PROF.

RAKESH RATHI’S CHEMISTRY TUTORIALS

QUALITATIVE ANALYSIS ANIONS
Preliminary Examination of the salt for identification of cation
The physical examination of the unknown salt involves the study of colour, smell and density.
1) Colour Test

Colour of given salt Ion

Yellowish Brown Fe3+
Blue Cu2+
Bright green Ni2+
Light green Fe2+

Experiment Observations Inference

Smell : Take a pinch of the salt
between your fingers and rub
with a drop of water
Density
Deliquescence
 Ammoniacal smell  NH 
4
 Vinegar like smell  CH3COOˉ
 Smell like that of rotten eggs  S2-
i) Heavy  Salt of Pb2+, or Ba2+,
ii) Light fluffy powder  Carbonate
Salt absorbs moisture and i) If coloured, may be Cu(NO3)2,
becomes paste like FeCl3
ii) If colourless, may be
Zn(NO3)2, chlorides of Zn2+,Mg2+
etc.

2) Dry Heating test

This test is performed by heating a small amount of salt in a dry test tube
Observations Inference
1. Gas evolved
a) Colourless and odourless gas CO2 gas-turns CO 23  present
lime water milky
b) Colourless gas with odour
I) H2S gas- Smells like rotten eggs, turns lead Hydrated S2-
acetate paper black.
II) HCl gas-Pungent smell, white fumes with Clˉ
ammonia, white ppt with silver nitrate solution
III) NH3 gas-characteristic smell, turns Nessler’s
NH 4+
solution brown.

c) Coloured gases-Pungent smell

I) NO2 gas-reddish brown, turns ferrous sulphate NO 2 or NO 3
solution black.
II) Cl2 gas-Greenish yellow, turns moist starch Clˉ
iodide(KI and starch ) paper blue
III) Br2 vapour-reddish brown, turns starch paper Brˉ
yellow.
IV) I2 vapours-Dark violet, turns starch paper Iˉ
blue.

2) Sublimate formed
a) White sublimate NH 4+
b) Black sublimate accompanied by violet Iˉ
vapours

1
 PROF. RAKESH RATHI’S CHEMISTRY TUTORIALS
3) Decrepitation A salt having no water of crystallisation may be
The salt decrepitates (make crackling sound) present. For example
Pb(NO3)2, NaCl, KBr

4) Residue
i) Yellow when hot and white when cold Zn2+ indicated
ii) Brown when hot and yellow when cold Pb2+ indicated
iii) White residue, glows on heating Ba2+, Ca2+ Mg2+, Al3+, etc. may be present
iv) Original salt blue becomes white on heating Hydrated CuSO4 indicated

3) Flame Test
The chlorides of several metals impart characteristic colour to the flame because they are volatile in non-
luminous flame
Colour of the Colour of the Inference
flame flame
observed by observed
naked eye through blue
glass
Green flame Same colour Cu2+
with blue as observed
centre without glass

Crimson red purple Sr2+

Apple green Bluish green Ba2+
Brick red Green Ca2+
White(dull Same Pb++
bluish)

4) Borax Bead Test

This test is employed only for coloured salts because borax (sodium pyro-borate) reacts with metal
salts to form metal borates or metals, which have characteristic colours.
On heating, borax loses its water of crystallisation and decomposes to give sodium metaborate and
boric anhydride.
Na2B4O7 .10H2O → Na2B4O7 + 10H2O
Borax
Na2B4O7 → 2NaBO2 + B2O3
Sodium metaborate Boric anhydride

On treatment with metal salt, boric anhydride forms metaborates of the metal which gives different
colours in oxidising and reducing flame. For example, in the case of copper sulphate, following reactions
occur.
CuSO4 + B2O3 
Non luminous flame
Cu(BO2)2 + SO3
Cupric metaborate
Blue

Two reactions may take place in the reducing flame:

(i) The blue Cu(BO2)2 is reduced to colourless cuprous metaborate as follows:
Luminous flame
2Cu(BO2)2 + 2NaBO2 + C   2CuBO2 + Na2B4O7 + CO
Or
(ii) Cupric metaborate may be reduced to metallic copper and the bead appears Red and opaque.
Luminous flame
2Cu(BO2)2 + 4NaBO2 + 2C   2Cu + 2Na2B4O7 + 2CO

2
 PROF. RAKESH RATHI’S CHEMISTRY TUTORIALS
Inference from the Borax bead test
Heating in oxidising (non-luminous) Heating in Reducing (luminous) Inference
flame flame

Colour of the salt Colour of the salt Colour of the salt Colour of the salt
bead (In cold) bead (In hot) bead (In cold) bead (In hot)
Blue Green Red opaque Colourless Cu2+
Reddish brown violet Grey Grey Ni2+

5) Charcoal Cavity Test

Metallic carbonate when heated in a charcoal cavity decomposes to give corresponding oxide. The oxide
appears as a coloured residue in the cavity. Sometimes oxide may be reduced to metal by the carbon of
the charcoal cavity. In certain cases, certain oxides partially undergo reduction to the metallic state
producing metallic beads or scales.
The steps for the tests are : -
Take a small piece of charcoal block and make a fine hole(cavity) in the centre of it.
Take a small amount of salt with excess of sodium carbonate and put it into the fine hole on the
charcoal.
The hole is known as a cavity and this test is known as a charcoal cavity.
Direct the flame on the cavity and note the colour
In case of CuSO4
CuSO4 + Na2CO3  Heat
 CuCO3 + Na2SO4
CuCO3  Heat
 CuO + CO2
CuO + C Heat
 Cu + CO
Red colour

In case of ZnSO4 :
ZnSO4 + Na2CO3  Heat
 ZnCO3 +Na2SO4
ZnCO3 Heat
 ZnO + CO2
Yellow when hot,
White when cold

In case of Pb(NO3)2 :
Pb(NO3)2 + Na2CO3  PbCO3 + 2NaNO3
PbCO3  PbO + CO2
Brown when hot,
Yellow when cold
PbO + C  Pb + CO
Grey bead

Residue Metallic bead Inference

Hot Cold
Yellow White None Zn2+
Brown Yellow Grey bead which Pb2+
marks the paper
None None Red beads or scales Cu2+
White residue None None Ba2+, Ca2+, Mg2+
which glows
Black None None Nothing definite – generally colored salt

3
 PROF. RAKESH RATHI’S CHEMISTRY TUTORIALS
6) Cobalt Nitrate Test
If the residue in the charcoal cavity is white, cobalt nitrate test is performed.
(i) Treat the residue with two or three drops of cobalt nitrate solution.
(ii) Heat it strongly in non-luminous flame with the help of a blow pipe and observe the colour of the
residue.

On heating, cobalt nitrate decomposes into cobalt (II) oxide, which gives a characteristic colour with
metal oxide present in the cavity.
Thus, with ZnO, Al2O3 and MgO, the following reactions occur.
2Co(NO3)2  Heat
 2CoO + 4NO2 + O2
Zinc salt
CoO + ZnO → CoO.ZnO
Green
Magnesium salt
CoO + MgO → CoO. MgO
Pink
Aluminium salt
CoO + Al2O3 → CoO. Al2O3
Blue
If black is formed, it means only cobalt oxide is present (no definite indication)

SYSTEMATIC ANALYSIS OF ANIONS

1) Carbonate (CO 2-3 )

i) Dilute HCl
The salt gives effervescence, due to the evolution of carbon dioxide
CO 2-
3 + 2H → CO2↑ + H2O
+

The gas gives white turbidity with lime water Ca(OH)2 and baryta water Ba(OH)2
CO2 + Ca2+ + 2OHˉ → CaCO3↓ + H2O
CO2 + Ba2+ + 2OHˉ → BaCO3↓ + H2O

On prolonged passage of carbon dioxide in lime water, the turbidity or milkiness slowly disappears due
to the formation of soluble hydrogen carbonate.
CaCO3↓ + CO2 + H2O → Ca(HCO3)2
Soluble

ii) Barium chloride or Calcium chloride solution:

The salt solution gives white ppt of barium or Calcium carbonate is obtained, which is soluble in
mineral acid.
CO 2-
3 + Ba
2+ → BaCO3↓

white
CO 3 + Ca → CaCO3↓
2- 2+

White

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

CO 2-
3 + 2Ag → Ag2CO3↓
+

White
The ppt so obtained is soluble in nitric acid and in ammonia, the white precipitate 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↑
4
 PROF. RAKESH RATHI’S CHEMISTRY TUTORIALS
iv) Magnesium sulphate test: White ppt is obtained with magnesium sulphate.
CO 2-
3 + Mg
2+ → MgCO3↓

White

2) Sulphide (S-2)

i) Dil HCl or Dil H2SO4 :

The salt solution gives colourless gas with a smell of rotten eggs (H2S) is evolved
S2- + 2H+ → H2S↑

ii) Lead acetate test:

The salt solution turns lead acetate paper black
(CH3COO)2Pb + H2S → PbS↓ + 2CH3COOH
Black

iii) Cadmium chloride /Cadmium Carbonate test

The salt solution gives yellow ppt. with CdCl2
Na2S + CdCl2 → CdS↓ + 2NaCl
Yellow
The salt solution gives yellow ppt. with CdCO3.

Na2S + CdCO3 → CdS↓ + 2Na2CO3

yellow

iv)Silver nitrate solution:

The salt solution gives black ppt. of silver sulphide insoluble in cold but soluble in hot dil nitric
acid.
S2- + 2Ag+ → Ag2S↓
Black

v) Sodium nitroprusside solution:

The salt solution with sodium carbonate extract turns sodium nitroprusside solution purple

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

Purple

3) Nitrites (NO21) :
i) Dil HCI and Dil. H2SO4 :
The salt solution on adding to solid nitrite in cold yield pale blue liquid (due to the presence of free
nitrous acid HNO, 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+ → HNO2
2HNO2 → H2O + N2O3
3HNO2 → HNO3 + 2NO↑ + H2O
2NO + O2 → 2NO2

ii) Silver nitrate solution

The salt solution gives white crystalline ppt. is obtained
NO 2 + Ag+ → AgNO2↓
white
5
 PROF. RAKESH RATHI’S CHEMISTRY TUTORIALS
iii) Acidified KI test
The salt solution gives 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 FeSO4.NO at the junction
of the two liquids.
NO 2 + CH3COOH → HNO2 + CH3COOˉ
3HNO2 → H2O + HNO3 + 2NO↑
Fe2+ + SO 24  + NO↑ → FeSO4.NO
Brown

v) Ferrous sulphate test

KNO2 + CH3COOH  CH3COOK + HNO2
3HNO2  HNO3 + 2NO + H2O
FeSO4 + NO  FeSO4.NO
(Dark brown)

vi) Sulphanilic acid — 1-naphthylamine reagent test (Griss-Ilosvay test)

On adding sulphanilic acid and 1-naphthylamine reagent to the water extract or acidified with acetic acid,
sulphanilic acid is diazotised in the reaction by nitrous acid formed. Diazotised acid couples with
1-naphthylamine to form a red azo-dye.

NO2–1 + CH3COOH HNO2 + CH3COO–

The test solution should be very dilute. In concentrated solutions reaction does not proceed beyond
diazotization.

vi) Diphenyl amine test

The salt solution will give blue colouration with diphenylamine

6
 PROF. RAKESH RATHI’S CHEMISTRY TUTORIALS
Preparation of sodium carbonate extract and configuration of anions
In the analysis of anions sometimes cations will interfere and gives precipitate with the reagents used
for identification of anions to overcome this the insoluble salts are converted to soluble sodium salts by
preparing sodium carbonate extract.
A 1: 3 of salt and Na2CO3 in dissolved in water and boiled, the filtrate is called Na2CO3 extract.
Example :- 3Pb(NO3)2 + 3Na2CO3  3PbCO3  + 6NaNO3

4) Chloride (Clˉ) :
Sodium carbonate extract is neutralized with dilute nitric acid and few drops of AgNO3 are added.

i) Silver nitrate solution

White, curdy ppt. of AgCl insoluble in water & in dil nitric acid, but soluble in dilute ammonia solution.
Cl-1+ Ag+ → AgCl ↓
AgCl↓ + 2NH3 → [Ag(NH3)2]Cl
Diammine silver (I) chloride
Ag(NH3)2Cl + 2H+ → AgCl + 2NH 4

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 + 2Clˉ → Mn2+ + Cl2 + 2SO 24  + 2H2O
Yellowish green

iii) Conc. H2SO4

The salt solution decomposes with the evolution of HCl.
Clˉ + H2SO4 → HCl + HSO 4
The 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. [NH3 + HCl → NH4Cl]

iv) Chromyl chloride test (CrO2Cl2)

When a mixture of potassium dichromate and sodium chloride (or KCl) is heated with concentrated
sulphuric acid, red vapours of chromyl chloride is evolved. On condensing, it gives oily red liquid.
This reaction is used in detection of chloride ions
K2Cr2O7 + 6H2SO4 + 4NaCl  2KHSO4 + 4NaHSO4 + 2CrO2Cl2 + 3H2O
Red oily

CrO2Cl2 + 4NaOH Na2CrO4 + 2NaCl + 2H2O

(CH3COO)2 Pb + Na2CrO4 PbCrO4 ↓ + 2CH3COONa

Sodium Lead chromate
Chromate (Yellow precipitate)

CrO42– ion formed in the reaction of chromyl chloride reacts with hydrogen peroxide to form chromium
pentoxide (CrO5) which dissolves in amyl alcohol to give blue colour.
K2Cr2O7 + 4H2SO4 + 4H2O2  2CrO5 + K2SO4 + + H2O
Blue

7
 PROF. RAKESH RATHI’S CHEMISTRY TUTORIALS
v) Lead acetate solution
White ppt of lead chloride is formed
Cl-1+ Ag+ → AgCl ↓
White 4

5) Bromide (Brˉ)

i) Conc. H2SO4
The salt solution gives reddish brown vapours of bromine.
2KBr + H2SO4 → K2SO4 + 2HBr
2HBr + H2SO4 → 2H2O + SO2↑ + Br2↑
(reddish brown)
Br2 vapours turn starch paper yellow

ii) Manganese dioxide and conc. sulphuric acid

When a mixture of solid bromide, MnO2 and conc. H2SO4 is heated ,reddish brown vapours of bromine
are evolved.
2KBr + MnO2 + 2H2SO4 → Br2↑ + K2SO4 + MnSO4 + 2H2O
(Reddish brown)
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
Brˉ + Ag+ → AgBr
NaBr + AgNO3 → NaNO3 + AgBr
(pale yellow precipitate)

iv) Lead acetate solution

The salt solution gives white crystalline ppt. of lead bromide which is soluble in boiling water.
2Brˉ + Pb+2 → PbBr2↓
white
v) Chlorine water
When this solution is added to a solution of bromide and chloroform free bromine liberated, which
colours the organic layer orange-brown.
2KBr + Cl2 (water) → 2KCl + Br2
Br2 + Chloroform → Orange brown colour

vi) Potassium dichromate & conc. H2SO4

When a mix of solid bromide, K2Cr2O7, and conc. H2SO4 is heated and passing the evolved vapors into
water, a yellowish brown solution is obtained.
2KBr + K2Cr2O7 + 7H2SO4 → 3Br2↑ + Cr2(SO4)3 + 4K2SO4 + 7H2O.

6) Iodide (I):

i) Conc. H2SO4:
The salt solution gives violet vapors of iodine
2Iˉ + 2H2SO4 → I2 + SO 24  + 2H2O + SO2↑
I2 + starch → Blue

On adding MnO2,the violet vapors become more dense

NaI + MnO2 + H2SO4 → I2 + MnSO4 + Na2SO4 + H2O

8
 PROF. RAKESH RATHI’S CHEMISTRY TUTORIALS
ii) Silver nitrate solution
The salt solution gives Yellow, curdy ppt. of silver iodide Agl, very slightly soluble in conc. ammonia
solution and insoluble in dil nitric acid.
NaI + AgNO3 → AgI + NaNO3
yellow ppt

iii) Lead acetate solution

The salt solution gives Yellow, curdy ppt. of lead iodide soluble in much hot water forming a colourless
solution & yielding golden yellow plates on cooling.
2Iˉ + Pb2+ → PbI2↓

iv) Potassium dichromate & conc. sulphuric acid

When a mix of solid bromide, K2Cr2O7, and conc. H2SO4 is heated and passing the evolved vapors into
water, violet iodine is liberated
6Iˉ + Cr2O 72  + 2H2SO4 → 3I2↑ + 2Cr3+ + 7SO 24  + 7H2O.
violet

v) Chlorine water:
Iodine is liberated, by the dropwise addition of chlorine water to iodide, and on addition of CHCI3 violet
coloured organic layer is obtained.
2Iˉ + Cl2 → I2 + 2Clˉ
I2 + chloroform → violet coloured layer.

vi) Copper sulphate solution:

The salt solution gives brown ppt. consisting of a mixture of copper (I) iodide & iodine and on addition
of hypo solution (S2O 32  ) brown ppt changes to white ppt.
4Iˉ + 2Cu2+ → 2CuI + I2
I2 + 2S2O 32  → 2Iˉ + S4O 62  .

vii) Mercury (II) chloride solution

The salt solution forms scarlet ppt. of HgI2
2Iˉ + HgCl2 → HgI2↓ + 2Cl.
This ppt. dissolves in excess of KI, forming tetraiodo mercurate (II) complex.
HgI2 + 2Iˉ → [HgI4]2-

7) Nitrate (NO 3 ) :
i) Conc H2SO4 :
The salt solution gives reddish-brown vapors of nitrogen dioxide
4NO 3 + 2H2SO4 → 4NO2↑ + 2SO 24  + 2H2O + O2↑
Reddish brown

ii) Brown ring test:

The iron (II) ion, Fe2+ reduces nitrate to nitric oxide. The nitric oxide formed reacts with Fe2+ to form a brown
coloured complex.

The test is carried out by adding dilute ferrous sulphate solution to an aqueous solution containing nitrate ion,
and then carefully adding concentrated sulphuric acid along the sides of the test tube.

9
 PROF. RAKESH RATHI’S CHEMISTRY TUTORIALS
A brown ring at the junction of the layers of the solution and sulphuric acid is obtained which confirms the
presence of nitrate ions in the solution
NO-3 + 3Fe2+ + 4H+  NO + 3Fe3+ + 2H2O
[Fe(H2O)6]2+ + NO  [Fe(H2O)5NO]2+ + H2O
Brown complex

iii) Action of heat

2NaNO3  2NaNO2 + O2
NH4NO3  N2O + 2H2O
AgNO3  2Ag + 2NO2 ↑ + H2O
Reddish brown
Pb(NO3)2  2 PbO + 4NO2 ↑ + H2O
Reddish brown
Cu(NO3)2  2CuO + 4NO2 ↑ + H2O
Reddish brown

8) Sulphate (SO42):
All sulphates except those of Ba, Pb, Sr are soluble in water sulphates of calcium and mercury(II) are
slightly soluble.

I) Barium Chloride solution

The salt solution gives 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
SO42 + Ba2+  BaSO4 
White ppt.

II) Mercury(II) nitrate solution

The salt solution gives yellow ppt. of basic mercury(II) sulphate
SO42 + 3Hg2+ + 2H2O  HgSO4.2HgO  + 4H+
Yellow ppt
III) HCl test
Boil a small amount of HCl in the test tube. Filter the contents & add BaCl2. A white ppt in soluble in
conc. HCl indicates presence of sulphate
2Cl + Ba2+  BaCl2 
White ppt.

10