𝐒𝐀𝐋𝐓 𝐀𝐍𝐀𝐋𝐘𝐒𝐈𝐒

Lab Manual | JEE Mains. | JEE Adv.

🧪 Salt Analysis: Introduction & Principles

Salt Analysis is also known as Qualitative Analysis.

It is the systematic determination of the anion and cation present in a salt or salt mixture.

A salt is formed from the reaction of an Acid and a Base (Neutralisation):

Acid + Base → Salt + H 2 O (Neutralisation)

HCl (Acid) + NaOH (Base) → NaCl + H 2 O

+
The Cation (Na ) is derived from the Base and is called the Basic radical.
−
The Anion (Cl ) is derived from the Acid and is called the Acid radical.
Identification Order: Anions are identified before cations.
Interfering Anions: Some anions may interfere during cation identification, and these anions are known as
interfering anions.
− 3− 3− 2− 2−
Examples: F , BO 3 , PO 4 , C 2 O 4 , SiO 4 .

Salt Analysis Procedure:

1. Preliminary Tests (physical appearance test, dry heating test, flame test, Borax bead test, phosphate
bead test, cobalt nitrate test, charcoal cavity test etc.).
2. Confirmatory Tests (wet tests).

🔥 Preliminary Tests (Initial Section)

+
Salt Analysis is part of Qualitative Analysis. A salt is composed of a Base (Basic radical, e.g., Na ) and an
−
Acid (Acid radical, e.g., Cl ).

Physical Appearance Test

Dry Heating Test
Flame test, Borax bead test, Phosphate bead test, Cobalt nitrate test, Charcoal cavity test, etc.

Flame Test

This test is mainly used for the detection of Alkali Metals and Alkaline Earth Metals (S-Block).

The metal salt is mixed with concentrated HCl to form a volatile metal chloride, which gives a characteristic
flame colour when heated in an oxidising flame.

l S l C Cl l l l Chl d
 Metal Salt + Conc. HCl → Volatile Metal Chloride

Note: Be and Mg do not give the flame test.

Characteristic Flame Colors:

Crimson Red: Li / Sr
Golden Yellow: Na
Lilac (Violet): K
Red-violet: Rb
Blue: Cs
Brick red: Ca
Apple Green: Ba
2+
Green with blue centre: Cu [CuCl 2 ]

Borax - Bead Test

This test is mainly used for d-Block metals, which have a variable oxidation state.

Borax (Na 2 B 4 O 7 ⋅ 10H 2 O) swells up on heating and decomposes to form a transparent glassy bead of
Boric Anhydride (B 2 O 3 ) and Sodium Metaborate (NaBO 2 ).

Δ Δ
−
−
Na 2 B 4 O 7 ⋅ 10H 2 O → Na 2 B 4 O 7 (swell up) → 2NaBO 2 + B 2 O 3 (Boric Anhydride)

The different colours observed are due to the formation of metaborates of the metal in different oxidation
states. On cooling it forms transparent glassy bead

Example: Copper Carbonate (CuCO 3 )

Oxidising Flame:

Δ
−
CuCO 3 → CuO + CO 2 ↑

CuO + B 2 O 3 → Cu(BO 2 ) 2 (Copper (II) metaborate) → Blue bead

Reducing Flame:

+C,NaBO 2
−
Cu(BO 2 ) 2 → CuBO 2 + Na 2 B 4 O 7 + CO ↑ (Colourless)

+C,NaBO 2
−
CuBO 2 → Cu (Red coloured bead)
 Borax Bead Test - Observed Colors

Metal In Oxidising Flame (in cold) In Reducing Flame (in cold)

Cu Blue (Cu
2+
) Red

Mn Violet red Colourless

Ni Brown Grey

3+ 2+
Fe Pale Yellow (Fe ) Green (Fe )

3+ 3+
Cr Green (Cr ) Green (Cr )

2+ 2+
Co Blue (Co ) Blue (Co )

Phosphate Bead Test (Microcosmic salt bead Test)

This is an alternate test for the Borax bead test.

Microcosmic salt (Na(NH 4 )HPO 4 ⋅ 4H 2 O) is heated to form Sodium meta Phosphate (NaPO 3 ), which
creates a transparent glassy bead.

Δ
Na(NH 4 )HPO 4 ⋅ 4H 2 O → NaPO 3 + NH 3 ↑ +H 2 O ↑
−

d-Block metals give a characteristic colour similar to that in the borax bead test in both oxidising and
reducing flames. (In simple word PBT result shown by d-block metal is similar to results of BBT.)

🔥 Dry Heating Test Observations

1. Coloured Gas with Odour

− −
Reddish Brown gas (NO 2 ↑): Suggests NO 2 or NO 3
−
Brown (Br 2 ↑): Suggests Br
−
Yellowish green (Cl 2 ): Suggests Cl
−
Violet black (I 2 ): Suggests I
• Inner cone is reducing flame due to the presence of unburnt fuel particles (or presence of 'c' particles)

2. Sublimate Formation

The solid deposits accumulated at the upper, colder portion of the test tube.

White Sublimate: NH 4 Cl, Hg 2 Cl 2 , HgCl 2

Yellow Sublimate: S, As 2 S 3 , Hg 2 I 2 , HgI 2
Black Sublimate: Hg 2 S, HgS

3. Residue Observation

Observation Inference (Metal Oxide)

Yellow when hot and White when cold ZnO

 Observation Inference (Metal Oxide)

Brown when hot and Yellow when cold PbO

💧 Solubility of Salts in Water (General Rules)

2− −
1. Carbonates (CO 3 ), Bicarbonates (HCO 3 )
2− + + + + + +
Carbonates (CO 3 ): All are insoluble except those of Na , K , Rb , Cs , NH 4 (Group IA and NH 4 ).
−
Bicarbonates (HCO 3 ): All are soluble except NaHCO 3 .

+ + + + +
Note: Bicarbonates of Na , K , Rb , Cs , NH 4 exist in solid phase. Others can exist in aqueous
form.

2− −
2. Sulphites (SO 3 ), Bisulphites (HSO 3 )
2− + + + + +
Sulphites (SO 3 ): All are insoluble except those of Na , K , Rb , Cs , NH 4 .
−
Bisulphites (HSO 3 ): All are soluble.
2−
3. Sulphides (S )
+ + + + +
Sulphides of K , Na , Rb , Cs , alkaline earth metals, and NH 4 are soluble; the rest are insoluble.
− 2−
Bisulphides (HS ) and Polysulphides (S n ) are generally soluble in water.
− − −
4. Nitrites (NO 2 ), Nitrates (NO 3 ), Acetates (CH 3 COO )
All are soluble except AgNO 2 , CH 3 COOAg, CH 3 COOCu, (CH 3 COO) 2 Hg, and BiONO 3
(Bismuth(III) oxynitrate).
AgNO 2 , CH 3 COOAg, and (CH 3 COO) 2 Hg are partially soluble and become insoluble when high

concentration of these ions are present.( I.P. > K_sp)

Ksp > I.P. [ Unsaturated].

Ksp = I.P. [ Saturated ].

Ksp < I.P. [ Precipitation occurs].

− − −
5. Halides (Cl , Br , I )
− − + 2+ 2+ +
Cl ,Br : All are soluble except those of Ag , Hg 2 , Pb , Cu .
− + 2+ 2+ + 3+
I :All are also soluble expect of Ag , Hg 2 , Pb , Cu , Bi .
PbCl 2 , PbBr 2 , PbI 2 become soluble in boiling water/hot water.
2−
6. Sulphates (SO 4 )
2+ 2+ 2+ 2+ 2+ +
All are soluble except Pb , Ba , Sr , Ca , Hg , Ag .
2+ 2+ 2+ +
Cd , Ca , Hg , Ag sulphates are partially soluble.
Basic sulphates of Hg, Cu are insoluble.
Cu(OH)2, CuSO4 HgO, HgSO4 (Insoluble in water)
3−
7. Phosphates (PO 4 )
+ + + + +
All are insoluble except those of Na , K , Rb , Cs , NH 4 .
− 2−
Primary (H 2 PO 4 ) and secondary (HPO 4 ) phosphates of alkali and alkaline earth metals are soluble.

8. Oxides
All are insoluble except Na 2 O, K 2 O, Rb 2 O, Cs 2 O, BaO, SrO.
CaO (quick lime) is partially soluble. MgO and BeO are insoluble.

🧪 Sodium Carbonate Extract (Soda Extract)

This is useful when the given salt is sparingly soluble / insoluble in water (e.g., BaSO 4 ).
 20 ml distill water
−
BaSO 4(s) + Na 2 CO 3(s) → BaCO 3 ↓ +Na 2 SO 4(aq.)
Boiled f or 10-15 min.

(1:3 mass ratio)

The soluble Na 2 SO 4(aq.) makes the SO

2−

4
anion available for testing.

2− −
All anions will be identified by soda extract except carbonates (CO 3 ) and bicarbonates (HCO 3 ).
The soda extract solution must be neutralised by a suitable acid before performing the anion test.
The anionic part of the acid used for neutralisation must be different from the anion that is to be identified.
Oxidising acid should not be used (e.g., concentrated H 2 SO 4 , concentrated HNO 3 ).

🔬 Anions: Classification and Tests

Anions are classified on the basis of their reaction with acid.

Class A: Gives Volatile Product with Acid

Sub Group-I: Gives Volatile Product with dil. HCl / dil. H 2 SO 4

2− − 2− − 2− 2− − −
Anions: CO 3 , HCO 3 , SO 3 , HSO 3 , S , S 2 O 3 , CH 3 COO , NO 2

+
H
2−
−
CO → CO 2 ↑ (Brisk effervescence)
3
+
H
−
HCO
− → CO 2 ↑
3
+
H
2−
−
SO → SO 2 ↑
3
+
H
−
−
HSO → SO 2 ↑
3
+
H
−
−
NO → NO ↑ +NO 2 ↑
2
+
H
2−
−
S → H 2 S ↑ (Rotten egg smell)
+
H
2−
S2 O
− → S ↓ +SO 2 ↑
3
+
H
−
−
CH 3 COO → CH 3 COOH ↑ (Vinegar smell)

Sub Group-II: Gives Volatile Product with conc. H 2 SO 4

− − − − 3− 2− −
Anions: F , Cl , Br , I , BO 3 , C 2 O 4 , NO 3

+
H
−
−
F → HF
+
H
−
−
Cl → HCl (White Fumes, Pungent)
+
H
−
−
Br → Br 2 (Reddish Brown Fumes)
+
H
−
−
I → I 2 (Violet Fumes / Violet-black)
+
H
3−
−
BO → H 3 BO 3 (White Fumes)
3
+
H
2−
−
C2 O → CO ↑ +CO 2 ↑
4
+
H
−
NO
− → NO 2 ↑ (Brown gas)
3
 Note: Br 2 imparts brown colour to the aqueous solution but NO 2 does not.

Class B: Does not Give Volatile Product with Acid

Sub Group-I: Identified By Precipitation (ppt.)

2− 3− 3− 3− 2−
Anions: SO 4 , PO 4 , AsO 3 (Arsenite), AsO 4 (Arsenate), CrO 4 (Chromate)

Sub Group-II: Identified By Redox Reaction

2− − 2 2−
Anions: Cr 2 O 7 , MnO 4 ,MnO 4 −,CrO 4 ,

Key Properties of Evolved Gases

CO 2 : Colourless, odourless, turns lime water milky (CaCO 3 ↓). Does not turn acidified K 2 Cr 2 O 7 filter
paper green.
+
SO 2 : Suffocation smell of Burning sulphur, turns lime water milky. Turns KMnO 4 /H colourless. Turns
+ 6+ 3+
K 2 Cr 2 O 7 /H filter paper green (Cr → Cr ).
H 2 S: Rotten egg smell. Turns lead acetate filter paper black.

CH 3 COOH: Vinegar smell.

NO 2 : Brown gas. Disproportionates in water (NO 2 + H 2 O → HNO 2 + HNO 3 ).

CO: Colourless gas, burns with blue flames, poisonous. Forms a black precipitate (Pd ↓) with PdCl 2
solution.
HCl: Colourless, acidic. Reacts with NH 4 OH to give NH 4 Cl (white dense fumes).

HF: Dissolves glass material (HF + SiO 2 → H 2 SiF 6 ).

2−
Test for Carbonate (CO 3 )

Solubility: All are insoluble except Group IA and (NH 4 ) 2 CO 3 . Li 2 CO 3 is sparingly soluble.
Lime Water Test:

CO 2 + Ca(OH) 2 (lime water) → CaCO 3 ↓ (White turbidity) + H 2 O

If excess CO 2 is passed, the white turbidity dissolves (clear solution):

H 2 O + CO 2 + CaCO 3 → Ca(HCO 3 ) 2 (Soluble)

2−
Precipitation Test (e.g., Pb(NO 3 ) 2 ): CO 3 + Pb(NO 3 ) 2 → PbCO 3 ↓ (White ppt). The ppt is soluble
in HNO 3 , CH 3 COOH, and excess NaOH (forming Na 2 [Pb(OH) 4 ]).