Systematic Qualitative Analysis of Inorganic Salt-XI & XII

I. Physical Examination of Salts

a. Colour of the Salt
Test Observation Inference

Blue Cu2+

Pale green Fe2+

Reddish brown Fe3+

Flesh colour Mn2+

Colour of the Salt

Bluish green Ni2+

Reddish pink Co2+/Co3+

Colourless Absence of Cu2+, Fe2+, Fe3+, Mn2+,

Ni2+, Co2+, Co3+ ions.

[Link] of the Salt

A small amount of the salt is taken on the watch glass, a drop of water is added. Mixed using
glass rod and inhaled.
Test Observation Inference

Ammonia smell NH4+ ions may be present.

(To get strong smell of NH3,
add 2 drops of NaOH and
then rub.)

Odour of the Salt Rotten egg smell S2-

Vinegar smell CH3COO-

Odourless Absence of NH4+, S2-, CH3COO-

[Link] State
Test Observation Inference

Crystalline solids Absence of MgCO3, CaCO3

State
Amorphous solids Presence of MgCO3, CaCO3
 [Link]

Test Observation Inference

Heavier Presence of Pb2+, Ba2+, Hg2+,

Cd2+
Density
Lighter Absence of Pb2+, Ba2+, Hg2+,
Cd2+

[Link]
A pinch of salt is taken and is exposed to air in the watch glass for some time.
A paste of the salt appears if the salt is deliquescent.

Test Observation Inference

Paste of salt appears. ZnCl2, FeCl3, Ca(NO3)2, MgCl2

Deliquescence is observed.
Deliquescency
Not deliquescent. Absence of ZnCl2, FeCl3,
Ca(NO3)2, MgCl2

b. Dry Heating Test

Test Observation Inference

Salt decomposes with the May be CO32-

liberation of colourless and
odourless gas

Salt forms white sublimate May be NH4Cl

Brown white sublimate May be NH4Br

Violet sublimate May be NH4I

Colourless suffocated smell May be SO32-

(burnt smell of sulphur)
Dry Heating Test
Reddish brown fumes with May be NO3
pungent odour

Decriptation observed Pb(NO3)2, Ba(NO3)2, NaCl

(crackling sound)

Salt swells May be PO43-

Salt melts May be MgCl2, (NH4)2SO4

Salt melts with the May be (CH3COO)2Pb

appearance brownish black
 at the bottom of the test tube

Loss of water of May be sulphate of Ag, Mg, Cr,

crystallisation Sr

[Link] Test
One gram of salt is taken and 2-3 drops of conc. HCl are added and a paste is
prepared with the help of a glass rod. This paste is taken with the help of glass
rod and exposed to non-luminous flame of burner.

Test Observation Inference

Golden yellow Na+

Lilac flame K+

Grassy green Ba2+

Brick red Ca2+

Crimson red Sr2+

Flame Test

Dull bluish white Pb2+

Parrot green Cu2+

Green flashes Zn2+

No characteristic coloured Absence of Na+, K+, Ba2+, Ca2+,

flame Sr2+, Pb2+, Cu2+, Zn2+.
Wet Tests: Analysis of Acid Radicals
Analysis of I-Group radicals (CO32-) [Group Reagent: Dilute H2SO4 Test]

Test Observation Inference

Colourless gas with brisk effervescence CO32- may be present.

Colourless gas with burnt smell of SO32- may be present.

One gram of salt is taken sulphur/suffocating gas
in a test tube and one drop
of dil. H2SO4 is added. Colourless gas with rotten egg smell S2- may be present
(sulphide).

Brown gas with pungent odour NO32- may be present.

 NOTE: If no changes are observed on treatment of the salt with dil. H 2SO4, then we need to
carry out the reaction with conc. H2SO4. If no reaction occurs in cold condition, the test tube
is heated. If salt contains Cl-, Br- and I-, they respond to cold conc. H2SO4. If NO3- and
CH3COO- are present, they respond to hot conc. H2SO4 only.

Analysis of II Gp-Acid Radicals {Cl1-,Br1-,I1-,[NO3]1-,[CH3COO]1-[C2O4]2-}

Test Observation Inference

1 g of salt is taken in a test tube Colourless gas with a strong pungent odour. May be Cl-.
and one drop of conc. H2SO4 is HCl gas is released.
added.
Glass rod dipped in NH4OH are Dense white fumes are seen.
exposed to these vapours.

Cl-1+ H2SO4 → HCl + [HSO4]-1

HCl + NH3 → NH4Cl

Pass the brown fumes / vapours Brown fumes with pungent odour are observed. May be Br - or
obtained through a test tube NO3-.
containing FeSO4 solution.
FeSO4 does not turn brown black. May be Br -.

[Br]-1 + H2SO4 → HBr + [HSO4]-1

FeSO4 turns brown black. May be NO3 -.

[NO3]- 1+ H2SO4 → HNO3 + [HSO4]-1

If no reaction occurs in cold Violet fumes are instantly evolved. May be I -.

conc. H2SO4 then the test tube is
heated. I- + H2SO4 → HI + [HSO4]-1

Colourless gas with vinegar odour is evolved. May be CH3COO-

.

CH3COO- + H2SO4 → CH3COOH + HSO4-

*If any of the above changes are observed, confirmatory tests are performed. If no
changes are observed, then tests for SO42- and PO43- are carried out.

Test for SO42- (BaCl2 Test)

1 ml of salt solution is taken and 1 A white ppt is formed which May be SO42-.
ml of BaCl2 solution is added to is insoluble in excess of dil.
this. HCl.

SO42- + BaCl2 → BaSO4 + 2Cl-

 Test for PO43-
1 ml of conc. HNO3 is added to the Yellow ppt is formed. May be PO43-.
salt in a test tube. The contents are
boiled and excess of ammonium
molybdate solution is added.

Confirmatory Tests:
1. CO32- (Lime Water Test)
To 1 g of salt in a test tube, dil Lime water turns milky. CO32- is confirmed.
HCl is added and CO2 gas
liberated is passed through lime
water taken in another test tube.

CO2 + Ca(OH)2 → CaCO3 + H2O

2. Sulphide Ion (S2- )

(a) Lead acetate test
To the aqueous solution of given Black ppt is obtained. S2- is confirmed.
salt, 1 ml of lead acetate is added.

Na2S + (CH3COO)2Pb → PbS ↓ + 2CH3COONa

(b) Sodium nitroprusside test:

To the aqueous solution of given Violet colouration is seen. S2- is confirmed.
salt, few drops of sodium
nitroprusside are added.

Na2S + Na2[Fe(CN)5NO] → Na4[Fe(CN)5NOS]

Sulphite Ion (SO32- )

To the aqueous solution of given Green colouration is seen. SO32- is confirmed.
salt, few drops of potassium
dichromate and dil. H2SO4 are
added.

6SO2 + 2Cr2O7-. + 4H+ → 4Cr3+ + 6SO42- + 2H2O

 3. Nitrite Ion (NO21- )
To the aqueous solution of given Solution turns dark brown or NO2- is confirmed.
salt, few drops of CH3COOH + black.
FeSO4 is added.

FeSO4 + NO → [Link]

4. Chloride Ion (Cl- )

(a) Silver Nitrate Test
To the aqueous solution of A curdy white ppt is obtained which is soluble Cl- is
given salt 1 ml of silver in excess NH4OH. confirmed
nitrate is added. .

Cl-1 +[AgNO3]-1→ AgCl + [NO3]-1

AgCl +2(NH3)Aq → [Ag(NH3)2]Cl

(b) Chromylchloride Test

1 g of salt + 1 g of K2Cr2O7 and then 1 ml of Yellow orange vapours are Cl- is confirmed.
conc. H2SO4 is added. formed.

4Cl- + K2Cr2O7 + 3H2SO4 → 2CrO2Cl2 + 2K+ + 3H2O + 3SO42-

Yellow orange vapour is passed through NaOH A yellow solution is formed.

solution.

CrO2Cl2 + 2NaOH → Na2CrO4 + 2NaCl + H2O

1 ml of dil. CH3COOH is added to the yellow Yellow ppt is formed.

solution + 1 ml of lead acetate.

Na2CrO4 + (CH3COO)2Pb → PbCrO4 + CH3COONa

5. Bromide Ion (Br- ) :Silver Nitrate Test

1 ml of salt solution + 1 ml of Pale yellow ppt which is Br- is confirmed.
AgNO3 solution partially soluble in excess of
NH4OH.

AgNO3 + Br- → AgBr + NO3-

AgBr + 2NH3 → [Ag(NH3)2]Br

[Link] Water Test (Orange Globule)

1ml of salt solution + 2 drops of An orange globule is Br- is confirmed.
CCl4 or CS2 + conc. solution of formed.
Cl2 water.
Shake well.

2Br- + Cl2 → Br2 + 2Cl-

5. Iodide Ion (I- ): Silver Nitrate Test

1 ml of salt solution + 1 ml of Curdy white or pale yellow I- is confirmed.

AgNO3 soluton ppt is formed which is
insoluble in excess of
NH4OH.

I- + AgNO3 → AgI + NO3-

(a) Globule Test

1 ml of salt solution + 2ml of CCl4 A violet globule is formed. I- is confirmed.
or CS2 + conc. solution of Cl2
water.
Shake well.

2I- + Cl2 → I2 + 2Cl-

[Link] Ion (NO3- )

(a) Copper Chips Test
1 ml of salt solution + conc H2SO4 Brown fumes are evolved. NO3- is confirmed.
+ heat strongly.

2NO3- + H2SO4 → 2HNO3 + SO42-

Few pieces of copper chips are Intense brown fumes are

added to the above test tube, only absorbed.
under hot conditions.

4HNO3 + Cu → Cu(NO3)2 + 2NO2 + 2H2O

b) Brown Ring Test

Add a small quantity of freshly prepared A dark brown ring is obtained at the NO3- is confirmed.
solution of FeSO4 + aqueous solution of junction of 2 layers.
salt + conc. H2SO4 slowly on the sides.

NO3- + H2SO4 → HNO3 + HSO4-

6FeSO4 + 3H2SO4 + 2HNO3 → 3Fe2(SO4)3 + 4H2O + 2NO

FeSO4 + NO + 5H2O → [Fe(NO)(H2O)5]SO4

 6. Acetate Ion (CH3COO- )
(a) Ester Test
Small quantity of salt + 2 ml of conc. H2SO4 and Pleasant fruity smell CH3COO- is confirmed.
heat. Now add 1 ml of ethanol and shake in a test of ester is evolved
tube. Pour the contents of the test tube in a beaker
full of water. Stirr well.

CH3COOH + C2H5OH → CH3COOC2H5 + H2O

b) Oxalic Acid Test

1 g of salt is taken in a water glass and some amount Vinegar odour is CH3COO- is
of oxalic acid is mixed with it and a mixture is obtained. confirmed.
rubbed with a drop of water.

CH3COO- + H2C2O4→ 2CH3COOH + [C2O4]2-

7. Sulphate Ion (SO42- )

(a) Lead Acetate Test
1 ml of salt solution is added to 1 A white ppt is formed. SO42- is
ml of lead acetate. confirmed.

SO42- + (CH3COO)2Pb → PbSO4 + 2CH3COO-

Hot ammonium acetate is added to White ppt dissolves.

the above ppt.

PbSO4 + 2CH3COONH4 → (CH3COO)2Pb + (NH4)2SO4

BASIC RADICALS IN THE SYLLABUS

NH4+, Pb2+, Cu2+, Al3+, Fe3+, Zn2+, Co3+, Ni2+, Mn2+, Ba2+, Sr2+, Ca2+, Mg2+

PROCEDURE

Analysis of ‘0’ Group Radicals (NH4+)

Test Observation Inference

1g of salt is added to 1ml of NaOH Ammoniacal/pungent smell Presence of NH4+.

in a test tube and heated on a flame. gas is evolved.
 ∆
NH4+ + NaOH→ NH3 + Na+ + H2O

Confirmatory Test
(a) Conc. HCl Test
The glass rod is dipped in conc. HCl Dense white fumes are NH4+ is confirmed.
and exposed to the above vapour evolved.
evolved.

NH3 + HCl → NH4Cl

(b) Nessler’s Reagent Test

To 1 ml of aqueous solution of salt A brown precipitate is NH4+ is confirmed.
1-2 drops of KOH is added and then formed.
Nessler’s reagent is added.

NH3 + 2K2[HgI4] + 3KOH → [Link] + 7KI + 2H2O

Note: Before going to analyse the basic radical the saturated/concentrated solution is
prepared by the following solvents. The resulting solution is said to be original solution
(O.S.).

Original Solution (O.S.)

Cold water: if not soluble → hot water: if not soluble → dil. HCl: if not soluble → conc.
HCl: if not soluble → dil. HNO3: if not soluble → conc. HNO3: if not soluble → aqua regia

Analysis of I Group Basic Radicals [Pb2+, Ag1+]

Test Observation Inference

To 1 ml of original solution dil. HCl A white precipitate is May be Pb2+ or Ag+.

is added in a test tube. formed.

Pb2+ + 2HCl → PbCl2 ↓ + 2H+

Confirmatory Test
The precipitate formed in the above step is dissolved in hot water and divided into 2 parts.
(a) Potassium Dichromate Test
Part I + K2CrO4 (1 ml) solution in a Yellow precipitate is Pb2+ is confirmed.
test tube. formed.

PbCl2 + K2CrO4 → PbCrO4 ↓ + 2KCl

(b) Potassium Iodide Test

Part II + KI (1 ml) solution in a test Yellow precipitate is Pb2+ is confirmed.
tube. formed.

PbCl2 + 2KI → PbI2 ↓ + 2KCl

Analysis of II Group Basic Radicals[Pb2+, Cu2+ Hg2+]

Test Observation Inference

1 ml of O.S. + 1 ml of dil. HCl + 1 Black precipitate is formed. Pb2+ or Cu2+ is formed.

ml of H2S in a test tube.

Pb2+ + H2S → PbS + 2H+

Cu2+ + H2S → CuS + 2H+

The black precipitate is dissolved in minimum quantity of 50% of HNO 3 acid. The resultant
of solution has 2 parts.

Part I + 1 ml of dil. H2SO4 + 1 ml of ethanol

----------------------- White ppt -- Pb2+ is indicated.
Dissolve the ppt in hot ammonium acetate solution and divide solution in two parts. Perform
potassium iodide and potassium chromate test as confirmatory test for lead ion same as that
of first group basic radical analysis.
----------------------- If there is no white precipitate then NH4OH is added in excess to IInd part
so that blue coloured solution is obtained. Divide it into 2 parts.
Presence of Cu is indicated.

Confirmatory Test for Copper

(a) Potassium Ferrocyanide Test
To Ist part of above solution A chocolate brown ppt is Cu2+ is confirmed.
potassium ferrocyanide is added in a formed.
test tube.

2Cu2+ + K4[Fe(CN)6] → Cu2[Fe(CN)6] + 4K+

(b) Potassium Iodide Test

To another part of the blue solution, A white colouration in brown ppt is formed. Cu2+ is confirmed.
½ ml of dil. CH3COOH and 1 ml of
KI is added.

2Cu2+ + 4KI → Cu2I2 + I2 + 4K+

Analysis for the III Group Basic Radical [Al3+, Fe3+]

Test Observation Inference

Excess of solid ammonium chloride Reddish brown ppt is formed. Fe3+ may be present.
and excess of NH4OH is added to 1
ml of O.S.

Fe3+ + 3NH4OH → Fe(OH)3 + 3NH4+

The ppt obtained in the above step is Gelatinous white precipitate is formed. Al3+ may be present.
dissolved in dil. HCl and the
solution is divided into 2 parts.

Al3+ + 3NH4OH → Al(OH)3 + 3NH4+

Confirmatory Test for Al3+ :Blue Lake Test

The above obtained solution is First appears red colour Al3+ is formed.
mixed with 1-2 drops of blue litmus followed by blue
and 1 ml of NH4OH. colouration.

NH4OH (little in excess) Blue ppt in solution. Al3+ is confirmed.

Al(OH)3 + 3HCl → AlCl3 + 3H2O → Red soln

AlCl3 + 3NH4OH → Al(OH)3 + 3NH4Cl

Analysis for the IV Group Basic Radical [Zn2+, Co3+, Ni2+, Mn2+]

Test Observation Inference

To 1 ml of O.S. NH4Cl, NH4OH Black ppt. Co2+, Ni2+ present.

and H2S are added.
Co(OH)2 + H2S → CoS + 2H2O
Ni(OH)2 + H2S → NiS + 2H2O

Buff or flesh ppt. Mn2+ present.

Mn(OH)2 + H2S → MnS + 2H2O

Dull white ppt. Zn2+ present.

Zn(OH)2 + H2S → ZnS + 2H2O

Confirmatory Tests for Zn2+ and Mn2+ (NaOH Test)

The white ppt is dissolve in small amount of dil HCl and H 2S is boiled. Mn2+ and Zn2+ are confirmed.
 MS + 2HCl → MCl2 + H2S (where M = Zn, Mn, Co, Ni)

Confirmatory Tests for Mn2+

(a) NaOH Test
To one part of the solution NaOH A white ppt is formed. Mn2+ is confirmed.
is added and shaken well.

MnCl2 + 2NaOH → Mn(OH)2 + 2NaCl

(b) Bromine Water Test

To 1 ml of above formed ppt Black and brown ppt. Mn2+ is confirmed.
bromine water is added.

Br2 + H2O → 2HBr + [O]

Mn(OH)2 + [O] → MnO(OH)2

Confirmatory Tests for Zn2+

a)NaOH Test
To 1 ml of the dissolved ppt A white ppt is formed. Zn2+ is confirmed.
solution small amount of NaOH is
added.

Excess of NaOH is added to same White ppt is dissolved.

ppt.

ZnCl2 + 2NaOH → Zn(OH)2 + 2NaCl

Zn(OH)2 + 2NaOH → Na2ZnO2 + 2H2O

(a) Potassium Ferrocyanide Test

To the other part of the dissolved White or prussian blue ppt is Zn2+ is formed.
ppt solution add 1 ml of formed.
K4[Fe(CN)6] and shake well.

ZnCl2 + K4[Fe(CN)6] → Zn2[Fe(CN)6] + 4KCl

Analysis for the V Group Basic Radicals [Ba2+, Sr2+, Ca2+, Mg2+]

Test Observation Inference

In this group while analysing the following order should be strictly followed: Ba 2+, Sr2+, Ca2+.

1 ml of O.S. + NH4Cl + NH4OH + White ppt is formed. Ba2+, Sr2+, Ca2+ is present.
(NH4)2CO3 are added.
 M2+ + (NH4)2CO3 → MCO3 + 2NH4+ (where M = Ba2+, Sr2+, Ca2+)

The white ppt is dissolved in small amount of CH3COOH and the solution is divided into three parts.

Confirmatory Test for Ba2+: K2CrO4 Test

Part 1 + 1 ml of K2CrO4 Yellow ppt is formed. Ba2+ is formed.

Ba2+ + K2CrO4 → BaCrO4 + 2NH4+

Confirmatory Test for Sr2+: (NH4)2SO4 Test

Part 2 + 1 ml of (NH4)2SO4 White ppt is formed. Sr2+ is confirmed.

Sr2+ + (NH4)2SO4 → SrSO4 + 2NH4+

Confirmatory Test for Ca2+: (NH4)2C2O4

Part 3 + 1 ml of (NH4)2C2O4 White ppt is formed. Ca2+ is confirmed.

Ca2+ + (NH4)2C2O4 → CaC2O4 + 2NH4+

Analysis for the VI Group Radicals: [Mg2+]

Test Observation Inference

1 ml of O.S. + NH4Cl + NH4OH + White ppt is formed on scratching the Mg2+ is present and
NaH2PO4 (or Na3PO4are added. sides of the test tube with a glass rod. confirmed.

3Mg2+ + 2(NH4)3PO4 → Mg3(PO4)2 + 6NH4+