Qualitative Analysis (Cations) English PC

QUALITATIVE ANALYSIS (CATIONS)
CONTENTS
Topic Page No.
Theory 01 – 25
Exercise - 1 26 – 32
Part - I : Subjective Questions
Part - II : Only One Option Correct Type
Part - III : Match the Columns
Part - I : Only One Option Correct Type
Part - II : Single And Double Value Integer Type
Part - III : One or More Than One Options Correct Type
Part - IV : Comprehensions
Part - I : JEE(ADVANCED) / IIT-JEE Problems (Previous Years)
Part - II : JEE(MAIN) / AIEEE Problems (Previous Years)
Answer Key 41 – 44
Advanced Level Problems 45 – 57
Part - I : PRACTICE TEST-1 (IIT-JEE (MAIN Pattern))
Part - II : NATIONAL STANDARD EXAMINATION IN CHEMISTRY (NSEC) STAGE-I
Part - III : ADDITIONAL THEORY
Part - IV : PRACTICE TEST-2 (IIT-JEE (ADVANCED Pattern))
Part - V : INTERNATIONAL CHEMISTRY OLYMPIAD (IChO) STAGE-V
ALP Key 58 – 59
ALP Solutions 60 – 67
JEE(ADVANCED) SYLLABUS
Qualitative Analysis (Cations) : Groups I to V (only Ag+, Hg2+, Cu2+, Pb2+, Bi3+, Fe3+, Cr3+, Al3+, Ca2+, Ba2+,
Zn2+, Mn2+ and Mg2+); Nitrate, halides (excluding fluoride), sulphate and sulphide.
JEE (MAIN) SYLLABUS

QUALITATIVE ANALYSIS : Chemical Principle involved in the qualitative salt analysis :
Cations - Pb2+, Cu2+, Al3+, Fe3+, Zn2+, Ni2+, Ca2+, Ba2+, Mg2+, NH4+.
Anions - CO32–, S2–, SO42–, NO3–, NO2–, Cl–, Br–, I–.
(Insoluble salts excluded).
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Qualitative Analysis (Cations)
PART-II
1. Physical Examination Of the Mixture :
The physical examination of the unknown mixture involves the study of colour, smell and density.
Table : 1
Physical Examination
Ex pe rim e nt Obse rva tions Infe re nce

(a ) Colour Blue or Bluish green Cu 2+ or Ni 2+
Greenish Ni 2+
Light green Fe 2+
Dark brown Fe 3+
Pink, violet Co 2+
Light pink, flesh colour or dull
earthy colour Mn 2+
Shows the absence of

W hite Cu 2+,Ni 2+,Fe2+,Fe3+
Mn 2+, Co 2+
(i) Heavy Salt of Pb 2+ or Ba 2+–
(b) De nsity
(ii) Light fluffy powder Carbonate salts
(i) If coloured, m ay be
Cu(NO 3)2 ,
Salt absorbs moisture and FeCl 3
(c) De lique sce nce becomes
(ii) If colourless, may be
paste like
Zn(NO 3)2 , chlorides of
Zn2+, Mg 2+ etc.
2. Charcoal Cavity Test :

This test is based on the fact that metallic carbonates when heated in a charcoal cavity decompose to give
corresponding oxides. The oxides appear as coloured incrustation or residue in the cavity. In certain cases,
the oxides formed partially undergo reduction to the metallic state producing metallic beads or scales.
Example :
(a) ZnSO4 + Na2CO3  ZnCO3 + Na2SO4
ZnCO3  ZnO (Yellow when hot, white when cold) + CO2 
(b) CuSO4 + Na2CO3  CuCO3 + Na2SO4

CuCO3  CuO + CO2
CuO + C  Cu (Reddish scales) + CO 
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ADVQUA -1
Table : 2
Observation Inference
Incrusta tion or Re sidue Me ta llic be a d
Yellow when hot, white when cold None Zn 2+
Grey bead which
Brown when hot, yellow when cold Pb 2+
marks the paper
No characteristic residue Red beads or scales Cu 2+
W hite residue which glows on heating None Ba 2+,Ca 2+ , Mg 2+
Nothing definite–generally
Black None
coloured salt
3. Cobalt Nitrate Test :

In case the residue is white in colour after charcoal cavity test, add a drop of cobalt nitrate in the charcoal
cavity. A drop of water is then added and the mass is heated in an oxidising flame using blow pipe. It is cooled
and one or two drops of cobalt nitrate solution is added and then again heated in the oxidising flame. Different
metal salts give different coloured mass as given in the table. To illustrate :
ZnSO4 + Na2 CO3  ZnCO3 + Na2 SO4 ; ZnCO3  ZnO + CO2
2Co (NO3)2  2CoO + 4 NO2 + O2 ; ZnO + CoO  ZnO. CoO (or CoZnO2)
(Rinmann's green)
Table : 3
S.No. Metal Colour of the mass
1. Zinc Green
2. Aluminium Blue
3. Magnesium Pink
4. Tin Bluish - green
Analysis of CATIONS (Basic Radicals) :

Table : 4
Group Group reagent Basic radical Composition and colour of

precipitate
Zero NaOH or Ca(OH)2 , heat if required NH4+ Ammonia gas is evolved.
1. Dil HCl Ag+ AgCl ; White
Hg22+ Hg2Cl2 ; White
Pb2+ PbCl2 ; White
2.(A) H2S in presence of dil HCl Hg2+ HgS ; Black
(Insoluble in YAS) Pb2+ PbS ; Black
Bi3+ Bi2S3 ; Black
Cu2+ CuS ; Black
Cd2+ CdS ; Yellow
2.(B) H2S in presence of dil HCl As3+ As2S3 ; Yellow
(Soluble in YAS) Sb3+ Sb2S3 ; Orange
Sn2+ SnS ; Brown
Sn4+ SnS2 ; Yellow
ADVQUA -2
3. NH4OH in presence of NH4Cl Fe3+ Fe(OH)3 ; Reddish brown

Cr3+ Cr(OH)3 ; Green
Al3+ Al(OH)3 ; Gelatinous white
4. H2S in presence of NH4OH Zn2+ ZnS ; White
and NH4Cl Mn2+ MnS ; Buff (or Pink)
Co2+ CoS ; Black
Ni2+ NiS ; Black
5. (NH4)2CO3 in presence of NH4OH Ba2+ BaCO3 ; White
Sr2+ SrCO3 ; White
Ca2+ CaCO3 ; White
6. Na2HPO4 in presence of NH4OH Mg2+ Mg(NH4)PO4 ; White
 [YAS = Yellow ammonium sulphide. (NH4)2Sx].

There are some important points which should be kept in mind while doing the analysis of cations.
1. Group 1st radicals (Ag+, Pb2+, Hg22+) are precipitated as chloride because the solubility product of these
chlorides (AgCl, PbCl2, Hg2Cl2) is less than the solubility products of chlorides of all other metal ions, which
remain in solution. Lead chloride is slightly soluble in water and therefore, lead is never completely precipitated
by adding dilute hydrochloric acid to a sample ; the rest of the lead ions are precipitated with H2S in acidic
medium together with the cations of the second group.
2. Group 2nd radicals are precipitated as sulphides because of their low solubility products whereas sulphides
of other metals remain in solution because of their high solubility products. HCl acts as a source of H+ which
decreases the concentration of S2– due to common ion effect. Hence, the concentration of S2– ion is too low
that it exceeds only the solubility products of the metal sulphides of IInd group.
We can not use H2SO4 inplace of HCl because some cations of higher groups i.e. vth group will also precipitate
as their sulphates like BaSO4, SrSO4, CaSO4 etc.
HNO3 can't be used in place of HCl. HNO3 is a powerful oxidising agent. HNO3 will oxidize H2S forming
sulphur (yellow precipitate) or colloidal solution causing confusion with CdS, As2S3 even though Cd2+ , As3+
will be absent. The colloidal solution is white-yellow and that cannot be filtered causing unnecessary trouble.
3. Group 3rd radicals are precipitated as hydroxides and the addition of NH4Cl suppresses the ionisation of
NH4OH so that only the group 3 cations are precipitated as hydroxides because of their low solubility
products.
(i) Excess of NH4Cl should not be added, as manganese will precipitate as MnO2.H2O
(ii) (NH4)2SO4 cannot be used in place of NH4Cl because the SO42– will also give the precipitate of BaSO4,
SrSO4 etc.
(iii) While proceeding for 3rd group from 2nd group, the filtrate of 2nd group is boiled off to remove the dissolved
H2S and then one drop of concentrated HNO3 is added and again boil so that if Fe2+ is present is oxidised to
Fe3+. The Ksp of Fe2+ is higher than Fe3+, therefore, it is partially precipitated and will thus interfere in the
analysis of 4th group radicals. In our scheme Fe2+ is not there even if it is present, we shall report only Fe3+
(Fe2+ needs other special tests).
(iv) If the medium remains acidic the hydroxides do not precipitate and we would think that Fe3+, Al3+, Cr3+ are
absent even though they may be present.
(v) In place of NH4OH, NaOH solution can't be used for the precipitation as their hydroxides because in
excess of it we get soluble complexes of Al3+ and Cr3+.
4. In 4th group, ammonium hydroxide increases the ionisation of H2S by removing H+ from H2S as unionised
water.
H2S 2H+ + S2– ; H+ + OH–  H2O
Now the excess of S ions is available and hence the ionic products of group 4th group cations exceeds their
2–
solubility products and will be precipitated. In case H2S is passed through a neutral solution, incomplete
precipitation will take place due to the formation of HCl, which decreases the ionisation of H2S. For example
MnCl2 + H2S  MnS + 2HCl
5. In 5th group the reagent ammonium carbonate should be added in alkaline or neutral medium. In the
absence of ammonia or ammonium ions, magnesium will also be precipitated.
ADVQUA -3
PREPARATION OF ORIGINAL SOLUTION (O.S) :
Original solution is used for the analysis of basic radicals except NH4+. It is prepared by dissolving given salt
or mixture in a suitable solvent as follows :
 H2O
 dil HCl
 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 filtrate is called as original solution (O.S.) and that is used for the detection of basic
radicals except NH4+.
ZERO GROUP :
1. AMMONIUM ION (NH4+) :
Sodium hydroxide solution : Ammonia gas is evolved on warming the solution containing ammonium salt
and sodium hydroxide.
NH4Cl + NaOH  NH3 + H2O + NaCl
 The gas can be identified by the following characteristics / reactions.
— Its characteristics smell.
— The evolution of the white fumes of ammonium chloride when a glass rod dipped in dilute HCl is held
in the vapour.
NH3 + HCl  NH4Cl  (white fumes)
— Its ability to turn filter paper moistened with Hg2(NO3)2 solution black.
Ha2(NO3)2 + 2NH3  Hg (NH2 ) NO 3  Hg + NH4NO3

black
— Its ability to turns filter paper moistened with CuSO4 solution deep blue.
CuSO4 + 4NH3  [Cu(NH3)4]SO4
— Filter paper moistened with a solution of manganese (II) chloride and hydrogen peroxide made
alkaline with ammonia gives a brown colour due to the oxidation of manganese.
2NH3 + Mn2+ + H2O2 + H2O  MnO(OH)2 + 2NH4+
 Nessler's reagent (Alkaline solution of potassium tetraiodidomercurate(II) :
Brown precipitate or brown or yellow colouration is obtained according to the amount of ammonia or
ammonium ions present. The precipitate is a basic mercury (II) amido–iodide. It is also known as
"IODIDE of MILLON's base.
NH4+ + 2[HgI4]2– + 4OH –  HgO Hg (NH2)I + 7I– + 3H2O
 Sodium hexanitrito–N–cobaltate (III) solution :
NH4+ ions gives a yellow precipitate with the reagent.
3NH4+ + [Co(NO2)6]3–  (NH4)3 [Co(NO2)6]
 Hexachloridoplatinate (IV) solution (i.e., hexachloroplatinic acid) :
NH4+ ions gives a yellow precipitate with the reagent .
2NH4+ + [PtCl6]2–  (NH4)2 [PtCl6]yellow
 Saturated sodium hydrogen tartrate solution (NaHC4H4O6) :
NH4+ ions gives a white precipitate with the reagent .
NH4+ + HC4H4O6–  NH4 HC4H4O6 
ADVQUA -4
Ist GROUP (Pb2+, Hg22+, Ag+) :
1. LEAD ION (Pb2+) :

 Dilute HCl solution : White precipitate is formed in cold solution.
Pb2+ + HCl  PbCI2  (white) + 2H+
White precipitate is soluble in hot water. White precipitate is also soluble in concentrated HCl or concentrated
KCl or excess dil. HCl.
PbCl2 + 2Cl–  [PbCl4]2– (colourless)
 Sodium hydroxide solution : White precipitate is formed which is soluble in excess of the reagent.
Pb2+ + 2OH–  Pb(OH)2  ; Pb(OH)2 + 2OH–  [Pb(OH)4]2–
[Pb(OH)4] + H2O2  PbO2  (black / brownish black) + 2H2O + 2OH–
2–
[Pb(OH)4]2– + S2O82–  PbO2  + 2H2O + 2SO42–

 Potassium iodide solution : A yellow precipitate is formed which is soluble in excess more concentrated
(6M) solution of the reagent. Yellow precipitate of PbI2 is moderately soluble in boiling water to give a colourless
solution.
PbCl2 + 2KI  PbI2  + 2KCl ; Pbl2 + KI K2[PbI4] soluble 
Yellow precipitate reappears on dilution with water. Yellow precipitate of PbI2 does not dissolve in excess of
dilute solution of KI.
 Potassium chromate solution (in neutral, acetic acid or ammonia solution) : A yellow precipitate is
formed.
PbCl2 + K2CrO4  PbCrO4  + 2KCl
Yellow precipitate is soluble in sodium hydroxide and HNO3 (nitric acid).
2PbCrO4 + 2H+ 2Pb2+ + Cr2O72– + H2O
–
PbCrO4 + 4OH [Pb(OH)4]2– + CrO42–
ADVQUA -5
Both reversible reactions on buffering the solution with ammonia or acetic acid respectively, PbCrO4
reprecipitates.
 Ammonia solution : With ammonia solution, Pb2+ gives a white precipitate of lead hydroxide.
Pb2+ + 2NH4OH  Pb(OH)2  + 2NH4+
 Dilute H2SO4 : White precipitate is formed which is soluble in more concentrated ammonium acetate (6M)
solution or ammonium tartrate in the presence of ammonia.
PbCl2 + H2SO4  PbSO4  + 2HCl
PbSO4  + 4CH3COO–  [Pb(CH3COO)4]2– + SO42–
2. MERCURY(I) ION (Hg22+) :
 Dilute HCl solution : White precipitate is formed in cold solution.
Hg22+ + 2HCl  Hg2Cl2  (white) + 2H+
 Ammonia solution : A mixture of mercury metal (black precipitate) and basic mercury (II) amido chloride
(white precipitate) is formed.
2Hg2Cl2 + 4NH4OH  HgO.Hg(NH2 ) Cl  Hg  + 3NH4Cl + 3H2O



black
 Dissolution of white precipitate (Hg2Cl2) in aquaregia :

3Hg2Cl2 + 2HNO3 + 6HCl  6HgCl2 + 2NO+ 4H2O
 Potassium iodide solution : A green precipitate is formed.
Hg22+ + 2I–  Hg2I2 
Green precipitate in excess of reagent undergoes disproportionation reaction and a soluble [HgI4]2_ ions and
black mercury are formed.
Hg2I2  + 2I–  [HgI4]2– + Hg (finely divided)
Boiling the mercury (I) iodide precipitate with water, disproportionation takes place and a mixture of red
mercury (II) iodide precipitate and black mercury is formed.
Hg2I2  HgI2  + Hg
 Potassium chromate solution : A red crystalline precipitate is formed which turns black when solution of
sodium hydroxide is added.
Hg22+ + CrO42–  Hg2CrO4 ; Hg2CrO4 + 2OH–  Hg2O + CrO42– + H2O
 Potassium cyanide solution : A black precipitate of mercury is obtained
Hg22+ + 2CN–  Hg  + Hg(CN)2 (soluble).
3. SILVER ION (Ag+) :
 Dilute hydrochloric acid/soluble chlorides : White precipitate is formed.
Ag+ + HCl  AgCl  + H+
The precipitate obtained after filtration is soluble in concentrated HCl.
AgCl + Cl– [AgCl2]–
On dilution with water, the equilibrium shifts back to the left and the precipitate reappears. Dilute ammonia
solution dissolves the precipitate forming a soluble complex.
AgCl + 2NH3 [Ag (NH3)2 ]+ + Cl–
Dilute nitric acid or hydrochloric acid neutralizes the excess ammonia and the precipitate reappears because
the equilibrium is shifted backwards.
[Ag(NH3)2]Cl + 2HNO3  AgCl (white) + 2NH4NO3.
 Potassium iodide solution : A bright yellow precipitate is formed which is insoluble in dilute ammonia but
partially soluble in concentrated ammonia.
Ag+ + I–  AgI
The yellow precipitate is soluble in KCN and in Na2S2O3.
AgI + 2CN–  [Ag(CN)2]– + I– ; AgI + 2S2O32–  [Ag(S2O3)2]3– + I–
 Potassium chromate solution : Red precipitate is formed which is soluble in dilute HNO3 and in ammonia solution.
2Ag+ + CrO42–  Ag2CrO4 
2Ag2CrO4  + 2H+ 4Ag+ + Cr2O72– + H2O
2Ag2CrO4  + 4NH3  2[Ag(NH3)2]+ + CrO42–
ADVQUA -6
 Disodium hydrogen phosphate solution : In neutral solution a yellow precipitate is formed with the reagent.
3Ag+ + HPO42–  Ag3PO4 + H+
The yellow precipitate is soluble in nitric acid and ammonia solution.
 Ammonia solution : Brown precipitate is formed.

2Ag+ + 2NH3 + H2O  Ag2O + 2NH4+
Precipitate dissolves in ammonia.
Ag2O  + 4NH3 + H2O  2[Ag(NH3)2]+ + 2OH–
IInd Group (Hg2+, Pb2+, Bi3+, Cu2+, Cd2+, As3+, Sb3+, Sn2+)
On the basis of the solubility of the precipitates of the sulphides of II group cations in yellow ammonium
sulphide, they have been classified into two subgroups as given below :
A : HgS, PbS, CuS, Bi2S3, all black but CdS is yellow. All insoluble in yellow ammonium sulphide.
B : SnS2, As2S3 are yellow, Sb2S3 is orange & SnS is dark brown All soluble in yellow ammonium sulphide.
IIA Group (Hg2+, Pb2+, Bi3+, Cu2+, *Cd2+)
ADVQUA -7
1. MERCURY (II) ION (Hg2+) :
 Precipitation with H2S in acidic medium : Black precipitate is formed. Precipitate insoluble in water,
hot dilute HNO3 ,alkali hydroxides, or colourless ammonium sulphide.
H
Hg2+ + H2S 
 HgS  + 2H+
Na2S (2M) dissolves the precipitate forming soluble complex.
HgS + S2–  [HgS2]2–
Aqua regia dissolves the precipitate.
3 HgS + 6 HCl + 2HNO3  3 HgCl2 + 3S  + 2NO  + 4 H2O
Under these circumstance HgCl2 is undissociated. When solution is heated white precipitate of sulphur
dissolves forming H2SO4.
2 HNO3 + S   SO42– + 2 H+ + 2NO 
 Stannous chloride solution : When added in moderate amounts silky white precipitate is formed.
2HgCl2 + SnCl2  SnCl4 + Hg2Cl2 
If more reagent is added, Hg (I) chloride is reduced to black precipitate of mercury.
Hg2Cl2 + SnCl2  SnCl4 + 2Hg 
 Potassium iodide solution : On slow addition red precipitate is formed.
Hg2+ + 2I–  HgI2 
Precipitate dissolves in excess of KI forming colourless soluble complex.
HgI2 + 2I–  [HgI4]2–
 KCN does not have any effect.
 Copper chips , sheet or coin : A black precipitate of mercury is formed.
Hg2+ + Cu  Hg  + Cu2+
 Sodium hydroxide solution : When added in small quantity brownish–red precipitate of varying composition
is formed and in stoichiometric amounts precipitate turns to yellow when Hg (II) oxide is formed.
Hg2+ + 2OH–  HgO  + H2O
Precipitate 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 precipitate of mixed composition (Mercury (II) oxide + Mercury (II) amido
nitrate) is formed with metal nitrate.
2 Hg2+ + NO3– + 4NH3 + H2O  HgO.Hg (NH2)NO3  + 3 NH4+
 Cobalt (II) thiocyanate test : When reagent is added to an aqueous solution of Hg2+ ions and the walls
of the test tube is stirred with a glass rod, deep–blue crystalline precipitate is formed.
Hg2+ + Co2+ + 4 SCN–  Co+2 [Hg(SCN)4]–2 or Hg [Co(NCS)4] 
 In place of Cobalt (II) thiocyanate, Co(CH3COO)2 and NH4SCN can be added to the aqueous solution
of Hg2+ ions.
2. COPPER ION (Cu2+) :

 Precipitation with H2S in acidic medium : Black precipitate is formed.
H
Cu2+ + H2S   CuS  + 2 H+
Precipitate is insoluble in boiling dilute (M) H2SO4 (distinction from cadmium), in NaOH, Na2S and (NH4)2S.
Precipitate dissolves in hot concentrated HNO3
3 CuS + 8HNO3  3Cu(NO3)2 (blue) + 2NO + 4H2O + 3S
When boiled for longer S is oxidised to H2SO4 and a clear solution of Cu(NO3)2 is obtained.
 KCN dissolves the precipitate forming a clear solution.
2 CuS  + 8 CN–  2 [Cu(CN)4]3– + S22– (disulphide ion)
 Ammonia solution : When added sparingly a blue precipitate of basic salt (basic copper sulphate) is
formed with CuSO4.
2Cu2+ + SO42– + 2 NH3 + 2 H2O  Cu(OH)2 .CuSO4  + 2NH4+
It is soluble in excess of reagent forming a deep blue colouration.
Cu(OH)2 .CuSO4 + 8NH3  2 [Cu(NH3)4]2+ + SO42– + 2 OH–
ADVQUA -8
 Sodium hydroxide in cold solution : A blue precipitate is formed.
Cu2+ + 2 OH –  Cu (OH)2 
Heat
Cu(OH)2   CuO(black) + H2O
Potassium iodide : It gives a white precipitate of Cu(I) iodide but the solution is intensely brown because
of the formation of tri–iodide ions (or iodine).
2 Cu2+ + 5 I–  Cu2I2  + I3–
The solution becomes colourless and a white precipitate is visible when excess of sodium thiosulphate
solution is added.
I3– + 2 S2O32–  3 I– + S4O62–
 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 precipitate.
2Cu2+ + K4Fe(CN)6  Cu2[Fe(CN)6]  + 4K+
 2 [Fe(CN)6]3– + 3 Cu2+  Cu3 [Fe(CN)6]2  (green)
(vi) Potassium cyanide : When added sparingly forms first a yellow precipitate.
Cu2+ + 2CN–  Cu(CN)2 (yellow)
Precipitate quickly decomposes into CuCN and cyanogen.
2 Cu(CN)2   2CuCN (white) + (CN)2  (highly poisonous)
Excess reagent dissolves the precipitate forming a colourless soluble complex.
CuCN  + 3 CN–  [Cu(CN)4]3–
Complex is so stable that H2S cannot precipitate Cu (I) sulphide (distinction from cadmium).
 Potassium thiocyanate solution : The Cu+2 ions solution initially gives a black precipitate which then
slowly decomposes to give white precipitate of Cu(I) thiocyanate.
Cu2+ + 2 SCN–  Cu(SCN)2 
2 Cu(SCN)2   2 CuSCN  + (SCN)2 
 Cu (II) thiocyanate can be immediately converted into Cu(I) thiocyanate by adding a suitable reducing
agent like saturated solution of sulphur dioxide.
2 Cu(SCN)2  + SO2 + 2 H2O  2 CuSCN  + 2 SCN– + SO42– + 4H+
Excess reagent dissolves the precipitate forming a colourless soluble complex.
Cu(SCN) + 3SCN–  [Cu(SCN)4]3–
3. BISMUTH ION (Bi3+) :

 Precipitation with H2S in acidic medium : Black precipitate is formed which is insoluble in cold dilute
HNO3 and yellow ammonium sulphide.

H
2Bi3+ + 3H2S   Bi2 S3  (black) + 6H+
Bi2 S3 + 8HNO3  2Bi (NO3)3 + 2NO + 3S + 4H2O
 Bi2S3 + 6 HCl (boiling concentrated)  2 Bi3+ + 6 Cl– + 3 H2S
 Sodium hydroxide : White precipitate is formed with the reagent.
Bi3+ + 3 OH–  Bi(OH)3
Very slightly soluble in excess reagent in cold solution but soluble in acids.
Bi(OH)3 + 3H+  Bi3+ + H2O
 Precipitate on boiling loses water and turns yellowish white which is oxidised to BiO3– by H2O2.
Bi(OH)3  BiO.OH + H2O
BiO.OH + H2O2  BiO3– + H+ + H2O
ADVQUA -9
 Dilution with water : Solution of bismuth salts gives white precipitate when water is added in larger
quantity.
Bi3+ + NO3– + H2O  BiO(NO3)  + 2H+
Bi3+ + Cl– + H2O  BiOCl  (bismuth oxychloride or bismuthyl chloride) + 2H+
Soluble in mineral acids (dilute) but insoluble in tartaric acid (distinction from antimony) and in alkali hydroxide
(distinction from tin).
 Potassium iodide : When the reagent is added dropwise to a solution containing Bi3+ ions, a black
precipitate is formed.
Bi3+ + 3–  Bi3 
The precipitate dissolves in excess KI forming orange coloured soluble complex.
Bi3 + – [Bi4]–
On dilution the reaction is reversed and black BiI3 is reprecipitated.
 On heating with water black precipitate of BiI3 turns orange.
BiI3  + H2O  BiOI  + 2H+ + 2I–
4. CADMIUM ION (Cd2+) (*Not in JEE advance syllabus) :

 Precipitation with H2S in acidic medium : Yellow precipitate is formed which dissolves in hot dilute
HNO3 .

H
Cd2+ + H2S 
 CdS  + 2H+
CdS + 8HNO3  3Cd (NO3)2 + 4H2O + 2NO + 3S
 Precipitate does not dissolve in KCN.
 Ammonia solution (Dropwise addition) : Ammonium hydroxide first gives white precipitate of Cd(OH)2
which gets dissolve in excess of reagent forming a soluble complex.
Cd2+ + 2 NH3 + 2 H2O Cd(OH)2  + 2 NH4+
Cd(OH)2 + 4 NH3  [Cd(NH3)4]2+ + 2 OH– .
 Potassium cyanide : Initially a white precipitate of Cd(CN)2 is formed which in excess of reagent dissolves
forming a soluble complex.
Cd2+ + 2 CN–  Cd(CN)2 
Cd(CN)2  + 2 CN–  [Cd(CN)4]2–
The colourless soluble complex is not too stable, therefore, reacts with H2S gas forming a yellow precipitate
of CdS.
[Cd(CN)4]2– + H2S  CdS  + 2 H+ + 4 CN–
 KI forms no precipitate (distinction from Copper)
5. LEAD ION (Pb2+) :

 Precipitation with H2S in acidic medium : Black precipitate is formed which is soluble in hot dilute
HNO3 .
Pb2+ + H2S  PbS  (black) + 2H+
3PbS + 8HNO3  3Pb(NO3)2 + 2NO + 4H2O + 3S
 Dilute H2SO4 : White precipitate is formed which is soluble in ammonium acetate.
Pb(NO3)2 + H2SO4  PbSO4  (white) + 2HNO3
PbSO4 + 2CH3 COONH4  (CH3COO)2 Pb + (NH4)2SO4(NH4)2[Pb(CH3 COO)4]
 Potassium iodide : Yellow precipitate is formed which is soluble in excess more concentrated (6M)
solution of the reagent. Yellow precipitate of PbI2 is moderately soluble in boiling water to give a colourless
solution.
(CH3COO)2 Pb + 2KI  2CH3 COOK + PbI2 yellow
 Potassium chromate : Yellow precipitate is formed.

(CH3COO)2 Pb + K2CrO4  2CH3 COOK + PbCrO4 (yellow)
ADVQUA - 10
IIB Group (As3+, Sb3+, Sn2+, Sn4+) (Not in JEE advance syllabus)
1. ARSENIC ION (As3+) :

 Precipitation with H2S in acidic medium : Yellow precipitate is formed which is soluble in warm
concentrated nitric acid, sodiumhydroxide solution and yellow ammonium sulphide.

H
2As3+ + 3H2S 
 As2 S3  + 6H+
3 As2S3  + 28 HNO3 + 4 H2O  6 AsO43– + 9 SO42– + 36 H+ + 28 NO 
As2S3  + 6OH–  AsO33– + AsS33– + 3 H2O
As2S3  +4 S22–  2 AsS43– + S32–
 Silver nitrate : Yellow precipitate of silver arsenite in neutral solution is formed with AsO33– ions.
AsO33– + 3 Ag+  Ag3AsO3 (yellow)
AsO43– + 3 Ag  Ag3AsO4  (brownish red)
The precipitate is soluble in both nitric acid and ammonia.
 Marsh's test : This test is based on the fact that all soluble compounds of arsenic are reduced by 'nascent'
hydrogen in acid solution to arsine (AsH3), a colourless, extremely poisonous gas with a garlic-like odour. If
the gas, mixed with hydrogen, is passed through a heated glass tube, it is decomposed into hydrogen and
metallic arsenic, which is deposited as a brownish-black 'mirror' just beyond the heated part of the tube.
Zn + H2SO4  ZnSO4 + 2 [H] ; AsCl3 + 3 [H]  AsH3  + 3 [Cl]
Heat
AsO43– + 4 Zn + 11 H+  AsH3  + 4 Zn2+ + 4H2O ; AsH3    As  + 3/2 H2 
2. ANTIMONY ION (Sb3+) :

 Precipitation with H2S in acidic medium : A orange red precipitate is formed from mildly acidic solutions.
H
Sb3+ + 3H2S  Sb2S3  (orange) + 6H+
Precipitate is soluble in warm concentrated HCl, in ammonium polysulphide and in alkali hydroxides.
Sb2S3  + 6 HCl  2 Sb3+ + 6 Cl– + 3 H2S 
Sb2S3  + 4 S22–  2 SbS43– + S32–
2Sb2S3  + 4 OH–  SbO2– + 3 SbS2– + 2 H2O
ADVQUA - 11
 Dilution with water : When water is poured in a solution of soluble SbCl3, a white precipitate of antimonyl
chloride (SbOCl) is formed, soluble in HCl. With a large excess of water, the hydrated oxide Sb2O3.xH2O is
produced.
SbCl3 + H2O  SbOCl + 2 HCl
 SbO+Cl– is soluble in tartaric acid but BiO+Cl– is insoluble in tartaric acid.

 Sodium hydroxide or Ammonia solution : White precipitate of hydrate of antimony (III) oxide Sb2O3.xH2O
is soluble in concentrated (5M) solution of caustic alkalies forming antimonites.
2 Sb3+ + 6 OH–  Sb2O3  + 3 H2O ; Sb2O3 + 2 OH–  2 SbO2– + H2O
 Potassium iodide solution : Yellow colouration is obtained owing to the formation of a complex salt.
Sb3+ + 6 I–  [SbI6]3–
 Reduction with zinc or tin : Sb3+ ions give black precipitate of metal.
2 Sb3+ + 3 Zn  2 Sb  + 3 Zn2+ ; 2 Sb3+ + 3 Sn  2 Sb  + 3 Sn2+
3. TIN (II) ION (Sn2+) AND TIN (IV) ION (Sn4+) :

 Precipitation with H2S in acidic medium :
Brown precipitate is obtained with Sn2+ which is soluble in concentrated HCl and yellow ammonium sulphide
forming thiostannate but not in colourless ammonium sulphide.
Sn2+ + H2S  SnS (brown) ; SnS  + S22–  SnS32– (thiostannate)
Sn4+ + 2H2S  SnS2  (yellow) + 4 H+
Precipitate is soluble in concentrated HCl (difference from As3+ and Hg2+) and in alkali hydroxide, and also in
ammonium sulphide and yellow ammonium sulphide.
 Sodium hydroxide solution : White precipitate of Sn(OH)2 is formed which is soluble in excess of
reagent.
Sn2+ + 2OH– Sn(OH)2  ; Sn(OH)2  + 2OH– [Sn(OH)4]2–
 With ammonia solution, white tin (II) hydroxide is precipitated, which cannot be dissolved in excess
ammonia.
 Reduction of stannic chloride to stannous chloride by iron filling or granulated zinc :
SnCl4 + Zn  SnCl2 + ZnCl2
 Mercuric chloride solution :

SnCl2 + 2HgCl2  Hg2Cl2  (silky white) + SnCl4
SnCl2 + Hg2Cl2  2Hg black or grey+ SnCl4
 HNO3 is not used because it acts as an oxidising agent and in solution it oxidises H2S to S according to the
following reaction.
H2S + [O]  H2O + S  (Yellow)
ADVQUA - 12
IIIrd Group (Al3+, Cr3+, Fe3+)
 Concentrated HNO3 is added to oxidise Fe2+ to Fe3+ if present.
 Solid NH4Cl should be added in excess other wise cations like Zn, Mn, Mg may be precipitated here.
To much excess of NH4Cl should be avoided other wise Cr is not precipitated and Al may form a
colloidal solution.
1. ALUMINIUM ION (Al3+) :

 Precipitation with NH4OH in presence of NH4Cl : White gelatinous precipitate is formed which is
slightly soluble in excess reagent. The solubility is decreased in the presence of ammonium salt. A small
portion of the precipitate passes into the solution as colloidal Al(OH)3 (Aluminium hydroxide sol), the sol is
coagulated on boiling the solution or upon the addition of soluble salt yielding a precipitate of Al(OH)3, known
as Al(OH)3 gel. For complete precipitation, add ammonia solution in excess and the mixture is boiled until,
the solution has a slight odour of NH3 .
NH 4 Cl
Al3+ + 3NH4OH    Al(OH)3  + 3NH4+
 Sodium hydroxide : A solution containing Al +3 ions give a white precipitate with the reagent.
Al3+ + 3OH–  Al(OH)3 
White precipitate dissolves in excess sodium hydroxide according to following reaction.
Al(OH)3 + OH– [Al(OH)4]–
The reaction is reversible and any reagent, which will reduce the hydroxyl ion concentration sufficiently
should cause the reaction to proceed from right to left with the consequent precipitation of aluminium hydroxide.
This may be effected with a solution of ammonium chloride (the hydroxyl ion concentration is reduced owing
to the formation of the weak base ammonia , which can be readily removed as ammonia gas by heating) or
by the addition of acid; in the latter case, a large excess of acid causes the precipitated hydroxide to
redissolve.
ADVQUA - 13
[Al(OH)4]– + NH4+  Al(OH)3  + NH3 + H2O
[Al(OH)4]– + H+ Al(OH)3  + H2O
Al(OH)3 + 3H+ (excess) Al3+ + 3 H2O
 Dry test : Aluminium compounds when heated with sodium carbonate upon charcoal gives a white infusible
solid, which glows when hot. If the residue is moistened with a little cobalt nitrate solution and again heated,
a blue infusible mass is obtained.
2 Al2O3 + 2 Co2+ + 4 NO3–  2 CoAl2O4 (thenard blue) + 4NO2  + O2 
Use of excess cobalt nitrate solution should be avoided since this will produce black cobalt oxide (Co3O4)
upon ignition, which will mask the blue colour.
2. IRON ION (Fe3+) :

 Precipitation with NH4OH in presence of NH4Cl : Gelatinous reddish brown precipitate is formed which
is insoluble in excess reagent but soluble in acids.
NH4 Cl
Fe3+ + 3NH4OH   Fe(OH)3  + 3NH4+
 Precipitation of iron(II) hydroxide occurs with ammonia solution. If larger amounts of ammonium ions
are present, the dissociation of NH4OH is suppressed and the concentration of OH– ions is lowered
to such an extent that solubility product of iron (II) hydroxide, Fe(OH)2 is not attained and precipitation
does not occur.
 Sodium hydroxide solution : Reddish brown precipitate is formed insoluble in excess reagent (distinction
from aluminium and chromium).
Fe3+ + 3OH–  Fe(OH)3 
 H2S gas in acidic solution : Fe3+ reduces to Fe2+ .
2 Fe3+ + H2S  2 Fe2+ + 2H+ + S  (milky-white)
If a neutral solution of iron (III) chloride is added to a freshly prepared saturated solution of H2S , bluish
colouration appears first, followed by precipitation of sulphur. The blue colour is due to a colloidal solution of
sulphur of extremely small particle size.
 This reaction can be used to test the freshness of H2S solution.
 Ammonium sulphide solution : Black precipitate consisting of Fe(II) sulphide and sulphur is formed.
2 Fe3+ + 3 S2–  2 FeS + S 
In HCl, the black precipitate of Fe(II) sulphide dissolves and white precipitate of sulphur becomes visible.
FeS  + 2H+  H2S  + Fe2+
 The damp iron (II) sulphide precipitate, when exposed to air, is slowly oxidised to brown iron(III)
hydroxide.
4 FeS  + 6 H2O + 3 O2  4 Fe(OH)3  + 4S 
 From alkaline solutions of ammonium sulphide, black iron(III) sulphide is obtained.
2 Fe3+ + 3S2–  Fe2S3 
On acidification with hydrochloric acid, iron (III) ions are reduced to iron (II) ions and sulphur is formed.
Fe2S3  + 4H+  2 Fe2+ + 2 H2S  + S 
 Potassium ferrocyanide (Potassium hexacyanidoferrate(II) ) : Intense blue precipitate (Prussian
blue) of iron(III) hexacyanidoferrate(II) is formed.
4Fe3+ + 3 [Fe(CN)6]4–  Fe4[Fe(CN)6]3 
This is insoluble in dilute acids but decomposes in concentrated HCl. A large excess of the reagent dissolves
it partly or entirely, when an intense blue solution is obtained. Sodium hydroxide turns the precipitate red.
Fe4 [Fe(CN)6]3  + 12 OH–  Fe(OH)3  + 3[Fe(CN)6]4–
 Oxalic acid also dissolves Prussian blue forming a blue-solution.
ADVQUA - 14
Important :
If iron(III) chloride is added to an excess of potassium hexacyanidoferrate (II), a product with the composition
of K Fe[Fe(CN)6] is formed. This tends to form colloidal solutions ("soluble Prussian blue") and can not be
filtered.
 Potassium ferricyanide (Potassium hexacyanidoferrate(III)) : A brown colouration is formed.

Fe3+ + [Fe(CN)6]3–  Fe[Fe(CN)6]
 Upon adding hydrogen peroxide or some tin(II) chloride solution, the hexacyanidoferrate(III) part of
the compound is reduced and Prussian blue is precipitated.
 Fe2+ gives dark blue precipitate with potassium ferricyanide. First hexacyanidoferrate(III) ions oxidise
iron(II) to iron(III), when hexacyanidoferrate(II) is formed.
Fe2+ + [Fe(CN)6]3–  Fe3+ + [Fe(CN)6]4–
and these ions combine to form a precipitate called Turnbull's blue.
4 Fe3+ + 3 [Fe(CN)6]4–  Fe4[Fe(CN)6]3
Note : Composition of this precipitate is identical to that of Prussian blue. Earlier the composition suggested was
Fe3[Fe(CN)6]2, hence different name.
3Fe2+ + 2K3 [Fe(CN)6]  Fe3 [Fe (CN)6]2 (ferrous ferric cyanide) + 6K+
Turnbull's blue
 Fe(II) in ammonical solution gives red solution with DMG– colouration fades on standing due to the
oxidation of the iron(II) complex. Fe (III) does not give such complex.
 In complete absence of air, Fe(II) ions produces white precipitate with potassium hexacyanidoferrate(II).
Fe2+ + 2K+ + [Fe(CN)6]4–  K2Fe [Fe(CN)6] 
Under ordinary atmospheric conditions a pale–blue precipitate is formed.
 Potassium thiocyanate (Potassium sulphocyanide) : In slightly acidic medium, a deep red colouration
is produced due to the formation of a non-dissociated iron(III) thiocyanate complex.
Fe3+ + 3 SCN–  Fe(SCN)3
This neutral molecule can be extracted by ether or amyl alcohol.
 With pure Fe(II) ions no colouration is obtained.
 Fluorides and Hg(II) ions bleach the red colour.

Fe(SCN)3 + 6F–  [FeF6]3– + 3 SCN–
2 Fe(SCN)3 + 3Hg2+  2 Fe3+ + 3 Hg (SCN)2
 Sodium acetate solution : A deep red colouration is obtained owing to the formation of
[Fe3(OH)2(CH3COO)6]+. The reaction becomes complete only if the strong acid which is formed, is removed
by the addition of an excess of the reagent, which acts as a buffer.
3 Fe3+ + 6 CH3COO– + 2 H2O [Fe3(OH)2(CH3COO)6]+ + 2H+
This deep red coloured solution on dilution with water and boiling gives reddish brown precipitate of basic
ferric acetate.
[Fe3(OH)2(CH3COO)6]+ + 4 H2O  3 Fe(OH)2CH3COO  + 3 CH3COOH + H+
The excess of acetate ion acts as a buffer and the reaction goes to completion.
ADVQUA - 15
 Disodium hydrogen phosphate solution : A yellowish–white precipitate is formed.

Fe3+ + HPO42–   FePO4  + H+
The reaction is reversible, because a strong acid is formed which dissolves the precipitate. It is advisable to
add small amounts of sodium acetate, which acts as a buffer.
3. CHROMIUM ION (Cr3+) :

 Precipitation with NH4OH in presence of NH4Cl : A grey-green to green gelatinous precipitate is
formed.
Cr3+ + 3 NH3 + 3 H2O  Cr(OH)3 + 3 NH4+
Precipitate is slightly soluble in excess of reagent in cold forming pink or violet coloured solution. On boiling
the solution, chromium hydroxide is reprecipitated.
Cr(OH)3  + 6 NH3   [Cr(NH3)6]3+ + 3OH–
 Sodium hydroxide solution : A green precipitate is formed.
Cr3+ + 3 OH–   Cr(OH)3 
The reaction is reversible. On addition of acids the precipitate dissolves. In excess of reagent the precipitate
dissolves readily forming chromites, the solution is green. The reaction is reversible ; on (slight) acidification
and also on boiling green precipitate of chromium(III) hydroxide is obtained.
Cr(OH)3 + OH– [Cr(OH)4]–
2NaOH + Br2  NaOBr + NaBr + H2O ; NaOBr  NaBr + [O]
2Cr(OH)3 + 4NaOH + 3[O]  2Na2 CrO4 + 5H2O.
The yellow solution of Na2CrO4 gave the following reactions with lead acetate, barium chloride and silver
nitrate solutions.
(a) Lead acetate solution : Yellow precipitate is formed.
CH3 OOH
CrO42– + Pb2+   PbCrO4 
(b) Barium chloride solution : Yellow precipitate is formed owing to the formation of barium chromate
which is insoluble in acetic acid.
CrO42– + Ba2+  BaCrO4 
(c) Silver nitrate solution : Red/Brick red precipitate is formed owing to the formation of silver chromate
which is soluble in ammonia solution and its acidified solution turns to orange because of the formation of
dichromate.
Na2CrO4 + 2AgNO3  Ag2CrO4  + 2NaNO3 .
 Acidified H2O2 test : On acidifying the yellow solution with dilute sulphuric acid and adding few drops of
ether or amyl alcohol to the mixture and finally adding some hydrogen peroxide, blue colouration is formed
which can be extracted into the organic layer by gently shaking.
Amyl alcohol
Na2CrO4 + H2SO4  Na2SO4 + H2CrO4 ; H2CrO4 + 2H2O2     CrO5 (blue colouration) + H2O
Blue colouration fades slowly due to the decomposition of perchromic acid (or chromium peroxide ) with the
liberation of oxygen.
4CrO5 + 6H2SO4  2Cr2 (SO4)3 + 7O2 + 6H2O
ADVQUA - 16
IVth GROUP (Zn2+, Mn2+, Ni2+, Co2+) :
1. MANGANESE ION (Mn2+) :

 Precipitation with H2S in presence of NH4OH + NH4Cl : A buff coloured (light pink) precipitate is
formed.
Mn2+ + S2–  MnS 
It is readily soluble in mineral acids (distinction with Ni and Co) and even in acetic acid (distinction with Ni,
Co and Zn).
MnS  + 2H+  Mn2+ + H2S ; MnS  + 2 CH3COOH  Mn2+ + H2S  + 2 CH3COO–
 Ammonia solution : Partial precipitation of white manganese(II) hydroxide takes place.
Mn2+ + 2 NH3 + 2H2O Mn(OH)2  + 2 NH4+
The precipitate is soluble in ammonium salts when the reaction proceeds towards left.
 Sodium hydroxide solution : Initially white precipitate of Mn(OH)2 is formed which is insoluble in
excess reagent and rapidly oxidised on exposure to air, becoming brown.
Mn2+ + 2 OH–  Mn(OH)2 
Mn(OH)2  + O2  2 MnO(OH)2 (hydrated manganese dioxide).
 With sodium hydroxide and bromine water initially a white precipitate is formed which immediately
turns to black owing to the formation of MnO2 .
Mn(OH)2  + Br2 + 2NaOH  MnO2(black) + 2NaBr + 2H2O
 Mn(OH)2  + H2O2  MnO (OH)2 (brown) + H2O
ADVQUA - 17
 Lead dioxide(PbO2) and concentrated nitric acid : On boiling a dilute solution of manganese(II) ions
with lead dioxide and a little concentrated nitric acid and allowing the suspended solid containing unattacked
lead dioxide to settle, the supernatant liquid acquired a violet-red (or purple) colour due to permanganic acid.
5 PbO2 + 2 Mn2+ + 4H+  2 MnO4– + 5Pb2+ + 2 H2O
 Sodium bismuthate (NaBiO3) solution : When sodium bismuthate (NaBiO3) is added to a cold solution
of manganese(II) ions in dilute nitric acid or in dilute sulphuric acid and the mixture stirred and then excess
reagent filtered off, a violet–red (or purple) solution of permanganate is produced.
2 Mn2+ + 5 NaBiO3 + 14 H+  2MnO4– + 5 Bi3+ + 5 Na+ + 7 H2O
 
2Mn(NO3)2 + 2Pb3O4 + 26HNO3  2HMnO4 (violet–red/purple) + 15Pb(NO3)2 + 12H2O
2. ZINC ION (Zn2+) :

 Precipitation with H2S in presence of NH4OH + NH4Cl : A white precipitate is formed. In neutral
solutions, precipitation is partial as H+ ions concentration produced depressed the ionisation of H2S .
Zn2+ + H2S ZnS + 2H+
The precipitate is soluble in dilute HCl.
ZnS + 2H+  Zn2+ + H2S 
 Sodium hydroxide solution : A white gelatinous precipitate is formed.
Zn2+ + 2 OH–  Zn(OH)2 
The precipitate is soluble in acids as well as in excess of the reagent.
Zn(OH)2 + 2 H+  Zn2+ + 2 H2O
Zn(OH)2 + 2 OH–  [Zn(OH)4]2–
 Thus, zinc hydroxide is amphoteric in nature.
 [Zn(OH)4]2– + S2–  ZnS  (white) + 4 OH–
 Ammonia solution : A white gelatinous precipitate is formed which is readily soluble in excess of the
reagent and in solutions of ammonium salts forming the tetraamminezinc(II).
Non–precipitation of Zn(OH)2 by ammonia solution in the presence of NH4Cl is due to the lowering of OH– ion
concentration to such a value that the Ksp of Zn(OH)2 is not attained.
Zn2+ + 2 NH3 + 2 H2O Zn(OH)2  + 2 NH4+
Zn(OH)2  + 4 NH3 [Zn(NH3)4]2+ + 2 OH–
 Potassium ferrocyanide (Potassium hexacyanidoferrate(II)) solution : A white precipitate of variable

composition is formed. If excess reagent is added, the composition of precipitate is K2Zn3[Fe(CN)6]2 .
3 Zn2+ + 2 K+ + 2 [Fe(CN)6]4–  K2Zn3[Fe(CN)6]2 
The precipitate is insoluble in dilute acids, but dissolves in sodium hydroxide readily.
K2Zn3 [Fe(CN)6]2 + 12 OH–  2 [Fe(CN)6]4– + 3 [Zn(OH)4]2–
This reaction can be used to distinguish zinc from aluminium.
3. COBALT ION (Co2+) : (Not in JEE advance syllabus)

 Precipitation with H2S in presence of NH4OH + NH4Cl : A black precipitate is formed. The black
precipitate of CoS is insoluble in dilute HCl or acetic acid but hot concentrated HNO3 or aquaregia dissolves
it and white sulphur remains. On longer heating the mixture becomes clear as because sulphur is oxidised
to sulphate.
2[Co(NH3)6]3+ + 3S2–  2CoS  + 12NH3 + S
NH 4OH
or CoCl2 + H2S   CoS  + 2HCl
3 CoS + 2 HNO3 + 6 H  3 Co2+ + 3 S  + 2NO  + 4 H2O
+
2CoS + 6HCl + 2HNO3  3CoCl2 + 2NO + 3S + 4H2O

 Solution on evaporation to dryness gives blue residue (CoCl2) which turns pink on adding water.
ADVQUA - 18
 Potassium nitrite solution : A yellow precipitate is formed from neutral solution of cobalt(II) ions.
CoCl2 + 7KNO2 + 2CH3COOH  K3[Co(NO2)6]  + H2O + 2KCl + 2CH3COOK + NO 
or Co2+ + 7NO2– + 2H+ + 3K+  K3[Co(NO2)6]  + NO  + H2O.
 Ammonium thiocyanate solution : A neutral or acid solution of cobalt(II) gives a blue colouration in amyl
alcohol or ether layer when a few crystals of ammonium thiocyanate are added.
Co2+ + 4 SCN–  [Co(SCN)4]2–
 In amyl alcohol or ether, the free acid H2[Co(SCN)4] is formed and dissolved by the organic solvent
(distinction from nickel)
 Sodium bicarbonate and bromine water test : To the test solution sodium bicarbonate is added in
excess followed by the bromine water. The mixture is slightly heated, the solution turns apple green.
CoCl2 + 2NaHCO3  Co(HCO3)2 + 2NaCl
Co(HCO3)2 + 4 NaHCO3  Na4 [Co(CO3)3] + 3H2O + 3CO2
Br2 + H2O  2HBr + [O]
2Na4 [Co(CO3)3] + H2O + [O]  2Na3 [Co(CO3)3 ] (green) + 2NaOH.
 Green solution of sodium cobalticarbonate is obtained.
 Sodium hydroxide solution : Cobalt(II) nitrate in cold gives a blue basic salt.
Co2+ + OH– + NO3–  Co(OH)NO3 
Upon warming with excess alkali, the basic salt is converted into a pink precipitate of Co(II) hydroxide.
Co(OH)NO3  + OH–  Co(OH)2  + NO3–
4. NICKEL ION (Ni2+) : (Not in JEE advance syllabus)
 Precipitation with H2S in presence of NH4OH + NH4Cl :
A black precipitate is formed which is insoluble in cold dilute HCl and CH3COOH but dissolves in hot
concentrated HNO3 and in aquaregia.
NH 4OH
NiCl2 + H2S  
 NiS  (Black) + 2HCl
3 NiS  + 2 HNO3 + 6 H+  3 Ni2+ + 2 NO  + 3 S  + 4 H2O
NiS + HNO3 + 3HCl  Ni2+ + S  + NOCl  + 2Cl– + 2H2O.
 Solution on evaporation to dryness gives yellow residue (NiCl2) which turns green on adding water.
 Dimethylglyoxime reagent : A red precipitate is obtained from the solution just made alkaline or acid
solutions buffered with sodium acetate.
NiCl2+ 2NH4OH + 2CH3 – C = NOH  (C4H7N2O2)2Ni + 2NH4Cl + 2H2O or [Ni(amg)2] 
(red)
 Fe(II) ions give red colouration, bismuth gives yellow precipitate and cobalt gives brown colouration
with DMG in ammonical solutions.
 Ni2+ gives black precipitate (Ni2O3) with sodium bicarbonate and bromine water on heating where as
Co2+ gives green coloured solution, this is the point of difference.
NiCl2 + 2NaHCO3  NiCO3 + 2NaCl + H2O ; 2NiCO3 + [O]  Ni2O3  (black) + 2CO2
ADVQUA - 19
Vth Group (Ba2+, Sr2+, Ca2+) :

IV Group filtrate  Boil off H2S then add (NH4)2CO3 (aq), NH4OH & NH4Cl (s)
White precipitate Filtrate,

(BaCO3, SrCO3 or CaCO3). move for VI group.

Dissolve in CH3COOH and divide into three parts
and test in the sequence given below.
I part + K2CrO4. II Part + (NH4)2SO4. III part + (NH4)2C2O4.

  
Yellow precipitate White precipitate White precipitate
(BaCrO4 insoluble in CH3COOH). (SrSO4). (CaC2 O4 ).
1.BARIUM ION ( Ba2+) :
 Precipitation with (NH4)2CO3 in presence of NH4OH + NH4Cl : A white precipitate is formed which is
soluble in acetic acid and dilute mineral acids
BaCl2 + (NH4)2CO3  BaCO3 + 2NH4Cl
BaCO3 + 2CH3COOH  Ba (CH3COO)2 + H2O + CO2
 Potassium chromate test : A yellow precipitate is formed, practically insoluble in water
Ba(CH3COO)2 + K2CrO4  BaCrO4  + 2CH3COOK
 Precipitate is insoluble in dilute acetic acid (distinction from strontium and calcium) but readily
soluble in mineral acids.
 Addition of acid to K2CrO4 changes the yellow colour of the solution to reddish–orange due to the
formation of dichromate.
2 H+ + 2 CrO42– Cr2O72– + H2O
 The solubility products of SrCrO4 and CaCrO4 are much larger than for BaCrO4 and hence they
require a larger CrO42– ion concentration to precipitate them. The addition of acetic acid to the
K2CrO4 solution lowers the CrO42– ion concentration sufficiently to prevent the precipitation of SrCrO4
and CaCrO4 but it is maintained high enough to precipitate BaCrO4.
2. STRONTIUM ION (Sr2+) :
 Precipitation with (NH4)2 CO3 in presence of NH4OH + NH4Cl :
A white precipitate is formed which is soluble in acetic acid.
SrCl2 + (NH4)2CO3  SrCO3 + 2NH4Cl
SrCO3 + 2CH3COOH  Sr(CH3COO)2 + H2O + CO2
 Ammonium sulphate solution : A white precipitate is formed which is slightly soluble in boiling
hydrochloric acid.
Sr(CH3COO)2 + (NH4)2SO4  SrSO4  + 2CH3COONH4
 The solubility of the precipitate in water is low but not negligible.
 The precipitate is insoluble in ammonium sulphate solution even on boiling (Distinction from calcium–
forms a soluble complex (NH4)2[Ca(SO4)2]) and slightly soluble in boiling HCl.
 It is almost completely converted into the corresponding carbonates by boiling with a concentrated
solution of sodium carbonate.
SrSO4 + CO32– SrCO3  + SO42–
ADVQUA - 20
3. CALCIUM ION (Ca2+) :
 Precipitation with (NH4)2CO3 in presence of NH4OH + NH4Cl : A white precipitate is formed. The
precipitate is soluble in water which contains excess carbonic acid (e.g freshly prepared soda water) because
of the formation of soluble hydrogen carbonate. On boiling precipitate reappears again, as CO2 is removed.
The precipitate is also soluble in acetic acid.
CaCl2 + (NH4)2CO3  CaCO3  + 2NH4Cl
CaCO3 + 2CH3COOH  Ca(CH3COO)2 + H2O + CO2
 Ammonium oxalate solution (concentrated) : A white precipitate is formed. The precipitation is facilitated
by making the solution alkaline. The precipitate is practically insoluble in water (Ksp = 2.6 × 10–9), insoluble
in acetic acid but readily soluble in mineral acids.
Ca(CH3COO)2 + (NH4)2C2O4  CaC2O4 + 2CH3COONH4
 Potassium hexacyanidoferrate (II) solution : White precipitate of a mixed salt is produced.
Ca2+ + 2 K+ + [Fe(CN)6]4–  K2Ca[Fe(CN)6] 
In presence of ammonium chloride the test is more sensitive and in this case K+ is replaced by NH4+ ions in
the precipitate.
 This test can be used to distinguish , calcium from strontium, barium and magnesium ions.
 The confirmatory test for the basic radicals of (V) group have to be done in the order of Ba2+, Sr2+
then Ca2+ (i.e BSC) because Ba2+ give positive test with all the reagents used in the confirmatory
test of these group radicals, K2CrO4, (NH4)2 SO4 & (NH4)2 C2O4. So performs the test for Sr2+ with
(NH4)2SO4 only when Ba2+ is absent. Similarly Sr2+ gives the test with both (NH4)2SO4 and (NH4)2C2O4.
So proceeds with Ca2+ only when Sr2+ is absent otherwise it will respond to ammonium oxalate test.
Vth GROUP :
1. MAGNESIUM ION (Mg2+) :
 Disodium hydrogen phosphate solution : To the filtrate of V group or Mg2+ ions solution add 1 ml
(NH4)2C2O4 solution and heat if white precipitate is formed then filter it. Now to filtrate add a solution of
disodium hydrogen phosphate. A white crystalline precipitate is formed in the presence of NH4Cl (prevent
precipitation of Mg(OH)2) and ammonia solution.
Mg2+ + NH3 + HPO42–  Mg(NH4)PO4 
 Precipitate is sparingly soluble in water, soluble in acetic acid and in mineral acids.
 The precipitate separates slowly from dilute solutions because of its tendency to form supersaturated
solution. This may be overcome by cooling and by rubbing the test tube beneath the surface of the
liquid with a glass rod.
A white flocculent precipitate of magnesium hydrogen phosphate is obtained in neutral solutions.
Mg2+ + HPO42–  MgHPO4 
 Ammonium phosphate can also be used.
 Ammonia solution : A white gelatinous precipitate is formed.
Mg2+ + 2 NH4OH  Mg(OH)2 + 2 NH4+
The precipitate obtained is sparingly soluble in water but readily soluble in ammonium salts.
Mg(OH)2 Mg+2 + 2 OH–
NH4Cl  NH4+ + Cl– ; NH4+ + OH–  NH4OH (weak base)
NH4+ ions 'remove' OH– causing the hydroxide to dissolve more. Not possible with NaCl.
 Ammonium carbonate solution : A white precipitate of basic magnesium carbonate is obtained in the
absence of NH4+ salts.
5 Mg2+ + 6 CO32– + 7 H2O  2 MgCO3.Mg(OH)2.5 H2O  + 2HCO3–
In the presence of NH4+ salts no precipitation occurs, because the equilibrium
NH4+ + CO32– NH3 + HCO3–
is shifted towards the formation of HCO3– ions. Ksp of the precipitate being high (Ksp of pure MgCO3 is
1 × 10–5 ), the concentration of carbonate ions necessary to produce a precipitate is not attained.
 Titan yellow (a water soluble yellow dyestuff) : It is adsorbed by Mg(OH)2 producing a deep red colour or
precipitate.
Dissolved the precipitate in dilute HCl (minimum quantity) and to 1 drop of this add 1 drop of NaOH solution
(2 M) followed by 1 drop of titan yellow solution a deep red colour solution or precipitate is obtained.
 Ba2+ and Ca2+ do not react but intensify the colour.
ADVQUA - 21
MISCELLANEOUS SOLVED PROBLEMS (MSPs)
1. Which of the following precipitate(s) does / do not dissolve in excess of ammonia solution ?
(A) Zn(OH)2 (B) Ni(OH)2 (C) Al(OH)3 (D) (B) and (C) both
Ans. (C)
Sol. (A) Zn(OH)2 + 4 NH3  [Zn(NH3)4]2+ (colourless solution) + 2OH–
(B) Ni(OH)2 + 6NH3  [Ni(NH3)6]2+ (deep blue solution) + 2OH–
(C) Al(OH)3 + NH3  No reaction.
2. Chocolate brown precipitate is formed with :

(A) Cu2+ ions and [Fe (CN)6]3– (B) Cu2+ ions and [Fe(CN)6]4–
(C) Fe3+ ions and [Fe (CN)6]4– (D) Fe2+ ions and dimethylglyoxime
Ans. (B)
Sol (A) Cu3 [Fe(CN)6]2 (green) ; (B) Cu2 [Fe(CN)6]  ( chocolate brown)
(C) Fe4[Fe(CN)6]3 (Prussian blue) ; (D) red solution of iron(II) dimethylglyoxime.
3. Colour of cobalt chloride solution is :

(A) pink (B) black (C) colourless (D) green
Ans. (A)
Sol. Anhydrous Co(II) salts are blue in colour while hydrated Co(II) salts are pink/red.
4. A red colouration or precipitate is not obtained when :

(A) Fe3+ reacts with potassium thiocyanate (B) Fe2+ reacts with dimethylglyoxime.
2+
(C) Hg reacts with potassium iodide. (D) None
Ans. (D)
Sol. (A) Fe3+ + 3SCN–  Fe(SCN)3 (red solution)
(B) Red solution of iron(II) dimethylglyoxime.
(C) Hg2– + 2I–  HgI2  (red).
5. Statement-1 : Addition of NH4OH to an aqueous solution of BaCl2 in presence of NH4Cl (excess) precipitates
Ba(OH)2.
Statement-2 : Ba(OH)2 is water soluble.
(A) Both Statement-1 and Statement-2 are true and Statement-2 is the correct explanation of Statement-1.
(B) Both Statement-1 and Statement-2 are true but Statement-2 is not correct explanation of Statement-1.
(C) Statement-1 is true but Statement-2 is false.
(D) Statement-1 is false but Statement-2 is true
Ans. (D)
Sol. Ba2+ ions does not give any precipitate with NH4OH solution in excess of NH4Cl because product formed,
Ba(OH)2 is soluble in water
6. Statement-1 : Sodium meta aluminate on boiling with ammonium chloride produces white gelatinous
precipitate.
Statement-2 : Aluminium hydroxide is formed which is not soluble in water
(A) Both Statement-1 and Statement-2 are true and Statement-2 is the correct explanation of Statement-1.
(B) Both Statement-1 and Statement-2 are true but Statement-2 is not correct explanation of Statement-1.
(C) Statement-1 is true but Statement-2 is false.
(D) Statement-1 is false but Statement-2 is true
Ans. (A)
NH4 Cl
Sol. [Al(OH)4]–   Al(OH)3  + OH–
boil
ADVQUA - 22
7. Which of the following statement(s) is (are) incorrect?
(A) Fe2+ ions give a dark blue precipitate with potassium hexacyanidoferrate (III) solution.
(B) Fe3+ ions give intense blue precipitate with potassium hexacyanidoferrate (II) solution.
(C) Fe3+ ions give a brown colouration with potassium hexacyanidoferrate (III) solution.
(D) Fe2+ ions give a deep red colouration with ammonium thiocyanate.
Ans. (D)
Sol. (A) Fe2+ + [Fe(CN)6]3–  Fe3 [Fe(CN)6]2
(B) 4Fe3+ + 3[Fe(CN)6]4–  Fe4[Fe(CN)6]3 (intense blue)
(C) Fe3+ + [Fe(CN)6]3–  Fe[Fe(CN)6] (brown colouration)
(D) Fe3+ + 4SCN–  Fe (SCN)3 (deep red colouration)
Fe2+ + 4 SCN–  No reaction
8. Consider the following statements :

S1 : Cu2+ ions are reduced to Cu+ by potassium iodide and potassium cyanide both, when taken in excess
S2 : H2S will precipitate the sulphide of all the metals from the solutions of chlorides of Cu, Zn and Cd if the
solution are aqueous.
S3 : The presence of magnesium is confirmed in qualitative analysis by the formation of a white
crystalline precipitate of MgNH4 PO4.
S4 : Calomel on reaction with potassium iodide gives red precipitate.
and arrange in the order of true /false.
(A) TTFF (B) TFTF (C) TTTT (D) TTTF
Ans. (D)
Sol. S1, S2 and S3 are correct statements.
S4 : Hg22+ + 2I–  Hg2I2  (green) [Calomel : Hg2Cl2]
9. Which of the following pair (s) of ions would be expected to form precipitate when dilute solutions are mixed?
(A) NH4+, [Co(NO2)6]3– (B) NH4+, CO32– (C) Fe3+, OH– (D) Ba2+, SO42–
Ans. (A,C,D)
Sol. (A) NH4+ + [Co(NO2)6]3–  (NH4)3 [Co(NO2)6]  (yellow)
(B) Ammonium and alkali metal carbonates are water soluble.
(C) Fe3+ + OH–  Fe(OH)3  (reddish - brown)
(D) Ba2+ + SO42–  BaSO4  (white)
Comprehension (Q.10 to Q.12)
Aqueous solution of salt (A)
NaOH(aq)/warm
Gas(B) Solution of salt (C)

Colourless gas which is FeSO4
alkaline in nature conc. H2SO4 Zn/NaOH /heat
dil.HCI
White fumes Brown ring (D) Gas(B)
at the junction
of the two layers
Salt (A) on heating gives a colourless neutral gas which supports combustion.
From the aforesaid, flow diagram, answer the following questions.
ADVQUA - 23
10. The compound (A) contains the following acid radical.

(A) NO2– (B) NO3– (C) Br– (D) SO32–
Ans. (B)
Sol. NO3– and NO2– both give brown ring test and reduction of NO3– and NO2– both give ammonia which with dilute
HCl gives dense white fumes.

if NH4NO3  N2O + 2H2O ; N2O supports the combustion

but NH4NO2  N2 + 2H2O ; Nitrogen does not supports combustion.
Hence, the anion is NO3–.
11. The basic radical of salt (A) and gas B both give brown precipitate with Nessler’s reagent. The composition
of the brown precipitate is :
(A) (NH4)2 [HgI4] (B) Hg(NH2) NO3 (C) HgO. Hg (NH2)I (D) (NH4)3[Co(NO2)6]
Ans. (C)
Sol. NH4+ + 2[HgI4]2– + 4OH–  HgO. Hg (NH2)I + 7I– + 3H2O
12. Which of the following statement is correct ?

(A) Salt (A) gives yellow precipitate with chloroplatinic acid as well as with sodium cobaltinitrite.
(B) The brown ring is formed due to the formation of nitroso ferrous sulphate [Fe(NO)]2+SO4–.
(C) Salt ‘C’ reacts with silver nitrate solution to form white precipitate.
(D) (A) and (B) both.
Ans. (D)
Sol. (A) 2NH4+ + [PtCI6]2–  (NH4)2 [PtCl6]  (yellow)
3NH4+ + [Co(NO2)]3–  (NH4)3 [Co(NO2)6]  (yellow)
(B) 2NO3– + 4H2SO4 + 6Fe2+  6Fe3+ + 2NO  + 4SO42– + 4H2O
SO42– + Fe2+ + NO  [Fe(NO)]2+ SO42–
(C) Ag NO3 + NaNO3  No reaction.

If the anion is NO2– then Ag+ + NO2–  Ag NO2  (white)
Reactions :
NH4NO3 + NaOH  NH3 + NaNO3

(A) (B) (C)
NH3+ HCI  NH4CI (White)
NO3– + 4Zn + 7OH– + 6H2O  NH3 + 4[Zn(OH)4]2–
True/False :
13. Magnesium is precipitated from its salt solution as only magnesium ammonium phosphate by adding disodium
hydrogen phosphate solution in absence of ammonium chloride and aqueous ammonia.
Sol. (False) Precipitation is carried out in presence of ammonium chloride and aqueous ammonia as they prevent
precipitation of magnesium hydroxide.
Mg2+ + NH3 + HPO42–  Mg (NH4) PO4  (white)
14. When a solution of nitrite acidified with dilute hydrochloric acid is treated with solid urea, the nitrite is
decomposed, and nitrogen and carbon dioxide are evolved.
Sol. (True) CO(NH2)2 + HNO2  2N2  + CO2  + 3H2O.
ADVQUA - 24
15. Solution of alkali metal cyanide containing freshly prepared iron (II) sulphate solution and dilute H2SO4 on
exposure to air produces prussian blue precipitate
Sol. (True) Fe2+ + 2 CN–  Fe(CN)2  ; Fe(CN)2  + 4CN–  [Fe(CN)6]4–
4Fe2+ + O2 + 4H+  4Fe3+ + 2H2O ; Fe3+ [Fe(CN)6]4–  Fe4[Fe(CN)6]3 
Subjective :
16. What happens when ?
(A) Aqueous solution of CrCl3 is added to ammonia solution.
(B) Ammonium carbonates reacts with MgCl2 (i) in absence of ammonium salts and (ii) in presence of
ammonium salts :
Sol. (A) Cr3+ + 3NH3 + 3H2O  Cr(OH)3  (green) + 3NH4+
Cr(OH)3 precipitate formed becomes slightly soluble in excess of precipitant in cold forming a violet
or pink solution containing [Cr(NH3)6] 3+ complex ions.
Cr(OH)3  + 6 NH3  [Cr(NH3)6]3+ + 3OH–
(B) (i) 5Mg2+ + 6 CO32 + 7H2O  4MgCO3. Mg(OH)2. 5 H2O  + 2HCO3–
White precipitate of basic magnesium carbonate is formed.
(ii) In presence of ammonium salts no precipitation occurs, because the equilibrium
NH4+ + CO32–  NH3+ HCO3–
is shifted towards the formation of HCO3– ions.
17. Salts given in column (I) reacts with the excess of reagents given in column (II) and form white /coloured
precipitates. Select the correct options for the salts given in column (I) with the reagent(s) given in the
column (II)
Column - I Column - II
(A) Zn (NO3)2 (p) Sodium hydroxide
(B) Cu (NO3)2 (q) Ammonia solution
(C) Fe(NO3)3 (r) Disodium hydrogen phosphate
(D) Ag(NO3)2 (s) Potassium ferrocyanide
Ans. (A - r, s) ; (B - p, r, s) ; (C - p, q, r) ; (D - p, q, r, s)
Sol. (A) Zn2+ + 2OH–  Zn(OH)2 (white) ;
Zn (OH)2 + 2OH–  [Zn(OH)4]2– (colourless soluble complex)
Zn2+ + 2NH3 + 2H2O  Zn (OH)2  (white) + 2NH4+
Zn(OH)2  + 4NH3  [Zn(NH3)4]2+ (colour less soluble complex) + 2OH–
3Zn2+ + 2HPO42–  Zn3 (PO4)2  (white) + 2H+
3 Zn2+ + 2K+ + 2[Fe(CN)6]4–  K2 Zn3 [Fe(CN)6]2  (bluish white)
(B) Cu2+ + 2OH–  Cu(OH)2  (blue)
Cu2+ + 4NH3  [Cu(NH3)4]2+ (deep blue soluble complex)
Cu2+ + 2HPO42–  Cu3(PO4)2 (blue) + 2H+
Cu2+ [Fe(CN)6]4–  Cu2[Fe(CN)6]  (chocolate brown)
(C) Fe3+ + 3OH–  Fe (OH)3  (reddish brown)
Fe3+ + 3NH3 + 3H2O  Fe(OH)3  (reddish brown) + 3NH4+
Fe3+ + HPO42–  FePO4  (yellowish-white) + H+
excess
4Fe3+ + 3 [Fe(CN)6]4–  Fe4 [Fe(CN)6]3  (intense blue)   KFeIII[Fe(CN)6]II.
K 4 [Fe(CN)6 ]
(soluble prussian blue)
+ –
(D) 2Ag + 2OH  Ag2O  (brown) + H2O
2Ag+ + 2NH3 + H2O  Ag2O (brown) + 2NH4+
4Ag+ + HPO42–  Ag3PO4  (yellow) + H+
4Ag+ + 3 [Fe(CN)6]4–  Ag4[Fe(CN)6]  (white)
ADVQUA - 25
 Marked Questions may have for Revision Questions.

PART - I : SUBJECTIVE QUESTIONS
Section (A) : Ist Group
A-1. Name of one chloride which is soluble in hot water as well as in excess of HCl.
A-2. Why do lead salts turn black on keeping for a long time in the laboratory ?
A-3. A metal salt forms a yellow precipitate (P) with potassium iodide solution and black precipitate (Q) with
acidified H2S. Yellow precipitate (P) does not dissolve in excess dilute solution of KI. Then metal salt could
be and also write the chemical equation.
A-4. When calomel reacts with ammonia solution, a black precipitate is formed. Write the chemical equation and
also name the reaction nature.
A-5. What products are formed when precipitate formed by the reaction of Hg22+ ions and excess of sodium
hydroxide solution is boiled ?
A-6. A metal salt forms a green precipitate with KI solutiion and white ppt with KCl. This green precipitate under
goes disproportionation reaction in excess of reagent which results in a soluble compound and black precipitate
then write the chemical equations and identify the cation in the original sample.
A-7. Why bright yellow precipitate of AgI is soluble in KCN and Na2S2O3 solution.
A-8. What happens when diammine argentate (I) reacts with hydrazine sulphate ?
A-9. Solid (A) is used in photographic film, Identify (A) to (E) ?
Section (B) : II A Group

B-1. Why Na2S cannot be used in place of H2S (in presence of HCl) as a reagent for IInd group cations ?
B-2. Does sodium hydroxide solution can be used to differentiate Hg(I) from Hg(II) ?
B-3. What happens when white precipitate of Bi(OH)3 is boiled ?
B-4. Is there any reaction other then cyanide reaction which can be used for the differentiation of Cu2+ and Cd2+
ions?
ADVQUA - 26
B-5. Identify A to F.
(F) K 4 [Fe(CN)6 ] BaCl2

  (A)   (B)  (C)
Chocolate Blue solution White ppt.
brown
(D) Hypo
  (E)
Brown ppt. Solution White ppt.
Section (C) : IIB Group

C-1. An original solution is prepared in conc. HCl when diluted a white ppt. is formed. What does it indicate ?
C-2. Can we use other reagent in place of yellow ammonium sulphide for separation of group-II (A) and group-II (B)
redicals ?
C-3. Why HNO3 can not be used in place of HCl as a reagent (H2S in presence of HCl) for IInd group cations ?
C-4. Which cation can be detected by "Marsh's test" ? Also write the balanced chemical reaction.
C-5. A metal salt (X) forms yellow precipitate with H2S in acidic medium. This yellow precipitate is soluble in conc.
HNO3 due to formation of compound (Y). Compound (Y) gives ammonium molybdate test then find the metal
salt (X).
C-6. Identify (A) based on the following facts :

(i). (A) reduces HgCl2 solution to white ppt. changing to grey.
(ii). (A) turns FeCl3 yellow coloured solution to green.
(iii). (A) gives white ppt. with NaOH soluble in excess of NaOH.
(iv). (A) gives yellow dirty ppt. on passing H2S gas, soluble in yellow ammonium sulphide (YAS).
(v). (A) gives chromyl chloride test.
Section (D) : IIIrd Group

D-1. Why is the original solution boiled with conc. HNO3 in group  ?
D-2. Why use of excess cobalt nitrate solution should be avoided in the dry test of aluminium compounds ?
D-3. Do Fe(III) salts and Fe(II) salts both give red colouration with dimethylglyoxime in ammonical solution. If not
then which iron salt gives red colouration with dimethylglyoxime ?
D-4. Which colour precipitate is formed by Fe(II) salt with potassium ferrocyanide, (i) in complete absence of air
and (ii) under ordinary atmospheric conditions ?
D-5. Which basic radical(s) decolourise acidic KMnO4 solution ?
Section (E) : IVth Group

E-1. Partial precipitation of Mn2+ as Mn(OH)2 occurs with ammonia solution but the precipitate is soluble in
ammonium salts. Explain ?
E-2. Why Zn(II) salt is not precipitated as Zn(OH)2 by ammonia solution in the presence of excess of ammonium
chloride ?
E-3. In the absence of copper ion, zinc ion form a white precipitate with the ammonium tetrathio-cyanatomercurate(II)
How the presence of Cu2+ ion affect this test ?
ADVQUA - 27
E-4. Identify (A) to (D).
(A)  (B) + (C) (On cooling (C) turns white)


Colourless water (Brown gas) (Yellow residue)
soluble compound
(D)
(White ppt.)
Section (F) : Vth, VIth and Zero Group

F-1. What is the formula of iodide of Millon's base ?
F-2. What happens when ammonia gas is passed into a solution of sodium cobaltinitrite ?
F-3. CaSO4 is insoluble in water but when excess of (NH4)2SO4 is added in CaCl2 solution, CaSO4 is not precipitated,
why ?
F-4. What will happen if the precipitation of Vth group cation by ammonium carbonate is uplaced by Na2CO3 ?
F-5. What happens when ammonium sulphate solution is added to a solution containing both Sr2+ and Ca2+ ions?
F-6. Which colour precipitate is obtained when a solution of Ca2+ ions reacts with potassium ferrocyanide.
F-7.

(A) (colourless solid)  (B) (residue) + (C) (gas) + (D) gas
(D)
Solution of (B)   milky
(A) gives brick red colour in flame and decolouries MnO4– /H+. Gas (C) burns with blue flame. Identify (A), (B)
(C) and (D).
PART - II : ONLY ONE OPTION CORRECT TYPE
Section (A) : Ist Group

A-1. A metal nitrate reacts with KI solution to give yellow precipitate which on addition of excess of more
concentrated solution (6 M) of KI dissolves forming a solution. The cation of metal nitrate is :
(A) Hg22+ (B) Ag+ (C) Pb2+ (D) Cu2+
A-2. Three separate samples of a solution of a single salt gave these results. One formed a white precipitate with
excess ammonia solution, one formed a white precipitate with dilute NaCl solution and one formed a black
precipitate with H2S. The salt could be :
(A) AgNO3 (B) Pb(NO3)2 (C) Hg(NO3)2 (D) Mn(NO3)2
A-3. Consider the following observation :
 CrO 24 –
Mn+ + HCl (dilute)  white precipitate  water soluble   yellow precipitate.
n+
The metal ion M will be :
(A) Hg2+ (B) Ag+ (C) Pb2+ (D) Sn2+
ADVQUA - 28
A-4. A white crystalline substance dissolves in water. On passing H2S in this solution, a black precipitate is
obtained. The black precipitate dissolves completely in hot HNO3. On adding a few drops of concentrated
H2SO4, a white precipitate is obtained. This precipitate is that of :
(A) BaSO4 (B) SrSO4 (C) PbSO4 (D) CdSO4
A-5. When calomel reacts with NH4OH solution the compound formed is :
(A) Hg2Cl2 (B) Hg(NH2)Cl (C) Hg(NH3)2Cl (D) HgCl2.NH3
A-6. Which of the following cations form coloured (not white) precipitates with aqueous solution of KI and this
precipitate does not dissolve in excess of reagent ?
(A) Hg2+ (B) Hg22  (C) Ag+ (D) Cu2+
A-7. Consider the following equilibrium :

AgCl  + 2NH3 [Ag(NH3)2]+ + Cl–
White ppt of AgCl appears on adding
(A) NH3 (B) aq. NaBr (C) aq. HNO3 (D) aq. NH4I
A-8. AgCl with NH3 forms a complex :

(A) [Ag(NH3)2]Cl (B) AgNO3 (C) [Ag(NH2)2]Cl (D) Ag mirror
Section (B) : IIA Group

B-1. Sometimes yellow turbidity appears while passing H2S gas even in slightly acidic medium in the absence of
 group radicals. This is because :
(A) sulphur is present in the mixture as impurity.
(B) IV group radicals are precipitated as sulphides.
(C) of the oxidation of H2S gas by some acid radicals.
(D)  group radicals are precipitated as hydroxides.
B-2. H2S in the presence of HCl precipitates  group but not V group because :
(A) HCl activates H2S (B) HCl increases concentration of Cl–
(C) HCl decreases concentration of S2– (D) HCl lowers the solubility of H2S in solution
B-3. When small amount of SnCl2 is added to a solution of Hg2+ ions, a silky white precipitate is obtained. The
silky white precipitate is due to the formation of :
(A) Hg2Cl2 (B) SnCl4 (C) Sn (D) Hg
B-4. When excess of dilute NH4OH is added to an aqueous solution of copper sulphate an intense blue colour is
developed. This is due to the formation of :
(A) [Cu(NH3)6]2+ (B) Cu(OH)2 (C) [Cu(NH3)4]2+ (D) (NH4)2SO4
B-5. A black sulphide is formed by the action of H2S on :

(A) cupric chloride (B) cadmium chloride (C) zinc chloride (D) ferric chloride.
B-6. Which one of the following salts will produce clear and transparent original solution in 2M HCl ?
(A) Ag2CO3 (B) Pb(CO3) (C) Hg2CO3 (D) CuCO3
B-7. When bismuth chloride is poured into a large volume of water the white precipitate produced is of :
(A) BiO.OH (B) Bi2 O3 (C) BiOCl (D) Bi (OH)3
B-8. In which of the following pairs the precipitates are red and black coloured respectively and both precipitates
are soluble in excess KI solution ?
(A) HgI2 , Hg2I2 (B) HgI2 , BiI3 (C) Cu2I2 , AgI (D) CdI2 , PbI2
ADVQUA - 29
B-9. Which diagram correctly represents change for given nitrate solution.
H2S
Cd(NO3 )2 CdS
dil.
dil.
CH3COOH
(A) HNO3 (B)
dil.
Cd(OH) 2 Cd(CH3 COO)2
NaOH
NaCN
Cd(NO3 )2 Cd(CN) 2
dil. NaCN
(C) HNO3 excess (D)
H2S 2–
CdS [Cd(CN) 4]
B-10. A metal chloride original solution (i.e. O.S) on mixing with K2CrO4 solution gives a yellow precipitate soluble
in aqueous sodium hydroxide. The metal may be :
(A) mercury (B) iron (C) silver (D) lead
Section (C) : IIB Group

C-1. As2S3 dissolve in NaOH solution to form
(A) Na3AsS4 (B) Na3AsO4 (C) Na3AsS3 (D) Na AsO2
C-2. When white crystalline precipitate of magnesium ammonium arsenate is treated with acidified silver nitrate
solution, precipitate of silver arsenate is formed . The colour of precipitate is :
(A) Yellow (B) Brownish red (C) White (D) Brownish black
C-3. Which of the following metal sulphide is soluble in YAS (yellow ammonium sulphide) :
(A) HgS (B) PbS (C) Bi2S3 (D) Sb2S3
Section (D) : IIIrd Group

D-1. When NH4Cl is added to a solution of NH4OH :
(A) the dissociation of NH4OH increases. (B) the concentration of OH– increases.
(C) the concentrations of both OH– an NH4+ increase. (D) the concentration of OH– ion decreases.
D-2. To avoid the precipitation of Hydroxides of Zn2+, Mn2+ and Ni2+ along with those of Fe3+, Al3+ and Cr3+ the third
group solution should be :
(A) Concentrated HNO3 is added (B) Treated with excess of NH4Cl
(C) Concentrated H2SO4 is added (D) Treated with excess of NH4OH
D-3. An inorganic lewis acid (X) fumes in moist air, and intensity of fumes increases when and rod dipped in
NH4OH is brought near to it. An acidic solution of (X) on addition of NH4Cl and NH4OH gives a precipitate
which dissolves in NaOH solution. An solution of (X) does not give precipitate with H2S Hence, compounds
(X) is :
(A) FeCl3 (B) AlCl3 (C) CrCl3 (D) ZnCl2
D-4. An original solution of an inorganic salt in dilute HCl gives a brown colouration with potassium hexacyanidoferrate
(III) and reddish brown colouration with sodium acetate solution. The cation of the salt is :
(A) Ni2+ (B) Fe3+ (C) Cu2+ (D) none
D-5. Turnbull’s blue is a .................... .

(A) ferricyanide (B) ferrous ferricyanide (C) ferrous cyanide (D) ferri ferrocyanide
D-6. Fe(OH)3 and Cr(OH)3 precipitates can be completely separated by :

(A) Aq. NH3 (B) HCl (C) NaOH/H2O2 (D) H2SO4
Section (E) : IVth Group

E-1. A coloured solution of a salt gives following reactions.
(i) It gives white precipitate with sodium hydroxide which becomes brown on exposure to air.
(ii) It gives white precipitate with ammonia solution which is soluble in ammonium salts.
(A) Mn2+ (B) Zn2+ (C) Al3+ (D) Ni2+
ADVQUA - 30
E-2. A metal salt form precipitate with H2S in presence of (NH4OH + NH4Cl) and this precipitate is soluble in acetic
acid then metal sulphide could be :
(A) ZnS (B) CoS (C) MnS (D) NiS
E-3. To increase significantly the concentration of free Zn2+ ion in a solution of the complex ion [Zn(NH3)4]2+
Zn2+ (aq) + 4NH 3 (aq) [Zn(NH3)4]2+ (aq)
add to the solution some :
(A) H2O (B) HCl (aq) (C) NH3(aq) (D) NH4Cl (aq)
E-4. An aqueous solution of colourless metal sulphate M, gives a white precipitate with NH4OH. This was soluble
in excess of NH4OH. On passing H2S gas through this solution a white precipitate is formed. The metal M in
the salt is :
(A) Ca (B) Ba (C) Al (D) Zn
E-5. A aqueous solution of colourless metal sulphate M gives a white ppt, with NH4OH. This is soluble in excess
of NH4OH . On passing H2S through this solution a white ppt is formed. The metal M in the salt is :
(A) Ca (B) Ba (C) Al (D) Zn
E-6. A metal salt cobalt form brown solution with excess of KCN solution. This brown solution yellow when boiled
for a longer time in air due to formation of :
(A) Co(CN)2 (B) K4[Co(CN)6] (C) K3[Co(CN)6] (D) K2 [Co(CN)6]
E-7. A metal salt solution when treated with dimethyl glyoxime and NH4OH gives a rose red complex. The metal
is :
(A) Ni (B) Zn (C) Co (D) Mn.
E-8. The ion that can not be precipited by H2S in presence of dil. HCl
(A) Pb2+ (B) Bi3+ (C) Cu2+ (D) Ni2+
Section (F) : Vth, VIth and Zero Group

F-1. Aqueous Solution of BaBr2 gives yellow precipitate with :
(A) K2CrO4 (B) AgNO3 (C) (CH3COO)2Pb (D) (A) and (B) both
F-2. The addition of K2CO3 (aq) to the following solution is expected to produce a precipitate in every case but that
one which does not produce precipitate is :
(A) BaCl2(aq) (B) CaBr2(aq) (C) Na2SO4(aq) (D) Pb(NO3)2 (aq)
F-3. An aqueous solution of salt gives white precipitate with AgNO3 solution as well as with dilute H2SO4. It may
be
(A) Pb(NO3)2 (B) Ba(NO3)2 (C) BaCl2 (D) CuCl2
F-4. Mg is not precipitated in V group because :
(A) MgCO3 is soluble in water. (B) Ksp of MgCO3 is high.
(C) MgCO3 is soluble in NH4OH. (D) None.
F-5. A metal salt solution form a yellow ppt with potassium chromate in acetic acid, a white ppt with dilute
sulphuric acid but gives no ppt with sodium chloride or iodide it is :
(A) Lead carbonate (B) Basic lead carbonate
(C) Barium nitrate (D) Strontium nitrate
F-6. The yellow precipitate formed by passing ammonia into Nessler’s reagent in due to the formation of
(A) Hgl42– (B) NH2O–Hg–Hgl (C) NH2–Hg–O–Hg–I (D) NH3–Hg–I
F-7. Orange coloured sodium cobaltinitrite Na3[Co(NO2)6] is used for the detection of K+ ions which gives ..... ppt.
due to the formation of Pot. Sod. Cobaltinitrite K2Na[Co(NO2)6]
(A) White (B) Orange (C) Yellow (D) Brown
ADVQUA - 31
PART - III : MATCH THE COLUMN
1. Match the colour of the precipitates listed in column-I with the suitable reagent(s) in column-II.
Column-I Column-II
(A) Bi3+ give(s) black precipitate with (p) H2S (saturated solution in water)
(B) Cu2+ give(s) black precipitate with (q) Potassium thiocyanate solution
(C) Zn2+ give(s) white precipitate with (r) Potassium iodide solution
(D) Ag+ give(s) white precipitate with (s) Potassium ferrocyanide solution
2. Match the precipitates listed in column-I with their suitable solvents listed in column-II.
Column I Column II
(precipitate) (solvent)
(A) AgCl (white) (p) Concentrated HCl.
(B) CuS (black) (q) Dilute ammonia solution (excess).
(C) Zn(OH)2 (white) (r) Potassium cyanide solution.
(D) Ba(CO3) (white) (s) Hot 50% nitric acid.
(t) Sodium hydroxide solution.
3. Match the basic radicals listed in column-I with the properties listed in column-II.
Column-I Column-II
(Basic radical) (Properties)
2+
(A) Mn (p) Forms coloured metaborate in oxidising flame in borax bead test.
(B) Cr3+ (q) Forms white precipitate with sodium hydroxide but on exposure to air
turns rapidly brown.
(C) Al3+ (r) With both potassium cyanide (not in excess) and ammonia solution
separately forms reddish brown precipitate.
(D) Fe3+ (s) With excess of sodium hydroxide forms soluble complex but on adding
acid to soluble complex, a precipitate is obtained which redissolves on
adding excess of acid.
 Marked Questions may have for Revision Questions.
PART - I : ONLY ONE OPTION CORRECT TYPE

1. Which of the following compound does not gives ppt with dil. HCl ?
(A) AgNO3 (B) Pb(NO3)2 (C) Hg2(NO3)2 (D) Hg(NO3)2
2. KI gives precipitate with all the cations given :
(A) Ag+, Hg22+, Pb2+ (B) Cu2+, Zn2+, Ni2+ (C) Na+, Ca2+, Mg2+ (D) Ag+, Ca2+, Sr2+
3. Three test tubes A, B, C cation Pb2+, Hg22+ and Ag+ (but unknown to each, aqueous solution NaOH is added
in excess). Following changes occur.
A : Black ppt, B : Brown ppt, C : White ppt but dissolves in excess of NaOH
A, B and C contain respectively :
(A) Pb2+, Hg22+, Ag+ (B) Hg22+, Ag+, Pb2+ (C) Ag+, Pb2+, Hg22+ (D) Ag+, Hg22+, Pb2+
4. dil. HCl

Salt mixture   white ppt.
salt mixture contains cations of :

(A) Pb2+ and Hg2+ (B) Pb2+ and Hg22+ (C) Pb2+ and Ag+ (D) None of these
ADVQUA - 32
5. A compound (X) reacts in the following ways.
The compound (X) is likely to be

(A) Pb(NO3)2 (B) CaCrO4 (C) Hg(NO3)2 (D) AgNO3
6. When excess of SnCl2 is added to a solution of HgCl2, a white ppt turning grey is obtained. The grey colour
is due to the formation of :
(A) Hg2Cl2 (B) SnCl2 (C) Sn (D) Hg
7. An aqueous solution of a substance gives a white ppt. on treatment with dil HCl, which dissolves on heating.
When hydrogen sulphide is passed through the hot acidic solution, a black ppt is obtained.The subtance is
a:
(A) Hg2+ salt (B) Cu2+ salt (C) Ag+ salt (D) Pb2+ salt
8. Three seperate sample of a solution of a single salt gave these results one formed a white precipitate with
excess of ammonia solution, one formed a white precipitate with dil. NaCl solution and one formed a black
precipitate with H2S. The salt could be :
(A) AgNO3 (B) Pb(NO3)2 (C) Hg(NO3)2 (D) MnSO4
9. In the separation of Cu2+ and Cd2+ in 2nd group qualitative analysis of cations tetraammine copper(II) sulphate
and tetrammine cadmium(II) sulphate react with KCN to form the corresponding cyano complexes. Which
one of the following pairs of the complexes and their relative stability enables the separation of Cu2+ and
Cd2+?
(A) K3[Cu(CN)4] more stable and K2[Cd(CN)4] less stable
(B) K2[Cu(CN)4] less stable and K2[Cd(CN)4] more stable
(C) K2[Cu(CN)4] more stable and K2[Cd(CN)4] less stable
(D) K3[Cu(CN)4] less stable and K2[Cd(CN)4] more stable
10. A pale green crystalline metal salt of M dissolves freely in water. On standing it gives a brown ppt on addition
of aqueous NaOH. The metal salt solution also gives a black ppt on bubbling H2S in basic medium. An
aqueous solution of the metal salt decolourizes the pink colour of the permanganate solution. The metal in
the metal salt solution is :
(A) copper (B) aluminum (C) lead (D) iron
11. K4[Fe(CN)6] can be used precipitate one or more out of Fe2+ , Fe3+, Zn2+, Cu2+, Ag+ , Ca2+ :
(A) only Fe2+, Fe3+ (B) only Fe3+,Zn2+,Cu2+ (C) all but not Ca2+ (D) all of these.
12. Ferric alum gives deep red colour with NH4SCN due to the formation of :
(A) Al(SCN)3 (B) [Fe(SCN)3]– (C) Fe(SCN)3 (D) None of these.
13. Nessler's reagent is used to detect.
(A) CrO42– (B) PO43– (C) MnO4– (D) NH4+
14. On the addition of a solution containing CrO42– & CH3COOH acid to the solution of Ba2+, Sr2+ and Ca2+ ions,
the ppt obtained first will be of :
(A) CaCrO4 (B) SrCrO4 (C) BaCrO4 (D) a mixture of all the three
15. A salt on treatment with dil. HCl gives a pungent smelling gas and a yellow precipitate. The salt gives green
flame when tested. The solution gives a yellow precipitate with potassium chromate. The salt is :
(A) NiSO4 (B) BaS2O3 (C) PbS2O3 (D) CuSO4
ADVQUA - 33
16. A chloride dissolves appreciably in cold water. When placed on a platinum wire in Bunsen flame, no distinctive
colour is noticed. The cation of chloride is :
(A) Mg2+ (B) Ba2+ (C) Pb2+ (D) Ca2+
17. In fifth group, (NH4)2CO3 is added to precipitate out the carbonates. We do not add Na2CO3 because :
(A) CaCO3 is soluble in Na2CO3
(B) Na2CO3 increases the solubility of fifth group carbonates
(C) MgCO3 will be precipitated out in fifth group
(D) none
18. A metal salt solution forms a yellow precipitate with potassium chromate in acetic acid, a white precipitate
with dilute sulphuric acid, but gives no precipitate with sodium chloride or iodide, it is :
(A) lead carbonate (B) basic lead carbonate
(C) barium carbonate (D) strontium carbonate
PART - II : SINGLE AND DOUBLE VALUE INTEGER TYPE

1. An aqueous solution contains Hg2+, Hg22+, Pb2+, Ag+, Bi3+ and Cd2+. Out of these, how many ions will
produce white precipitate with dilute HCl ?
2. A solution of Hg2+ ion on treatment with a solution of cobalt(II) thiocyanate gives rise to a deep blue crystalline
precipitate. Then the coordination number of mercury in the deep blue coloured compound is :
dil.HCl
3. As3+ + H2S    "yellow ppt of A"
A + yellow ammonium sulphide  C + D

How many different type of oxidation states of sulphur are possible in "C" and "D".
4.
The sum of number of p-pbonds present in gas (Y) & (Z) ?

5. An alcoholic solution of dimethylglyoxime is added to an aqueous solution of nickel(II) chloride. Slow
addition of ammonium hydroxide led to the precipitation of a bright-red coloured metal complex.
Find out the number of hydrogen bonds present in the structure of the complex.
6. In how many of the following reactions, one of the product is obtained as a yellow precipitate :
(a) Ba2+ + CrO42–  product (b) NH4+ + [PtCl6]2–  product
(c) NH4+ + [Co(NO2)6]3–  product (d) Ca2+ + [Fe(CN)6]4– + K+  product
(e) Sr2+ + CO32–  product
7. Total number of metal nitrates given below, which give the following reaction,
Excess NH3.H2 O
No change in colour and
number ppt remains in the
test tube
aq. solution of Metal Nitrate
AgNO3, Pb(NO3)2, Cu(NO3)2, Cd(NO3)2, Zn(NO3)3, Ni(NO3)2, Al(NO3)2
ADVQUA - 34
8. Aqueous CuSO4 decolorizes on addition of KCN due to formation of complex (A).
In complex "A". If
(i) Number of d orbitals participating in hybridisation is / are 'a'
(ii) Coordination number of Cu is "c".
then find 8a + 5c.
9. Co2+ + CN–  "A" (reddish brown) ppt.

"A" + CN– (excess)  "B" (brown solution)
"B" + O2 + 2H2O  "C" (yellow solution)
then find (a + b) for complex "C" if a = coordination number of Co
b = charge on complex (consider the magnitude)
10^. How many of the following reactions give yellow ppt.
(i) NaBr + AgNO3  (ii) NaI + AgNO3
(iii) NaBr + Pb(NO3)2  (iv) NaI + Pb(NO3)2 
(v) Na2S + Cd(CH3COO)2  (vi) K2CrO4 + Pb(CH3COO)2 
(vii) K2CrO4 + AgNO3 
(viii) NaBr + Chlorine water (excess) 
PART - III : ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. An aqueous solution containing Hg2+, Hg22+, Pb2+ and Cd2+ ions will give precipitates of ........... with HCl.
(A) HgCl2 (B) Hg2Cl2 (C) PbCl2 (D) CdCl2
2. Which of the following is/are correctly matched ?

(A) BiI3   Black (B) Cu2I2   White precipitate
(C) PbI2   Yellow precipitate (D) HgI2   Red precipitate
3. Which of the following are completely soluble in concentrated ammonia solution?
(A) AgCl (B) AgBr (C) Ag2CrO4 (D) Ag
boiled
4. Hg2I2 (green)   products
with H2O
Which of the following statement is / are correct with respect to the products ?
(A) Black precipitate of mercury(I) oxide is formed.
(B) Violet colour gas is evolved.
(C) Red precipitate of HgI2 is formed.
(D) Mercury is obtained
5. Cu2+ ions give white precipitate with :
(A) potassium iodide solution. (B) potassium thiocyanate and saturated solution of SO2.
(C) excess of potassium cyanide solution. (D) potassium hydroxide solution.
6. Which of the following statements is/are true ?
(A) Ag+ ions do not give white precipitate with excess of concentrated HCl.
(B) Cu2+ ions produce a white precipitate when KCN solution is added in a small quantity.
(C) Hg2+ ions give deep blue precipitate with cobalt acetate and ammonium thiocyanate.
(D) Black precipitate of BiI3 turns orange when heated with water.
7. K solution is the reagent for :
(A) Hg2+ (B) Pb2+ (C) Ag+ (D) Cu2+
8. Which of the following cations form(s) black precipitate(s) with H2S (g) ?
(A) Cu2+ (B) Sb3+ (C) Pb2+ (D) Bi3+
9. Which of the following process result in a prussain blue ppt ?
(A) Fe2+ + [Fe(CN)6]3–  (B) Fe2+ + [Fe(CN)6]4– 
SnCl2
3+
(C) Fe + [Fe(CN)6] 3–
(D) Fe3+ + [Fe(CN)6]3  P  
ADVQUA - 35
10. Which of the following statement(s) is /are false ?
(A) Fe3+ gives red precipitate with dimethyl glyoxime in alkaline solution.
(B) Cu2+ ion with potassium iodide solution gives a dirty brownish white precipitate which turns white on
adding hypo solution.
(C) A filter paper soaked in mercurous nitrate turns black in contact with ammonia gas.
(D) Ag2O does not dissolve in nitric acid and ammonia solution.
11. Which of the following statements is/are correct ?

(A) An aqueous solution of Co(II) thiocyanate (10% freshly prepared) and mercuric nitrate solution taken in
equal volumes on stirring the wall of the vessel with a glass rod produce deep-blue precipitate.
(B) White precipitate of Al(OH)3 is soluble in sodium hydroxide as well as in ammonia solution.
(C) Green precipitate of Cr(OH)3 readily dissolves in excess of sodium hydroxide forming a green solution.
(D) Chromium (III) salts give green coloured borax bead in both oxidising and reducing flame.
12. Which of the following mixture of cations can be separated by adding excess NH3 solution ?
(A) Zn2+, Mn2+ (B) Zn2+, Cd2+ (C) Zn2+, Pb2+ (D) Zn2+, Cu2+
13. Co2+ + KCN (not in excess)  precipitate.

Select the correct statement(s) with respect to the precipitate.
(A) It is yellow in colour.
(B) It is reddish-brown in colour.
(C) It dissolves in excess of the reagent forming a brown solution.
(D) It is obtained when brown solution (option (C)) is acidified with dilute HCl in the cold.
14. CoCl2 + KNO2 + CH3COOH  [X] + H2O + KCl + CH3COOK + NO

(Unbalanced equation)
Which is / are correct for 'X'?
(A) X is a yellow crystalline solid which is insoluble in water.
(B) X is a green coloured compounds known as Rinman's green.
(C) IUPAC name of X is potassium hexanitrito –N– cobaltate (II)
(D) The compound X is an inner orbital complex.
15. Which of the following is/are correct for potassium ferrocyanide ?
(A) It gives a brown precipitate with Cu2+ ions.
(B) It gives a white precipitate of mixed salt with Ca2+ ions.
(C) It in excess gives a bluish white/white precipitate with Zn2+.
(D) It develops a deep red colouration with Fe3+.
PART - IV : COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension # 1
H S ( g)
Aqueous solution of ‘A’ 2  Black precipitate ‘B’, soluble in 50% HNO3 forming ‘C’.
White precipitate dissolves in Black precipitate ‘D’

hydrochloric acid but on dilution with
water again white turbidity appears 'E'.
Moreover, the salt 'A' on heating with solid K2Cr2O7 and concentrated H2SO4 produces deep red vapours
which dissolve in sodium hydroxide solution forming a yellow solution. This yellow solution gives yellow
precipitate with Ba(NO3)2 solution.
ADVQUA - 36
On the basis of the aforesaid characteristic informations answer the following questions :
1. Acidified solution of ‘A’, on treatment with KI gives black precipitate 'F' which dissolves in excess of reagent
forming the coloured compound 'G'. The chemical composition of 'F' and 'G' are respectively :
(A) HgI2 and [HgI4]2– (B) PbI2 and [PbI4]2– (C) BiI3 and [BiI4]– (D) Cu2I2 and CuI2.
2. The black precipitate 'F' on heating with water produces :
(A) Hg(OH)2 (B) BiOI (C) BiO.OH (D) CuO.OH
3. Select the correct statement.
(A) Aqueous solution of 'A' reacts with AgNO3 solution to give white precipitate which turns into yellow on
treatment with sodium arsenite.
(B) Aqueous solution of 'A' produces white precipitate with sodium hydroxide which turns into yellowish-white
on boiling.
(C) White turbidity 'E' is soluble in dilute mineral acids.
(D) All of these.
Reaction involved in comprehension :

2Bi3+ (A) + 3H2S H
 Bi2 S3  (black) (B) + 6 H
+
Bi2 S3 + 8HNO3  2Bi (NO3)3 (C) + 2NO + 3S + 4H2O

NaOH
Bi3+ + 3OH–  Bi(OH)3 (white) ; 2Bi(OH)3  (white) + 3[Sn(OH)4]2–  2Bi (D) + 3[Sn(OH)6]2–
NH4OH
Bi3+ + 3OH–   Bi(OH)3 (white) ; Bi(OH)3 (white) + 3HCl  BiCl3 + 3H2O
BiCl3 + H2O  BiOCl  (bismuth oxychloride) (E) + 2HCl

4NaCl + K2Cr2O7 + 3H2SO4 (conc.)  2CrO2Cl2 (deep red vapours) + 2Na2SO4 + K2SO4 + 3H2O
CrO2Cl2 + 4OH–  CrO42– + 2Cl– + 2H2O
CrO42– + Ba2+  BaCrO4 (yellow).
Comprehension # 2
A student was given a sample of colourless solution containing three cations and was asked to identify the
cations. Student carried out a series of reactions as given below.
4. Precipitates ‘A’, ‘B’ and ‘C’ are respectively :

(A) Al(OH)3, BaSO4 and AgCl (B) AgCl, BaSO4 and Zn(OH)2
(C) AgCl, Ca(OH)2 and ZnSO4 (D) ZnCl2, BaSO4 and Al(OH)3
5. White precipitate 'A' is not soluble in :

(A) NH3 (B) 2M HCl (C) KCN (D) Na2S2O3
ADVQUA - 37
6. Which of the following statement is correct ?
(A) Precipitate 'C' gives Rinmann's green test.
(B) Precipitate 'B' is appreciably soluble in boiling concentrated H2SO4.
(C) Precipitate (A) on exposure to sunlight or ultraviolet radiations turns black.
(D) All of these.
PART - I : JEE (ADVANCED) / IIT-JEE PROBLEMS (PREVIOUS YEARS)

* Marked Questions may have more than one correct option.
1. A metal nitrate reacts with KI to give a black precipitate which on addition of excess of KI is converted into
orange colour solution. The cation of the metal nitrate is : [JEE - 2005, 3/84]
(A) Hg2+ (B) Bi3+ (C) Pb2+ (D) Cu+
2. In the given reaction sequence, Identify (A) and (B).
 
SCN F ( excess )
Fe3+ +  
 A   colourless(B)
(Excess ) Blood red
(a) Write the IUPAC name of (A) and (B).

(b) Find out the spin only magnetic moment of B. [JEE 2005, 4/144]
3. A white precipitate is obtained when a solution is diluted with H2O and boiled. On addition of excess NH4Cl/
NH4OH, the volume of precipitate decreases leaving behind a white gelatinous precipitate. Identify the precipitate
which dissolves in ammonia solution or NH4Cl. [JEE 2006, 3/184]
(A) Al(OH)3 (B) Zn(OH)2 (C) Mg(OH)2 (D) Ca(OH)2
4. In blue solution of copper sulphate excess of KCN is added then solution becomes colourless due to the
formation of : [JEE 2006, 3/184]
(A) [Cu(CN)4]2– (B) Cu2+ get reduced to form [Cu(CN)4]3–
(C) Cu(CN)2 (D) CuCN
5. MgSO4 + NH4OH + Na2HPO4  white crystalline precipitate. The formula of crystalline precipitate is :
[JEE 2006, 3/184]
(A) MgCl2. MgSO4 (B) MgSO4 (C) Mg(NH4)PO4 (D) Mg(PO4)2
6. A solution of a metal ion when treated with K gives a red precipitate which dissolves in excess K to give a
colourless solution. Moreover, the solution of metal ion on treatment with a solution of cobalt(II) thiocyanate
gives rise to a deep blue crystalline precipitate. The metal ion is : [JEE - 2007, 3/162]
(A) Pb2+ (B) Hg2+ (C) Cu2+ (D) Co2+
7.* A solution of colourless salt H on boiling with excess NaOH produces a non-flammable gas. The gas evolu-
tion ceases after some time. On addition of Zn dust to the same solution, the gas evolution restarts. The
colourless salt(s) H is (are) : [JEE 2008, 4/163]
(A) NH4NO3 (B) NH4NO2 (C) NH4Cl (D) (NH4)2SO4
Paragraph for Question Nos. 8 to 10

p-Amino-N, N-dimethylaniline is added to a strongly acidic solution of X. The resulting solution is treated with
a few drops of aqueous solution of Y to yield blue coloration due to the formation of methylene blue. Treatment
of the aqueous solution of Y with the reagent potassium hexacyanoferrate(II) leads to the formation of an
intense blue precipitate. The precipitate dissolves on excess addition of the reagent. Similarly, treatment of
the solution of Y with the solution of potassium hexacyanoferrate(III) leads to a brown coloration due to the
formation of Z.
ADVQUA - 38
8. The compound X is : [JEE 2009, 4/160]
(A) NaNO3 (B) NaCl (C) Na2SO4 (D) Na2S
9. The compound Y is : [JEE 2009, 4/160]
(A) MgCl2 (B) FeCl2 (C) FeCl3 (D) ZnCl2
10. The compound Z is : [JEE 2009, 4/160]
(A) Mg2[Fe(CN)6] (B) Fe[Fe(CN)6] (C) Fe4[Fe(CN)6]3 (D) K2Zn3[Fe(CN)6]2
Paragraph for Question Nos. 11 to 13

When a metal rod M is dipped into an aqueous colourless concentrated solution of compound N the solution
turns light blue. Addition of aqueous NaCl to the blue solution gives a white precipitate O. Addition of aqueous
NH3 dissolves O and gives an intense blue solution.
11. The metal rod M is : [JEE 2011, 3/180]

(A) Fe (B) Cu (C) Ni (D) Co
12. The compound N is : [JEE 2011, 3/180]
(A) AgNO3 (B) Zn(NO3)2 (C) Al(NO3)3 (D) Pb(NO3)2
13. The final solution contains [JEE 2011, 3/180]
(A) [Pb(NH3)4]2+ and [CoCl4]2– (B) [Al(NH3)4]3+ and [Cu(NH3)4]2+
(C) [Ag(NH3)2]+ and [Cu(NH3)4]2+ (D) [Ag(NH3)2]+ and [Ni(NH3)6]2+
14. Passing H2S gas into a mixture of Mn2+, Ni2+, Cu2+ and Hg2+ ions in an acidified aqueous solution precipitates:
[JEE 2011, 3/180]
(A) CuS and HgS (B) MnS and CuS (C) MnS and NiS (D) NiS and HgS
15.* For the given aqueous reaction which of the statement(s) is (are) true ? [JEE 2012, 4/136]
(A) The first reaction is a redox reaction

(B) White precipitate is Zn3[Fe(CN)6]2
(C) Addition of filtrate to starch solution gives blue colour.
(D) White precipitate is soluble in NaOH solution
16. Concentrated nitric acid, upon long standing, turns yellow-brown due to the formation of :
[JEE(Advanced) 2013, 2/120]
(A) NO (B) NO2 (C) N2O (D) N2O4
17. Upon treatment with ammoniacal H2S, the metal ion that precipitates as a sulphide is :
[JEE(Advanced) 2013, 2/120]
(A) Fe(III) (B) Al (III) (C) Mg(II) (D) Zn(II)
Paragraph for Question 18 and 19

An aqueous solution of a mixture of two inorganic salts, when treated with dilute HCl, gave a precipitate (P)
and a filtrate (Q). The precipitate P was found to dissolve in hot water. The filtrate (Q) remained unchanged,
when treated with H2S in a dilute mineral acid medium. However, it gave a precipitate (R) with H2S in an
ammoniacal medium. The precipitate R gave a coloured solution (S), when treated with H2O2 in an aqueous
NaOH medium.
ADVQUA - 39
18. The precipitate P contains [JEE(Advanced) 2013, 3/120]
(A) Pb2+ (B) Hg22+ (C) Ag+ (D) Hg2+
19. The coloured solution S contains [JEE(Advanced) 2013, 3/120]
(A) Fe2(SO4)3 (B) CuSO4 (C) ZnSO4 (D) Na2CrO4
20. Among PbS, CuS, HgS, MnS, Ag2S, NiS, CoS, Bi 2S3 and SnS2, the total number of BLACK coloured
sulphides is : [JEE(Advanced) 2014, 3/120]
21. The pair(s) of ions where BOTH the ions are precipitated upon passing H2S gas in presence of dilute HCl,
is(are) [JEE(Advnaced) 2015, 4/168]
2+ 2+ 3+ 3+ 2+ 2+
(A) Ba , Zn (B) Bi , Fe (C) Cu , Pb (D) Hg2+, Bi3+
PART - II : JEE (MAIN) / AIEEE PROBLEMS (PREVIOUS YEARS)

1. Which one of the following statement is correct ? [AIEEE 2003, 3/225]
(1) From a mixed precipitate of AgCl and AgI, ammonia solution dissolves only AgCl.
(2) Ferric ions gave a deep green precipitate on adding potassium ferrocyanide solution.
(3) On boiling a solution having K+, Ca2+ and HCO3– ions we get a precipitate of K2Ca(CO3)2.
(4) Manganese salts give a violet borax bead test in the reducing flame .
2. A red solid is insoluble in water. However it becomes soluble if some K is added to water. Heating the red
solid in a test tube results in liberation of some violet coloured fumes and droplets of a metal appear on the
cooler parts of the test tube. The red solid is : [AIEEE 2003, 3/225]
(1) (NH4)2 Cr2O7 (2) Hg2 (3) HgO (4) Pb3O4.
3. Which of the following compounds is not colored yellow ? [JEE(Main) 2015, 4/120]
(1) Zn2[Fe(CN)6] (2) K3[Co(NO2)6]
(3) (NH4)3[As(Mo3O10)4] (4) BaCrO4
ADVQUA - 40
EXERCISE - 1
PART - I
A-1. PbCl2 is soluble in hot water and it also dissolves in concentrated HCl and KCl solutions forming soluble
complex. ; PbCl2 + 2HCl  H2PbCl4 (soluble complex).
A-2. Pb2+ + H2S (atmospheric)  PbS (black) + 2H+.
A-3. PbCl2 + 2KI 

 PbI2(yellow) + 2KCl ; PbCl2 + H2S 
 PbS (Black)
PbI2 + KI K2(PbI4) (aq)
A-4. Hg2Cl2 + 2 NH4OH  HgNH Cl  ( white)  Hg  (black ) + NH4Cl + 2 H2O

2
black
Disproportionation reaction.
A-5. Hg22+ + 2OH–  Hg2O  (black) + H2O

Hg2O   HgO  + Hg  (grey) ; Disproportionation reaction.
A-6. Hg22   2 – 
 Hg2  2 
green
A-7. AgI + 2CN–  [Ag(CN)2]– + I–, AgI + 2S2O32–  [Ag(S2O3)2]3– + I–

for formation of soluble complex
A-8. 4[Ag(NH3)2]+ + H2N–NH2.H2SO4  4Ag + N2 + 6NH4+ +2NH3+SO42–
A-9. (A) is AgBr (present in photographic plate)

AgBr + 2Na2S2O3  Na3[Ag(S2O3)2] + NaBr
soluble
(B)
NH3 HClHNO3
[Ag(NH3 )2 Cl]  AgCl  Ag2 S

(E) (D) (C)
B-1. With Na2S, along with 2nd group cations, some cations of higher groups i.e., IIIrd and IVth groups may be
precipitated because the higher concentration of S2– ions is obtained according to following reaction.
Na2S 2 Na+ + S2–
To precipitate IInd group cations lower concentration of S2– ions is required (because of low Ksp of IInd group
sulphides) and this can be obtained easily by H2S in presence of dilute HCl.
H2S 2 H+ + S2– ; HCl H+ + Cl–
Due to common ion effect the ionisation of H2S is suppressed and the concentration of S2– ions obtained is
just sufficient to precipitate the cations of IInd group.
ADVQUA - 41
B-2. Yes, Hg2+ + 2OH– 
 HgO + H2O
yellow
Hg22+ + 2OH– 
 Hg2O + H2O
black
B-3. It turns yellowish–white owing to the formation of BiO.OH .

Bi(OH)3  BiO.OH  + H2O
B-4. Yes. By the reaction of ammonia according to the following reactions.

Cu2+ + 4NH3  [Cu(NH3)4]2+ (deep blue solution).
Cd2+ + 4NH3  [Cd(NH3)4]2+ (colourless solution).
B-5. (A) : CuSO4 (B) : BaSO4 (C) : HCl (D) : (Cu2I2 + I3–)
(E) (Cu2I2 + I– + S4O62–) (F) Cu2 [Fe(CN)6]
C-1. Presence of Sb3+ or Bi3+ their chloride hydrolyse to oxychlorides in presence of excess of water.
BiCl3 + H2O  BiOCl + 2HCl
SbCl3 + H2O  SbOCl + 2HCl
C-2. Yes, If Sn2+ is absent then NaOH, KOH or colourless ammonium sulphide may be used. Except SnS, all the
sulphides of group-II (B) are soluble in these solutions also.
C-3. HNO3 is a powerful oxidising solution. Causing confusion with CdS, AS2S3 (both yellow ppt) . Colloidal
solution can not be filtered causing unnecessary trouble.
C-4. As3+

H
C-5. AsCl3 (x) + 3H2S  As2S3  (yellow) + 6HCl
3As2S3 + 28HNO3+4H2O  6H3AsO4(y)+ 9SO2–
4
+18H+ + 28 NO
H3 AsO4(y) + 12 NH4MaO4+21 HNO3  (NH4) AsO4.12MoO3(yellow)+21 NH4NO3+12H2O
C-6. (A) is SnCl2
D-1. Fe2+ salt are oxidised to Fe3+ salt by boiling with conc. HNO3, before adding NH4Cl and NH4OH, otherwise
Fe2+ would not be precipitated in group .
D-2. 2Al2O3 +2CO2+ + 4NO3– 

 2COAl2O4 (thenard blue) +4NO2+ O2
In case of excess of Co(NO3)2, CoAl2O3 will produce black cobalt oxide (CO3O4), which will mask the blue
colour.
D-3. Only Fe(II) salts give soluble red iron(II) dimethylglyoxime in ammonical solution.
D-4. (i) White precipitate, K2Fe[Fe(CN)6] and (ii) Pale blue precipitate.
D-5. Ferrous and stannous (Fe2+ and Sn2+) both act as reducing agents and decolourize acidic KMnO4.
MnO4– + 5Fe2+ + 8H+  5Fe3+ + Mn2+ + 4H2O.
E-1. Mn2+ + 2 NH3 + 2 H2O Mn(OH)2  (white) + NH4+ .

In presence of ammonium salts, the reaction proceeds in backward direction.
E-2. Zn2+ + 2 NH3 + 2 H2O Zn(OH)2 + 2 NH4+

It is due to the lowering of OH– ion concentration because of common ion effect of NH4+ to such a value that
the Ksp of Zn(OH)2 is not attained.
ADVQUA - 42
E-3. 
 Cu2+ + [Hg(SCN)4]2–  Cu[Hg(SCN)4]

* In the presence of the copper ions, the copper complex Co-precipitated with that of zinc complex and
colour become violet
E-4. (A) : Zn (NO3)2 (B) : NO2 (C) : ZnO (D) : ZnS
F-1. Hg2ONH2I or or . HgO
F-2. A yellow precipitate of ammonium cobaltinitrite is formed.

3 NH4+ + Na3[Co(NO2)6]  (NH4)3 [Co(NO2)6] (yellow) + 3 Na+
F-3. Because CaSO4 precipitate form a complex with (NH4)2 SO4 which is water soluble
CaSO4 + (NH4)2SO4   (NH4)2Ca(SO4)2 (soluble)
F-4. Mg2+ ions will also be precipitated.
F-5. Sr2+ + NH4+ + SO42–  SrSO4  (white) + NH4+

Ca2+ + 2 NH4+ + 2 SO42–  (NH4)2[Ca(SO4)2] (soluble complex).
F-6. White precipitate is obtained.

Ca2+ + 2K+ + [Fe(CN)6]4–  K2Ca[Fe(CN)6] 
F-7. (A) : CaC2O4 (B) : CaO (C) : CO (D) : CO2
PART - II
A-1. (C) A-2. (B) A-3. (C) A-4. (C) A-5. (B)
A-6. (B) A-7. (C) A-8. (A) B-1. (C) B-2. (C)
B-3. (A) B-4. (C) B-5. (A) B-6. (D) B-7. (C)
B-8. (B) B-9. (C) B-10. (D) C-1. (C) C-2. (B)
C-3. (D) D-1. (D) D-2. (B) D-3. (B) D-4. (B)
D-5. (B) D-6. (C) E-1. (A) E-2. (C) E-3. (B)
E-4. (D) E-5. (D) E-6. (C) E-7. (A) E-8. (D)
F-1. (D) F-2. (C) F-3. (C) F-4. (B) F-5. (C)
F-6. (C) F-7. (C)
PART - III
1. (A - p,r) ; (B - p,q) ; (C - p,s) ; (D - q,s) 2. (A - p,q,r ; B - r,s ; C - p,q,s,t ; D - p,s)
3. (A - p,q ; B - p,s ; C - s ; D - p,r)
EXERCISE - 2
PART - I
1. (D) 2. (A) 3. (B) 4. (C) 5. (D)
6. (D) 7. (D) 8. (B) 9. (A) 10. (D)
11. (D) 12. (C) 13. (D) 14. (C) 15. (B)
16. (A) 17. (C) 18. (C)
ADVQUA - 43
PART - II
1. 3 2. 4 3. 3 4. 4 5. 2
6. 3 7. 3 8. 20 9. a=6 ; b=3,a+b=9
10^. 5
PART - III
1. (B,C) 2. (A,B,C,D) 3. (A,B,C) 4. (C,D) 5. (A,B)
6. (A,B,C,D) 7. (A,B,C,D) 8. (A,C,D) 9. (A,D) 10. (A,D)
11. (A,C,D) 12. (A,C) 13. (B,C,D) 14. (A,D) 15. (A,B,C)
PART - IV
1. (C) 2. (B) 3. (D) 4. (B) 5. (B)
6. (D)
EXERCISE - 3
PART - I
1. (B) 2. (a) (A) = Pentaaquathiocyanato-S-iron(III); (B) = Hexafluoridoferrate(III) (b) 5.93 B.M.
3. (B) 4. (B) 5. (C) 6. (B) 7.* (A)
8. (D) 9. (C) 10. (B) 11. (B) 12. (A)
13. (C) 14. (A) 15.* (A,C,D) 16. (B) 17. (D)
18. (A) 19. (D) 20. 7 21. (C)
PART - II
1. (1) 2. (2) 3. (1)
ADVQUA - 44
This Section is not meant for classroom discussion. It is being given to promote self-study
and self testing amongst the Resonance students.
PART - I : PRACTICE TEST-1 (IIT-JEE (MAIN Pattern))

Max. Marks : 120 Max. Time : 1 Hr.
Important Instructions
1. The test is of 1 hour duration.
2. The Test Booklet consists of 30 questions. The maximum marks are 120.
3. Each question is allotted 4 (four) marks for correct response.
4. Candidates will be awarded marks as stated above in Instructions No. 3 for correct response of each question.
¼ (one fourth) marks will be deducted for indicating incorrect response of each question. No deduction from
the total score will be made if no response is indicated for an item in the answer sheet.
5. There is only one correct response for each question. Filling up more than one response in any question will
be treated as wrong response and marks for wrong response will be deducted accordingly as per instructions
4 above.
1. Identify the compound which turns black with ammonia solution.
(1) Lead chloride (2) Mercurous chloride
(3) Mercuric chloride (4) Silver chloride
2. A white crystalline substance dissolves in water. On passing H2S in this solution, a black precipitate is
obtained. The black precipitate dissolves completely in hot HNO3. On adding a few drops of concentrated
H2SO4, a white precipitate is obtained which is soluble in ammonium acetate. The white precipitate is that of:
(1) BaSO4 (2) SrSO4 (3) PbSO4 (4) Ag2SO4
3. The composition of golden spangles is :
(1) PbCrO4 (2) PbI2 (3) As2S3 (4) BaCrO4
4. In which of the following solvents, AgBr will have the highest solubility ?
(1) 10–3 M NaBr (2) 10–3 M NH4OH (3) Pure water (4) 10–3 M HBr
5. Which one among the following pairs of ions can not be separated by passing H2S gas in presence of dilute
hydrochloric acid?
(1) Cd2+, Sn2+ (2) Al3+, Hg2+ (3) Zn2+, Cu2+ (4) Ni2+, Bi3+
6. Which of the following is not precipitated as sulphide by passing H2S in the presence of concentrated HCl ?
(1) Copper (2) Arsenic (3) Cadmium (4) Lead
7. Which of the following metal cation is reduced from its higher oxidation state (+2) to (+1) by both KI solution
and excess of KCN solution ?
(1) Zn2+ (2) Hg2+ (3) Cu2+ (4) None
8. Which of the following reagents give an orange coloured soluble complex when dissolved in excess with Bi+3
ions ?
(1) Ammonia solution (excess).
(2) Dilution in water
(3) Potassium iodide solution.
(4) Freshly prepared 0.125 M alkaline sodium tetrahydroxidostannate (II) solution.
9. Which of the following ions on reaction with NaOH and subsequent heating produce black ppt.
(1) Cu+2 (2) Zn+2 (3) Al+3 (4) Sn+2
ADVQUA - 45
10. FeCl3 + K3[Fe(CN)6] + H2O2  Precipitate. The colour of the precipitate is :
(1) sky blue (2) brown (3) prussian blue (4) white
ether
11. CrO42– + H+ + H2O2   X + H2O
Identify the correct statement with respect to X.
(1) It is an acid anhydride of chromic acid.
(2) It is a red colour compound which can be extracted easily into the ethereal phase.
(3) It is chromium peroxide which produces blue colouration in ethereal layer on gentle shaking.
(4) It is Cr2O3 which is used as a green pigment.
12. White precipitate of Mn(OH)2 on heating with PbO2 and concentrated HNO3 gives red-violet (purple) colour
due to the formation of :
(1) HMnO4 (2) Mn2O7 (3) MnO(OH)2 (4) PbMnO4
13. Zn(OH)2 precipitate is soluble in :
(1) excess of sodium hydroxide (2) excess of ammonia solution
(3) solutions of ammonium salts (4) all of these
14. Select the correct statement with respect to Ca2+ ions.
(1) K2CrO4 gives white precipitate in the presence of acetic acid.
(2) Potassium hexacyanidoferrate (II) solution gives white precipitate.
(3) It gives lilac colour in Bunsen flame.
(4) Prolonged passage of carbon dioxide gas through its aqueous solution produces white precipitate.
15. A mixture of two salts is not water soluble but dissolves completely in dilute HCl to form a colourless
solution. The mixture could be :
(1) AgNO3 and KBr (2) BaCO3 and ZnS
(3) FeSO4 and Na2CO3 (4) Mn(NO3)2 and MgSO4
16. The reagents, NH4Cl and aqueous NH3 will precipitate :
(1) Ca2+ (2) Al3+ (3) Mg2+ (4) Zn2+ .
17. In the precipitation of the iron group in qualitative analysis, ammonium chloride is added before adding
ammonium hydroxide to :
(1) decrease concentration of OH– ions (2) prevent interference by phosphate ions
–
(3) increase concentration of Cl ions (4) increase concentration of NH4+ ions
18. Fe2+ does not give prussian blue colour with K4[Fe(CN)6] but on its reaction with (X), prussian blue colour
appears (X) can be :
(1) MnO4–/ H+ (2) Zn/NaOH (3) NH3 (aq) (4) all true
19. Select the correct statement with respect to Fe3+ ions.
(1) Iron (III) ions react with H2S in acidic solution to give a black precipitate of Fe2S3.
(2) Iron (III) ions react with ammonium sulphide to give the black precipitate of Fe2S3.
(3) Iron (III) ions react with ammonium thiocyanate solution to produce deep red colouration.
(4) All of these
20. Which of the following cation does not give red colour precipitate/solution with dimethylglyoxime (DMG) in
alkaline solution ?
(1) Zn+2 (2) Ni+2 (3) Fe2+ (4) both (1) and (3)
21. A suspension containing insoluble substances ZnS, MnS, HgS, Ag2S and FeS, is treated with 2N HCl. On
filtering, the filtrate contains appreciable amounts of which one of the following?
(1) Zinc and mercury (2) Silver and iron
(3) Manganese and mercury (4) Zinc, manganese and iron
22. Potassium chromate K2CrO4 is NOT used to identify.

(1) Pb+2 (2) Ba+2 (3) Ag+ (4) Ca+2
ADVQUA - 46
23. When H2S gas is passed through HCl containing aqueous solution of CuCl2 , HgCl2, BiCl3, and CaCl2 it does
not precipitate out :
(1) CuS (2) HgS (3) Bi2S3 (4) CaS
24. Ag2S is soluble in NaCN due to formation of :

(1) Na[Ag(CN)2] (2) Ag(CN)2 (3) Na2[Ag(CN)3] (4) Na2[Ag(CN)2]
25. Cu2+ and Ag+ are both present in the same solution. To precipitate one of the ions and leave the other in
soluton, which reagent should be added :
(1) H2S (aq) (2) HCl (aq) (3) HNO3 (aq) (4) NH4NO3 (aq)
aq. NH3
26. Aqueous (A) + K2CrO4  (B)   (C)
(Red ppt.) (soluble)
A is :
(1) AgNO3 (2) Pb(NO3)2 (3) Hg2(NO3)2 (4) Ca(NO3)2
27. The ion most difficult to remove as a precipitate is :
(1) Ag+ (2) NH4+ (3) Fe3+ (4) Cu2+
28. CuSO4 reacts with NH4OH to give deep blue complex of :

(1) [Cu(NH3)4]SO4 (2) [Cu(NH3)4](OH)2 (3) Both (1) and (2) (4) none of these
29. Thenard blue is :
(1) Cu(NH3)4SO4 (2) CoAl2O4 (3) K2Fe[Fe(CN)6] (4) Fe4[Fe(CN)6]3
30. Among the species A (CrCl3), B (CuS), C (AlCl3), D (ZnCl2), which will be soluble in excess of NaOH ?
(1) A,C and D (2) C and D only (3) B and C only (4) A and D only
Practice Test-1 (IIT-JEE (Main Pattern))

OBJECTIVE RESPONSE SHEET (ORS)
Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22 23 24 25 26 27 28 29 30
Ans.
PART - II : NATIONAL STANDARD EXAMINATION IN CHEMISTRY (NSEC) STAGE-I

1. A 0.1 M solution of certain cation will precipitate with 0.1 M solutions of all these anions OH–, CO3–2 &
SO4–2. This description is true for the cation. [NSEC-2000]
(A) Fe2+ (B) Mg2+ (C) Ba2+ (D) Pb2+
2. If H2S gas is passed in a acidified ZnSO4, the precipitation of ZnS does not take place because
[NSEC-2002]
(A) Ksp of ZnS is not exceeded (B) Ksp of ZnS is decreases
(C) Ksp of ZnS is increases (D) none of these
3. A solution containing Co2+ , Zn2+ and AI3+ is mixed with an excess of KSCN solution. The resulting solution
besides the unreacted ions, should contain [NSEC-2003]
(A) [Co(SCN)6]4- (B) [Zn(NCS)6]2- (C) AI(SCN)3 (D) Zn(SCN)2.
ADVQUA - 47
4. The blue pigment prussian blue is an iron complex with formula [NSEC-2003]
(A) K4[Fe(CN)6] (B) K2[Fe(CN)4(NH3)2]
(C) Fe4[Fe(CN)6]3 (D) Na2[Fe(CN)5NO].
5. When H2S is passed through a solution containing Cu2+ , Cd2+ and an excess of cyanide ions, cadmium
sulphide precipitates while copper ions remain in solution. This is because [NSEC-2003]
(A) Cu2+ forms a stable complex with cyanide while Cd2+ does not
(B) Cu2+ forms a more stable complex with cyanide than Cd2+
(C) Cu2+ does not form a sulphide
(D) both CdS and CuS are formed, but CuS is soluble.
6. Generation of a blue colour which is not due to metal ammonia complex formation is seen when
[NSEC-2003]
(A) sodium is dissolved in liquid ammonia
(B) copper (II) sulphate is reacted with ammonium hydroxide
(C) cobalt (II) chloride is reacted with ammonium hydroxide
(D) formaldehyde is reacted with ammonuim hydroxide.
7. There is a mixture of Cu(II) chloride and Fe (II) sulphate. The best way to separate the metal ions from this
mixture in qualitative analysis is by treating it with [NSEC-2003]
(A) hydrogen sulphide in mild acidic medium, where only Cu(II) sulphide will be precipitated
(B) ammonium hydroxide buffer, where only Fe(II) hydroxide will be precipitated
(C) hydrogen sulphide in mild acidic medium, where only Fe(II) sulphide will be precipitated
(D) ammonium hydroxide buffer, where only Cu(II) hydroxide will be precipitated.
8. Aqueous solutions having equimolar quantities of Pb(NO3)2, AgNO3, AgSO4, BaCl2 and K2CrO4 are allowed to
react and the reaction mixture is then filtered. Which ions in the filtrate in appreciable quantity ?
[NSEC-2007]
(A) Pb2+, Ag+, Ba2+, K+, NO3, SO42 CrO42 Cl (B) Ba2+, K+, NO3, CrO42
(C) Pb2+, Ba2+, K+, NO3,CrO42 (D) K+, NO3
9. 1 mL of concentrated aqueous ammonia is added dropwise to 1 mL of a dilute aqueous solution of Cu(II).

What observations can be made during this process ? [NSEC-2008]
(A) The colorless Cu(II) nitrate solution turns blue and yields a dark blue precipitate
(B) The colorless copper (II) nitrate solution yields a white precipitate which turns dark blue upon standing.
(C) The light blue copper (II) nitrate solution yields a white precipitate which redissolves to form a dark blue
solution.
(D) The light blue copper (II) nitrate solution turns dark
10. Two white solids, lead (II) chloride and silver chloride can be distinguished from each other by -
[NSEC-2008]
(A) adding cold water to each : the silver chloride will dissolve.
(B) adding hot water to each : the lead (II) chloride will dissolve.
(C) adding sodium chloride solution to each : the lead (II) chloride will become warm and release chlorine
gas.
(D) adding zinc chloride solution to each : the silver chloride will change to metallic silver.
11. CuSO4 reacts with KCN to form water insoluble CuCN. This insoluble precipitate dissolves in excess of KCN,
due to formation of the following complex [NSEC-2008]
(A) K2[Cu(CN)4] (B) K3[Cu(CN)4] (C) Cu(CN)2 (D) Cu[KCu(CN)4]
12. The pair of cations which cannot be separated by H2S in a 0.3N acid solution is - [NSEC-2011]
(A) Al+++, Hg++ (B) Bi+++, Pb++ (C) Zn++, Cu++ (D) Ni++, Cd++
13. An aqueous of a salt ‘X’ gives white precipitate with dilute H2SO4. The same solution with a few drops of aq.
KI gives golden yellow precipitate which dissolves on heating. The salt ‘X’ is : [NSEC-2012]
(A) Ba(NO3)2 (B) Sr(NO3)2 (C) Pb(NO3)2 (D) Zn(NO3)2
ADVQUA - 48
14. The ions which give black precipitates on passing H2S gas in acidic medium are [NSEC-2013]
(A) Al3+ and Ni2+ (B) Ni2+ and Co2+ (C) Cu2+ and Bi3+ (D) Zn2+ and Mn2+
15. The pair of compounds that will not react with each other in an aqueous solution, at room temperature is
[NSEC-2014]
(A) FeCl3 ,SnCl2 (B) HgCl2 ,SnCl2 (C) FeCl2 ,SnCl2 (D) FeCl3 ,K
16. The colorless salt that gives white precipitate with BaCl2 in aqueous HCl is [NSEC-2014]
(A) K 2SO 4 (B) K 2SO3 (C) KNO3 (D) KBr
PART - III : ADDITIONAL PROBLEMS
SUBJECTIVE QUESTIONS
1. Does mercuric sulphide dissolve in sodium sulphide solution (of 2M) ?
2. What happens when black precipitate of HgS is dissolved in aquaregia ?

3. Which basic radical is tested with the help of alkaline sodium stannite solution ?
4. Does tartaric acid can be used to distinguish SbOCl and BiOCl ?
5. What happens when Mn(II) ions free from chloride ions react with acidified solution of (NH4)2S2O8 or K2S2O8
in presence of a few drops of AgNO3 solution ?
6. How bromine water test (Alkaline medium) can be used to distinguish between Co2+ and Ni2+ ions ?
7. A mixture consists (A) (red solid) and (B) (colourless solid) which gives lilac colour in flame.
(a) Mixture gives black precipitate (C) on passing H2S (g).
(b) (C) is soluble in aquaregia and on evaporation of aquaregia and adding SnCl 2 gives
greyish black precipitate (D).
The salt solution with NH4OH gives a brown precipitate.
(i) The sodium extract of the salt with CCl4/FeCl3 gives a violet layer.
(ii) The sodium extract gives yellow precipitate with AgNO3 solution which is insoluble in dilute ammonia
solution.
Identify (A) and (B), and the precipitates (C) and (D). [JEE 2003, 4/60]
8. When a crystaline compound (X) is heated with K2Cr2O7 and concentrated H2SO4, a deep red gas (A) is
evolved. On passing (A) into caustic soda solution, a yellow coloured solution of (B) is obtained. Neutralizing
the solution of (B) with acetic acid and on subsequent addition of lead acetate a yellow precipitate (C) is
obtained. When (X) is heated with NaOH solution, a colourless gas is evolved and on passing this gas into
K2Hg4 solution, a reddish brown precipitate (D) is formed. Identify (A), (B), (C), (D) and (X). Write the equations
of reactions involved. [JEE 2002, 5/150]
ONLY ONE OPTION CORRECT TYPE

9. Dissolution of white precipitate of Hg2Cl2 in aquaregia evolved the gas
(A) Cl2 (B) NO (C) NO2 (D) HCl
10. White ppt of silver gives brown ppt on boiling but when it is heated (>300°C), then a metallic black ppt. is
obtained. Identify the compound of silver having white ppt.
(A) Ag2SO3 (B) Ag2S2O3 (C) Ag2CO3 (D) AgCl
11. Which of the following reagents gives white precipitate with Hg(NO3)2 solution ?
(A) Cobalt (II) thiocyanate (B) Tin (II) chloride (excess)
(C) Ammonia solution (D) Potassium cyanide solution
ADVQUA - 49
12. Which of the following is insoluble in dil. HNO3 but dissolves in aquaregia ?
(A) HgS (B) PbS (C) Bi2 S3 (D) CuS.
13. In regards to Sn2+ and Sn+4 which statement is incorrect -
(A) Sn2+ sulphides is black while Sn+4 sulphide is golden yellow.
(B) Sn2+ sulphides is Brown while Sn+4 sulphide is golden yellow.
(C) Both sulphides dissolve in HCl.
(D) Both chloride does not react with HgCl2.
14. Which metal sulphide is soluble in concentrated HCl ?
(A) AS2S3 (B) SnS (C) HgS (D) None of these
15. SnCl2 solution, when treated with excess of KOH on heating produces
(A) K2SnO2 (B) K2SnO3 (C) K4SnO4 (D) K3SnO3
16. Intense blue precipitate of Fe4[Fe(CN)6]3 and potassium hydroxide solution when mixed gives :
(A) K2Fe[Fe(CN)6] - white precipitate (B) Fe(OH)3 - reddish–brown precipitate
(C) Fe(CN)3 – reddish–brown precipitate (D) KFe[Fe(CN)6] - Turnbull's blue
17. CoS (black) obtained in group IV of salt analysis is dissolved in aqua regia and is treated with an excess of
NaHCO3 and then Br2 water. An apple green coloured stable complex is formed. It is :
(A) sodium cobaltocarbonate (B) sodium cobaltibromide
(C) sodium cobalticarbonate (D) sodium cobaltobromide
18. [SDC_Jan 2015]
Colour of precipitate of " X " is :

(A) green (B) black (C) yellow (D) Reddish Brown
19. The presence of magnesium is confirmed in the qualitative analysis by :
(A) titan yellow solution + 2M NaOH solution (B) disodium hydrogen phosphate +NH4Cl + NH3 (aq.)
(C) magneson(I) reagent (D) all of these
20. To a solution of a substance, gradual addition of ammonium hydroxide results in a brownish black
precipitate which does not dissolve in excess of NH4OH. However, when KI (not in excess) is added to the
original solution, a green precipitate is formed. The solution contained :
(A) Lead salt (B) Silver salt (C) Mercurous salt (D) Copper salt.
21. Which of following is soluble in yellow ammonium sulphide ?
(A) CdS (B) CuS (C) SnS (D) PbS
22. A mixture of chlorides of cadmium, chromium, iron and aluminium was dissolved in water acidified with HCl
and hydrogen sulphide gas was passed for sufficient time. It was filtered, boiled and a few drops of nitric acid
were added while boiling. To this solution ammonium chloride and sodium hydroxide were added in excess
of filtered. The filtrate shall give test for :
(A) sodium and iron ion (B) sodium, chromium and aluminium ion
(C) aluminium and iron ion (D) sodium, iron, cadmium and aluminium ion.
23. Which one of the following cations will give a green coloured ash when a piece of filter paper dipped in a
solution containing its salt and Co(NO3)2 is burned ?
(A) Cu2+ (B) Mg2+ (C) Al3+ (D) Zn2+
24. To avoid the precipitation of hydroxides of Ni2+, Co2+, Mn2+ along with those of the third group cations, the
solutions should be :
(A) heated with few drops of concentrated HNO3. (B) boiled with excess of ammonium chloride.
(C) concentrated to small volume. (D) none of these.
ADVQUA - 50
25. A metal M and its compound can give the following observable changes in a sequence of reactions,
very dilute Colourless solution   White  excess  White 
  
aqueous
M HNO
   
   Colourless  H2S / OH –
  precipitate
3 and no gas is evolved  NaOH precipitate NaOH(aq.) solution   
The metal M can be :
(A) Mg (B) Pb (C) Zn (D) Sn
26. Identify the correct order of solubility of Na2S, CuS and ZnS in aqueous medium. [JEE 2002, 3/150]
(A) CuS > ZnS > Na2S (B) ZnS > Na2S < CuS
(C) Na2S > CuS > ZnS (D) Na2S > ZnS > CuS
SINGLE AND DOUBLE VALUE INTEGER TYPE

27. When a metal rod M is dipped into a aqueous, colourless conc. solution of compound N, which is a nitrate
of metal ‘P’, the solution turns light blue. Addition of aqueous. NaCl to the blue solution given a white ppt ‘O’.
Addition of aqueous NH3, dissolve ‘O’ and give an deep blue solution. The final solution contains [M(NH3)x]n+
and [P(NH3)y]m+. (M) & (N) both belongs to same groups in periodic table. Calculate the value of x + y + n +
m?
dil.HCl
28. Snn+ + H2S    (A) Yellow ppt.
If yellow ppt of (A) has "p" number of atom (per molecule). Then what is the value of (p + n).
29. Na2CrO4 + dil.H2SO4  Na2SO4 + H2CrO4

amyl alcohol
H2CrO4 + 2H2O2      'A' (blue colouration) + H2O
then find a + b, if a = number of O – O bonds in ''A''
b = number of Cr – O (sigma) bonds in ''A''
30. NaBiO3 + Mn(NO3)2 + HNO3  Product
Sum of oxidation number of Bi, N and Mn in products
31. Solution of AsO43– ion containing considerable excess of HNO3 on boiling with Ammonium molybdate test
gives a yellow crystalline precipitate (X). Number of oxygen atom present in per molecule of precipitated (X)
are :
ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

32. Which of the following statement(s) is/are correct ?
(A) Yellow precipitated of silver arsenite is soluble in both nitric acid and ammonia.
(B) Potassium cyanide when added in very small quantity to copper sulphate solution, produces first yellow
precipitate which quickly converts in to white precipitate.
(C) Black precipitate of BiI3 turns orange on heating with water.
(D) White precipitate of Bi(OH)3 turns yellowish brown, when boiled.
33. Ammonium molybdate is used to detect the radical :
(A) PO43– (B) AsO43– (C) Cu2+ (D) Ag+
34. Which of the following sulphides do not dissolve in 50% HNO3 but dissolve in aquaregia ?
(A) CoS (B) NiS (C) CuS (D) HgS
35. Ni + H2SO4 (hot and concentrated)  X(g).

The liberated gas (select the correct statement(s)) :
(A) develops blue colour spots on the filter paper moistened with potassium iodate and starch solution.
(B) turns acidified K2Cr2O7 solution green.
(C) produces black precipitate with lead acetate solution.
(D) reacts with Cl2 water to produce an acid which gives white fumes with ammonia.
ADVQUA - 51
36. Select the incorrect statement(s).
(A) Ammonium ions produce yellow colour solution with sodium hexanitrito-N-cobaltate (III).
(B) Ammonia gas develops a brown colour on filter paper moistened with a solution of MnCl2 and H2O2.
(C) Ammonium ions produce white precipitate with saturated sodium hydrogen tartrate solution.
(D) Ammonium salts in presence of sodium hydroxide solution produces red precipitate with 4-nitrobenzene
diazonium chloride reagent.
37. Which of the following statements is incorrect?
(A ) The black precipitate 'D' is of bismuth.
(B) The black precipitate 'D' is of Hg + Hg(NH2)NO3.
(C) Aqueous solution of 'A' gives yellow precipitate with freshly prepared 10% solution of pyrogallol.
(D) Aqueous solution of 'A' gives red precipitate with 8-hydroxyquinoline (5%) and potassium iodide (6M) in
acidic medium.
PART - IV : PRACTICE TEST-2 (IIT-JEE (ADVANCED Pattern))

Max. Time : 1 Hr. Max. Marks : 66
Important Instructions
A. General %
1. The test is of 1 hour duration.
2. The Test Booklet consists of 22 questions. The maximum marks are 66.
B. Question Paper Format :
3. Each part consists of five sections.
4. Section 1 contains 7 multiple choice questions. Each question has four choices (A), (B), (C) and (D)
out of which ONE is correct.
5. Section 2 contains 5 multiple choice questions. Each question has four choices (A), (B), (C) and (D)
out of which ONE OR MORE THAN ONE are correct.
6. Section 3 contains 6 questions. The answer to each of the questions is a single-digit integer, ranging
from 0 to 9 (both inclusive).
7. Section 4 contains 1 paragraphs each describing theory, experiment and data etc. 3 questions relate
to paragraph. Each question pertaining to a partcular passage should have only one correct answer
among the four given choices (A), (B), (C) and (D).
8. Section 5 contains 1 multiple choice questions. Question has two lists (list-1 : P, Q, R and S; List-2 :
1, 2, 3 and 4). The options for the correct match are provided as (A), (B), (C) and (D) out of which ONLY
ONE is correct.
C. Marking Scheme :
9. For each question in Section 1, 4 and 5 you will be awarded 3 marks if you darken the bubble
corresponding to the correct answer and zero mark if no bubble is darkened. In all other cases, minus
one (– 1) mark will be awarded.
10. For each question in Section 2, you will be awarded 3 marks. If you darken all the bubble(s) corresponding
to the correct answer(s) and zero mark. If no bubbles are darkened. No negative marks will be answered
for incorrect answer in this section.
11. For each question in Section 3, you will be awarded 3 marks if you darken only the bubble corresponding
to the correct answer and zero mark if no bubble is darkened. No negative marks will be awarded for
incorrect answer in this section.
SECTION-1 : (Only One option correct Type)

This section contains 7 multiple choice questions. Each questions has four choices (A), (B), (C) and
(D) out of which Only ONE option is correct.
1. A solution containing SCN– ions can be used to test one or more out of : Fe3+, Co2+ , Cu2+, Ag+ and Hg2+.
(A) Fe3+ and Co2+ only (B) Co2+, Cu2+, Ag+ and Hg2+
3+ 2+ 2+ 2+
(C) Fe , Cu , Co and Hg (D) all
ADVQUA - 52
2. A blue colouration (in solution or precipitate) is not obtained when :
(A) ammonium hydroxide dissolves in copper sulphate.
(B) cobalt chloride reacts with NH4SCN in presence of amyl alcohol.
(C) ferric chloride reacts with sodium ferrocyanide.
(D) aqueous ammonia reacts with white precipitate of silver (I) chloride.
3. A metal nitrate solution reacts with dilute hydrochloric acid to give a white precipitate which is soluble in
concentrated potassium chloride. White precipitate on passing of hydrogen sulphide gas is converted into
black precipitate. The black precipitate on boiling with hydrogen peroxide (3%) is converted again to a white
precipitate which is soluble in ammonium acetate. The cation of the metal nitrate is :
(A) Pb2+ (B) Ag+ (C) Hg2+ (D) Bi3+
4. A metal nitrate solution does not give white precipitate with concentrated hydrochloric acid but on dilution
with water produces a white precipitate. The metal nitrate solution with K2CrO4 and Na2HPO4 reagents gives
red and yellow precipitates respectively which are soluble in ammonia solution. The cation of the metal
nitrate is :
(A) Pb2+ (B) Ag+ (C) Cu2+ (D) Bi3+
5. Which of the following pairs comprise the red precipitates ?
(A) Ag2CrO4 and Hg2CrO4 (B) HgI2 and Ni(dmg)2
(C) BiOI and Cu2[Fe(CN)6] (D) (A) and (B) both
6. A coloured solution of an inorganic salt reacts with potassium thiocyanate to give first a black precipitate,
which slowly turns white. The salt solution also gives black precipitate with H2S gas in slightly acidic medium.
The black precipitate dissolves in potassium cyanide forming a colourless solution. The basic radical present
in the inorganic salt is :
(A) Bi3+ (B) Cu2+ (C) Hg2+ (D) None
7. Select the incorrect statement.
(A) Marsh's test involves the reduction of soluble arsenic compound to arsine by nascent hydrogen in acidic
solution and its subsequent decomposition into hydrogen and metallic arsenic as a brownish-black mirror on
heating in a glass tube mixed with hydrogen.
(B) Ammonical silver nitrate gives metallic silver mirror with saturated solution of hydrazine sulphate.
(C) Red precipitate of silver (I) chromate is soluble in dilute nitric acid and ammonia solution.
(D) None of these
Section-2 : (One or More than one options correct Type)

This section contains 5 multipole choice questions. Each questions has four choices (A), (B), (C) and
(D) out of which ONE or MORE THAN ONE are correct.
8. The following can be used to regulate the concentration of OH¯ ions for the scheme of basic radical analysis
(III group).
(A) NH4NO3 (B) NH4Cl (C) (NH4)2SO4 (D) (NH4)2CO3
9. White precipitate of PbSO4 gets dissolved in :
(A) concentrated H2SO4 on heating (B) concentrated NaOH
(C) (NH4)2CO3 (D) dilute HNO3
10. Select the correct statement(s).
(A) In group III, Fe3+ and Cr3+ can be differentiated by increasing NH4+ ion concentration
(B) In Vth group, Na2CO3 is added to precipitate out only the carbonates of Ba2+, Sr2+ and Ca2+.
(C) Like brown ring test, diphenylamine test is given only by salts containing NO3–.
(D) Sodium chloride on heating with aqueous solution of K2Cr2O7 and concentrated H2SO4 produces deep red
vapours.
ADVQUA - 53
11. Which of the following statement(s) is/are not correct ?
(A) Nickel salts give rosy red precipitate with dimethyl glyoxime in excess of NH4OH.
(B) Fe (III) salts give red colour with potassium sulphocyanide.
(C) In nitroprusside, the iron and NO exist as Fe(III) and NO.
(D) Mn (II) salts give white precipitate with NaOH which turns brown on adding Br2 water.
12. Potassium ferrocyanide is used for testing
(A) Cu2+ and Zn2+ (B) Fe3+ and Ca2+ (C) Ag+ and Zn2+ (D) Th4+ and Cu2+
Section-3 : (One Integer Value Correct Type.)

This section contains 6 questions. Each question, when worked out will result in one integer from
0 to 9 (both inclusive)
13. How many of the following pairs of ions can be separated by H2S in dilute HCl ?
Bi3+ and Sn4+, Al3+ and Hg2+, Cd2+ and Zn2+, Fe3+ and Cu2+, As3+ and Sb3+
14. In how many of the following reactions, one of the product is obtained as a yellow precipitate ?
Ba2+ (aq) + CrO42– (aq)  product
Ag+ (aq) + Br – (aq)  product
Pb2+ (aq) + I– (aq)  product
NH4+ (aq) + [PtCl6]2– (aq)  product
15. In how many of the following cases solubility of salt is greater in acidic solution than in pure water?
AgCl, AgCN, MnS,
Zn(OH)2, Ag3PO4, AgNO2,
Al(OH)3, CH3COOAg, BaSO3
16. How many statements are correct ?

(i) Like CO32–, SO32– also gives test with lime water.
(ii) In the test of NO3– , brown ring is formed due to the formation of [Fe (H2O)5 NO]2+ .
(iii) Aqueous solution of Ag+ ions gives brick red/red precipitate with K2CrO4.
(iv) Lead salts turn black on prolonged exposure in a chemical laboratory.
(v) In analysis of group IInd cations, H2S gas is passed in presence of hydrochloric acid to enhance the
concentration of S2– ions.
(vi) Aqueous solution of Cu2+ ions forms a green complex with K4[Fe(CN)6].
17. How many of the following reaction result in the formation of colored precipitate (not white).
(a) HgCl2 + SnCl2 (excess)  (b) HgCl2 + KI 
(c) Pb(NO3)2 + KCl  (d) NH4Cl + NO2– + Co3+ 
(e) Ni2+ + + NH4OH 
aq. Pb 2 
(f) K2Cr2O7 + conc.H2SO4 + Cl2  A  B  
 ?
NaOH
(g) K2CrO4 + Hg22+  (h) Hg2+ + Co2+ + SCN– 
(i) Cu2+ + I– 
(k) Cd2+ + CN– 
18._ Which of the following sulphides are not black in colour.

PbS, CdS, As2S3, Sb2S3, SnS, CoS, HgS, ZnS, MnS.
ADVQUA - 54
SECTION-4 : Comprehension Type (Only One options correct)

This section contains 1 paragraphs, each describing theory, experiments, data etc. 3 questions relate to the
paragraph. Each question has only one correct answer among the four given options (A), (B), (C) and (D)
Paragraph For Questions 19 to 21
19. Compound (A) is :

(A) HgI2 (B) K2HgI4 (C) Hg(NO3)2 (D) Hg2(NO3)2
20. (D) + (NH4)2SO4  brown ppt. (G). Hence, compound (G) is :
in basic medium
(A) HgI2 (B) NH4I (C) HgO.Hg(NH2)I (D) Hg(NH2)I
21. White ppt. (B) + (NH3  Black ppt. (H). Hence, (H) is due to the formation of :
in basic medium
(A) Hg(NH2)CI (B) Hg (C) Hg(NH2)Cl + Hg (D) Hg(NH2)2
SECTION-5 : Matching List Type (Only One options correct)

This section contains 1 questions, each having two matching lists. Choices for the correct combination
of elements from List-I and List-II are given as options (A), (B), (C) and (D) out of which one is correct
22. Match the reactions/reaction conditions listed in column-I with the characteristics/ precipitate colour of the
reaction products listed in column-II.
Column  Column 

(P) 2NiS + 2HNO3 + 6HCl      
extract with water
(1) Black precipitate & its chloride imparts greenish blue
flame.
amyl alcohol
(Q) CoCl2 + 4NH4 CNS 
 (2) Blue colour in organic layer.

(R) CuCl2 + NaOH  (3) White precipitate soluble in ammonium acetate.
(S) Sr(CH3COO)2 + (NH4)2 C2O4  (4) Green colour solution.
(T) H2SO4 + PbCl2  (5) Yellow precipitate soluble in NaOH.
(U) Na2CrO4 + (CH3OO)2 Pb  (6) Scarlet / red precipitate.
(V) HgCl2 + KI (Not in excess)  (7) White precipitate & its chloride imparts crimson flame.
Code :
P Q R S T U V
(A) 1 3 2 4 7 6 5
(B) 3 2 7 6 5 4 1
(C) 4 2 1 7 3 5 6
(D) 7 3 5 6 4 2 1
ADVQUA - 55
Practice Test-2 ( (IIT-JEE (ADVANCED Pattern))
OBJECTIVE RESPONSE SHEET (ORS)
Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22
Ans.
PART - V : INTERNATIONAL CHEMISTRY OLYMPIAD (IChO) STAGE-V

Problem 1 [IChO-1998]
The following 8 steps describe the procedure for analyzing a sample of an alloy that contains tin and lead.
1. A 0.4062 g sample of alloy was dissolved by heating it in a small beaker with a mixture of 11 M hydrochloric
acid and 16 M nitirc acid, The beaker was heated unitl all the alloy dissolved. In this procedure, lead is
oxidised to Pb(II) and in becomes Sn(IV) .
2. After 5 minutes of heating to expel oxides of nitrogen and chlorine, then a precipitate of some tin compounds
and a lead compound appeared.
3. A 25.00 mL a liquid of 0.20000 M N2EDTA solution was added. The precipitate dissolved and a clear, colourless
solution was obtained.
4. This solution was quantitatively transferred to a 250.0 mL volumetric flask and made up to the mark with
distilled water.
5. A 25.00 mL a liquid of this solution was treated with 15 mL of a 30% w/v solution of hexamine
(hexamethylenetramine), 130 mL of water and two drops of Xylenol Orange solution. The pH of the solution
was 6.
6. The clear, yellow solution from step 5 was titrated with standard 0.009970 M lead nitrate solution until the
colour just changed from yellow to red. The titre at this endpoint was 24.05 mL.
7. 2.0 g of solid NaF was added to the titration flask The solution immediately turned back to yellow.
8. The solution was titrated with more standard 0.009970 M lead nitrate solution until the colour changed to red
again. The titre at this endpoint was 15.00 mL.
Hexamine and Xylenol Orange have the structures shown below. The pKb of hexamine is 9.5. Xylenol Orange
red is below pH 4, yellow above pH 5.
N
N N
N
Hexamine
O
||
O S
OH O
||
||
O OH
||
O O
||
||
HO OH
OH OH
Xylenol Orange (Xo)
ADVQUA - 56
K’ MY is the conditional formation constant =  KMY K’ MY for the formation of the EDTA complexes of Pb(II)
and Sn (IV), in the presence and absence of fluoride, are shown in the following figure.
Sn + ESTA
22
STA
20 Pb + E
18
16 Pb + ESTA + F
14
12
10
8
6 Sn + EDTA + F
4
2
0
-2 1 2 3 4 5 6 7 8 9 10 11 12
-4
1.1 What is the lead compound that precipitates in step 2 ?

1.2 Write a balanced ionic equation that explains the disappearance of the lead compound that precipitated in
step 3 (at pH 6).
1.3 What is the purpose of hexamine in step 5 of this analysis?
1.4 What is the purpose of Xylenol Orange in this analysis?
1.5 Write balanced ionic equations for the reactions that occur (i) during the titration and (ii) are responsible for
the colour change at the endpoint in step 6 of the analysis.
1.6 What is the purpose of NaF in step 7 of this analysis ?
1.7 Write a balanced ionic equation for the reaction that occurs in step 7.
1.8 Write a balanced equation that explains why the colour changed from red to yellow in step 7 of this analysis.
1.9 Write a balanced ionic equation that explains why the lines on the graph above of log K’MY versus. pH for Pb
+ EDTA and Pb + EDTA + F are coincident below pH 2.
1.10 Calculate the percentage by mass of Sn and Pb in the alloy.
ADVQUA - 57
PART - I
1. (2) 2. (3) 3. (2) 4. (2) 5. (1)
6. (3) 7. (3) 8. (3) 9. (1) 10. (3)
11. (3) 12. (1) 13. (4) 14. (2) 15. (2)
16. (2) 17. (1) 18. (1) 19. (3) 20. (1)
21. (4) 22. (4) 23. (4) 24. (1) 25. (2)
26. (1) 27. (2) 28. (1) 29. (2) 30. (1)
PART - II
1. (D) 2. (A) 3. (C) 4. (C) 5. (B)
6. (A) 7. (A) 8. (D) 9. (C) 10. (B)
11. (B) 12. (B) 13. (C) 14. (C) 15. (C)
16. (A)
PART - III
1. Yes , forming a soluble complex.
HgS + S2–   [HgS2]2–
2. 3HgS +6HCl +2HNO3 

 3HgCl2 +3S + 2NO +4 H2O
3. Bi3+ ; Bi3+ + 3OH– 

 Bi(OH)3  ; 2Bi(OH)3  + 3[Sn(OH)4]2– 
 2Bi  (black) + 3[Sn(OH)6]2–.
4. Yes : SbOCl is soluble in tartaric acid but BiOCl is insoluble in tartaric acid.
5. Reddish–violet colouration is obtained owing to the formation of MnO4–.

2 Mn2+ + 5 S2O82– + 8 H2O   MnO4– + 10 SO42– + 16 H+
AgNO3 acts as catalyst.
6. Ni2+ gives black ppt (Ni2O3) with NaHCO3 and bromine water on heating. Where as Co2+ gives green coloured
solution.
NiCl2 + 2NaHCO3   NiCO3 + 2NaCl + H2O
2 NiCO3 +[O]   Ni2O3  (Black) +2CO2
7. (A), (B), (C) and (D) are HgI2, KI, HgS and Hg respectively.
8. (X) = NH4Cl, (A) = CrO2Cl2 , (B) = Na2CrO4 , (C) = PbCrO4 , (D) =
9. (B) 10. (C) 11. (C) 12. (A) 13. (A)
14. (B) 15. (A) 16. (B) 17. (C) 18. (B)
19. (D) 20. (C) 21. (C) 22. (B) 23. (D)
24. (B) 25. (C) 26. (D) 27. 9 28. 7
29. 2+5=7 30. 7 + 3 + 5 = 15 31. 40 32. (A,B,C) 33. (A,B)

34. (A,B,D) 35. (A,B,D) 36. (A,D) 37. (B)
ADVQUA - 58
PART - IV
1. (D) 2. (D) 3. (A) 4. (B) 5. (D)
6. (B) 7. (D) 8. (A,B) 9. (A,B) 10. (A)
11. (C) 12. (A,B,C,D) 13. 3 14. 4 15. 8
16. 4 17. 07 18. 6 19. (D) 20. (C)
21. (C) 22. (C)
PART - V
1.1 PbCl2 or any hydroxo species etc.
1.2 PbCI2(s) + H2Y2–  PbY2– + 2H+ + 2 Cl– or similar
1.3 It forms a pH buffer.
1.4 It is a metallochromic indicator.

1.5 (i) The reaction that occurs during the titration:
Pb2+ + H2Y2–  PbY2– + 2 H+
(ii) At the endpoint, a slight excess of Pb2+ forms a red complex with the xylenol orange indicator:
Pb2+ + XO (yellow)  PbXO2+ (red)
1.6 The role of the NaF: It forms a complex with tin.
1.7 From the graph of log K'MY VS pH, it can be seen that the fluoride forms a stable complex with Sn4+ but not
with Pb2+ at pH 6, displacing EDTA:
SnY + nF– + 2H+  SnFn(n–4)– + H2Y2– where n is typically 4 - 6.
1.8 The released EDTA destroys the small amount of red PbXO complex, producing free (yellow) XO. (Charge on
XO ignored)
H2Y2– + PbXO2+  PbY2– + XO(yellow) + 2 H+
1.9 Below pH 2, F– is protonated and does not compete effectively with Y for Pb2+ H+ + F–  HF.
1.10 The percentage by mass of Sn and Pb in the alloy:
The amount of EDTA in excess from the amount of standard Pb2+ titrant:
n(EDTA) = n(Pb2+) = 0.02405 dm3 × 0.009970 mol dm–3 = 2.398 × 10–4 mol.
The original amount of EDTA:
n(EDTA)init. = 0.1  25.00 dm3  0.2000 mol dm-3 = 5.000 10-4 mol
EDTA consumed by the Pb2+ and Sn4+ in a 25 cm3 aliquot:
n(EDTA)consumed = 5.000 × 10–4 – 2.398 × 10–4 mol = 2.602 × 10–4 mol = n(Pb2+ + Sn4+) in a 25 cm3 aliquot.
The amount of EDTA released from SnY by reaction with fluoride:
n(EDTA) released = n(Pb2+)stand. = 15.00 cm3 × 0.009970 mol dm–3 = 1.496 × 10–4 mol
= n(Sn4+) in the 25 cm3 aliquot
in a 25 cm3 aliquot n(Pb2+) = (2.602 × 10–4 – 1.496 × 10–4) mol = 1.106 × 10–4 mol
In the original 0.4062 g sample of alloy:
m(Sn) = 10 × 1.496 × 10–4 mol × 118.69 g mol–1 = 0.1776 g
m(Pb) = 10 × 1.106 × 10–4 mol × 207.19 g mol–1 = 0.2292 g
The percentages of tin and lead:
Sn: 100 × (0.1776 / 0.4062) = 43.7 %
Pb: 100 × (0.2292 / 0.4062) = 56.4 %
ADVQUA - 59
PART - I
Cl
1. Hg2Cl2 + 2NH3  Hg  (white) + Hg (black) + NH4Cl
NH2
 
Black
2. The white precipitate obtained with H2SO4 is that of PbSO4. The white crystalline substance may be that of
Pb(NO3)2.
Pb2+ + S2–  PbS  (black) ; 3PbS  + 8HNO3  3Pb2+ + 6NO3– + 3S  + 2NO + 4H2O
Pb2+ + SO42–  PbSO4  (white)
PbSO4 + 2CH3COONH4  (NH4)2[Pb(CH3COO)4] + (NH4)2SO4
BaS and SrS are not precipitated. Ag2SO4 is white precipitate but does not dissolve in ammonium acetate.
3. PbI2 is yellow (known as golden spangles).
4. AgBr has the highest solubility in 10–3 M NH4OH
AgBr dissolves in all other solvents poorly.
5. Both Cd2+ and Sn2+ are precipitated as yellow sulphides in the presence of dilute HCl.
6. Cd2+ + H2S  CdS + 2H+, reaction is reversible; if the concentration of strong acid in the solution is
above 0.5 M, precipitation is incomplete. Concentrated acid dissolves the precipitate for the same reason.
7. 2Cu2+ + 4I–  Cu2I2 + I2

Cu2+ + 3CN–  CuCN  + (CN)2
8. (1) Bi3+ + 3NH4OH  Bi(OH)3 (white) + 3NH4+

(2) Bi3+ + NO3– + H2O  BiO(NO3)  (white) + 2H+
Bi3+ + Cl– + H2O  BiOCl  (white) + 2H+
(3) Bi3+ + 3I–  BiI3 (black) ; BiI3 + I–  [BiI4]– (orange solution)
(4) Bi3+ + 3OH–  Bi(OH)3 (white) ; 2Bi(OH)3 + 3[Sn(OH)4]2–  2Bi(black) + 3[Sn(OH)6]2–
9. (1) Cu+2 + 2OH–  Cu(OH)2 

 CuO  +H2O
black ppt.
(2) Zn+2 + 2OH–  Zn(OH)2
white ppt.
(3) Al+3 + 3OH–  Al(OH)3
white ppt.
(4) Sn+2 + 2OH–  Sn(OH)2
white ppt.
10. On adding H2O2 in alkaline medium or SnCl2 solution in acidic medium, the [Fe(CN)6]3– part of the compound
is reduced and prussian blue is precipitated.
11. CrO42– + 2H+ + 2H2O2  CrO5 (chromium peroxide) + 3H2O

It in etheral layer develops blue colouration.
12. Mn(OH)2 + 2HNO3  Mn(NO3)2 + 2H2O.

2Mn(NO3)2 + 5PbO2 + 6HNO3  2HMnO4 (red – violet or purple colour) + 5Pb(NO3)2 + 2H2O.
ADVQUA - 60
13. (1) Zn(OH)2 + 2OH– [Zn(OH)4]2–
(2) and (3) Zn(OH)2 + 4NH3 [Zn(NH3)4]2+ + 2OH–
or NH4+
14. (1) No precipitate with K2CrO4 in acetic acid as its Ksp is high.
(2) Ca2+ + 2K+ + [Fe(CN)6]4–  K2Ca[Fe(CN)6] (white)
(3) It imparts brick red colour to Bunsen flame.
(4) Ca(HCO3)2 is formed which is water soluble.
15. (2) BaCO3 + ZnS mixture dissolves in HCl but is insoluble in water. Further the solution in HCl will be
colourless due to the formation of soluble BaCl2 and ZnCl2.
16. The KSP of Al(OH)3 is low as compared to that of the hydroxides of other metals. The OH– concentration
provided by ammonium hydroxide in presence of NH4Cl is just sufficient to precipitate Al3+ as Al(OH)3.
NH4 Cl
Al3+ + NH3 + H2O   Al(OH)3  (gelatinous white) + NH4+ .
17. Group 3rd radicals are precipitated as hydroxides and the addition of NH4Cl suppresses the ionisation of
NH4OH so that only the group 3 cations are precipitated as hydroxides because of their low solubility
products.
18. MnO4– in acidic medium oxidises Fe2+ to Fe3+.
19. (1) 2Fe3+ + H2S  2Fe2+ + 2H+ + S (white)

(2) 2Fe3+ + 3S2–  2FeS (black) + S
(3) Fe3+ + 3SCN–  Fe(SCN)3 deep red colouration
20. Ni2+ and Fe2+ both on reaction with alkaline solution of dimethyl glyoxime give red precipitate and red solution
respectively but not zinc.
21. Ag2S + 2HCl  AgCl  + 2H2S ; HgS is also insoluble in 2N HCl so silver and mercury do not pass into
filtrate while ZnS, MnS and FeS dissolve in 2N HCl forming their soluble chlorides and thus pass into filtrate.
22. (1) Pb+2 + CrO–2

4  PbCrO4 (yellow ppt)
(2) Ba+2 + CrO–2

4
 BaCrO4 (Yellow ppt)
(3) Ag + CrO–2

4
 Ag2CrO4 (Brick like red ppt)
(4) Ca+2 + CrO–2

4
 CaCrO4 (soluble)
23. CaS belongs to Vth group and precipitate by H2S in presence of NH4OH and NH4Cl
24. Ag2S + NaCN  Na[Ag(CN)2] (soluble)
25._ (1) Cu2+ + H2S  CuS (ppt.)

Ag2+ + H2S  Ag2S (ppt.)
(2) Cu2+ + HCl  CuCl2 (soluble)
Ag2+ + HCl  AgCl (ppt.)
with HNO3 and (NH4)2NO3 both Ag+ and Cu2+ form soluble compound.
NH
 Ag(NH3 )2   CrO 24–

26. 2Ag   CrO 24 –  Ag2CrO 4  
3
( red ppt.) ( So lub le)
27. Because NH4+ form soluble compounds.
28. CuSO4 + NH4OH  [Cu(NH3)4]SO4 + H2O
ADVQUA - 61
29. 2Al2O3 + 2Co+2 + 4NO3–  2CoAl2O4 (thenard blue) + 4NO2 + O2
30. CrCl3 + NaOH  Cr(OH)3  [Cr(OH4)]– (soluble)
AlCl3 + NaOH  Al(OH)3  [Al(OH4)]– (soluble)
ZnCl2 + NaOH  Zn(OH)2  [Zn(OH4)]2– (soluble)

CuCl2 + NaOH  Cu(OH)2  (not soluble in excess NaOH)
PART - III
7. (A) + (B)  lilac colour in flame. So one of the cation may be K+ .
H2 S ( g )
(a) (A) + (B)   (C) black precipitate.
so lub le Evaporatio n SnCl2
(b) (C)   soluble     Residue   Greyish black precipitate (D).
in aqua regia
NH4 OH
(A) + (B)   brown precipitate. So second cation may be Hg2+.
CCl 4 / FeCl3
(i) Sodium carbonate extract of salt    violet colour..
AgNO 3 NH3
(ii) Sodium extract of salt   yellow precipitate   soluble.
So the anion may be I .
–
(a) HgI2 + H2S  HgS (C)  (black) + 2HI.

(b) 3HgS + 6HCl + 2HNO3  3HgCl2 + 2NO + 4H2O + S.
HgCl2 + SnCl2  Hg  (D) (greyish black) + SnCl4.
2KI (B) + HgI2 (A)  K2[HgI4] (colourless).

2K2[HgI4] + NH3 + 3KOH  [HgOHg(NH2)I]  ( brown).
Sodium carbonate extract of salt contains NaI.
CCl4
2NaI + 2Fe3+   I2  (violet)+ 2Na+ + 2Fe2+.
I2 dissolves in CCl4 giving violet colour solution.
AgNO3 + NaI  AgI  (yellow) + NaNO3.
AgI is insoluble in ammonia solution.
So, (A), (B), (C) and (D) are HgI2, KI, HgS and Hg respectively.
8. 4Cl– + Cr2O72– + 6H+  2CrO2Cl2  (A)(deep red) + 3H2O

CrO2Cl2 + 4OH–  CrO42– (B)(yellow solution) + 2Cl– + 2H2O
CrO42– + Pb2+  PbCrO4  (C)(yellow)
NH4Cl + NaOH  NaCl + NH3 + H2O
NH3 + K2Hg4 + H2O  (D) + 4K + 3H
So, (X) = NH4Cl, (A) = CrO2Cl2 , (B) = Na2CrO4 , (C) = PbCrO4 , (D) =
ADVQUA - 62
9. aquaregia is HNO3 + HCl
1 : 3
3Hg2Cl2 + 2HNO3 + 6HCl 
 6HgCl2 +2NO + 4H2O
10.
11. (A) Hg2+ + Co2+ + 4SCN–  Co[Hg(SCN)4 (deep blue) ;

(B) 2Hg2+ + Sn2+ + 2Cl–  Hg2Cl2 (white) + Sn4+ ; Hg2Cl2 + Sn2+  Hg  (black) + Sn4+ + 2Cl–
(C) 2Hg2+ + NO3– + 4NH3 + H2O  HgO.Hg(NH2)NO3 (white)
(D) KCN no effect i.e. no reaction.
12. PbS, Bi2S3 and CuS dissolve in dilute HNO3 forming nitrates but HgS dissolves in aquaregia forming HgCl2.
13. Sn2+ chloride react with HgCl2 and formed black or grey ppt of Hg
SnCl2 + HgCl2  SnCl4 + Hg2Cl2
SnCl2 + HgCl2  SnCl4 + 2Hg (black grey ppt)
Sn+4 does not react with HgCl2. It is first treated with Aluminium foil which reduces Sn+4 to Sn+2 (Stannous
ion); then it with HgCl2
3SnCl4 + 2Al  2AlCl3 + 3SnCl2 (Stannous chloride)
15. SnCl2 + KOH 

 SnO
SnO + KOH (excess) 
 K2SnO2 + 2H2O
16. Fe4[Fe(CN)6]3 + 12OH–  4Fe(OH)3  (reddish brown) + 3[Fe(CN)6]4–
17. 2CoS + 6HCl + 2HNO3  3CoCl2 + 2NO + 3S + 4H2O

CoCl2 + 6NaHCO3  Na4 [Co(CO3)3] + 2NaCl + 3H2O + 3CO2
2Na4 [Co(CO3)3] + Br2  2Na3 [Co(CO3)3] + 2NaBr
(Green)
18. NiCl2 + KCN (excess)  K2[Ni(CN)4]
19. (A) titan yellow is absorbed by magnesium hydroxide producing a deep-red colour or precipitate.
(B) Mg2+ + NH3 + HPO42–  Mg(NH4)PO4  (white).
(C) Blue lake is formed by the adsorption of reagent on Mg(OH)2.
Cl
20. Hg2Cl2 + 2NH3  Hg  (white) + Hg (black) + NH4Cl
NH2

black
Hg22+ + 2I–  Hg2I2  (green)
21. Sn2+ belongs to second B group.
ADVQUA - 63
boiled
 CdS (yellow ppt.) + Filtrate (Cr , Fe , Al )  

22. dil. HCl
(Cd2+, Cr3+, Fe2+, Al3+) + H2S  3+ 2+ 3+
 HNO3
(Cr3+, Fe3+, Al3+) excess

  Fe(OH) (ppt.) + Filtrate, (Na+, Cr(OH) –, Al(OH) –, )
NH OH & NaOH
4 3 4 4
23. The filter paper ash test is substitute for cobalt nitrate charcoal cavity test. Double oxide ZnO.CoO formed is
green in colour. It is called Rinmann's green.
24. Function of strong electrolyte NH4Cl is to suppress the ionisation of NH4OH so that the concentration of OH–
ions in the solution is decreased but it is sufficient to precipitate the third group basic radicals because the
solubility product of group III hydroxides is lower than IV, V and VI group hydroxides. The Cr(OH)3 is slightly
soluble in excess of precipitant, upon boiling the solution, Cr(OH)3 is precipitated.
25. 4Zn + 10H+ + NO 3–  4Zn2+ + NH4+ + 3H2O.
Zn2+ + 2OH–  Zn(OH)2  (white) ; Zn(OH)2 + 2OH–  [Zn(OH)4]2–.

[Zn(OH)4]2– + H2S  ZnS  (white) + 2OH– + 2H2O.
26. Sodium sulphide is water soluble and K sp of ZnS is higher than that of CuS. So correct order is
Na2S > ZnS > CuS
27. Metal P is Ag & metal M is Cu.
NaCl
Cu + 2AgNO3  Cu(NO3 )2 + 2Ag + AgNO3 Cu(NO3)2 + AgCl
(M) (P)
Blue solution Whit e ppt
NH3 (excess)
[Cu(NH3) 4] 2 + + [Ag(NH 3) 2]+

 x = 4, y = 2, m = 1, n = 2
 x+y+m+n=4+2+2+1=9
dil.HCl
28. Sn4+ + H2S  
 SnS2 (yellow ppt)
n = 4, p = 3, n + p = 7
29. A is CrO5
30. HMnO4 + Bi(NO3)2 + NaNO3
31. AsO43– + NO3 + (NH4)MoO4  (NH4)3AsMo12O40
32. (A) Correct.

(B) Cu2+ + 2CN–  Cu(CN)2 (yellow)
2Cu(CN)2  2Cu(CN)2 (white) + (CN)2
boiled
(C) BiI3 + H2O   BiOI (orange) + 2HI

(D) Bi(OH)3  BiO.OH (yellowish white) + H2O
33.  PO43– and AsO43– both radical give ammonium molybdate test.
34. CuS dissolves in 50% HNO3 ; 3CuS + 8HNO3  3Cu2+ + 6NO3– + 3S + 2NO + 4H2O
But NiS, CoS and HgS do not dissolve in 50% HNO3 and dissolve in aquaregia forming their chlorides.
ADVQUA - 64
35. (A) 5SO2 + 2IO3– + 4H2O  I2 + 5SO42– + 8H+ ; I2 + starch)  blue colour..
(B) 2H+ + 3SO2 + Cr2O72–  2Cr3+ (green ) + 3SO42– + H2O
(C) Pb2+ + SO32–  PbSO3  (white)
(D) SO2 + 2H2O + Cl2  H2SO4 + HCl
HCl + NH3  NH4Cl
Ni + H2SO4 + 2H+  Ni2+ + SO2 [X] + 2H2O
With dilute H2SO4, hydrogen gas is liberated.
36. (A) 3NH4+ + [Co(NO2)5]3–  (NH4)3[Co(NO2)6] (yellow)

(B) 2NH3 + Mn2+ + H2O2 + H2O  MnO(OH)2 (brown) + 2NH4+
(C) NH4+ + HC4H4O6–  NH4HC4H4O6(white)
(D) O2N N=N—Cl + NH4+ + 2OH–  O2N N=NONH4 (red colouration) + Cl– + H2O
37. (A) Bi3+ + 3 OH–  Bi(OH)3  ; 2Bi(OH)3  + [Sn(OH)4]2–  2Bi  + 3 [Sn(OH)6]2–.
(B) is not correct as 'D' is precipitate of bismuth.
(C) Bi3+ + C6H3(OH)3  Bi(C6H3O3 )  (yellow) + 3H+.
(D) Bi3+ + C9H7ON + H+ + 4I–  C9H7ON. HBiI4  (red)
PART - IV
ether
1. CoCl2 + 4NH4SCN   (NH4)2 [Co(SCN)4] (blue colour in ethereal layer) + 2NH4Cl.
2+ –
Cu + 3SCN  CuSCN (white) + (SCN)2 .
ether
FeCl3 + 3NH4SCN   Fe(SCN)3 (blood red colour) + 3NH4Cl.
+ –
Ag + SCN  AgSCN  (white).
Co2+ + 4SCN– + Hg2+  Co[Hg(SCN)4]  (deep blue) or Hg[Co(NCS)4].
2. (A), (B) and (C) all gives blue colouration in solution or blue precipitate.
(D) AgCl  + 2NH3  [Ag(NH3)2]+ Cl– (colourless solution)
3. Pb2+ + 2Cl–  PbCl2 (white) ; PbCl2 + 2Cl–  [PbCl4] 2– (colourless soluble complex)
PbCl2 + H2S  PbS (black) + 2HCl
PbS + 4H2O2  PbSO4 (white) + 4H2O
PbSO4 + 2CH3COONH4  (NH4)2SO4 + (NH4)2[Pb(CH3COO)4]
4. Ag+ + 2Cl–  [AgCl2]– (soluble complex) ; Ag+ + Cl– (dilute HCl)  AgCl (white)
2Ag+ + CrO42–  Ag2CrO4(red) ; Ag2CrO4 + NH3  2[Ag(NH3)2]+ + CrO42–
3Ag+ + HPO42–  Ag3PO4 (yellow) + H+ ; Ag3 PO4 + 6NH3   [Ag(NH3)2 ]+ + PO43–
5. (A) Both are red precipitates

(B) Ni2+ + 2dmg + NH4OH  Ni(dmg)2  (red)
(C) BiOI (orange) and Cu2[Fe(CN)6] (brown)
6. Cu2+ + 2SCN–  Cu(SCN)2 (black)

2Cu(SCN)2  2CuSCN (white) + (SCN)2
H
Cu2+ + H2S 
 CuS (black) + 2H+
2CuS + 8CN–  2[Cu(CN)4]3– + S22–
ADVQUA - 65

7. (A) As3+ + 3Zn + 3H+  AsH3  + 3Zn2+ ; 4AsH3  4As  + 6H2 
(B) 4[Ag(NH3)2]+ + H2N–NH2.H2SO4  4Ag  + N2  + 6NH4+ + 2NH3  + SO42–
(C) 2Ag2CrO4  + 2H+ 4Ag+ + Cr2O72– + H2O
Ag2CrO4  + 4NH3 2[Ag(NH3)2]+ + CrO42–
So, all statements are correct.
8. (NH4)2 CO3 and (NH4)2 SO4 can not be used as they would also precipitate the IV and Vth group cations.
9. (A) PbSO4 + H2SO4 (hot and concentrated)  Pb2+ + 2HSO4– (soluble)
(B) It dissolves forming Na2[Pb(OH)4] soluble complex.
10. (A) Cr3+ + 3NH3 + 3H2O Cr(OH)3 + 3NH4+
The above reaction is reversible. On addition of NH4+ , shifts to backward direction. Thus if excess of
NH4+ salt is added, then precipitation of Cr(OH)3 will not take place. However, because of very small
Ksp of iron (III) hydroxide complete precipitation will take place even in the presence of ammonium
salts. (Ksp = 3.8 × 10–38)
(B) Concentration of CO32– provided by Na2CO3 in aqueous solution is just sufficient to precipitate Mg2+
ion as MgCO3 along with Ba2+ , Ca2+ and Sr2+ as their carbonates.
(C) The oxidising anions like MnO4–, Cr2O72–, ClO4–, etc., also respond to this test.
(D) K2Cr2O7 + NaCl + H2SO4  CrO2Cl2
11. Iron and NO exist as Fe(II) and NO+ respectively.

12. (A) Cu2 [Fe(CN)6] ; K2 Zn3 [Fe(CN)6]2 ; (B) Fe4 [Fe(CN)6]3 ; K2Ca [Fe(CN)6]
(C) Ag4[Fe(CN)6] ; K2Zn3 [Fe(CN)6] ; (D) Th[Fe(CN)6] ; Cu2[Fe(CN)6]

H
13. (1) Al3+ and Hg2+  HgS  (black) + Al3+ (in solution)
H2S

H
(2) Cu2+ and Zn2+  CuS  (black) + Zn2+ (in solution)
H2S

H
(3) Cd2+ and Zn2+  CdS  (yellow) + Zn2+ (in solution)
H2S
14. Ba2+ (aq) + CrO42– (aq)  BaCrO4  (yellow)

Ag+ (aq) + Br – (aq)  AgBr  (yellow)
Pb2+ (aq) + 2I– (aq)  PbI2  (yellow)
2NH4+ (aq) + [PtCl6]2– (aq)  (NH4)2 [PtCl6]  (yellow)
15. AgCN, MnS, Ag3PO4, Zn(OH)2, AgNO2, FeS, BaSO3, Al(OH)3, CH3COOAg  solubility in acidic solution
is greater than that in pure water due to protonation of anion.
16. TTTTFF
(i) SO32– + Ca (OH)2  CaSO3  (white) + H2O
CO32– + Ca (OH)2  CaCO3  (white) + H2O
(ii) FeSO4 + NO + 5H2O  [Fe(H2O)5 NO]2+ SO42–
(iii) 2AgNO3 + K2CrO4  Ag2CrO4  (red) + 2KNO3
(iv) Pb2+ + H2S  PbS + 2H+
(v) S2– concentration in presence of dil HCl is sufficient to ppt the IInd group cations only. Due to common ion
effect ionization of H2S is suppressed.
(iv) 2Cu2+ + [Fe(CN)6]4-  Cu2[Fe(CN)6]  (chocolate brown)
ADVQUA - 66
17. (a) HgCl2 + SnCl2 (excess) Hg + SnCl4
black precipitated
(b) HgCl2 + KI  K2HgI4 (soluble)
(d) NH4Cl + NO2– + Co3+ (NH4)3 [Co(NO2)6]  yellow
(e) Ni2+ + + NH4OH Ni(dmg)2  (red)
aq. Pb 2
(f) K2Cr2O7 + conc.H2SO4 + Cl2  CrO2Cl2  Na CrO   PbCrO4
NaOH 2 4
(g) K2CrO4 + Hg22+  HgCrO4 (red ppt.)

(h) Hg2+ + Co2+ + SCN–  Co[Hg(SCN)4] or Hg[Co(NCS)4] (deepblue crystalline ppt.)
18. PbS  Black, CdS  yellow, As2S3  yellow, Sb2S3  Orange, SnS  Brown, CoS  Black,
HgS  Black, ZnS  White, MnS  Pink.
(19-21)
K2[HgI4] + OH– + (NH4)2SO4  HgO.Hg(NH2)I (brown ppt)

(D) (G)
HgCl2 + NH3  Hg(NH2)Cl + Hg (black ppt)

(B) (H)
NO–2 / NO3– + dil. HCl/con.HCl  NO

 Fe2+ NO + 5H2O  [Fe(H2O)5NO]2
22. (P) Aqueous solutions of nickel (II) salts are green, owing to the colour of the [Ni(H2O)6]2+ complex.
(Q) Co2+ + 4SCN–  [Co(SCN)4]2– (blue colour complex). In amyl alcohol or diethyl ether dissolves forming
H2[Co(SCN)4].

(R) Cu2+ + 2OH–  Cu(OH2)  (blue) ; Cu(OH)2   CuO  (black) + H2O. Copper salts imparts
greenish blue colour to the Bunsen flame.
(S) Sr2+ + 2C2O42–  SrC2O4  (white) .
Strontium salts imparts crimson colour to the Bunsen burner.
(T) Pb2+ + SO42–  PbSO4  (white) ; PbSO4  + 2CH3COONH4  (CH3COO)2Pb + (NH4)2SO4.
(U) CrO42 + Pb2+  PbCrO4  (yellow) ; PbCrO4  + 4OH– [Pb(OH)4]2– + CrO42–.
2+ – 
(V) Hg + 2I  HgI2  (scarlet / red).
ADVQUA - 67

Qualitative Analysis (Cations) English PC

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Qualitative Analysis (Cations) English PC

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QUALITATIVE ANALYSIS (CATIONS)

JEE (MAIN) SYLLABUS

Ex pe rim e nt Obse rva tions Infe re nce

Shows the absence of

2. Charcoal Cavity Test :

(b) CuSO4 + Na2CO3  CuCO3 + Na2SO4

3. Cobalt Nitrate Test :

S.No. Metal Colour of the mass

4. Tin Bluish - green

Analysis of CATIONS (Basic Radicals) :

Group Group reagent Basic radical Composition and colour of

3. NH4OH in presence of NH4Cl Fe3+ Fe(OH)3 ; Reddish brown

 [YAS = Yellow ammonium sulphide. (NH4)2Sx].

1. LEAD ION (Pb2+) :

[Pb(OH)4]2– + S2O82–  PbO2  + 2H2O + 2SO42–

 Dissolution of white precipitate (Hg2Cl2) in aquaregia :

 Ammonia solution : Brown precipitate is formed.

2. COPPER ION (Cu2+) :

3. BISMUTH ION (Bi3+) :

4. CADMIUM ION (Cd2+) (*Not in JEE advance syllabus) :

5. LEAD ION (Pb2+) :

 Potassium chromate : Yellow precipitate is formed.

1. ARSENIC ION (As3+) :

2. ANTIMONY ION (Sb3+) :

3. TIN (II) ION (Sn2+) AND TIN (IV) ION (Sn4+) :

 Mercuric chloride solution :

 Concentrated HNO3 is added to oxidise Fe2+ to Fe3+ if present.

1. ALUMINIUM ION (Al3+) :

2. IRON ION (Fe3+) :

 Potassium ferricyanide (Potassium hexacyanidoferrate(III)) : A brown colouration is formed.

 Fluorides and Hg(II) ions bleach the red colour.

 Disodium hydrogen phosphate solution : A yellowish–white precipitate is formed.

3. CHROMIUM ION (Cr3+) :

1. MANGANESE ION (Mn2+) :

2. ZINC ION (Zn2+) :

 Potassium ferrocyanide (Potassium hexacyanidoferrate(II)) solution : A white precipitate of variable

3. COBALT ION (Co2+) : (Not in JEE advance syllabus)

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

Vth Group (Ba2+, Sr2+, Ca2+) :

White precipitate Filtrate,

I part + K2CrO4. II Part + (NH4)2SO4. III part + (NH4)2C2O4.

2. Chocolate brown precipitate is formed with :

3. Colour of cobalt chloride solution is :

4. A red colouration or precipitate is not obtained when :

8. Consider the following statements :

Comprehension (Q.10 to Q.12)

Aqueous solution of salt (A)

Gas(B) Solution of salt (C)

10. The compound (A) contains the following acid radical.

12. Which of the following statement is correct ?

3NH4+ + [Co(NO2)]3–  (NH4)3 [Co(NO2)6]  (yellow)

(B) 2NO3– + 4H2SO4 + 6Fe2+  6Fe3+ + 2NO  + 4SO42– + 4H2O

SO42– + Fe2+ + NO  [Fe(NO)]2+ SO42–

(C) Ag NO3 + NaNO3  No reaction.

NH4NO3 + NaOH  NH3 + NaNO3

NH3+ HCI  NH4CI (White)

NO3– + 4Zn + 7OH– + 6H2O  NH3 + 4[Zn(OH)4]2–

 Marked Questions may have for Revision Questions.

A-9. Solid (A) is used in photographic film, Identify (A) to (E) ?

Section (B) : II A Group

B-3. What happens when white precipitate of Bi(OH)3 is boiled ?

(F) K 4 [Fe(CN)6 ] BaCl2

Section (C) : IIB Group

C-6. Identify (A) based on the following facts :