas ‘Y’. Identify ‘X’
and ‘Y’.
(a) X = CO2, Y = Cl2 (b) X = Cl2, Y = CO2

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[Type text]

(c) X = Cl2, Y = H2 (d) X2 = H2, Y = Cl2

18. Chromyl ion is :

(a) CrO2+ (b) CrO22 +
(c) CrO 2 + (d) CrO23+

19. H2S gas is passed into aqueous solution of Zn(CH3COO)2 and ZnCl2 in test tubes I and II
separately. Then ZnS is precipitated :
(a) in I (b) in II
(c) in both (d) in none of these

20. Which reagent is used to remove SO42 − and Cl− :

(a) NaOH (b) Pb(NO3)2
(c) BaSO4 (d) KOH

LEVEL – II

1. An inorganic salt is heated with ethyl alcohol and conc. H2SO4; vapours evolved produces
green-edged flame on ignition; it indicates the presence of :
(a) F− (b) C2O42 −
(c) BO33− (d) ClO3−

2. A solution of the given mixture was prepared in conc. HCl. On diluting this solution with
water, a turbidity appears. This indicates the presence of :
(a) As 3+ (b) Hg 2 +
(c) Sb 3+ (d) Cu 2 +

3. A light green coloured salt soluble in water gives black precipitate on passing H2S which
dissolves readily in HCl. The metal ion present is:
(a) Co2+ (b) Fe2+
2+
(c) Ni (d) Mn2+

4. The salt used for performing ‘bead test’ in qualitative inorganic analysis is
(a) K2SO4.Al2(SO4)3.24H2O (b) FeSO4.(NH4)2SO4.6H2O
(c) Na(NH4)HPO4.4H2O (d) CaSO4.2H2O

5. Out of the following compounds gives a white precipitate with aqueous AgNO3 and a
green flame test. The compound is
(a) NaCl (b) KCl
(c) BaCl2 (d) CaCl2

6. An inorganic mixture was treated with excess of dil. H2SO4. Effervescences were
produced. The solution was heated till effervescences ceased. After this a small pinch of
MnO2 was added. Fresh effervescence was produced. Seelct the correct statements:

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[Type text]

(a) Mixture contains CO32 − ions (b) Mixture contains C2 O 24− ions
(c) Mixture contains SO32− ions (d) Mixture contains both CO32 − and C2 O 42− ions

7. In third group of qualitative analysis, the precipitate employed is a mixture of NH4Cl and
NH4OH. If NH4Cl is not available in the laboratory and the mixture does not contain
Mn2+, we can use
(a) (NH4)2SO4 (b) (NH4)2CO3
(c) NH4NO3 (d) all of these

8. A compound produced blue mass in cobalt nitrate test and formed a brown ring with
FeSO4 and conc.H2SO4. The probable compound is:
(a) Al(NO3)3 (b) Zn(NO3)2
(c) Cu(NO3)2 (d) MgCl2

9. A solution of Na2C2O4, when added to a solution containing Ba2+, Sr2+ and Ca2+ ions, will
precipitate
(a) Ca2+ ions (b) Ca2+ and Sn2+ ions
2+ 2+ 2+
(c) Ba , Sr and Ca ions (d) none of these

10. Which of the following give(s) canary yellow ppt. with ammonium molybdate?
(a) PO34− (b) As3+
(c) Both (a) and (b) (d) None of these

SECTION – II May be more than one choice

1. Nitrogen dioxide can be obtained by heating :

(a) KNO3 (b) Pb(NO3)2
(c) LiNO3 (d) AgNO3

2. The cation which gives yellow ppt. with K2CrO4 in acetic acid is:
(a) Ba2+ (b) Pb2+
2+
(c) Ca (d) K+

3. Which of the following anions is not easily removed by precipitation from its aqueous
solution :
(a) NO3− (b) CH3COO−
(c) SO42 − (d) I−

4. When oxalic acid is heated with conc. H2SO4, it produces:

(a) CO (b) CO2
(c) SO2 (d) SO3

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[Type text]

5. Iodine imparts brown colour to :

(a) Water (b) Ether
(c) Alcohol (d) Chloroform

6. Hydrogen iodide cannot be made by the action of concentrated sulphuric acid on

potassium iodide because :
(a) H2SO4 in an oxidizing agent (b) HI is stronger acid than H2SO4
(c) HI is strong reducing agent (d) H2SO4 is stronger acid then HI

7. A solution giving yellow ppt. with ammonium molybdate contains :

(a) PO43− (b) As 3+
3+
(c) Bi (d) none of these

8. Addition of FeCl3 to K4[Fe(CN)6] gives :

(a) Prussian blue (b) Fe4[Fe(CN)6]3
(c) Ferri-ferrocyanide (d) none of these

9. KCN is used for separating :

(a) Co2+ and Ni2+ (b) Mn2+ and Zn2+
(c) Ba2+ and Ca2+ (d) Cu2+ and Cd2+

10. An aqueous solution contains Hg2+, Hg22 + , Pb2+ and Cd2+. The addition of HCl(6N) will
precipitate :
(a) Hg2Cl2 (b) PbCl2
(c) HgCl2 (d) CdCl2

SECTION – III Comprehension Type Questions

Write-up I

A compound (A) is greenish crystalline salt, which gave the following results.
i) Addition of BaCl2 solution to the solution of (A) results in the formation of white ppt.
(B). which is insoluble in dil HCl.
ii) On heating (A), water vapours and two oxides of sulphur, (C) and (D) are liberated
leaving a red brown residue (E).
iii) (E) dissolves in warm conc. HCl to give a yellow solution (F).
iv) With H2S, the solution (F) yields a pale yellow ppt. (G), which when filtered, leaves a
greenish filtrate (H).
v) Solution (F) on treatment with thiocynate ions gives blood red coloured compound (I).

1. Compound (A) is
(a) CuSO4 (b) MnSO4
(c) FeSO4 (d) Na2SO4

[Type text]
[Type text]

2. White ppt (B) is of

(a) K2SO4 (b) BaSO4
(c) FeSO4 (d) CuSO4

3. The yellow solution is of

(a) FeCl3 (b) CuCl2
(c) PbCl2 (d) MnCl2

4. The pale yellow ppt (G) is

(a) BaSO4 (b) PbCl2
(c) FeSO4 (d) S

Write-up II

A black coloured compound (A) on reaction with dil. H2SO4 gives a gas (B) which on
passing in a solution of an acid (C) gives a white turbidity (D). Gas (B) when passed in an
acidified solution of a compound (E) gives a ppt. (F) soluble in dil. HNO3. After boiling
this solution when an excess of NH4OH is added, a blue coloured compound (G) is
formed. To this solution on addition of acetic acid and aq. K4Fe(CN)6, a chocolate
precipitate (H) is obtained. On addition of an aqueous solution ofBaCl2 to an aqueous
solution of (E), a white ppt. insoluble in HNO3 is obtained.

5. The white turbidity (D) is due to

(a) H2S (b) CuS
(c) S (d) SO2

6. The PPT. (F) is

(a) FeSO4 (b) PbSO4
(c) CoSO4 (d) CuSO4

7. The chocolate coloured ppt (H) is

(a) K2Cr[Fe(CN)6] (b) Cu4[Fe(CN)6]
(c) K2Cu2 [Fe(CN)6] (d) K3Cu [Fe(CN4)4]

8. The gas (B) is

(a) SO2 (b) CO2
(c) S′ (d) NH3

Write-up III

A well known orange crystalline compound (A) when burnt imparts violet colour to
flame. (A) on treating with (B) and cone. H2SO4 gives red gas (C) which gives red yellow
solution (D) with alkaline water. (D) on treating with acetic acid and lead acetate gives
yellow precipitate (E). (B) sublimes on heating. Also on heating (B) with NaOH, gas (F)
is formed which gives white fumes with HCl.

9. The red gas (C) would be

[Type text]
[Type text]

(a) Br2 (b) Cl2

(c) CrO2Cl2 (d) Cr(OCl)Cl

10. Yellow solution (D) is

(a) Na2CrO4 (b) Cr2O3
(c) PbCrO4 (d) Na2Cr2O7

11. The yellow ppt (E) is of

(a) Na2CrO4 (b) PbCrO4
(c) PbCr2O7 (d) K2Cr2O7

12. The compounds (A) and (B) are

(a) Na2CrO4 and NH4Cl (b) Na2Cr2O7 & NH4Cl
(c) K2Cr2O7 and NaCl (d) NH4Cl, Na2CrO4

Answers to Assignments
SECTION - I

Level - I

1. (b) 2. (c) 3. (d) 4. (c)

5. (d) 6. (a) 7. (b) 8. (b)
9. (a) 10. (d) 11. (d) 12. (d)
13. (a) 14. (d) 15. (a) 16. (b)
17. (c) 18. (b) 19. (a) 20. (b)

Level - II

1. (c) 2. (c) 3. (b) 4. (c)

5. (c) 6. (d) 7. (c) 8. (a)
9. (c) 10. (c)

SECTION – II

1. (b), (c), (d) 2. (a), (b) 3. (a), (b) 4. (a), (b)

5. (b), (c) 6. (a), (c) 7. (a), (b) 8. (a), (b), (c)
9. (a), (d) 10. (a), (b)

SECTION - III

1. (c) 2. (b) 3. (a) 4. (d)

5. (c) 6. (d) 7. (b) 8. (a)

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 Chemistry : Qualitative Analysis - 61

9. (c) 10. (a) 11. (b) 12. (b)

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