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Salt Analysis

Qualitative analysis involves identification of ions (cations and

anion) of a salt or a mixture of salts through their characteristic
reactions. The process involves.

1. Analysis of anions
2. Analysis of cations.

Group I
Anions which liberate gases with dil. HCl or dil. H2SO4
.CO2−3 , HCO−3 , SO2−3 , S2−, S2O−3 , NO−2
Group II
Gases or acid vapours evolved with conc. H2SO4 (Cl−, Br−, I− ,NO−3)
Group III
Anions which do not liberate any gas with dil HCl or conc.H2SO4.
They are detected by precipitation (SO2−4 , PO3−4)
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

S.No. Salts Colour

1 Copper Salts Bluish Green

2 Nickel Salts Greenish Blue

3 Chromium Salts Dark Green

4 Cobalt Salts Pinkish or purple

5 Manganese salts Light Pink

6 Ferrous Salts Light green

7 Ferric Salts Pale Yellow

2. Action of Heat (Colour of Residue)

S.No. Colour Residue

1 Yellow(hot) and white (cold) ZnO

Reddish brown(hot) and yellow

2 PbO

3 Black(hot) and Red(cold) HgO, Pb3O4

4 Black(hot) and Red Brown(cold) Fe2O3

5 Decrepitation Pb(NO3)2, NaCl

6 White sublimate Ammonium salts

3. Gases

S.No. Nature Gases

1 Colourless and odourless O2, CO2, N2

S.No. Nature Gases


2 Colourless and odour NH3, SO2, HCl, H2S

NO2 (brown), Br2 (reddish

3 Coloured gases
brown), I2(violet), Cl2 (greenish yellow)

4. Flame Test

Metals Colour

Li Crimson Red

Na Golden Yellow

K Violet

Ca Brick Red

Sr Crimson

Ba Apple Green

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.

Class A: Includes anions that are identified by volatile products

obtained on treatment with acids. It is further divided into two sub

1. Gases evolved with dil HCl / dil H2SO4.

2. 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:

1. Precipitation reactions
2. Oxidation and reduction in solution

Class A.1
Anions which evolve gases on reaction with dil. HCl/dil. H2SO4. It
includes -CO2−3,SO2−3,S2−,NO−2,CH3COO−,S2O2−3
1. Carbonate (CO2−3)

(i) Dilute HCl : gives effervescence, due to the evolution of carbon


CO2−3+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

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

CO2−3+Ba2+ → BaCO3 ↓

CO2−3+Ca2+ → CaCO3 ↓

(iii) Silver nitrate solution : White ppt. of silver carbonate is obtained

CO2−3+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

Ag2CO3 ↓ → CO2↓+Ag2O↓

2. Sulphites (SO2−3)

(i) Dilute HCl or Dilute H2SO4 : decomposes with the evolution of

sulphur dioxide

SO2−3+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(green)+H2O

(iii) Lime water : On passing the gas through lime water, a milky
precipitate is formed.

SO2+Ca(OH)2 → CaSO3(milky) ↑ +H2O

Precipitate dissolves on prolonged passage of the gas, due to the

formation of soluble hydrogensulphite ions

CaSO3 ↓ +SO2+H2O→ +Ca(HSO3)2

(iv) Barium chloride or Strontium chloride solution : Salt solutions

gives white ppt of barium or strontium sulphite.

SO2−3+Ba2+ → BaSO3 ↓

SO2−3+Sr2+ → SrSO3 ↓

3. Sulphide (S2−)

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


(iii) Salt solution gives yellow ppt. with CdCl2

Na2S+CdCl2 → CdS(yellow)↓ +2NaCl

(iv) Silver nitrate solution : black ppt. of silver sulphide insoluble in

cold but soluble in hot dil nitricacid.

S2++2Ag+ → Ag2S↓

(v) Sodium nitroprusside solution : Turns sodium nitroprusside

solution purple

Na2S+Na2[Fe(CN)5NO]→ Na4[Fe(CN)5NOS]
4. Nitrites (NO−2)

(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

NO−2+H+ → HNO22HNO3 → H2O+N2O33HNO2 → HNO3+2NO↑

+H2O2NO↑+O2↑ → 2NO2↑

Following tests performed with an aqueous salt solution.

(ii)Silver nitrate solution : White crystalline ppt. is obtained

NO−2 + 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]SO4at the junction of the two liquids.


2OFe2++SO2−4+NO↑→ [Fe,NO]SO4

5. Acetate (CH3COO−)

(i) Dilute Sulphuric Acid: Smell of vinegar


(ii) Iron (III) Chloride Solution: Gives deep - red colouration

CH3COONa+FeCl3→ (CH3COO)3Fe (Brown colour)+3NaCl

6. Thiosulphates(S2O2−3)

(i) Dil Hydrochloric acid : Gives sulphur & sulphur dioxide

S2O2−3+2H+ → S↓ +SO2↑+H2O

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

I2+2S2O2−3→ 2I+S4O2−6

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

S2O2−3+Ba2+→ Ba2S2O3↓

But no ppt. is obtained with CaCl2solution

(iv) Silver nitrate solution : Gives white ppt. of silver thiosulphate

S2O2−3+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.

S2O2−3+Pb2+→ PbS2O3↓

On boiling it turns black due to the formation of PbS.

PbS2O3↓+H2O → PbS↓+2H++SO2−4

Class A.2
Gases or acid vapours evolved with conc. Sulphuric acid, it
includes Cl−,Br−,I−,NO−3

1. Chloride (Cl−)

(i) Conc. H2SO4 : decomposes with the evolution of HCl.


Gas so produced

1. Turns blue litmus paper red

2. Gives white fumes ofNH4Cl 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 MnO2and conc.H2SO4, yellowish green
colour is obtained

MnO2+2H2SO4+2Cl− → Mn2++Cl2↑+2SO2−4+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]ClAg(NH3)2Cl+2H+ →
(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 CrO2Cl2are formed.

K2Cr2O7+4NaCl+6H2SO4 ⟶ 2KHSO4+4NaHSO4+2CrO2Cl2↑+3H2

Chlorides of mercury, owing to their slight ionization, do not respond

to this test and only partial conversion to CrO2Cl2occurs with the
chlorides of lead, silver, antimony and tin.

When chromyl chloride vapours are passed into sodium hydroxide a

yellow solution of sodium chromateis formed which when treated
with lead acetate gives yellow ppt. of lead chromate.

CrO2Cl2+2NaOH→Na2CrO4(Yellow solution)+2HClNa2CrO4+(CH3
COO)2Pb→2CH3COONa+PbCrO4↓ (yellow ppt.)

2. Bromide (Br−)

(i) Conc. H2SO4: Gives reddish brown vapours of bromine

2KBr+H2SO4→ K2SO4+2HBr2HBr+H2SO4→2H2SO4+SO2↑+Br2↑

(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 dilute but readily soluble in
concentrated 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+Br2Br2+chloroform→ orange red colour

(vi) Potassium dichromate & 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+SO2−4+2H2O+SO2↑

The following tests are performed with the salt solution.

(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 colour less solution & yielding golden
yellow plates (spangles) on cooling

2I−+Pb2+ → PbI2↓

(iv) Potassium dichromate & conc. sulphuric acid: Iodine is liberated

6I−+Cr2O2−7+2H2SO4 → 3I2↑+2cr3++7SO2−4+7H2O

(v) Chlorine water: Iodine is liberated, by the drop wise addition of

chlorine water to iodide, and on addition of CHCl3violet 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 addition of hypo solution
brown ppt changes to white ppt.

4I−+2Cu2+ → 2CuI+I2I2+2S2O2−3 → 2I−+S4O2−6

(vii) Mercury (II) chloride solution: Forms scarlet ppt. of HgI2

2I−+HgCl2→ HgI2↓+2Cl−

This ppt. dissolves in excess of KI, forming tetraiodo mercurate (II)

4. Nitrate (NO−3)

i) Conc H2SO4: Gives reddish - brown vapours of nitrogen dioxide

4NO−3+2H2SO4 → 4NO2↑+2SO2−4+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. H2SO4is poured slowly
down the side of the test - tube, a brown ring is obtained.

2NO−3+4H2SO4+6Fe2+→ 6Fe3++2NO+4SO−4+4H2OFe2++NO↑ → [

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.


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↑

Class B.1
1. Sulphate (SO2−4)

All sulphates except those of Ba, Pb, Sr are soluble in water.

Sulphates of calcium and mercury(II) ares lightly soluble. The
following tests are performed with the salt solution.

(i) Barium chloride solution: White ppt. of barium

sulphate BaSO4 insoluble in warm dil. hydrochloric acid and in
dilute nitric acid, but moderately soluble in boiling, conc.
hydrochloric acid.

(ii) Mercury (II) nitrate solution : Gives yellow ppt. of basic mercury
(II) sulphate.

SO2−4+3Hg2+ +2H2O → HgSO4.2HgO↓+4H+

Class B.2
1. Chromate (CrO2−4) and Dichromate(Cr2O2−7)

Metallic chromates gives yellow solution when dissolved in water. In

the presence of H+ chromates are converted into dichromates
(orange-red solution).

2CrO2−4+2H+⇌ Cr2O2−7+H2OCrO2−4+2OH−⇌ 2CrO2−4+H2O

It may also be expressed as :

2CrO2−4+2H+⇌2HCrO−4⇌ Cr2O2−7+H2O

(i) Barium chloride solution: Pale - yellow ppt. of barium chromate

soluble in dilute mineral acids but insoluble in water and acetic acid.

CrO2−4+Ba2+ → BaCrO4↓

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

Cr2O2−7+2Ba2++H2O ⇌2BaCrO4↓+2H+

If sodium hydroxide or sodium acetate is added, precipitation

becomes quantitative.

(ii) Silver nitrate solution: Brownish - red ppt. of silver

chromate Ag2CrO4which is soluble in dil. nitric acid & in ammonia
solution, but is insoluble in acetic acid.

CrO2−4+2Ag+ →Ag2CrO4↓2Ag2CrO4+2H+→4Ag++Cr2O2−7+H2OA
g2CrO4↓+4NH3→2[Ag(NH3)2]+ +CrO2−4Ag2CrO4↓+2Cl−→2AgCl+

A reddish brown ppt. of silver dichromate Ag2Cr2O7 is formed with a

conc. solution of a dichromate

Cr2O2−7+2Ag+→ Ag2Cr2O7

(iii) Lead acetate solution: Yellow ppt. of lead

chromate PbCrO4 insoluble in acetic acid, but soluble in dil nitric

**(iv) H2O2 a deep blue solution of chromiumpenta oxide is obtained

CrO2−4+2H+ +2H2O2→CrO5+3H2O

Cr+3 Salt.

2. Permanganate (MnO−4)

(i) Hydrogen peroxide : It decolourises acidified potassium

permanganate solution


(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)



(iii) Action of heat : On heating, a residue of potassium

manganate K2MnO4 and black manganesedioxide remains behind.
Upon extracting with water and filtering, a green solution of potassium
manganateis obtained

2KMnO4 → K2MnO4+MnO2+O2↑

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

Group Ions Colour & Precipitate
Group I dil. HCl Pb2+,Hg+,Ag+ PbCl2,HgCl2,AgCl- white
Hg2+,Cu2+,Bi3+,Cd2+, A
Group II & H2S in
s3+,As5+,Sb3+,Sb5+,Sn5 Yellow CdS,As2S3,As2S6,SnS2
Group II A dil HCl
Group II B – Sn4+
In Fe(OH)3 (brown),Al(OH)3(white
Group III A Fe3+,Al3+,Cr3+
presence ),Cr(OH)3 (green)
of NH4Cl
H2S in ZnS white or grey, Black -
Group III B presence Ni2+,Co2+,Mn2+,Zn2+ CoS,NiS, MnS - Buff (light
of NH3 & pink)
Group Ions Colour & Precipitate
NH4Cl or
Group IV presence Ba2+,Sr2+,Ca2+ BaCO3,SrCO3,CaCO3- white
of NH4Cl
common Mg^{2+},Na^+,K^+,NH_4
Group V –
group ^+

Points to Remember:-

1. Group I radicals (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 ofS2−- is only
sufficient to precipitate the Group II radicals only.
3. Group III A radicals are precipitated as hydroxides and
the NH4OH so that only the group III A radicals are
precipitated because of their low solubility product. Note:

1. Excess of of NH4Cl should be added otherwise manganese

will be ppt. as MnO2.H2O.
2. (NH4)2SO4 can’t be used in place of NH4Clbecause
the SO2−4 will ppt. barium as BaSO4.
3. NH4NO3 can’t be used in place
of NH4Clbecause NO−3 ions will
oxidise Mn2+ to Mn3+ and thus Mn(OH)3 will be
precipitated in III A group.
4. Only Al(OH)3 is soluble in excess of NaOHfollowed by
boiling to form sodium metaluminate
while Fe(OH)3 and Cr(OH)3 are insoluble.
4. Ammonium hydroxide increases the ionisation of H2Sas
unionised water by removing H+ from H2S in unionised water
H2S ⇌2H++S2−, H+ +OH−→H2O
Now excess of H2S is passed through a neutral solution,
incomplete precipitation will take place due to the formation of
HCl which decreases the ionization of H2S.
Identification of Basic Radicals
All confirmatory tests for basic radicals are performed with the salt

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

(a) K2CrO4. The ppt. is insoluble in acetic acid but soluble in NaOH


(b) Pb(NO3)2+2KI→PbI2↓+2KNO3(Yellow)

AgCl is soluble in NH4OH


Hg2Cl2+2NH4OH⟶H2N−Hg−Cl + Hg↓ + NH4Cl + 2H2O

Amino mercuric chloride.

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

(i) SnCl2, give white precipitate turning black.



(ii) Cu+2 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 (Deep blue in colour)+4H2O

Cu2+ ions give chocolate precipitate with K4Fe(CN)6


(iii)Bi+3 ions in solution of HCl on addition of water give white

cloudy precipitate.

BiCl3+H2O→BiOCl↓(white ppt.)+2HCl

When treated with sodium stannite a black ppt. is obtained.


(iv) Cd+2 ions in solution, with ammonium hydroxide gives a white

precipitate which dissolves.


3. Group II B (As3+,As5+,Sb3+,Sb5+,Sn3+,Sn4+)


As+3−→−−−−−OxidationHNO3 As+5(as H3AsO4)


(ii)HgCl2 , which turns black on standing.



(iii)SbCl3 , on addition of water give white precipitate.


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

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


(ii) Precipitate of BaCl2 to this solution gives yellow precipitate

2CrO4+BaCl2→BaCrO4↓(yellow ppt.)+2NaClFe(OH)3 is insoluble in

(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+3H2OFeCl3+3KCNS→Fe(CNS)3(blood red)

+3KClAlso on addition of K4Fe(CN)6 to this solution,a prussian blue
colour is obtained.FeCl3+3K4Fe(CN)6→Fe4[Fe(CN)6]3(prussia blue c

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

(i)Ni+2 is present.

+2KHCO3+[O]→2K3[Co(CO3)3](Apple green colour)+2K2CO3+H2O
Ni2O3↓(black ppt.)+2Na2CO3+2H2O

(ii)Zn+2 ions in solution give a white precipitate with NaOH, which

dissolves in excess of NaOH



(iii)Mn+2ions in solution give pink precipitate with NaOHturning

black or brown on heating.


Mn(OH)2+[O]−→Δ MnO2(brown or black)+H2O

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

(i) Ba+2 ions in solution give

(a) Yellow precipitate with K2CrO4


(b) White precipitate with (NH4)2SO4


(c) White precipitate with (NH4)2C2O4


(ii) Sr+2 ions give white precipitate

with (NH4)2SO4 and (NH4)2C2O4


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


7. Group V (NH+4,Na+,K+,Mg+2)

(i) All ammonium salts on heating with alkali say NaOH give a
colourless, pungent smelling gas (NH3).


(a) Gas evolved gives white fumes with a rod dipped in conc. HCl
NH3+HCl→NH4Cl↑(white fumes)

(b) Paper soaked in NH3

CuSO4+4NH3→[Cu(NH3)4]SO4(deep blue)

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


(d) An aqueous solution of an ammonium gives a brown ppt. with

Nessler’s reagent (alkaline solution of potassium
tetraiodomercurate(II) ).

(ii) Potassium salts give a yellow ppt. with sodium cobaltinitrite


(iii) Sodium salts give a heavy white ppt. with potassium dihydrogen

KH2SbO4+NaCl→NaH2SbO4↓(white ppt.)+KCl

(iv) Mg2+ gives white ppt. of magnesium hydroxide with sodium



The ppt. obtained is sparingly soluble in water but readily soluble in

ammonium salt.