Qualitative Analysis Colours and Detailed

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30. Q U A L I TAT I V E
A N A LY S I S
1. INTRODUCTION
Salt → Cation (C+ ) + Anion (A − )

 
from base from acid
(basic radical) (acidic radical)
Determination of quality of any salt mixture is called Qualitative analysis or Salt analysis.
Flowchart 30.1: Procedure of salt analysis

3 0 . 2 | Qualitative Analysis
2. PHYSICAL APPEARANCE
Table 30.1: Physical properties
Experiment Observation Inference

Color (due to d-d transition of e- in Blue or bluish green Cu2+ or Ni2+
d-block elements and f-f transition Green Ni+2
of e- in f-block elements)
Reddish brown Fe+2
Pink violet
Fe+3
Light pink
Co+2
White
Mn+2
Absence of above transition metals ions
Ba+2 ,Sn+2 ,Ca+2 ,Mg+2 , Al+3 , Zn+2 etc 
 
Smell Rotten egg S2-
Vinegar CH3COO-
Ammonical NH4+
Density Heavy
Light powder Pb+2 ,Ba+2 can beCO32−
Deliquescence: Colorless → Mg+2 , Al+3 , Zn+2

Colored → Cu+2 ,Fe+3
Deliquescence → Substance absorbs moisture from the atmosphere until it dissolves 
 
in the absorbed water and forms a solution 
Hygroscopic → Substance absorbs and hold water molecules from the surroundings 
 
(Water of crystallisation)
3. DRY HEATING TESTS

Table 30.2: Dry tests
Observation Inference
1. Gas evolved:
Colorless + odorless CO32− ,HCO3−
Colorless
(
Rotten egg H2S ↑ ) S2 −
Vinegar like CH3COOH CH3COO −
Burning sulphur SO32− , S2O32− , S2−
Ammonical
NH+4
Colored (Pungent Smell) Cl−

NO3− , NO2−
(
Reddish brown NO2 ↑ )
Yellowish green Cl−
(
Reddish brown Br2 ↑ ) Br −
(
Violet black I2 ↑ ) I−
Chem i str y | 30.3
Observation Inference
2. Sublimate: Decomposition of solid substance and deposition White⇾NH4Cl,Hg(I),Hg(II) chlorides As(III),Sb(III) or Se(IV)
in the upper portion of test-tube. Yellow⇾ S , As2 S3 ,Hg(I) / Hg(II)iodides
 
free exception
sulphur to above
3. Decripitation: Decomposition with crackling sound on

heating. Salts not having water of crystallization. {halides of alkali metals , Pb (NO ) } 3 2
4. Fusion: Salts with water of crystallization will fuse generally. CuSO 4 .5H2O,FeSO 4 .7H2 O
5. Swelling:
PO 43− , BO33−
6. Residue:
Yellow when hot and white when cold ZnO
Brown when hot and yellow when cold PbO
White residue which glows on heating Ba+2 , Sr +2 , Ca+2 , Mg+2
Original salt is blue in color, becomes white on heating Cu2+ or CuSO4
Colored salts become brown or black on heating Co+2 ,Fe+3 ,Fe+2 ,Cr +3 ,Cu+2 ,Ni+2 ,Mn+2 ,etc
4. OTHER DRY TESTS

Figure 30.1: Different regions of flame Figure 30.2: Diagram showing non luminous and luminous flame
5. CHARCOAL CAVITY TEST

Charcoal piece (Carbon)
ZnSO 4 + Na2CO3 → ZnCO3 + Na2SO 4
 Bunsen burner
charcoal will
absorbNa2SO 4

ZnCO3 → ZnO + CO2
CuSO 4 → CuO → Cu

reddish residue
of metallic Cu
Metal carbonate decompose on heating to form metal oxides and Salt + Na2CO3
may further get reduced to metal especially if metals are less reactive
Figure 30.3: Set up for charcoal cavity test
(e.g Ag, Cu, gold).
Charcoal absorbs the anion formed by Na.
6. COBALT NITRATE TEST

Residue of charcoal cavity test + cobalt nitrate.
If residue in charcoal cavity test is white, then this test is performed.
Table 30.3: Charcoal cavity test
Test Inference
Distinct colour residue is obtained for different metal cations.
(
Residue+ Co NO3 )2 + ∆
They are mixed cobalt-metal oxides.
(
E.g. 2Co NO
3 )2 → 2CoO + 4NO2 + O2
ZnO + CoO → ZnO.CoO

 
 
 CoZnO2 
   
Rinman' s green
ZnO.CoO Green
Al2O3.CoO Blue
MgO.CoO Pink
SnO.CoO Bluish
7. FLAME TEST
Generally, alkali and alkaline earth metal salts impart characteristic color to the flame. For this metals only, the
electronic de-excitation will be in visible range. To perform this test, the metal salts are converted into their
corresponding chlorides [generally, these metal chlorides are volatile] (volatile ⇾ vaporizes easily)
Figure 30.4: Steps to preform flame test

Chem i str y | 30.5
Table 30.4: Flame test for transition metals
Sr. No. Metals Color of flame

1 Sr , Li Crimson Red
2 Ca Brick Red
3 Ba Apple Green
4 K Violet (lilac)
5 Cu Blue Green
6 Na Golden Yellow
7 Ni Brown
8. BORAX BEAD TEST

Borax → salt of boric acid [Na2B4O7.10H2O]. The
free end of Pt wire is coiled into a small loop. This
loop is heated in Bunsen flame until it is red hot
and then is quickly dipped into powdered form of
solid. The adhering solid is held in the hottest
part of the flame. At first, salt loses water of Pt. Wire
Red Hot
crystallization and shrinks on the loop forming a
colorless, transparent glass like bead consisting of Figure 30.5: Heating a Pt wire
mixture of sodium meta borate and boric anhydride.
∆ ∆
Na2B 4 O7 .10H2O  → Na2B 4 O7  → NaBO2 + B2O3

colorless,tranparent glasslikebead.
The bead is moistened and dipped into the finely powdered subs. (salt) so that a minute of it sticks to the bead and
this bead is heated in lower reducing flame, is allowed to cool and the color is observed. This is then heated in an
oxidizing flame, allowed to cooled and color is observed again.
Coloured beads are due to the formation of various coloured transition metal borates. The Bead “R” and Bead “O”
is due to the variable oxidation states of the metal ions.
CuCO3 ∆
 CuO + CO2
CuO + B2O3 → Cu (BO2 )

2
blue colored bead is oxdising flame
2Cu(BO2 )3 + 2NaBO2 + C → CuBO2 + Na2B 4 O7 + CO
Copper (I) metaborate → Colorless
2Cu(BO2 )3 + 4NaBO2 + 2C → 2CuBO2 + 2Na2B 4 O7 + 2CO

Red colored
bead in
reducing flame
Table 30.5: Colour of flame of different ions during borax bead test
Color in oxidizing flame Color in reducing flame

Metal When Hot When Cold When Hot When Cold
Copper Green Blue Colorless Brown red
Color in oxidizing flame Color in reducing flame

Metal When Hot When Cold When Hot When Cold
Iron Brown yellow Pale yellow Bottle green Bottle green
Chromium Green Green Green Green
Cobalt Blue Blue Blue Blue
Manganese Violet Red Grey Grey
Nickel Violet Brown Grey Grey
Non luminous flame = Oxidizing flame.

Luminous flame = Reducing flame.
9. MICROCOSMIC SALT BEAD TEST
∆
Na(NH4 ).HPO 4 .4H2O  → NaPO3 + H2O ↑ NH3 ↑
  
micro cosmic
salt
(Ammonium sodium phosphate)
Na(NH4).HPO4 when heated first, colorless transparent bead of sodium metaphosphate is obtained.
This combines with metallic oxide to form orthophosphate which are of characteristic colors.
It will have color similar to borax bead test.
NaPO3 + CoO → NaCoPO 4 orthophosphate

(blue color)
10. CONFIRMATORY TESTS (WET TESTS)
Table 30.6: Wet tests
Sr. No. Acid radical Characteristics

1
CO32− All carbonates are ppt. except Na+ ,K + ,Rb + ,Cs+ ,NH+4
2 All bicarbonates are soluble (i.e. are found in soln. phase only).
HCO3−
Only alkali metals NH+4 bicarbonate can be obtained in solid form or can be isolated.
3
SO32− All sulphides are insoluble except group I- NH+4
4
S2 − The acid , bisulphide, polysulphides of alkali metal & NH+4 are soluble, rest are ppt.
Generally S2- ppt are common.
Sn2+ 
 are normally soluble
HS − 
5 NO2− ,NO3− ,CH3 COO − All are soluble except AgNO2,CH3COOAg, CH3COOHg
Chem i str y | 30.7
Sr. No. Acid radical Characteristics

6
All soluble except Ag+ ,Hg22+ ,Cu+ ,BiO + ,SbO + , Pb +2
Cl− 
soluble in
hot water
7 + +2 + +2
Br − All except Ag , Pb
 ,Cu ,Hg2
soluble in
hot water
8
I− All soluble except Ag+ ,Hg22+ ,Hg+2 ,Cu+ ,Bi+3 ,Pb +2
+2 +2
9 All soluble except Pb , Ba
SO24−
Sr +2 ,Ca+2 or Hg(II)
 
slightly soluble
Basic sulphates of Hg, Bi and Cr are insoluble but these dissolves in dil.HCl or dil. HNO3
E.g. HgO . HgSO 4 → insoluble

 


(basic) (neutral salt)
10 All phosphates are ppt except

PO34−
Grp I + NH+4
 
slightly
soluble
Primary phosphates of alkaline earth metals are also soluble (dihydrogen phosphate)
(
E.g. Mg H2PO 4 )2
11. ANALYSIS OF ANIONIC OR ACIDIC RADICAL
Flowchart 30.2: Analysis of anionic or acidic radical

Table 30.7: Analysis of group A and group B radicals
Group A (dil H2SO4)

Sr. No. Observation Gases Inference
1 Effervescence of a colorless & odorless gas , which turns lime water milky CO2 2−
CO32-, HCO3
2 Evolution of colorless, suffocating gas with burning sulphur smell which SO2 SO32-
turns K2Cr2O7 paper green
Cr2O72– + SO2 → Cr3+(green)

3 Evolution of colorless gas with rotten egg smell which turns lead acetate H 2S
paper black(PbS) S2 −
4 Evolution of pungent smelling reddish brown gas which turns starch iodide NO2 NO2−
paper blue
I-+NO2 → I2 (I2+starch-blue complex)

5 Evolution of colorless gas having vinegar like smell CH3COOH CH3COO-
Group A(conc. H2SO4)
1 Colorless, pungent smelling gas which gives white fumes with rod dipped in HCl Cl-
NH3 (conc. H2SO4 cant oxidise Cl− to Cl2 )
2 Reddish brown gas with pungent smell and intensity of these fumes/ Br2 Br-
vapours increase on addition of a pinch of MnO2 & these also turn starch
iodide paper orange red.
3 Evolution of violet vapours which turn starch paper blue I2 I–
4 Evolution of brown fumes, intensity of which increase on addition of Cu NO2 NO3-
pieces/turnings and turns starch iodide paper blue.
Group B Ppt.
1 Water extract (WE)+sodium carbonate extract+soda extract(SE)+BaCl2(aq) White insoluble SO42-
ppt.
2 WE+SE+conc.HNO3(1N or 2N)+ammonium molybdate Canary yellow PO43-
ppt.
12. SODIUM CARBONATE EXTRACT
Filter paper
2g salt +
Funnel
3 times Na2CO3 Wire gauze
+ 20 ml distilled
Tripod stand
water
Burner Beaker
Sodium carbonate
extract
Figure 30.6: Set up for preparation of sodium carbonate extract
Sodium carbonate reacts with other inorganic salts to form water soluble salt of acid radical and the cation of salt
will be ppt. in the form of CO32-. SE is used when given salt is partially soluble or insoluble in water. Cation of the
salt interfere with the test of acid radical.
Chem i str y | 30.9
Dil.H2SO4 grp (CO32-,CO2)

Table 30.8: Sodium carbonate extract test
Sr. No. Reagent Observation Remarks

1 Dil.H2SO4 Colorless, Some carbonates like FeCO3,MgCO3
and CaCO3 should be powdered for
CO32− + H2SO 4 → SO24− + H2O + CO2 Odourless, brisk
 appreciable reaction.
H2CO3 Effervescence gas
2 Lime water Ca(OH)2 White turbidity White turbidity dissolves in dil. acid
liberating CO2 gas.
Ca(OH)2 + CO2 → CaCO3 ↓ (For CaCO3, prolonged
passage of CO2 CaCO3 ↓ + HCl
 → CaCl2 + CO2 ↑ +H2O
Ba(OH)2 + CO2 → BaCO3 ↓
dissolves the turbidity) dil.
CaCO3+CO2 →
Ca(HCO3)2
3 MgSO4/BaCl2 soln (colorless) White
Mg2++CO32- → MgCO3
Mg2++2HCO3 → Mg(HCO3)2
∆
Mg(HCO3 )2  → MgCO3 ↓ +CO2 + H2O
4 AgNO3 soln. White ppt(dissolves in Carbonates are more easily polarized

NH3 or HNO3)
2Ag +CO3 → AgCO3
+ 2-
Metal carbonates are generally constant
∆ or Yellow/brown ppt. and not stable to heat.
AgCO3 →
s tanding
Ag2O + CO2
∆ 1
 → 2Ag + O2
2
5 HgCl2/Hg(NO3)2 Reddish brown ppt
Hg2++HCO3 →-No reaction
Hg2++3CO32-+3H2O→3HgO.Hg(CO3)2.Hg(CO3)2
(basic mercuric carbonate)
6 Phenolphthalein (HPh) CO32-+HPh = Pink
HCO3+HPh = Colo rless
ACTION OF HEAT
∆
Bicarbonates  → Carbonates
∆
2NaHCO3  → Na2CO3 + CO2 ↑ +H2O
∆
Carbonates  → metal oxide + CO2

 exception Na+ , K + , Rb+ , Cs+ 
 
 
Li2CO3 → Li2O + CO2 ; PbCO3 → PbO + CO2
Carbonates of less reactive metals

∆
 Ag, Au,Hg,Cu  → metal + CO2 ↑ +O2 ↑
∆ 1
Ag2CO3  → 2Ag + CO2 ↑ + O2 ↑
2
3 0 . 1 0 | Qualitative Analysis
Table 30.9: Confirmatory test for sulphite radical
S. No. Reagent Observation Remarks
SO32−
1 Dil.H2SO4 Colorless, suffocating

burning sulphur smelling
SO32− + H2SO 4 ( aq) → SO2 ↑ + H2O + SO24−
gas.
Above gas+lime/baryta water Milkiness If both SO32-,CO32- are
present,then SO32- will
Ca(OH)2 + SO2 → CaSO3 ↓ +H2O
be oxidized to SO42- by
K2Cr2O7
On prolonged passage, milkiness disappears No milkiness (a) and (b) not given by
CO32-
CaSO3+H2O+SO2 → Ca(HSO3)2
3+ 2− Green
a) acidifiedK 2Cr2O7 + SO2 → Cr
 + SO 4
   green
moist filter paper
Blue
b) SO2 + IO3− → I2 + SO24−
 
starchiodate (blue)
filter paper
2 BaCl2 Soln. White ppt. BaSO3 dissolves in-
Ba2+ + SO32− → BaSO3 ↓ (i) Dil.HCl BaSO3 + HCl →

On exposure to air, changes to BaSO4. SO2+H2O + BaCl2
Oxidising agents show such changes. (ii) Dil.H2SO4
−
H2O2 → H2O;Br2 → Br BaSO3 + H2SO4 → SO32-
HNO3 → NO; MnO −4 → Mn+2
Sodium nitroprusside Rosy-red coloration If both SO32- and S2- are
present, this test is not
Na[Fe(CN)5NO]+ SO32- → Na4[Fe(CN)5NO]SO3
used.
3 AgNO3 Soln. No Visible change
Ag+ + SO32− → [Ag(SO3 )]−


soluble
sulphito argentate
On adding more AgNO3 to the above complex White ppt.
[Ag(SO3)]-+Ag+ → Ag2SO3 Dissolves in NH3 and dil.

HNO3
Dissolves in excess of SO32-
Ag2SO3+SO32- → 2[Ag(SO3)]-(aq)
−
2  Ag ( SO3 )  
∆
→ 2Ag ↓ +SO24− + SO2
Chem i str y | 30.11
S. No. Reagent Observation Remarks

4 Pb(NO3)2/ Pb(CH3COO)2 White
+2 O2
Pb + SO32− → PbSO3  → PbSO 4
5 Zn + H2SO 4 (aq)
Zn + SO32− + H+ → Zn+2 + H2S ↑ +H2O
Illustration 1: M2X.7H2O(A) has water and M2X (M is monovalent alkaline cation and X is divalent anion) in 1:1 ratio
by wt. (A). On reaction with dil. H2SO4 gives a gas that turns K2Cr2O7/H+ soln green. Identify (A) and explain.
Sol: Anion → SO32− M2SO3

2x+32+48 = 18x7 = 126
2x = 46 ⇒ x = 23
A ⇾ Na2SO3
Table 30.10: Confirmatory tests for sulphide and nitrite ion
S2- Reagent Observation Reaction

1 Dil H2SO4 Colorless, rotten egg smell.
S2-+H2SO4 → H2S+SO42-
Black
(i) Above gas + Pb NO3 ( )2 / Pb ( CH3COO)2 →PbS ↓

moist filter paper
Yellow
(ii) Cd+2 + H2S → CdS ↓
All sulphide
2OH−
(iii) Pb +2 
→ Pb OH ( )2 ↓ 2OH− One ppt except Al2S3 (aq.)
2−
PbS + 2H2O + 2OH − H2S
 → Pb
 ((OH)4  H2S+Al(OH)3
2 Oxidising agent Yellow/white ppt.

− H2S +2
(i) MnO 4  →S ↓ +Mn
2− H2S
(ii) Cr2O7  →S ↓ +Cr 3+
− H2S
(iii) I3  → 3I + S +
3 Sodium Nitroprusside Purple colour
S2− + Na2 Fe ( CN) NO  → Na4 Fe ( CN) NO 

 5   5 
4 Methylene blue test Methylene blue

H3C CH3
N
(CH3)2N + N(CH3)2
S
3+ 2+ + +
+ Fe (soln.) + H2S + Fe +NH4 + H
N
NH2
N, N-Dimethyl phenyl diamine
NO2- Reagent Observation Reaction

1 Dil.H2SO4 Pale blue liquid (contains
HNO2+N2O3) gives reddish
Dil.H2SO4 + solid nitrites
brown NO2 fumes-Pungent
smell)
2 BaCl2 soln.
Ba2+ + NO3− → No Reaction
3 Conc.AgNO3 White ppt

+
Ag + NO2− → AgNO2
4 KI Soln (excess) Yellow brown vapours
2NO2− + 3I− + 4H+ ⇒ I3− + 2NO ↑ +H2O
5 Decolourised by a soln. of
MnO 4 − (acidic)
nitrite
NO2− + MnO 4 − → NO3− + Mn+2 (No gas)
6 Solid urea
NO2− + urea → N2 ↑ +CO2 ↑

acidified
7 Solid thiourea SCN– ions can be

confirmed by reaction
(NH2 )2 CS + NO
 2
−
→ H+ + N2 ↑ +SCN− + H2O
with FeCl3 + HCl
acidified
Blood red colour

Fe3+ + 3SCN− → ↓ Fe ( SCN)
3
(aq.)
13. BROWN RING TEST

When nitrite solution is added carefully along the sides of test tube to a saturated solution of FeSO4, acidified
with acetic acid or dil. H2SO4, a brown ring is formed due to formation of complex of variable composition best
represented as
Brown
Solution of Ring
+2
nitrite [Fe(H2O)5NO]
(NO-2)
Saturated
FeSO4 Solution
+
dil H2SO4
Reaction : NO-2 + H
+
HNO2
3HNO2 HNO3+ 2NO + H2O
2+ 2-
NO + Fe + + SO4 + 5H2O [Fe(H2O)5NO]SO4
Figure 30.7: Brown ring test for estimation of unsaturation
NO3− will also give similar test if NO − and NO3− both are present, then NO − can be selectively decomposed by
2 2
using
Sulphamic acid (NH2 − SO3H)
O

HO − S − NH2 + 2HNO2 → N2 ↑ + SO 42− + 2H+ + H2O

O
Sodium oxide (NaN3)
NO2− + N3− + H+ → N2 ↑ +SO 42− + 2H+ + H2O
Boil the mixture with NH4Cl
NO2− is decomposed to N2
NaNO2 + NH4 Cl → N2 ↑ +SO 42− + 2H+ + H2O
Table 30.11: Confirmatory test for acetate ion
CH3COO‒ Test Observation Remarks
1 Vinegar like smell All acetate are soluble

Dil.H2SO4
except.
CH3COO − + H+ → CH3COOH
CH3COOAg and
CH3COOHg
2 AgNO3 Soln: CH3COO − + Ag+ → CH3COOAg White ppt.
3 BaCl2 soln: BaCl2 + CH3COO– → No reaction

4 Fruity smell of an
C2H5OH + conc.H2SO 4
ester
( 2 − 3ml) (1ml)
+1gm acetate salt+heat
5 Neutral FeCl3 Red blood soln

−
6CH3COO + 3Fe +3
+ 2H2O → Fe3 (H2O )  ( CH3COO )
 2 6
Above redblood soln. ∆

4H2O Reddish brown
Illustration 2: An aqueous solution of salt containing an anion Xn− gives the following reactions: It gives the purple
or violet coloration with sodium nitroprusside solution. It liberates a colorless, unpleasant smelling gas with dilute
H2SO4 which turns lead acetate paper black. Identify the anion ( Xn− ) and write the chemical reactions involved.
Sol: Xn− is S2- because

2− 4−
Fe ( CN) NO  + S2− → Fe ( CN) NOS  (purple or violet coloration)
 5   5 
S2− + H2SO 4 → H2S ↑ (colorless, unpleasant smelling) SO 4 + H2S + Pb ( CH3COO )2 → PbS ↓ (black) + 2CH3COOH
2−
Illustration 3: Sulphite on treatment with dil H2SO4 liberates a gas which:

Turns lead acetate paper black
Turns with blue flame
Smells like vinegar
Turns acidified K solution green
Sol: SO32− + H2SO 4 → SO2 + SO 42− + H2O

SO2 turns acidified K 2Cr2O7 solution green
K 2Cr2O7 + H2SO 4 + 3SO2 → Cr2 ( SO 4 ) (Green) + K 2SO 4 + H2O
3
Therefore , (iv) option is correct.
Illustration 4: A colorless pungent smelling gas (x) is obtained when a salt is reacted with dil. H2SO4. The gas (X)
responds to the following properties.
It turns lime water milky
It turns acidified potassium dichromate solution green
It gives white turbidity when H2S gas is passed through it aqueous solution.
Its aqueous solution in NaOH gives a white ppt. with barium chloride which dissolves in dil HCl liberating (X).
Identify (X) and write the chemical equations involved.
Sol: As gas X turns lime water milky it may be CO2 or SO2. But CO2 is colorless and odorless , so ‘X’ may be SO2 .
This is further , confirmed by the following reactions:
SO32− + H2SO 4 → SO 42− + SO2 + H2O
Ca(OH)2 + SO2 → CaSO3 (Milky) + H2O
K 2Cr2O7 + H2SO 4 + 3SO2 → K 2SO 4 + Cr2 ( SO 4 ) (Green) + H2O

3
SO2 + 2H2S → 3S ↓ (White) + 2H2O
SO2 + 2NaOH → Na2SO3 + H2O
Na2SO3 + BaCl2 → BaSO3 ↓ (White) + 2NaCl
BaSO3 + 2HCl → BaCl2 (Soluble) + SO2 + H2O

Conc: H2SO4 group

Table 30.12: Confirmatory test for chloride ion
[Cl‒] Reagent Observation Remarks
1 − H SO Dipped rod of Being a stronger oxidizing agent, Cl2 is

Cl 2 4 → HCl ↑ +HSO −
  4 NH3+HCl=white fumes not produced.
of NH4Cl
+ H3PO 4
↓
HCl ↑ +H2PO 4 −
2 Yellowish green; turns Permanently bleaches dyes by oxidation

MnO ( OH) + 2H2SO 4 + 2Cl− →
2 iodide paper blue
Mn+2 + Cl2 ↑ +2SO24− + 3H2O
3 White ppt soluble in

Ag+ + Cl− → AgCl ↓
NH3
( AgNO3 )
Yellow (distinct from
AgCl + AsO33− arsenite → Ag3 ASO3 ↓
AgBr/AgI)
4 2+ White ppt-soluble in hot

Pb
 + 2Cl− → PbCl2
water) conc.HCl/KCl
Pb( CH3COO )
2
5 Chromyl chloride test Red vapours Cl2 & K2Cr2O7.have equal oxidizing
power. Br- & I-don’t give similar test since
K2Cr2O7+conc.H2SO4 + 4Cl- → CrO2Cl2
Cr2O72- oxidises Br-, KI- to Br2 & I2
Bright yellow ppt.
CrO24− + Pb+2 → PbCrO 4 ↓
Illustration 5: Comp X imparts imparts a golden yellow flame and shows following reaction
(1) Zn (powder) when boiled with conc. Ag. Soln of X dissolves and H2 gas is evolved .
(2) When Ag. Soln of X is added to Ag Soln of SnCl2, a white ppt is obtain which dissolves in excess of X
When dissolved in Zn which is amphoteric, H2O gas is evolved which signified Basic nature
NaOH + Zn → Na2 ZnO2

NaOH + ZnCl2 → Sn(OH)2 → Na2SnO2
Illustration 6: A gaseous mixture of X, Y, Z when passed into acidified K2Cr2O7, gas X was absorbed and soln turned
green. The remainder mixture was passed through lime which turned milky by absorbing gas Y. The residue gas
when passed through alc. pyrogallol solution turned black.
Sol: K2Cr2O7 and lime water to differentiate between SO2 and CO2 .pyrogallol is used to absorb O2 gas Q.
Illustration 7: Colourless salt (A) gives apple green flame with conc. HCl,(A) or reaction with dil. H2SO4 gives brown
fumes (D) turing KI starch paper blue
(A) + CH3COOH + K 2CrO 4 →Yellow
yellow ppt
ppt (A) + H2SO 4 → White ppt (C) +(D)

(D) + CH3NH2 → CH3OH + H2O + gas (E) (E) + Mg → (F)
(F)+ H2O → NH2

Identify A to F
Sol: Apple green → Ba2+

Brown fumes with dil H2SO 4 → NO2−
Ba(NO2 )2 + CH3COOH + K 2CrO 4 → BaCrO 4 (yellow ppt)
Ba(NO2 )2 + H2SO 4 → BaSO 4 + HNO2


whiteppt
HNO2 + CH3NH2 → CH3OH + H2O + N2 ↑

N2 + Mg → Mg3N2
Mg3N2 + H2O → NH3
Table 30.13: Confirmatory test for bromide ion
–
Br Reagent Observation Remarks
1 Reddish brown Br2 vapours and pungent
i) 2Br − + SO24−+ + 4H+ → Br2 + SO2 + 2H2O
smell
ii) Br − + H3PO 4 → HBr + H2PO −4
2 Pinch of MnO2 added to above test-tube. Intensity of coloured fumes increases. Fluorescence Cl2,
− 2+ Irritating pungent smell. Br2, I2,
Br + MnO2 → Br2 + Mn + H2O
Bleaches litmus paper. Colourless red violet
Filter paper dipped in fluorescein
dye(yellow) turns red.
Turns starch iodide paper blue.
3 Ag+ + Br − → AgBr ↓ Pale yellow ppt.
(AgNO3 ) Dissolves in conc. NH3, KCN hypo soln.
4 Pb+2+2Br-→PbBr2 (Pb-acetate) White ppt.Soluble in conc.HBr or conc, KBr
5 8HNO3+6Br- → 3Br2↑+NO↑+6NO3-+4H2O
6 K 2Cr2O7 + H2SO 4 + Br − → Br2 + Cr +3
7 Layer test Br2 vapours colours the soln orange red.
With Cl2 water.
i)Cl2 water + Br − → Br2 ↑

 
Dropwise
ii) Above soln. +CHCl3+shake Upper layer: colourless

Lower layer: Red brown
Greater solubility of Br2 in organic solvent
iii) Excess of Cl2water Yellow soln.
− −
Br + Cl2 → Br2 + 2Cl
Br2 + Cl2 → 2BrCl
Table 30.14: Confirmatory test for Iodide ion
I‒ Reagent Observation Remarks

1 Violet coloured vapours All are soluble except
HI + HSO −4 I2 ↑ +SO2 ↑ Ag+,Hg+2, Cu+, Pb+2, Pb+2 =
↑ ↑ soluble in hot water
I + H2SO 4
↓ ↓
I2 ↑ +S ↓ I2 ↑ +H2S ↑
– –
Feasible only with I , not with Br
HI is a good reducing agent
2 Intensity of violet vapours

MnO2 + H2SO 4 + I− → I2 + Mn+2
increase
3 Yellow.
Ag+ + I − → AgI ↓
 Soluble in KCN,
AgNO3
Partially soluble in conc. NH3.
4 +2 − Yellow
Pb
 + 2I → PbI2 ↓
Pb −acetate
5
I− + K 2Cr2O7 + H2SO 4 → I2 + Cr 3+
6
KNO2 + I− + H2SO 4 → I3− + NO ↑ +H2O
7 Scarlet Red
HgCl2 + 2I − → HgI2 ↓ +2Cl− K 2 HgI 4  + KOH
  
2−
HgI2 + 2I − → HgI 4  Nessler ' sreagent
Used for detection of NH4+

and NH3
8 Iodometric Titrations
i) 2Cu+2 + 2I − → 2Cu+ + I2
ii) I2 + 2S2O32− → 2I − + S 4 O62−
9 2FeCl3 + 3I− → 2Fe+2 + I3−
10 Layer Test Brown soln.

–
Cl2 water +I → I2
Above solution. + CHCl3 Upper layer: Colourless lower

layer: violet layer
Excess of Cl2 water Colourless iodic acid formed

− −
i) Cl2 + I → Cl + I2
I 2 + I − → I3 −
ii) I − + 8Cl + 9H O →
3 2 2
3IO3− + 16Cl− + 18H+

Remark for HgCl2

K2[HgI4] + KOH as alkaline solution of K2HgI4 . Is called Nessler’s reagent used for detection of NH4+or NH3
Table 30.15: Confirmatory test for nitrate ion
‒
NO3 Reagent Observation Remarks
1 All nitrate are soluble
i) NO3− + H2SO 4 → HNO3
+HSO 4 −
Reddish Brown
1
ii) 2HNO → 2NO ↑ + O ↑ H O
3 2 2 2
2
2 Cu turnings+Above soln.→ Intensity of above colour increases
+2 2−
Cu + 2NO ↑ +4SO 4 + 4H2O
3 Diphenyl /blue ring test Blue complex
NO3 + ( C6H5 ) NH ↓
−
2
Ph2 − N − N − Ph2
4 Brown Ring Test
Brown ring Test

3 – 4 ml conc. H2SO4 + 2ml of NO-3 solution +mix+cool the mixture under a stream of cold water+ saturated
solution of FeSO4 from the side of the test tube to form a layer on the top of the liquid. A brown ring will formed
at the junction of two liquids. This brown ring complex is unstable and decomposes on shaking or on heating into
NO and a yellow colour solution of Fe+3 ion.
Reduction of NO3− or NO2− is alkaline medium into NH+4 or NH3 can be done by Zn, Al , Devarda’s Alloy(50% Cu,
45% Al, 5% Zn)
NO3− + 4Zn + 7OH− + 6H2O → NH3 ↑ +4[Zn(OH)4 ]−
3NO3− + 8Al + 5OH− + 18H2O → 3NH3 ↑ +8[Zn(OH)4 ]−
Action of heat on nitrate

∆
Alkali metal nitrate  → Metal nitrate + O2
∆ 1
NaNO3  → NaNO2 + O2
2
(E xcept Li)
∆
Metal nitrate  → Metal oxide + NO2 + O2
(E xcept Na+ ,K + ,Rb+ , Cs+ )
∆ 1
3LiNO3  → Li2O + 2NO2 + O2
2
∆
2Cu(NO3 )2  → 2CuO + 4NO2 + O2
∆
2Pb(NO3 )2  → 2PbO + 4NO2 + O2
∆
2Hg(NO3 )2  → 2Hg + 4NO2 + O2
∆
2AgNO3  → 2Ag + 4NO2 + O2
∆
NH4NO3  → N2O + 2H2O
∆
NH4NO2  → N2 + 2H2O
∆
N2H5NO2  → N2H + 2H2O
Nitrogen oxides are supporter of combustion as these fumes in to N2 and O2.
N2O → Supporter of combustion (better than air)

2N2O → 2N2 + O2
 
66.67% 33.33%
Air → O2

20%
Table 30.16: Confirmatory test for sulphate ion
‒
SO42 Reagent Observation Remarks
1 +2 2− White ppt. All sulphates are

Ba
 + SO 4 → BaSO 4 ↓ soluble except
BaCl2 Insoluble in dil.HCl
Ba+2,Pb+2,Sn+2,Ag+,Ca+2
Soluble in hot, conc. H2SO4 which are partially soluble.
2 2Ag+ 2− White ppt.
 + SO 4 → Ag2SO 4 ↓
AgNO3
3 Pb +2 2− White ppt
 + SO 4 → PbSO 4 ↓
Pb(NO3 )
2
4 Yellow ppt.
3Hg+2 + SO 42− + 2H2O ↓ 2HgO.HgSO 4

Hg(NO3 )
2
5 Match Stick Test White ppt

+2 2−
Ba + SO 4 → BaSO 4 ↓
Above ppt + Na2CO3 Purple coloration

(s)


paste
Apply paste on wooden piece of match stick+Burn in

reducing flame+Dip in sodium nitroprusside soln.
i) Paste → BaCO3 + Na2SO 4
ii) Na2SO 4 + 4C → Na2S + 4CO ↑
 ( )5
iii) Na2S + Na2 Fe CN NO 
 
S 2 −
  
Na4 Fe( CN) NOS 
 5 
Table 30.17: Confirmatory test for phosphate ion
‒
PO43 Reagent Observation Remarks
1 White ppt
 + PO 4 → Ba3 (PO 4 )2 ↓
+2 3−
Ba
BaCl2
2 + 3− White ppt
3Ag
 + PO 4 → Ag3PO 4 ↓
AgNO3 Soluble in NH3, KCN, hypo, etc.
3 Magnesia
i) PO 43− + Mg+2
 + NH4
+
White ppt.
3 2 Mg(NO )
 
( ) +
Mg NH PO ↓ +Mg →Mg PO ↓
4 4 3 4
White ppt
ii) AsO 43− + Mg+2 + NH4 +
 
Brownish red ppt
( 4 ) 4
+
Mg NH AsO ↓ +Mg →Mg AsO ↓
3 4
4 Canary yellow ppt.

PO 43− + conc.HNO3+ammonium molybdate (excess)
(NH4 )2 MoO4 ↓ (NH4 )3 PO4 .12MoO3 ↓
+H2O + NH4NO3 + NaNO3
Table 30.18: Confirmatory test for borate ion
‒
BO33 Reagent Observation Remarks
0.2g salt+Conc. H2SO4(1ml)+C2H5OH(4- Green edged flame

5ml)+.Ignite on a Bunsen flame.
3H SO
2 4 → 2H BO
2Na3BO3 
−3Na SO 3 3
2 4
3C2H5OH
2H3BO3 
−3H2O
→(C2H5 )3 BO3
Group O
1 - Ammoniacal smell
NH4 + + dil.NaOH
- White fumes (NH4Cl) with HCl
↓
- HgNO3 on filter paper becomes black (Hg)
NH3 ↑ +H2O + Na+
- Red litmus turns blue
- (MnCl2+H2O2)on filter paper becomes brown
black (MnO2[MnO(OH)2])
2
NH4 + + K 2 HgI 4 
−
OH
+ 
Nessler 'sreagent
↓
HgO.Hg NH I
2 ( )
3 Yellow ppt
3NH4 + + Na3 Co (NO2 ) 
 6
↓
(NH4 )3 Co (NO2 )6  ↓ +3Na+
4 Yellow ppt
2NH4 + + Na2 PtCl6  NH4 + salts
are insoluble
↓
(NH4 )2 PtCl6  ↓ +2Na+
Illustration 8: A compound (A) of S, Cl and O has vapour density of 67.5 (approx). It reacts with water to form two
acids and reacts with KOH to form two salts (B) and (C) while (B) gives white ppt. with AgNO3 solution and (C) gives
white ppt. with BaCl2 solution. Identify (A), (B) & (C).
Sol: As mixture gives white ppt. with BaCl2 and AgNO3, it should be SO42- and Cl- ions. As SO2Cl2 when dissolves in
water gives, a mixture of H2SO4 & HCl which then reacts with KOH to form KCl and K2SO4. Therefore (A) is SO2Cl2
and (B) & (C) are K2SO4 and KCl respectively.
Vapour density of SO2Cl2 = molecular weight/2.
Vapour density of SO2Cl2 = 135/2 = 67.2.
Illustration 9: Na2S2O3 + I2 → NaI + ………[X], [X] is:

(A) Na2S4O6 (B) Na2SO4 (C) Na2S (D) Na3ISO4
Sol: 2Na2S2O3 + I2 → 2NaI + Na2S4O6

Therefore A is correct option.
Illustration 10: Column I and II contains four entries each. Entries of column I are to be matched with some entries
of column II. Each entry of column I may have the matching with one or more than one entries of column II.
Column I Column II
(A) Colourless gas evolved on addition of dil. H2SO4 (p) Cl-
(B) White ppt. on addition of AgNO3 (q) S2-

(C) Ppt. with solution containing Pb+2 ions (r) NO2−
(D) Its acidified salt solution decolourises pink KMnO4 solution. 2−
(s) SO3
Sol: A → p, q, s; B → p, r, s; C → p, q, s; D → p, q, r, s
(A) Cl− + H2SO 4 → HCl ↑ (C olourless) + HSO −4 ; S2− + 2H+ → H2S ↑ (C olourless)
NO2− + 2H+ → NO2 ↑ (Redish brown) + H2O ; SO32− + 2H+ → SO2 ↑ (C olourless) + H2O
(B) Ag+ + Cl− → AgCl ↓ (White) ; Ag+ + S2− → Ag2S ↓ (Black)
Ag+ + NO2− → Ag NO2 ↓ (White) ; 2Ag+ + SO32− → Ag2SO3 ↓ (White)
(C) Pb2+ + 2Cl− → PbCl2 ↓ (White) ; Pb2+ + S2− → PbS ↓ (Black)
Pb2+ + NO2− → PbNO2 (Soluble) ; Pb2+ + SO32− → PbSO3 ↓ (White)

(D) 2MnO −4 + 16HCl → 5Cl2 + 2Mn2+ + 6Cl− + 8H2O

2MnO −4 + 5H2S + 6H+ → Mn2+ + 5S ↓ +8H2O
2MnO −4 + 5NO2− + 6H+ → Mn2+ + 5NO3− + 3H2O
2MnO −4 + 5SO2− + 2H2O → 2Mn2+ + 5SO24− + 4H+
Classification of Cation Radicals: For the purpose of systematic qualitative analysis, the cations are classified into
various groups and the classification is based on whether the cation with the given group reagent and forms a ppt or not
Table 30.19: Classification of cation radicals
Group Cation Reagent Observation

Zero NH4 +
NaOH or Ca(OH)2, heat if Ammonium gas is evolved.
required AgCl 

I. Ag+ Hg2+2 Pb+2 dil. HCl Hg2Cl2  White
PbCl2 
II (A) Cu+2, Hg+2, Pb+2, Bi+3, Cd+2 H2S gas in dil. HCl insoluble
Cu+2  CuS
in YAS (Yellow Ammonium 
Sulphide) (NH4)2Sn Hg+2  HgS black

Pb+2  PbS

Bi+3  Bi2S3
CdS → yellow CdS

II (B) SnS → Brown ppt.
Sn+2 ,Sn+4 , As+3 , As+5 ,Sb+3 ,Sb+5
SnS2, As2S3 → Yellow
Sb2S3 → Orange
As2S5 → Yellow solution
Sb2S5 → Orange solution
III Fe , Al , Cr
+3 +3 +3
NH4OH in presence of NH4Cl Fe(OH)3 → Reddish brown
Al(OH)3 → Gelatinous white
Cr(OH)3 → Dirty/ grey green
IV Mn+2, Co+2, Zn+2, Ni+2 H2S in presence of NH4OH and NiS, CoS → Black
NH4Cl ZnS → Dirty black
MnS → Buff colored (light pink)
(V) Ba , Sr , Ca
+2 +2 +2
(NH4)2CO3 in presence of NH4OH
BaCO3 
and NH4Cl Na2HPO4 in presence 
of NH4OH and NH4Cl SrCO3  White ppt
CaCO3 
Mg(NH4)PO4 ↓ (White)
Preparation of Original Solution (O.S): Original solution is used for the analysis if basic radicals except NH4+. It is
prepared by dissolving given salt or mixture in a suitable solvent as follows:
1. H 2O 2. Dil. HCl 3. Conc. HCl
∆
Salt or Mixt.+ H2O → Soluble (then H2O is suitable solvent)
If given salt or mixture is insoluble in H2O,then it is dissolved in dil. HCl.
∆
Salt or Mixt.+dil. HCl  → Soluble (then dil HCl is taken as solvent)
If given salt or mixture is insoluble in dilute HCl, then it is dissolved in conc. HCl.
∆
Salt or Mixt.+conc. HCl  → Soluble
In this way after selecting suitable solvent, given salt or mixture is dissolved in small quantity in the solvent and
filtered. Obtained filtered is called as original solution (O.S.) and that is used for the detection of basic radicals
except NH4+.
Remarks:
1. Pb+2 is placed in both group I and group II because PbCl2 is soluble is not water and all of Pb+2 is not separated
by addition of HCl.
2. In group II, only those sulphides are ppt. which have very low values of Ksp for this. H2S gas is added in acidic
medium. Dil. HNO3 cant be added to prevent oxidation of H2S to sulphur. (It is yellow and may be confused
with CdS). Dil. H2SO4 cant be added to prevent the formation of ppt. of sulphates.
3. Before proceeding with test of group III, the solution is boiled to remove dissolved H2S gas to prevent ppt.
of sulphides in group III. Then dil. HNO3 is added as we don’t have to perform tests with Fe+2.HNO3 oxidises
Fe+2 to Fe+3
4. NH4OH is added in presence of NH4Cl to decrease the degree of dissociation of NH4OH by common ion effect.
So, only those salts are ppt. which have low values of Ksp. (NH4)2SO4 and (NH4)2CO3 cannot be used in place
of NH4Cl to prevent the ppt of carbonates and sulphates.
5. For the test of group IV, H2S is added in presence of NH4OH to increase the degree of dissociation of H2S
resulting in increase of S2- conc. So that sulphides of higher values of Ksp can be separated.
6. We cant use NaCO3 in test of group V as Na2CO3 is highly soluble resulting in high conc. of CO32− which may
lead to ppt of group VI, Mg+2 ions.
Table 30.20: Classification of cation radicals
Group 0:
Reagent Observation Remarks
1. Dil.NaOH NH+4 +dil. NaOH → NH3 ↑ +H2O+Na Ammoniacal smell forms white fumes
in presence of HCl. NH3(g)+HCl
→ NH4Cl(g) (dense White fumes)
Filter paper dipped in HgNO3 (aq.)
becomes black
3→ NH
HgNO3 
Hg + Hg(NH2 )NO3 ↓
Black
white
Filter paper dipped in red litmus

become blue
Filter paper dipped in MnCl2+H2O2
(aq.) Becomes brown black due to
formation of MnO2 [MnO(OH)2]
2. Test with K2HgI4 Yellow / brown
NH+4 + K 2 [HgI 4 ] + OH− → Hg(NH2 )I + 2K ⊕
  
Nesslare' s reagent basic mercuric
amido iodide
3. Test with Yellow ppt.

3NH+4 + Na3 [Co(NO2 )6 ] → (NH4 )3 [Co(NO2 )6 ]+ 3Na+
Na3[Co(NO2)6] Yellow
4. Na2[PtCl6] or H2 Yellow ppt

[PtCl6] {sodiumchloro 2NH+4 +Na2[PtCl6] → (NH4)2[PtCl6] ↓ +2Na+
Generally, NH+4 salts are insoluble.
palatinate} or
{chloropalatinate acid}
Group I
Flowchart 30.3: Systematic path for the analysis of group I radicals

Table 30.21: Analysis of group I and group II radical
Pb2+ Test/Reagents Observation
Dilute HCl solution: White ppt is formed in cold solution.
Pb2+ +HCI → PbCI2 ↓ (white) + 2H+ White ppt is soluble in hot water. White ppt is also
− 2− soluble in concentrated HCl or concentrated KCI.
PbCl2 ↓ +2Cl → PbCl4 
Sodium hydroxide solution White ppt is formed which is soluble in excess of

Pb 2+
+ 2OH → Pb ( OH) ↓;
− the reagent.
2
2− Black/brownish black
Pb ( OH) ↓ +2OH− → Pb ( OH) 
2  4
2−
Pb ( OH)  + H2O2 → PbO2 ↓ +2H2O + 2OH−
 4
2−
Pb ( OH)  + S2O82− → PbO2 ↓ +2H2O + 2SO24−
 4
Potassium iodide solution A yellow ppt is formed which is soluble in excess

more conc.(6M) soln of the reagent.
PbCl2 + 2Kl → Pbl2 ↓ +2KCl;
Yellow ppt of Pbl2 is moderately soluble in boiling
Pbl2 + Kl → K 2 Pbl4  ↓
water to give a colourless solution.
Yellow ppt reappears on dilution with water. Yellow

ppt of Pbl2 does not dissolve in excess of dilute
solution of Kl.
Potassium chromate solution (in neutral, acetic or A yellow ppt is formed.

ammonia solution)
Yellow ppt is soluble in sodium hydroxide and
PbCl2 + K 2CrO 4 → PbCrO 4 ↓ 2KCl HNO3 (nitric acid).Both reversible reactions on
++  22 −−22 buffering the solution with ammonia or acetic acid
2PbCrO
2PbCrO
2PbCrO4444 +
2PbCrO + 2H
++ 2H  2Pb
2H++ 
2H 
 2Pb
2Pb22 +
2Pb + Cr
++ Cr2222O
Cr
Cr O
O77−77−22 +
O +H
++ H2222O
H
H O
O
O respectively, PbCrO4 reprecipitates.
22−−
Pb( OH
OH)  +
22−−
 Pb
22−−
 (( ))4444
PbCrO
PbCrO
PbCrO4444 +
PbCrO + 4OH
++ 4OH
4OH 
4OH 
 Pb
Pb OH
OH + CrO
++ CrO
CrO244244−−
CrO
Ammonia solution With ammonia solution, Pb2+ gives a white ppt of

lead hydroxide
Pb2+ + 2NH4 OH → Pb ( OH) ↓ +2NH+4
2
Dilute H2SO4: White ppt is formed which is soluble in more conc.

ammonium acetate (6M) solution or ammonium
PbCl2 + H2SO 4 → PbSO 4 ↓ +2HCl tartrate in the presence of ammonia.
2−
PbSO 4 ↓ +4CH3COO − → Pb ( CH3COO )  + SO24− Hot,conc.H2SO4 dissolves the ppt due to the
 4
2− formation of PbHSO4.
PbSO 4 ↓ +2C 4H4 O62− → Pb ( C 4H4 O6 )  + SO24−
 2
PbSO 4 ↓ +H2SO 4 → Pb2 + 2HSO −4

Hg22+ Test/Reagents Observation
Dilute HCl solution White ppt is formed in cold solution.
Hg22+ + 2HCl → Hg2Cl2 ↓ ( white ) + 2H+
Ammonia solution A mixture of mercury metal (black ppt) and basic

2Hg2Cl2 + 4NH4 OH → HgO.Hg (NH2 ) Cl ↓ +Hg ↓ mercury (II) amido chloride (white ppt) is formed.
+3NH4 Cl + 3H2O
Dissolution of white ppt. Hg2Cl2 in aquaregia (a) Stannous chloride test: White ppt is formed
which finally turns to black.
3Hg2Cl2 + 2HNO3 + 6HCl → 6HgCl + 2NO + 4H2O
(b) Potassium iodide test: Scarlet/red ppt is
2HgCl2 + SnCl2 → Hg2Cl2 ↓ +SnCl4 ; formed which is soluble in excess of the reagent.
Hg2Cl2 + SnCl2 → 2Hg ↓ (black ) + 2SnCl4
(c) Copper chips test: Shining grey deposition of
HgCl2 + KI → HgI2 ↓ +2KCl; mercury on copper chips is formed.
HgI2 + KI(excess) → K 2 HgI 4  ( soluble )
HgCl2 + Cu → Hg ↓ +CuCl2
Potassium iodide solution: A green ppt is formed. Green ppt in excess of reagent undergoes
2+ − disproportionation reaction and a soluble
Hg2 + 2l → Hg2l2 ↓
2−
Hgl4  ions and black mercury are formed.
Hg2l2 + 2l− → Hgl4  + Hg ↓ ( finely divided)
2−
Boiling the mercury (l) iodide ppt with water,

Hg2l2 → Hgl2 ↓ +Hg ↓
disproportionation takes place and a mixture of red
mercury (ll) iodide ppt and black mercury is formed.
Potassium chromate solution A red crystalline ppt is formed which turns black
when solution of sodium hydroxide is added.
Hg22+ + CrO 42− → Hg2CrO 4 ↓;
Hg2CrO 4 + 2OH− → Hg2O ↓ +CrO 42− + H2O
Potassium cyanide solution A black ppt of mercury is obtained
Hg2 2+
+ 2CN → Hg ↓ +Hg ( CN) ( soluble ) .
−
2
(Ag+) Dilute hydrochloric acid/soluble chlorides White ppt
Ag+ + HCl → AgCl ↓ +H+ Soluble in conc.HCl

− On dilution with water, the equilibrium shifts back
AgCl + Cl− →  AgCl2  to the left and the ppt reappears. Dil.ammonia
+ solution dissolves the ppt forming a soluble
AgCl + 2NH3 →  Ag (NH3 )  + Cl−
 2 complex.
 Ag (NH )  Cl + 2HNO → AgCl ↓ +2NH NO Dil.HNO3 or HCl neutralizes the excess ammonia
 3 2 3 4 3
and the ppt reappears because the equilibrium is
shifted backwards.
Potassium iodide solution A bright yellow ppt. is formed which is insoluble in

+ − dilute ammonia but partially soluble in concentrated
Ag + l → Agl ↓
ammonia. The yellow ppt. is soluble in KCN and in
−
Agl + 2CN− →  Ag ( CN)  + l− ; Na2S2O3.
 2
3−
Agl + 2S2O32 →  Ag ( S2O3 )  + l−
 2
Potassium chromate solution Red ppt. is formed which is soluble in dilute HNO3
++ 2− and in ammonia solution.
2Ag
2Ag +
CrO44422−−
++CrO → Ag
→ Ag222CrO
CrO444 ↓↓
2−
2Ag222CrO
2Ag CrO444 ++2H + 2H+++
4Ag++ ++Cr
 4Ag
2H 
 Cr222O
+
O77722−− ++H
H222O
O
++
Ag (NH
NH )  ++CrO
 ( 333)222
+
2Ag222CrO
2Ag CrO444 ++ 4NH
4NH333 →
→ 22Ag CrO444222−−−
Disodium hydrogen phosphate solution In neutral solution a yellow ppt. is formed with the
reagent. The yellow ppt. is soluble in nitric acid and
3Ag+ + HPO 42− → Ag3PO 4 ↓ +H+
ammonia solution.
Hydrazine sulphate (saturated) With diammineargentate (l) reagent forms finely

+ divided silver which adheres to the cleaned glass
4  Ag (NH3 )  + H2N − NH2 .H2SO 4 → walls of the test tube forming an attractive mirror.
 2
4Ag ↓ +N2 ↑ +6NH4 + + 2NH3 + SO 42−
Ammonia solution
2Ag+ + 2NH3 + H2O → Ag2O ↓ +2NH4 + Brown ppt. is formed

+
Ag2O ↓ +4NH3 + H2O → 2  Ag (NH3 )  + 2OH− Ppt. dissolves in ammonia.
 2
Hg2+ Test/Reagents Observation
Precipitation with H2S in acidic medium Black ppt. is formed.

+
H
Hg2+ + H2S → HgS ↓ +2H+ Insoluble in water, hot dilHNO3, alkali hydroxides, or
2− colourless ammonium sulphide.
HgS + S2− → HgS2 
Na2S(2M) dissolves the ppt. forming soluble
3HgS + 6HCl + 2HNO3 → complex.
3HgCl2 + 3S ↓ +2NO ↑ +4H2O Aqua regia dissolves the ppt.
2− +
2HNO3 + S → SO 4 + 2H + 2NO ↑ HgCl2 is undissociated. On heating, white ppt. of
sulphur dissolves forming H2SO4.
Stannous chloride solution When added in moderate amounts silky white ppt.
is formed.
2HgCl2 + SnCl2 → SnCl4 + Hg2Cl2 ↓
If more reagent is added, Hg (I) chloride is reduced
HgCl2 + SnCl2 → SnCl4 + 2Hg2 ↓
to black ppt. of mercury.
Potassium iodide solution On slow addition red ppt. is formed. Ppt. dissolves
2+ − in excess of Kl forming colourless soluble complex.
Hg + 2I → HgI2 ↓
KCN does not have any effect.
2−
HgI2 + 2I − → HgI 4 
Copper chips, sheet or coin A black ppt. of mercury is formed.

2+ 2+
Hg + Cu → Hg ↓ +Cu
Sodium hydroxide solution When added in small quantity brownish-red ppt. of

varying composition is formed and in stoichiometric
Hg2+ + 2OH− → HgO ↓ +H2O
amounts ppt. turns to yellow when Hg (II) oxide
is formed. Ppt. is insoluble in excess reagent but
dissolves readily in acids and this can be used to
differentiate Hg (I) from Hg (II).
Ammonia solution White ppt. of mixed composition (Mercury (II)

2Hg 2+ −
+ NO3 + 4NH3 + H2O → oxide+Mercury (II) amido nitrate) is formed with
metal nitrate.
HgO.Hg (NH2 ) NO3 ↓ +3NH4 +
Cobalt (II) thiocyanate test When reagent is added to an aqueous solution of

2 Hg2+ ions and the walls of the test tube is stirred with
 (
Hg 2+
+ CO 2+
+ 4SCN → CO − +2 Hg SCN)  ↓
4 a glass rod, deep-blue crystalline ppt. is formed. In
place of Cobalt (II) thiocyanate, Co(CH3COO) and
NH4SCN can be added to the aqueous solution of
Hg2+ ions.
Cu2+ Test/Reagents Observation
Precipitation with H2S in acidic medium Black ppt. is formed.

H+
Cu2+ + H2S 
→ CuS ↓ +2H+ Ppt. is insoluble in boiling dilute (M) H2SO4
(distinction from cadmium), in NaOH,
3CuS + 8HNO3 →
Na2S and (NH4 ) S. Ppt. dissolves in hot conc.
3Cu (NO3 ) (blue ) + 2NO + 4H2O + 3S 2
2 HNO3
3−
2CuS ↓ +8CN− → 2 Cu ( CN)  + S 22 − When boiled for longer, S is oxidized to H2SO4 and
 4
a clear solution of Cu(NO3)2 is obtained.
KCN dissolves the ppt. forming a clear solution.

(disulphide ion)
Ammonia Solution When added sparingly a blue ppt. of basic salt

2
2Cu + SO 4 2−
+ 2NH3 + 2H2O → (basic copper sulphate) is formed with CuSO4.
Cu ( OH) .CuSO 4 ↓ +2NH4 + It is soluble in excess of reagent forming a deep

2
blue colouration.
Cu ( OH) .CuSO 4 + 8NH3 →
2
2+
2 Cu (NH3 )  + SO 42− + 2OH−
 4
Sodium hydroxide in cold solution A blue ppt. is formed.
Cu2 + 2 OH− → Cu ( OH) ↓

2
Cu ( OH) → CuO ↓ (black ) + H2O

Heat
2
Potassium iodide It gives a white ppt. of Cu (l) iodide but the solution
2+ − − is intensely brown because of the formation of tri-
2Cu + 5l → Cu2l2 ↓ +l3
iodide ions (or iodine). The soln becomes colourless
l3− + 2S2O32− → 3l− + S 4 O62− and a white ppt. is visible when excess of sodium
thiosulphate solution is added. These reactions are
used in quantitative analysis for the iodometric
determination of copper.
Potassium ferrocyanide (Potassium hexacyanidoferrate

(II) solution Cu2+ ions gives brown/chocolate brown ppt.
2Cu2+ + K 4Fe ( CN) → Cu2 Fe ( CN)  ↓ +4K +

6  6
3−
2 Fe ( CN)  + 3Cu2+ → Cu3 Fe ( CN)  ↓ Green
 6  6 2
Potassium cyanide When added sparingly forms first a yellow ppt.

which decomposes into CuCN and cyanogen.
Cu 2+
+ 2CN → Cu ( CN) ↓
−
2
Excess reagent dissolves the ppt. forming a
2Cu ( CN) → 2CuCN ↓ ( white ) +
2 colourless soluble complex.
( CN)2 ↑ (highlypoisonous ) Complex is so stable that H2S cannot ppt. Cu(l)
3−
CuCN + 3CN− → Cu ( CN)  sulphide (distinction from cadmium).
 4
Potassium thiocyanate solution

+2
The Cu ions solution initially gives a black ppt.
Cu+2 + 2SCN− → Cu ( SCN) ↓ which then slowly decomposes to give white ppt. of
2
2Cu ( SCN) → 2CuSCN ↓ + ( SCN) ↑ Cu (l) thiocyanate.
2 2
Cu (ll) thiocyanate can be immediately converted
2Cu ( SCN) + SO2 + 2H2O →
2 into Cu (l) thiocyanate by adding a suitable reducing
2CuSCN + 2SCN− + SO 42− + 4H+ agent like saturated solution of SO2.
Bi3+ Test/Reagents Observation
Precipitation with H2S in acidic medium Black ppt. is formed which is insoluble in cold dilute
HNO3 and yellow ammonium sulphide.
H+
→ Bi2S3 ↓ (black ) + 6H+
2Bi3+ + 3H2S 
Bi2S3 + 8HNO3 → 2Bi (NO3 ) + 2NO + 3S + 4H2O
3
Bi2S3 + 6HCl(boiling,conc.) → 2Bi3 + 6Cl− + 3H2S
Sodium hydroxide White ppt. is formed with the reagent,slightly

soluble in excess reagent in cold solution but
Bi3+ + 3OH− → Bi ( OH) ↓
3 soluble in acids. Ppt. on boiling loses water and
Bi ( OH) + 3H+ → Bi3+ + H2O turns yellowish white which is oxidised to BiO3– by
3
H2O2.
Bi ( OH) → BiO.OH ↓ +H2O
3
BiO.OH + H2O2 → BiO3− + H+ + H2O
Ammonia solution White basic salt of variable composition is formed.
Bi3+ + NO3− + 2NH3 + 2H2O → Bi ( OH) NO3 ↓ +2NH4 +

2
Alkaline sodium stannite (Sodium A black ppt. of metallic bismuth is obtained.

tetrahydroxidostannate (ll))
The reagent must be freshly prepared and test must
Bi3+
+ 3OH → Bi ( OH) ↓
− be carried out in cold solution.
3
2− 2−
2Bi ( OH) + Sn ( OH)  → 2Bi ↓ +3 Sn ( OH) 
3  4  6
Dilution with water Solution of bismuth salts gives white ppt. when
water is added in larger quantity. Soluble in
Bi3+ + NO3− + H2O → BiO (NO3 ) ↓ +2H+ mineral acids (dilute) but insoluble in tartaric acid
Bi3+ + Cl− + H2O → BiOCl
 ↓ + 2H+ (distinction from antimony) and in alkali hydroxide
bismuthoxychloride (distinction from tin).
or bismuthylchloriode
Potassium iodide When the reagent is added dropwise to a solution

3+
3+
Bi −
+ 3I → BiI3 ↓ containing Bi ions, a black ppt. is formed. The
− ppt. dissolves in excess Kl forming orange coloured
BiI3 + I − → BiI 4  soluble complex. On dilution the reaction is
BiI3 ↓ +H2O → BiOl ↓ +2H+ + 2l− reversed and black BiI3 turns orange.
(Cd2+) Test/Reagents Observation
Precipitation with H2S in acidic medium Yellow ppt. is formed which dissolves in hot dil.
HNO3.
H+
Cd2+ + H2S 
→ CdS ↓ +2H+
Ppt. does not dissolve in KCN.
CdS + 8HNO3 → 3Cd (NO3 ) + 4H2O + 2NO + 3S
2
Ammonia solution (Dropwise addition) Ammonium hydroxide first gives white ppt. of
Cd(OH)2 which gets dissolve in excess of reagent
Cd2+ + 2NH3 + 2H2O → Cd ( OH) ↓ +2NH4 +
2 forming a soluble complex.
2+
Cd ( OH) + 4NH3 → Cd (NH3 )  + 2OH−
2  4
Potassium cyanide White ppt. of Cd(CN)2 is formed which in excess of

reagent dissolves forming a soluble complex.
Cd2+ + 2CN− → Cd ( CN) ↓
2
2− The colourless soluble complex is unstable,therefore,
Cd ( CN) + 2CN → Cd ( CN) 
−
reacts with H2S gas forming a yellow ppt. of CdS.
2  4
2−
Cd ( CN)  + H2S → CdS ↓ +2H+ + 4CN− Kl forms no ppt. (distinction from Copper)
 4
Sodium hydroxide White ppt. is obtained which insoluble in excess of

Cd 2+
( aq) + 2NaOH( aq) → Cd ( OH)2 ↓ +2Na + NaOH
Illustration 11: When NaOH solution is mixed with aqueous solution of a salt ‘A’, and warmed, a black ppt. is formed.
Black ppt. is filtered and dissolved in concentrated HNO3 by boiling. The resulting solution gives a chocolate brown
coloured ppt. with potassium ferrocyanide solution. The filtrate obtained after filtering off the black ppt., upon
warming with Zn and NaOH evolves an alkaline pungent smelling gas. The resulting solution also responds to the
brown ring test. The filtrate does not evolve N2 gas when it is boiled with urea in the presence of H2SO4. Identify
the cation and anion present in the salt ‘A’.
Sol: Cu(NO3)2 + NaOH → Cu(OH)2 ↓ (Blue) + 2NaNO3

∆
Cu(OH)2 ↓ CuO ↓ (Black) + H2O
4Zn + NaNO3 + 7NaOH → 4Na2ZnO2 + 2H2O + NH3 ↑ (Pungent smelling alkaline gas)
∆
CuO + 2HNO3 Cu(NO3)2 + H2O
2Cu(NO3)2 + K4 [Fe(CN)6] → Cu2 [Fe(CN)6] ↓ (Chocolate brown) + 4KNO3
Illustration 12: A compound on heating with an excess of caustic soda solution liberates a gas (B) which gives
while fumes on exposure of HCl. The resultant alkaline solution thus obtained after heating again liberates the
same gas (B) when heated with zinc powder. Compound (A) on heating alone gives a neutral oxide of nitrogen not
nitrogen gas. Identify (A) and (B) and give the relevant chemical reactions.
Sol: As NH3 gives white fumes with HCl, therefore, (B) should be NH3 and (A) should be the salt of ammonium.
Further we know that nitrite of ammonium gives a NH3 with Zn and alkali and when heated alone gives neutral
oxide (N2O) not N2. Hence the salt should be ammonium nitrate not ammonium nitrite.
NH4NO3 (A) + NaOH → NaNO3 + H2O + NH3 ↑ (B ) ;NH3 + HCl → NH4 Cl ( White fumes )
Zn/NaOH
NaNO3 + 8 H  → NaOH + 2H2O + NH3 ;NH4NO3 → N2O (Neutral) + 2H2O
Illustration 13: A certain metal (A) is boiled with dilute HNO3 to give a salt (B) and an neutral oxide of nitrogen (C).
An aqueous solution of (B) gives a white ppt. (D) with brine which is soluble in ammonium hydroxide. An aqueous
solution of (B) also gives red/brick red ppt., (E) with potassium chromate solution. Identify (A) to (E) and write the
chemical reactions involved.
Sol: As solution of (B) gives white ppt. with NaCl (aq) ppt. is soluble in ammonium hydroxide, it may be of silver
salt. Further it gives brick red ppt. with K2CrO4, therefore, metal (A) may be silver.
3Ag(A) + 4HNO3 → 3AgNO3 (B) + NO ( C ) + 2H2O;
AgNO3 + NaCl → AgCl ↓ ( White ) (D) + NaNO3
AgCl + 2NH4 OH →  Ag (NH3 )  Cl ( Soluble ) + 2H2O
 2
2AgNO3 + K 2CrO 4 → Ag2CrO 4 ↓ (Red / Brick red) (E) + 2KNO3
Illustration 14: Which of the following salt will give white ppt. with the solution containing Pb2+ ions?
(A) Na2CO3 (B) NaCl (C) Na2SO3 (D) All of these
Sol: Pb + CO3 → PbCO3 ↓ ( White )

2+ 2−
Pb2+ + 2Cl− → PbCl2 ↓ ( White )

Pb2+ + SO32− → PbSO3 ↓ ( White )
Therefore, (D) option is correct.
Table 30.22: Some important reactions of group III radicals
Fe+3 Test/Reagents Observation

Potassium ferrocyanide (Potassium hexacyanidoferrate (ll)) Intense blue ppt. (Prussian blue) of
4−
iron (lll) hexacyanidoferrate (ll) is
4Fe+3 + 3 Fe ( CN)  → Fe4 Fe ( CN)  ↓ formed.
 6  8 3
4− This is insoluble in dilute acids but

Fe4 Fe ( CN)  + 12OH− → Fe ( OH) ↓ +3 Fe ( CN)  decomposes in concentrated HCl. A
 8 3 3  6
large excess of the reagent dissolves
it partly or entirely, when an intense
blue solution is obtained. Sodium
hydroxide turns the ppt. red.
Oxalic acid also dissolves Prussian

blue forming a blue-solution.
Important:
If iron (lll) chloride is added to an excess of potassium hexacyanidoferrate (ll), a product with the composition of
( )6 
KFe Fe CN  is formed. This tends to form colloidal solutions (‘soluble Prussian blue’) and can not be filtered.

Potassium ferricyanide (Potassium hexacyanidoferrate (lll)) A brown colouration is formed.

3− Upon adding hydrogen peroxide or
Fe3+ + Fe ( CN)  → Fe Fe ( CN)  some tin (ll) chloride solution, the
 6  6
3− 4− hexacyanidoferrate (lll) part of the
Fe2+ + Fe ( CN)  → Fe + Fe ( CN)  compound is reduced and Prussian
 6  6
blue is ppt..
4−
4Fe3+ + 3 Fe ( CN)  → Fe4 + Fe ( CN)  Fe2+ gives dark blue ppt. with
 6  6 3
potassium ferricyanide. First
hexacyanidoferrate (lll) ions
oxidise iron (ll) to iron (lll), when
hexacyanidoferrate (ll) is formed.
And these ions combine to form a

ppt. called Turnbull’s blue.
Note: Composition of this ppt. is identical to that of Prussian blue. Earlier the composition suggested was
Fe3 Fe ( CN)  , hence different name.

 6 2
3Fe2+ + 2K 3 Fe ( CN)  → Fe3 Fe ( CN)  (Ferrous ferric cyanide)+ 6K +

 6  6 2

Turnbull’s blue
Fe (ll) in ammonical solution gives red solution with DMG-colouration fades on standing due to the oxidation of iron (ll)
complex. Fe (lll) does not give such complex.
In complete absence of air, Fe (ll) ions produces white ppt. with potassium hexacyanidoferrate (ll).
4−
Fe2 + 2K + + Fe ( CN)  → K 2Fe Fe ( CN)  ↓
 6  6
Under ordinary atmospheric conditions a pale-blue ppt. is formed.

Cr+3 Test/Reagents Observation
Acidified H2O2 test
Na2CrO 4 + H2SO 4 → Na2SO 4 + H2CrO 4 ; Blue colouration

Amylalchohol
H2CrO 4 + 2H2O2 
→ CrO5 + H2O On acidifying the yellow solution
with dil.H2SO4+few drops of
4CrO5 + 6H2SO 4 → 2Cr2 ( SO 4 ) + 7O2 + 6H2O ether/amyl alcohol +H2O2= Blue
3
colouration ,can be extracted into
the organic layer by gently shaking.
Blue colouration fades slowly due

to the decomposition of perchromic
acid (or chromium peroxide) with
the liberation of oxygen.
Tests for: In excess of NaOH. Sodium
meta-aluminate (soluble). White
Al ( OH) + NaOH → NaAlO2 + 2H2O gelatinous ppt.
3
NaAlO2 + H2O + NH4 Cl → Al ( OH) + NaCl + NH3

3
Fe3+ Test/Reagents Observation

Tests for
Fe ( OH) + 3HCl → FeCl3 + 3H2O ( )

Red brown Fe OH dissolves in dil.
3
3 HCl as
4FeCl3 + 3K 4 Fe ( CN)  → Fe4 Fe ( CN)  + 12KCl ( )6 
Reaction with K 4 Fe CN  :
 6  6 3 
FeCl3 + KSCN → Fe ( SCN) Cl2 + KCl Ferric ferrocyanide (Dark Blue)
Reaction with KCNS:
Ferrithiocyanate (dark red colour)

Cr3+
Test/Reagents Observation
Tests for On boiling with
( CH3COO )2 Pb / CH3COOH NaOH / Br2 ,Cr ( OH) gives

3
2NaOH + Br2 → NaOBr + NaBr + H2O sodium chromate which gives

yellow ppt. of PbCrO4 with
NaOBr → NaBr + O 
Yellow solution
2Cr ( OH) + 4NaOH + 3 O  → 2Na2CrO 4 + 5H2O
3
Yellow solution
Yellow ppt.
Na2CrO 4 + ( CH3COO ) Pb → PbCrO 4 ↓ +2CH3COONa
2
Yellowppt. Yellow solution
2Cr ( OH) + 2Na2CO3 + 3KNO3 → 2Na2CrO 4 + 3KNO2 + 3H2O + 2CO2
3
Yellow solution Yellow ppt.
Na2CrO 4 + ( CH3COO ) Pb → PbCrO 4 ↓ +2CH3COONa

2
Yellowppt.
Illustration 15: A black coloured compound (A) on reaction with dil. H2SO4 gives a gas (B) and a green colour
solution. The gas (B) on passing in a solution of an acid (C) gives a white/yellow turbidity (D). Gas (B) when passed
in acidified solution of (E) gives a ppt. (F) soluble in dil HNO3. After boiling this solution when excess of NH4OH is
added, a blue coloured compound (G) is formed. To this solution on addition of acetic acid and aqueous potassium
ferrocyanide a chocolate coloured ppt. (H) is obtained. On addition of an aqueous solution of BaCl2 to an aqueous
solution of (E), a white ppt. insoluble in HNO3 is obtained. Green colour solution on reaction with ammonium
hydroxide in presence of air gives reddish brown ppt.. Identify (A) to (H).
Sol: FeS ( A ) + H2SO 4 → FeSO 4 + H2S (B )

HNO3 ( C ) → NO2 + H2O + O;H2S + O → H2O + S ↓ (D )
CuSO 4 (E ) + H2S → CuS ↓ (F ) + H2SO 4
3CuS + 8HNO3 → 3Cu (NO3 ) + 2NO ↑ +4H2O + 3S ↓
2
2+
Cu2+ + 4NH3 → Cu (NH3 )  ( G)
 4
2Cu + K 4Fe ( CN) → Cu2 Fe ( CN)  ↓ (H) + 4K +

2+
6  6
Ba + SO 4 → BaSO 4 ↓ ( white )
2 2−
Fe2+ + 2H+ + O → Fe3+ + H2O

Fe3+ + 3NH3 + 3H2O → Fe ( OH) ↓ (reddish brown) + 3NH4 +
3
Hence,(A)
= FeS;(B)
= H2S;(C)
= HNO3 =
;(D) S;(E)
= CuSO 4=
;(F) CuS;
 ( 3 )4  (
(G) Cu NH  NO3 ) ;(H) Cu2 Fe ( CN) 
=
2  6
3CuS + 8HNO3 → 3Cu (NO3 ) + 2NO ↑ +4H2O + 3S ↓
2
2+
Cu2+ + 4NH → Cu (NH )4  ( G)
3 0 . 3 4 | Qualitative
3 Analysis
3
2Cu2+ + K 4Fe ( CN) → Cu2 Fe ( CN)  ↓ (H) + 4K +

6  6
Ba + SO 4 → BaSO 4 ↓ ( white )
2 2−
Fe2+ + 2H+ + O → Fe3+ + H2O

Fe3+ + 3NH3 + 3H2O → Fe ( OH) ↓ (reddish brown) + 3NH4 +
3
Hence,(A)
= FeS;(B)
= H2S;(C)
= HNO3 =
;(D) S;(E)
= CuSO 4=
;(F) CuS;
 ( 3 )4  (
(G) Cu NH  NO3 ) ;(H) Cu2 Fe ( CN) 
=
2  6
Flowchart 30.4: Systematic path for the analysis of group IV radicals

14. REACTIONS OF Ni2+ (NICKEL) AND Co2+ (COBALT)

The black ppt. is dissolved in aqua-regia.
3NiS + 6HCl + 2HNO3 → 3NiCl2 + 2NO + 3S + 4H2O

3CoS + 6HCl + 2HNO3 → 3CoCl2 + 2NO + 3S + 4H2O
The solution is evaporated to dryness and residue extracted with dilute HCl. It is divided into three parts.
Table 30.23: Some important reaction of group IV
Part I Part II Part III

Excess CH3COOH (excess)+KNO2=yellow ppt. confirms Solution containing either nickel or cobalt is treated
NH4OH+ the presence of cobalt. with NaHCO3 and bromine water. Appearance of apple
dimethyl green colour confirms the presence of cobalt. If no
KNO2 + CH3COOH → CH3. COOK + HNO2
glyoxime = apple green colour is observed, the solution is heated
rosy red ppt. CoCl2 + 2KNO2 → Co (NO2 ) + 2KCl when black ppt. is formed, which shows the presence
2
if nickel is Co (NO2 ) + 2HNO2 → Co (NO2 ) + NO + H2O of nickel.
2 3
present CoCl2 + 2NaHCO3 → Co (HCO3 ) + 2NaCl
Co (NO2 ) + 3KNO2 → K 3 Co (NO2 )  2
 6
Co (HCO3 ) + 4NaHCO3 → Na4 Co ( CO3 ) 3H2O
3
2 3
+3CO2 Br2 + H2O → 2HBr + O
2Na4 Co ( CO3 ) + H2O + O → 2Na3Co ( CO3 ) + NaOH
3 3
Sod. cobalt carbonate
(Green colouration)
NiCl2 + 2NaHCO3 → NiCO3 + 2NaCl + H2O + CO2
2NiCO3 + O → Ni2O3 + 2CO2
Black
Zn2+ (zinc)
The sulphide dissolves in HCl.
ZnS + 2HCl → ZnCl2 + H2S
When the solution is treated with NaOH, first a white ppt. appears which dissolves in excess of NaOH
ZnCl2 + 2NaOH → Zn ( OH) ↓ +2NaCl

2
Whiteppt.
Zn ( OH) + 2NaOH → Na2 ZnO2 + 2H2O
2
Soluble
On passing H2S , white ppt. of zinc sulphide is formed,
Na2 ZnO2 + H2S → ZnS + 2NaOH

Whiteppt
Mn2+ (manganese)
Manganese sulphide dissolves in HCl.
MnS + 2HCl → MnCl2 + H2S
On heating the solution with NaOH and Br2 -water, manganese dioxide gets ppt..
MnCl2 + 2NaOH → Mn ( OH) + 2NaCl

2
Mn ( OH) + O → MnO2 + H2O
2
The ppt. is treated with excess of HNO3 and PbO2 or Pb3O4 (red lead). The contents are heated. The formation of
permanganic acid imparts pink colour to the supernatant liquid.
2MnO2 + 4HNO3 → 2Mn (NO3 ) + 2H2O + O2

2
2Mn (NO3 ) + 5Pb3O 4 + 26HNO3 → 2HMnO 4 + 15Pb (NO3 ) + 12H2O
2 2
Permanganic acid(pink)
BaCO3 + 2CH3COOH → ( CH3COO ) Ba + CO2 + H2O

2
SrCO3 + 2CH3COOH → ( CH3COO ) Sr + CO2 + H2O
2
CaCO3 + 2CH3COOH → ( CH3COO ) Ca + CO2 + H2O
2
Flowchart 5: For the analysis of group V radical

GROUP V (Ba (II), Sr (II), Ca (II))

Ammonium carbonate ppt. V group radicals in the form of carbonates.These carbonates are soluble in acetic acid.
Table 30.24: Confirmatory test for group V radicals
Ba2+ Test/Reagents Observation

White ppt.
Ba ( CH3COO ) + K 2CrO 4 → BaCrO 4 ↓ +2CH3COOK
2
Ba ( CH3COO ) + (NH4 ) SO 4 → BaSO 4 ↓ +2CH3COONH4
2 2
Ba ( CH3COO ) + (NH4 ) C2O 4 → BaC2O 4 ↓ +2CH3COONH4
2 2
White ppt.
Sr ( CH3COO ) + (NH4 ) SO 4 → SrSO 4 ↓ +2CH3COONH4
2 2
Whiteppt.
White ppt.
White ppt.
Sr ( CH3COO ) (NH4 ) C2O 4 → SrC2O 4 ↓ +2CH3COONH4
2 2
Calcium chlorate and calcium
Ca ( CH3COO ) + (NH4 ) C2O 4 → CaC2O 4 ↓ +2CH3COONH4 sulphate are soluble.
2 2
Whiteppt.
White ppt.
VITH GROUP
Table 30.25: Confirmatory test for group VI radical
Mg2+ Test/Reagents Observation

Disodium hydrogen phosphate solution White crystalline ppt. is formed in
presence of NH4Cl prevent precipitation
2
Mg + NH3 + HPO 4 2−
→ Mg (NH4 ) PO 4 ↓
of Mg(OH)2 and NH3 soln
Mg2 + HPO 42− → MgHPO 4 ↓
white flocculent ppt.
Ammonia solution White gelatinous ppt is sparingly
soluble in water but readily soluble in
Mg2 + 2NH4 OH → Mg ( OH) ↓ +2NH4 +
2 ammonium salts.
Mg ( OH) → Mg +2
+ 2OH−
2 NH4 + ions ‘remove’ OH− causing the
NH4 Cl → NH4 + + Cl− ; hydroxide to dissolve more. Not possible
with NaCl.
NH4 + + OH− → NH4 OH(weak base)
Ammonium carbonate solution +

Absence of NH4 salts.
5Mg 2+
+ 6CO32− + 7H2O → 2MgCO3 .Mg ( OH) .5H2O ↓ +2HCO3 −
2 In the presence of NH4 + salts no
NH4 + + CO32− → NH3 + HCO3− precipitation occurs, because the
equilibrium is shifted towards the
formation of HCO3− ions. K sp of the
ppt. being high (Ksp of pure MgCO3
−5
is 1 × 10 ), the concentration of
carbonate ions necessary to produce a
ppt. is not attained.
4-(4-Nitrophenyl azo resorcinol) or Magneson I Ppt. is dissolved in dilute HCl (min.)
+NaOH +0.5ml magneson-I reagent =
MgCl2 + 2NaOH → Mg ( OH) + 2NaCl
2 Blue lake
Magneson reagent = p-nitrobenzene-azo resorcinol, a dye stuff,
absorbed over Mg(OH)2 to give a blue coloured lake.
Titan yellow (a water soluble yellow dyestuff) Deep red colour or ppt.
It is adsorbed by Mg(OH)2
Dissolve ppt. in dil.HCl(min.)+1 drop of NaOH soln (2M) + 1 drop titan Deep red colour solution or ppt. is
yellow soln obtained.
Ba2+ andCa2+ do not react but intensify

the colour.
Table 30.26: Action of heat on different compounds
(a) Some oxides liberate O2: (e) Some sulphates liberate SO 2 :

Heat Heat
2HgO → 2Hg + O2 ↑ 2MgSO 4  → 2MgO + 2SO2 + O2
(Red) (Silvery deposit) Heat (hightemp)
2ZnSO 4 
→ 2ZnO + 2SO2 + O2
Heat
2Pb3 O 4 → 6PbO + O2 ↑ Heat
2BeSO 4  → 2BeO + 2SO2 + O2
(Red) (Yellow)
(f) Some sulphates lose water of crystallization:
Heat
2PbO2 → 2PbO + O2 ↑
Heat 2 ( CaSO 4 .2H2O ) 
Heat
→ 2 ( CaSO 4 .H2O ) + 2H2O
2Ag2O  → 4Ag + O2 ↑
70°C 100°C
ZnSO 4 .7H2O → ZnSO 4 .6H2O  →
(b) Some carbonates liberate CO: −H O
2 −5H O 2
450°C
Heat
CuCO3  → CuO + CO2 ↑ ZnSO 4 .H2O 
−H2O
→ ZnSO 4
(Green) (black) (g) Some nitrates liberate NO2 and O2:

Heat
ZnCO3 → ZnO + CO2 ↑
2Zn (NO3 ) 
Heat
→ 2ZnO + 4NO2 + O2
(white) Yellow (hot) 2
white Brown
white(cold)
Heat 2Cu (NO3 ) 
Heat
→ 2CuO + 4NO2 + O2
2Ag2CO3  → 4Ag + 2CO2 ↑ +O2 ↑ 2
Heat
CaCO3 → CaO + CO2 ↑ 2Pb (NO3 ) 
Heat
→ 2PbO + 4NO2 + O2
2
Heat
MgCO3 → MgO + CO2 ↑ 2Mg (NO3 ) 
Heat
→ 2MgO + 4NO2 + O2
2
2Ca (NO3 ) 

Heat Heat
Li2CO3 → Li2O + CO2 ↑ → 2CaO + 4NO2 + O2
2
Heat
(c) Some bicarbonates liberate CO2 : 2LiNO3 → Li2O + 2NO2 + 1 / 2O2
2NaHCO3 → Na2CO3 + CO2 + H2O Hg (NO3 ) 

Heat
→ Hg + 2NO2 + O2
2
NH4HCO3 → NH3 + CO2 + H2O Heat
2AgNO3  → 2Ag + 2NO2 + O2
2Co (NO3 ) 
Heat
→ 2CoO + 4NO2 + O2
(d) Some sulphates liberate SO3 : 2
Heat
CuSO 4 .5H2O  → CuSO 4 ; (h) Some nitrates liberate O2 :
−5H O 2
Heat
Heat
 → CuO + SO3 2NaNO3  → 2NaNO2 + O2
Heat
Heat
2FeSO 4  → .Fe2O3 + SO 2 + SO3 2AgNO3  → 2AgNO2 + O2
Al2 ( SO 4 ) 
Re dHot
→ Al2O3 + 3SO3
3
(i) Some nitrates liberate N2O: (k) Some chlorides decompose as:
Heat Heat
NH4NO3  → N2O + 2H2O 2FeCl3  → 2FeCl2 + Cl2
Heat
2CuCl2  → Cu2Cl2 + Cl2
(j) Hydrated chlorides liberate HCl: Heat
NH4 Cl  → NH3 + HCl
Heat
2  AlCl3 .6H2O   → Al2O3 + 6HCl + 9H2O Heat
Hg2Cl2  → HgCl2 + Hg
Heat
MgCl2 .6H2O → MgO + 2HCl + 5H2O
(l) Some other salts decompose as:
Heat
ZnCl2 .2H2O  → Zn ( OH) Cl + HCl + H2O
2 ( ZnCl2 .H2O ) 
Heat
→ Zn2OCl2 + 2HCl + H2O (NH4 )2 Cr2O7 
Heat
→ N2 + Cr2O3 + 4H2O
Heat orange Green
2 FeCl3 .6H2O   → Fe2O3 + 6HCl + 9H2O
Heat
4K 2Cr2O7 → 4K 2CrO 4 + 2Cr2O3 + 3O2
Heat
SnCl2 .2H2O  → Sn ( OH) Cl + HCl + H2O Heat
NH4NO2  → N2 + 2H2O
Heat
NH4NO3  → N2 + 2H2O
2Mg (NH4 ) PO 4 
Heat
→ Mg2P2O7 + H2O + 2NH3
2Zn (NH4 ) PO 4 
Heat
→ Zn2P2O7 + H2O + 2NH3
( CH3COO )2 Pb 
Heat
→ PbCO3 + CH3COCH3
Heat
FeC2O 4  → FeO + CO2 + CO
Heat
SnC2O 4  → SnO + CO2 + CO
Heat
CaC2O 4  → CaCO3 + CO
K 4 Fe ( CN)  
Heat
→ 4KCN + Fe + 2C + N2
 6
100°C 160°C
H3BO3  → HBO2  → H2B 4 O7 ;
Red Hot
→ B2O3
Heat
2KCiO3  → 2KCl + 3O2
Heat
2KMnO 4  → K 2MnO 4 + MnO2 + O2
Heat
Na2B 4 O7 .10H2O 
−10H O
→ Na2B 4 O7 ;
2
Heat
 → 2NaBO2 + B2O3

(Glassy bead)
Na (NH44) )HPO  ∆
Na(NH HPO44  NH33 ++NaPO
→ NH NaPO33++HH
2O
2
O
Table 30.27: Different colored inorganic compounds
Black Coloured Blue Coloured Compounds Green Coloured Compounds Yellow Coloured
Compounds Compounds
Light Blue
1. PbS 1. Cu(OH)2 1. Ni(OH)2 (Green ppt.) 1. As2S3
2. Ag2S 2. Cu(NO3)2 2. Hg2I2 (Green ppt.) 2. As2S5
3. CuS 3. CuCl2 3. Cr2O3 (Green solid) 3. CdS
4. Cu2S 4. CuSO4.5H2O (Blue vitrol) 4. Cr2(SO4)3 4. SnS2 (Artificial gold)

Black Coloured Blue Coloured Compounds Green Coloured Compounds Yellow Coloured
Compounds Compounds
5. NiS 5. Zn2[Fe(CN)6] (Bluwish white 5. CrCl3 5. FeS2 (Fool’s gold)
6. CoS ppt) 6. FeSO4. 7H2O 6. (NH4)2Sx (where X=2 to 5)
7. HgS 6. Co(OH)2 7. FeCl2 7. PbCrO4
8. FeS 8. FeSO4.(NH4)2SO4.6H2O 8. BaCrO4
9. NiO Deep Blue (Mohr’s salt) 9. SrCrO4
10. MnO 1. [Cu(NH3)4]SO4 (Swizzer’s 9. Na2MnO4 10. AgBr (light yellow)
reagent) 10. K2MnO4
11. FeO 11 AgI (Dark yellow)
2. [Cu(NH3)4](NO3)2 11. B(OC2H5)3 (Burns with green
12. CuO 12. PbI2
3. Fe4[Fe(CN)6]3 (Prussian’s blue) edge flame)
13. PbO2 13. PbO (in Cold)
4. Fe3[Fe(CN)6]2 (Turnbull’s blue) 12. CoO.ZnO (Riemann’s green)
14. MnO2 14. ZnO (in Hot)
5. Na4[Fe(CN)5(NOS)] (Violet)
15. Mn3O4 15. HgO(Yellow ppt.)
16. Fe3O4 16. Na2O2(Pale yellow)
17. Co3O4 17. Ag3PO4
18. Ni(OH)3 18. Ag2CO3
19. Cu3P2 19. Ag3AsO4
20. BiI3 20. Cu(CN)2
21. Hg+Hg(NH2)Cl 21. K3[Co(NO2)6]
22. (NH4)3PO4.12MoO3
23. (NH4)3AsO4.12MoO3
24. Na2CrO4
25. CrO42-(Yellow in solution)
Red Coloured Brown Coloured Compounds Orange Coloured Pink Coloured

Compounds Compounds Compounds
1. Ag2CrO4 (Brick red) 1. SnS 1. Sb2S3 Mn(OH)2
2. Hg2CrO4 (Brick red) 2. Bi2S3 2. Sb2S5 MnS
3. HgI3 (Scarlet red) 3. CdO 3. KO3 MnO4-
4. Pb3O4 (2PbO + PbO2) 4. PbO2 4. CsO2 (pink or purple in aq.soln)
5. CrO2Cl2 (Reddish Brown) 5. Fe(OH)3 (Reddish Brown) 5. Cr2O72- (orange in aq. soln) Co(CN)2
6. Fe(CH3COO)3 6. Fe2O3 (Reddish Brown solid) (NH4)2SnCl6

(Blood red)
CoCl2.6H2O
7. Fe(SCN)3 (Blood Red) 7. Fe2(CO3)3
8. AsI3 8. Cu2O (Reddish Brown)
9. SbI3 9. Ag3AsO4 (Reddish Brown)
10. SnI2 10. Cu2I2 + I3− (Brown ppt.)
11 CuBr2 11 Cu2[Fe(CN)6] (Chocolate Brown)
12. [Ni(DMG)2] (Rosy red) 12. NO2 (Brown gas)
13. [Fe(H2O)5(NO)]SO4 (Brown ring)

POINTS TO REMEMBER
An aqueous solution containing :

+ +2 +2 +2 +3 +2 +2 +2
Ag , Hg2 , Pb , Hg , Bi , Cu , Ni , Mn ,
+3 +3 +2 +2 +2 + + +2
Fe , Al , Ba , Sr , Ca , K , Na , Mg
Add dilute HCl

Precipitate forms Ions remain in soln.
Group II-V:
Group I:
+2 +2 +3 +2 +2 +2 +3 +3
AgCl(s) Pb ,Hg ,Bi ,Cu , Ni ,Mn ,Fe ,Al
Hg2Cl2(s) Ba
+2
,Sr
+2
,Ca
+2
,NH4+, K ,Na
+ +
,Mg
+2
PbCl2(s)
Add H2S in 0.3 M HCl

Group II: Group III-V:
PbS(s) +2 +3 +3 +3 +2 +2
Ni ,Mn ,Fe ,Al , Ba ,Sr ,
HgS(s) +2 + + +2
Ca ,NH4+ , K ,Na ,Mg
Bi2S2(s)
CuS(s) Add H2S in basic soln.
(NH3/NH4Cl buffer).

Group III: Group IV-V:
NiS(s) Ba
+2 +2
, Sr , Ca
+2
MnS(s) + + +2
NH4+ , K ,Na , Mg
FeS(s)
Al(OH)3(s) Add (NH4)2CO3 in basic
soln. (NH3/NH4Cl buffer).

Group IV: Group V:
+
BaCO3(s) NH4 , K+ ,
+2
Na+ , Mg
SrCO3(s)
CaCO3(s)
Solved Examples
JEE Main/Boards Sol: Gas X is soluble in water forming basic solution

because it turns red litmus blue. Hence, the gas may
Example 1: A colourless solid (A) liberates a brown be NH3.
gas (B) on acidification, a colourless alkaline gas (C) on NH3 + H2O → NH4 OH
treatment with NaOH and a colourless non-reactive gas
CuSO 4 + 4NH4POH →[Cu(NH3 )4 ]SO 4 + 4H2O
(D) on heating. If heating of (A) is continued, it completely
disappears. Identify the compounds (A) to (D). (T etra− amine cupric
sulphate) D eep blue
Sol: (A) From the given data it appears to be NH4NO2.
Ferric chloride gives brown ppt. of Fe(OH)3
This can be explained by the following reaction
FeCl3 + 3NH4 OH → Fe(OH)3 + 3NH4 Cl
With mineral acid NH4NO2 yields Nitrous acid which
eventually gets converted to Nitric acid liberating NO. (Brown precipitate)
NO with oxygen forms brown coloured NO2 gas. Brown ppt. is soluble in HNO3
(1) NH4NO2 + HCl → NH4 Cl+ HNO2 Fe(OH)3 + 3HNO3 → Fe(NO3 )3 + 3H2O
(A) Nitrous acid (Soluble complex)
3HNO2 → HNO3 + H2O + 2NO
(Nitric acid)
*** NaCl on heating with conc. H2SO4 gives HCl
whereas NaBr and NaI gives Br2 and I2 respectively.
2NO + O2 → 2NO2 Why?
(Brown gas) (B)
[Hint: NaCl + H2SO 4 → NaHSO 4 + HCl
NH4NO2 with NaOH gives out Sodium nitrite and NaBr + H2SO 4 → NaHSO 4 + HBr
ammonia gas.
2HBr + H2SO 4 → Br2 + SO2 + 2H2O
(2) NH4NO2 + NaOH → NaNO2 + NH3 ↑ +H O
(C) Ammonia gas
2 HBr and HI are reducing agent whereas H2SO4 is
oxidising agent and thus Br2 and I2 are formed.]
On heating it gives off colourless Nitrogen gas and
water.
Example 3: A compound (A) on heating with an excess
(3) NH4NO2 → ∆
N2 ↑ + 2H2O of caustic soda solution liberates a gas (B) which gives
Non−reactive (D) white fumes on exposure of HCl. Heating it continued to
expel the gas completely. The resultant alkaline solution
*** Both NO2 and Br2 are brown gases. How can they again liberates the same gas (B) when heated with zinc
be identified if placed separately in two containers? powder. However the compound (A), when heated alone
does not give nitrogen. Identify (A) and (B).
[Hint: Water is added in both the container. Br2
forms yellow solution whereas NO2 forms colourless
Sol: We all know that NH3 with HCl gives white fumes of
solution.]
NH4Cl with popping noise.
Hence it should be NH3. Thus, compound (A) must be
Example 2: An aqueous solution of gas (X) shows the
an ammonium salt.
following reactions
Also we know that nitrates and nitrites on heating with
(a) It turns red litmus blue.
Zn and alkali liberate NH3 gas. Hence the compound (A)
(b) When added in excess to a copper sulphate solution, should be ammonium nitrate or nitrite
a deep blue colour is obtained.
But compound (A) does not give N2 on heating hence it
(c) On addition of FeCl3 solution, a brown ppt., soluble in may not be ammonium nitrite.
dilute HNO3 is obtained. Identify (X) and give equations
for the reactions at step (b) and (c).
Reactions involved: Example 5: (i) Solution salt of an acid (A) is formed on

boiling white phosphorus with NaOH solution.
NH4NO3 + NaOH → NaNO3 + H2O + NH3 ↑
(ii) On passing chlorine through phosphorus kept fused
(A) under water, another acid (B) is formed which on strong
heating gives metaphosphoorus acid.
NH3 + HCl → NH4 Cl
(White fumes) (iii) Phosphorus on treatment with conc. HNO3 gives an
acid (C) which ais also formed by the action of dilute
Zn/NaOH
NaNO3 + 8[H]  → NaNO3 + 2H2O + NH3 ↑ H2SO4 on powdered phosphorite rock.
(iv) (A) on treatment with a solution of HgCl2 first gives a
*** Why original solution is not prepared in conc.
white ppt. of compound (D) and then grey ppt. (E).
HNO3 ?
Identify (A) to (E) and write balanced chemical equations
[Hint: HNO3 is an oxidising agent which on
for the reactions at step (i) to (iv)
decomposition gives oxygen. A yellow ppt. of
sulphur is obtained in presence of HNO3 when H2S
is passed for detecting the radicals of group II and Sol: ( i) P4 + 3NaOH + 3H2O → 3NaH2PO2 + PH3
group IV. H2S + 2HNO2 → 2NO2 + 2H2O + S ] (Sodium hypophosphate)
Example 4: An inorganic compound (A) shows the Thus, acid (A) is H3PO2, i.e. , hypophosphorus acid
following reactions.
(ii) 2P + 3Cl2 + 6H2O → 2H3PO3 + 6HCl
(i) It is white solid and exists as dimmer; gives fumes of
(Phosphorus acid)
(B) with wet air.
(ii) It sublimes on 180° C and forms monomer if heated Thus, acid (B) is H3PO3
to 400° C.
(iii) P4 + 20HNO3 → 4H3PO 4 + 20NO2 + 4H2O
(iii) Its aqueous solution turns blue litmus to red.
(C)
(iv) Addition of NH4OH and NaOH separately to a
solution of (A) gives white ppt. which is however soluble P4 + 10HNO3 → 4H3PO 4 + 10NO2 + 4H2O
in excess of NaOH. Phoshoric acid(C)
Thus acid (C) is H3PO4
Sol: (i) (A) is a characteristic dimerized compound which
sublimes on 180° C and forms monomer if heated to (iv) H3PO2 + 2H2O → H3PO 4 + 4H
400° C and thus, (A) is (AlCl3)2 or Al2Cl6
180°C 400°C
Al2Cl6(s)  → Al2Cl6(v)  → 2AlCl3 HgCl2 + 2H → Hg2Cl2 + 2HCl
(white)(D)
(ii) It fumes with wet air
Al2Cl6 + 6H2O → 2Al(OH)3 + 6HCl ↑ Hg2Cl2 + 2H → 2Hg + 2HCl

Fumes(B) (Grey)(E)
*** During testing of Cl- and Br- by chloroform

(iii) Its solution in water is acidic due to hydrolysis
test, CHCl3 layer first turns violet and then brown,
2AlCl3 + 6H2O → 2Al(OH)3 + 6HCl(aq) confirming the presence of I- and Br- respectively.
(iv) (A) gives white ppt. with NH4OH, soluble in excess When layer turns brown then violet colour
of NaOH. disappears or not and why?
[Hint: Violet and brown colours are due to oxidation
Al2Cl6 + 6NH4 OH → 2Al(OH)3 + 6NH4 Cl
of I- to I2 and Br- to Br2 respectively. The violet
Al2Cl6 + 6NaOH → 2AlOH+ 6NaCl colour of I2 disappears when layer is brown due to
formation of ( IO3− ) (iodate ion) which is colourless.]
Example 6: (i) A black coloured compound (B) is formed Note: *** Subquestions placed after the answers
on passing hydrogen sulphide through the solution of a
compound (A) in NH4OH.
JEE Advanced/Boards
(ii) (B) on treatment with hydrochloric acid and potassium Example 1: (i) An ore (A) on roasting with sodium
chlorate gives (A). carbonate and lime in the presence of air gives two
(iii) (A) on treatment with potassium cyanide gives a buff compounds, (B) and (C).
coloured ppt. which dissolves in excess of this reagent (ii) The solution of (B) in conc. HCl on treatment with
forming a compound (C). potassium ferricyanide gives a blue colour or ppt. of
(iv) The compound (C) is changes into a compound (D) compound (D).
when its aqueous solution is boiled. (iii) The aqueous solution of (C) on treatment with conc.
(v) The solution of (A) was treated with excess of sodium H2SO4 gives a yellow coloured compound (E).
bicarbonate and then with bromine water. On cooling (iv) Compound (E) when treated with KCl gives an
and shaking for some time, a green colour compound orange-red compound (F) which is used an oxidizing
(E) is formed. No change is observed on heating. Identify reagent.
(A) to (E) and gives chemical equations for the reactions
at steps (i) to (v). (v) The solution of (F) on treatment with oxalic acid and
then with an excess of potassium oxalate gives blue
Sol: Here it is given that a black coloured compound (B) crystals of compound (G).
is formed on passing hydrogen sulphide through the Identify (A) to (G) and give balanced chemical equations
solution of a compound (A) in NH4OH. for reactions at steps (i) to (v).
This indicates that (A) is salt of the IV group radicals
( )
Co2+ , Ni2+ or Zn2+ . Sol: (a) Reaction (i) suggests that the ore contains Fe.
Further it is given that on treatment with potassium (b) Reaction (ii) and (iv) suggests that the ore also
cyanide (A) gives a buff coloured ppt. which dissolves in contains chromium.
excess of this reagent forming a compound (C). Reaction (i), (iii) and (IV) are involved in the preparation
Which appears to be a cobalt salt (CoCl2) of K2Cr2O7 from chromite ore, FeOCr2O3.
Hence the given reactions can be written as below
(i) CoCl2 + 2NH4 OH+ H2S → CoS + 2NH4 Cl + 2H2O
lime
(A) (B) (i) 4FeO.Cr2O3 + 8Na2CO3 + 7O2 →
(Rosting)
2Fe2O3 ↓ +8Na2CrO 4 + 8C
(B)
Chromite ore (A) (B) (C)
(ii) CoS + 2HCl + O  → CoCl2 + H2O + S
lime
(from KClO ) (i) 4FeO.Cr2O3 + 8Na2CO3 + 7O2 →
(Rosting)
2Fe2O3 ↓ +8Na2CrO 4 + 8CO2 ↑
3
Chromite ore (A)
2KClO3 → 2KCl + 3O2 (B) (C)
(ii) Fe2O3 + 6HCl → 2FeCl3 + 3H2O
(iii) CoCl2 + 2KCN → Co(CN)2 ↓ +2KCl
buff coloured 4FeCl3 + 3K 4 [Fe(CN)6 ] → Fe4 [Fe(CN)6 ]3 + 12KCl
Blue(D)
CO(CN)2 + 4KCN → K 4 [Co(CN)6 ]
(iii) 2Na2CrO 4 + H2SO 4 → Na2 Cr6 O3 + Na2SO 4 + H2O
(iv) 2K 4 [CO(CN)6 ] + O + H2O → 2K 3 [Co(CN)6 ] + 2KOH soluble (C) Yellow colour (E)
(D)
(iv) Na2Cr2O7 + 2KCl → K 2 Cr2 O7 + 2NaCl
(v) CoCl2 + 6NaHCO3 → Na4 [Co(CO3 )3 ] + 2NaCl+ 3CO2 + 3H2O(E) (F)
oCl2 + 6NaHCO3 
→ Na4 [Co(CO3 )3 ] + 2NaCl+ 3CO2 + 3H2O
K 2 Cr2 O7 (F) is well known oxidizing agent.
2Na4 [Co(CO3 )3 ] + 2NaHCO3 + O → 2Na3 [Co(CO3 )3 ] + 2Na

(v)2CO + 2HO
Cr23(C 2O4 )3 + 3K 2 C2 O 4 → 2K 3 [Cr(C2 O 4 )3 ] + Cr2 (C2O 4 )3
(E)(v) Cr (C O ) + 3K C O Potassium oxalate
→ 2K 3 [Cr(C Potassium trioxalatochromium
CO3 + O → 2Na3 [Co(CO3 )3 ] + 2Na2CO3 + H2O 2 2 4 3 2 2 4  2 O 4 )3 ] + Cr2 (C2 O 4 )3
Blue crystals (G)
Potassium oxalate Potassium trioxalatochromium
(E)
Blue crystals (G)
*** Chromyl chloride test for chlorides is not (iv) FeSO 4 + K 3 [Fe(CN)6 ] → KFe[Fe(CN)6 ] + K 2SO 4
performed if mixture contain chlorates, why? (D) (E)
[Hint: Because ions react with H2SO4 to
ClO3−
form chlorine dioxide (yellow greenish gas) which Example 3: A white substance A reacts with dilute
dissolves in H2SO4 forming orange-yellow solution. H2SO4 to produce a colourless gas B and a colourless
This solution is highly explosive. solution C. The reaction between B and acidified K2Cr2O7
solution produces a green solution and a slightly
3KClO3 + 3H2SO 4 → 2ClO2 + ClO −4 + 3SO24− + 4H+ + 3K + + H2O
coloured participate D. The substance D burns in air to
O −4 + 3SO24− + 4H+ + 3K + + H2O ] produce a gas E which reacts with B to yield D and a
colourless liquid. Anhydrous copper sulphate is turned
Example 2: (i) A black mineral (A) on heating in presence blue on addition of this colourless liquid. Addition of
of air gives a gas (B). aqueous NH3 or NaOH to C produces first a participate
which dissolves in the excess of the respective reagent
(ii) The mineral (A) on reaction with dilute H2SO4 gives a to produce a clear solution in each case. Identify A, B, C,
gas (C) and solution of a compound (D). D and E. Write the equation of the reactions involved.
(iii) On passing gas (C) into an aqueous solution of (B) a
white turbidity is obtained. Sol:
dil.H2SO4
(iv) The aqueous solution of compound (D) on reaction

A B +C
with potassium ferricyanide gives a blue compound (E). (White) (Colourless) (Colourless solution)
Identify (A) to (E) and give chemical equations for +

reactions at steps (i) to (iv). K2Cr2O7/H
Sol: Summary of the given statement can be written as:

Green solution + D
dilH SO
2 4 → Black mineral A  O
2 → Gas B i)H O
2 →White turbidity (Burns in air to form E)
Gas C + Solution of D ← ii)gas C (Coloured)
O i)H O CuSO4
2 → Gas B
Black mineral A  2 →White turbidity

E +B D + Colourless liquid Blue

ii)gas C
Aq.NH3 Excess of
D C
or NaOH
Precipitate
reagent
Clear solution
K3[Fe(CN)6] The above set leads to following conclusions.

(i) Because Gas (B) is colourless and turns acidified
Blue compound E K2Cr2O7 solution green, it appers to be H2S.
(ii) H2S gas is obtained by the reaction of dil. H2SO4 on
Compound D foms blue coloured solution of E by
A, thus A must be a sulphide.
ton treatment of potassium ferricyanide.This indicates
that compound D contains Fe2+ ion which is also the (iii) Zns sulphide is white thus it indicates that A is ZnS
constituent ion of the compound A. Further it is given
that A, is a black mineral of Fe2+ ion, so it has to be ZnS +H2SO4(dil) ZnSO4 +H2S
ferrous sulphide (FeS) which is confirmed by following (A) (C) (B)
reaction: 3H2S +K2Cr2O7 K2SO4 + Cr2(SO4)3 + 7H2O + 3S
(B) (green) (D)
(i) 4FeS + 7 O2 → 2Fe2O3 + 4SO2
2H2S(B)
(A) (B) S + O2 SO2 2H2S + 3S
(D) (E) (Colourless liq) (D)
(ii) FeS + H2S O 4 → FeSO 4 + H2S + S

CuSO4(white)
(A) (D) (C)
(iii) a) SO2 + H2 O → H2SO3

CuSO4. 5H2O (blue)
2NaOH
b) 2H2 S + H2 SO3 → 3S + 3H2O ZnSO4 + 2NaOH Zn(OH)2 Na2ZnO2 + 2H2O
(C) (Soluble)
(C) Turbidity
*** Before testing II group, iodide ions are separated. acid should be CuS; hence (F) must be CuS and thus (B)
Why? is H2S.
[Hint: Because I- ions react with air to form I2 which (iv) According to first point compound (E) contains
reacts with H2S and give white or light yellow ppt. of SO24− hence (E) must be CuSO4.
sulphur i.e., why I- are removed by boiling original
(v) Gas (B) (identified as H2S) is obtained by the
solution with NaNO2.
decomposition of black coloured compound (A) with
4HI + O2 → 2H2O + 2I2 ; I2 + H2S → 2HI + S ] dil. H2SO4. Hence (A) must be sulphide of Cu, Pb, Hg,
and Fe. Co, Ni, etc.
Example 4: A black coloured compound (A) on Thus the various compounds from (A) to (H) and their
reaction with dilute sulphuric acid gives a gas (B) which reactions can be written as below.
on passing in a solution of an acid (C) gives a white
turbidity (D). Gas (B) when passed in acidified solution FeS + H2SO 4 → FeSO 4 + H2S ↑
of a compound (E) gives a ppt. (F) soluble in dilute Ferrous sulphide (A) Hydrogen sulphide (B)
nitric acid. After boiling this solution when an excess

of ammonium hydroxide is added, a blue coloured H2S + HNO3 → 2H2O + 2NO2 + S ↓
Hydrogen sulphide(B) Nitric acid(C) Sulphur (turbidity, D)
compound (G) is formed. To this solution on addition
of acetic acid and aqueous potassium ferrocyanide
H2S + HNO3 → 2H2O + 2NO2 + S↓
a chocolate ppt.sulphide(B)
Hydrogen (H) is obtained. On addition of an
Nitric acid(C) Sulphur (turbidity, D)
aqueous solution of barium chloride to an aqueous
solution (E), a white ppt. insoluble in HNO3 is obtained. in presence
Identify from (A) to (H). CuSO 4 + H2S 
of dil.HCl
→ CuS ↓ + H2SO 4
Copper sulphide(E) (B) Copper sulphide(F)
Sol: Summary we can draw from the given Data:

3CuS + 8HNO3 → 3Cu(NO3 )2 + 2NO+ 3S + 4H2 O
Dil.H2SO4 Acid (F)
Black compound Gas White turbidity
(A) (B) (D) Cu(NO3 )2 + H2SO 4 → CuSO 4 + 2HNO3
(E) + Acid CuS O 4 + 4NH4 OH → [Cu(NH3 )4 ]SO 4 + 4H2O

Cupric ammonium sulphate
(blue compound (G))
Dil
Solution Precipitate(Soluble in dil. HNO3)
HNO3
(F) [Cu(NH3 )4 ]SO 4 + 4CH3COOH → CuSO 4 + 4CH3COONH4
i) Boil (G)
ii) NH4OH
2CuS O 4 + K 4 [Fe(CN)6 ] → Cu2 [Fe(C)6 ] ↓ + 2K 2SO 4
Ptassium ferrocyanide Cupric ferrocyanide
CH3COOH (Chocolate precipitate, H)
Blue compound Chocolate ppt.
Aq.K4[Fe(CN6]
(G) (H) CuSO 4 + BaCl2 → BaSO 4 ↓ +CuCl2
BaCl2 (E) Barium sulphate
E(aq. solution) White precipitate(insoluble in HNO3) (insoluble in water)
(i) Aqueous solution of compound E with BaCl2 to give Thus the compounds (A) to (H) are
white ppt. which is insoluble in nitric acid indicates that
A = Ferrous sulphide, FeS,
the salt (E) contains SO24− ions.
B = Hydrogen sulphide, H2S,
(ii) Compound (G) with potassium ferricyanide in
presence of acidic acid to give chocolate ppt. (H) this C = Nitric acid, HNO3
indicates that (G) must contain Cu2+ and hence (H) has D = sulphur, S,
to be cupric ferricyanide, Cu2 [Fe (CN) 6].
E = Copper sulphate, CuSO4,
(iii) As compound (G) is derived from (F), compound F= Copper sulphide, CuS,
(F) also contains Cu2+. Further since (F) is derived from
the reaction of the gas (B) and compound (E), (E) must G = Cupric ammonium sulphate, [Cu(NH3 )4 ]SO 4
contain Cu2+ ion. Ppt. of Cu2+ ion soluble in dilute nitric H = Cupric ferricyanide, Cu2 [Fe(CN)6 ]
*** An original solution is prepared in conc. HCl. Example 6: A substance X dissolves in hot conc. HCl
When diluted a while ppt. is formed. What does it to give solution which when treated with caustic soda
indicate? solution gives a white ppt. which however dissolves
in excess of caustic soda solution giving a strongly
[Hint: Formation of White ppt indicates the
solution. On heating X with sulphur, a brown powder
Presence of Sb+3 or Bi+3. Their chlorides hydrolyse
Y is formed which dissolved on warming with yellow
to oxychlorides in presence of excess of water.
ammonium sulphide solution. The solution gives a grey
BiCl3 + H2O → BiOCl + 2HCl ; ppt. with HCl. When X is heated in air, a white powder
Z is obtained which can be dissolved in conc. H2SO4.
SbCl3 + H2O → SbOCl + 2HCl ]
When Z is fused with NaOH, extracted with hot water,
Example 5: (i) The yellow coloured ppt. of compound then treated with mineral acid, white gelatinous ppt.
(A) is formed on passing H2S through a neutral solution is obtained. Identify X, Y, Z and give the reactions
of salt (B). involved.
(ii) (A) is soluble in hot dilute HNO3 but insoluble in
yellow ammonium sulphide. Sol:
(iii) The solution of (B) on treatment with small quantity conc.HCl NaOH
X → Solution  NaOH
→ White ppt.  → Solution
of NH3 gives a white ppt. which become soluble in (Strongly
excess of its forming a compound (C). reducing)
(iv) The solution of (B) gives white ppt. with small

concentration of KCN which becomes soluble in excess
S (NH ) S HCl
of this reagent forming a compound (D). X  4 2
→ Brown powder → Solution 
→ Grey ppt.
Y
(v) The solution of (D) on treatment with H2S gives (A).
air i)NaOH HCl
X  → White powder  → Solution 
→ Gelatinous ↓
(vi) The solution of (B) in dil. HCl on treatment with a heat ii)hot water
Z(soluble only white

solution of BaCl2 gives a white ppt. of compound (E)
in conc .H2SO 4 )
which is insoluble in conc. HNO3.
Identify (A) to (E) and give chemical equations for the
reactions at steps (a) to (c) to (f) (i) Solution of X (with HCl) reacts with NaOH and forms
white ppt.This ppt dissolves in excess of NaOH to
Sol: Yellow ppt. of CdS is (A) give solution which has strongly reducing nature. This
reducing properties of this solution points out that the
(i) CdSO 4 + H2S → CdS + H2SO 4
(a)
solution might be containing sodium stannite and here
(B) (A) X must be tin.
(ii) CdS + 2HNO3 → Cd(NO3 )2 + H2S

(b) (ii) The nature of X as tin is confirmed by its reaction with
S forming SnS2 which dissolves in yellow ammonium
soluble
sulphide but regenerates in presence of HCl.
CdS → Insoluble in yellow ammonium sulphide. Thus the various reactions and nature of X, Y, and Z can
be written as below.
CdSO 4 + 2NH4 OH → Cd(OH)2 + (NH4 )2 SO 4
(i) Sn+ 2HCl → SnCl2 + H2
(iii)
(c) Cd(OH)2 + 4NH4 OH →[Cd(NH3 )4 ](OH)2 + 4H2O (X)
(C) SnCl2 + 2NaOH → Sn(OH)2 + 2NaCl
(iv)
(d) CdS O2 + 2KCN → Cd(CN)2 + K 2 SO 4 Sn(OH)2 + 2NaOH → Na2SnO2 + 2H2O
white Sodium stannite
(Strongly reducing)
Cd(CN)2 + 2KCN → K 2 [Cd(CN)4 ]

(ii) Sn + 2S → SnS2
(D)soluble
SnS2 + (NH4 )2 S →(NH4 )2 SnS3
(v) K 2 [Cd(CN)4 ] + H2S → CdS + 2KCN + 2HCN
(e)
(vi)
(f) CdSO 4 + BaCl2 → BaSO 4 + CdCl2 (NH4 )2 SnS3 + 2HCl → SnS2 + 2NH4 Cl + H2S
(E)
(iii) Sn+ O2 → SnO2 (Soluble only in conc. H2SO4) (Remember: NO3− ions are not attacked by dil. Acids.).
(Z)
Consequently, A must be compound of NO3− which can
SnO2 + 2NaOH → Na2SnO3 + H2O give NO3− (B) on heating.
Na2SnO3 + 2HCl → H2SnO3 ↓ +2NaCl Thus compound A is NaNO3.

Stannic acid Reactions are as follows:
Example 7: A colourless solid A on heating gives (i) 2NaNO3 → 2NaNO2 + N2 ↑

(A) (B) (C)
a white solid B and a colourless gas, C; B gives off
(ii)
(ii)2NaNO2 + H2SO 4 (dil.) → NaSO 4 + 2HNO2
reddish brown fumes on treatment with dilute acids. (A)
On heating with NH4Cl, B gives a colourless gas D and
3HNO2 → HNO3 + H2O + 2NO
a residue E. The compound A also gives a colourless
gas F on heating with ammonium sulphide and white
residue G. Both E and G impart bright yellow colour 3NO + O2 → 2NO2 ↑
Re ddish brown fumes
to Bunsen flames. The gas C forms white powder with
strongly heated magnesium metal. The white powder (iv) 2NaNO3 + (NH4 )2 SO 4 → Na2SO 4 + 2NH3 ↑+ 2HNO3
forms magnesium hydroxide with water. The gas D, on (A) (G) (F)
the other hand, is absorbed by heated calcium which
gives off ammonia on hydrolysis. Identify the substance heat
(iii) NaNO2 + NH4 Cl  → NaCl + N2 ↑+ 2H2O
A to G and gives reactions for the changes involved. (A) (E) (D)
Sol: It is advisable to summarize the given facts in the (iv) 2NaNO2 + (NH4 )2 SO 4 → Na2SO 4 + 2NH3 ↑+ 2HNO3
form of a chart. (A) (G) (F)
(NH4 )2 SO 4
A → G + F
Heat Colourless residue Colourless gas (v) 2Mg + O2 → 2MgO
(C) White powder
Heat
A  → B + C
Colourless solid Colourless solid Colourless gas
MgO + H2O → 2Mg(OH)2
NH Cl
4 →
B  D + E
Heat Colourless residue Residue (vi) 3Ca + N2 → Ca3 N2
Dil. HCl (D)
B 
→ Reddish brown fumes
Ca3 N2 + 6H2O → 2Ca(OH)2 + 2NH3 ↑
2 → Mg(OH) H O
C + Mg → White powder  2
Colourless residue
Thus substance (A) to (G) can be represented as
H2O
D + Ca (Heated)  → NH3 (A) NaNO3 (B) NaNO2 (C) O2
Colourless residue
(D) N2 (E) NaCl (F) NH3 (G) Na2SO4

The above reactions lead to the following conclusions.
(A) And (D) on reaction with calcium forms a compound Note: *** Subquestions placed after the answers
which on hydrolysis gives ammonia, this indicates that
D must be nitrogen.
Compound (B), Residues E and G burns with yellow
flame this indicates that these are sodium salts. Hence
compound B (which give E) and A (which give G) must
be sodium salts.
(C) The colourless solid B with dilute acid gives reddish
brown fumes, the reddish brown fumes are probably
of NO2.
Hence compound B must be nitrite
JEE Main/Boards
Exercise 1 Q.7 Explain, while performing qualitative analysis of

basic radicals of third group, why ammonium chloride is
added in excess before adding ammonium hydroxide?
Q.1 Sometimes, a white ppt. is obtained even in the
absence of members of Ist group on the addition of
HCl. Explain it. Q.8 What happens when
(i) Copper sulphate is treated with excess of NH4OH
Q.2 Give examples and explain with equations:
(ii) Bismuth chloride is treated with sodium stannite in
(i) Two colourless solution give a black ppt. on mixing. presence of NaOH
(ii) Two colourless solution give a red ppt. on mixing, (iii) Stannous chloride is treated with mercuric chloride
soluble in excess of one of them.
(iv) Excess of water is added to concentrated solution of
(iii) Two colourless solutions give a white ppt. on mixing, antimony chloride
soluble in ammonium hydroxide.
(iv) Two colourless solution give a yellow ppt. on mixing. Q.9 (i) What is the function of concentrated HNO3 in
third group?
Q.3 What is yellow ammonium sulphide? Why is yellow (ii) Will you add HNO3 in third group even if iron is
ammonium sulphide and not ordinary ammonium given in ferric state in the mixture?
sulphide used for the separation of II A and II B sub-
(iii) Can you use NaCl and NaOH instead of NH4Cl and
groups?
NH4OH in third group?
Q.4 A certain inorganic compound (X) shows the

Q.10 Identify compounds A to G from the following
following reactions:
reactions
(i) On passing H2S through an acidified solution of (X) a heat KI
A (white crystals)  → B + C ; C  → I2 A
brown ppt. is obtained. solidsolution
gas
(ii) The ppt. obtained at step (i) dissolve in excess of HNO NH

NaOH
3 → Solution D  3→
yellow ammonium sulphide. B  → E ↓ 
brown
(iii) On adding an aqueous solution of NaOH to a SolutionF 
H CO OH
→ Black precipitate
solution of (X), first a white ppt. is obtained which
dissolves in excess of NaOH. Q.11 Complete the following
(iv) The aqueous solution of (X) reduce ferric chloride.
Acid
(i) PbS+ Acid → Gas → Yellow ppt.
Identify the cation of (X) and give chemical equations (A) C (B) (D)
for reactions at steps (i), (iii) and (iv) NH4 OH
(ii) A + H2 S  → White ppt.+ 2HCl
(B)
Q.5 A mixture of the three gases A, B and C is passes NaOH
first into an acidified dichromate solution when A is A + NaOH 
(C)
→ ppt.  → solution
(D)
absorbed turning the solution green. The remainder
of the gas is passed through an excess of lime water heat in air
(iii) Pbs  B
→ A + PbS  → Pb + SO2
which turns milky, resulting in the absorption of B. The
residual gas C is absorbed by an alkaline pyrogallol
solution. However, the original gaseous mixture does Q.12 Explain the following:
not turn lead acetate paper black. Identify A, B and C. (i) Lead (Pb2+) is placed in the first as well as second
group of qualitative analysis.
Q.6 You are given unlabelled four packets of white
(ii) The colour of mercurous chloride, Hg2Cl2 , change
substance of zinc, namely ZnO, Zn(OH)2, ZnCO3 and
from white to black when treated with ammonia.
ZnS. How will you proceed to identify each of them?
(iii) During the qualitative analysis of a mixture Q.16 A certain metal (A) is boiled in dilute nitric acid to
containing Cu2+ and Zn2+ ions, H2S gas is passes give a salt (B) and an oxide of nitrogen (C). An aqueous
through an acidified solution containing these ions in solution of (B) with brine gives a ppt. (D) which is
order to test Cu2+ alone. Explain briefly. solution in ammonium hydroxide. On adding aqueous
solution of (B) to hypo solution, a white ppt. (E) is
Q.13 Identify the unknown species and complete the obtained. (E) on standing turns to a black compound
following: (F). Identify (A) to (F).
(i) (A)+BaCl2 → White ppt.

Q.17 A yellow solid (A) is unaffected by acids and bases.
(ii) NaOH+(B) → NH3 gas It is not soluble in water. It dissolves slowly in hot conc.
HNO3 and a brown gas (B) is released. The solid (A)
(iii) (C)+MnO2+H2SO4 → Violet vapours dissolves only in a boiling solution of sodium sulphite
giving a clear solution (C). Acidification (C) causes a
(iv) (D)+K2Cr2O7+H2SO4 → Green coloured solution colourless gas (D) to be liberated, accompanied by an
appearance of a milky ppt. (E) in the solution. Identify
(v) (E) Heat
 → Yellow compound (A) to (E).
Colourless
solid
Q.18 State, whether the following statements are true
or False:
Q.14 Fill in the blanks
(a) AgCl dissolve in NH4OH.
(a) Lime water is used for the test of…………
(b) Sb2S3 is yellow in colour.
(b) Acetates are………… in water.
(c) Copper suplhate forms a violet colour with potassium
(c) Nitrates when treated with conc. H2SO4 evolve………….
ferrocyanide solution.
gas.
(d) Both phosphate and arsenic ions give yellow
(d) Chromyl chloride test is performed for……….
ppt. when heated with nitric acid and ammonium
(e) Chlorides of …………… are insoluble in dilute HCl. molybdate.
(f) H2S is used as a group reagent in……… group in………. (e) Addition of ammonium chloride to a sodium
medium while in……………. group in……………medium. containing ferric and magnesium ions is essential for
(g) HgS is……………… in dilute HNO3 selective precipitation of ferric hydroxide by aqueous
ammonia.
(h) Yellow ammonium sulphide dissolves sulphides
of……………. (f) Ammonium sulphate can be used in place of
ammonium chloride in third group.
(i) Group reagent for third group radicals is…………
(g) Iodine is liberated when an iodine in heated with
( j) If metal ions of group III are ppt. by NH4Cl medium
conc. H2SO4.
and NH4OH without prior oxidation by concentrated
HNO3 …………….is not completely ppt.. (h) It is not necessary to use HNO3 in the third group if
ferric compound is given in a mixture.
(k) colour of zinc sulphide is …..
(l) In V group, K2CrO4 is used for the test of…………. (i) In the test of acetate radical, neutral ferric chloride
is used.
(m) ……………… ppt. is formed when Na2HPO4 is added
to magnesium salt in presence of NH4OH. ( j) Nessler’s reagent is the alkaline solution of K2HgI4.
(n) Ammonium thiocyanate is used in the detection (k) The solubility product of cadmium sulphide is
of………….. highest amongst the sulphides of second group.
(l) Cobalt can be tested with dimethyl glyoxime.
Q.15 A compound on heating with an excess of caustic
(m) Cobalt salt with KNO2 and acetic acid gives yellow
soda solution liberates a gas (B), which gives white
ppt..
fumes on exposure to HCl. Heating is continued to
expel the gas completely. The resultant alkaline solution (n) The carbonates of barium, strontium and calcium
again liberates the same gas (B), when heated with zinc are soluble in acid.
powder. However, the compound (A), when heated
alone, does not give nitrogen. Identify (A) and (B).
Q.19 Explain with proper reasoning. Exercise 2

(a) The aqueous solution of ferric chloride can not be
stored. It is always acidified with hydrochloric acid. Single Correct Choice Type
(b) The aqueous solution of FeCl3, possesses yellow Q.1 Which of the following gives a suffocating gas
colour. The colour becomes green on passing H2S gas. when treated with dilute HCl?
(c) The aqueous solution of K2Cr2O7, is orange. On (A) Carbonate (B) Sulphite
adding an alkali, it turns yellow.
(C) Sulphate (D) Borate
(d) In the test of oxalate, the evolved gas burns with
blue flame inly initially.
Q.2 The acidic solution of a salt produces blue colour
(e) Why yellow ammonium sulphide is used in group (II) with KI starch solution. The salt may be
sulphides separation?
(A) Sulphite (B) Bromide
(f) Why zinc sulphide is not ppt. when H2S is passed
(C) Nitrite (D) Chloride
through ZnCl2 solution.
(g) CaSO4 is insoluble but it is not ppt. when excess of Q.3 Sulphite on treatment with dil, H2SO4 liberates a
(NH4)2SO4 is added to CaCl2. gas which
(h) Why (NH4Cl+NH4OH) and not [(NH4)2SO4+NH4OH] (A) Turns lead acetate paper black
is used in group (III) analysis?
(B) Burns with blue flame
(i) Why is it necessary to added few drops of conc.
HNO3 to the filtrate of group (II) before the use of (C) Smells like vinegar
NH4Cl+NH4OH. (D) Turns acidified K2Cr2O7 paper green
( j) Why NaOH cannot be used to separate Al(OH)3 and
Zn(OH)2? Q.4 A gas is evolved which burns with blue flame when
the mixture is heated with conc. H2SO4. The mixture
Q.20 A certain salt (X) gives the following tests: contains.
(i) Its aqueous solution is alkaline to litmus. (A) Carbonate (B) Oxalate
(ii) On strongly heating it swells to give glassy material. (C) Nitrate (D) Nitrite
(iii) When concentrated H2SO4 is added to a hot

concentrated solution. Q.5 Mercurous chloride turns black on treatment with
ammonium hydroxide. This is due to the formation of
Identify the salt (X) and give the equations for the
reactions. (A) Hg(NH2)Cl (B) Hg2Cl2.NH4OH
(C) Hg and HgNH2Cl (D) HgCl2.NH4OH
Q.21 An aqueous solution of a gas (X) shows the
following reactions. Q.6 Bromine vapours turn starch iodide paper
(i) It turns red litmus blue. (A) Violet (B) Blue
(ii) When added in excess to copper sulphate solution (C) Yellow (D) Red
deep blue colour is obtained.
(iii) On addition to a ferric chloride solution a brown ppt. Q.7 A mixture when heated with dil. H2SO4 does not
soluble in dilute nitric acid is obtained. Identify (X) and evolve brown vapours but when heated with conc.
give equations for the reactions at steps (ii) and (iii). H2SO4, brown vapours are obtained. The vapours when
brought in contact with silver nitrate solution do not
give any ppt.. The mixture contains.
(A) NO2− (B) NO3−
(C) Cr (D) Br −
Q.8 Ammonium dichromate is used in some fireworks. Q.16 When dimethyl glyoxime solution is added to
The green coloured powder blown in air is due to an aqueous solution of nickel (II) chloride followed by
ammonium hydroxide:
(A) CrO3 (B) Cr2O3 (C) Cr (D) CrO(O2)
(A) No ppt. is obtained
Q.9 A mixture, on heating with conc. H2SO4 and MnO2, (B) A blue coloured ppt. is obtained
liberates brown vapours of
(C) A red coloured ppt. is obtained
(A) Br2 (B) NO2 (C) HBr (D) I2
(D) A black coloured ppt. is obtained
Q.10 A white solid is first heated with dil. H2SO4 and

Q.17 An organic salt when heated evolves a coloured
then with conc. H2SO4. No action was observed in
gas which bleaches moist litmus paper. The evolved gas
wither case. The solid salt contains.
is
(A) Sulphide (B) Sulphite
(A) NO2 (B) Cl2 (C) Br2 (D) I2
(C) Thiosulphate (D) Sulphate
Q.18 Which of the following metal oxides is white in
Q.11 A light yellow ppt. is formed in the second group colour but becomes yellow in heating?
of the qualitative analysis on passing H2S even when
(A) AgO (B) Ag2O (C) FeO (D) ZnO
no radical of second group is present. This is due to
presence of …………… in the mixture:
Q.19 A white ppt. obtained in the analysis of a mixture
(A) Phosphate (B) Acetate
becomes black on treatment with NH4OH. It may be.
(C) Oxalate (D) Nitrate
(A) PbCl2 (B) AgCl (C) HgCl2 (D) Hg2Cl2
Q.12 On adding water to BiCl3 solution in HCl, the

Q.20 Which one among the following soluble in excess
compound formed is
of NaOH?
(A) Bi2O3 (B) Bi(OH)3
(A) Fe(OH)3 (B) Al(OH)3
(C) BiOCl (D) BiOCl2
(C) Cr(OH)3 (D) Mn(OH)2
Q.13 The sulphide which is insoluble in 30% HNO3 is

Q.21 Which compound does not dissolve in hot dil.
(A) HgS (B) CuS (C) PbS (D) CdS HNO3
(A) HgS (B) PbS (C) CuS (D) CdS
Q.14 NiS is separated from ZnS by treating with
(A) NaOH Q.22 An aqueous solution of FeSO4Al2(AO4)3 and
chrome alum is heated with excess of Na2O2 and
(B) Conc.HCl
filtered. The materials obtained are
(C) Yellow ammonium sulphide
(A) A colourless filtrate and a green residue
(D) Aqua-regia
(B) A yellow filtrate and green residue
Q15.Soda extract is prepared by (C) A yellow filtrate and a brown residue
(A) Fusing soda and mixture and then extracting with (D) A green filtrate and a brown residue
water
Q.23 All ammonium salts liberate ammonia when
(B) Dissolving NaHCO3 and misture in dil. HCl
(A) Heated
(C) Boiling Na2CO3 and mixture in dil. HCl
(B) Heated with caustic soda
(D) Boiling Na2CO3 and mixture in distilled water
(C) Heated with H2SO4
(D) Heated with HaNO2
Q.24 One of the following compounds gives a white Q.31 Concentrated aqueous sodium hydroxide can
ppt. with aqueous AgNO3 and a green flame test. separate a mixture of
(A) NaCl (B) KCl (C) BaCl2 (D) CaCl2 (A) Al3+ and Sn2+ (B) Al3+ and Fe3+
(C) Al3+ and Zn2+ (D) Zn2+ and Pb2+
Q.25 Which one of the following pairs of ions cannot
be separated by H2S in dilute hydrochloric acid?
Q.32 Potassium ferricyanide [potassium hexacyano
(A) Bi3+, Sn4+ (B) Al3+, Hg2+ ferrate (III)] has
(C) Zn2+Cu2+ (D) Ni2+, Cu2+ (A) Fe(II) (B) Fe(III) (C) Cu(II) (D) Cd(II)
Q.26 When H2S is passes through an ammonium salt Q.33 Which of the following sulphate is insoluble in
solution X, a white ppt is obtained. The X can be water?
(A) Cobalt salt (B) Nickel salt (A) CuSO4 (B) CdSO4 (C) PbSO4 (D) Bi2(SO4)3
(C) Manganese salt (D) Zinc salt
Q.34 Calcium burns in nitrogen to produce a white
powder which dissolve in sufficient water to produce
Q.27 The best explanation for the solubility of MnS in
a gas (A) and an alkaline solution. The solution on
dil. HCl in salt
exposure to air produces a thin solid layer of (B) on the
(A) Solubility product of MnCl2 is less than that of MnS surface. Identify the compounds A and B.
(B) Concentration of Mn2+ is lowered by the formation (A) C2H2, CaCO3 (B) NH3, CaCO3
of complex ions with chloride ions.
(C) NH3, Ca(OH)2 (D) CH4, CaCO3
(C) Concentration of sulphide ions is lowered by
oxidation to free sulphur.
Q.35 A gas ‘X’ is passed through water to form a
(D) Concentration of sulphide ions is lowered by saturated solution. The aqueous solution on treatment
formation of the weak acid H2S with silver nitrate gives a white ppt.. The saturated
aqueous solution also dissolve magnesium ribbon with
Q.28 A white solid is first heated with dilute H2SO 4 the evolution of a colourless gas ‘Y’. Identify ‘X’ and ‘Y’.
and when with concentrated. No action is observed in (A) X=CO2, Y=Cl2 (B) X=Cl2, Y=CO2
either case. The solid contains.
(C) X=Cl2, Y=H2 (D) X2=H2, Y=Cl2
(A) Sulphide (B) Sulphide
(C) Sulphate (D) Thiosulphate
Previous Years' Questions
Q.29 The salt used for performing ‘bead test’ in
Q.1 A gas ‘X’ is passed through water to form a
qualitative inorganic analysis is
saturated solution. The aqueous solution on treatment
(A) K2SO4.Al2(SO4)3.24H2O with silver nitrate gives a white ppt.. The saturated
aqueous solution also dissolves magnesium ribbon
(B) FeSO4.(NH4)2SO4.6H2O
with evolution of a colourless gas ‘Y’. Identify ‘X’ and ‘Y’.
(C) Na(NH4)HPO4.4H2O (2002)
(D) CaSO4.2H2O
Q.2 [X]+H2SO4 → [Y] a colourless gas with irritating
Q.30 The only cation present in a slightly acidic solution smell [Y]+K2Cr2O7+H2SO4 → green solution [X] and
are Fe3+, Zn2+ and Cu2+. The reagent which when added [Y] are (2003)
in excess to this solution would identify and separate (A) SO32− ,SO2 (B) C l− , HCl
Fe3+ in one step is
(C) S2-, H2S (D) CO32− ,CO2
(A) 2MHCl (B) 6 M NH3
(C) 6 M NaOH (D) H2S gas
Q.3 A sodium salt of an unknown anion when treated with Statement-II: Solubility product of CdS is more than
MgCl2 gives white ppt. only on boiling. The anion is (2004) that of NiS. (1989)
(A) SO24− (B) HCO3− (C) CO32− (D) NO3−
Q.8 Statement-I: Sulphate is estimated as BaSO4, not
as MgSO4.
Q.4 (NH4)2Cr2O7 on heating gives a gas is also given by
(2004) Statement-II: Ionic radius of Mg2+ is smaller than that
of Ba2+ (1998)
(A) Heating NH4NO2 (B) Heating NH4NO3
(C) Mg3N2+H2O (D) Na(comp.)+ H2O2 Q.9 An aqueous solution FeSO4. Al2(SO4)3 and chrome
alum is heated with excess of Na2O2 and filtered. The
Q.5 A metal nitrate reacts with KI to give a black ppt. materials obtaining are (1996)
which on addition of excess of KI convert into orange (A) A colourless filtrate and a green residue
colour solution. The cation of metal nitrate (2005) (B) A yellow filtrate and a green residue
(A) Hg 2+
(B) Bi3+
(C) Sm 2+
(D) Pb 2+
(C) A yellow filtrate and a brown residue
(D) A green filtrate and brown residue
Q.6 A solution when diluted with H2O and boiled, it
gives a white ppt. On addition of excess NH4Cl/NH4OH, Q.10 In nitroprusside ion the iron and NO exist as Fe (II)
the volume of ppt. decreases leaving behind a white and NO+ rather than Fe(III) and NO. These forms can be
gelatinous ppt. Identify the ppt which dissolves in differentiated by (1998)
NH4OH/NH4Cl. (2002)
(A) Estimating the concentration of iron
(A) Zn(OH)2 (B) Al(OH)3
(B) Measuring the concentration of CN
(C) Mg(OH)2 (D) Ca(OH)2 (C) Measuring the solid state magnetic moment
(A) If both assertion and reason are true and reason is (D) Thermally decomposing the compound
the correct explanation of assertion, then mark (a)
Q.11 An aqueous solution if a substance gives a white
(B) If both assertion and reason are true but R is not the
ppt. on treatment with dilute hydrochloride acid, which
correct explanation of assertion, then mark (b)
dissolves on heating. When hydrogen sulphide is
(C) If assertion is true but reason is false, then mark (c) passed through the hot acid solution, a black ppt. is
(D) If both assertion and reason are false, then mark (d) obtained. The substance is a (2000)
(A) Hg32+ salt (B) Cr 2+ salt
Q.7 Statement-I: A very dilute acidic solution of Cd2+
(C) Ag+ salt (D) Pb2+ salt
and Ni2+ gives yellow ppt. of CdS on passing H2S.
JEE Advanced/Boards
Exercise 1 (iv) An acidic solution of (X) does not give a ppt. with
H2S. Identify (X) and give chemical equations for
reactions at steps (i) to (iii).
Q.1 An inorganic Lewis acid(X) shows the following
reactions:
Q.2 An aqueous solution of salt (A) gives white ppt.
(i) It fumes in moist air.
(B) with NaCl solution. The filtrate gives black ppt., (C)
(ii) The intensity of fumes increases when a rod dipped when H2S is passed into it. Compound (B) dissolves
in NH4OH is brought near to it. in hot water and the solution gives a yellow ppt., (D)
on treatment with sodium iodide and cooling. The
(iii) An acidic solution of (X) on addition of NH4Cl and
compound (A) does not give any gas with dilute HCl
NH4OH gives a ppt. which dissolves in NaOH solution.
but liberates a reddish-brown gas on heating. Identify
the compounds (A) to (D).
Q.3 A mixture of two salts was treated as follows: (iii) (A) on treatment with potassium cyanide gives a
buff colored ppt. which dissolves in excess of this
(a) The mixture was heated with manganese dioxide
reagent forming a compound (C).
and concentrated H2SO4, when yellowish green gas was
liberated. (iv) The compound (C) is changed into a compound (D)
when its aqueous solution boiled.
(b) The mixture on heating with NaOH solution gave a
gas which turn red litmus blue. (v) The solution of (A) was treated with excess of sodium
bicarbonate and then with bromine water. On cooling
(c) Its solution in water gave blue ppt. with potassium
and shaking for same time, a green colour of compound
ferricyanide and red colouration with NH4CNS.
(E) is formed. No change is observed on heating.
Q.4 An unknown inorganic compound (X) loses its Identify (A) to (E) and give chemical equations for the
water of crystallization on heating and its aqueous reactions at steps (a) to (e).
solution gives the following reactions.
Q.8 A colourless solid (A) on hydrolysis produces a
(i) It gives a white turbidity with dilute hydrochloric acid
heavy white ppt. (B). Solid (A) gives a clear solution
solution.
in conc. HCl; however, when added to large amount
(ii) It decolourises a solution of iodine in potassium of water, it again gives ppt. (B). When H2S is passed
iodide. through a suspensions of (A) or (B), a brown black ppt.
(iii) It gives white ppt. with silver nitrate solution which of (C) is obtained. Compound (A) liberates a gas (D) on
turns black on standing. treating with H2SO4. The gas (D) is water soluble and
gives white ppt. (E) with solution of mecurous salt but
not with mercuric salt. Identify (A) to (E). Also report (A),
Q.5 Identify the compound (X) and give chemical (B), (C) if (C) is orange ppt..
equations for the reactions at steps (i), (ii) and (iii). A
certain compound (X) shows the following reactions.
Q.9 Identify the unknown species and complete the
(i) When KI is added to an aqueous suspension of (X) following
containing acetic acid, iodine is liberated. Heat
(i) (A) + NaOH  → NaCl + NH3 + H2O .
(ii) When CO2 is passed through an aqueous suspension
of (X) the turbidity transforms to a ppt.. (ii) NH3 + CO2 + H2O → (B).
(iii) When a paste of (X) in water is heated with ethyl (iii) (B) + NaCl →(C) + NH4Cl.
alcohol a product of anesthetic use is obtained. Identify Heat
(iv) (C)  → Na2CO3 + H2O + (D) .
(X) and write down chemical equation for reactions at
steps (i), (ii) and (iii).
Q.10 Element A burns in nitrogen to give an ionic
compound B. Compound B reacts with water to give
Q.6 Identify the unknown species and complete the C and D. A solution of C becomes ‘milky’ on bubbling
following carbon dioxide. Identify A, B, C and D.
(i) (A) + dil.H2SO4 + K2Cr2O7 → (B) green coloured
Q.11 An inorganic compound (A) in its aqueous
(A) + dil.H2SO4 + (C) → (B) MnSO4
solution produced a white ppt. With NaOH, which gets
H O
2 → (D)
(A) + O2  dissolved in excess of NaOH. The aqueous solution of
(A) also produced white ppt. With NH4OH which also
(D) + BaCl2 → White ppt.
dissolved in excess of NH4OH. Also its aqueous solution
Heat
(ii) (A)aq. + Zn  → (B)gas produced light yellow ppt. with AgNO3 solution, soluble
Heat in dil. HNO3, identify (A).
(A)aq. + (C)  → PH3
Heat
(A)aq. + NH4 Cl  → (D)gas
Q.12 (i) An aqueous solution of a compound (A) is acidic
towards litmus and (A) is sublimed at about 300° C .
Q.7 (i) A black coloured compound (B) is formed on
(ii) (A) on treatment with an excess of NH4SNC gives a red
passing hydrogen sulphide through the solution of a
coloured compound (B) and on treatment with a solution
compound (A) in NH4OH.
of K4[Fe(CN)6] gives a blue coloured compound (C).
(ii) (B) on treatment with hydrochloric acid and KCIO3 (iii) (A) on heating with excess of K2Cr2O7 in presence of
gives (A). concentrated H2SO4 evolves deep red vapours of (D).
(iv) On passing the vapours of (D) into a solution of (iv) On adding a solution of (A) into the solution of
NaOH and then adding the solutions of acetic acid and cupric chloride, a white ppt. is first formed which
lead acetate, a yellow ppt. of compound (E) is obtained. dissolves on adding excess of (A) forming a compound
(E). Identify (A) to (E) and give chemical equations for
Identify (A) to (E) and give chemical equations for the
the reactions at steps (i) to (iv).
reactions at steps (ii) to (iv).
Q.17 A metal chloride (X) shows the following reactions:

Q.13 An aqueous solution of gas (X) gives the following
reactions. (i) When H2S is passed in an acidified aqueous solution
of (X), a black ppt. is obtained.
(i) It decolourizes on acidified K2Cr2O7 solution.
(ii) The ppt. obtained at step (i) is not soluble in yellow
(ii) On boiling it with H2O2, cooling it and then adding
ammonium sulphide.
an aqueous solution of BaCl2 a ppt. insoluble in dilute
hydrochloric acid is obtained. (iii) When a solution of stannous chloride is added to an
aqueous solution of (X) a white ppt. is obtained which
(iii) On passing H2S in the solution, a white turbidity is
turns grey on addition of more of stannous chloride.
obtained.
(iv) When an aqueous solution of KI is added to an
Identify (X) and gives equations for the reactions at
aqueous solution of (X) a red ppt. is obtained which
steps (i),(ii) and (iii).
dissolves on addition of excess of KI.
Q.14 A colourless solid A, when placed into water, Identify (X) and write down the equations for the
produces a heavy white ppt. B. Solid A gives a clear reactions at steps (i), (iii) and (iv).
solution in conc. HCl; however when added to large
amount of water, it again gives ppt. of B which dissolves Q.18 A well known orange crystalline compound (A)
in dilute HCl. When H2S is passed through the suspension when burnt imparts violet colour of fame. (A) on treating
of A or B, a brown black ppt. (C) is obtained. Compound with (B) and conc. H2SO4 gives red gas (C) which gives
A liberates a gas D with conc. H2SO4. The gas D is water red yellow solution (D) with alkaline H2SO4 gives red
soluble and gives white ppt. E with solution of mercurous gas (C) which gives red yellow solution (D) with alkaline
salts but not with mercuric salts. Identify A to E. water. (D) on treating with acetic acid and lead acetate
gives yellow ppt. (E). (B) sublimes on heating. Also on
Q.15 (i) A blue coloured compound (A) on heating heating (B) NaOH, gas (F) is formed which gives white
gives two products, (B) and (C). fumes with HCl. What are (A) to (F)?
(ii) A metal (D) is deposited on passing hydrogen

Q.19 Complete and balance the following chemical
through heated (B).
equations:
(iii) The solution of (B) in HCl on treatment with
(i) Au + HCl + HNO3 → ....... + ....... + H2O
K4Fe(CN)6 gives a chocolate brown coloured ppt. of
compound (E). (ii) C + HNO3 (conc.) → CO2 + ....... + H2O
(iv) (C) turns lime water milky which disappears on (iii) Sn + KOH(hot) + H2O → ....... + .......
continuous passage of (C) forming a compound (F).
(iv) Cu(OH)2 + NH4NO3 + NH4 OH(aq) → ....... + H2O
Identify (A) to (F) and give chemical equations for the
reactions at steps (i) to (iv).
Q.20 A gaseous mixture containing (X), (Y) and (Z)
gases, when passed into acidified K2Cr2O7 solution, gas
Q.16 (i) An inorganic compound (A) is formed on
(X) was absorbed and the solution was turned green.
passing a gas (B) through a concentrated liquor
The remainder gas mixture was then pass through
containing sodium sulphide and sodium sulphite.
lime water, which turns milky by absorbing gas (Y). The
(ii) On adding (A) in to a dilute solution of silver nitrate, residual gas when passed through alkaline pyrogallol
a white ppt. appears which quickly changes into black solution, it turned black. Identify gas (X), (Y) and (Z) and
coloured compound (C). explain the reaction involved.
(iii) On adding two or three drops of ferric chloride into
the excess of solution of (A), a violet coloured compound
(D) is formed. This colour disappears quickly.
Exercise 2 Q.7 Assertion: In the analysis of group III-radicals

NaOH can also be used as group reagent.
Single Correct Choice Type
Reason: NaOH can be used only in the presence of
Q.1 Which compound does not dissolve in hot dil. NaCl as ppt. agent for group III.
HNO3 ?
Q.8 Assertion: In charcoal cavity test in intimate mixture
(A) HgS (B) PbS (C) CuS (D) CdS of salt and Na2CO3 is heated on a charcoal block.
Reason: Charcoal cavity test is meant only for coloured
Q.2 An aqueous solution of FeSO4Al2(SO4)3 and chrome
salts
alum is heated with excess of Na2SO3 and filtered. The
materials obtained are
Q.9 Assertion: Match-stick test is meant for all sulphur
(A) A colorless filtrate and a green residue containing radicals.
(B) A yellow filtrate and a green residue Reason: Match-stick test is not given by Na2S.
(C) A yellow filtrate and a brown residue
(D) A green filtrate and a brown residue Q.10 Assertion: CdS and As2S3 both have yellow colour.
Reason: CdS and As2S3 can be separated by yellow
Q.3 Magnesium carbonate does not ppt. with the ammonium sulphide.
carbonates of group V radicals in presence of NH4OH
and NH4Cl because Comprehension Type
(A) MgCO3 is soluble in water. The following observation were made on Na2CrO4 and
(B) MgCO3 is soluble in NH4OH Na2Cr2O7.
(C) MgCO3 is soluble in NH4Cl (A) When CO2 was passed over Na2CrO4, then Na2Cr2O7
was formed.
(D) MgCO3 is soluble in (NH4)2CO3
(B) When Zn is added to acidic solution of Na2Cr2O7, the
colour changes from orange to green, then to blue and
Q.4 The extent of splitting in d-orbitals is more when then back to green.
the chromium in the solution is in
(C) Na2CrO4 when added to a nitrate salt solution gave a
(A) +1 oxidation state (B) +2 oxidation state yellow coloured ppt. which after separation and drying
(C) +3 oxidation state (D) +6 oxidation state followed by flame test gave a green coloured flame.
Assertion Reasoning Type Q.11 What is the function of CO2 in the first observation?
(A) If both assertion and reason are true and reason is (A) Acts as an oxidising agent
the correct explanation of assertion, then mark (A) (B) Acts as a reducing agent
(B) If both assertion and reason are true but reason is (C) Produces chromium and oxygen
not the correct explanation of assertion, then mark (B) (C) Makes the solution acidic
(C) If assertion is true but reason is false, then mark (C)
(D) If both assertion and reason are false, then mark (D) Q.12 The reason for the colour Na2Cr2O7 solution to first
change from orange to green on adding Zn is because
Q.5 Assertion: Ammonium phosphomolybdate is a
yellow coloured ppt. (A) Zn is reducing agent and changes Cr+4 to Cr+3
(B) Zn is a reducing agent and changes Cr+6 to Cr+3
Reason: Yellow colour of compound is due to
ammonium ions. (C) Zn is a reducing agent and it reduces Cr+6 to Cr+2
(D) None of these
Q.6 Assertion: Ring test for nitrates is performed from
the water extract of the salt. Q.13 The second change in colour in the solution that
Reason: All nitrates are generally soluble in water. is from green to blue is due to the conversation of
(A) Cr+3 to Cr+1 (B) Cr+3 to Cr
(C) Cr+3 to Cr+2 (D) Cr+3 to Cr+4
Q.14 The nitrate salt which gives a yellow ppt. with Paragraph 1: p- amino –N, N- dimethylaniline is added
Na2CrO4 and yellow ppt. gives green flame with bunsen to a strongly acidic solution of X. The resulting solution
burner is treated with a few drops of aqueous solution of Y to
yield blue colouration due to the formation of methylene
(A) Pb2+ (B) Ca2+ (C) Mg2+ (D) Ba2+
blue. Treatment of the aqueous solution of Y with the
reagent potassium hexacyanoferrate (II) leads to the
formation of an intense blue ppt.. The ppt. dissolves
Previous Years' Questions on excess addition of the reagent. Similarly, treatment
Q.1 MgSO4 on reaction with NH4OH and Na2HPO4 forms of the solution of Y with the solution of potassium
a white crystalline ppt. What is its formula? (2006) hexacyanoferrate (III) leads to a brown colouration due
to formation of Z.
(A) Mg(NH4)PO4 (B) Mg3(PO4)2
(C) MgCl2 . MgSO4 (D) MgSO4 Q.7 The compound X, is (2009)
(A) NaNO3 (B) NaCl (C) Na2SO4 (D) Na2S
Q.2 A solution of metal ion when treated with KI gives
a red ppt. which dissolves in excess KI in excess KI to
give a colourless solution. Moreover, the solution of Q.8 The compound Y, is (2009)
metal ion on treatment with a solution of cobalt (II) (A) MgCl2 (B) FeCl2 (C) FeCl3 (D) ZnCl2
thiocyanate gives rise to a deep blue crystalline ppt.
The metal ion is (2007)
Q.9 The compound Z, is (2009)
(A) Pb2+ (B) Hg2+ (C) Cu2+ (D) Co2+
(A) Mg2[Fe(CN)6] (B) Fe[Fe(CN)6]
Q.3 Passing H2S gas into a mixture of Mn2+, Ni2+, Cu2+, (C) Fe4[Fe(CN)6]3 (D) K2Zn3[Fe(CN)6]2
and Hg2+ ions in an acidified aqueous solution ppt. −
SCN (excess)
(2011) Q.10 Fe3+  → Blood red (A)
F (excess) −
(A) CuS and HgS (B) MnS and CuS  → Colourless (B)
(C) MnS and NiS (D) NiS and HgS Identify A and B. (a) Write IUPAC name of A and B.
(b) Find out spin only magnetic moment of B. (2005)
Q.4 The reagents, NH4Cl and aqueous NH3 will ppt.
(1991)
Q.11
(A) Ca2+ (B) Al3+ (C) Bi3+ (D) Mg2+
Moist air Zn
B ← MCl4  → A
(E) Zn2+ (W hite fumes M = (T ransition (Purple Colour)
having smell) element colourless)
Q.5 Which of the following statement (s) is (are) correct

Identify the metal M and hence, MCl4. Explain the
with reference to the ferrous and ferric ions? (1998)
difference in colours of MCl4 and A. (2005)
(A) Fe3+ gives brown colour with potassium ferricyanide
(B) Fe2+ gives blue ppt. with potassium ferricyanide Paragraph 2: An aqueous solution of a mixture of two
inorganic salts, when treated with dilute HCl, gave a
(C) Fe gives red colour with potassium ferricyanide
3+
precipitate (P) and a filtrate (Q). The precipitate P was
(D) Fe2+ gives brown colour with ammonium thiocyanate found to dissolve in hot water. The filtrate (Q) remained
unchanged, when treated with H2S in a dilute mineral
Q.6 A solution of colourless salt H on boiling with acid medium. However, it gave a precipitate (R) with
excess NaOH produces a non-flammable gas. The gas H2S in anammoniacal medium. The precipitate R gave
evolution ceases after sometime. Upon addition of Zn a coloured solution (S), when treated with H2O2 in an
dust to the same solution, the gas evolution restarts. aqueous NaOH medium.
The colourless salt (s) H is (are) (2008)
(A) NH4NO3 (B) NH4NO2 Q.12 The precipitate P contains (2013)
(C) NH4Cl (D) (NH4)2SO4 (A) Pb2+ (B) Hg2+ (C) Ag+ (D) Hg2+
Q.13 The coloured solution S contains (2013) Ag

S2O2−3  →
+
X
Ag
 →
+
Y
(2016)
(A) Fe2 ( SO 4 )
Clear solution White precipitate
(B) CuSO 4
3 With time

→ Z
(C) ZnSO 4 (D) Na2CrO 4 Black precipitate
3−
Q.14 The reagent(s) that can selectively precipitate S2− (A)  Ag ( S2O3 )  , Ag2S2O3 , Ag2S
 2
from a mixture of S2− and SO 2−4 in aqueous solution is
5−
(are) (2016) (B)  Ag ( S2O3 )  , Ag2S2O3 , Ag2S
 2
(A) CuCl2 (B) BaCI2
3−
(C)  Ag ( SO3 )  , Ag2S2O3 , Ag
(C) Pb ( OOCCH3 ) (D) Na2 Fe ( CN) NO   2
2  5 
3−
(D)  Ag ( SO3 )  , Ag2S2O 4 , Ag
Q.15 In the following reaction sequence in aqueous  3
solution, the species X, Y and Z, respectively, are
PlancEssential Questions
JEE Main/Boards JEE Advanced/Boards
Exercise 1 Exercise 1
Q.2 Q.3 Q.10 Q.1 Q.4 Q.6
Q.19 (f,i) Q.11 Q.15 Q.18
Exercise 2 Exercise 2
Q.2 Q.7 Q.15 Q.5
Q.24 Q.30
Previous Years Questions
Previous Years' Questions Q.5 Q.10 Q.11
Q.2 Q.6
Answer Key
JEE Main/Boards
Exercise 2
Q.1 B Q.2 C Q.3 D Q.4 B Q.5 C Q.6 B
Q.7 B Q.8 B Q.9 A Q.10 D Q.11 A Q.12 C
Q.13 A Q.14 B Q.15 D Q.16 C Q.17 A Q.18 D
Q.19 D Q.20 B Q.21 A Q.22 C Q.23 B Q.24 C
Q.25 A Q.26 D Q.27 D Q.28 C Q.29 C Q.30 B
Q.31 B Q.32 B Q.33 C Q.34 B Q.35 C

Q.1 X-Cl2, Y-H2 Q.2 A Q.3 B Q.4 A Q.5 B Q.6 A
Q.7 C Q.8 B Q.9 C Q.10 C Q.11 D
JEE Advanced/Boards
Exercise 2
Q.1 A Q.2 C Q.3 C Q.4 D
Assertion Reasoning Type
Q.5 C Q.6 A Q.7 D Q.8 C Q.9 C Q.10 B
Comprehension Type
Q.11 D Q.12 B Q.13 C Q.14 D

Q.1 A Q.2 B Q.3 A Q.4 B, C Q.5 B, C Q.6 A, B
Q.7 D Q.8 C Q.9 B Q.12 A Q.13 D Q.14 A, C

Q.15 A
Solutions
JEE Main/Boards B + Ca(OH)2 → White ppt

∴ B = CO2
Exercise 1 C + Alkaline pyrogallol → Absorbed
Single Correct Choice Type ∴ C = O2

A + B + C + Lead acetate → Does not turn black
Sol 1: It due to the formation of PbCl2.
∴ A = SO2 ; B = CO2 ; C = O2
Sol.2 (i) Lead salt + sulphide → PbS (black)
Sol 6: ZnO, Zn (OH)2, ZnCO3 and ZnS
E.g Pb(CH3COO)2 + Na2S → PbS + 2CH3COONa
∆
(ii) HgCl2 + 2KI → Hg I2 + KCl Zn(OH)2  → H2O + ZnO
red
(Yellow when hot
Hg I2 + KCl → K2HgI4 (soluble)
white when cold)
(iii) AgNO3 + NaCl → AgCl + NaNO3
white ZnCO3 → CO2 + ZnO
AgCl + 2NH4OH → Ag(NH3)2Cl + 2H2O

(iv) Pb(NO3)2 + 2KI → Pb I2 + 2KNO3
yellow Ca(OH)2 → CaCO3
Sol 3: Yellow ammonia sulphide. (turns lime water milky)

YAS = yellow ammonium sulphide (NH4)2 SX ∆
ZnO  → no gas
The group II A and II B elements are differentiated on
∆
the basis of their solubility in YAS. ZnS  → with dil H2SO4 gives H2S
The group 2A elements are insoluble in YAS and 2B
elements soluble in YAS, whereas they are all insoluble Sol 7: To decrease the conc. of (OH-) ion in solution as
in sulphides. if ( NH+4 ) ion, conc. is high. Due to common ion effect,
the conc. of OH– ions is maintained low.
Sol 4: X + H2S + acid gas → Brown ppt.
Sol 8: (i) CuSO4 + 2NH4OH → Cu(OH)2 + (NH4)2SO4
Brown ppt → soluble in YAS
Cu(OH)2 + (NH4)2 SO4 + 2NH4 OH → Cu(NH3)4 SO4 +
excess
→ soluble
X + NaOH → white ppt  2H2O excess
NaOH
X(aq) + FeCl3 → FeCl2 + ……. . (ii) BiCl3 + 2Na2SnO2 + 6NaOH → 2Bi + 3Na2SnO3 +
6NaCl + 3H2O
X is a group 2B salt which gives a brown sulphide ∴ X
is Sn+2 (iii) 2HgCl2 + SnCl2 →Hg2Cl2 + SnCl4
SnCl + NaOH → Sn(OH)2 + 2NaCl HgCl2 + SnCl2 → 2Hg + SnCl4
Sn(OH)2 + 2NaOH → Na2SnO2 (iv) SbCl3 + H2O → SbOCl + 2HCl
(Strongly reducing)
Sol 9: Conc. HNO3 is added for the
Sn+2 + 2FeO3 → Sn4+ + 2FeCl2
(i) Oxidation of metal to its highest oxidation state
(ii) No
Sol 5: A + K2Cl2O7 → Green soluble
(iii) No. NaOH is a strong base
A = SO2/H2S
∴ It has high conc of OH– ions. ∴ So, when H2S gas is passed through acidified solution
contain Cu2+ and Zn2+ only. Cu2+ ions will precipitate out
∆
Sol 10: A(White crystals)  → B + C due to low conc, of S2– ion.
solid gas
KI
C → I2 Sol 13: (a) A + BaCl2 → White ppt
Sol
HNO
B  NaOH
3 → solution D  → A = H2SO4 or some sulphate
(b) NaOH + B → NH3(g)
E ↑ Sol F
brown B = NH+4 salt
HCOOH
(c) C + MnO-4 + H2SO4 → Violet vapours
C = iodide
Black ppt
(d) D + K2Cr2O7 + H2SO4 → Green soluble
∆ 1 D = Some reducing agent
A = AgNO3  → Ag + NO2 + O2
2
∆
Ag 
HNO
3 → D = AgNO (e) E  → Yellow component
3
KI E = ZnO
O2  → I2
AgNO3 
NaOH
→ E ↓ Sol 14: (a) CO32−
low
E = AgO (b) Soluble
NH (c) NO2
AgO 
3 → F = [Ag (NH ) OH]
3 2
(d) Chloride ions
Acid (e) Ist group (Pb2+ Ag+ Hg+)
Sol 11: (i)PbS + Acid → Gas  → Yellow ppt.
B D
(f) II group → Acidic medium
Acid (A) : dil HCl of H2SO4
IV group → Alkaline medium
B = H 2S
(g) Insoluble
C = conc. HNO3
(h) Group IIB
D = S (yellow ppt)
(i) NH4OH
NH OH
(ii) A + H2S 
4 → White ppt. + 2HCl ( j) Fe (iron)
A = ZnCl2+H2S 
4 NH OH
→ ZnS + 2HCl (k) White
(l) Ba2+↑
ZnCl2 + NaOH → Zn(OH)2 
NaOH
→ Na2ZnO2 (m) White
(iii) PbS  ∆ in
→ A + PbS → Pb + SO2 (n) Co2+ + Fe3+ ion
air
A = PbO ∆
Sol 15: A  → B↑+C
NaOH
HCl
Sol 12: (i) PbCl2 is formed after Ist group partly soluble B  → white green ∴ B = NH3
in water and hence Pb2+ ions pass to the first group Zn
C  → B
filtrate, i. e. to the II group and is detected in the test
∆
for IInd group as well. A No N2 ;A= NH4NO2
→ Hg (NH2 ) Cl + Hg
NH OH
(ii) Hg2Cl2 4 Sol 16: A = AgNO3
white Black
Ag + DilHNO3 → AgNO3 + NO
(iii) Ksp (CuS) < Ksp (ZnS)
AgNO3 + Brine → AgCl
Ionisation of H2S is further suppressed in presence of
NH OH
acid (common ion effect). AgCl 
4 → Ag (NH)3Cl
AgNO3 + H2S2O3 → Ag2S2O3 (b) FeCl3 + H2S → 2FeCl2 +2HCl + S

yellow green
Ag2S2O3 → Ag2S
Due to the reduction of FeCl3, the colour changes.
∴ A = Ag B =Ag NO3
(c) K2Cr2O7 + alkali → CrO24− + H2O
C = NO D = Ag Cl
the dichromate changes to yellow colored chromate.
E = Ag2S2O3 F = Ag2S
(d) CO is evolved along with CO2. CO2 burns with blue
flame while CO2 prevents burning
Sol 17:
H2C2O4 
∆
→ H2O + CO + CO2
A = sulphur
hot conc HNO CO diffuses faster than CO2. Once CO burns with blue
S = →
3 NO2 + H2SO4
(brown) flame, it is put off by CO2 which diffuse later.
Na SO
S 
2 3 → Na S O (C)
2 2 3 (e) YAS possess excess free sulphur. It combines with
group 2B sulphide which convert it and forms Sulphates
Na2S2O3 (acidified) → Na2S 4 O6 + NaOH from soluble complex will (NH4)2S
white
E.g: SnS + S → SnS2
NH4 OH
Sol 18: (a) AgCl  → Ag(NH3 )2 Cl SnS2 + (NH4)2S → (NH4)2SnS3
(soluble)
true (f) Reaction of ZnCl2 with H2S produces HCl which
dissolve ZnS.
(b) Sb2S3 (is orange in colour) false
dissolves
(c) CuSO4 + K4FeCN6 → CuFeCN6 + K2SO4 (g) CaSO4 → forming a stable complex
(NH4 )2
choclote ppt
False CaSO4 + (NH4)2 → (NH4)2 Ca(SO4)2
(d) True
(h) Presence of SO24− brings preicipitation of group V
(e) True
ion such as Ca2+, Ba2+ etc.
(f) False, sulphates of V group radicals will be precipitated
(i) Adding of conc. HNO3 serves 2 purposes
conc. H2SO 4
(g) I 
–
→ I2 true (1) It precipitates the dissolved H2S
(h) False IInd group ferric salts are reduced as H2S. Hence (2) It convert Fe2+ → Fe3+ ions
it is always necessary to use HNO3 in IIIrd grp.
( j) Al(OH)3 and Zn(OH)2 dissolve in NaOH
(i) True 3(CH3COO )2Ca + FeCl3 → 2Fe (CH3COO)3 +
–
3CaCl2 Al(OH)3+NaOH → NaAlO2 +2H2O

soluble
( j) K2HgI4 alkaline true Zn(OH)2+2NaOH → Na2 ZnO2 +2H2O
(k) True soluble
(l) False Ni can be tested with dimethyl glyoxime as it ∆

Sol 20: X (aq)  → Alkaline
forms a colored complex.
∆
(m) Co2+ + KNO3+ acetic acid → Yellow ppt. A  → Swells to give glassy material
CoCl2 + KNO3 → K3[Co(NO2)6] Conc, H SO

2 4 → Crystals
X 
Yellow X is an alkali metal salt and as it swells up to give a
(n) BaCO3, SnCO3, CaCO3 are soluble in acid to give glassy mass, it may be borax.
corresponding sulphates or chloride. True ∴ X is borax
Na2B4O7 + 7H2O → 2NaOH + 4H3BO3
Sol 19: (a) FeCl3 is a salt of weak base and a strong acid.
It readily hydrolyses to form Fe(OH)3 Na2B4O7. 10H2O → Na2B4O7+10H2O
∆
FeCl3 + 3H2O Fe(OH)3 + 3HCl Na2B4O7 2NaBO2 + B2O3
addition of HCl prevents hydrolysis glassy mass
Na2B4O7 + H2SO4 + 5H2O → Na2SO4 + 4H3BO3 X+conc. H2SO4

∆
brown vapours
weak acid
AgNO3
Sol 21: X(aq) → Red litmus blue
∴ X is basic no ppt.
excess
X  → Deep blue colour Brown vapours = NO2
CuSO 4
X + FeCl3 Brown ppt (Soluble in dil. HNO3) X → Nitrate NO3−
∴ X must be NH3 as X + CuSO4 → Deep blue solution

Sol 8: (B) (NH4)2Cr2O7 → Cr2O3
CuSO4+4NH3 → Cu(OH)3 + 3NH4Cl
3NH3 + 3H2O + FeCl3 → Fe(OH)3 + 3NH4Cl Sol 9: (A) Only brown gas was Br2
Fe(OH)3+3HNO3 → Fe(NO3)3+H2O
Sol 10: (D)
White solid + dil H2SO4 →

Exercise 2 No action
Conc. H2SO4 observed
∆
Sol 1: (B) Sulphite + HCl → S (Suffocating)
Salt contains sulphate
Sol 2: (C) CuNO3 + KI(Starch) → blue
Sol 11: (A) IInd group MS (is yellow)
Sol 3: (D) SO3− + dil H2SO4 → SO2 When no radical of group II is present
Phosphate is present in mix.
∴
K2Cr2O7 Sol 12: (C) BiCl3 + H2O → BiOCl

Green
Sol 13: (A) HgS is insoluble in dil. HNO3
∆
Sol 4: (B) Oxalate  → CO + CO2
(C2O24− )
Sol 14: (B) NiS and ZnS are seperated by Conc. HCl
ZnS dissolved in dil HCl
burns with blue flame
Where ZnS + 2HCl → ZnCl2 + H2S
NiS is insoluble in dil HCl.
Sol 5: (C) Hg2Cl2 +NH4OH → Hg + HgNH2CI 
Sol 15: (D) Heating Na2CO3 mix in distilled water.
Black
Sol 16: (C) Dimethyl glyoxime + Ni → Red coloured
complex ppt.
Sol 6: (B) Br2 + KI → Blue
Sol 17: (A) NO2 bleaches moist litmus paper.
∆
Sol 7: (B) X + dil. H2SO4  → do not evolve brown
vapour ∆
Sol 18: (D) ZnO  → ZnO
white yellow
Sol 19: (D) White ppt + NH4OH → black Sol 34: (B) Ca + N2 → Ca3N
Compound is Hg2Cl2 Ca3N + 6H2O → 3Ca(OH)2 + NH3
Hg2Cl2 + NH4OH → Hg + HgNH2Cl Ca(OH)2 + CO2 → CaCO3
∴ gas = NH3 and solid = CaCO3
Sol 20: (B) Al(OH)3 + NaOH (excess) → Na[Al(OH)4]
Soluble complex
Sol 35: (C) X + H2O → Saturated solution
Sol 21: (A) HgS does not dissolve in hot dil. HNO3. X(ag) + AgNO3 → White ppt. AgCl
X(ag) + Mg → Colourless gas MgCl2
Sol 22: (C) An aqueous solution of FeSO4Al2(AO4)3 X = Cl2 ; Y = H2
and chrome alum is heated with excess of Na2O2 and
filtered. The materials obtained are a yellow filtrate and
a brown residue Previous Years’ Questions
∆
Sol 23: (B) NH+4 (salt) + NaOH  → NH3 Sol 1: Cl2 + H2O → HCl + HOCl
‘X’
Sol 24: (C) Green frame ∴ Cation is Ba2+
HCl + AgNO3 → AgCl ↓ (White) + HNO3
BaCl2 + 2Ag+ → 2AgCl + Ba2+
White 2HCl + Mg → MgCl2 + H2(g) ↑ Y
y
Sol 25: (A) Bi and Sn both belong to IInd group. Both
give precipitate. Sol 2: (A) SO32− + H2SO 4 → SO2 ↑ + H2O + SO24−
X Y
Sol 26: (D) H2S + NH4OH + X → White ppt. SO2 is a colourless gas with irritating odour.
ZnCl2 SO2 + K2Cr2O7 + H2SO4 → K2SO4 + Cr2 (SO 4 )3 + H2O
∴ X = Zinc salt Green
solution
Sol 27: (D) Conc. of S2– ion is covered by formation of Sol 3: (B) A sodium salt of an unknown anion when
weak acid H2S. treated with MgCl gives white precipitate (MgCO3) only
on boiling. Hence, the action must be HCO3− ion.
∆
Sol 28: (C) A white solid is first heated with dilute and MgCl2 + 2NaHCO3  → MgCO3 + 2NaCl + H2O +
when with concentrated. No action is observed in either CO2
case. The solid contains sulphate.
Sol 4: (A) Both (NH4)2Cr2O7 and NH4NO2 on heating
Sol 29: (C) Bead’s test’s salt is Na(NH4)HPO4. 4H2O gives nitrogen gas.
I −
−
Sol 30: (B) To separate Fe from Zn and Cu, use excess Sol 5: (B) Bi3+ + 3I– → BiI3 ↓ → [BiI4 ]
Excess
NH3 Black Orange
solution
Sol 31:(B) Al and Fe can be separated by NaOH excess Sol.6: (A) Zn2+ + 2H2O → Zn(OH)2 ↓ + 2H +
Al + NaOH → Al(OH)3 White
Al(OH)3 + NaOH → NaAlO2 Sol 7: (C) Cation Cd2+ belongs to group II white Ni2+
belongs to group I of analytical group. Group II radicals
Sol 32: (B) K4[Fe(CN)6], Fe+3 ferricyanide are precipitated by passing H2S(g) through acidic
solution of salt but radicals of group III are precipitated
by passing H2S(g) in NH3/NH4Cl buffer solution of salt
Sol 33: (C) PbSO4 is water insoluble.
due to greater solubility products of later salts.
Sol 8: (B) As MgSO4 is soluble in water, so not used for 2 K HgI

Mix 
4→
brown ppt.
estimation of SO24− ion.
The mixture contains Fe+2 and Fe+3 (from NH+4 ) (from
test b and d) and Cl– from test A.
Sol 9: (C) Yellow filtrate contain CrO5 and brown residue
Conc, H SO
contain Fe2O3. ∴ The reactions are Cl– + MgO 
2 4 → Cl
2
∆
NH+4 + NaOH  → NH3
Sol 10: (C) Fe(II) and Fe(III) will have different values of
magnetic moment due to different number of unpaired Fe+2 → K4FeCN3
electrons in their d-orbitals. Fe+3 → Blue ppt will be K4FeCN6
K HgI
Sol 11: (D) PbCl2 is soluble in hot water and PbS (black) NH3 
2 4 → Brown ppt.
is formed on passing H2S(g) through acidic solution.

∆
Sol 4: X . nH2O  → X + nH2O
JEE Advanced/Boards with dil HCl

X(aq) → White turns brown
KI + X → Decolourises
Exercise 1
Ag NO3 + X → White ppt
Sol 1: X (Lewis acid → fumes in moist air)
X + NH4OH → fumes intensity increases black or strong
X (acidic) + NH4Cl + NH4OH → ppt → soluble in NaOH
X + H2S → No ppt. X containing S2O32− as it decolourises I– which also
coincides with the other 2 statement I and (II)
X is some chloride as its fumes increases in presence
of NH4OH hence the compound is Na2S2O3. 5H2O
X + NH4Cl + NH4OH → ppt → soluble in NaOH ∆

Na2S2O3. 5H2O  → Na2S2O3+5H2O↑
∴ X = AlCl3 or ZnCl2
(i) Na2S2O3 + 2HCl → 2NaCl + H2O
But X is a Lewis acid ∴ X = AlCl3
+ SO2 + S (Turbidity)
Sol 2: A(aq) → B (ppt) + O solution
NaCl
(ii) 2Na2S2O3+I2 → Na2S4O6 + 2NaI
H2S
C  → Black ppt
(iii) Na2S2O3 + 2AgNO3 → Ag2S2O3↓ + 2NaNO3
hot water +Na I2
B  → Yellow ppt. White ppt.
dil. HCl
→ X no gas reddish brown gas
A  Ag2S2O3 + H2O → Ag2S↓ + H2SO4
∆

Black
A = Pb(NO3)2
B = PbCl2 Sol 5: X + CH3COO– + KI → I2
Pb 
H S
2 → PbS (black) CO2 + aq(X) → ppt.
X (H2O) + ethyl alcohol →
Pb2+ + KI → PbI2 yellow
Product = Ester
Sol 3: Salt + MgO2  X = CaOCl2 bleaching powder

→ Yellow greenish gas
Conc. H2SO 4
∆ (i) CaOCl2 + CH3COOH → (CH3COO)2 Ca + Cl2 + H2O

Mix + NaOH  → Red litmus blue
2KI + Cl2 → 2KCl + I2
X (aq) → Blue ppt K4(Fe3CN3)
(ii) CaOCl2 + CO2 → CaCO3 + Cl2
and let NH4CNS
(iii) CaOCl2 + H2O → Ca(OH)2 + Cl2
C2H5OH + Cl2 → CH3CHO + 2HCl CoCl2 + NaHCO3 → Na4Co(CO3)3 + H2O + 3CO2

CH3CHO + 3Cl2 → CCl3CHO + 3HCl Br2 + H2O → HBr + O
CCl3CHO + 2Ca(OH)2 → CHCl3 + (HCOO)2Ca 2Na4Co(CO3)3 + H2O + O → 2Na3Co(CO3)3 + NaOH
sod. cobalt carbonate
Sol 6: A = SO2
(green)
SO2 + dil. H2SO4 + K2Cr2O7 → K2SO4 + Cr2(SO4)3
∆
SO2 + dil. H2SO4 + KMnO4 → MnSO4 Sol 8: A + H2O  → White ppt. (B)
SO2 + O2 → H2SO4 A + conc. HCl → Clear solution
H2SO4 + BaCl2 → BaSO4
Excess H2O
A = SO2
B = Cr2(SO4)3 B precipitate
H2S
C = KMnO4 A/B  → Brown / Black ppt. (C)
D = H2SO4 A + H2SO4 → D
D + Hg+(Salt) → White E
heat
Sol 7: (i)A(aq) + Zn  → B
∴ D = Cl2, E = Hg2Cl2
heat
A(aq) + C → PH3 A = BiCl3, B = BiOCl, C = BiS
A(aq) + NH4Cl → (D) gas D = HCl, E = Hg2Cl2
(ii) A = NaOH/KOH C = P4 BiCl3 + H2O → Bi(OH)3 + 2HCl
B = H2 D = NH3 Bi(OH)3 + HCl → Clear BiCl3
CO : CoS BiCl3 + H2O (Excess) → BiOCl
↓ ↓ BiCl3 + H2S → BiS (Brownish black)
NH4 OH
A + H2S  → B (black) D = HCl and E = Hg2Cl2
B CoS + HCl + KClO3 → A(CoCl2) Sol 9: A = NH4Cl

A + KCN buff coloured ppt. B = NH4HCO3
(COCl2 )
A C = NaHCO3
Excess NH4CO3+NaCl → NaHCO3 + NH4Cl
reagent ∆
NaHCO3 → Na2CO3 + H2O + CO2
C D = CO2.
Co(CN)6
∆
A (aq)  → B Sol 10: A + N2 → B
COCl2
B = H2O → C + D
Br
A + NaHCO3 (excess) → 
2→
C + CO2 → Milky soln
H2O
A = CoCl2 ∴ C = Ca(OH)2
B = CoS A = Ca
C = K4[Co(CN)6] B = Ca3N2
E = 2Na3Co(CO3)3 Green C = Ca(OH)2

D = NH3
CoCl2+H2S+NH4OH → CoS (black)
CoS + HCl + KClO3 → CoCl2
CoCl2 + KCN → K3 [Co(CN)6]
Sol 11: A(aq) + NaOH → White ppt Sol 13: R + K2Cr2O7 → Decolourises
X + H2O2 → + Aq. BaCl2 → A ppt
Excess NaOH
Soluble
in dil
Dissolves
HCl

A(aq) + NH4OH → White ppt
H2 + X → Turbidity
Excess NH4OH According to the reaction X = SO2
K2Cr2O7 + 4H2SO4 → K2SO4 + Cr2(SO4)3 + 4H2O + 3O
Dissolves
H2O + SO2 +O → H2SO4
AgNO3 + A → Yellow ppt. H2O2 + SO2 → H2SO4
dil HNO
3 → Solution
 H2SO4 + BaCl2 → BaSO4 + 2HCl
∴ A = AlBr3. H2S + SO2 → 3S↓ + 2H2O
Sol 12: A(acidic) → Sublimes at 300°C Sol 14: Refer theory.
A + NH4 SNC → B ∆
Excess Red compound Sol 15: A  → B+C
B + H2 → D (Metal)
A + K4FeCN6 → Blue compound
(C) = Fe4 (Fe(CN)6)3 [B + HCl + K4Fe(CN)6] → Chocolate ppt.
(E)
∴ A = Fe
A + K2Cr2O7 + conc. H2SO4 → D C + Ca(OH)2 → Milkiness 
excess C
→ Clear solution (F)
(Deep red vapour) 2CrO2Cl2 E = Cu2[Fe(CN)6]
∴ Cl
∴ A is a copper compound
D + NaOH + CH3COOH +
C = CO2/SO2
Pb(CH3COO)2 F = CaHCO3/Ca
E A = CuSO4
Yellow B = SO2 + CuO

CuSO4 → 2CuO + SO2
∴ A = FeCl3 B = Fe(SCN)3
CuO + H2 → Cu
C = Fe4[Fe(CN)6]3 D = CrO2Cl
CuO + K4Fe(CN)6 = Cu2[Fe(CN)6]
E = PbCrO4
SO2+Ca(OH)2 → CaSO4 → CaS2O3
∴ Reactions are
FeCl3 + NH4SNC → Fe(SCN)3
Sol 16: B + conc. liquor+NaS + NaSO2 → A
FeCl3 + K4 [Fe(CN)]6 →Fe4[Fe(CN)6]3
A + Dil AgNO3 → White ppt. → C (Black)
FeCl3 + K2Cr2O7 + H2SO4 → 2CrO2Cl2 + Fe2(SO4)3
FeCl3 + A → Violet coloured D (Disappear)
CrO2Cl2 + NaOH + CH3COOH + Pb(CH3COO)2 → PbCrO4
+ CH3COONa A + CuCl2 → White ppt.
Excess
E
A contains S2O32− ion from (ii) and A = Na2S2O3 E = PbCrO4

SO2 + conc. EtOH + NaS + NaSO2 → Na2S2O3 A = K2Cr2O7
Na2S2O3 + dil AgNO3 → Ag2S2O3

Sol 19: (i) Au + HCl + HNO3 → HAuCl4 + 3NO2 + 3H2O
White ppt.
(ii) C + 4HNO3 (conc) → CO + 4NO2 + 2H2O
(iii) Sn + 2KOH (hot) + H2O → K2SnO3 + 2H2
(iv) Cu(OH)2 + 2NH4NO3 + 2NH4OH → Cu(NH3)4(NO3)2
AgS (Black)
+ 4H2O
FeCl3 + 3Na2S2O3 → Fe2(S2O3)3 +3NaCl
Sol 20: K2Cr2O7 + (Mix) → X absorbed solution
Violet
green solution
CuCl2+ Na2S2O3 → NH4[Cu6(S2O3)5]
(Y + Z) + Ca(OH) → Milky
Sol 17: MCl (Z) Alkali pyragallol → Black
MCl + H2S (acidified) → black ppt ∴ Z = O2, Y = CO2 X = SO2
(not soluble in YAS) (i) 3SO2 + K2Cr2O7 + H2SO4 → H2SO4 + Cr2(SO4)3 + H2O
∴ MS is group IIA (ii) Ca(OH)2+CO2 → CaCO3↓ + H2O
SnCl2
SnCl2+X → White ppt. → Grey (iii) O2 + Pyragallol → Absorbed
Excess
Excess
KI + X → Red ppt.  → Dissolve
KI
Exercise 2
Acc. To these facts, X = HgCl2
+
H
HgCl2 + H2S → HgS + 2HCl
Black Sol 1: (A) Theoretical : HgS does not dissolve in hot
dil. HNO3.
2HgCl2 + SnCl2 → Hg2Cl2 + SnCl4
White
Sol 2: (C) FeSO4. Al2(SO4) and chrome alum + Na2SO3
HgCl2 + SnCl2 → Hg ↓ + SnCl4 ∆
Grey
 → (C) a yellow filtrate and brown residue.
HgCl2 + 2KI → HgI2 + 2KCl

Red
Sol 3: (C) MgCO3 is soluble in NH4Cl forming MgCl2.
Hg I2 + 2KI → K2HgI4
Sol 4: (D) Excess of splitting ∝ oxidation state.
∆
Sol 18: A  → Violet colour flame
Assertion Reasoning Type
∴ A contains Cr
Sol 5: (C) Yellow colour of compound is not due to
A + B + conc. H2SO4 → C (Red gas)
NH+4 ion (as NH+4 ion does not impart colour to its
C + alk H2SO4 → Red yellow solution D molecules).
D + CH3COOH → Yellow ppt.
Sol 6: (A) (A) Both statements are true.
B + NaOH → F (fumes)
∴ F = NH3 Sol 7: (D) both statements are false as NaOH will react
B = NH4Cl with salt and not form ether hydroxide.
C = CrO2Cl2
Sol 8: (C) Charcoal cavity test can only be used for non
D = Na2CrO4 coloured salt,.
Sol 9: (C) All S containing molecules give match state Fe2+ + K3[Fe(CN)6] → KFe[Fe(CN)6] + 2K+
test.
The red colour of Fe3+ion with potassium thiocyanate is
due to formation of [Fe(SCN)3].
Sol 10: (B) Both Statement true but reason does not
explain assertion. Fe3+ + 3KSCN → [ Fe(SCN)3 ] + 3K+
red coloured
Comprehension Type
Sol 6: (A, B) NH4NO3 + NaOH → NaNO3 + NH3 +
Sol 11-14: (D, B, C, D) H 2O
(a) Na2CrO4 + CO2 → Na2Cr2O7 NH4NO2 + NaOH → NaNO2 + NH3 + H2O
(b) Zn + acidic Na2Cr2O7 → Green Cr2O3 Sol 7: (D) Sol 8: (C) Sol 9: (B)
Orange The comprehension describing methylene-blue test.
NMe2
NMe2
Burn
2-
S +2 + Fe (III)
Green S
2-
+2 + Fe (III)
CO2 acts to make the solution acidic NH2

NH2
H2O + CO2 → H2CO3
Zn is the reducing agent Me2N
+
+
S NMe2
Me2N NMe2
Cr+6 to Cr+3 S
Cr+3 to Cr+2 (blue in colour) N

N
Blue solution
Previous Years’ Questions
Blue solution
Therefore,
Sol 1: (A) MgSO4 + NH4OH + Na2HPO4 → 1. X is Na2S
Mg(NH4 )PO 4 ↓ + Na2SO4 + H2O 2. Y is FeCl3
white
3. Compound Z is Fe[Fe(CN)6]
Sol 2: (B) Hg2+ + 2I– → HgI2 (red)

Sol 10: (a) Fe3+ + 3SCN– → [ Fe(SCN)3 ] (blood red
HgI2 + 2KI → K 2 [ HgI 4 ] colouration) A
soluble
3−
Hg + Co(SCN)2 → Co[ Hg(SCN)4 ]
2+ Fe(SCN)3 + F– (excess) → [ FeF6 ] + 3SCN–
blue B
(b) Magnetic moment ( µs ) = n(n + 2) BM

Sol 3: (A) In acidic medium, H2S is very feebly ionized
giving very small concentration of sulphide ion for
= 3S BM
precipitation. Therefore, the most insoluble salts CuS
and HgS are precipitated only. = 5.92 BM
Sol 4: (B, C) Both Al3+ and Bi3+ are precipitated as their Zn

Sol 11: MCl4  → Purple coloured compound (A)
hydroxides. colourless
moist
M → B (white fumes)
Sol 5: (B, C) The blue precipitate of Fe ion with
2+
tr. metal air
potassium ferricyanide is due to formation of Turnbull’s ⇒ M = Ti, A=[Ti(H2O)6]3+; B = TiO2

blue KFe[Fe(CN)6].
Ti (IV) contains no d-electron, while d-d transition of

single electron of Ti (III) will cause colour change.
Hot
Sol 12: (A) Pb+2 + 2HCl → PbCl2 
Water
→ Soluble
Sol 13: (D)

Hot
Pb+2 + 2HCI → PbCI2 
Water
→ Soluble
→ Cr ( OH) ↓
H S
Cr +3 
2
Ammxmiacal 3
Cr ( OH) 
NaOH
H O
→ Na2CrO 4
3 2 3 Yellow solution
Sol 14: (A, C) (A) CuCI2 + S −2 → CuS ↓ +2CI −

Black ppt
2−
CuCI2 + SO 4 → No. ppt
(B) BaCI2 + S −2 → BaS + 2CI −

No.ppt
BaCI2 + SO 4 −2 → BaSO 4 ↓ 2CI−

White ppt
(C) Pb ( OAc ) SO −2 → PbS ↓ + 2CH3 − COO −

2 (Black ppt )
Pb ( OAc ) + S −2 → PbSO 4 ↓+ 2CH3 − COO −

2
Black ppt
PbS can be selective ppt out first as Ksp s much less than
K sp of PbSO 4
K sp of PBS= 3 × 10−28
K sp of PbSO=
4 25 × 10−8
(D) Na2 Fe ( CN) NO  + S −2 → Fe ( CN) NOS 

 5   5 
Purple Colour
Na2 Fe ( CN) NO  + SO 42− → No. ppt

 5 
Sol 15: (A)

+ 3−
S2O2−3 →  Ag ( S2O3 ) 
Ag
 2
(X)
Ag+
→ Ag2S2O3 → Ag2S(Black ppt)
(Y) (Z)

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2017-18 100 &

2500 + 1000 (New) Problems

5000+Illustrations and Solved Examples

Salt → Cation (C+ ) + Anion (A − )

Flowchart 30.1: Procedure of salt analysis

Experiment Observation Inference

Deliquescence: Colorless → Mg+2 , Al+3 , Zn+2

3. DRY HEATING TESTS

Colored (Pungent Smell) Cl−

3. Decripitation: Decomposition with crackling sound on

4. OTHER DRY TESTS

5. CHARCOAL CAVITY TEST

6. COBALT NITRATE TEST

Table 30.3: Charcoal cavity test

Figure 30.4: Steps to preform flame test

Table 30.4: Flame test for transition metals

Sr. No. Metals Color of flame

8. BORAX BEAD TEST

CuO + B2O3 → Cu (BO2 )

2Cu(BO2 )3 + 2NaBO2 + C → CuBO2 + Na2B 4 O7 + CO

Copper (I) metaborate → Colorless

2Cu(BO2 )3 + 4NaBO2 + 2C → 2CuBO2 + 2Na2B 4 O7 + 2CO

Color in oxidizing flame Color in reducing flame

Color in oxidizing flame Color in reducing flame

Non luminous flame = Oxidizing flame.

9. MICROCOSMIC SALT BEAD TEST

(Ammonium sodium phosphate)

10. CONFIRMATORY TESTS (WET TESTS)

Table 30.6: Wet tests

Sr. No. Acid radical Characteristics

Generally S2- ppt are common.

Sr. No. Acid radical Characteristics

E.g. HgO . HgSO 4 → insoluble

10 All phosphates are ppt except

11. ANALYSIS OF ANIONIC OR ACIDIC RADICAL

Flowchart 30.2: Analysis of anionic or acidic radical

Table 30.7: Analysis of group A and group B radicals

Group A (dil H2SO4)

Cr2O72– + SO2 → Cr3+(green)

I-+NO2 → I2 (I2+starch-blue complex)

12. SODIUM CARBONATE EXTRACT

Figure 30.6: Set up for preparation of sodium carbonate extract

Dil.H2SO4 grp (CO32-,CO2)

Sr. No. Reagent Observation Remarks

3 MgSO4/BaCl2 soln (colorless) White

4 AgNO3 soln. White ppt(dissolves in Carbonates are more easily polarized

Hg2++HCO3 →-No reaction

HCO3+HPh = Colo rless

Li2CO3 → Li2O + CO2 ; PbCO3 → PbO + CO2

Carbonates of less reactive metals

Table 30.9: Confirmatory test for sulphite radical

S. No. Reagent Observation Remarks

1 Dil.H2SO4 Colorless, suffocating

2 BaCl2 Soln. White ppt. BaSO3 dissolves in-

Ba2+ + SO32− → BaSO3 ↓ (i) Dil.HCl BaSO3 + HCl →

Ag+ + SO32− → [Ag(SO3 )]−

On adding more AgNO3 to the above complex White ppt.

[Ag(SO3)]-+Ag+ → Ag2SO3 Dissolves in NH3 and dil.

S. No. Reagent Observation Remarks