BMC INTERNATIONAL

COLLEGE
QUALITATIVE ANALYSIS
Reference Notes
2015
(Video Version)
Part IV (QA3)

Qualitative Analysis Notes

6.

Other reactions

6.1

Acidified potassium manganate(VII)/

hydrogen peroxide as oxidizing agents

BMC 2015

The acidified purple manganate(VII) solution is reduced to almost colourless

manganese(II) ion.
The hydrogen peroxide is reduced to water.
Cr2O72 + 3 SO32 + 8 H+ 2 Cr3+ + 3 SO42 + 4 H2O

2 Fe2+ + 2 H+ + H2O2 2 Fe3+ + 2 H2O

2+

5 Fe

+ 8 H+ + MnO4 5 Fe3+ + Mn2+ + 4 H2O

6 Fe2+ + 14 H+ + Cr2O72 6 Fe3+ + 2 Cr3+ + 7 H2O

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 BMC 2015

Qualitative Analysis Notes

6.2

Reduction of nitrate(NO3) or nitrite(NO2 ) by aluminium/zinc/Devardas alloy to

ammonia
When a nitrate or a nitrite is heated with any of the above reagents in the presence of aqueous
sodium hydroxide, ammonia gas is liberated.
8 Al + 5 OH- + 18 H2O + 3 NO3 8 Al(OH)4- + 3 NH3
2 Al + OH + 5 H2O + NO2 2 Al(OH)4 + NH3

The ammonia produced turns moist red litmus blue and gives dense white fumes with HCl.

6.3

Oxidation of aqueous iodide to iodine

Colourless solutions of potassium iodide are easily oxidized to brown iodine solutions by
a variety of oxidizing agents
6 I + Cr2O72 + 14 H+ 2 Cr3+ + 7 H2O + 3 I2

2 Fe3+ + 2 I 2 Fe2+ + I2

2 I

+ H2O2 + 2 H+

2 H2O +

I2

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 BMC 2015

Qualitative Analysis Notes

2 Cu2+ + 4 I CuI(s) + I2(aq)

I2 (aq) + 2 S2O32 (aq) 2 I (aq) + S4O62 (aq)

6.4

A white ppt of copper(I) iodide is observed

together with the brown iodine solution
When thiosulfate is added, the brown solution of I2
is decolourised, leaving behind the white ppt of
CuI.

Chromate(VI) Dichromate(VI) Equilibrium

No longer used in practical examination from Nov 2011

6.5

Reaction of copper(II) with conc HCl

Copper(II) compounds like CuO, dissolves in concentrated HCl to give a yellow solution.
CuO + 4 HCl CuCl42 + H2O + 2 H+
Yellow
When this solution is diluted gradually, the colour changes to green and upon further dilution a
blue solution will be obtained.
Cu(H2O)62+ + 4 Cl
CuCl42 + 6 H2O

yellow

blue

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Qualitative Analysis Notes

6.6

BMC 2015

Halides with conc sulfuric acid

(i)

With solid chloride, hydrogen chloride gas is evolved on slight warming.

Cl + H2SO4 HSO4 + HCl

(ii)

With solid bromide, a reddish-brown solution is formed which on warming gives

reddish brown vapours of bromine gas together with hydrogen bromide gas. The
hydrogen bromide gas initially formed is oxidised to bromine by the conc. acid.
Br + H2SO4 HSO4 + HBr
2 HBr + H2SO4 Br2 + SO2 + 2 H2O

(iii)

With solid iodide, brown iodine which on warming gives violet vapours, together with
hydrogen iodide, sulfur dioxide, hydrogen sulfide and sulfur are produced.

I + H2SO4 HSO4 + HI
2 HI + H2SO4 I2 + SO2 + 2 H2O
6 HI + H2SO4 3 I2 + S + 4 H2O
8 HI + H2SO4 4 I2 + H2S + 4 H2O

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 BMC 2015

Qualitative Analysis Notes

6.7

Oxidation of bromide and iodide by chlorine water (obtained by acidifying NaOCl),

followed by the addition of an organic solvent
Br and I ions are oxidised by Cl2 water (acidified NaClO) to their respective halogens in
aqueous solution.
OCl + 2 X + 2 H+ X2 + Cl + H2O

(X=Br, I)

When an organic solvent ( eg. CH2Cl2, CHCl3) is added to the reaction mixture and shaken, the
organic layer becomes coloured due to the halogen dissolved in it.
Colour of aqueous layer
Pale green
yellow orange
brown

Cl

Colour of organic layer

colourless
reddish-brown
purplish/violet

Br

Anion
Cl
Br
I

Solubilities of Common Ionic Compounds in Water

The knowledge of the solubilities of common ionic compounds in water is extremely useful in
qualitative analysis as cations and anions are identified by precipitates formed with common
laboratory reagents.
Type of Salt
+

1. Na , K , NH4

2. NO3

All Na , K and NH4 salts are soluble.

All nitrates are soluble.

3. NO2

Solubility in Water
+

All nitrites are soluble except AgNO2.

4. Cl , Br , I

All halides are soluble except those of Ag+ and Pb2+.

PbCl2, PbBr2 and PbI2 are soluble in hot water.

5. SO42

All sulfates are soluble except those of Ba2+, Ca2+, Pb2+.

6. SO32

Only sulfites of Na+, K+, NH4+ are soluble.

7. CO32

Only carbonates of Na+, K+, NH4+ are soluble.

8. OH

Only hydroxides of Na+, K+, Ba2+ are soluble.

Ca(OH)2 is sparingly soluble.

9. CrO42

No longer used in practical examination from Nov 2011

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