SALT ANALYSIS THEORY

SALT ANALYSIS
Principles of qualitative analysis group I to V excluding interfering radicals.
The detection of cations (basic radicals)and anions(acidic radicals) in a salt or in a mixture is known as
Qualitative Analysis.
Some Important Observations during Qualitative Analysis
1. List of different coloured salts

2. Action of Heat (Colour of Residue)

3. Gases

4. Flame Test

Classification Of Anions
Methods available for the detection of anions are not as systematic as those used for the detection of
cations. Furthermore anions are classified essentially on the basis of process employed.

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Class A: Includes anions that are identified by volatile products obtained on treatment with acids.It is further
divided into two sub groups.
(i) Gases evolved with dil HCl/ dil H2SO4.
(ii) Gases or acid vapours evolved with conc H2SO4
Class B: Includes anions that are identified by their reactions in solution. It is subdivided into two groups:
(i) Precipitation reactions
(ii) Oxidation and reduction in solution
Class A (i): Anions which evolve gases on reaction with dil. HCl/dil. H2SO4.
It includes - CO32-, SO32-, S2-, NO2-, CH3COO-, S2O32-
1. Carbonate (CO32- ) :
(i) Dilute HCl : gives effervescence, due to the evolution of carbon dioxide
CO32- + 2H+  CO2 + H2O
The gas gives white turbidity with lime water and baryta water
CO2 + Ca2+ + 2OH-  CaCO3  + H2O
CO2 + Ba2+ + 2OH-  BaCO3  + H2O
On prolonged passage of carbon dioxide in lime water, the turbidity slowly disappears due to the
formation of soluble hydrogen carbonate.
CaCO3  + CO2 + H2O  Ca(HCO3)2
The following tests performed with then aqueous salts solution.
(ii) Barium chloride or Calcium chloride solution: White ppt of barium or Calcium carbonate is
obtained, which is soluble in mineral acid.
CO32- + Ba2+  BaCO3 
CO32- + Ca2+  CaCO3 
(iii) Silver nitrate solution : White ppt of silver carbonate is obtained.
CO32- + 2Ag+  Ag2CO3
The ppt so obtained is soluble in nitric acid and in ammonia, the ppt becomes yellow or brown on
addition of excess reagent and same may also be happened if the mix is boiled, due to the formation of
silver oxide
Ag2CO3  Ag2O  + CO2 
2. Sulphites (SO32-):
(i) Dilute HCl or Dilute H2SO4 : decomposes with the evolution of sulphur dioxide
SO32- + 2H+  SO2 + H2O
The gas has a suffocating odour of burning sulphur.
(ii) Acidified potassium dichromate solution: The gas turns filter paper moistened with acidified
potassium dichromate solution, green due to the formation of Cr3+ions.
SO2 + K2Cr2O7 + H2SO4  K2SO4 + Cr2(SO4)3 + H2O
green
(iii) Lime water : On passing the gas through lime water, a milky ppt is formed.
SO2 + Ca(OH)2  CaSO3  + H2O
milky
Precipitate dissolves on prolonged passage of the gas, due to the formation of soluble hydrogen
sulphite ions.
CaSO3  + SO2 + H2O  Ca(HSO3)2.

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(iv) Barium chloride or Strontium chloride solution : Salt solutions gives white ppt of barium or
strontium sulphite.

SO 23   Ba 2   BaSO 3 

SO23   Sr 2   SrSO3 
3. Sulphide (S-2) :
(i) Dil HCl or Dil H2SO4 : A colourless gas with a smell of rotten eggs (H2S) is evolved
S2- + 2H+  H2S
(ii) The gas turns lead acetate paper black
(CH3COO)2Pb + H2S  PbS  + 2CH3COOH
black
(iii) Salt solution gives yellow ppt. with CdCl2
Na2S + CdCl2  CdS + 2NaCl
yellow
(iv) Silver nitrate solution : black ppt. of silver sulphide insoluble in cold but soluble in hot dil nitric
acid.
S2- + 2Ag+  Ag2S 
(v) Sodium nitroprusside solution : Turns sodium nitroprusside solution purple
Na2S + Na2[Fe(CN)5NO]  Na4[Fe(CN)5NOS]

4. Nitrites (NO2-) :
(i) Dil HCl and Dil. H2SO4: Adding to solid nitrite in cold yield pale blue liquid (due to the presence
of free nitrous acid HNO2 or its anhydride N2O3) & the evolution of brown fumes of nitrogen dioxide, the
latter being largely produced by combination of nitric oxide with the oxygen of the air
NO2- + H+  HNO2
2HNO2  H2O + N2O3
3HNO2  HNO3 + 2NO + H2O
2NO + O2  2NO2
Following tests performed with an aqueous salt solution.
(ii) Silver nitrate solution : White crystalline ppt. is obtained
NO2- + Ag+  AgNO2
(iii) Turns acidified KI - starch paper blue
2KI + 2NO2  2KNO2 + I2 
Starch + I2  Blue Colour
(iv) Brown ring test: When the nitrite solution is added carefully to a conc. solution of Iron(II)
sulphate acidified with dil acetic acid or with dilute sulphuric acid, a brown ring, due to the formation
of [Fe,NO]SO4 at the junction of the two liquids.
NO2- + CH3COOH  HNO2 + CH3COO-
3HNO2  H2O + HNO3 + 2NO
Fe2+ + SO42- + NO  [Fe, NO]SO4.

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5. Acetate (CH3COO-) :
(i) Dilute Sulphuric Acid: Smell of vinegar
CH3COO- + H+  CH3COOH 
(ii) Iron (III) Chloride Solution: Gives deep - red colouration
CH3COONa + FeCl3  (CH3COO)3Fe + 3NaCl
Brown colour

6. Thiosulphates ( S 2 O 2
3
):
(i) Dil Hydrochloric acid : Gives sulphur & sulphur di oxide

S2O 23  + 2H+  S  + SO2 + H2O

(ii) Iodine Solution : Decolourise due to formation of tetrathionate ion

I2 + 2S2O 23   2I- + S4O62-

(iii) Barium chloride solution : White ppt. of barium thiosulphate is formed

S2O 23  + Ba2+  BaS2O3 

But no ppt. is obtained with CaCl2 solution.
(iv) Silver nitrate solution : Gives white ppt. of silver thiosulphate.

S2O 23  + 2Ag+  Ag2S2O3 

The ppt. is unstable, turning dark on standing, due to the formation of silver sulphide.
Ag2S2O3 + H2O  Ag2S + H2SO4
(v) Lead acetate or Lead nitrate solution : Gives white ppt.

S 2 O 32 + Pb2+  PbS2O3 

On boiling it turns black due to the formation of PbS.
PbS2O3  + H2O  PbS  + 2H+ + SO42-
Class A(ii): Gases or acid vapours evolved with conc. Sulphuric acid
It includes - Cl-, Br-, I-, NO3-.
1. Chloride (Cl-) :
(i) Conc. H2SO4 : decomposes with the evolution of HCl.

Cl- + H2SO4  HCl + HSO 4

Gas so produced
1. Turns blue litmus paper red
2. Gives white fumes of NH4Cl when a glass rod moistened with ammonia solution is brought to the
mouth of test tube.
(ii) Manganese dioxide and conc. sulphuric acid: When a solid chloride is treated with MnO2 and
conc. H2SO4, yellowish green colour is obtained.
MnO2 + 2H2SO4 + 2Cl-  Mn2+ + Cl2 + 2SO42- + 2H2O
The following tests are performed with the salt solution.
(iii) Silver nitrate solution: White, curdy ppt. of AgCl insoluble in water & in dil nitric acid, but
soluble in dilute ammonia solution.
Cl- + Ag+  AgCl 
AgCl  + 2NH3  [Ag(NH3)2]Cl
Ag(NH3)2Cl + 2H+  AgCl + 2NH4+.

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(iv) Lead acetate solution: White ppt. of lead chloride is formed

2Cl- + Pb+2  PbCl2 
(v) Chromyl chloride test : When a mix containing chloride ion is heated with K2Cr2O7 and conc.
H2SO4 orange red fumes of chromyl chloride (CrO2Cl2) are formed.
K2Cr2O7 + 4NaCl + 6H2SO4  2KHSO4 + 4NaHSO4 + 2CrO2Cl2  + 3H2O
orange – red fumes
Chlorides of mercury, owing to their slight ionization, do not respond to this test and only partial
conversion to CrO2Cl2 occurs with the chlorides of lead, silver, antimony and tin.
When chromyl chloride vapours are passed into sodium hydroxide a yellow solution of sodium chromate
is formed which when treated with lead acetate gives yellow ppt. of lead chromate.
CrO2Cl2 + 2NaOH  Na2CrO4 + 2HCl
Yellow solution
Na2CrO4 + (CH3COO)2 Pb  2CH3COONa + PbCrO4 
(yellow ppt.)
2. Bromide (Br-)
(i) Conc. H2SO4 : Gives reddish brown vapours of bromine.
2KBr + H2SO4  K2SO4 + 2HBr
2HBr + H2SO4  2H2O + SO2  + Br2
(reddish brown)
(ii) Manganese dioxide and conc. sulphuric acid : When a mix of solid bromide, MnO2 and conc.
H2SO4 is heated reddish brown vapours of bromine are evolved.
2KBr + MnO2 + 2H2SO4  Br2  + K2SO4 + MnSO4 + 2H2O
The following tests are performed with the salt solution.
(iii) Silver nitrate solution: A pale yellow ppt. of silver bromide is obtained. This ppt. is sparingly
soluble in dil but readily soluble in conc. ammonia solution and insoluble in dil. HNO3.
Br- + Ag+  AgBr
(iv) Lead acetate solution: White crystalline ppt. of lead bromide which is soluble in
boiling water.
2Br- + Pb+2  PbBr2 
(v) Chlorine water: When this solution is added to a solution of bromide and chloroform free
bromine is liberated, which colours the organic layer
orange – red.
2KBr + Cl2 (water)  2KCl + Br2
Br2 + Chloroform  Orange red colour
(vi) Potassium dichromate & conc. H2SO4: When a mix of solid bromide, K2Cr2O7, and conc. H2SO4
is heated and passing the evolved vapours into water, a yellowish brown solution is obtained.
2KBr + K2Cr2O7 + 7H2SO4  3Br2  + Cr2(SO4)3 + 4K2SO4 + 7H2O.
3. Iodide (I-) :
(i) Conc. H2SO4 : Gives violet vapours of iodine
2I- + 2H2SO4  I2 + SO42- + 2H2O + SO2 
violet vapours
The following tests are performed with the salt solution.

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(ii) Silver nitrate solution: Yellow, curdy ppt. of silver iodide AgI, very slightly soluble in conc.
ammonia solution and insoluble in dil nitric acid.
I- + Ag+  AgI
(iii) Lead acetate solution: Yellow, curdy ppt. of lead iodide soluble in much hot water forming a
colourless solution & yielding golden yellow plates (spangles) on cooling.
2I- + Pb2+  PbI2
(iv) Potassium dichromate & conc. sulphuric acid: Iodine is liberated
6I- + Cr2O72- + 2H2SO4  3I2  + 2Cr3+ + 7SO42- + 7H2O.
(v) Chlorine water: Iodine is liberated, by the dropwise addition of chlorine water to iodide, and
on addition of CHCl3 violet coloured organic layer is obtained.
2I- + Cl2  I2 + 2Cl-
I2 + chloroform  violet coloured layer.
(vi) Copper sulphate solution: Gives brown ppt. consisting of a mixture of copper (I) iodide &
iodine and on additon of hypo solution brown ppt changes to
white ppt.
4I- + 2Cu2+  2CuI + I2
I2 + 2S2O32-  2I- + S4O62-.
v(ii) Mercury (II) chloride solution: Forms scarlet ppt. of HgI2
2I- + HgCl2  HgI2  + 2Cl-.
This ppt. dissolves in excess of KI, forming tetraiodo mercurate (II) complex.
HgI2 + 2I-  [HgI4]2-

4. Nitrate (NO3- ) :
(i) Conc H2SO4 : Gives reddish - brown vapours of nitrogen dioxide
4NO3- + 2H2SO4  4NO2 + 2SO42- + 2H2O + O2
The following tests are performed with the salt solution.
(ii) Brown ring test : When a freshly prepared solution of iron (II) sulphate is added to nitrate
solution & conc. H2SO4 is poured slowly down the side of the test - tube, a brown ring is obtained.
2NO3- + 4H2SO4 + 6Fe2+  6Fe3+ +2NO + 4SO4- + 4H2O
Fe2+ + NO  [Fe(NO)]2+
On shaking and warming the mix, the brown colour disappears, nitric oxide is evolved and a
yellow solution of Iron(III) ions remains.
Action of heat : The result varies with the metal
1. Nitrates of sodium and potassium evolve oxygen (test with glowing splint) & leave solid
nitrites (brown fumes with dilute acid)
2NaNO3  2NaNO2 + O2.
2. Ammonium nitrate yields dinitrogen oxide & steam
NH4NO3  N2O  + 2H2O.
3. Nitrates of the noble metals leave a residue of the metal and a mix of nitrogen dioxide
and oxygen is evolved.
2AgNO3  2Ag + 2NO2  + O2.
4. Nitrates of other metals, such as those of lead and copper, evolve oxygen and nitrogen
dioxide and leave a residue of the oxide.
2Pb(NO3)2  2PbO + 4NO2 + O2.

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Class B (i) Precipitation reaction : SO42-

(ii) Oxidation and reduction in solution - CrO42 - ,Cr2O 72 , MnO4-

1. Sulphate (SO42-):
All sulphates except those of Ba, Pb, Sr are soluble in water. Sulphates of calcium and mercury(II) are
slightly soluble. The following tests are performed with the salt solution.
(i) Barium chloride solution: White ppt. of barium sulphate BaSO4 insoluble in warm dil. hydro-
chloric acid and in dilute nitric acid, but moderately soluble in boiling, conc. hydrochloric acid.
SO42- + Ba2+  BaSO4 
(ii) Mercury (II) nitrate solution : Gives yellow ppt. of basic mercury (II) sulphate.
SO42- + 3Hg2+ + 2H2O  HgSO4.2HgO  + 4H+

2. Chromate CrO42 -and Dichromate (Cr2O 72 ) :

Metallic chromates gives yellow solution when dissolved in water. In the presence of H+ chromates are
converted into dichromates (orange-red solution).

2CrO 42 + 2H+ Cr2O 72 + H2O

Cr2O 72 + 2OH- 2CrO 42 + H2O

It may also be expressed as :

2CrO 42 + 2H+ 2HCrO4- Cr2O7-2 + H2O

(i) Barium chloride solution: Pale - yellow ppt. of barium chromate soluble in dilute mineral acids
but insoluble in water and acetic acid.

CrO 42 + Ba2+  BaCrO4 

Dichromate ions also gives the same ppt. but due to the formation of strong acid precipitation
is partial.

Cr2O 72 + 2Ba2+ + H2O 2 BaCrO4  + 2H+

If sodium hydroxide or sodium acetate is added, precipitation becomes quantitative.
(ii) Silver nitrate solution: Brownish - red ppt. of silver chromate Ag2CrO4 which is soluble in dil.
nitric acid & in ammonia solution, but is insoluble in acetic acid.
CrO42- + 2Ag+  Ag2CrO4 
2 Ag2CrO4 + 2H+  4 Ag+ + Cr2O72- + H2O
Ag2CrO4  + 4NH3  2[Ag(NH3)2]+ + CrO42-
Ag2CrO4  + 2Cl-  2AgCl + CrO42-
A reddish brown ppt. of silver dichromate Ag2Cr2O7 is formed with a conc. solution of a
dichromate.
Cr2O72- + 2Ag+  Ag2Cr2O7
(iii) Lead acetate solution: Yellow ppt. of lead chromate PbCrO4 insoluble in acetic acid, but
soluble in dil nitric acid
CrO42- + Pb2+  PbCrO4 .
2PbCrO4  + 2H+ 2Pb2+ + Cr2O72- + H2O.
(iv) H2O2: If an acidic solution of a chromate is treated with H2O2 a deep blue solution of chromium
penta oxide is obtained.
CrO42- + 2H+ + 2H2O2  CrO5 + 3H2O
CrO5 is unstable and it decomposes yielding oxygen and a green solution of a Cr+3 Salt.

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3. Permanganate MnO 4 :

(i) Hydrogen peroxide : It decolourises acidified potassium permanganate solution

2MnO4- + 5H2O2 + 6H+  5O2  + 2Mn2+ + 8H2O.
(ii) Iron (II) sulphate, in the presence of sulphuric acid, reduces permanganate to manganese (II).
The solution becomes yellow because of the formation of iron (III) ions
MnO4- + 5Fe2+ + 8H+  5Fe3+ + Mn2+ + 4H2O
(iii) Action of heat : On heating, a residue of potassium manganate K2MnO4 and black manganese
dioxide remains behind. Upon extracting with water and filtering, a green solution of potassium manga-
nate is obtained.
2KMnO4  K2MnO4 + MnO2 + O2.

Exercise 1: (i) How to distinguish between CO3  and SO3  ions?

(ii) A gas turns red litmus paper into blue and forms white fume with HCl, identify
the gas

Classification of Cations
For the purpose of systematic qualitative analysis, cations are classified into five groups on the basis
of their behaviour with some reagents and classification is based on whether a cation reacts with
these reagents by the formation of precipitate or not (solubility difference)

Group reagent: Hydrocholoric acid, hydrogen sulphide, ammonium sulphide and ammonium carbonate.

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Points to Remember
1. Group I radicals (Ag+, Pb+2 Hg22+) are precipitated as chlorides because the solubility product of these
chlorides (AgCl, PbCl2, Hg2Cl2) is less than the solubility products of all other chlorides which remain in
solution.

2. Group II radicals are precipitated as sulphides because sulphides of other metals remain in solution
because of their high solubility products, HCl acts as a source of H+ and thus decreases the conc. of
S2- due to common ion effect. Hence decreased conc. of S2- is only sufficient to precipitate the Group
II radicals only.

3. Group III A radicals are precipitated as hydroxides and the NH4Cl suppresses the ionisation of NH4OH so
that only the group III A radicals are precipitated because of their low solubility product.
Note:
(i) Excess of NH4Cl should be added otherwise manganese will be ppt. as MnO2.H2O.
(ii) (NH4)2SO4 can’t be used in place of NH4Cl because the SO42- will ppt. barium as BaSO4.
(iii) NH4NO3 can’t be used in place of NH4Cl because NO3- ions will oxidise Mn2+ to Mn3+ and thus
Mn(OH)3 will be precipitated in III A group.
(iv) Only Al(OH)3 is soluble in excess of NaOH followed by boiling to form sodium metaluminate while
Fe(OH)3 and Cr(OH)3 are insoluble.

4. Ammonium hydroxide increases the ionisation of H2S by removing H+ from H2S as unionised water
H2S 2H+ + S2-. H+ + OH-  H2O
Now excess of S2- ions are available and hence the ionic product of hydroxides of Group III B exceed
their solubility product and ppt. will be obtained.In case H2S is passed through a neutral solution,
incomplete precipitation will take place due to the formation of HCl which decreases the ionization of
H2S.
MnCl2 + H2S  MnS + 2HCl

Identification of Basic Radicals

All confirmatory tests for basic radicals are performed with the salt solution.

1. Group I (Pb2+, Ag+, Hg+)

(a) PbCl2 gives a yellow ppt. with K2CrO4. The ppt. is insoluble in acetic acid but soluble in NaOH
Pb(NO3)2 + K2CrO4  PbCrO4  + 2KNO3
Yellow ppt.
PbCrO4 + 4NaOH  Na2[PbO2] + Na2CrO4 + 2H2O
(b) Pb(NO3)2 + 2KI  PbI2  + 2KNO3
(Yellow)
PbCl2 + 2KI (excess)  K2[PbI4]

2. AgCl is soluble in NH4OH forming a complex while Hg2Cl2 forms a black ppt. with NH4OH.
AgCl + 2NH4OH  Ag(NH2)2Cl + 2H2O
Hg2Cl2 + 2NH4OH  H2N  Hg  Cl + Hg + NH4Cl + 2H2O
Amino mercuric Chloride

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2. Group II A (Hg2+, Cu2+, Bi3+, Cd2+)

(i) Hg+2ions in solution, on addition of SnCl2, give white precipitate turning black.
2Hg+2 + SnCl  Sn+4 + Hg2Cl2 
White
Hg2Cl2 + SnCl2  SnCl4 + 2Hg 
Black
+2
(ii) Cu ions in solution gives a pale blue precipitate which gives a deep blue colour with excess of
NH4OH
Cu+2 + 4NH4OH  [Cu(NH3)4 ]+2 + 4H2O
Deep blue in colour
+2
Cu ions give chocolate precipitate with K4Fe(CN)6.
+2
2Cu + K4Fe(CN)6  Cu2[Fe(CN)6] + 4K+
(iii) Bi+3 ions in solution of HCl on addition of water give white cloudy precipitate.
BiCl3 + H2O  BiOCl  + 2HCl
White ppt.
When treated with sodium stannite a black ppt. is obtained.
2BiCl3 + 3Na2SnO2  2Bi  + 3Na2SnO3 + 6NaCl + 3H2O
black
+2
(iv) Cd ions in solution, with ammonium hydroxide gives a white precipitate which dissolves .
Cd+2 + 2NH4OH  Cd(OH)2  + 2NH4+
Yellow
Cd(OH)2 + 4NH4OH [Cd(NH3 )4] (OH)2
3. Group II B (As3+, As5+, Sb3+, Sb5+, Sn3+, Sn4+)
(v) As+3 ions in solution give yellow precipitate with ammonium molybadate and HNO3.

As+3 HNO3
As+5 (as H3AsO4)
Oxidation

H3AsO4 +12(NH4)2MoO4 +21HNO3 (NH4)3 AsMo12O40 + 21NH4NO3 + 12H2O

Yellow ppt.
2+
(vi) Sn ions in solution as SnCl2 give white ppt. with HgCl2 ,which turns black on standing.
SnCl2 + 2HgCl2  SnCl4 + Hg2Cl2 
White
Hg2Cl2 + SnCl2 SnCl4 + 2Hg 
Black
v(ii) Sb+3 ions in solution as SbCl3 , on addition of water give white precipitate.
SbCl3 + H2O  SbOCl + 2HCI
White

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4. Group III A (Al3+, Fe3+, Cr3+)

(i) White precipitate of Al(OH)3 is soluble in NaOH

Al(OH)3 + NaOH  NaAlO2 + 2H2O

(ii) Precipitate of Cr(OH)3 is soluble in NaOH + Br2 water and addition of BaCl2 to this solution gives
yellow precipitate.
Br2 + H2O  2HBr + (O)
2Cr(OH)3 + 4NaOH + 3(O)  2Na2CrO4 + 5H2O
Na2CrO4 + BaCl2  BaCrO4  + 2NaCl
Yellow ppt.
Fe(OH)3 is insoluble in NaOH

(iii) Brown precipitate of Fe(OH)3 is dissolved in HCl and addition of KCNS to this solution gives
blood red colour.
Fe(OH)3 + 3HCl  FeCl3 + 3H2O
FeCl3 + 3KCNS  Fe(CNS)3 + 3KCl
blood red
Also on addition of K4Fe(CN)6 to this solution, a prussian blue colour is obtained.
FeCl3 + 3K4Fe(CN)6  Fe4[Fe(CN)6]3 + 12KCl
prussian blue colour

5. Group III B (Ni2+, Co2+, Mn2+, Zn2+)

(i) Ni+2 and Co+2 ions in solution, on addition of KHCO3 and Br2 water give apple green
colour if Co+2 is present and black precipitate if Ni+2 is present.
CoCl2 + 6KHCO3  K4[Co(CO3)3] + 2KCl + 3CO2 + 3H2O
2K4[Co(CO3)3] + 2KHCO3 + [O]  2K3[Co(CO3)3] + 2K2CO3 + H2O
Apple green colour
NiCl2 + 2KHCO3  NiCO3 + 2KCl + H2O + CO2
2NiCO3 + 4NaOH + [O]  Ni2O3  + 2Na2CO3 + 2H2O
Black ppt.

(ii) Zn+2 ions in solution give a white precipitate with NaOH, which dissolves in excess of NaOH.
Zn+2 + 2NaOH  Zn(OH)2  + 2Na+
White
Zn(OH)2 + 2NaOH  Na2ZnO2 + 2H2O
Soluble

(iii) Mn+2 ions in solution give pink precipitate with NaOH turning black or brown on heating.
Mn+2 + 2NaOH Mn(OH)2 + 2Na+
Pink
Δ
Mn(OH)2 + [O]  MnO2 + H2O
Brown or
black

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 Page # 12 SALT ANALYSIS THEORY

6. Group IV (Ba2+, Sr2+, Ca2+)

(i) Ba+2 ions in solution give

(a) Yellow precipitate with K2CrO4

Ba+2 + K2CrO4  BaCrO4  + 2K+
Yellow

(b) White precipitate with (NH4)2SO4

Ba+2 + (NH4)2 SO4  BaSO4 + 2 NH 4

White

(c) White precipitate with (NH4)2 C2O4

Ba+2 + (NH4)2C2O4  BaC2O4 + 2 NH 4

White

(ii) Sr+2 ions give white precipitate with (NH4)2SO4 and (NH4)2C2O4

Sr+2 + (NH4)2SO4  SrSO4 + 2 NH 4

White ppt.

Sr+2 + (NH4)2C2O4  SrC2O4 + 2 NH 4

White

(iii) Ca+2 ions give white precipitate with (NH4)2 C2O4 only.

Ca+2 + (NH4)2C2O4  CaC2O4  + 2 NH 4

White

7. Group V (NH4+, Na+, K+, Mg+2)

(i) All ammonium salts on heating with alkali say NaOH give a colourless, pungent smelling gas (
NH3).
NH4Cl + NaOH  NaCl + NH3  + H2O

(a) Gas evolved gives white fumes with a rod dipped in conc. HCl
NH3 + HCl  NH4Cl 
White fumes

(b) Paper soaked in CuSO4 solution, becomes deep blue due to complex formation with NH3.
CuSO4 + 4NH3  [Cu(NH3)4]SO4
deep blue

(c) With Hg2 (NO3)2 , a black colour is obtained

Hg2(NO3)2 + 2NH3  Hg  + Hg(NH2)NO3  + NH4NO3
black

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 SALT ANALYSIS THEORY Page # 13

(d) An aqueous solution of an ammonium gives a brown ppt. with Nessler’s reagent(alkaline solution
of potassium tetraiodomercurate(II) ).
Hg

NH4Cl + 2K2HgI4 + 3KOH  O NH2I + 4KI + 2H2O + 3NaI

Hg
(Brown)
(Iodide of Millon's base)
(ii) Potassium salts give a yellow ppt. with sodium cobaltinitrite
Na3[Co(NO2)6] + 3KCl  K3[Co(NO2)6] + 3NaCl
yellow
(iii) Sodium salts give a heavy white ppt. with potassium dihydrogen antimonate
KH2SbO4 + NaCl  NaH2SbO4  + KCl
White ppt.
(iv) Mg2+ gives white ppt. of magnesium hydroxide with sodium hydroxide
Mg2+ + 2NH3 + 2H2O  Mg(OH)2  + 2NH4+
The ppt. obtained is sparingly soluble in water but readily soluble in ammonium salt.

Problem 1: An aqueous solution of gas (X) shows the following reactions :-

(i) It turns red litmus blue.
(ii) When added in excess to a copper sulphate solution, a deep blue colour is obtained.
(iii) On addition of FeCl3 solution a brown ppt. soluble in dilute nitric acid is obtained.
Identify (X) and give equations for the reactions at step (ii) & (iii)
Solution: X - NH3
Reactions : (i) CuSO4 + 4NH4OH  Cu(NH3)4 SO4 + H2O
deep blue
(ii) FeCl3 + 3NH4OH  Fe(OH)3  + 3NH4Cl
brown ppt.
Fe(OH)3 + 3HNO3  Fe(NO3)3 + 3H2O
Soluble
Problem 2: An aqueous solution of a gas (X) gives the following reactions:
(i) It decolourizes an acidified K2Cr2O7 solution.
(ii) On boiling with H2O2 , cooling it and then adding an aqueous solution of BaCl2, a white ppt.
insoluble in dilute HCl is obtained.
(iii) On passing H2S into the solution, turbidity is obtained.
Identify (X) and give equations for the steps (i), (ii), (iii) .
Solution: X - SO2
Reactions : (i) K2Cr2O7 + H2SO4 + 3SO2  K2SO4 + Cr2 (SO3 )3 + H2O
(ii) SO2 + H2O2  H2SO4
H2SO4 + BaCl2  BaSO4  + 2HCl
white ppt.
(iii) SO2 + 2H2S  3S + 2H2O
white
turbidity

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 Page # 14 SALT ANALYSIS THEORY

Problem 3: A white amorphous powder (A) on strongly heating gives a colourless non-combustible
gas (B) and solid (C). The gas (B) turns lime water milky and turbidity disappears with the
passage of excess of gas.The solution of (C) in dilute HCl gives a white ppt. with an aqueous
solution of K4[Fe(CN)6]. The solution of (A) in dilute HCl gives a white ppt. (D) on passing H2S
in presence of excess of NH4OH. Identify (A) to (D) by giving chemical equations.
Solution: (A) - ZnCO3 (B) - CO2 (C) - ZnO (D) - ZnS
Reactions : (i) ZnCO3  ZnO + CO2
(A) (C) (B)
(ii) CO2 + Ca(OH)2  CaCO3 + H2O
(B) White
CaCO3 + H2O + CO2  Ca(HCO3)2
Excess Soluble
(iii) ZnO + 2HCl  ZnCl2 + H2O
2ZnCl2 + K4Fe(CN)6  Zn2[Fe(CN)6] + 4KCl
White ppt.
(iv) ZnCl2 + H2S  ZnS + 2HCl
(D)
Problem 4: A certain compound (X) is used in laboratory for analysis. Its aq. solution gave the follow-
ing reactions.
(i) On addition to copper sulphate solution, a brown ppt. is obtained which turns white on addition
of excess of Na2S2O3 solution.
(ii) On addition to Ag+ ion solution, a yellow ppt. is obtained which is insoluble in NH4OH. Iden-
tify (X), giving reactions
Solution: X - KI
Reactions : (i) 2CuSO4 + 2KI  2CuI2 + K2SO4
2CuI2  Cu2I2 + I2
white
I2 + 2Na2S2O3  Na2S4O6 + 2NaI
(ii) Ag+ + KI  AgI + K+
Yellow ppt.
The white ppt. of Cu2I2 is coloured brown due to the presence of I2. On adding sodium thiosulphate, I2
is consumed. Therefore the ppt. appears white.
Problem 5: An aqueous solution of inorganic compound (X) gives the following reactions:
(i) With an aq. solution of barium chloride a ppt. insoluble in dil. HCl is obtained.
(ii) Addition of excess of KI gives a brown ppt. which turns white on addition of excess of hypo.
(iii) With an aqueous solution of K4[Fe(CN)6] a chocolate coloured ppt. is obtained.
Identify (X) and give equations for the reactions for (i), (ii) and (iii) observations.
Solution: X - CuSO4
Reactions : (i) CuSO4 + BaCl2  BaSO4 + CuCl2
White ppt.
(insoluble in HC(I)
(ii) 2CuSO4 + 4KI  2CuI2 + 2K2SO4

Cu2I2 + I2
I2 + Na2S2O3  Na2S4O6 + 2NaI

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 SALT ANALYSIS THEORY Page # 15

(iii) CuSO4 + K4[Fe(CN)6]  Cu2 [Fe(CN)6] + 2 K2SO4

Chocolate
Coloured ppt.

Problem 6: An aq. solution of an inorganic compound (X) shows the following reactions.
(i) It decolorizes an acidified KMnO 4 solution accompanied with evolution
of O2.
(ii) It liberates I2 from acidified KI solution.
(iii) It gives brown ppt. with alkaline KMnO4 solution with evolution of O2.
(iv) It is used to restore old oil paintings. Identify (X) and give chemical reactions for the steps (i)
to (iv).
Solution: X - H2O2
Reactions: (i) 5H2O2+2KMnO4+3H2SO4 K2SO4+2MnSO4+8H2O +5O2
(ii) H2O2 + 2KI + H2SO4  I2 + K2SO4 + 2H2O
(iii) 3H2O2 + 2KMnO4  2MnO2  + 2KOH + 3O2 + 2H2O
(iv) 4H2O2 + PbS  PbSO4 + 4H2O
white
Problem 7: A certain compound (X) shows the following reactions :
(i) When KI is added to an aq. suspension of (X) containing acetic acid, iodine is liberated
(ii) When CO2 is passed through an aq. suspension of (X) the turbidity transforms to a ppt.
(iii) When a paste of (X) in water is heated with ethyl alcohol a product of anaesthetic use is ob-
tained.
Identify (X) and write down chemical equations for reactions involved in steps (i), (ii) and (iii)
.
Solution: X - CaOCl2
Reactions: (i)CaOCl2 +2CH3COOH  Ca(CH3COO)2 + Cl2 + H2O
2KI + Cl2  2KCl + I2
(ii) CaOCl2(aq) + CO2  CaCO3 + Cl2
white ppt.
(iii) CaOCl2 + H2O  Ca(OH)2 + Cl2
C2H5OH + Cl2  CH3CHO + 2HCI
Ca( OH) 2
CH3CHO + 3Cl2  CCl3CHO    CHCl3
Anaesthetic
Problem 8: An inorganic Lewis acid (X) shows the following reactions :
(i) It fumes in moist air.
(ii) The intensity of fumes increases when a rod dipped in NH4OH is brought near it.
(iii) An acidic solution of (X) on addition of NH4Cl and NH4OH gives a precipitate which dissolves in
NaOH solution.
(iv) An acidic solution of (X) does not give a precipitate with H2S. Identify (X) and give chemical
equation for steps (i) to (iii) .

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 Page # 16 SALT ANALYSIS THEORY

Solution: X - AlCl3
Reactions : (i) AlCl3 + 3H2O  Al(OH)3 + 3HCl 
fumes
(ii) HCl + NH4OH  NH4Cl + H2O
White fumes
(iii) AlCl3 + 3NH4OH  Al(OH)3 + 3NH4Cl
White ppt.
Al(OH)3 + NaOH  NaAlO2 + 2H2O
Soluble
Problem 9: (i) A black mineral (A) on treatment with dilute sodium cyanide solution in presence of
air gives a clear solution of (B) and (C).
(ii) The solution of (B) on reaction with zinc gives a precipitate of metal (D).
(iii) (D) is dissolved in dil. HNO3 and the resulting solution gives a white precipitate (E) with dil.
HCl.
(iv) (E) on fusion with sodium carbonate gives (D).
(v) (E) dissolves in aqueous solution of ammonia giving a colourless solution of (F). Identify (A) to
(F) and give chemical equations for reactions involved in steps (i) to (v).
Solution: (A) - Ag2S (B) - NaAg(CN)2
(C) - Na2SO4 (D) Ag
(E) AgCl (F) - Ag(NH3)2Cl
Reactions : (i) Ag2S + 4NaCN+2O2  2NaAg(CN)2 + Na2SO4
(A) (B) (C)
(ii) 2NaAg(CN)2 + Zn  Na2Zn(CN)4 + 2Ag
(D)
(iii) 3Ag + 4HNO3  3AgNO3 + NO + 2H2O
HCl
(iv) AgNO3  AgCl + HNO3
(v) AgCl + 2NH3  Ag(NH3)2Cl
(E) (F)
(vi) 4AgCl + 2Na2CO3  4Ag + 4NaCl + 2CO2 + O2

Problem 10: A solid laboratory reagent (A) gives the following reactions.
(i) It imparts green colour to flame.
(ii) Its solution does not give ppt. on passing H2S.
(iii) When it is heated with K2Cr2O7 and conc. H2SO4 a red gas is evolved. The gas when passed in
aq. NaOH solution turns it yellow. Identify (A) giving chemical reactions.
Solution: A - BaCl2
Reactions : (i) 2BaCl2 + K2Cr2O7 + 3H2SO4 K2SO4 + 2CrO2Cl2 + 2BaSO4 + 3H2O
red gas
(ii) CrO2Cl2 + 4NaOH  Na2CrO4 + 2NaCl + 2H2O
yellow
solution

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 SALT ANALYSIS THEORY Page # 17

Problem 11: NH4SCN can be used to test one or more out of Fe3+, Co2+ , Cu2+
(A) Fe3+ only (B) Co2+, Cu2+ (C) Fe3+, Cu2+ (D) All
Solution: (D)

Problem 12: Ag2S is soluble in NaCN due to formation of

(A) Na[Ag(CN)2] (B) Ag(CN)2 (C) Na2Ag(CN)3 (D) Na2[Ag(CN)2]
Solution: (A)

Problem 13: There is foul smell in presence of moisture with

(A) AlCl3 (B) Al2(SO4)3 (C) FeS (D) FeSO4
Solution: (C)

Problem 14: AgNO3 on treatment with hypo gives white ppt. changing to black after some time. Black
ppt. is
(A) Ag2S2O3 (B) Ag2SO4 (C) Ag2S4O6 (D) Ag2S
Solution: (D)

Problem 15: Yellow coloured solution of FeCl3 changes to light green when
(A) SnCl2 is added (B) Zn is added
(C) H2S gas is passed (D) Any one of the above is added.
Solution: (D)

Problem 16: Fe(OH)3 and Cr(OH)3 precipitate are separated by

(A) [Ag(NH3)2]+ (B) HCl (C) NaOH/H2O2 (D) H2SO4
Solution: (C)

Problem 17: Evolution of deep red vapours when an inorganic salt is mixed with powdered K2Cr2O7
and heated with conc. H2SO4 confirms the presence of a
(A) chloride (B) fluoride (C) borate (D) phosphate
Solution: (A)

Problem 18: Which of the following would enable you to remove SO42– ions from a mixture of SO42-
,C2O42- and Cl– ions?
(A) NaOH (B) KOH (C) Ba(OH)2 (D) BaSO4
Solution: (C)

Problem 19: Which of the following sulphates is insoluble in water?

(A) CuSO4 (B) CdSO4 (C) PbSO4 (D) Bi(SO4)3
Solution: (C)

Problem 20: A fire work gave bright crimson light. It probably contained a salt of
(A) Ca (B) Sr (C) Ba (D) Mg
Solution: (B)

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