VMC Salt Analysis

Vidyamandir Classes Inorganic Qualitative Analysis
Inorganic Qualitative Analysis

Inorganic Qualitative Analysis involve indentification of cationic part and anionic part of a salt by using dry
test and wet test. Identification of cationic part is called as basic radical analysis while identification of
anionic part is called as acid radical analysis.
IDENTIFICATION OF ACIDIC/BASIC RADICALS Section - 1
[A] Physical Appearance of salt :

1. Colour :
2. Feel of Salt :
[B] Effect of Heating on Salts :

1. When a gas is evolved :
(a) Coloured gas :
(i) NO2, (Brown) turns starch Iodine paper blue.
Substance : Nitrites and Nitrates of heavy metals

e.g., 2Cu(NO3)2 
 CuO + 4NO2 + O2
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Inorganic Qualitative Analysis Vidyamandir Classes
(ii) Br2 (Reddish Brown) turns starch paper yellow.

Substance : Bromide
e.g.,  2CdO + 2Br 
2CdBr2 + O2  2
(iii) I2 (Violet) turns starch paper blue
Substance : Iodides
e.g.,  2CdO + 2I 
2CdI2 + O2  2
(iv) Cl2 (Greenish Yellow) bleaches moist litmus paper.
Substance : Chlorides

e.g., CuCl2 + H2O   [CuO + 2HCl] 
 Cu + H2O + 1/2Cl2
(moisture)
(b) Colourless gas (odourless) :
(i) O2 supports glowing.
Alkali nitrates

2KNO3 
 2KNO2 + O2
(ii) CO2 turns lime water milky.
Carbonates/Oxalates

CaCO3   CaO + CO2
(iii) CO burns with blue coloured flame.

CaC 2O4  CaO+ CO  + CO2 
(c) Colourless gas (with odour) :
(i) NH3 turns red litmus blue.
Ammonium salts

(NH4)2SO4 
 NH4HSO4 + NH3
(ii) SO2  Smell of burning sulphur, turns acidified K2Cr2O7 paper green.
Sulphites, thiosulphates
 CaO + SO SO
2  Cr (SO )
CaSO3  2 ;
K 2Cr2O7  2 4 3
Acidified
(iii) HCl pungent smell, white fumes with ammonia
Hydrated Chlorides
CaCl2.6H2O 
 Ca(OH)2 + 4H2O + 2HCl
H S
2  PbS
(iv) H2S  Smell of rotten egg, turns lead acetate paper black Pb(CH3COO)2 
Lead Acetate
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Sulphides

Na2S + 2H2O 
 2NaOH + H2S
2. A residue (oxide) is left and colour :
[C] Properties of Gases :

[D] Flame Test :

Some salts, especially the chlorides, of the groups 1 and
2 (except Be and Mg) of the periodic table, when placed
in the flame, get volatilised and impart characteristic colour
to the flame. The test is carried out by placing a mixture
of the salt and concen trated HCl (so as to con vert the
salt into the chloride) in a flame with the help of a plati-
num wire.
The platinum wire used for the test must be clean. It is
cleaned by dipping it in concentrated HCl and placing it
in a flame. The process is repeated till the wire imparts
no colour to the flame.
The clean wire is again moistened with a fresh sample
of concentrated HCl. Then it is made to touch the given
inorganic sample so that some of it adheres to the wire,
and is finally placed in the flame. The colour impacted to
the flame is noted.
3. Substance melts : Salts of alkali metals and salts having water of crystallization.
4. Substance makes crackling noise : NaCl, KI, Pb(NO3)2, Ba(NO3)2

5. Substance Swells : Alums, borates and phosphates
6. Substance sublimes and colour of sublimate is :

[E] Borax Bead test and Microcosmic Bead test :

Borax Bead test
Coloured salts like those of copper, iron, chromium, manganese, cobalt and nickel respond to this test.
The free end of clean platinum wire is made into a loop by curling it around a pencil or ball-pen tip. The
wire is placed in a Bunsen flame and the red-hot loop is introduced into a bulk of solid borax. The solid
clings to the loop. On being heated in the flame, the solid first swells due to the loss of water of crystallization
(in the form of vapour) and then forms a colourless, transparent bead upon the loop, called the borax bead.
heat heat 2 NaBO2 + B2O3

Na 2 B4 O7 10 H 2O 
Na 2 B4O7 

10 H 2 O Sodium metaborate Boron(III) oxide

Borax bead
A borax bead is thus a solid solution of sodium metaborate and boron(III) oxide. The hot bead is made to
touch the sample so that a small particle of the latter adheres to the bead. On being heated again in the
uppermost part of the flame, the bead becomes coloured due to the formation of the coloured metaborate
of the corresponding metal.
CuO+ B2O3  Cu(BO2 ) 2 Fe 2O3 + 3B2O3  2 Fe(BO2 )3

Copper(II) metaborate Iron(III) metaborate
Blue Yellow
FeO+ B2O3  Fe(BO2 )2 Cr2O3 + 3 B2O3  2 Cr(BO 2 )3

Iron(II) metaborate Chromium (III) metaborate
Green Green
CoO+ B2O3  Co(BO 2 )2

Cobalt(II) metaborate
Blue
A more detailed analysis can be made by heated the bead in the different zone of the flame____ oxidiaing and
reducing__ and then looking at the colour of the bead when cooled. The different colour, when they arise, are
due to the different oxidation state of the metal. For example, a copper salt will give a blue bead due to the
formation of copper(II) metaborate in the oxidising flame, but a red opaque bead due the reduction of
copper to the metallic state in the reducing flame. Similarly, an iron salt gives a yellow bead in an oxidising
flame [due to the formation of iron (III) metaborate], but a green bead in the reducing flame [due to the
formation of iron (II) metaborate]. The colours of the beads in oxidising and reducing flames for various
metals are given in Table 1.
Microcosmic Bead test :
Sodium ammonium hydrogenphosphate tetrahydrate, Na(NH 4 ) HPO 4  4 H 2O, called microcosmic salt,
gives on fusion a similar glassy, colourless bead as borax does. The bead consists of sodium metaphosphate.

The test is carried out in the same manner as the boraxbead test. The beads are coloured due to the
formation of coloured orthophosphates, the colours for the corresponding metals being the same as those of
borax beads (Table 1).
heat
Na(NH 4 ) HPO4  4 H 2O 
 NaPO3 + NH3  +5H 2O 
Sodiummetaphosphate
heat
CuO + NaPO3 
 NaCuPO4
Sodium Copper(II) orthoposphate
Blue
Table 1 : Colours of Borax and Microcosmic Salt Beads
Charcoal Cavity Tests :

A small amount of the sample is thoroughly mixed
with twice its bulk of Na2CO3 or fusion mixture
(an equimolar mixture of Na2CO3 and K2CO3 ; this
has a lower melting point than Na2CO3). A cavity is
made in a charcoal block with the help of a small
coin. The mixture is placed in the cavity and made to
settle with the help of a drop of water. Two such
blocks are prepared ––one for being heated in an
oxidising flame and the other in a reducing flame.
Heating in an oxidising flame (Cobalt nitrate test)
An oxidising flame is played over the mixture with help
of a blow pipe. If the mass glows, a drop of Co(NO3)2
solution is added to it and the mass is again heated for a
few seconds.
The colour of the mass is noted.On being heated, the salt reacts with Na2CO3 (or fusion mixture) to form
the oxide of the corresponding metal. Co(NO3)2 decomposes to CoO. The oxides of Al, Zn and Mg form
coloured compounds or solid solutions with CoO.
Al2 (SO 4 )3  3Na 2CO3 

 Al2O3  3 Na 2SO 4  3CO 2 CoO  Al2O3 
 CoAl2O4

ZnSO 4  Na 2CO3 
 ZnO  Na 2SO 4  CO2 CoO  ZnO 
 CoZnO2
MgSO 4  Na 2CO3  MgO  Na 2SO 4  CO2 CoO  MgO 

 CoMgO2
1
Co(NO3 ) 2  CoO  2NO2  O 2
2
Heating in a reducing flame :

The mixture is subjected to a reducing flame (using a blow pipe) consistently for a couple of minutes. One
reaction with fusion mixture, lead and copper salts form PbO and CuO, which are reduced to the respective
metals.
Pb appears as a white metallic bead which, when washed with water and rubbed on a piece of paper, leaves
a pencil mark on it. Cu appears as very small, red-brown particles in the charcoal cavity.
Fe appears as black magnetic mass in the classical cavity.
[F] Solubility Table :

Illustration - 1 Give reasons for the following : Liquid oxygen sticks to the poles of a magnet but liquid
nitrogen does not.
SOLUTION :
Based on molecular orbital theory, electronic configuration of O2 is
1s 2 ,  *1s 2 , 2 s 2 ,  *2 s 2 , 2 p x2 , 2 p 2y , 2 p z2 ,  *2 p1y ,  *2 p1z ,  * 2 px0

Thus, oxygen molecule has two unpaired electrons in its molecular orbitals and hence it is paramagnetic and
sticks to the poles of magnet.
Electronic configuration of N 2 is 1s 2 ,  *1s 2 , 2s 2 ,  *2s 2 , 2 p 2y , 2 p z2 , 2 p 2x ,  * 2 p 0y  * 2 pz0 ,  *2 p 0x
All molecular orbitals are completely filled. Thus, nitrogen molecule is diamagnetic and therefore does not
stick to the poles of the magnet.
Illustration - 2 A white solid (X) on heating upto 300C decomposes into its constituent elements (Y) and
(Z). (Y) is black violet solid at RTP while (Z) is a gas with a paramagnetic moment of about 2.8 B.M. (X) can
be reduced to (Y) by colourless poisonous gas (A). (Y) dissolves completely in hypo solution to give a colourless
solution and turns starch paper blue. Identify the unknowns.
SOLUTION :
 reduction of
X(solid) 
Y(solid) + Z(gas) X + A(g) 
Y
300° C Colourless X
 =2.8B.M.
& poisonous
Strach hypo
Blue 
Y  Colourless solution
Paper
The set of properties of (Y) says that it is white colour solid compound of iodine and may be I2O5 .
A colourless poisonous gas which can reduce I2O5 into iodine is CO as
I2O5 + 5CO  I2 + 5CO2
In this circumstances Z must be oxygen. We know that oxygen molecule has two unpaired electrons in its
antibonding molecular orbital, so it must be of dipole moment equal to 2(2  2) B.M. i.e. 2.82 B.M.
So (X) = I2O5 (Y) = I2 (A) = CO (Z) = O 2

Illustration - 3 An orange solid (A) on heating gives a green residue (B), a colourless gas (C) and water
vapour. The dry gas (C) on passing over heated Mg gave a white solid (D). (D) on reaction with water gave
a gas (E) which formed dense white fumes with HCl. Identify (A) to (E) giving reactions.
SOLUTION :
According to question,

Orange solid  Green residue + Colourless gas + H 2O
(A) (B) (C)
heated Mg 2  gas (E) H O HCl

(C) 
 whitesolid(D)   white dense fumes
(i) Since HCl forms dense white fumes on reaction with gas (E), (E) should be ammonia.
(ii) On hydrolysis of white solid (D), NH3 is formed. So, (D) should be Mg3 N 2 .
(iii) Since, compound (D) is formed by the reaction of gas (D) with Mg. So, the colourless gas (C) must
be nitrogen.
(iv) (A) must be ammonium dichromate (orange colour). On heating it, green residue is obtained, which
must be Cr2O3 .
Reactions Involved :
 
(NH 4 )2 Cr2O7 
 N 2 + Cr2O3 + 4 H 2O N 2 + 3Mg 
 Mg 3 N 2
(A) (C) (B) (D)
 
Mg3 N 2 + 6 H 2O 
 3Mg(OH) 2 + 2 NH3 NH3 + HCl 
 NH 4Cl
(D) (E) (E)
Illustration - 4 A certain slat (X) gives the following tests :

(i) Its aqueous solution is alkaline to litmus.
(ii) On strongly heating it swells to give glassy material.
(iii) When concentrated H 2 SO4 is added to a hot concentrated solution of (X), white crystals of a weak
acid separate out. Identify (X) and write down the chemical equations for reactions at steps (i), (ii)
and (iii).
SOLUTION :
(i) Aqueous solution of salt (X) is alkaline to litmus. So, (X) may be an alkali metal salt.
(ii) On strong heating, salt (X) swells to give glassy material. So, it may be borax.
(iii) Further, when (X) is treated with conc. H 2SO 4 , white crystal of weak acid (i.e. boric acid) sepa-
rates out. This fact also supports that salt (X) is borax.
Hence, salt (X) is borax (Na 2 B4O7 10 H 2O)

Illustration -4
The chemical equations for reactions at steps (i), (ii) and (iii) are shown below:
(i) Na 2 B4O7 + 7 H 2O  2 NaOH+ 4 H3BO3
(X) alkali
heat heat
(ii) Na 2 B4 O7 10 H 2O 
 Na 2B4O7 +10 H 2O Na 2 B4O7 
 2 NaBO 2 + B2O3

Glassy material
(iii) Na 2 B4O7 + H 2SO 4 + 5H 2O  Na 2SO4 + 4 H3BO3

Weak acid
Illustration - 5 When 20.02 gm of a white solid (X) is heated, 4.4 gm of an acid gas (A) and 1.8 gm of
neutral gas (B) are evolved leaving behind a solid residue (Y) of weight 13.8 gm. (A) turns lime water milky
and (B) condenses into liquid which changes anhydrous copper sulphate blue. The aqueous solution of (Y) is
alkaline to litmus and gives 19.7 gm of white ppt. (Z) with barium chloride solution. (Z) gives carbon dioxide
with an acid. Identify (A), (B), (X), (Y) and (Z).
SOLUTION :
According to question,

X 
 (A) + (B) + (Y)
20.02 gm 4.4 gm 1.8 gm 13.8 gm
(i) (A) turns lime water milky, so it may be CO 2 or SO 2 .

(ii) The neutral gas (B) condenses into liquid which changes anhydrous copper sulphate blue. So (B) is
H 2O.
(iii) The aqueous solution of (Y) is alkaline and gives white ppt. (Z) with barium chloride solution.
Solution, (Y) is metal carbonate.
(iv) Since, (Y) and (A) are formed from (X). So (X) is a metal bicarbonate.

2 MHCO3 
 CO2 + H 2O+ M 2CO3
(X) (A) (B) (Y)
 4.4gm CO 2 is obtained from 20.02 gm MHCO3

20.02
 44 gm CO 2 is obtained × 44 gm MHCO3 = 200.2 gm
4.4
200.2
 Molecular weight of MHCO3 = = 100.1
2
 M  1  12  (16  3)  100.1 or M  100.1  61  39.1
Hence, atomic weight of M is 39.1 and the metal is potassium.

Reaction Involved : 2 KHCO3  CO2 + H 2O+ K 2 CO3
(X) (A) (B) (Y)

ACID RADICALS Section - 2
Radicals tested by dilute HCl/H2SO4 : Radical tested by concentrated H2SO4 :
(A) Major Reactions in detection of Acid Radicals :

1. Carbonate : (CO32–)
CO32 + dil HCl/H2SO4 

 CO2
CO2 with Ca(OH)2 

 milky solution
Na2CO3 + H2SO4 
 Na2SO4 + H2O + CO2 
Confirm :
CO2 + Ca(OH)2   CaCO3  + H2O

(White or milky solution)
 If excess of CO2 is there :
CO 2 + CaCO3 + H 2O  Ca(HCO3 )2 (aq)

Colourless
2. Sulphite : (SO32–)
dil H 2 SO4
SO32   gives SO2
(suffocating smell)
Na2SO3 + H2SO4 
 Na2SO4 + H2O + SO2
Confirm :
(a) SO2 + H2SO4 + K2Cr2O7 
 Cr2 (SO4 )3

(b) SO2 + Ca(OH)2 

 CaSO3 + H2O
(Milky)
3. Sulphide : (S2–)
S2 
dil H 2 SO 4
 H2S  (Pungent smelling)
(smell like ratten eggs.)
FeS + H2SO4 
 FeSO4 + H2S
Na 2S+ H 2SO 4  Na 2SO 4 + H 2S 

Confirm :
2 HS
(a) (CH3COO)2 Pb   PbS 
(Lead acetate)
paper
2Na [Fe(CN) (NO)]

5
(b) Na 2S 
 Na 4[Fe(CN)5 NOS]
(c) CdCO3 + Na2S  CdS  + Na 2CO3
4. Nitrite : (NO2–) On treatment with dil acid, a nitrite salt decomposes to give NO, which in
contact with air forms reddish-brown NO2 gas.
dil H SO
2 4 NO 
NO2  2 2NaNO2 + H2SO4 
 Na2SO4 + 2HNO2
3HNO2 
 HNO3 + 2NO  + H2O 2NO + O2 
 2NO2
(air)
Confirm :
(a) Brown ring test : FeSO4 + NO 

 Fe(NO)SO4
Brown Ring
(b) 2KI + 2NO2 

 2KNO2 + I2
I2 + starch 
 starch iodide complex (blue)
5. Acetate : (CH3COO–)
dil H 2 SO 4
CH3COO   acetic acid (vapours smelling of vinegar)
2CH3COONa + H2SO4 
 Na2SO4 + 2CH3COOH (acetic acid)
Confirm :
CH3COONa(aq) + FeCl3 
 (CH3COO)3Fe + 3NaCl

6. Chloride : (Cl–)
Cl 
conc.
HCl 
H 2SO4
NaCl + H2SO4 
 Na2SO4 + 2HCl , NH4OH + HCl 
 NH4Cl + H2O
conc. white fumes
Confirm :
(a)  AgCl  + HNO3
AgNO3 + HCl  [AgCl  white ppt dissolved in NH 4OH]
AgCl + 2NH4OH 
 Ag(NH3)2Cl + 2H2O
(Soluble complex)
Ag(NH3)2Cl + 2HNO3 
 AgCl  + 2NH4 NO3
(ppt. appears again)
(b) Chromyl Chloride Test :
NaCl + H2SO4 
 NaHSO4 + HCl
K 2Cr2O7 + 2H2SO4 
 2KHSO4 + 2CrO3 + H2O
2HCl + CrO3 
 CrO2Cl2 + H2O
CrO2Cl2 + 4NaOH 
 Na2CrO4 + 2NaCl + + 2H2O
Na2CrO4 + (CH3COO)2Pb 
 PbCrO4 + 2CH3COONa
Na2CrO4 + BaCl2 
 BaCrO 4  + 2NaCl
Na2CrO4 + 2AgNO3 
 Ag2CrO4 + 2NaNO3
Note : Chromyl chloride test is not shown by insoluble chlorides.

7. Bromide : (Br–)
conc. H 2 SO4
Br   HBr + Br2 2KBr + H2SO4 
 K2SO4 + 2HBr
2HBr + H2SO4 
 2H2O + SO2 + Br2 
Confirm :
(a)  AgBr  + NaNO3
NaBr + AgNO3 
AgBr + NH4OH 
 [Ag(NH3)2]Br + 2H2O
partially soluble

(b) 2KBr + Cl2(water) 

 2KCl + Br2
Br2 + chloroform 
 Reddish Brown coloured chloroform.
To differentiate between Br2 and NO2 as both redish brown in colour.
(i) Brown vapour of Br2 on passing on passing in H2O, gives brown colour, but NO2 does not impart
colour to water.
(ii) Cl2 water liberates Br2 from bromide which dissolves in CHCl3 or CCl4 to impart it orange brown
colour.
2NaBr + Cl2 
 2NaCl + Br2
Br2 + CHCl3 
 Reddish Brown coloured chloroform layer
8. Iodide (I–)
conc.
I 
H SO
I2 
2 4
2KI + H2SO4 (conc.) 

 K2SO4 + 2HI 2HI + H2SO4 
 2H2O + SO2 + I2
2KI + MnO2 + 3H2SO4 

 2KHSO4 + MnSO4 + 2H2O + I2 
Confirm :
(a) I2 + starch 
 Blue coloured complex
(b)  AgI  + NaNO3
NaI + AgNO3  AgI  + NH4OH   Insoluble
(c) KI + Cl2 water 
 2KCl + I2 I2 + chloroform 
 Violet coloured chloroform. (layer)
9. Oxalate : (C2O42–)
conc. H SO
2 4 CO + CO
C2O42  2
(i) Oxalates are decomposed by conc. H2SO4 to give CO2 and CO. The latter burns with blue
flame, while the former turns lime water milky.
C OONa C OOH C OOH

|  H 2 SO4  Na2 SO4  | 
|  CO  CO2  H 2O
COONa COOH COOH
Sod.oxalate Oxalic acid
CO2 + Ca(OH)2  CaCO3 + H2O

(ii) Oxalate salt on reaction with dil. H2SO4 and MnO2 gives more intensive effervescence of
CO2 .
Na2C2O4 + 2H2SO4 (dil) + MnO2 

 Na2SO4 + MnSO4 + 2CO2 + 2H2O

Confirm :
(a) CO burns with blue flame (2CO + O2 
 CO2).
(b) Na2C2O4 + CaCl2 

 CaC2O4 + 2NaCl
(c) Oxalate decolourises acidified KMnO4 solution.
2KMnO4 +3H2SO4 
 K2SO4 + 2MnSO4 + 3H2O + 5[O]
colourless
 10 CO2 + 5H2O
H2C2O4 + 5[O] (acidified KMnO4) 
10. Fluoride (F–)

conc.
F 
H SO
HF  NaF + H2SO4 
 Na2SO4 + 2HF 
2 4
Confirm :
(a) SiO2 + 4HF 
 SiF4 + 2H2O (Glass is soluble in aqueous solution of HF)
(glass)
3SiF4 + 3H2O 
 2H2SiF6 + H4SiO4 (waxy deposit)
Soluble Hydrofluorosilicic Acid
(b) NaF + CaCl2 

 CaF2 + 2NaCl
11. Phosphate : (PO43–)

HNO (amm.molybdate)
3
PO43 
 yellow ppt.
Ba3(PO4)2 + 6HNO3 
 3Ba(NO3)2 + 2H3PO4
 (NH4)3PO4.12MoO3 +12H2O + 21NH4NO3

H3PO4 + 12(NH4)2MoO4 + 21 HNO3 
Ammonium molybdate Ammonium phosphomolybdate
12. Sulphate : (SO42–)
(a)  BaSO4 + 2NaCl

Na2SO4 + BaCl2  BaSO4 + HNO3 
 Insoluble
BaSO4 is in soluble in hot water and hot conc. HNO3
(b)  PbSO4 + 2CH3COONa

Na2SO4 + (CH3COO)2Pb 
PbSO 4 is soluble in ammonium acetate solution.

13. Nitrate (NO3–)

NaNO3 + H2SO4 
 NaHSO4 + HNO3 4HNO3 
 4NO2  + O2 + 2H2O
Confirm : Brown Ring test (same as nitrite)
NaNO3 + H2SO4 
 NaHSO4 + HNO3
6FeSO4 + 3H2SO4 + 2HNO3 

 3Fe2(SO4)3 + 4H2O + 2NO
FeSO4 + NO 
 [Fe(NO)]SO4
Note : Since, both nitrite and nitrate are responding to ring test, nitrite is removed
(when both are present together) by heating with NH4Cl or with urea/dil H2SO4.
NaNO2 + NH4Cl 
 NaCl + NH NO
4 2
NH4NO2 
 N2 + 2H2O
Illustration - 6 A well known orange crystalline compound (A) when burnt impart violet colour to the
flame. (A) on treating with (B) and conc. H 2SO 4 gives red gas (C) which gives yellow solution (D) with
alkaline water. (D) on treatment 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. What are (A)
to (F) ?
SOLUTION :
(i) Since, (B) sublimes on heating and also gives gas (F) with NaOH which forms white fumes with
HCl. So (B) is NH 4 Cl.
(ii) (A) on treatment with (B) and conc. H 2SO 4 gives red gas (C) i.e. CrO 2Cl2 . So, (A) is
K 2Cr2O7 .
Reaction Involved
(i) K 2Cr2O7 + 4 NH 4Cl+ 3H 2SO4  K 2SO 4 + 2CrO 2Cl2 + 2(NH 4 )2 SO 4 + 3H 2 O
(C)
(ii) CrO2Cl2 + 4 NaOH  Na 2CrO 4 + 2 NaCl+ 2 H 2 O

(D)
(iii) Na 2CrO 4 + (CH3COO)2 Pb  PbCrO 4  2CH3COONa

(E)
(iv) 
NH 4Cl(s)  NH 4Cl(g)

(v) NH 4Cl+ NaOH 
 NaCl+ NH3 + H 2O
(F)
(vi) NH3 + HCl  NH 4Cl

(F)

NOW ATTEMPT IN-CHAPTER EXERCISE-A BEFORE PROCEEDING AHEAD IN THIS EBOOK
GROUP OF BASIC RADICALS AND REAGENTS Section - 3
(A) Precipitation of Group Radicals

Zero Group radicals are not precipitated.
I. Group radicals are precipitated in the form of their chlorides.
AgCl PbCl2 Hg2Cl2
II. Group radicals are precipitated in the form of their sulphides.

II.A HgS PbS CuS CdS Bi2S3 or Bi 2S3
II.B As2S3 Sb2S3 SnS SnS2
Sulphides of II.A not soluble while sulphides II.B soluble in yellow ammonimum sulphide.
III. Group radicals are precipitated in the form of their hydroxides.

Fe(OH)3 Cr(OH)3 Al(OH)3
IV. Group radicals are precipated in the form of their sulphides.

MnS CoS ZnS NiS
V. Group radicals are precipated in the form of their carbonates.
BaCO3 SrCO3 CaCO3
VI. Group radicals is precipitated in the form of its Ammonium Phosphate.
Mg(NH4)PO4

(B) Basic Radicals

Zero Group NH4+, K+, Na+
1. Ammonium salts when heated with NaOH gives off ammonia.
NH4Cl + NaOH 
 NaCl + H O + NH 
2 3
HCl + NH3 
 NH Cl (Dense white fumes)
4
Evolution of NH3 is confirmed by :

(a) A paper soaked in CuSO4 solution becomes deep blue by NH3 due to complex formation.
CuSO4 + 4NH3 
 [Cu(NH3)4]SO4
(b)  Hg(NH
Hg2(NO3)2 + 2NH3  
) NO3 + Hg + NH 4 NO3
2 
Black
Note : 1. All nitrates and nitrites on reduction will give ammonia
Zn + 2HCl  ZnCl2 + 2[H]

Lucas Reagent
NaNO3 + 8[H] 
 NH + 2H O + NaOH
3 2
NaNO2 + 6[H] 
 NH3 + H2O + NaOH
2. All nitrates on decomposition give oxygen, metal oxide, O2

Exception :

NH4NO3 
 

2AgNO3 
 2Ag + 2NO2 + O2

2NaNO3 
 2NaNO2 + O2
3. All nitrites on decomposition give nitrogen.

Exception :

N2H5NO2 
 N3H + 2H2O

2. Ammonium salts give brown precipitate with Nessler’s reagent (K2HgI4).

2 K 2HgI4 + 4 KOH + NH4Cl  I Hg O Hg  NH 2 + 7 KI + KCl + 3H2 O
Nessler’s reagent :
HgCl2 + 2KI  HgI2  + 2KCl
NH OH
4
HgI2 + 2KI K 2HgI4  [HgO.HgNH2 ] I
Iodide of Million's base
Heating effect on ammonium salts :

[If anionic part is oxidising in nature, then N 2 will be the product (some times N 2O )]
[If anionic part is weakly oxidising or non oxidising in nature then NH3 will be the product.]
(NH 4 ) 2 Cr2O7  N 2 + Cr2O3 + 4 H 2O (NH 4 ) 2 HPO4  HPO3 + H 2O+ 2 NH3

NH 4 NO 2  N 2 + 2 H 2O (NH 4 ) 2 SO 4  NH3 + H 2SO 4
NH 4 NO3  N 2O+ 2 H 2O 2(NH 4 )3 PO 4  2 NH3 + P2O5 + 3H 2O
2 NH 4ClO4  N 2 + Cl2 + 2 O2 + 4 H 2O (NH 4 )2 CO3  2 NH3 + H 2O+ CO 2
2 NH 4 IO3  N 2 + I2 + O2 + 4 H 2O
Purple
Complex formation reaction :
AgOH(s) + 2 NH 4OH  [Ag(NH3 )2 ]OH+ 2 H2 O
4 NH OH
CuSO 4 + NH 4OH  Cu(OH) 2  [Cu(NH3 ) 4 ]SO4
Switzer's reagent

Cu(OH)2 
 CuO+ H 2O
2CuO+ C6 H12O6  Cu 2O+ C6 H12O7
Glucose Gluconic Acid
C dSO 4 + NH 4OH  Cd(OH)2  [Cd(NH3 )4 SO4 + H 2O

Soluble complex
NiCl2 + NH 4OH  Ni(OH) 2  [Ni(NH3 ]6 Cl2 + H2 O

NH 4OH+ HCl  NH 4Cl+ H 2O
SnCl4 + 2 NH 4Cl  (NH 4 )2 SnCl6 (Pink salt : used as mordant)
CrCl3 + 3 NH 4OH  Cr(OH)3 + 3 NH 4 Cl
AlCl3 + 3 NH 4OH  Al(OH)3 + 3 NH 4 Cl

FeCl3 + 3 NH 4OH  Fe(OH)3 + 3 NH 4 Cl

HgCl2 + 2 NH 4OH  Hg(NH 2 ) Cl+ NH 4 Cl+ 2 H2 O
Na 2Cr2O7 + 2 NH 4OH  (NH 4 )2 Cr2O7 + 2 NaOH

(NH 4 ) 2 Cr2O7  Cr2O3 + N 2 + 4 H 2O
3Mg + N 2  Mg3 N 2
Mg3 N 2 + 6 H 2O  3Mg(OH)2 + 2 NH3
3. Potassium salts gives yellow precipitate with sodium cobaltinitrite.
Na3[Co(NO2)6] + 3KCl 
 K3[Co(NO2)6] + 3NaCl
4. Sodium salts give thick white precipitate with potasium dihydrogen antimonate.
 NaH2SbO4  + KCl
KH2SbO4 + NaCl 
Illustration - 7
The gas liberated on heating a mixture of two salts with NaOH, gives a reddish brown
precipitate with an alkaline solution of K 2 HgI 4 . The aqueous solution of the mixture on treatment with
BaCl2 gives a white precipitate which is sparingly soluble in conc. HCl. On heating the mixture with K 2Cr2O7
and conc. H 2 SO4 , red vapours (A) are produced. The aqueous solution of the mixture gives as deep blue
colouration (B) with potassium ferricyanide. Identify the radical in the given mixture and write the balanced
equations for the formation of A and B.
SOLUTION :
(i) The gas liberated on heating a mixture of two salts with NaOH gives a reddish brown ppt. with
K 2 HgI4 . So, the gas is NH3 and the salt is an ammonium salt.
(ii) The aqueous solution gives white ppt. with BaCl2 (sparingly soluble in HCl). So, the mixture contain
SO 24 ion .
(iii) On heating the mixture with K 2Cr2O7 and conc. H 2SO 4 . red vapours of CrO 2Cl2 are produced.
This shows the presence of Cl ion .

(iv) Formation of blue colour by aqueous solution with K3[Fe(CN)6 ]indicates the presence of Fe2+ ion.
Reaction Involved :
(i) NH 4 Cl+ NaOH  NH3 + NaCl+ H2 O
2 K 2 HgI4 + 4 KOH + NH 4Cl  I Hg  O  Hg  NH 2 + 7 KI+ KCl+ 3H 2 O

(ii) FeSO 4 + BaCl2  BaSO 4 + FeCl2
(iii) 4 NH 4Cl + K 2Cr2O7 + 3H 2SO4  2CrO 2Cl2 + K 2SO 4 + 3H 2O + 2(NH 4 )2 SO 4
(iv) 3FeSO 4 + 2 K 3[Fe(CN)6 ]  Fe3[Fe(CN)6 ]2 + 3K 2SO4
HgCl2 + 2 NH 4OH  Hg(NH 2 ) Cl.Hg + NH 4 Cl + 2 H2 O
Ist Group Ag + , Pb 2+ , Hg 2+
2 (Mercurous)
Group Reagent : Dilute HCl

The radicals are precipitated as their chlorides because the solubility product of these chlorides
(AgCl, PbCl2,Hg2Cl2) is less than the solubility product of all other chlorides which remain is solution.
Pb(NO3)2 + 2HCl 
 PbCl2  + 2HNO3
AgNO3 + HCl 
 AgCl  + HNO3
 Hg2Cl2  2HNO3
Hg2(NO3)2 + 2HCl 
Confirm :
1. PbCl2 is soluble in hot water whereas AgCl and Hg2Cl2 are insoluble in hot water.
2. PbCl2 gives yellow precipitate with K2CrO4. The precipitate is insoluble in acetic acid but soluble in
NaOH.
 PbCrO4  + 2KCl
PbCl2 + K2CrO4 
2Ag+ + CrO4–2 
 Ag2CrO4
Ag + + KI 
 AgI+ K +
[Ag(S2O3 ) 2 ]3 + 4 Na +
Ag + + 2 Na 2S2O3 
3. PbCl2 + KI 
 PbI2 + 2KCl
KI
PbI2 K 2 [PbI4 ]soluble
Excess
4. AgCl is soluble in NH4OH : AgCl + NH4OH 

 Ag(NH3)2Cl + 2H2O
5. Hg2Cl2 forms black precipitate with NH4OH. Black precipitate is dissolved in aqua-regia.
HgCl2 + 2 NH 4OH  Hg(NH 2 ) Cl.Hg + NH 4 Cl + 2 H 2 O

HNO3 + 3HCl(aqua regia)  NOCl+ 2 H 2 O+ 2[Cl]

1 : 3
Hg(NH 2 ) Cl Hg + 6[Cl]  2 HgCl2 + N 2 + 4 HCl
HgCl2 + 2 KI  HgI2 + 2 KCl
HgI2 + 2 KI  K 2 HgI4
Nessler's reagent
Hg 2 (NO3 )2 + K 2CrO 4  Hg 2CrO 4 + 2 KNO3
Confirm :
(a) 2 HgCl2 + SnCl2  Hg 2Cl2 + SnCl4
Hg 2Cl2 + SnCl 2  2 Hg   SnCl 4
(b) HgCl2 + Cu  CuCl2 + Hg 2Cl2
Hg 2Cl2 + Cu  2 Hg + CuCl2
IInd Group II A : Hg 2+ , Pb2+ , Bi3+ ,Cu 2+ , Cd 2+
II B : As3+ ,Sb3+ ,Sn 2+ ,Sn 4+
Group Reagent : H2S(g) in Presence of HCl

These radicals are precipitated as their sulphides while the sulphides of other metals remain in solution be-
cause of their high solubility product. HCl acts as a source of H+ and thus decreases the concentration of S2
(common-ion-effect). Hence the decreased concentration of S2 is sufficient to precipitate the IInd group
metals due to their low ksp values. (Group IV metals have high solubility products)
HgS PbS CuS CdS Bi 2S3 or Bi 2S3
As 2S3 Sb2S3 SnS SnS2
1. PbS, CdS are precipitated in dilution only due to higher K sp . .
hot water cooling

PbCl2   Disolved  ppt of PbCl2 mreappears
White

Pb+2 + CrO4–2 
 PbCrO4
Pb+2 + SO4–2 
 PbSO4
NaOH Oxidised
Pb+2 + OH   Pb(OH)2 
Na 2 PbO2  Na 2 PbO3
(XS)
300 C
PbS + 3/2O2   PbO + SO2
900 C
PbO 
 PbO
Note : (i) Colour change on heating due to the change in crystal structure.
(ii) Pb(NO3)2 decomposes with cracking noise
 
2Pb(NO3)2 
 2PbO + 4NO2 + O2 ,
2PbCO3 
 2PbO + 2CO2
 470C  470C 1
Pb(OH)2  2 PbCO3  Pb3O4 + CO2 + CO+ H 2O, Pb3O 4   3 PbO + O 2
White lead 2

(CH3COO)2 Pb 
 CH3  CO CH3 + Pb+ CO2
(sugar of lead) (Acetone)
2. IIA sulphides are insoluble in yellow ammonium sulphides and IIB sulphides are soluble in it.
3. HgS is insoluble in dilute HNO3 while PbS, Bi2S3, CuS, CdS are soluble in it.
4. In water, Bi2S3, CuS, CdS etc are soluble to give respective hydroxides, but PbSO4 is not soluble.
5. Hydroxides formed above in (4) :
Bi(OH)3 is insoluble in NH4OH.
Cu(OH)2 and Cd(OH)2 form soluble complexes.
 2Bi(OH)3 + 3(NH4)2SO4
Bi(SO4)3 + 6NH4OH 
CuSO4 + 4NH4OH 
 [Cu(NH3) 4]SO4 + 4H2O
[Cu(NH3)4]SO4 + 4CH3COOH  CuSO4 + 4CH3COONH4
CuSO4 + K4Fe(CN)6  Cu2[Fe(CN)6 ] + 2K2SO4
CdSO4 + 4NH4OH  [Cd(NH3)4]SO4 + 4H2O
(Colourless)
[Cd(NH3)4] SO4 + H2S  CdS  + (NH4)2 SO4 + 2NH3

Note : HgS is only sulphide of second group which does not disolve in conc. HNO3
So we need Aquaregia (HCl + HNO3) to disolve it.
3 : 1
3HgS + 6 HCl+ 2 HNO3  3HgCl2 + 2 NO+ 3S+ 4 H 2O
Sample : 1 2 HgCl2 + SnCl2  Hg 2Cl2  +SnCl4

Hg 2Cl2  +SnCl2  2 Hg  +SnCl4
Sample : 2 Hg 2Cl2 + 2 KI  HgI2  +2 KCl
HgI 2  +2 KI  K 2 HgI4
Nessler's reagent
Pb 2+
1. Pb(NO3 )2 + K 2CrO4  PbCrO4 + 2 KNO3
PbCrO4  + 4 NaOH  Na 2 PbO 2 + Na 2CrO 4(aq) + 2 H 2O
2. Pb(NO3 )2 + K 2SO 4  PbSO 4 + 2 KNO3

PbSO4 is soluble in ammonium acetate
PbSO4 + 2CH3COONH 4  (NH 4 )2 SO4 + (CH3COO)2 Pb
Cu 2 +
1. 2Cu(NO3 )2 + K 4 [Fe(CN)6 ]  Cu 2 [Fe(CN)6 ] + 4 KNO3
2. 
Cu(NO3 )2 + 2 KI  CuI 2  +2 KNO3 2CuI2   Cu 2 I2 + I2
Cu 2I 2 + 3KI  K 3[CuI4 ] I2 + KI  KI3

3. Cu(NO3 )2 + 2 NaOH  Cu(OH)2  +2 NaNO3

Cu(OH)2   CuO  + H 2O
2 CuO  + C6 H12O6  Cu 2O  + C6 H12O7
4. 2Cu(NO3 )2 + 2 Na 2S2O3  Cu 2 (NO3 )2 + Na 2S4O6 + 2 NaNO3
Cu 2 (NO3 )2 + Na 2S2O3  Cu 2S2O3 + 2 NaNO3

3Cu 2S2O3 + 2 Na 2S2O3  Na 4[Cu 6 (S2O3 )5 ]

465 complex
5. Cu 2+ and Cd 2+ separation is based on fact that in presence of KCN, only Cd 2+ is precipitated as

sulphides on passing H2S.
6. Arsenic sulphides is insoluble in conc. HCl while Sb3+ ,Sn 2+ sulphides are soluble. Sb2S3 can be pre-
cipitated in presence of oxalic acid.
7. CuSO 4 + 2 KCN  Cu(CN) 2 + K 2SO4
2Cu(CN)4  Cu 2 (CN)2 + (CN)2 [ CN  is a pseudo halide ion and (CN)2 is pseudo halogen
known as Cyanogen.]
Cu 2 (CN)2 + 6 KCN  K3[Cu(CN)4 ]
 Properties :
· Effect of Heat :
 100°C 230°C
CuSO4  5H2O 
 CuSO4  4 H2O 
 CuSO4  2 H2O 
 CuSO4
 H 2O  H 2O 2 H 2O
 1
CuSO4   CuO+ SO2 + O 2
720°C 2
1100° C 1
2CuO   C u 2O+ O2
2
Bi3+ Bi(OH)3 is soluble in dilute HCl to form BiCl3 which is tested in two ways.
Bi(OH)3 + 3HCl  BiCl3 + 3H 2 O
(a) BiCl3 + H 2O  BiOCl  +2 HCl
(b) 2 BiCl3 + 2 Na 2SnO 2 + 6 NaOH  2 Bi  +3 Na 2SnO3 + 6 NaCl+ 3 H 2O.
cd 2+
Tests : 3CdS + 8 HNO3  3Cd(NO3 )2 + 3S+ 4 H 2O
Yellow
Sample : 1 2Cd(NO3 )2 + K 4 [Fe(CN)6 ]  Cd 2 [Fe(CN)6 ] + 4 KNO3

Sample : 2 Cd(NO3 )2 + 2 NH 4OH  Cd(OH) 2  +2 NH 4 NO3
Cd(NO3 )2 + 6 NH 4OH   Cd(NH3 )4 (OH)2  + 2 NH 4 NO3 + 4 H 2O
 Cd(NH3 )2  (OH) 2 + H2S  CdS  +4 NH3 + 2 H 2O

Sample : 3 Cd(NO3 )2 + 2 KCN  Cd(CN)2 + 2 KNO3
Cd(CN)2 + 2 KCN  K 2  Cd(CN)4 
K 2  Cd(CN)4  + H 2S  CdS  +2 KCN+ 2 HCN
Sample : 4 Cd(NO3 )2 + 2 NaOH  Cd(OH)2  2 NaNO3


Cd(OH)2   CdO  + H 2O
As3+
Tests : As 2S3 (soluble in ammonium sulphide)
Sb3+
Sample : 1 Sb 2S3 + 2(NH 4 ) 2 S2  Sb2S5 + 2(NH 4 )2 S
Soluble
Sample : 2 SbCl3 + H 2O  SbOCl+ 2 HCl
Sample : 1 2SbCl3 + 3H 2S  Sb 2S3 + 6 HCl
Sn 2+ and Sn 4+
Test : SnS  + (NH 4 ) 2 S2  SnS2  + (NH 4 ) 2 S
SnS2  (NH 4 ) 2 S  (NH 4 )2 SnS3
SnS2  + 4 HCl  SnCl4 + 2 H 2S 
SnCl2  + Fe  FeCl2 + SnCl2
SnCl2 + HgCl2  Hg 2Cl2  +SnCl4
Hg 2Cl2 + SnCl2  Hg  +SnCl4
SnCl4 + 2 NH 4Cl  (NH 4 )2 SnCl6
Note : (NH 4 ) 2 SnCl6 or pink salt is used as mordant which holds the dyes in clothes.

IIIrd Group Fe3+, Al3+, Cr3+
Fe+2 (Some imporant reaction)

FeSO4 + NO  FeSO4.NO
Nitrosoferrous sulphate
Note : Oxidation state of NO is + 1 in Fe compound. so the oxidation state of Fe in FeSO4.NO is + 1. It is

paramagnetic, its magnetic moment is 3.87 and it is coloured due to the odd electron of NO is fluctuating
in between Fe+ and NO.
FeSO4.7H2O + NO  [Fe(H2O)5NO]SO4 + 2H2O
(This reaction is employed fop separation of NO gas from other gases)
Group Reagent : NH4OH in presence of NH4Cl

Metals ions are precipitated as Hydroxides. NH4Cl is added to suppress the concentration of NH4OH by
common-ion effect, so that only IIIrd group radicals are precipitated. The Ksp value of IIIrd group hydrox-
ides is less as compared to IV/VI group hydroxides.
1. Excess of NH4Cl should be added otherwise manganese will be precipitated in IIIrd group as
MnO2.H2O.
2. (NH4)2SO4 cannot be used in place of NH4Cl since SO42 will precipitate Barium (if present) as
BaSO4.
3. NH4NO3 can’t be used otherwise NO3 will oxidise Mn2+ to Mn3+ and thus Mn(OH)3 will be
precipitated.
4. Only Al(OH)3 is soluble in excess of NaOH followed by boiling to form sodium metal aluminate,
while Fe(OH)3 and Cr(OH)3 are insoluble.
Al(OH)3 + NaOH  Na[AlO2] + 2H2O
(Aluminate, soluble)

5. Cr(OH)3 is soluble in NaOH and bromine water forming sodium chromate while Fe(OH)3 is in-
soluble.
Cr(OH)3 + NaOH  Na[CrO2] + 2H2O
soluble
Fe3+ ion
(a) FeCl3 + 3KCNS  Fe(CNS)3 + 3KCl
Potassium thiocyanate Ferric thiocyanate
(b) 4FeCl3 + 3K4[Fe(CN)6]  Fe4[Fe(CN)6]3 + 12 KCl
Ferriferrocyanate
IVth Group CO2+, Ni2+, Zn2+, Mn2+

Group Reagent : H2S in ammonical solution, NH4OH (NH4Cl is also added)
Radicals are precipitated as sulphides which are insoluble in NH4OH.
CoS ; NiS ; MnS ; ZnS

(Ammonium hydroxide increases the concentration of S2 by increasing the ionisation of H2S by removing
H+ ions in the form of H2O)
 Now the excess of S2 ions are available and hence the ionic product of IV group sulphides exceeds
their solubility product and thus a precipitate will be obtained.
 NH4Cl is used to check the precipitation of V and VI group radicals as hydroxide and sulphides
because in presence of NH4Cl, concentration of OH is fairly Low.
1. ZnS and MnS are soluble is cold dilute HCl, while NiS and CoS are insoluble.
2. Zn(OH)2 is soluble in excess of NaOH forming sodium Zincate while Mn(OH)2 insoluble.
ZnCl2 + 2NaOH  Zn(OH)2 2NaCl ; Zn(OH)2 + 2NaOH  Na2ZnO2 + 2H2O
(Soluble Zincate)
Mn+2 MnS Buff Colour


MnS  +2 HCl 
 MnCl2 + H2S 
MnCl2 + 2 NaOH  Mn(OH)2 + 2 NaCl
1
Mn(OH) 2  O 2  MnO2 + H 2O
2
MnO 2 + PbO 2 + HNO3  HMnO 4 + Pb(NO3 )2 + H 2O

MnSO 4 + 2 Na 2CO3 + 2 KNO3 
 Na 2 MnO 4 + 2 KNO 2 + 2 CO 2 + Na 2SO 4

fusion mixture
3 Na 2 MnO 4 + 4 H 2SO4  2 NaMnO 4 + 4 NaHSO 4 + MnO 2 + 2 H 2 O
Zn 2+
Zn 2+ ion is tested in two ways.

(a) Na 2 ZnO 2 + H 2S  ZnS  +2 NaOH
(b) Na 2 ZnO 2 + CH3COOH  (CH3COO)2 Zn+ 2 NaOH
2(CH3COO) Zn + K 4 [Fe(CN)6 ]  Zn 2 [Fe(CN)6 ] + 4 CH3COOK
Pot .ferrocyanide Zinc ferrocyanide
3. Separation of Co2+ and Ni2+ : Sulphides of Co 2+ and Ni 2+ are soluble in aqua-regia.
Co 2+ and Ni 2+ chlorides form soluble complexes with KCN.

3CoS + 6HCl + 2HNO3  3CoCl2 + 2NO +3S + 4H2O
3NiS + 6HCl + 2HNO3  3NiCl2 + 2NO + 3S + 4H2O

(a) CoCl2 + 2KCN  Co(CN)2 + 2KCl

[O]
Co(CN) 2  4KCN 
 K 4 [(Co(CN)6 ]   K 3[Co(CN)6 ]
KCN
Pot.cobaltocyanide
(b) NiCl2 + 2KCN  Ni(CN)2 + 2KCl
Ni(CN)2 + 2KCN  K2[Ni(CN)4]

Pot. nickelocyanide
When NaOH and Br2 water is treated with potassium cobaltocyanide, it is oxidised to very stable complex,
potassium Cobalticyanide.
2NaOH + Br2  NaBr + NaOBr + H 2O (NaOBr  NaBr + O)
2K4[CO(CN)6] + (O) + H2O  2 K 3[Co(CN)6 ]+ 2 KOH

Stable
 Nickel complex decomposes forming black Nickel oxide.
2K2[Ni(CN)4] + 4NaOH + [O]  Ni2O3  + 4NaCN + 4KCN + 2H2O
Nickel salts react with dimethyl glyoxime in presence of NH4OH to give rose red precipitate of
Nickel dimethyl Glyoxime.
 Cobalt salts give blue colour with ammonium thiocynate (not KSCN)
CoCl2 + 4NH4SCN  (NH4)2 [Co(SCN)4] + 2NH4Cl
Cobalt salt solution in acetic acid gives a bright yellow precipitate yellow precipitate of potassium cobaltinitrite
with KNO2.
Vth Group Ba2+ , Sr2+ , Ca2+
1st part + K 2CrO 4 If Ba 2+ is absent, use 2nd part If Ba 2  and Sr 2+ both are absent,
soln. Yellow precipitate Add (NH 4 )2 SO4 solution use the 3rd part.
White precipitate Add (NH 4 )2 C 2O4 White
precipitate
Ba 2  present Sr 2+ present Ca 2+ present
Group Reagent : (NH4)2CO3 in NH4Cl and NH4OH

Radicals are precipitated as carbonates insoluble in NH4OH. NH4Cl is used to suppress the ionisation of
NH4OH and (NH4)2CO3 this is to check the precipitation of Mg(OH)2 and MgCO3 since solubility product
of Mg(OH)2 and MgCO3 is high. NH4Cl should not be added in excess since high concentration of NH4+

ions will decrease the ionisation of (NH4)2CO3 to such an extent that the sufficient CO32 ions will not be
present even to precipitate Vth group.
1. BaCO3, SrCO3 and CaCO3 are soluble in CH3COOH forming acetates.
MCO3 + 2 CH3COOH  (CH3COO)2 M + H2O + CO2
M = Ba 2+ , Ca 2+ ,Sr 2+ acetate
Tests
Note : This is done in B(Ba).S(Sr).C(Ca) trend only, otherwise all be precipitated at same time. BaC2O4,SrC2O4
is white ppt and BaSO4, SrSO4 is also white ppt.
2. Potassium Chromate treatment results in formation of insoluble barium chromate. (Others are soluble).
(CH3COO)2 Ba + K2CrO4  BaCrO4 + 2CH3COOK
3. Ammonia sulphate results in precipitation of strontium sulphate and calcium sulphate. CaSO4 formed is
dissolved in ammonia sulphate.
(CH3COO)2Sr + (NH4)2SO4  SrSO4 + 2CH3COONH4
CaSO4 + (NH4)2SO4  (NH4)2 [Ca(SO4)2]
formed soluble
4. Soluble complex (NH4)2[Ca(SO4)2] gives a white precipitate with ammonium oxalate.
(NH4)2[Ca(SO4)2] + (NH4)2C2O4  CaC2O4 + 2(NH4)2SO4
Ca 2+ + K 4 [Fe(CN)6 ] 
 K 2Ca[Fe(CN)6 
VIth Group Mg2+

Reagent : Disodium hydrogen phosphate, Na2HPO4
MgSO4 + Na2HPO4+ NH4OH  Mg(NH4)PO4 + N2SO4 + H2O

Mg+2
Test :
1. MgCl2 + NH4OH + Na2HPO4  Mg(NH 4 ) PO 4 + 2NaCl + H2O

2. MgCO3 
 MgO + CoO  MgO  CoO (Cobalt pink)
 CO2
Co(NO3 )2  CoO + 2 NO 2 +1/ 2O 2

MgO + CoO  MgO  CoO (Cobalt pink)
Illustration - 8 An inorganic lewis acid (X) shows the following reactions :

(i) It fumes in moist air.
(ii) The intensity of fumes increases when a rod dipped in ammonia solution is brought near to it.
(iii) An acidic solution of (X) on addition of NH 4Cl and NH 3 solution gives a precipitate which dissolves
in NaOH solution.
(iv) An acidic solution of (X) does not give a precipitate with H 2 S .
Identify (X) and give chemical equation for steps (i) to (iii).
SOLUTION :
According to question, an organic Lewis acid (X) fumes in moist air the intensity of fumes increase when a
rod dipped in NH3 solution is brought near to it. These reactions clearly indicates that (X) is a metal
chloride which is hydrolysed in moist air giving hydrochloric acid and fumes becomes dense when a rod
dipped in NH3 solution is brought near it due to the formation of NH 4 Cl. An acidic solution of (X) on
addition of NH 4Cl and ammonia solution gives a ppt. soluble in NaOH solution. This means that the metal
chloride must be AlCl3 which does not give ppt. When H 2S is passed in acidic solution of (X). Hence (X)
is AlCl3 a lewis acid.
The chemical equations for the reaction at step (i), (ii) and (iii) are as follows :
(i) AlCl3 + 3 H 2O(from mosit air)  3 HCl+ Al(OH)3
Fumes
(ii) HCl + NH3 + H 2O  NH 4Cl + H 2O
Dense
(iii) AlCl3 + 3 NH3 + 3H 2O  Al(OH)3 + 3 NH 4 Cl
Al(OH)3 + NaOH  NaAlO2 + 2 H 2O
Soluble

Illustration - 9 On the basis of following reactions identify (A), (B), (C) and (D) and write down their
chemical formulae.
heat heat
(i) (A) aq.  Zn 
( B) gas (ii) (A) aq  (C ) 
 PH 3
heat
(iii) (A) aq.  NH 4Cl 
( D ) gas
SOLUTION :
(i) (A) is an alkali or a mineral acid because Zn is an amphotric metal and evolve H 2 gas. So, the
equation is
heat
2 NaOH+ Zn 
 Na 2 ZnO2 + H2 or Zn+ 2 H+  Zn 2+ + H2
(A) (B)
(ii) We known that, PH3 gas is obtained from the reaction of phosphorus and alkali. So (A) is NaOH
and (C) is phosphorus and the equation is
heat
3 NaOH+ 3H 2O+ P4 
 PH3 + 3 NaH 2 PO 2
(A) (C)
(iii) (A) i.e. NaOH reacts with NH 4Cl to give a gas D (i.e. NH3 ). So, the equation is
heat
NaOH+ NH 4Cl 
 NH3 + NaCl+ H 2O
(A) (D)
Illustration - 10 (i) An inorganic compound (A) is formed on passing a gas (B) through a concentrated
liquor containing sodium sulphite.
(ii) On adding (A) into a dilute solution of silver nitrate, a white precipitate appears which quickly changes
into a black coloured compound (C).
(iii) On adding two or three drops of ferric chloride into excess of solution of (A), a violet coloured com-
pound (D) is formed. This colour disappears quickly.
(iv) On adding solution of (A) into the solution of cupric chloride a white precipitate is first formed which
dissolves on adding excess of (A) forming a compound (E).
Identify (A) to (E) and give chemical equations for the reactions at steps (i) to (iv).
SOLUTION :
(i) An inorganic compound, Na 2S2O3 (sodium thiosulphate) is formed by the reaction of concentrated
solution of Na 2S and Na 2SO3 with I2 vapours.
Na 2S+ Na 2S2O3 + I2  Na 2S2O3 + 2 NaI
(B) (A)

(ii) When Na 2S2O3 solution is added into a dilute solution of silver nitrate, a white precipitate of
Ag 2S2O3 (silver thiosulphate) is formed which quickly changes into a black coloured compound
i.e. Ag 2S (silver sulphide).
2 AgNO3 + Na 2S2O3  2 NaNO3 + Ag 2S2O3
Ag 2S2O3 + H 2O  Ag 2S+ H 2SO 4
(A)
(iii) When two or three drops of ferric chloride is added into the solution of Na 2S2O3 , a violet coloured
compound is formed i.e. Fe 2 (S2O3 )3 .
3 Na 2S2O3 + 2 FeCl3  Fe2 (S2O3 )3 + 6 NaCl

(D)
But violet colour disappear quickly due to the formation of FeCl2 .
2 Na 2S2O3 + 2 FeCl3  2 NaCl + 2 FeCl2 + Na 2S4 O6
(iv) When solution of Na 2S2O3 is added into a solution of CuCl2 , a white precipitate of Cu 2S2O3 is
first formed which dissolves on adding excess of Na 2S2O3 solution due to the formation of a com-
pound Na 4 [Cu 6 (S2O3 )5 ].
2CuCl2 + 2 Na 2S2O3  2CuCl+ Na 2S4O6 + 2 NaCl

or
Cu 2Cl2
Cu 2Cl2 + Na 2S2O3  Cu 2S2O3 + 2 NaCl
2CuCl2 + 3 Na 2S2O3  Cu 2S2O3 + Na 2S4O6 + 4 NaCl
3Cu 2S2O3 + 2 Na 2S2O3  Na 4[Cu 6 (S2O3 )5 ]
(E)
Illustration - 11 An unknown solid mixture contains one or two of the following :

CaCO3 , BaCl2 , AgNO3 , Na2 SO4 , ZnSO4 and NaOH . The mixture is completely soluble in water and the
solution gives pink colour with phenolphthalein. When dilute hydrochloric acid is gradually added to the
above solution, a precipitate is formed which dissolves with further addition of the acid. What is (are) present
in the solid? Give equations to explain the appearance of the precipitate and its dissociation.
SOLUTION :
(i) The solution gives pink colour with phenolphthalein, so it must contain NaOH as one of the constituent.
(ii) ZnSO 4 forms soluble sodium zincate in the presence of NaOH only
ZnSO 4 + 4 NaOH  Na 2 ZnO2 + Na 2SO4 + 2 H 2O
Soluble

(iii) When dil. HCl is added to soluble Na 2 ZnO 2 , a white ppt. of Zn(OH)2 is formed
Na 2 ZnO 2 + 2 HCl  2 NaCl+ Zn(OH)2
(iv)v) On adding more of dil. HCl, Zn(OH)2 ppt. dissolves and soluble ZnCl2 is formed.
Zn(OH)2 + 2 HCl  ZnCl2 + 2 H 2O
Soluble
If other pairs of the given compounds are taken into consideration, then the above reaction will not be
possible. This is because CaCO3 is insoluble in water, BaCl2 and AgNO3 if present together would give
ppt. of AgCl on adding water. BaCl2 and Na 2SO4 would give a ppt. of BaSO 4 on adding water..
Illustration - 12 (i) A black coloured compound (B) is formed on passing hydrogen sulphide through the
solution of a compound (A) in NH 3 solution.

(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 sometime, 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 :
(i) A black coloured compound CoS is formed on passing hydrogen sulphide through the solution of a
compound, CoCl2 to ammonia solution
3 NH +H O
2  CoS  +2 HCl
CoCl2 + H 2S 
(ii) CoS on treatment with HCl and KClO3 again gives CoCl2
CoS+ 2 HCl+ KClO3  CoCl2 + KCl+ H 2O+ SO 2 
(iii) CoCl2 on treatment with potassium cyanide, gives a buff coloured precipitate of Co(CN)2 which
dissolves excess of this reagent forming a complex compound potassium cobaltocyanide.
(iv) The above formed compound is changed into a compound potassium cobaltocyanide when its
aqueous solution is boiled.
CoCl2 + 2 KCN  Co(CN)2 + 2 KCl
Co(CN)2 + 4 KCN  K 4 [Co(CN)6 ]
Potassium Cobaltocyanide
(D)

(v) When the solution of CoCl2 is treated with excess of NaHCO3 and then with Br2 water and
after cooling and shaking, a green coloured compound is formed.
CoCl2 + 2 NaHCO3  Co(HCO3 )2 + 2 NaCl
Co(HCO3 )2 + 4 NaHCO3  Na 4[Co(CO3 )3 ] + 3H 2 O
Br2 + H 2O  2 HBr+[O]
Na 4 [Co(CO3 )3 ] + H 2O+[O]  Na 2 [Co(CO3 )3 ]+ 2 NaOH

[E]
Sodium Tricarbonatocobaltate(III)
Illustration - 13 A white crystalline compound (A) swells up on heating and give violet colour flame on
burning. Its aqueous solution gives :
(A) White ppt. with BaCl2
(B) White gelatinous ppt. with excess of NH 4OH which dissolves in NaOH but reappears on boiling with
conc. NH 4Cl solution.
SOLUTION :
(i) Since, (A) gives violet colour flame on burning, it must be containing K + ions.
(ii) Aqueous solution of (A) gives white ppt. with BaCl2 . So, it also contains SO 24  ions.
(iii) Again, since aqueous solution of (A) gives gelatinous ppt. with excess ammonia solution, it also
contains Al3+ ions.
Hence, (A) which contains K + , Al3+ and SO24  ions with swelling properties (on heating) must be
K 2SO 4  Al2 (SO4 )3  24 H 2O.
Reactions Involved :
(i) SO 24  + BaCl2  BaSO 4 + 2 Cl
(ii) Al3+ + 3 NH 3 + 3 H 2O  Al(OH)3 + 3 NH +4

Al(OH)3 + NaOH  NaAlO2 + 2 H 2 O
(Soluble)

Illustration - 14 An aqueous solution of an unknown compound (X) gives the following reactions :
(i) It gives brown ppt. with alkaline KMnO 4 solution.
(ii) It forms HCl and evolves O2 when reacted with Cl2 gas.
(iii) It liberates I 2 from an acidified KI solution.
(iv) It gives orange yellow colour with acidified titanic sulphate solution.
Identify (X) and give the chemical equations for the reactions (i), (ii), (iii).
SOLUTION :
From reaction (iv), it is clear that the unknown compound (X) is H 2O 2 .
Ti(SO4 )2 + 2 H 2O+ H 2O2  H 2TiO 2 + 2 H 2SO 4
(X) Pertitanic acid
(i) 2 KMnO 4 + 2 KOH  2 K 2 MnO 4 + H 2O+ O

H 2O 2 + O  H 2O+ O2
(X)
or 2 KMnO 4 + 2 KOH+ H 2O 2  2 K 2MnO 4 + 2 H 2O+ O 2

(X)
2 K 2 MnO 4 + 2 H 2O  2 MnO 2 + O 2 + 4 KOH

(ii) H 2O 2 + Cl2  2 HCl+ O 2
(iii) H 2O 2 + 2 KI+ H 2SO 4  K 2SO 4 + 2 H 2O+ I 2 
(X)
So, the unknown compound (X) is H 2O 2 .
Illustration - 15 When gas (A) is passed through dry KOH at low temperature, a deep red coloured compound
(B) and a gas (C) are obtained. The gas (A) on reaction with but-2-ene following by treatment with Zn / H 2O
yields acetaldehyde.
Identify (A), (B) and (C).
SOLUTION :
Since, the gas (A) on reaction with but-2-ene followed by treatment with Zn / H 2O yields acetaldehyde,
(A) is ozone (O3 ).
Hydrolysis
O3 + CH3  CH = CH  CH3  CH3  CH  O CH  CH3 
 2 CH3CHO
(A) but  2  ene | | Zn/ H 2O Acetaldehyde
O  O
Mono ozonide

When gas (A) (i.e. O3 ) is passed through dry KOH at low temperature, a deep coloured compound (B),
KO3 , and a gas (C), O 2 , are obtained. The reaction is shown below :
5O3 + 2 KOH  2 KO3 + H 2O(g) + 5O 2

(B) (C)
Potassium ozonide
Hence, A = O3 , B = KO3 , C = O2
Illustration - 16 Gradual addition of KI solution to Bi ( NO ) solution initially produce a dark brown

3 3
precipitate which dissolve in excess of KI to give a clear yellow solution. Write chemical equation for the
above reactions.
SOLUTION :
Bi(NO3 )3 hydrolyses to give HNO3 (oxidising agent) which produce a dark brown ppt. I2 , from KI
solution. I2 dissolve in excess of KI to give a clear yellow solution (KI3 ).
Bi(NO3 )3 + H 2O  [Bi(OH)(NO3 )2 ] + HNO3
NO3 + 2 I + 4 H +  I2 + NO+ 2 H 2O
I2 + KI  KI3
Illustration - 17 An inorganic compound (X), which is transparent like glass is a strong reducing agent. Its
hydrolysis in water gives a white turbidity (Y). Aqueous solution of (X) give a white ppt. (Z) with aqueous
NaOH, which is soluble in excess NaOH. (X) reduces auric chloride to produce purple of cassius. (X) also
reduces I 2 and gives chromyl chloride test.
Identify (X), (Y) and (Z) and give the reactions involved.
SOLUTION :
(i) Since, (X) gives chromyl chloride test, it must be containing Cl ion.
(ii) (X) also gives white ppt. with aqueous NaOH, soluble in excess NaOH. So (X) may be containing
Zn 2+ ,Sn 2+ or Al3+ ion.
(iii) (X) is also a strong reducing agent. So, (X) is SnCl2
Reaction Involved :
(i) SnCl2 + H 2O  Sn(OH) Cl+ HCl
(X) (Y)

(ii) SnCl2 + 2 NaOH  Sn(OH)2 + 2 NaCl

(Z)
Sn(OH)2 + NaOH  Na 2SnO 2 + 2 H 2O
(iii) 3SnCl2 + 2 AuCl3  3SnCl4 + 2 Au

Purple of cassius
(Colloidal gold)
(iv) SnCl2 + 2 HCl+ I2  SnCl4 + 2 HI
IN-CHAPTER EXERCISE - B
Subjective Type :
1. When a white powder (A) is strongly heated, it gives off a colorless, odourless gas (B)which turns
lime water milky (C) and if the passage of this gas is continued, the milkiness disappears and gives
a solution (D). The solid residue (E) is yellow when hot but turns white on cooling. Identify (A) to (E)
with the help of equations.
2. A compound on heating with an excess of caustic soda solution liberates a gas (B ) which gives white
fumes on the exposure to HCl. Heating is continued to expel the gas completely. The resultant alka
line solution again liberates the same gas (B) when heated with Zinc powder. However; the com
pound (A), when heated alone, does not give nitrogen. Identify (A) and (B).
3. An aqueous solution of salt (A) gives a white crystalline precipitate (B) with NaCl solution. The
filtrate gives a black precipitate (C) when H 2 S is passed into it. The compounds (A) does not give
any gas with dilute HCl but liberates a reddish brown gas on heating. Identify compounds from (A) to
(D) with help of equations.
4. A white substance (A) on heating with excess of dil. HCl gave an offensive smelling gas (B) and a
solution (C). The solution (C) on treatment with aqueous ammonia did not give any precipitate but
on treatment with NaOH solution gave a precipitate (D) which dissolves in excess of NaOH solution.
(A) on strong heating in air gave a strong smelling gas (E) and a solid (F). Solid (F) dissolved
completely in HCl and the solution gave a precipitate with BaCl2 in acid solution.
Identify (A) to (F) and give the chemical equations.
5. An unknown solid mixture contains one or two of the following CaCO3 , BaCl2 , AgNO3 , Na2 SO4 ,
ZnSO4 and NaOH . The mixture is completely soluble in water and the solution gives pink colour
with phenolphthalein.

When dil. HCl acid is gradually added to the above solution a precipitate is formed which dissolved
with further addition of the acid. Give composition of mixture and equation.
6. Compound (A) is greenish solid which gives the following :
(i) The addion of BaCl2 solution to a solution of (A) results in the formation of white precipitate
(B) which is insoluble in dil HCl.
(ii) on heating, water vapours and two oxides of sulphur (C) and (D) are liberated leaving a red
brown residue (E).
(iii) Compound (E) dissolves in warm concentrated HCl to give a yellow solution (F).
(iv) With H 2 S gas, the solution (F) yields a yellow white ppt. (G) which when filtered leaves
greenish filtrate (H)
Identify the compounds (A) to (H).
7. A hydrated metallic salt (A), light green in colour, on careful heating gives a white anhydrous residue
(B). (B) is soluble with water and its aqueous solution reacts with NO to give a dark brown compound
(C). (B) On strong heating gives a brown residue (D) and a mixture of two gases (E) and (F). The
gaseous mixture when passed through acidified permanganate discharges the pink colour and when
passed through acidified BaCl2 solution gave a white precipitate. Identify (A) to (F).
8. An unknown inorganic compound (X) loses its water of crystallization on heating an its aqueous solution
gives the following reactions.
(i) It gives turbidity with dil HCl acid
(ii) It decolourises a solution of iodine in KI
(iii) It gives a white precipitate with AgNO3 which turns black on standing.
Identify the compound (X) with help of reaction.
9. The compound (A) is light green solid. It gives the following tests.
(i) It dissolved in dil H 2 SO4 . NO gas is produced.
(ii) A drop of KMnO4 is added to the above solution. The pink colour disappears.
(iii) Compound (A) is heated strongly Gases (B) & (C) with pungent smell come out (A brown
residue (D) is left behing).
(iv) The gas mixture (B) and (C) is passes into dichromate solution. The solution turns greens.
(v) The green solution from step (iv) gives a white precipitate (E) with a solution of barium nitrate.
(vi) Residue (D) from step (iii) is heated on charcoal in a reducing flame it gives a magnetic substance.
Identify the various compounds.
10. A white amorphous powder (A) on heating yields a colourless, non combustible gas (B) and a solid
(C). The latter compound assumes a yellow colour on heating and changes to white on cooling.
Compound (C) dissolves in dulute acids and the resulting solution gives a white precipitate on add-

ing K 4 [ Fe(CN )6 ] solution. The compound (A) dissolved in dil HCl with the evolution of gas which
is identical in all respects with (B). The gas (B) turns lime water milky but the milki-ness disappears
with the continuous passage of the gas. The solution of (A) as obtained above, gives a white precipi
tate (D) on the addition of excess of NH 4OH and passing H 2 S . Another portion of the solution
gives initially a white precipitate (E) on the addition of NaOH solution which dissolved on further
addition of the base. Identify (A) to (E) with equations.
11. An Unknown inorganic compound (A) gave the following reactions
(i) (A) on heating gave a residue, oxygen and an oxide of nitrogen.
(ii) Aqueous solution of (A) on addition of tap water gave a turbidity which did not dissolve in
nitric acid.
(iii) The turbidity dissolved in ammonium hydroxide. Identify (A) and gave all balanced reactions.
12. A certain inorganic compound (A) on heating loses its water of crystallization. On further heating a
blackish brown powder (B) and two oxides of Sulphur (C) and (D) are obtained. The powder (B) on
boiling with HCl acid gives a yellow solution (E) on treatment with thiocyanate ions gives a blood
red coloured compound (H). Identify (A) to (H).
13. A mixture of two salts was treated as follows
(i) The mixture was heated with manganese dioxide and concentrated sulphuric acid, when yellow
greenish gas was liberated.
(ii) The mixture on heating with NaOH solution gave a gas which turned red litmus blue.
(iii) Its solution in water gave blue precipitate with potassium ferrocyanide and red colouration
with the ammonium thiocyanate.
(iv) The mixture was boiled with potassium hydroxide and the liberated gas was bubbled through
an alkaline solution of K 2 HgI 4 to give brown precipitate. Identify two salts. Give ionic
equations for reactions in step (i), (ii) and (iii).
14. When 16.8g of a while solid (X) was heated 4.4 g (A) that turned lime water milky was driven off
together with 1.8 g of a gas (B)which condensed to a colour less liquid. The solid that remained (Y)
dissolved in water to give an alkaline solution, which with excess of BaCl2 solution a white precipitate
(Z). The precipitate effervesced with acid giving off CO2 gas. Identify (A), (B) and (Y) and write
down equation for thermal decomposition of (X).
15. When a white crystalline compound (X) is heated with K 2Cr2O7 and concentrated H 2 SO4 , a reddish
brown gas (A) is evolved. On passing (B) into caustic soda solution, a yellow coloured solution of (B)
is obtained. Neutralizing the solution of (B) with acetic acid and on subsequent addition of lead
acetate, a yellow precipitate (C) is obtained. When (X) is heated with NaOH solution, a colourless

gas is evolved and on passing this gas into K 2 HgI 4 solution, a reddish brown precipitated (D) is
formed. Identify (A), (B), (C), (D) and (X). Also give the equations involved.
16. An aqueous solution of an inorganic compound (X) yielded a white precipitate when treated with dil
HNO3 acid and silver nitrate. Another sample of solution of (X) when treated with NaOH gave a
white precipitate first, which dissolved in the excess of NaOH yielding colourless solution, when
H 2 S gas was passed through that solution a white precipitate was obtained . Identify the compound
(X) and give all reactions.
17. A black coloured compound (A) on reaction with dil. H 2 SO4 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 an acidified solution of
a compound (E) gives a precipitate (F) soluble in dil. HNO3 . 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 of (E) a white precipitate
insoluble in HNO3 is obtained. Identify (A) to (H).
18. A mixture of three X,Y,Z are passed first into an acidified dichromate solution when (X) is absorbed
turning the solution green. The remainder of the mixture is passed through an excess of lime water
which turns milky, resulting in the absorption of (Y). The residue gas (Z) is absorbed by an alkaline
pyrogallol solution. However the original gaseous mixture does not turn lead acetate paper black.
Identity X,Y,Z.
19. A green solution (A) of a metal chloride on treatment with NaOH and H2O2 gives a yellow solution
(B) which turns orange on acidification. The solution (orange) on crystallization gives a solid (C),
which on heating with NaCl and conc. H2SO4 yields a red volatile liquid (D). On adding ammonia to
orange crystals of (E) are formed. (E) decomposes on heating to give steam, N and green solid (F).
Identify (A) to (F).
20. A pale yellow compound (A) is insoluble in mineral acid but soluble in conc. aq. NH 3 forming (B),
(A) also reacts with conc. H 2 SO4 and MnO2 to give brown fumes of (D). If the solution of (C) is
boiled, a black ppt. (E) is obtained (E) can be dissolved in HNO3 giving solution (F) which on
treatment with HCl yields white ppt. (G) which can be dissolved in aqueous NH 3 giving solution
(H). Identify from (A) to (H).
21. A white solid (A) loses on heating one sixth of us weight and becomes a yellow solid (B). (B), on
heating in air gains weight and gives a red solid (C). (C) is partly soluble in dil. HNO3 leaving a
brown residue (D). (A) is soluble in dil HNO3 giving effervescence to give a solution (E). (E) reacts

with NaOH followed by Cl2 water to give (D). (A) does not appreciably dissolve in dil HCl or
H 2 SO4 . Identify (A) to (E).
22. An inorganic white crystalline solid (A) is soluble in H 2O. Its solution gives black ppt. (B) with H 2 S
gas which on dissolution in HNO3 (conc.) again forms (A). (A), reacts with H 2 SO4 to give white
solid (C) which dissolves in ammonium acetate to give (D). This solution gives a yellow ppt (E) with
KI. The compound (A) on heating with copper turnings and conc. H 2 SO4 evolves a brown gas (F).
(A) reacts with cold FeSO4 and conc. H 2 SO4 to give a brown substance (G) which becomes
colourless on heating. Identify the compounds (A) to (G).
23. From the reaction below, identify A, B, C, D, ————————————
dil
A  B (Green)
 H 2 SO4
(a) (i) A is ————————
K 2Cr2O7
(ii) A  dil H 2 SO4  C 

 MnSO4 B is ——————————
Ba Cl
2  E  white
(iii) A  O2  D  C is ———————
H 2O
(b) (i)  A is ——————————

A(aq )  Zn  B ( gas )
(ii)  B is ——————————
A(aq )  C 
 PH 3
(iii)  C is———————
A(aq )  NH 4Cl 
 D ( gas)
D is ———————
(C) NaOH
A
 NaCl  NaOCl
B
 NaNO2  NaNO3
C D E
2 X Y I
 NaHSO3  Na2 SO3  Na2 S 2O3 

24. You are given an unknown solution that may contain one or more of given ions.
Cr 3  , Mn 2  , Fe 2  , Cu 2  , Ag  , Zn 2  , Hg 22  , Hg 2 
(i)) Addition of HCl gives no ppt. which of the ions must be present ?
(ii) Subsequent addition of H 2 S and heating in acid produces a black ppt, insoluble in HNO3 ,
which of the ions must be present?
(iii) Filtering off the ppt (in II) removing H 2 S by boiling and after neutralizing the acid (by
ammonia), a greenish ppt. is obtained, which is soluble in excess of NaOH. Which ion must be
present ?
25. A colour salt (A) when heated with alkali gives a gas (B). (A) on reaction with CaCl2 solution give
a white precipitate (A). The gas (B) gives white fumes with HCl and (C) decolourises acidified KMnO4 .
Identify A, B and C. Give all the reactions involved.
26. A salt (A) on heating gives a colourless gas (B) which dissolves in water to give a neutral solution &
leaves no residue. (A) on warming with NaOH gives a pungent smelling gas (C) which turns mercurous
nitrate paper black. The solution after warming with NaOH and on treatment with Al Powder gives
a further supply of gas (C). Identify A, B, C.
27. A salt (A) on warming with NaOH solution gives out a pungent smelling gas (A). which when passed
through a solution of copper sulphate gives it a deep blue solution. To the alkaline solution of above,
when A powder is added, a further quantity of (B) evolves. (A) when heated carefully to a temperaturee
above 240C decomposes completely without leaving any residue into two gases (C) and (D). (D)
exists as a liquid below 100C and (C) can be liquefied by applying pressure at room temperature.
The gas (C) when moderately inhaled induces laughter. Identify A, B, C, D. Name the analytical
reagent (E) formed by addition of mercuric chloride to excess of KI solution. Indicate the colour of
ppt. that the gas (B) would form with (E).
28. The solution of salt (A) answers the brown ring test and gives a black ppt. with H 2 S in HCl. It gives
with alkali a yellow ppt. and a scarlet red ppt. with KI dissolving in excess of KI. What is (A) ? What
happens when :
(i) A is heated ?
(ii) If solution of (A) treated with SnCl2 / HCl in hot & cold conditions
29. There black powders (A), (B), (C) are kept in three dishes. (A) dissolves in dil H 2 SO4 to give a blue
solution. Moistened with HCl, (A) gives a green colour in flame test. (A) does not dissolve in dil HCl
but when boiled with conc. HCl, dissolves giving chlorine. This solution with H 2 S in ammoniacal

solution produces of flesh coloured ppt. (C) does not dissolved in HCl but when heated with KNO3 ,
burns away evolving a gas which turns lime water milky. What are (A), (B), and (C) ?
30. A certain alloy is dissolved in hot conc. HNO3 and the solution evaporated till the residue is just
moist. Water and HCl are then added and thus the solution obtained is treated with H 2 S . A black
ppt. is obtained which, filtered off, dissolves in hot dil. HNO3 to yield a blue solution which become
deep blue on adding NH 4OH . The filtrate after treatment with H 2 S yields a black ppt. with
ammonia. But if the filtrate is thoroughly boiled and treated with dimethyl glyoxime in NH 4 solution,
a rose red ppt is formed, Identify the metals of alloy.
31. A white crystalline solid, dissolves in water. The solution effervesces with NaHCO3 and decolourises
KMnO4 / H  . Conc. H 2 SO4 decomposes the solid without blackening, yielding a mixture of gases,
one of which turns lime water milky and the other burns with a blue flame and is not only poisonous
but absorbed by ammoniacal Cu2Cl2 . Identify the solid.
Determine its equivalent weight as reducing and oxidizing agent.
NOW ATTEMPT IN-CHAPTER EXERCISE-B FOR REMAINING QUESTIONS IN THIS EBOOK
NOW ATTEMPT OBJECTIVE WORKSHEET BEFORE PROCEEDING AHEAD IN THIS EBOOK
SOLUTIONS - IN-CHAPTER EXERCISE - B
1. A  ZnCO3 ; B  CO2 ; C  CaCO3 ; D  Ca  HCO3 2 ; E  ZnO
2. A  NH 4 NO3 ; B  NH3
3. A  Pb  NO3 2 ; B  PbCl2 ; C  PbS ; D  PbI 2 ;
 1
Pb  NO3 2 
 PbO  2NO2  O2
2
Reddish
brown
4. A  ZnS ; B  H 2S ; C  ZnCl2 ; D  Zn  OH 2 ;

ZnS  O 2 
 ZnSO4  SO3 
(F) (E)
5. ZnSO 4 and NaOH

6. A  FeSO4  7H 2O ; B  BaSO4 ; C  SO 2 ; D  SO3
E  Fe 2O3 ; F  FeCl3 ; G  S ; H  FeCl2
Self Study Course for IITJEE with Online Support Solutions 45

7. A  FeSO 4  7H 2O ; B  FeSO4 ; C  FeSO 4 .NO or [Fe  H 2O 5 NO]SO 4
D  Fe 2O3 ; E  SO 2 ; F  SO3
8. Na 2S2O3  5H 2O ; 
Na 2S2O3  5H2O   Na 2S2O3  5H 2O ;
Na 2S2O3  2HCl 
 2NaCl  SO2  S  H 2O
turbidity
2Na 2S2O3  KI3 

 2NaI  KI  Na 2S4O6
(Solution of ;
iodine in KI)
Na 2S2O3 2AgNO3 
 Ag 2S2O3(s)  2NaNO3
(while)
Ag 2S2O3  H 2O 
 Ag 2S(s)  H 2SO 4
(black)
9. A  FeSO 4  7H 2O ; B  SO2 , C  SO3 ; D  Fe 2O3 ; BaSO4 ;
FeSO4  H2SO4 
 No action
 K 2SO 4  5Fe2 SO 4 3  2MnSO 4  8H 2O

10FeSO 4  2KMnO 4  8H 2SO 4 

2FeSO4  7H 2O 
 Fe 2O3(s)  SO 2 (g)  SO3(g)  14H 2O(g)
 K 2SO 4  Cr2 SO4 3

SO 2 (g)  SO3(g)  K 2Cr2O7 
green solution
Cr2  SO4 3  Ba  NO3 2 

 BaSO 4 (s)  Cr  NO3 3(aq) ;
3Fe2O3  C 
 2Fe3O4  CO
Magnetic substance
10. A  ZnCO3 ; B  CO2 ; C  ZnO ; D  ZnS ; E  Zn  OH 2

ZnCO3  ZnO(s)  CO2 (g) ; ZnO(s)  2HCl(aq) 
 ZnCl2(aq)  H 2O()
2ZnCl2 (aq)  K 4  Fe(CN) 6  

 Zn 2  Fe(CN) 6 (s)  4KCl(aq)
White
46 Solutions Self Study Course for IITJEE with Online Support

CO 2  Ca(OH)2 
 CaCO3(s)  Ca  HCO3 2 (aq)
CaCO3  CO 2  H 2O 
;
Milkiness
ZnCl2(aq)  2NH 4OH (aq)  H2S(g) 

 ZnS(s)  2NH 4Cl  2H2O
White
 Zn  OH 2(s)  2NaCl
ZnCl2 (aq)  2NaOH  ;
Zn  OH  2  2NaOH 
 Na 2 ZnO 2(aq)  2H 2O
 1
11. A  AgNO3 ; AgNO3  Ag (s)  O 2 (g)  NO 2 (g) ;
2

AgNO3(aq)  Cl(aq) 
 AgCl(s)
From tap water Turbidity
because of presence
of bleaching powder
  Ag(NH3 ) 2  Cl(aq)  2H 2O
AgCl(s)  2NH 4OH (aq) 
12. A  FeSO4  7H2O ; B  Fe2O3 ; C  SO2 ; D  SO3
E  FeCl3 ; F  S; G  FeCl2 ; H  Fe(SCN)3

FeSO4  7H 2 O 
 FeSO 4  7H 2O ; 2FeSO4 
 Fe O + SO + SO
2 3 2 3
Fe2O3 + 6HCl 
 2FeCl + 3H O
3 2 ; 2FeCl3 + H2S 
 2FeCl + S + 2HCl
2
FeCl3 + SCN– 
 Fe (SCN) + 3Cl–
3
13. NH4Cl ; FeCl3 ; 4FeCl3 + 6H2SO4 + 3MnO2 

 Fe (SO ) + 3MnCl + 6H O + 3Cl
2 4 3 2 2 2
4NH4Cl + 2H2SO4 + MnO2 

 2(NH ) SO + MnCl + Cl + 2H O
4 2 4 2 2 2

NH4Cl + NaOH  NaCl + NH3(g)
4FeCl3 + 3K 4 [Fe(CN)6 ] 
 Fe4 [Fe(CN)6 ]3(s) + 12KCl
Blue precipitate
 Fe SCN 3  3NH 4Cl

FeCl3  3NH 4SCN 
Red colouration
14. X  NaHCO3 ; A  CO2 ; B  H2O(g) ; Y  Na2CO3 ; Z  BaCO3


2NaHCO3   Na2CO3(s) + CO2 (g) + H2 O(g)

15. X  NH 4Cl ; A  CrO2Cl2; B  Na2CrO4 ; C  PbCrO4

4NH 4Cl  K 2Cr2O7  5H 2SO4  4NH 4 HSO 4  K 2SO4  2CrO2Cl2  3H 2O
CrO2Cl2  4NaOH  Na 2CrO 4  2NaCl  2H 2O
Na 2CrO 4  Pb  CH 3COO  2  PbCrO 4  2CH3COONa
16. ZnCl2 ; ZnCl2 + 2AgNO3  Zn(NO3)2 + 2AgCl(s)

ZnCl2 + NaOH  Zn (OH)2 (s) + 2NaCl
Zn(OH)2 + 2NaOH  Na2ZnO2 (aq) + H2O ; Na2ZnO2 + H2S  ZnS(s) + Na2S + H2O
17. A  CuS ; C  H2SO3 ; E  CuSO4
B  H2S ; D  S; G   Cu  NH3  4  SO 4 ; H  Cu 2  Fe  CN 4 
18. X  SO2 ; Y  CO2 ; Z  O2
19. A  CrCl3 ; B  Na2CrO4 ;C  Na2Cr2O7 ; D  CrO2Cl2

E  (NH4)2 Cr2O7 ; F  Cr2 O3
20. A  AgBr ; B  [Ag(NH3)2]Br ; C  Ag2S2O3 ; E  Ag2S

F  AgNO3 ; G  AgCl ; H  [Ag(NH3)2]Cl
21. A  PbCO3 ; B  PbO ; C  Pb3O4 ; D  PbO2 ; E  Pb(NO3)2
22. A  AgNO3 ; B  Ag2S; C  Ag2SO4 ; D  CH3COOAg.

E  AgI ; F  NO2 ; G  [Fe(H2O)5NO]SO4
23. (1) A  SO2 ; B  Cr2(SO4)3 ; C  KMnO4 ; D  H2SO4 ; E  BaSO4

(2) A  NaOH ; B  H2 ; C  P4 ; D  NH3
(3) A  Cl2 ; B  NO2 ; C  SO2 ; D  Na2CO3 ; E  S
X  NaI ; Y  Na2S4O6
24. (i) Cr3+, Mn2+ Fe2+, Cu2+, Zn2+, Hg2+

(ii) Hg2+
(iii) Cr3+
48 Solutions Self Study Course for IITJEE with Online Support

25. A  (NH4)2 C2O4 ; B  NH3 ; C  CaC2O4
26. A  NH4NO3 ; B  N2O ; C  NH3
27. A  NH4NO3 ; B  NH3 ; C  N2O ; D  H2O ; E  Nessler’s Reagent

(B) + (E) Brown coloured ppt.
28. A  Hg(NO3)2

Hg(NO3)2  Hg + 2NO2 + O2
2Hg(NO3)2 + SnCl2 
 Hg Cl + Sn (NO )
2 2 3 4
29. A  CuS
B  MnO2
C  Charcoal
30. Cu and Ni
31. Na2 C2 O 4
Mo
EReducing agent=
2

Vidyamandir Classes
My Chapter Notes
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Vidyamandir Classes Inorganic Qualitative Analysis

Inorganic Qualitative Analysis

IDENTIFICATION OF ACIDIC/BASIC RADICALS Section - 1

[A] Physical Appearance of salt :

[B] Effect of Heating on Salts :

Self Study Course for IITJEE with Online Support Section 1 1

(ii) Br2 (Reddish Brown) turns starch paper yellow.

2 Section 1 Self Study Course for IITJEE with Online Support

[C] Properties of Gases :

Self Study Course for IITJEE with Online Support Section 1 3

[D] Flame Test :

4. Substance makes crackling noise : NaCl, KI, Pb(NO3)2, Ba(NO3)2

4 Section 1 Self Study Course for IITJEE with Online Support

[E] Borax Bead test and Microcosmic Bead test :

heat heat 2 NaBO2 + B2O3

CuO+ B2O3  Cu(BO2 ) 2 Fe 2O3 + 3B2O3  2 Fe(BO2 )3

FeO+ B2O3  Fe(BO2 )2 Cr2O3 + 3 B2O3  2 Cr(BO 2 )3

CoO+ B2O3  Co(BO 2 )2

Self Study Course for IITJEE with Online Support Section 1 5

Table 1 : Colours of Borax and Microcosmic Salt Beads

Charcoal Cavity Tests :

Al2 (SO 4 )3  3Na 2CO3 

6 Section 1 Self Study Course for IITJEE with Online Support

MgSO 4  Na 2CO3  MgO  Na 2SO 4  CO2 CoO  MgO 

Heating in a reducing flame :

Self Study Course for IITJEE with Online Support Section 1 7

1s 2 ,  *1s 2 , 2 s 2 ,  *2 s 2 , 2 p x2 , 2 p 2y , 2 p z2 ,  *2 p1y ,  *2 p1z ,  * 2 px0

8 Section 1 Self Study Course for IITJEE with Online Support

heated Mg 2  gas (E) H O HCl

Illustration - 4 A certain slat (X) gives the following tests :

Self Study Course for IITJEE with Online Support Section 1 9

(iii) Na 2 B4O7 + H 2SO 4 + 5H 2O  Na 2SO4 + 4 H3BO3

(i) (A) turns lime water milky, so it may be CO 2 or SO 2 .

 4.4gm CO 2 is obtained from 20.02 gm MHCO3

10 Section 1 Self Study Course for IITJEE with Online Support

ACID RADICALS Section - 2

Radicals tested by dilute HCl/H2SO4 : Radical tested by concentrated H2SO4 :

(A) Major Reactions in detection of Acid Radicals :

CO32 + dil HCl/H2SO4 

CO2 with Ca(OH)2 

CO2 + Ca(OH)2   CaCO3  + H2O

CO 2 + CaCO3 + H 2O  Ca(HCO3 )2 (aq)

Self Study Course for IITJEE with Online Support Section 2 11

(b) SO2 + Ca(OH)2 

Na 2S+ H 2SO 4  Na 2SO 4 + H 2S 

2Na [Fe(CN) (NO)]

(a) Brown ring test : FeSO4 + NO 

(b) 2KI + 2NO2 

12 Section 2 Self Study Course for IITJEE with Online Support

Note : Chromyl chloride test is not shown by insoluble chlorides.

Self Study Course for IITJEE with Online Support Section 2 13

(b) 2KBr + Cl2(water) 

2KI + H2SO4 (conc.) 

2KI + MnO2 + 3H2SO4 

C OONa C OOH C OOH

CO2 + Ca(OH)2  CaCO3 + H2O

Na2C2O4 + 2H2SO4 (dil) + MnO2 

1s 2 ,  1s 2 , 2 s 2 ,  2 s 2 , 2 p x2 , 2 p 2y , 2 p z2 ,  2 p1y ,  2 p1z ,  * 2 px0