CHAPTER

16 Salt Analysis

INTRODUCTION
Qualitative analysis involves the detection of cation(s) and anion(s) of a salt or a mixture of salts.

Preliminary Test
1. Physical appearance (smell):
Table: 1

Take a pinch of the salt between your fingers and rub with a drop of water
Smell Inference
Ammoniacal 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.
3. Flame test:
Table: 2

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

4. Borax Bead test:

On heating, borax forms a colourless glassy bead of NaBO2 and B2O3 .
∆ ∆
2
Na B4O7.10H2O  → 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)
 5. Solubility Chart:
Table: 3

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 in water.

9. SO42– The sulphates of barium, silver 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 dissolve 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.

Analysis of ANIONS (Acidic Radicals)

Analysis of anions (acidic radicals) can be broadly divided into 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 into 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: 4
Observation Inference
Gas Radical
Effervescence with the evolution of a colourless and odourless gas which turns
CO2 CO32–
lime water milky
Evolution of colourless gas having smell of rotten egg which turns lead acetate
H 2S S2–
paper black.
Colourless gas having suffocating odour (like burning sulphur) which turns
SO2 SO32–
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–
All above are
No peculiar gas is evolved. –
absent

P Salt Analysis 47
W

(b) Concentrated Sulphuric acid group: The anions of this group liberate acid vapours or gases with conc. H2SO4.
Table: 5
Observation Inference
Gas Radical
Colourless gas with pungent smell which gives dense white fumes with a glass
HCl Cl–
rod dipped in NH4OH.
Reddish brown gas with pungent smell, intensity of reddish brown fumes
increases on addition of a pinch of solid MnO2. Also, it turns starch paper, Br2 Br –
orange red.
Evolution of violet vapours which turns starch paper, blue. I2 I–
Evolution of reddish brown fumes which intensifies on addition of copper turnings
or bits of filter paper. Starch iodide paper develops a blue–black spot due to the NO2 NO3–
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.
Observation Inference
W.E. or S.E. + BaCl2(aq) → White precipitate, insoluble in dil. HCl and HNO3 SO42–
W.E or S.E + conc. HNO3 (1–2 mL) + ammonium molybdate and boil PO43–

→ Canary yellow precipitate

Classification of Cations
Cations are classified into five groups on the basis of their behaviour with some reagents.
Table: 6

Group Group Reagent Ions Colour and Ppt.

Group I dil. HCl Pb2+ , Hg+, Ag+ PbCl2, Hg2Cl2, AgCl-White
Cds, As2S3, As2S5, SnS2 -Yellow
Group II A H2S in dil. HCl Hg2+, Cu2+, Bi3+, Cd2+ HgS, CuS,Pbs, Bi2S3 - Black Sb2S3,
Group II B As3+, As5+, Sb3+, Sb5+, Sn2+, Sn4+ Sb2S5 - Orange; SnS - Brown
Group III NH4OH in presence of NH4Cl Fe3+, Al3+, Cr3+ Fe(OH)3 - Brown; Al(OH)3 - White;
Cr(OH)3 - Green
Group IV H2S in presence of NH3 and Ni , Co , Mn , Zn
2+ +2 +2 +2
ZnS - White or grey; CoS, NiS - Black;
NH4Cl or (NH4)S MnS - Buff ( light pink )
Group V (NH4)2CO3 in presence of Ba , Sr , Ca
+2 +2 +2
BaCO3, SrCO3, CaCO3 - White
NH4Cl and NH4OH
Group VI No common group reagent Mg2+, Na+, K+ Mg(NH4)PO4 - White

48 JEE (XII) Module-4 PW