Qualitative Analysis (Anion) Theory PDF

Qualitative Analysis (Anion)
PART-1
Introduction :
Qualitative analysis involves the detection of cation(s) and anion(s) of a salt or a mixture of salts.
The systematic procedure for qualitative analysis of an inorganic salt involves the following steps :
(a) Preliminary tests
 Physical appearance (colour and smell).
 Dry heating test.
 Flame test.
 Borax bead test.
 Charcoal cavity test.
 Charcoal cavity and cobalt nitrate test.
(b) Wet tests for acid radicals.
(c) Wet tests (group analysis) for basic radicals.
Section (A) : Heating in dry test tube

1. Physical appearance (smell).
Table : 1
Physical Examination
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. These observations are tabulated below along with the inferences that you can
draw.
Table : 2
Observation Inference
1. Gas evolved
(a) Colourless and odourless gas
CO2 gas – turns lime water milky CO32–
(b) Colourless gas with odour
(i) H2S gas – Smells like rotten eggs, turns lead acetate paper black. Hydrated S2– or S2–
(ii) SO2 gas – Characteristic suffocating smell of burning sulphur turns
SO32–
acidified potassium dichromate solution or paper green.
(iii) HCl gas – Pungent smell, white fumes with ammonia, white
Cl–
precipitate with silver nitrate solution.
(iv) Acetic acid vapours–Characteristic vinegar like smell. CH3COO–
(v) NH3 gas– Characteristic smell, turns Nessler's solution brown. NH4+
(c) Coloured gases – Pungent smell
(i) NO2 gas – Reddish brown, turns ferrous sulphate solution
NO2– or NO3–
brownish black.
(ii) Cl2 gas – Greenish yellow, turns starch iodide paper blue. Cl–
(iii) Br2 vapours – Reddish brown, turns starch paper orange red. Br–
(iv) I2 vapours – Dark violet, turns starch paper blue. –
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ADVQUA- 1
2. Sublimate formed 
(a) White sublimate NH4+
(b) Black sublimate accompanied by violet vapours. –
3. Fusion 
Alkali metal salts or
The mixture fuses. salt containing water
of crystallisation.
4. Swelling 
The mixture swells up into voluminous mass. PO43–, BO33– indicated
5. Residue
(i) Yellow when hot, white when cold. Zn2+
(ii) Brown when hot and yellow when cold. Pb2+
Hydrated CuSO4
(iii) Original salt blue becomes white on heating.
indicated
Co2+, Fe2+, Fe3+, Cr3+,
(iv) Coloured salt becomes brown or black on indicated. Cu2+, Ni2+, Mn2+
heating.
Note :
 Use a perfectly dry test–tube for performing thes test. While drying a test–tube, keeps it in slanting
position with its mouth slightly downwards so that the drops of water which condense on the upper
cooler parts, do not fall back on the hot bottom, as this may break the tube.
 For testing a gas, a filter paper strip dipped in the appropriate reagent is brought near the mouth of the
test tube or alternatively the reagent is taken in a gas–detector and the gas is passed through it.
Figure : Detection of gas evolved.

 Do not heat the tube strongly at one point as it may break.
Section (B) : Flame and borax bead test

3. Flame test :
The chlorides of the metals are more volatile as compared to other salts and these are prepared in situ
by mixing the compounds with a little concentrated hydrochloric acid. On heating in a non-luminous
Bunsen flame they are volatilized and impart a characteristic colour to the flame as these absorb
energy from the flame and transmit the same as light as characteristic colour.
ADVQUA- 2
Table : 3
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
Figure : Flame test

4. Borax Bead test :
On Heating borax forms a colourless glassy bead of NaBO2 and B2O3 .
 
Na2B4O7.10H2O  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)
However, in reducing flame the colours may be different due to different reactions.
2Cu(BO2)2 + C  2CuBO2 + B2O3 + CO
2Cu(BO2)2 + 2C  2Cu (brown red/red and opaque bead) + 2B2O3 + 2CO.
Following metals impart a characteristic colour to the Bunsen flame :
Na, Li, K, Sr, Rb, Cs, Be, Ca, Cu
Table : 4
Colour in oxidising flame Colour in reducing flame
Metal
When Hot When Cold When Hot When Cold
Copper Green Blue Colourless Brown red
Iron Brown yellow Pale yellow/Yellow Bottle green Bottle green
Chromium Yellow Green Green Green
Cobalt Blue Blue Blue Blue
Manganese Violet/Amethyst Red/Amethyst Grey/Colourless Grey/Colourless
Nickel Violet Brown/Reddish brown Grey Grey
 Non luminous flame is called oxidising flame.  Luminous flame is called reducing flame.
ADVQUA- 3
Figure : Borax bead test

 All acid radicals which are in JEE syllabus are colourless and diamagnetic. Hence the colour of the
salts is only due to the basic radicals.
5. Charcoal Cavity Test :
This test is based on the fact that metallic carbonates when heated in a charcoal cavity decompose to
give corresponding oxides. The oxides appear as coloured incrustation or residue in the cavity. In
certain cases, the oxides formed partially undergo reduction to the metallic state producing metallic
beads or scales.
Example :
(a) ZnSO4 + Na2CO3  ZnCO3 + Na2SO4
ZnCO3  ZnO (Yellow when hot, white when cold) + CO 2
(b) CuSO4 + Na2CO3  CuCO3 + Na2SO4
CuCO3  CuO + CO2
CuO + C  Cu (Reddish scales) + CO

Table : 5
Observation
Inference
Incrustation or Residue Metallic bead
Yellow when hot, white when cold None Zn2+
Grey bead which
Brown when hot, yellow when cold Pb2+
marks the paper
No characteristic residue Red beads or scales Cu2+
White residue which glows on heating None Ba2+,Ca2+, Mg2+
Nothing definite–generally
Black None
coloured salt
6. Cobalt Nitrate Test :

In case the residue is white in colour after charcoal cavity test, add a drop of cobalt nitrate in the
charcoal cavity. A drop of water is then added and the mass is heated in an oxidising flame using blow
pipe. It is cooled and one or two drops of cobalt nitrate solution is added and then again heated in the
oxidising flame. Different metal salts give different coloured mass as given in the table. To illustrate :
ZnSO4 + Na2 CO3  ZnCO3 + Na2 SO4 ; ZnCO3  ZnO + CO2
2Co (NO3)2  2CoO + 4 NO2 + O2 ; ZnO + CoO  ZnO. CoO (or CoZnO2)
(Rinmann's green)
ADVQUA- 4
Table : 6
S.No. Metal Colour of the mass
1. Zinc Green
2. Aluminium Blue
3. Magnesium Pink
4. Tin Bluish – green
Table : 7
SOLUBILITY CHART
S.No. Anion Solubility / Exception
Except carbonates of alkali metals and of ammonium, all other normal
1. CO32–
carbonates are insoluble.
Only the sulphites of the alkali metals and of ammonium are water soluble.
2. SO32–
The sulphite of other metals are either sparingly soluble or insoluble.
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
3. S2–
earths are sparingly soluble, but are gradually changed by contact with water
into soluble hydrogen sulphides.
– Almost all nitrites and nitrates are soluble in water. AgNO 2 is sparingly
NO2 ,
4. – soluble. Nitrates of mercury and bismuth give basic salts on treatment with
NO3
water. These are soluble in dilute nitric acid.
– Acetates are water soluble except Ag(I) and Hg(II) acetates which are
5. CH3COO
sparingly soluble.
Most chlorides are soluble in water. PbCl 2 (sparingly soluble in cold but readily
6. Cl– soluble in boiling water), Hg2Cl2, AgCl, CuCl, BiOCl, SbOCl and Hg2OCl2 are
insoluble in water.
Silver, mercury(I) and copper(I), bromides are insoluble. Lead bromide is
7. Br– sparingly soluble in cold but more soluble in boiling water. All other bromides
are soluble in water.
– Silver, mercury(I), mercury(II), copper(I), lead and bismuth(III) iodides are the
8. I
least soluble salts. All other iodides are water soluble.
The sulphates of barium, silver lead are insoluble in water, those of calcium
2– and mercury(II) are slightly soluble. Some basic sulphates of mercury,
9. SO4
bismuth and chromium are also insoluble, but these dissolves in dilute
hydrochloric or nitric acid.
The phosphate of the alkali metals, with the exception of lithium and
ammonium, are soluble in water; the primary phosphate of the alkaline earth
10. PO43– 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 in to 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 in to 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 : 8
Inference
Observation
Gas Radical
Effervescence with the evolution of a colourless and odourless gas which
CO2 CO32–
turns lime water milky.
Evolution of colourless gas having smell of rotten egg which turns lead
H2S S2–
acetate 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
ADVQUA- 5
(i) FeSO4 solution brownish-black and NO2 NO2–
(ii) wet starch –iodide paper blue.
HAC(g) CH3COO–
Colourless gas having smell of vinegar.
All above
No peculiar gas is evolved. –
are absent
(b) Concentrated Sulphuric acid group : The anions of this group liberate acid vapours or gases with
conc. H2SO4.
Table : 9
Inference
Observation
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 orange Br2 Br–
red.
Evolution of violet vapours which turns starch paper blue. I2 I–
Evolution of reddish brown fumes which intensifies on addition of copper turnings
NO2 NO3–
or bits of filter paper.
Starch iodide paper develops a blue–black spot due to the 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.
Table : 10
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
 W.E. = Water extract. (Salt is dissolved in distilled water)
 S.E. = Sodium carbonate extract
Preparation of sodium carbonate extract :

Take 1-2 g of salt/salts mixture and three times the amount of pure solid sodium carbonate in a borosil
conical flask. Add 20 mL of distilled water and boil the contents for 10 minutes. Cool the solution and
then filter. The Filtrate is termed as "Sodium carbonate extract".
Sodium carbonate reacts with the inorganic salt to form water soluble sodium salt of the acid radical.
BaCl2 + Na2CO3  BaCO3  (white) + 2NaCl (aq)
Cd3 (PO4)2 + 3Na2CO3  3CdCO3  + 2Na3 PO4 (aq)
Sodium carbonate extract is used when
(a) salt is only partially soluble in water or insoluble
(b) cations interfere with the tests for acid radicals or the coloured salt solutions may be too intense in
colour that the test results are not too clear.
 As sodium carbonate extract contains excess of sodium carbonate, it should be neutralised with a
suitable acid before proceeding for analysis of an anion.
Note : S.E. is not used for testing CO32–or HCO3– ions.
ADVQUA- 6
Figure : Preparation of sodium carbonate extract

Individual tests :
Section (C) : dil. HCl / dil. H2SO4 group
(A) GROUP 'A' RADICALS :
(a) DILUTE SULPHURIC ACID/DILUTE HYDROCHLORIC ACID GROUP :
1. CARBONATE ION (CO32–) :
 Dilute H2SO4 test : A colourless odourless gas is evolved with brisk effervescence.
CaCO3 + H2SO4  CaSO4 + H2O + CO2 
 Lime water/Baryta water (Ba(OH)2) test : The liberated gas can be identified by its property of rendering
lime water (or baryta water) turbid.
CO2 + Ca(OH)2  CaCO3  milky+ H2O
On prolonged passage of CO2 the milkiness disappears.

CaCO3 + CO2 + H2O  Ca(HCO3)2 (soluble)   CaCO3 + H2O + CO2
 Magnesium sulphate test (for soluble carbonates) :
CO32– (aq) + MgSO4 (aq)  MgCO3  (white) + SO42– (aq)
 Silver nitrate solution : White precipitate is formed
CO32– + Ag+  Ag2CO3
  White precipitate is soluble in HNO3 and ammonia. The precipitate becomes yellow or brown upon
addition of excess reagent owing to the formation of silver oxide ; the same happens if the mixture is
boiled.
Ag2CO3  Ag2O  + CO2 
 Phenolphthalein is turned pink by soluble carbonates and colourless by soluble hydrogen carbonates.
 Mercury(II) chloride does not form precipitate with hydrogen carbonate ions, while in a solution of normal
carbonates a reddish–brown precipitate of basic mercury(II) carbonate (3HgO. HgCO3=Hg4O3CO3) is
formed.
CO32– + 4 Hg2+ + 3 H2O  Hg4O3.CO3  + 6H+
Note: Lime water milky test is also shown by SO 2 but CO2 does not turn the filter paper soaked in acidified
K2Cr2O7 green.
 Soluble bicarbonates give white precipitate with MgSO4 (aq) / MgCl2(aq) only on heating.

Mg2+ + 2HCO3–  Mg(HCO3)2   MgCO3  + H2O + CO2
 Action of heat :
ADVQUA- 7
Bicarbonates : 2NaHCO3  Na2CO3 + H2O + CO2
Carbonates : Except carbonates of Na, K, Rb, Cs ; the Li 2CO3 and all alkaline earth metals decompose
as given below :
Li2CO3  Li2O + CO2 ; MgCO3  MgO + CO2 ; Ag2CO3  2Ag + CO2
 CaCO3  
 CaO + CO2
2. SULPHITE ION (SO32–) :
 Dilute H2SO4 test : Decomposition of salt is more rapidly on warming, with the evolution of sulphur
dioxide.
CaSO3 + H2SO4  CaSO4 + H2O + SO2 
SO2 has suffocating odour of burning sulphur.
 Acidified potassium dichromate test : The filter paper dipped in acidified K2Cr2O7 turns green.
Cr2O72– + 2H+ + 3SO2  2Cr3+ (green) + 3SO42– + H2O.
 Barium chloride/Strontium chloride solution : White precipitate of barium (or strontium) sulphite is
obtained.
SO32– + Ba2+/Sr2+  BaSO3/SrSO3  (white).
 White precipitate dissolves in dilute HCl, when sulphur dioxide is evolved.
BaSO3  + 2H+  Ba2+ + SO2  + H2O.
White precipitate (BaSO3) on standing is slowly oxidised to sulphate which is insoluble in dilute mineral
acids. This change is rapidly effected by warming with bromine water, a little concentrated nitric acid or
with hydrogen peroxide.
2 BaSO3  + O2  2 BaSO4 
BaSO3 + Br2 + H2O  2 BaSO4 + 2 HBr
  Hence, reddish brown colour of bromine water is decolourised.
3BaSO3  + 2 HNO3 3 BaSO4  + 2NO  + H2O
BaSO3  + H2O2  BaSO4  + H2O
 These reactions are not given by carbonates (distinction from carbonates).
 Zinc and sulphuric acid test : Hydrogen sulphide gas is evolved.
SO32– + 3Zn2+ + 8H+  H2S  + 3Zn2+ + 3H2O
 Lime water test : A white turbidity is formed. The precipitate dissolves on prolonged passage of the gas,
due to the formation of hydrogen sulphite ions.
Ca(OH)2 + SO2  CaSO3(milky) + H2O
CaSO3  + SO2 + H2O  Ca(HSO3)2 (soluble)
 A turbidity is also produced by carbonates; sulphur dioxide must therefore be first removed when testing
for the latter. This may be affected by adding potassium dichromate solution to the test–tube before
acidifying. The dichromate oxidizes and destroys the sulphur dioxide without affecting the carbon dioxide.
 Lead acetate or lead nitrate solution : White precipitate of PbSO3 is obtained.
SO32– + Pb2+  PbSO3 (white)
White precipitate gets soluble in dil. HNO 3 on boiling. The precipitate is oxidized by atmospheric oxygen
and PbSO4 is formed.
2PbSO3  + O2  2PbSO4 
3. SULPHIDE ION (S2–) :
 Dilute H2SO4 test : Pungent smelling gas like that of rotten egg is obtained.
S2– + 2H+ H2S 
 Lead acetate test : Filter paper moistened with lead acetate solution turns black.
(CH3COO)2Pb + H2S  PbS  (black) + 2CH3COOH.
 Sodium nitroprusside test : Purple coloration is obtained.
S2– + [Fe(CN)5 (NO)]2–  [Fe(CN)5NOS]4– (purple).
It is a ligand change reaction not a redox where NO+ changes to (NOS)–1.
No reaction occurs with solution of H2S or free gas. If however, filter paper moistened with a solution of
the reagent is made alkaline with NaOH or NH3 solution, a purple colouration is produced with free H2S
also.
Note: H2S does not provide sufficient concentration of S2– ions so that it does not give sodium nitroprusside
test. Solubility is low 0.1 M and K1 is just 10–7.
 Cadmium carbonate suspension/ Cadmium acetate solution : Yellow precipitate is formed.
Na2S + CdCO3  CdS + Na2CO3
ADVQUA- 8
 Filter paper moistened with cadmium acetate when brought in contact with evolving gas it turns yellow.
S2– + 2H+  H2S ; H2S + Cd2+  CdS  (yellow) + 2H+.
 Silver nitrate solution : Black precipitate is formed which is insoluble in cold, but soluble in hot, dilute
nitric acid.
Ag+ + S2–  Ag2S (black)
 Methylene blue test : NN–Dimethyl–p–phenylenediamine is converted by iron(III) chloride and hydrogen
sulphide in strongly acid solution into the water–soluble dyestuff, methylene blue. This is a sensitive test
for soluble sulphides and hydrogen sulphide.
4. NITRITE ION (NO2¯ ) :
 Dilute H2SO4 test : Solid nitrite in cold produces a transient pale blue liquid (due to the presence of free
nitrous acid, HNO2 or its anhydride, N2O3) first and then evolution of pungent smelling reddish brown
vapours of NO2 takes place.
NO2– + H+  HNO2 ; (2HNO2  H2O + N2O3);
3HNO2  HNO3 + 2NO + H2O; 2NO + O2  2NO2
 Starch iodide test : The addition of a nitrite solution to a solution of potassium iodide, followed by
acidification with acetic acid or with dilute sulphuric acid, results in the liberation of iodine, which may be
identified by the blue colour produced with starch paste. A similar result is obtained by dipping potassium
iodide–starch paper moistened with a little dilute acid into the solution.
2NO2– + 3I– + 4CH3COOH  I3– + 2NO + 4CH3COO– + 2H2O
Starch + I3–  Blue (starch iodine adsorption complex)
 Ferrous sulphate test (Brown ring test) : When the nitrite solution is added carefully to a concentrated
solution of iron(II) sulphate acidified with dilute acetic acid or dilute sulphuric acid, a brown ring appears
due to the formation of [Fe(H2O)5NO]SO4 at the junction of the two liquids. If the addition has not been
made slowly and caustiously, a brown colouration results.
NO2– + CH3COOH  HNO2 + CH3COO–
3HNO2  H2O + HNO3 + 2NO 
Fe2+ + SO42– + NO   [Fe(H2O)5 NO]SO4 (brown ring complex)
 Thiourea test : When a dilute acetic acid solution of a nitrite is treated with a little solid thiourea,
nitrogen is evolved and thiocyanic acid is produced. The latter may be identified by the red colour
produced with dilute HCl and FeCl3 solution.
NaNO2 + CH3COOH  HNO2 + CH3COONa
HNO2 + H2NCSNH2(s) (thiourea)  N2 + HSCN + 2H2O
dil. HCl
FeCl3 + 3HSCN   Fe(SCN)3 (blood red colouration) + 3HCl
 Acidified potassium permanganate solution : Pink colour of KMnO 4 is decolourised by a solution
of a nitrite, but no gas is evolved.
5 NO2– + 2 MnO4– + 6 H+  5 NO3– + 2 Mn2+ + 3 H2O
 Silver nitrate solution : White crystalline precipitate of silver nitrite from concentrated solutions.
NO2– + Ag+  AgNO2 (white)
5. ACETATE ION (CH3COO¯)
 With dilute H2SO4 a vinegar like smell is obtained.
(CH3COO)2Ca + H2SO4  2CH3COOH + CaSO4
 Neutral ferric chloride test : A deep red/ blood red colouration (no precipitate) indicates the
presence of acetate.
6CH3COO– + 3Fe3+ + 2H2O  [Fe3(OH)2(CH3COO)6]+ + 2H+
 When solution is diluted with water and boiled, brownish red precipitate of basic iron (III) acetate is
obtained.
[Fe3(OH)2(CH3COO)6]+ + 4H2O  Boil
 3Fe(OH)2CH3COO  + 3CH3COOH + H+
 Silver nitrate solution test : A white crystalline precipitate is produced in concentrated solution in the
cold.
CH3COO– + Ag+ CH3COOAg (white)
Precipitate is more soluble in boiling water and readily soluble in dilute ammonia solution.
Section (D) : Conc. H2SO4 group
(b) CONC. H2SO4 GROUP :
ADVQUA- 9
1. CHLORIDE ION (Cl¯) :
 Concentrated H2SO4 test : Colourless pungent smelling gas (HCl) is evolved which gives fumes of
NH4Cl when a glass rod dipped in aq. ammonia is brought in contact with evolving gas.
Cl– + H2SO4  HCl + HSO4–
 NH4OH + HCl  NH4Cl  (white fumes) + H2O.
 2NaCl + MnO2 + 2H2SO4 (conc.)  Na2SO4 + MnSO4 + 2H2O + Cl2
 Silver nitrate test :
Cl– + Ag+  AgCl  (white)
With sodium arsenite it is converted into yellow precipitate (distinction from AgBr and AgI) but
insoluble in dilute nitric acid.
3AgCl + AsO33–  Ag3AsO3 (yellow) + 3Cl–.
 White precipitate is soluble in aqueous ammonia and precipitate reappears with HNO3.
AgCl + 2NH4OH [Ag(NH3)2]Cl (Soluble) + 2H2O
[Ag(NH3)2]Cl + 2H+  AgCl  + 2NH4+.
 Chromyl chloride test :
4Cl–(s) + Cr2O72–(s) + 6H+ (conc.)  2CrO2Cl2 (deep red vapours) + 3H2O
When deep red vapours are passed into sodium hydroxide solution, a yellow solution of sodium
chromate is formed, which when treated with lead acetate gives yellow precipitate of lead chromate.
CrO2Cl2 + 4OH–  CrO42– + 2Cl– + 2H2O
CrO42– + Pb+2  PbCrO4 (yellow)
Note :
1. Heavy metal chlorides such as Hg2Cl2, HgCl2, SnCl2, AgCl, PbCl2 and SbCl3, CuCl do not respond to
this test due to their high covalent character as a result of which sufficient free Cl – are not available.
This test is given generally by ionic chlorides.
2. Test should be carried out in a dry test tube otherwise chromic acid will be formed.
CrO2Cl2 + 2H2O  H2CrO4 + 2HCl
3. Br– and I– must be absent for this test because they are oxidized by Cr 2O72– into Br2 (brown vapours)
and I2 (violet vapours) respectively. Both Br2 and I2 produce colourless solution with NaOH solution.
4. NO2–, NO3– and ClO2– radicals also interfere with this test and so should be absent.
2. BROMIDE ION (Br¯) :

 Concentrated H2SO4 test : First a reddish-brown solution is formed, then reddish-brown bromine
vapour accompanies the hydrogen bromide (fuming in moist air) is evolved.
2NaBr + H2SO4  Na2SO4 + 2HBr
2HBr + H2SO4  Br2 + 2H2O + SO2
  2KBr + MnO2 + 2H2SO4  Br2+ K2SO4 + MnSO4 + 2H2O
 Silver nitrate test : Pale yellow precipitate is formed
NaBr + AgNO3  AgBr  + NaNO3
 Yellow precipitate is partially soluble in dilute aqueous ammonia but readily dissolves in concentrated
ammonia solution.
AgBr + 2NH4OH  [Ag(NH3)2] Br + H2O
 Lead acetate test : Bromides on treatment with lead acetate solution, gives a white crystalline
precipitate of lead bromide, which is soluble in boiling water giving colourless solution.
2Br– + Pb+2  PbBr2(white)
 Chlorine water test (organic layer test) : When to a sodium carbonate extract of metal bromide
containing CCl4, CHCl3 or CS2, chlorine water is added and the content is shaken and then allow to
settle down reddish brown colour is obtained in organic layer.
2Br– + Cl2  2Cl– + Br2  .
Br2 + CHCl3 / CCl4  Br2 dissolve to give reddish brown colour in organic layer.
With excess of chlorine water, the bromine is converted into yellow bromine monochloride and a pale
yellow solution results.
Br2 + Cl2   2BrCl
 Starch paper test : When starch paper is brought in contact with evolving bromine gas orange red
spots are produced.
Br2 + starch  starch bromine adsorption complex (orange red)
ADVQUA- 10
 Potassium dichromate and concentrated H2SO4 : When a mixture of solid bromide, K2Cr2O7 and
concentrated H2SO4 is heated and evolved vapours are passed through water, a orange red solution is
obtained.
6KBr + K2Cr2O7 + 7H2SO4  3Br2 + Cr2(SO4)3 + 4K2SO4 + 7H2O
3. IODIDE ION ¯) :
 Concentrated H2SO4 test : Pungent smelling violet vapours are evolved.
2Na + H2SO4  Na2SO4 + 2HI
2HI + H2SO4  I2 (dark violet) + 2H2O + SO2
 Evolution of dark violet fumes intensifies on adding a pinch of MnO2.
3I– + MnO2 + 2H2SO4  I3–  + Mn2+ + 2SO42– + 2H2S
 Starch paper test : Iodides are readily oxidised in acid solution to free iodine; the free iodine may than
be identified by deep blue colouration produced with starch solution.
3I– + 2NO2– + 4H+  I3– + 2NO  + 2H2O.
 Silver nitrate test : Bright yellow precipitate is formed.
I– + Ag+  AgI  (bright yellow)
 Bright yellow precipitate is insoluble in dilute aqueous ammonia but is partially soluble in concentrated
ammonia solution.
 Chlorine water test (organic layer test) : When chlorine water is added to a solution of iodide, free
iodine is liberated which colours the solution brown and on shaking with CS2, CHCl3 or CCl4, it
dissolves in organic layer forming a violet solution, which settles below the aqueous layer.
2NaI + Cl2  2NaCl + I2
I2 + CHCl3  I2 dissolves to give violet colour in organic layer.
 Lead acetate solution : A yellow precipitate is formed which is soluble in hot water forming a
colourless solution and yielding golden yellow plates ('spangles') on cooling.
2I– + Pb+2  PbI2 (yellow)
 Potassium dichromate and concentrated sulphuric acid : Violet vapours are liberated, and no
chromate is present in distillate.
6I– + Cr2O72 + 2H2SO4  3I2 + Cr3+ +7SO42– + 7H2O
 Action of heat : Most of halides are stable but few decompose as
2FeCl3  2FeCl2 + Cl2 ; MgCl2.6H2O  MgO + 2HCl + 5H2O
Hg2Cl2  HgCl2 + Hg ; NH4Cl  NH3 + HCl
2CuI2  CuI + I2 (without heating)
NH3 HNO3 Na2S2O3 NaCN/KCN
Solvent
Precipitate
AgCl Completely soluble Insoluble Soluble Soluble
AgBr Partially soluble Insoluble Soluble Soluble
AgI Insoluble Insoluble Soluble Soluble
Note : In NH3, Ag+ forms soluble complex of [Ag(NH3)2]+

In Na3S2O3, Ag+ forms soluble complex of [Ag(S2O3)2]3–
In NaCN, Ag+ forms soluble complex of [Ag(CN)2]–
4. NITRATE ION (NO3¯) :
 Concentrated H2SO4 test : Pungent smelling reddish brown vapours are evolved.
4NO3– + 2H2SO4  4NO2  + O2 + 2SO42– + 2H2O
 Addition of bright copper turnings or paper pellets intensifies the evolution of reddish brown gas.
2NO3– + 4H2SO4 + 3Cu  3Cu2+ + 2NO  + 4SO42– + 4H2O ; 2NO  + O2  2NO2 
4 C (paper pellet) + 4HNO3  2H2O + 4NO2 + 4CO2.
 Brown ring test : When a freshly prepared saturated solution of iron (II) sulphate is added to nitrate
solution and then concentrated H2SO4 is added slowly from the side of the test tube, a brown ring is
obtained at the junction of two layers.
ADVQUA- 11
NaNO3 + H2SO4  NaHSO4 + HNO3

6FeSO4 + 2HNO3 + 3H2SO4  3Fe2(SO4)3 + 2NO + 4H2O
or 2NO3– + 4H2SO4 + 6Fe2+  6Fe3+ + 2NO  + 4SO42– + 4H2O.
Fe2+ + NO  + 5H2O  [Fe(H2O)5 NO+]2+ (brown ring).
Some important points related to brown ring test are :
Note :
1. Shaking and warming are not allowed for this test because on shaking and warming the mixture, NO
escapes and a yellow solution of iron(III) ions is obtained.
2. Bromides and iodides interfere in brown ring test as liberated halogens obscure the brown ring. Nitrites
also interfere the brown ring test and can be removed by adding a little sulphamic acid, or urea.
H2NHSO3 + NO2–  N2  + SO42– + H+ + H2O
NO2– + H+  HCl
 HNO2
CO(NH2)2 + 2HNO2  2N2  + CO2  + 3H2O
3. FeSO4 solution must be freshly prepared because Fe2+ ion is very reactive towards aerial oxidation and
gets converted to Fe3+, which does not give this test.
 Diphenyl amine test : Blue ring is formed at the junction of two liquids (reagent and nitrate salt
solutions).
NaNO3 + H2SO4  NaHSO4 + HNO3
2HNO3  H2O + 2NO2 + [O]
2C6H5NHC6H5 + [O]  (C6H5)2 N – N (C6H5)2 (blue ring) + H2O.
 This test is also given by various oxidising agents like CrO 42–, Cr2O72–, ClO3–, BrO3–, IO3–, NO2– etc.
T O distinguish Br2 with NO2 (both are reddish brown gases)
(a) Br2 + starch–iodide paper  Blue black colour spots do not develop immediately as Br2 is a weaker
oxidising agent whereas NO2 being strong oxidising agent develops the blue black colour immediately.
(b) Bromine develops orange–red colour spots on starch paper.
Section (E) : Precipitation Reactions
(B) GROUP 'B' RADICALS :
Group of anions which do not give any gas with dilute as well as concentrated H 2SO4 in cold but
give precipitate with certain reagents :
These acid radicals are identified in inorganic salts by their individual tests as given below
1. SULPHATE ION (SO42–) :
 Barium chloride test :
W.E. or S.E. + Barium chloride (aq)  White precipitate
Na2SO4 + BaCl2  BaSO4 white+ 2NaCl.
 White precipitate is insoluble in warm dil. HNO 3 as well as HCl but moderately soluble in boiling
concentrated hydrochloric acid and conc. H2SO4.
PbSO4 + H2SO4  PbHSO4(soluble)
 Lead acetate test :
W.E. or S.E. + Lead acetate  white precipitate
Na2SO4 + (CH3COO)2Pb  PbSO4 White + 2CH3COONa
 White precipitate soluble in excess of hot ammonium acetate and ammonium tartrate.
PbSO4 + 2CH3COONH4  (NH4)2 [Pb(CH3COO)4] soluble. + (NH4)2SO4
PbSO4 + (NH4)2 C4H4O6  (NH4)2SO4 + (NH4)2 [Pb(C4H4O6)2]soluble
ADVQUA- 12
 Match stick test :
(a) W.E. or S.E. + Barium chloride  white precipitate
Na2SO4 + BaCl2  2NaCl + BaSO4  (white)
(b) White precipitate + Na2 CO3(s) mix and apply the paste on the end of the carbonized match stick or
a wooden splinter. Put it in the reducing flame.
BaSO4 (s) + Na2CO3(s)  Na2SO4 + BaCO3  (white)
Na2SO4 + 4C  Na2 S + 4CO
(c) Now dip the match stick in sodium nitroprusside solution, purple colour near the fused mass is
developed.
Na2S + Na2 [Fe(CN)5 NO]  Na4 [Fe(CN)5 NOS] (purple)
 Silver nitrate test : White precipitate is obtained.
SO42– + 2Ag+  Ag2SO4 (white ppt.)
2. PHOSPHATE ION (PO43– ) :
 Ammonium molybdate test :
Na2HPO4(aq) + 12(NH4)2MoO4 + 23HNO3  (NH4)3[P(Mo3O10)4](canary yellow) + 2NaNO3 + 21NH4NO3 + 12H2O
 Some times ammonium phosphomolybdate is also represented by the formula (NH4)3 PO4.12MoO3
 Magnesium nitrate or magnesia mixture test : W.E. or S.E + Magnesium nitrate reagent (3-4 mL)
and allows to stand for 4-5 minutes, white crystalline precipitate is formed.
Na2HPO4 (aq) + Mg(NO3)2 (aq) + NH4OH(aq)  Mg(NH4) PO4  (white) + 2NaNO3 + H2O
Magnesia mixture is a solution containing MgCl2, NH4Cl and a little aqueous NH3.
 PO43– also gives BaCl2 test due to the formation of white precipitate of Ba3 (PO4)2 . So phosphate test
should be carried out first and then conclude if PO 43– is present or absent before proceeding with the
test for SO42–.
 Silver nitrate solution : Yellow precipitate is formed which is soluble in dilute ammonia and in dilute
nitric acid.
PO43– + 3Ag+  Ag3PO4 (yellow)
Ag3PO4 + 6NH3  3[Ag(NH3)2]+ + PO43– ;
Ag3PO4 + 2H+  H2PO4– + 3Ag+
 Iron (III) chloride solution : Yellowish-white precipitate of FePO4 is obtained
HPO42– + Fe3+  FePO4 
3. BORATE ION (BO33–) :
Salt (0.2 g) + conc. H2SO4 (1 mL) + Ethyl alcohol (4-5 mL) mix in a test tube and then heat. Ignite the
evolved vapours with the help of Bunsen flame, green edged flame is obtained.
2Na3BO3 + 3H2SO4  3Na2 SO4 + 2H3BO3
3C2H5OH + H3BO3  (C2 H5)3BO3 or (C2H5O)3B + 3H2O
Note :
1. Use of methyl alcohol is preferred due to high volatility of the product formed is B(OMe)3
2. Copper and barium salts also interfere with this test because they give similar green flame and so
should be absent.
ADVQUA- 13
MISCELLANEOUS SOLVED PROBLEMS (MSPs)

1. Pink colour of acidified KMnO4 is decolourised but there is no evolution of any gas. This may happen
with the compound containing the following acid radical.
(A) SO32– (B) NO2– (C) S2– (D) All of these
Ans. (D)
Sol. (A) 5SO32– + 2MnO4– + 6H+  2Mn2+ + 5SO42– + 3H2O
(B) 2MnO4– + 5NO2– + 6H+  2Mn2+ + 5NO3– + 3H2O
(C) 2MnO4– + H2S + 6H+  2Mn2+ + 5S  + 8H2O
2. Which of the following gives a precipitate with Pb(NO 3)2 but not with Ba(NO3)2?
(A) Sodium chloride (B) Sodium acetate
(C) Sodium nitrate (D) Disodium hydrogen phosphate
Ans. (A)
Sol. (A) Pb2+ + 2Cl–  PbCl2(white) ; Ba2+ + 2Cl–  BaCl2(water soluble)
(B) (CH3COO)2 Pb and (CH3COO)2Ba both are water soluble salts.
(C) Nitrates are mostly soluble in water
(D) 3Pb2+ + 2HPO42–  Pb3(PO4)2  (white) + 2H+ ; Ba2+ + HPO42–  BaHPO4  (white)
3. When H2S gas is passed through an ammonical salt solution X, a slightly white precipitate is formed.
The X can be :
(A) a cobalt salt (B) a lead salt (C) a zinc salt (D) a silver salt
Ans. (C)
Sol. Zn2+ + H2S  ZnS  (white) + 2H+
4. Which anion does not liberate any gas with dilute as well as conc. H2SO4. 
(A) NO2– (B) NO3– (C) SO32– (D) SO42–
Ans. (D)
5. A salt having BO33– on burning with alcohol and conc. H2SO4 gives, which colour edge flame. 
(A) green (B) yellow (C) red (D) white
Ans. (A)
Sol. 3Na3BO3 + 3H2SO4  3Na2SO4 + 2H3BO3
3C2H5OH + H3BO3  (C2H5)3BO3 + 3H2O
(green)
6. When solution of KCl, KF and KBr are treated with I2 ? 
(A) Cl2 and Br2 are evolved (B) Cl2 is evolved
(C) Cl2, F2 and Br2 are evolved (D) None of these
Ans. (D)
Sol. I2 is weak oxidising agent.
It does not oxidise the F–, Cl–, Br–.
7. A mixture when rubbed with organic acid smells like vinegar. It contains :
(A) Sulphate (B) Nitrate (C) Nitrite (D) Acetate
Ans. (D)
8. Nitrate & Nitrite both give brown ring test, can be distinguish by –
(A) HOSO2NH2 (Sulphonic acid) (B) NH2HgO.HgI (Million base)
(C) FeSO4 (D) None
Ans. (A)
9. Which reagent is used to remove SO42– or Cl– from water? 
(A) NaOH (B) Pb(NO3)2 (C) BaSO4 (D) KOH
Ans. (B)
Sol. Pb2+ + SO42+ PbSO4  (ppt)
Pb2+ + Cl– PbCl2  (ppt)
Others does not from precipitate with both anions.
ADVQUA- 14
10.* Which of the following statements is/are correct for chromyl chloride test? 
(A) Formation of chromyl chloride vapour (B) Liberation of chlorine gas
(C) Formation of lead chromate (D) Formation of reddish-brown vapour
Ans. (A,C,D)
Sol. Cl– + K2Cr2O7 + H+ CrO 2 Cl2 (red-brown vapour) 
NaOH
 Na2CrO4
(CH3COO)2 Pb
  PbCrO 4
(Chromyl Yellow (sodium Lead chromate
chloride) chromate) (Yellow )
11.* Which of the following statements are incorrect? 

(A) In thiourea test for nitrite, a green coloured solution is obtained.
(B) It is not necessary to carried out the chromyl chloride test in a dry test tube.
(C) Suspension of CdCO3 gives black precipitate with Na2S solution.
(D) In PbNO3, the brown ring test can be performed with its water extract.
Ans. (A,B,C,D)
Sol. It is deep red colouration due to the formation of Fe(SCN)3.
In presence of moisture, CrO2Cl2 + H2O  H2CrO4 + HCl.
CdS (Yellow precipitate).
White precipitate of PbSO4 is formed and hence brown ring is not visible.
12.* Conc. H2SO4 will not give any gas with : 
(A) ZnSO4 (B) Ba3(PO4)2 (C) Mg3(BO2)2 (D) NaNO3
Ans. (A,B,C)
Sol. Only NO3– belong to conc. H2SO4 anion group.
13. Why does only the organic layer assure colour and not the aqueous layer when the tests for halides are
done ?
Ans. Both Br2 and I2 are covalent. They have preference for organic layer.
14. What will happen when free bromine, iodine and chlorine separately react with a yellow dye stuff,
fluorescein?
Ans. With free bromine it will convert into red tetra bromo fluorescein and with iodine into the red violet
coloured iodoeosin. But chlorine tends to bleach the reagent.
ADVQUA- 15

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Qualitative Analysis (Anion)

Section (A) : Heating in dry test tube

2. Dry Heating Test :

Figure : Detection of gas evolved.

Section (B) : Flame and borax bead test

Figure : Flame test

Figure : Borax bead test

6. Cobalt Nitrate Test :

Analysis of ANIONS (Acidic Radicals) :

Preparation of sodium carbonate extract :

Figure : Preparation of sodium carbonate extract

2. BROMIDE ION (Br¯) :

NH3 HNO3 Na2S2O3 NaCN/KCN

Note : In NH3, Ag+ forms soluble complex of [Ag(NH3)2]+

NaNO3 + H2SO4  NaHSO4 + HNO3

MISCELLANEOUS SOLVED PROBLEMS (MSPs)

11.* Which of the following statements are incorrect? 

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