Qualitative Analysis (Part-1)

Introduction :
Qualitative analysis involves the detection of cation(s) and anion(s) of a salt or a mixture of salts.
The systematic procedure for qualitative analysis of an inorganic salt involves the following steps :
(a) Preliminary tests
 Physical appearance (colour and smell).
 Dry heating test.
 Charcoal cavity test.
 Charcoal cavity and cobalt nitrate test.
 Flame test.
 Borax bead test.
 Dilute sulphuric acid test.
 Potassium permanganate test.
 Concentrated sulphuric acid test.
 Tests for sulphate, phosphate and borate.
(b) Wet tests for acid radicals.
(c) Wet tests (group analysis) for basic radicals.
1. Physical appearance (smell).
Table : 1
Physical Examination

Take a pinch of the salt between your fingers and rub with a drop of water

Smell Inference

Ammonical smell NH4+

Vinegar like smell CH3COO–
Smell like that of rotten eggs S2–

2. Dry Heating Test :

This test is performed by heating a small amount of mixture in a dry test tube. Quite valuable information can be
generated by carefully performing and noting the observations here. On heating some salts undergo decomposition
thus evolving the gases or may undergo characteristic changes in the colour of residue. These observations are
tabulated below along with the inferences that you can draw.
Table : 2

Observation Inference
1. Gas evolved
(a) Colourless and odourless gas
CO2 gas – turns lime water milky CO32–
(b) Colourless gas with odour
(i) H2S gas–Smells like rotten eggs, turns Hydrated S2–
lead acetate paper black.
(ii) SO2 gas–Characteristic suffocating SO32–
smell, turns acidified potassium dichromate
solution or paper green.
(iii) HCl gas – Pungent smell, white fumes with Cl–
ammonia, white precipitate with silver nitrate solution.
(iv) Acetic acid vapours–Characteristic vinegar CH3COO–
like smell.
(v) NH3 gas– Characteristic smell, turns NH4+
Nessler's solution brown.

QUALITATIVE ANALYSIS # 145

(c) Coloured gases – Pungent smell
(i) NO2 gas – Reddish brown, turns ferrous NO2– or NO3–
sulphate solution black.
(ii) Cl2 gas – Greenish yellow, turns starch Cl–
iodide paper blue.
(iii) Br2 vapours – Reddish brown, turns starch Br–
paper orange red.
(iv) I2 vapours – Dark violet, turns starch paper –
blue.
2. Sublimate formed
(a) White sublimate NH4+
(b) Black sublimate accompanied by violet –
vapours.
3. Fusion
The mixture fuses. Alkali metal salts or salt containing water of
crystallisation.
4. Swelling
The mixture swells up into voluminous mass. PO43– , BO33– indicated
5. Residue
(i) Yellow when hot, white when cold. Zn2+
(ii) Brown when hot and yellow when cold Pb2+
(iii) Original salt blue becomes white on heating Hydrated CuSO4 indicated
(iv) Coloured salt becomes brown or black on Co2+ , Fe2+, Fe3+ , Cr3+ , Cu2+ , Ni2+ , Mn2+
heating. indicated.

Note :
 Use a perfectly dry test–tube for performing this test. While drying a test–tube, keeps it in slanting
position with its mouth slightly downwards so that the drops of water which condense on the upper
cooler parts, do not fall back on the hot bottom, as this may break the tube.

 For testing a gas, a filter paper strip dipped in the appropriate reagent is brought near the mouth of the
test tube or alternatively the reagent is taken in a gas–detector and the gas is passed through it.

Figure : Detection of gas evolved.

 Do not heat the tube strongly at one point as it may break.

QUALITATIVE ANALYSIS # 146
3. Flame test :
The chlorides of the metals are more volatile as compared to other salts and these are prepared in situ by mixing
the compounds with a little concentrated hydrochloric acid. On heating in a non-luminous Bunsen flame they
are volatilized and impart a characteristic colour to the flame as these absorb energy from the flame and
transmit the same as light as characteristic colour .
Table : 3
Colour of Flame Inference
Crimson Red / Carmine Red Lithium
Golden yellow Sodium
Violet/Lilac Potassium
Brick red Calcium
Crimson Strontium
Apple Green/Yellowish Green Barium
Green with a Blue centre/Greenish Blue Copper

Figure : Flame test

Table : 4
SOLUBILITY CHART
S.No. Anion Solubility / Exception
1. CO32– Except carbonates of alkali metals and of ammonium, all other normal carbonates are
insoluble.
2. SO32– Only the sulphites of the alkali metals and of ammonium are water soluble. The sulphite
of other metals are either sparingly soluble or insoluble.
3. S2– The acid, normal and polysulphide of alkali metals are soluble in water. The normal sulphides
of most other metals are insoluble; those of the alkaline earths are sparingly soluble, but
are gradually changed by contact with water into soluble hydrogen sulphides.
4. NO2– , NO3– Almost all nitrites and nitrates are soluble in water. AgNO2 is sparingly soluble. Nitrates
of mercury and bismuth give basic salts on treatment with water. These are soluble in
dilute nitric acid.
5. CH3COO– Acetates are water soluble except Ag(I) and Hg(II) acetates which are sparingly soluble.
6. Cl– Most chlorides are soluble in water. PbCl2 (sparingly soluble in cold but readily soluble
in boiling water), Hg2Cl2, AgCl, CuCl, BiOCl, SbOCl and Hg2OCl2 are insoluble in water.
7. Br– Silver, mercury(I) and copper(I), bromides are insoluble. Lead bromide is sparingly soluble in
cold but more soluble in boiling water. All other bromides are soluble in water.
8. I– Silver, mercury(I), mercury(II), copper(I), lead and bismuth(III) iodides are the least
soluble salts. All other iodides are water soluble.
9. SO42– The sulphates of barium, strontium and lead are insoluble in water, those of calcium and
mercury(II) are slightly soluble. Some basic sulphates of mercury, bismuth and chromium
are also insoluble, but these dissolves in dilute hydrochloric or nitric acid.
10 PO43– The phosphate of the alkali metals, with the exception of lithium and ammonium, are
soluble in water ; the primary phosphate of the alkaline earth metals are soluble. All
the phosphates of the other metals and also the secondary and tertiary phosphate of
the alkaline earth metals are sparingly soluble or insoluble in water.

QUALITATIVE ANALYSIS # 147

Analysis of ANIONS (Acidic Radicals) :
Analysis of anions (acidic radicals) can be broadly divided in to two groups.
(A) GROUP 'A' RADICALS : It involves those anions which are characterised by volatile products by reaction with
HCl/ H2SO4 It is further subdivided in to two groups as given below.
(a) Dilute Sulphuric acid/Dilute Hydrochloric acid : The anions of this group liberate gases or acid vapours
with dilute sulphuric acid/hydrochloric acid.
Table : 5

Inference
Observation
Gas Radical
Effervescence with the evolution of a colourless CO2 CO32–
and odourless gas which turns lime water milky.
Evolution of colourless gas having smell of rotten
egg which turns lead acetate paper black. H2S S2–
Colourless gas having suffocating odour (like burning SO2 SO32–
sulphur) which turns acidified K2Cr2O7 paper green.
Evolution of reddish brown pungent smelling gas which turns
(i) FeSO4 solution brownish-black and NO2 NO2–
(ii) wet starch –iodide paper blue.
Colourless gas having smell of vinegar. HAC(g) CH3COO–

No peculiar gas is evolved. – All above are absent

(b) Concentrated Sulphuric acid group : The anions of this group liberate acid vapours or gases with conc. H2SO4.
Table : 6
Inference
Observation
Gas Radical

Colourless gas with pungent smell which gives dense HCl Cl–
white fumes with a glass rod dipped in NH4OH.
Reddish brown gas with pungent smell, intensity of Br 2 Br–
reddish brown fumes increases on addition of a pinch
of solid MnO2. Also it turns starch paper orange red.
Evolution of violet vapours which turns starch paper blue. I2 I–
Evolution of reddish brown fumes which intensifies on NO2 NO3–
addition of copper turnings or bits of filter paper.
Starch iodide paper develops a blue–black spot
due to the formation of a I2–starch complex.
(NO2 liberated acts as oxidising agent).

(B) GROUP 'B' RADICALS : Anions of this group do not give acid vapours or gases with dilute as well as concentrated
H2SO4 but are characterised by their specific reactions in solutions. This group is further sub divided into two
groups based on the type of the reactions.
(a) Oxidation and reduction in solutions : CrO42–, Cr2O72– etc.
(b) Precipitation reactions : These are given by SO42–, PO43– etc.
Table : 7
Observation Inference
W.E. or S.E. + BaCl2(aq)  White precipitate insoluble SO42–
in dil. HCl and HNO3.
W.E or S.E + conc HNO3 (1–2 mL) + PO43–
ammonium molybdate and boil  Canary yellow precipitate
 W.E. = Water extract. (Salt is dissolved in distilled water)
 S.E. = Sodium carbonate extract

QUALITATIVE ANALYSIS # 148

Preparation of sodium carbonate extract :
Take 1-2 g of salt/salts mixture and three times the amount of pure solid sodium carbonate in a borosil conical
flask. Add 20 mL of distilled water and boil the contents for 10 minutes. Cool the solution and then filter. The
Filtrate is termed as "Sodium carbonate extract".
Sodium carbonate reacts with the inorganic salt to form water soluble sodium salt of the acid radical.
BaCl2 + Na2CO3  BaCO3  (white) + 2NaCl (aq)
Cd3 (PO4)2 + 3Na2CO3  3CdCO3  + 2Na3 PO4 (aq)
Sodium carbonate extract is used when
(a) salt is only partially soluble in water or insoluble
(b) cations interfere with the tests for acid radicals or the coloured salt solutions may be too intense in colour
that the test results are not too clear.
 As sodium carbonate extract contains excess of sodium carbonate, it should be neutralised with a
suitable acid before proceeding for analysis of an anion.

Figure : Preparation of sodium carbonate extract

Individual tests :
(A) GROUP 'A' RADICALS :
(a) DILUTE SULPHURIC ACID/DILUTE HYDROCHLORIC ACID GROUP :
1. CARBONATE ION (CO32–) :
 Dilute H2SO4 test : A colourless odourless gas is evolved with brisk effervescence.
CaCO3 + H2SO4  CaSO4 + H2O + CO2 
 Lime water/Baryta water (Ba(OH)2) test : The liberated gas can be identified by its property of rendering
lime water (or baryta water) turbid.
CO2 + Ca(OH)2  CaCO3  milky+ H2O
On prolonged passage of CO2 the milkiness disappears.

CaCO3 + CO2 + H2O  Ca(HCO3)2 (soluble)  CaCO3 + H2O + CO2
 Magnesium sulphate test (for soluble carbonates) :
CO32– (aq) + MgSO4 (aq)  MgCO3  (white) + SO42– (aq)
 Silver nitrate solution : White precipitate is formed
CO32– + Ag+  Ag2CO3
White precipitate is soluble in HNO3 and ammonia. The precipitate becomes yellow or brown upon
addition of excess reagent owing to the formation of silver oxide ; the same happens if the mixture is
boiled.
Ag2CO3  Ag2O  + CO2 
 Phenolphthalein is turned pink by soluble carbonates and colourless by soluble hydrogen carbonates.
 Mercury(II) chloride does not form precipitate with hydrogen carbonate ions, while in a solution of
normal carbonates a reddish–brown precipitate of basic mercury(II) carbonate (3HgO. HgCO3 = Hg4O3CO3)
is formed.
CO32– + 4 Hg2+ + 3 H2O  Hg4O3CO3  + 6H+
QUALITATIVE ANALYSIS # 149
 Lime water milky test is also shown by SO2 but CO2 does not turn the filter paper soaked in acidified
K2Cr2O7 green.
 Soluble bicarbonates give white precipitate with MgSO4 (aq) / MgCl2(aq) only on heating.

Mg2+ + 2HCO3–  Mg(HCO3)2  MgCO3  + H2O + CO2
 Action of heat :
Bicarbonates : 2NaHCO3  Na2CO3 + H2O + CO2
Carbonates : Except carbonates of Na, K, Rb, Cs ; the Li2CO3 and all alkaline earth metals decompose
as given below :
Li2CO3  Li2O + CO2 ; MgCO3  MgO + CO2 ; Ag2CO3  2Ag + CO2

 
CaCO3  CaO + CO2
2. SULPHITE ION (SO32–) :
 Dilute H2SO4 test : Decomposition of salt is more rapidly on warming, with the evolution of sulphur
dioxide.
CaSO3 + H2SO4  CaSO4 + H2O + SO2 
SO2 has suffocating odour of burning sulphur.
 Acidified potassium dichromate test : The filter paper dipped in acidified K2Cr2O7 turns green.
Cr2O72– + 2H+ + 3SO2  2Cr3+ (green) + 3SO42– + H2O.
 Barium chloride/Strontium chloride solution : White precipitate of barium (or strontium) sulphite is
obtained.
SO32– + Ba2+/Sr2+  BaSO3/SrSO3  (white).
 White precipitate dissolves in dilute HCl, when sulphur dioxide is evolved.
BaSO3  + 2H+  Ba2+ + SO2  + H2O.
White precipitate (BaSO3) on standing is slowly oxidised to sulphate which is insoluble in dilute mineral
acids. This change is rapidly effected by warming with bromine water, a little concentrated nitric acid or
with hydrogen peroxide.
2 BaSO3  + O2  2 BaSO4 
BaSO3 + Br2 + H2O  2 BaSO4 + 2 Br– + 2H+
Hence, reddish brown colour of bromine water is decolourised.
3BaSO3  + 2 HNO3  3 BaSO4  + 2NO  + H2O
BaSO3  + H2O2  BaSO4  + H2O
 These reactions are not given by carbonates (distinction from carbonates).
 Zinc and sulphuric acid test : Hydrogen sulphide gas is evolved.
SO32– + 3Zn2+ + 8H+  H2S  + 3Zn2+ + 3H2O
 Lime water test : A white precipitate is formed. The precipitate dissolves on prolonged passage of the
gas, due to the formation of hydrogen sulphite ions.
Ca(OH)2 + SO2  CaSO3 (milky) + H2O
CaSO3  + SO2 + H2O  Ca(HSO3)2 (soluble)
 A turbidity is also produced by carbonates ; sulphur dioxide must therefore be first removed when
testing for the latter. This may be affected by adding potassium dichromate solution to the test–tube
before acidifying. The dichromate oxidizes and destroys the sulphur dioxide without affecting the carbon
dioxide.
 Lead acetate or lead nitrate solution : White precipitate of PbSO3 is obtained.
SO32– + Pb2+  PbSO3 
White precipitate gets soluble in dil. HNO3 on boiling. The precipitate is oxidized by atmospheric
oxygen and PbSO4 is formed.
2PbSO3  + O2  2PbSO4 
3. SULPHIDE ION (S2–) :
 Dilute H2SO4 test : Pungent smelling gas like that of rotten egg is obtained.
S2– + 2H+  H2S 

QUALITATIVE ANALYSIS # 150

 Lead acetate test : Filter paper moistened with lead acetate solution turns black.
(CH3COO)2Pb + H2S  PbS  (black) + 2CH3COOH.
 Sodium nitroprusside test : Purple coloration is obtained.
S2– + [Fe(CN)5 (NO)]2–  [Fe(CN)5NOS]4– (violet).
It is a ligand change reaction not a redox where NO+ changes to (NOS)–1.
No reaction occurs with solution of H2S or free gas. If however, filter paper moistened with a solution of
the reagent is made alkaline with NaOH or NH3 solution, a purple colouration is produced with free H2S
also.
 H2S does not provide sufficient concentration of S2– ions so that it does not give sodium nitroprusside
test. Solubility is low 0.1 M and K1 is just 10–7.
 Cadmium carbonate suspension/ Cadmium acetate solution : Yellow precipitate is formed.
Na2S + CdCO3  CdS + Na2CO3
 Filter paper moistened with cadmium acetate when brought in contact with evolving gas it turns yellow.
S2– + 2H+  H2S ; H2S + Cd2+  CdS  + 2H+.
 Silver nitrate solution : Black precipitate is formed which is insoluble in cold, but soluble in hot, dilute
nitric acid.
Ag+ + S2–  Ag2S 
 Methylene blue test : NN–Dimethyl–p–phenylenediamine is converted by iron(III) chloride and hydrogen
sulphide in strongly acid solution into the water–soluble dyestuff, methylene blue. This is a sensitive
test for soluble sulphides and hydrogen sulphide.
4. NITRITE ION (NO2¯ ) :
 Dilute H2SO4 test : Solid nitrite in cold produces a transient pale blue liquid (due to the presence of free
nitrous acid, HNO2 or its anhydride, N2O3) first and then evolution of pungent smelling reddish brown
vapours of NO2 takes place.
NO2– + H+  HNO2 ; (2HNO2  H2O + N2O3);
3HNO2  HNO3 + 2NO + H2O ; 2NO + O2  2NO2 
 Starch iodide test : The addition of a nitrite solution to a solution of potassium iodide, followed by
acidification with acetic acid or with dilute sulphuric acid, results in the liberation of iodine, which may
be identified by the blue colour produced with starch paste. A similar result is obtained by dipping
potassium iodide–starch paper moistened with a little dilute acid into the solution.
2NO2– + 3I– + 4CH3COOH  I3– + 2NO + 4CH3COO– + 2H2O
Starch + I3–  Blue (starch iodine adsorption complex)
 Ferrous sulphate test (Brown ring test) : When the nitrite solution is added carefully to a concentrated
solution of iron(II) sulphate acidified with dilute acetic acid or dilute sulphuric acid, a brown ring appears
due to the formation of [Fe(H2O)5NO]SO4 at the junction of the two liquids. If the addition has not been
made slowly and caustiously, a brown colouration results.
NO2– + CH3COOH  HNO2 + CH3COO–
3HNO2  H2O + HNO3 + 2NO 
Fe2+ + SO42– + NO   [Fe, NO]SO4
 Thiourea test : When a dilute acetic acid solution of a nitrite is treated with a little solid thiourea,
nitrogen is evolved and thiocyanic acid is produced. The latter may be identified by the red colour
produced with dilute HCl and FeCl3 solution.
NaNO2 + CH3COOH  HNO2 + CH3COONa
HNO2 + H2NCSNH2(s) (thiourea)  N2 + HSCN + 2H2O
dil HCl
FeCl3 + 3HSCN   Fe(SCN)3 (blood red colouration) + 3HCl

 Acidified potassium permanganate solution : Pink colour of KMnO4 is decolourised by a solution of

a nitrite, but no gas is evolved.
5 NO2– + 2 MnO4– + 6 H+  5 NO3– + 2 Mn2+ + 3 H2O

QUALITATIVE ANALYSIS # 151

  Silver nitrate solution : White crystalline precipitate of silver nitrite from concentrated solutions.
NO2– + Ag+  AgNO2 

5. ACETATE ION (CH3COO¯)

 With dilute H2SO4 a vinegar like smell is obtained.
(CH3COO)2Ca + H2SO4  2CH3COOH + CaSO4
 Neutral ferric chloride test : A deep red/ blood red colouration (no precipitate) indicates the presence
of acetate.
6CH3COO– + 3Fe3+ + 2H2O  [Fe3(OH)2(CH3COO)6]+ + 2H+
 When solution is diluted with water and boiled, brownish red precipitate of basic iron (III) acetate is
obtained.
Boil
[Fe3(OH)2(CH3COO)6]+ + 4H2O   3Fe(OH)2CH3COO  + 3CH3COOH + H+
 Silver nitrate solution test : A white crystalline precipitate is produced in concentrated solution in the
cold.
CH3COO– + Ag+ CH3COOAg 
Precipitate is more soluble in boiling water and readily soluble in dilute ammonia solution.

(b) CONC . H2SO4 GROUP :

1. CHLORIDE ION (Cl¯) :
 Concentrated H2SO4 test : Colourless pungent smelling gas is evolved which gives fumes of NH4Cl
when a glass rod dipped in aq. ammonia is brought in contact with evolving gas.
Cl– + H2SO4  HCl + HSO4–
 NH4OH + HCl  NH4Cl  (white fumes) + H2O.
 2NaCl + MnO2 + 2H2SO4 (conc.)  Na2SO4 + MnSO4 + 2H2O + Cl2
 Silver nitrate test :
Cl– + Ag+  AgCl  (white)
With sodium arsenite it is converted into yellow precipitate (distinction from AgBr and AgI) but insoluble
in dilute nitric acid.
3AgCl  + AsO33–  Ag3AsO3  + 3Cl–.
 White precipitate is soluble in aqueous ammonia and precipitate reappears with HNO 3.
AgCl + 2NH4OH  [ Ag(NH3)2]Cl (Soluble) + 2H2O
[Ag(NH3)2]Cl + 2H+  AgCl  + 2NH4+.
 Chromyl chloride test :
4Cl– + Cr2O72– + 6H+ (conc.)  2CrO2Cl2 (deep red vapours) + 3H2O
When deep red vapours are passed into sodium hydroxide solution, a yellow solution of sodium chromate
is formed, which when treated with lead acetate gives yellow precipitate of lead chromate.
CrO2Cl2 + 4OH–  CrO42– + 2Cl– + 2H2O
CrO42– + Pb+2  PbCrO4 (yellow)
 Heavy metal chlorides such as Hg2Cl2, HgCl2, SnCl2, AgCl, PbCl2 and SbCl3 do not respond to this test
as they are partially dissociated. This test is given generally by ionic chlorides.
 Test should be carried out in a dry test tube otherwise chromic acid will be formed.
CrO2Cl2 + 2H2O  H2CrO4 + 2HCl
2. BROMIDE ION (Br¯) :
 Concentrated H2SO4 test : First a reddish-brown solution is formed, then reddish-brown bromine vapour
accompanies the hydrogen bromide (fuming in moist air) is evolved.
2NaBr + H2SO4  Na2SO4 + 2HBr
2HBr + H2SO4  Br2 + 2H2O + SO2
 2KBr + MnO2 + 2H2SO4  Br2+ K2SO4 + MnSO4 + 2H2O
 Silver nitrate test : Pale yellow precipitate is formed
NaBr + AgNO3  AgBr  + NaNO3
 Yellow precipitate is partially soluble in dilute aqueous ammonia but readily dissolves in concentrated
ammonia solution.
AgBr + 2NH4OH  [Ag(NH3)2] Br + H2O

QUALITATIVE ANALYSIS # 152

 Lead acetate test : Bromides on treatment with lead acetate solution, gives a white crystalline
precipitate of lead bromide, which is soluble in boiling water giving colourless solution.
2Br– + Pb+2  PbBr2 
 Chlorine water test (organic layer test) : When to a sodium carbonate extract of metal bromide
containing CCl4, CHCl3 or CS2, chlorine water is added and the content is shaken and then allow to
settle down reddish brown colour is obtained in organic layer.
2Br– + Cl2  2Cl– + Br2  .
Br2 + CHCl3 / CCl4  Br2 dissolve to give reddish brown colour in organic layer..
With excess of chlorine water, the bromine is converted into yellow bromine monochloride and a
pale yellow solution results.
Br2 + Cl2   2BrCl
 Starch paper test : When starch paper is brought in contact with evolving bromine gas orange red
spots are produced.
Br2 + starch  starch bromine adsorption complex (orange red)
 Potassium dichromate and concentrated H2SO4 : When a mixture of solid bromide, K2Cr2O7
and concentrated H2SO4 is heated and evolved vapours are passed through water, a orange red
solution is obtained.
6KBr + K2Cr2O7 + 7H2SO4  3Br2 + Cr2(SO4)3 + 4K2SO4 + 7H2O
3. IODIDE ION ¯) :
 Concentrated H2SO4 test : Pungent smelling violet vapours are evolved.
2Na + H2SO4  Na2SO4 + 2HI
2HI + H2SO4  I2  (dark violet) + 2H2O + SO2
 Evolution of dark violet fumes intensifies on adding a pinch of MnO 2.
3I– + MnO2 + 2H2SO4  I3–  + Mn2+ + 2SO42– + 2H2S
 Starch paper test : Iodides are readily oxidised in acid solution to free iodine; the free iodine may
than be identified by deep blue colouration produced with starch solution.
3I– + 2NO2– + 4H+  I3– + 2NO  + 2H2O.
 Silver nitrate test : Bright yellow precipitate is formed.
I– + Ag+  AgI 
 Bright yellow precipitate is insoluble in dilute aqueous ammonia but is partially soluble in concentrated
ammonia solution.
 Chlorine water test (organic layer test) : When chlorine water is added to a solution of iodide,
free iodine is liberated which colours the solution brown and on shaking with CS2, CHCl3 or CCl4, it
dissolves in organic layer forming a violet solution, which settles below the aqueous layer.
2NaI + Cl2  2NaCl + I2
I2 + CHCl3  I2 dissolves to give violet colour in organic layer..
If excess of chlorine water is added, I2 is oxidised to iodic acid (colourless).
I3– + 8Cl2 + 9H2O  3 I O3 + 16Cl– + 18 H+
 Lead acetate solution : A yellow precipitate is formed which is soluble in hot water forming a
colourless solution and yielding golden yellow plates ('spangles') on cooling.
2I– + Pb+2  PbI2 
 Potassium dichromate and concentrated sulphuric acid : Violet vapours are liberated, and no
chromate is present in distillate.
6I– + Cr2O72 + 2H2SO4  3I2 + Cr3+ +7SO42– + 7H2O
 Action of heat :
Most of halides are stable but few decompose as
2FeCl3  2FeCl2 + Cl2 ; MgCl2 . 6H2O  MgO + 2HCl + 5H2O
Hg2Cl2  HgCl2 + Hg ; NH4Cl  NH3 + HCl
2CuI2  Cu2I2 + I2 (without heating)

QUALITATIVE ANALYSIS # 153

 4. NITRATE ION (NO3¯) :
 Concentrated H2SO4 test : Pungent smelling reddish brown vapours are evolved.
4NO3– + 2H2SO4  4NO2  + O2 + 2SO42– + 2H2O
 Addition of bright copper turnings or paper pellets intensifies the evolution of reddish brown gas.
2NO3– + 4H2SO4 + 3Cu  3Cu2+ + 2NO  + 4SO42– + 4H2O ; 2NO  + O2  2NO2 
4 C (paper pellet) + 4HNO3  2H2O + 4NO2 + 4CO2.
 Brown ring test : When a freshly prepared saturated solution of iron (II) sulphate is added to nitrate
solution and then concentrated H2SO4 is added slowly from the side of the test tube, a brown ring is
obtained at the junction of two layers.
NaNO3 + H2SO4  NaHSO4 + HNO3
6FeSO4 + 2HNO3 + 3H2SO4  3Fe2(SO4)3 + 2NO + 4H2O
or 2NO3– + 4H2SO4 + 6Fe2+  6Fe3+ + 2NO  + 4SO42– + 4H2O.
Fe2+ + NO  + 5H2O  [Fe(H2O)5 NO+]2+ (brown ring).

Figure : Brown ring test

 On shaking and warming the mixture, NO escapes and a yellow solution of iron(III) ions is obtained.
 Bromides and iodides interfere in brown ring test as liberated halogens obscure the brown ring. Nitrites
also interfere the brown ring test and can be removed by adding a little sulphamic acid, or urea.
H2NHSO3 + NO2–  N2  + SO42– + H+ + H2O
HCl
NO2– + H+  HNO2
CO(NH2)2 + 2HNO2  2N2  + CO2  + 3H2O
 Diphenyl amine test : Blue ring is formed at the junction of two liquids (reagent and nitrate salt
solutions).
NaNO3 + H2SO4  NaHSO4 + HNO3
2HNO3  H2O + 2NO2 + [O]
2C6H5NHC6H5 + [O]  (C6H5)2 N – N (C6H5)2 (blue ring) + H2O.
 This test is also given by various oxidising agents like CrO 42– , Cr2O72–, ClO3– , BrO3– , IO3–, NO2– etc.
TO distinguish Br2 with NO2 (both are reddish brown gases)
(a) Br2 + starch–iodide paper  Blue black colour spots do not develop immediately as Br2 is a weaker
oxidising agent whereas NO2 being strong oxidising agent develops the blue black colour immediately.
(b) Bromine develops orange–red colour spots on starch paper.

(B) GROUP 'B' RADICALS :

Group of anions which do not give any gas with dilute as well as concentrated H 2SO4 in cold but give
precipitate with certain reagents :
These acid radicals are identified in inorganic salts by their individual tests as given below
1. SULPHATE ION (SO42–) :
 Barium chloride test :
W.E. or S.E. + Barium chloride (aq)  White precipitate
Na2SO4 + BaCl2  BaSO4 white+ 2NaCl.
 White precipitate is insoluble in warm dil. HNO3 as well as HCl but moderately soluble in boiling
concentrated hydrochloric acid.

QUALITATIVE ANALYSIS # 154

  Lead acetate test :
W.E. or S.E. + Lead acetate  white precipitate
Na2SO4 + (CH3COO)2Pb  PbSO4 White + 2CH3COONa
 White precipitate soluble in excess of hot ammonium acetate.
PbSO4 + 2CH3COONH4  (CH3COO)2Pb (soluble) + (NH4)2SO4

 Match stick test :

(a) W.E. or S.E. + Barium chloride  white precipitate
Na2SO4 + BaCl2  2NaCl + BaSO4  (white)
(b) White precipitate + Na2 CO3(s) mix and apply the paste on the end of the carbonized match stick or
a wooden splinter. Put it in the reducing flame.
BaSO4 (s) + Na2CO3(s)  Na2SO4 + BaCO3  (white)
Na2SO4 + 4C  Na2 S + 4CO
(c) Now dip the match stick in sodium nitroprusside solution, purple colour near the fused mass is
developed.
Na2S + Na2 [Fe(CN)5 NO]  Na4 [Fe(CN)5 NOS] (purple)
 Mercury II chloride test : Yellow precipitate is formed
SO42– + 3Hg2+ + 2H2O  HgSO4. 2H2O (basic mercury II sulphate) + 4H+
 Silver nitrate test : White precipitate is obtained.
SO42– + 2Ag+  Ag2SO4 

2. PHOSPHATE ION (PO43– ) :

 Ammonium molybdate test :

Na2 HPO4 (aq) + 12(NH4)2MoO4 + 23HNO3  (NH4)3PMo12O40  (canary yellow) + 2NaNO3 + 21NH4NO3 + 12H2O
 Some times ammonium phosphomolybdate is also represented by the formula (NH4)3 PO4 . 12MoO3

 Magnesium nitrate or magnesia mixture test : W.E. or S.E + Magnesium nitrate reagent (3-4 mL)
and allows to stand for 4-5 minutes, white crystalline precipitate is formed.
Na2HPO4 (aq) + Mg(NO3)2 (aq) + NH4OH(aq)  Mg(NH4) PO4  (white) + 2NaNO3 + H2O
Magnesia mixture is a solution containing MgCl2, NH4Cl and a little aqueous NH3.
 PO43– also gives BaCl2 test due to the formation of white precipitate of Ba3 (PO4)2 . So phosphate test
should be carried out first and then conclude if PO43– is present or absent before proceeding with the
test for SO42–.

 Silver nitrate solution : Yellow precipitate is formed which is soluble in dilute ammonia and in dilute nitric
acid.
PO43– + 3Ag+  Ag3PO4 
Ag3PO4 + 6NH3  3[Ag(NH3)2]+ + PO43– ; Ag3PO4 + 2H+  H2PO4– + 3Ag+

 Iron (III) chloride solution : Yellowish-white precipitate of FePO4 is obtained

HPO42– + Fe3+  FePO4 

3. BORATE ION (BO33–) :

Salt (0.2 g) + conc. H2SO4 (1 mL) + Ethyl alcohol (4-5 mL) mix in a test tube and then heat. Ignite the
evolved vapours with the help of Bunsen flame, green edged flame is obtained.
2Na3BO3 + 3H2SO4  3Na2 SO4 + 2H3BO3
3C2H5OH + H3BO3  (C2 H5)3 BO3 + 3H2O

QUALITATIVE ANALYSIS # 155

Qualitative Analysis (Part-2)
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 Cu2+ or Ni 2+
Greenish Ni 2+
Light green Fe2+
Dark brown Fe3+
Pink, violet Co 2+
Light pink, flesh colour or dull
earthy colour Mn 2+

Shows the absence of

W hite Cu 2+,Ni 2+,Fe 2+,Fe3+
Mn2+, Co2+
(i) Heavy Salt of Pb2+ or Ba 2+–
(b) De nsity
(ii) Light fluffy powder Carbonate salts
(i) If coloured, may be
Cu(NO 3 )2,
Salt absorbs moisture and FeCl3
(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 
Table : 2

Observation Inference
Incrusta tion or Re sidue M e ta llic be a d
Yellow when hot, white when cold None Zn 2+
Grey bead which
Brown when hot, yellow when cold Pb2+
marks the paper
No characteristic residue Red beads or scales Cu2+
W hite residue which glows on heating None Ba ,Ca 2+, Mg 2+
2+

Nothing definite–generally
Black None
coloured salt

QUALITATIVE ANALYSIS # 156

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

4. Borax Bead test :

On Heating borax forms a colourless glassy bead of NaBO2 and B2O3 .
 
Na2B4O7.10H2O  Na2B4O7  2NaBO2 + B2O3
On heating with a coloured salt , the glassy bead forms a coloured metaborate in oxidising flame.
For example, in oxidising flame copper salts give blue bead.
CuSO4  CuO + SO3 ; CuO + B2O3  Cu(BO2)2 (blue bead)
However, in reducing flame the colours may be different due to different reactions.
2Cu(BO2)2 + C  2CuBO2 + B2O3 + CO
2Cu(BO2)2 + 2C  2Cu (brown red/red and opaque bead) + 2B2O3 + 2CO.
Table : 4
Colour in oxidising flame Colour in reducing flame
Metal
When Hot When Cold When Hot When Cold
Copper Green Blue Colourless Brown red
Iron Brown yellow Pale yellow/Yellow Bottle green Bottle green
Chromium Yellow Green Green Green
Cobalt Blue Blue Blue Blue
Manganese Violet/Amethyst Red/Amethyst Grey/Colourless Grey/Colourless
Nickel Violet Brown/Reddish brown Grey Grey

 Non luminous flame is called oxidising flame.  Luminous flame is called reducing flame.

QUALITATIVE ANALYSIS # 157

 Figure : Borax bead test
 All acid radicals which are in JEE syllabus are colourless and diamagnetic. Hence the colour of the
salts is only due to the basic radicals.

Analysis of CATIONS (Basic Radicals) :

Table : 5

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
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 , HgCl2) 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 H 2S 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, As 2S3 even though Cd2+ , As3+ will be
absent. The colloidal solution is white-yellow and that cannot be filtered causing unnecessary trouble.

QUALITATIVE ANALYSIS # 158

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 MnO 2.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 Fe 3+, 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 H 2S. 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.
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.
2HgNO3 + 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+
QUALITATIVE ANALYSIS # 159
  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.
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 
 4-Nitrobenzene - diazonium chloride reagent : NH4+ gives red colouration with the reagent in
presence of sodium hydroxide.

O 2N N=N—Cl + NH4+ + OH–  O2N N=NONH4 + Cl– + H2O

Ist GROUP (Pb2+, Hg22+, Ag+) :

QUALITATIVE ANALYSIS # 160

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.
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]2– + H2O2  PbO2  (black / brownish black) + 2H2O + 2OH–
[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] 
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–
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–
PbSO4  + 2C4H4O62–  [Pb(C4H4O6)2]2– + SO42–
Hot concentrated H2SO4 dissolves the precipitate due to the formation of PbHSO4.
PbSO4  + H2SO4  Pb2+ + 2HSO4–

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
(a) Stannous chloride test : White precipitate is formed which finally turns to black.
2HgCl2 + SnCl2  Hg2Cl2  + SnCl4 ; Hg2Cl2 + SnCl2  2Hg  (black) + 2SnCl4
(b) Potassium iodide test : Scarlet/red precipitate is formed which is soluble in excess of the reagent.
HgCl2 + KI  HgI2  + 2KCl ; Hg2 + KI (excess)  K2[Hg4] (soluble)
(c) Copper chips test : Shining grey deposition of mercury on copper chips is formed.
HgCl2 + Cu  Hg (grey) + CuCl2

QUALITATIVE ANALYSIS # 161

 Potassium iodide solution : A green precipitate is formed.
Hg22+ + 2I–  Hg2I2 
Green precipitate in excess of reagent undergoes disproportionation reaction and a soluble [HgI 4]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–
 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.
 Hydrazine sulphate (saturated) : With diammineargentate (I) reagent forms finely divided silver which adheres
to the cleaned glass walls of the test tube forming an attractive mirror.
4[Ag(NH3)2]+ + H2N–NH2.H2SO4  4Ag + N2 + 6NH4+ + 2NH3 + SO42–
 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 :

QUALITATIVE ANALYSIS # 162

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+)

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+
Na S (2M) dissolves the precipitate forming soluble complex.
2
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 

QUALITATIVE ANALYSIS # 163

  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 
 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–
 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.

QUALITATIVE ANALYSIS # 164

  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+

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 BiO 3– by H2O2.
Bi(OH)3  BiO.OH + H2O
BiO.OH + H2O2  BiO3– + H+ + H2O
 Ammonia solution : White basic salt of variable composition is formed. Approximate chemical reaction is :
Bi3+ + NO3– + 2 NH3 + 2 H2O  Bi(OH)2 NO3  + 2 NH4+
 Alkaline sodium stannite (Sodium tetrahydroxidostannate (II)) : A black precipitate of metallic bismuth
is obtained.
Bi3+ + 3 OH–  Bi(OH)3 
2Bi(OH)3  + [Sn(OH)4]2–  2Bi  + 3 [Sn(OH)6]2–
(OA) (RA)

 The reagent must be freshly prepared and test must be carried out in cold solution.

 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).

QUALITATIVE ANALYSIS # 165

  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 HNO 3
.
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)

 Sodium hydroxide : White precipitate is obtained which is not soluble in excess of sodium hydroxide.

Cd2+ (aq) +2NaOH (aq)  Cd(OH)2  + 2Na+

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)2 SO4
 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)

QUALITATIVE ANALYSIS # 166

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 AsO 33– ions.
AsO33– + 3 Ag+  Ag3AsO3 (yellow)
AsO43– + 3 Ag  Ag3AsO4  (brownish red)
The precipitate is soluble in both nitric acid and ammonia.

 Magnesia mixture : White crystalline precipitate of magnesium ammonium arsenate Mg(NH 4)

AsO4.6 H2O is formed from neutral or ammonical solution. Upon treating the white precipitate with silver nitrate
solution containing a few drops of acetic acid, red silver arsenate is formed (distinction from phosphate).
H3AsO4 + MgSO4 + 3NH4OH  Mg(NH4)AsO4 + (NH4)2SO4 + 3H2O
MgNH4AsO4  + 3 Ag+  Ag3AsO4  + Mg2+ + NH4+

 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 
 Ammonium molybdate test : Solution of AsO43– ion containing considerable excess of HNO3 on boiling with
reagent gives a yellow crystalline precipitate.
H3AsO4 + 12(NH4)2 MoO4 + 21HNO3  (NH4)3 AsO4 . 12MoO3 + 21NH4NO3 + 12H2O
or AsO43– + 12MoO42– + 3NH4+ + 24H+  (NH4)3 AsMo12O40  + 12H2O.

QUALITATIVE ANALYSIS # 167

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
 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 Sb 2O3.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 H 2S to S according to the
following reaction.
H2S + [O]  H2O + S  (Yellow)

QUALITATIVE ANALYSIS # 168

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.

QUALITATIVE ANALYSIS # 169

 [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

 Lake test :
AlCl3 + 3NH4OH  Al(OH)3  (white) + 3 NH4Cl

The precipitation of aluminium hydroxide is done in presence of blue litmus. Originally the solution will appear
red when the group precipitate is dissolved in HCl as blue litmus turns red in acid medium. On adding large
excess of NH4OH, Al(OH)3 will be reprecipitated and will adsorb the litmus as it is flocculent by nature. After a
while a blue mass will be seen floating in a colourless solution as all the colour from the solution will adsorbed.

 Sodium acetate solution : No precipitate is obtained in cold , neutral solution but on boiling with excess
reagent, a voluminous precipitate of basic aluminium acetate is formed.
Al3+ + 3 CH3COO– + 2 H2O  Al(OH)2CH3COO  (white basic salt) + CH3COOH

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

Al3+ + HPO42– AlPO4  + H+
The reaction is reversible; strong acids dissolves the precipitate. However, the precipitate is insoluble in acetic
acid (difference from phosphates of alkaline earths, which are soluble). The precipitate can also be dissolved in
sodium hydroxide.

 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 (Co 3O4) 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.
NH 4 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.
 Ksp of iron(III) hydroxide is so small (3.8 × 10–38) that complete precipitation take place even in the
presence of ammonium salts.
 Fe(OH)3  Heat
 Fe2O3 + 3 H2O
Oxide is soluble with difficulty in dilute acids but dissolves on vigorous boiling with concentrated HCl.
Fe2O3 + 6 H+  2 Fe3+ + 3 H2O
 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 H 2S , 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+
QUALITATIVE ANALYSIS # 170
  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.
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.

QUALITATIVE ANALYSIS # 171

 [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.
 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]–
 On adding H2O2 to the alkaline solution of [Cr(OH)4]– , a yellow solution is obtained.
2 [Cr(OH)4]– + 3 H2O2 + 2 OH–  2 CrO42– + 8 H2O
 The green precipitate of Cr(OH)3 can be dissolved by using any of the following methods.
(A) Fusion with fusion mixture (Na2CO3 + KNO3)
2 Cr(OH)3 + 2Na2CO3 + 3 KNO3  2 Na2CrO4 + 3 KNO2 + 2 CO2 + 3 H2O
Fused mass on extraction with water gives yellow solution of Na2CrO4 .
(B) 2 Cr(OH)3 + 3 Na2O2  2Na2 CrO4 + 2NaOH + H2O
(C) Precipitate is heated with NaOH and bromine water.
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.
CrO42– + Pb2+   PbCrO4 
CH3OOH

(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

 1,5–Diphenylcarbazide test : In dilute mineral acid solution the reagent produces a soluble violet colour with
chromate. During the reaction, chromate is reduced to chromium (III) and diphenylcarbazone is formed; these
reaction products in turn produce a complex with the characteristic colour.

QUALITATIVE ANALYSIS # 172

  Phenanthroline test : Green precipitate dissolved in dilute HCl (minimum quantity) gives red colouration with
the reagent.

IV th GROUP (Zn 2+ , Mn 2+ , Ni 2+ , Co 2+ ) :

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–

QUALITATIVE ANALYSIS # 173

  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
 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
 Disodium hydrogen phosphate solution : A pink precipitate of Mn(NH4) PO4 . 7 H2O is formed in presence
of ammonia or ammonium ions.
Mn2+ + NH3 + HPO42–  Mn(NH4)PO4 
If ammonium salts are absent, pink precipitate of manganese(II) phosphate is formed.
3 Mn2+ + HPO42–  Mn3(PO4)2  + 2 H+
Both precipitates are soluble in acids.
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–
 Disodium hydrogen phosphate solution : White precipitate of zinc phosphate is formed.
3 Zn2+ + HPO42– Zn3(PO4)2  + 2H+
In presence of ammonium ions zinc ammonium phosphate is formed.
Zn2+ + NH4+ + HPO42– Zn(NH4) PO4  + H+
Both precipitates are soluble in dilute acids, when the reactions are reversed.
Both precipitates are soluble in ammonia :
Zn3(PO4)2 + 12 NH3  3 [Zn(NH3)4]2+ + 2 PO43–
Zn(NH4)PO4 + 3 NH3  [Zn(NH3)4]2+ + HPO42–

QUALITATIVE ANALYSIS # 174

  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.
 Ammonium tetrathiocyanatomercurate(II) – copper sulphate test : Test solution faintly acidic with a few
drops of MH2SO4 or 2MCH3COOH and 0.1 mL of 0.25 M CuSO4 solution followed by 2 mL of the reagent
produces a violet precipitate. Zinc ions alone forms a white precipitate with the reagent in the absence of copper
ions.
Zn2+ + [Hg(SCN)4]2–  Zn [Hg(SCN)4]  .
In the presence of the copper ions, the copper complex coprecipitated with that of zinc and the violet (or
blackish–purple) precipitate consists of mixed crystals of Zn[Hg(SCN)4] + Cu[Hg(SCN)4].
 Diphenylthiocarbazone (dithizone) test : Dithizone forms complexes with a number of metal ions, which
can be extracted with chloroform. The zinc complex, formed in neutral, alkaline or acetic acid solutions, is red
in colour.
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 HNO 3 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
or CoCl2 + H2S 4  CoS  + 2HCl
NH OH

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.
 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–
 Ammonia solution : In absence of ammonium salt, its small amount precipitates a blue basic salt.
Co2+ + NH3 + H2O + NO3–  Co(OH)NO3  + NH4+
The excess of the reagent dissolves the precipitate, when hexaamminecobalt(II) ions are formed.
Co(OH)NO3  + 6 NH3  [Co(NH3)6]2+ + NO3– + OH–
 Potassium cyanide solution :
Co2+ + 2 CN–  Co(CN)2  (reddish brown / buff coloured)
In excess of reagent, a brown solution of a soluble complex is formed.
Co(CN)2  + 4 CN–  [Co(CN)6]4–
On acidification precipitate reappears.
[Co(CN)6]4– + 4 H+ (cold and dilute)  Co(CN)2  + 4HCN 

QUALITATIVE ANALYSIS # 175

  If brown solution is boiled for a longer time in air or some H2O2 is added and solution is heated it
turns yellow.
4 [Co(CN)6]4– + O2 + 2 H2O  4 [Co(CN)6]3– (yellow solution) + 4 OH–
2 [Co(CN)6]4– + H2O2  2 [Co(CN)6]3– (yellow solution) + 2 OH–
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.
NiCl2 + H2S 4  NiS  (Black) + 2HCl
NH OH

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
(red)
 Fe(II) ions give red colouration, bismuth gives yellow precipitate and cobalt gives brown colouration
with DMG in ammonical solutions.
 Bromine water test (alkaline medium) : A black precipitate of Ni2O3 is formed.
NiCl2 + 2NaOH (excess)  Ni(OH)2  (green) + 2 NaCl
Green precipitate is formed which gradually turns black on adding bromine water.

Br2 + H2O  2HBr + [O] ; 2Ni(OH)2 + H2O + [O]  2 Ni(OH)3   Ni2O3 + 3H2O
(black)
 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
 Cyanide test : A green precipitate is formed which dissolves in excess of reagent forming a yellow coloured
solution.
NiCl2 + 2KCN  Ni(CN)2  + 2KCl ;
Ni(CN)2 + 2KCN  K2[Ni(CN)4] ;
Complex on heating with sodium hypobromite (NaOH + Br2 water) solution gives a black precipitate (distinction
from cobalt).
NaOH + Br2  NaBrO + HBr
boil
2K2[Ni(CN)4] + 4NaOH + 9NaBrO  4NaCNO + 9NaBr + Ni2O3  (black) + 4KCNO +2H2O

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 ).
QUALITATIVE ANALYSIS # 176
1.BARIUM ION ( Ba2+) :
 Precipitation with (NH4)2 CO3 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–
3. CALCIUM ION (Ca2+) :
 Precipitation with (NH4)2 CO3 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.

QUALITATIVE ANALYSIS # 177

  The confirmatory test for the basic radicals of (V) group have to be done in the order of Ba 2+, 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 NH 4Cl (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.
 4–(4–Nitrophenyl azo resorcinol) or Magneson I : Precipitate is dissolved in dilute HCl (minimum quantity)
and to this sodium hydroxide solution is added followed by addition of 0.5 mL of magneson–I reagent. A blue
lake is formed.
MgCl2 + 2NaOH  Mg(OH)2 + 2NaCl
Magneson reagent is p-nitrobenzene-azo resorcinol a dye stuff which is adsorbed over Mg(OH) 2 to produce
a blue coloured lake.
 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.

QUALITATIVE ANALYSIS # 178

 MISCELLANEOUS SOLVED PROBLEMS (MSPs)
1. BaCl2 solution gives a white precipitate with a solution of a salt, which dissolves in dilute hydrochloric acid with
the evolution of colourless, pungent smelling gas. The gas as well as the salt both are used as bleaching agent
in the textile industries. The salt contains:
(A) sulphite (B) sulphide (C) acetate (D) carbonate
Ans. (A)
Sol. Ba2+ + SO32–  BaSO3  (white)
BaSO3 + 2HCl  BaCl2 + SO2(colourless pungent smelling gas) + H2O
SO32– and SO2 both act as bleaching agent.
2. 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.

3. Chocolate brown precipitate is formed with :

(A) Cu2+ ions and [Fe (CN)6]3– (B) Cu2+ ions and [Fe(CN)6]4–
(C) Fe2+ 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.
4. Pink colour of acidified KMnO4 is decolourised but there is no evolution of any gas. This may happen with the
compound containing the following acid radical.
(A) SO32– (B) NO 2– (C) S2– (D) All of these
Ans. (D)
Sol. (A) 5SO32– + 2MnO4– + 6H+  2Mn2+ + 5SO42– + 3H2O
(B) 2MnO4– + 5NO2– + 6H+  2Mn2+ + 5NO3– + 3H2O
(C) 2MnO4– + H2S + 6H+  2Mn2+ + 5S  + 8H2O
5. Which of the following gives a precipitate with Pb(NO3)2 but not with Ba(NO3)2?
(A) Sodium chloride (B) Sodium acetate
(C) Sodium nitrate (D) Disodium hydrogen phosphate
Ans. (A)
Ans. (A) Pb2+ + 2Cl–  PbCl2(white) ; Ba2+ + 2Cl–  BaCl2(water soluble)
(B) (CH3COO)2 Pb and (CH3COO)2Ba both are water soluble salts.
(C) Nitrates are mostly soluble in water
(D) 3Pb2+ + 2HPO42–  Pb3(PO4)2  (white) + 2H+ ; Ba2+ + HPO42–  BaHPO4  (white)

6. 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.

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

(A) Fe3+ reacts with potassium thiocyanate (B) Fe2+ reacts with dimethylglyoxime.
(C) Hg reacts with potassium iodide.
2+
(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).

QUALITATIVE ANALYSIS # 179

8. When H2S gas is passed through an ammonical salt solution X, a slightly white precipitate is formed. The X can
be :
(A) a cobalt salt (B) a lead salt (C) a zinc salt (D) a silver salt
Ans. (C)
Sol. Zn2+ + H2S  ZnS  (white) + 2H+

9. Consider the following statement :

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 is aqueous.
S3 : The presence of magnesium is confirmed in qualitative analysis by the formation of a white crystal
line 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)

10. 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

11. Statement - 1 : Sodium meta aluminate on boiling with ammonium chloride produces white gelatinous precipi-
tate.
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)

Sol. [Al(OH)4]–   Al(OH)3  + OH–

NH4Cl
boil

12. 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]4–
4Fe3+ + 3 [Fe(CN)6]4–  Fe4[Fe(CN)6]3(turnbull's blue)
(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

QUALITATIVE ANALYSIS # 180

13. 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.14 to Q.16)

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.

14. 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–.

15. The basic radical of salt (A) and gas B both gives 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
Hence the cation is NH4+.

16. 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]4–  (NH4)2 [PtCl6]  (yellow)

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

QUALITATIVE ANALYSIS # 181

 (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 :
17. 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)
18. When a solution of nitrite acidified with dilute hydrochloric acid is treated with solid urea, the nitrite is decom-
posed, and nitrogen and carbon dioxide are evolved.
Sol. (True) CO(NH2)2 + HNO2  2N2  + CO2  + 3H2O.

19. Solution of alkali metal cyanide containing freshly prepared iron (II) sulphate solution and dilute H 2SO4 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 :
20. 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 ammo-
nium 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 CO23 + 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.
21. 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)
QUALITATIVE ANALYSIS # 182
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)  KFe [Fe(CN)6].
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)

QUALITATIVE ANALYSIS # 183