Qualitative Analysis Colours and Detailed
Qualitative Analysis Colours and Detailed
Qualitative Analysis Colours and Detailed
op kers
Class 12 T
By E ran culty
-JE Fa r
IIT enior emie .
S fP r es
o titut
Ins
CHEMISTRY
FOR JEE MAIN & ADVANCED
SECOND
EDITION
Exhaustive Theory
(Now Revised)
Formula Sheet
9000+ Problems
based on latest JEE pattern
Plancess Concepts
Topic Covered Tips & Tricks, Facts, Notes, Misconceptions,
Key Take Aways, Problem Solving Tactics
Qualita ve Analysis
PlancEssential
Questions recommended for revision
30. Q U A L I TAT I V E
A N A LY S I S
1. INTRODUCTION
Determination of quality of any salt mixture is called Qualitative analysis or Salt analysis.
2. PHYSICAL APPEARANCE
Table 30.1: Physical properties
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
(
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
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
Figure 30.1: Different regions of flame Figure 30.2: Diagram showing non luminous and luminous flame
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.
3 0 . 4 | Qualitative Analysis
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)
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
Table 30.5: Colour of flame of different ions during borax bead test
∆
Na(NH4 ).HPO 4 .4H2O → NaPO3 + H2O ↑ NH3 ↑
micro cosmic
salt
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)
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.
Sn2+
are normally soluble
HS −
5 NO2− ,NO3− ,CH3 COO − All are soluble except AgNO2,CH3COOAg, CH3COOHg
Chem i str y | 30.7
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
Primary phosphates of alkaline earth metals are also soluble (dihydrogen phosphate)
(
E.g. Mg H2PO 4 )2
2 Evolution of colorless, suffocating gas with burning sulphur smell which SO2 SO32-
turns K2Cr2O7 paper green
4 Evolution of pungent smelling reddish brown gas which turns starch iodide NO2 NO2−
paper blue
Filter paper
2g salt +
Funnel
3 times Na2CO3 Wire gauze
+ 20 ml distilled
Tripod stand
water
Burner Beaker
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
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
Mg2++CO32- → MgCO3
Mg2++2HCO3 → Mg(HCO3)2
∆
Mg(HCO3 )2 → MgCO3 ↓ +CO2 + H2O
∆ 1
→ 2Ag + O2
2
5 HgCl2/Hg(NO3)2 Reddish brown ppt
Hg2++3CO32-+3H2O→3HgO.Hg(CO3)2.Hg(CO3)2
(basic mercuric carbonate)
6 Phenolphthalein (HPh) CO32-+HPh = Pink
ACTION OF HEAT
∆
Bicarbonates → Carbonates
∆
2NaHCO3 → Na2CO3 + CO2 ↑ +H2O
∆
Carbonates → metal oxide + CO2
exception Na+ , K + , Rb+ , Cs+
SO32−
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
Ag2SO3+SO32- → 2[Ag(SO3)]-(aq)
−
2 Ag ( SO3 )
∆
→ 2Ag ↓ +SO24− + SO2
Chem i str y | 30.11
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.
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
H3C CH3
N
(CH3)2N + N(CH3)2
S
3+ 2+ + +
+ Fe (soln.) + H2S + Fe +NH4 + H
N
NH2
N, N-Dimethyl phenyl diamine
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
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
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
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.
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:
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
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)
3 0 . 1 6 | Qualitative Analysis
–
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.
5 8HNO3+6Br- → 3Br2↑+NO↑+6NO3-+4H2O
6 K 2Cr2O7 + H2SO 4 + Br − → Br2 + Cr +3
I + H2SO 4
↓ ↓
I2 ↑ +S ↓ I2 ↑ +H2S ↑
– –
Feasible only with I , not with Br
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
i) 2Cu+2 + 2I − → 2Cu+ + I2
I 2 + I − → I3 −
ii) I − + 8Cl + 9H O →
3 2 2
‒
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
NO3 + ( C6H5 ) NH ↓
−
2
Ph2 − N − N − Ph2
∆ 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
Chem i str y | 30.19
∆
NH4NO3 → N2O + 2H2O
∆
NH4NO2 → N2 + 2H2O
∆
N2H5NO2 → N2H + 2H2O
Air → O2
20%
‒
SO42 Reagent Observation Remarks
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
iii) Na2S + Na2 Fe CN NO
S 2 −
Na4 Fe( CN) NOS
5
3 0 . 2 0 | Qualitative Analysis
‒
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
‒
BO33 Reagent Observation Remarks
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 ( )
Chem i str y | 30.21
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 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-
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
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
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
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
Chem i str y | 30.23
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.
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
Group I
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
+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−
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
Hg2 2+
+ 2CN → Hg ↓ +Hg ( CN) ( soluble ) .
−
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 →
→ 22Ag 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.
Ammonia solution
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
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.
3−
2 Fe ( CN) + 3Cu2+ → Cu3 Fe ( CN) ↓ Green
6 6 2
Chem i str y | 30.29
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
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
3 0 . 3 0 | Qualitative Analysis
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
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’.
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.
Chem i str y | 30.31
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
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.
3 0 . 3 2 | Qualitative Analysis
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
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).
Ba + SO 4 → BaSO 4 ↓ ( white )
2 2−
( 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
Ba + SO 4 → BaSO 4 ↓ ( white )
2 2−
( 3 )4 (
(G) Cu NH NO3 ) ;(H) Cu2 Fe ( CN)
=
2 6
The solution is evaporated to dryness and residue extracted with dilute HCl. It is divided into three parts.
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
Mn2+ (manganese)
Manganese sulphide dissolves in HCl.
MnS + 2HCl → MnCl2 + H2S
On heating the solution with NaOH and Br2 -water, manganese dioxide gets ppt..
3 0 . 3 6 | Qualitative Analysis
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.
VITH GROUP
Table 30.25: Confirmatory test for group VI radical
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.
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
Chem i str y | 30.39
(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
Black Coloured Blue Coloured Compounds Green Coloured Compounds Yellow Coloured
Compounds Compounds
Light Blue
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)
5. CrO2Cl2 (Reddish Brown) 5. Fe(OH)3 (Reddish Brown) 5. Cr2O72- (orange in aq. soln) Co(CN)2
POINTS TO REMEMBER
PbCl2(s)
Add H2S in 0.3 M HCl
Solved Examples
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).
Chem i str y | 30.43
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
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.
*** 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)
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
*** 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)
(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 ]
Chem i str y | 30.47
*** 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)
(d) CdS O2 + 2KCN → Cd(CN)2 + K 2 SO 4 Sn(OH)2 + 2NaOH → Na2SnO2 + 2H2O
white Sodium stannite
(Strongly reducing)
(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.
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
JEE Main/Boards
(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).
(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).
Chem i str y | 30.51
(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
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
(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
Chem i str y | 30.53
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
3 0 . 5 4 | Qualitative Analysis
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).
Chem i str y | 30.55
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).
3 0 . 5 6 | Qualitative Analysis
(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.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)?
(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
3 0 . 5 8 | Qualitative Analysis
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)
(C) NH4Cl (D) (NH4)2SO4 (A) Pb2+ (B) Hg2+ (C) Ag+ (D) Hg2+
Chem i str y | 30.59
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
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
3 0 . 6 0 | Qualitative Analysis
Answer Key
JEE Main/Boards
Exercise 2
Single Correct Choice Type
JEE Advanced/Boards
Exercise 2
Single Correct Choice Type
Comprehension Type
Solutions
∴ 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
Chem i str y | 30.63
AgNO3
Sol 21: X(aq) → Red litmus blue
∴ X is basic no ppt.
excess
X → Deep blue colour Brown vapours = NO2
CuSO 4
Fe(OH)3+3HNO3 → Fe(NO3)3+H2O
Sol 10: (D)
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
Chem i str y | 30.65
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.
3 0 . 6 6 | Qualitative Analysis
∆
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.
Pb
H S
2 → PbS (black) CO2 + aq(X) → ppt.
X (H2O) + ethyl alcohol →
Pb2+ + KI → PbI2 yellow
Product = Ester
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
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 + 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
E
Chem i str y | 30.69
Excess
KI + X → Red ppt. → Dissolve
KI
Exercise 2
Acc. To these facts, X = HgCl2
+
Single Correct Choice Type
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.
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,.
3 0 . 7 0 | Qualitative Analysis
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)
soluble
3−
Hg + Co(SCN)2 → Co[ Hg(SCN)4 ]
2+ Fe(SCN)3 + F– (excess) → [ FeF6 ] + 3SCN–
blue B
Hot
Sol 12: (A) Pb+2 + 2HCl → PbCl2
Water
→ Soluble
→ Cr ( OH) ↓
H S
Cr +3
2
Ammxmiacal 3
Cr ( OH)
NaOH
H O
→ Na2CrO 4
3 2 3 Yellow solution
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