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CHM-CAPE-QA-01

Qualitative Analysis: Identification of substances based on their reactions and physical characteristics.
Copyright 2014 Mark December

Cation Analysis
To about 1 cm3/ 0.001 dm3 portions of the solution of the unknown substance, add the reagents shown in the table below, drop wise until
they are present in excess.
Cations
Ammonium -

NH4+

Addition of NaOH

Addition of NH3 (aq)

No precipitate formed. Warm the solution Solutions mix and no precipitate forms.
gently, ammonia gas will evolve.
Smell the product to detect the gas or place
damp red litmus in the gas. Damp red litmus
turns blue. Or dip a glass rod into the solution
and place in conc. HCl or any other hydrogen
halide. Ammonia gas forms white fumes with
the conc. HCl.

Confirmatory Test
Warm the solution with dil. Aqueous
NaOH. Ammonia gas evolves.
NH4Cl(aq) + NaOH(aq) NH3(g) + NaCl(aq)
+ H2O(I)

NH4+(aq) + OH-(aq) NH3 (g) + H2O (l)


Sodium Na+

No precipitate

No precipitate

Do a flame test. Sodium gives a yellow


flame.

Potassium K+

No precipitate

No precipitate

Do a flame test. Potassium gives a lilac


flame.

Copper (II) Cu2+

Pale blue precipitate, turns black on heating. Blue precipitate. Soluble in excess aqueous Add potassium iodide, KI.
Insoluble in excess alkali.
ammonia forming a deep blue solution Brown solution, White precipitate.
containing the tetraamine copper (II) ion,
2+
Cu (aq) + 2OH (aq) Cu(OH)2(s)
[Cu(NH3)4]2+.
2Cu2+(aq) + 4I- (aq) 2CuI (s) + I2 (aq)
White Brown
2+
Cu (aq) + 2OH (aq) Cu(OH)2 (s)
Cu2+(s) + 4NH3 (aq) [Cu(NH3)4]2+
Tetraamine copper (II) ion

CHM-CAPE-QA-01

Cations
Iron (II) / Ferrous

Addition of NaOH
Fe2+

Addition of NH3 (aq)

Dirty green precipitate, turns brown on Dirty green precipitate, turns brown in air due Add potassium hexacyanoferrate (III)
exposure to air. Insoluble in excess alkali.
to atmospheric oxidation of the ion to Fe3+ ions. solution, K3Fe(CN)6. Dark blue
Insoluble in excess aqueous ammonia.
precipitate formed.
Fe2+(aq) + 2OH-(aq) Fe(OH)2 (s)

Fe2+(aq) + 2OH-(aq) Fe(OH)3 (s)


Fe2+(aq) Fe3+(aq) + e-

Iron (III) /Ferric Fe3+

Confirmatory Test

Red-brown precipitate. Insoluble in excess


alkali.
Fe3+(aq) + 3OH-(aq) Fe(OH)3 (s)

Red-brown precipitate. Insoluble in excess


alkali.
Fe3+(aq) + 3OH-(aq) Fe(OH)3 (s)

Fe2+(aq) + [Fe(CN)6]3- (aq)


Fe(III)4[Fe(II)(CN)6]3 (s)
Add potassium hexacyanoferrate (II)
solution, K4Fe(CN)6 (aq). Dark blue
precipitate formed.
Fe3+(aq) + [Fe(CN)6]4- (aq)
Fe(III)4[Fe(II)(CN)6]3 (s)
OR
Add ammonium thiocyanate solution,
NH4SCN (aq) or potassium thiocyanate
solution, KSCN (aq). Blood red solution
formed.
With SCN- (aq):
Fe3+(aq) + SCN-(aq) + 5H2O(l)
[Fe(H2O)5SCN]2+ (aq)

Chromium (III) Cr3+

Grey-green precipitate. Soluble in excess


alkali.
Cr3+(aq) + 3OH-(aq) Cr(OH)3 (s)
Cr(OH)3 (s) + 3NaOH(aq) Na3Cr(OH)6 (aq)
Sodium chromate (III)

Grey-green precipitate. Soluble in excess


alkali.
Cr3+(aq) + 3OH-(aq) Cr(OH)3 (s)
Cr3+(s) + 6NH3 (aq) [Cr(NH3)6]3+ (aq)
Tetraamine zinc (II) ion

CHM-CAPE-QA-01

Cations
Manganese (II)

Mn2+

Addition of NaOH

Addition of NH3 (aq)

Cream precipitate. Insoluble in excess alkali.

Cream precipitate. Insoluble in excess alkali.

Mn2+(aq) + 2OH-(aq) Mn(OH)2 (s)


Nickel (II) Ni2+

Green precipitate. Insoluble in excess alkali.


Ni2+(aq) + 2OH-(aq) Ni(OH)2 (s)

Confirmatory Test

Mn2+(aq) + 2OH-(aq) Mn(OH)2 (s)


Green precipitate. Soluble in excess alkali
producing a violet-purple colour as the
tetraamine nickel (II) ion forms.
Ni2+(aq) + 2OH-(aq) Ni(OH)2 (s)
Ni2+(s) + 4NH3 (aq) [Ni(NH3)4]2+
Tetraamine nickel (II) ion

Cobalt (II) Co2+

Blue-green precipitate. Insoluble in excess.


Co2+(aq) + 2OH-(aq) Co(OH)2 (s)

Blue-green precipitate. Soluble in excess.


Co2+(aq) + 2OH-(aq) Co(OH)2 (s)
Co3+(s) + 6NH3 (aq) [Co(NH3)6]3+
Hexaamine cobalt (III)

Lead (II) Pb2+

White precipitate. Soluble in excess alkali.


Pb2+(aq) + 2OH- Pb(OH)2 (s) --- White

White precipitate. Insoluble in excess


aqueous ammonia.
Pb2+(aq) + 2OH- Pb(OH)2 (s) --- White

Add potassium iodide solution, KI (aq).


Yellow precipitate formed.
Pb2+(aq) + 2I-(aq) PbI2 (s)
Add potassium chromate solution,
K2CrO4 (aq). Yellow precipitate formed.

Pb(OH)2 (s) + 2NaOH(aq) Na2Pb(OH)4 (aq)


Sodium plumbate (II)

Pb2+(aq) + CrO42- (aq) PbCrO4 (s)


Most lead salts are insoluble- SO42-,
CO32-, Cl-. The chloride is soluble in
hot solution.

CHM-CAPE-QA-01

Cations
Zinc

Zn2+

Addition of NaOH
White precipitate. Soluble in excess alkali.
Zn2+(aq) + 2OH- Zn(OH)2 (s) --- White
Zn(OH)2 (s) + 2NaOH(aq) Na2Zn(OH)4 (aq)
Sodium zincate

Aluminium Al3+

White precipitate. Soluble in excess alkali.


Al3+(aq) + 3OH- Al(OH)3 (s) --- White

Addition of NH3 (aq)

Confirmatory Test

White precipitate. Soluble in excess aqueous


ammonia forming tetraamine zinc (II) ion,
[Zn(NH3)4]2+.
Zn2+(aq) + 2OH- Zn(OH)2 (s) --- White
Zn2+(s) + 4NH3 (aq) [Zn(NH3)4]2+ (aq)
Tetraamine zinc (II) ion
White precipitate. Insoluble in excess Solutions are acidic hence pH < 7, blue
aqueous ammonia.
litmus goes red/pink and effervesces
with CO32- / HCO3-.
3+
Al (aq) + 3OH Al(OH)3 (s) --- White

Al(OH)3 (s) + NaOH(aq) NaAl(OH)4 (aq)


Sodium aluminate
Calcium Ca2+

White precipitate. Insoluble in excess alkali.

No precipitate.

Ca2+(aq) + 2OH-(aq) Ca(OH)2 (s) --- White

Add sodium carbonate, Na2CO3. White


precipitate formed.
Ca2+(aq) + CO32-(aq) CaCO3 (s) --- White
OR
Do a flame test. Calcium gives a brickred flame.

Magnesium Ma2+

White precipitate. Insoluble in excess alkali.


Mg2+(aq) + 2OH-(aq) Mg(OH)2 (s) --- White

No precipitate

CHM-CAPE-QA-01

Cations
Strontium

Sr2+

Addition of NaOH
White precipitate. Insoluble in excess alkali.

Addition of NH3 (aq)


No precipitate

Do a flame test. Strontium gives a


crimson flame.

No precipitate

Do a flame test. Barium gives a yellowgreen (apple green) flame.

Sr2+(aq) + 2OH-(aq) Sr(OH)2 (s) --- White


Barium Ba2+

White precipitate. Insoluble in excess alkali.


Ba2+(aq) + 2OH-(aq) Ba(OH)2 (s) --- White

Confirmatory Test

CHM-CAPE-QA-01

Anion Analysis
Anions in the solid state can be tested by the action of heat, dilute nitric or hydrochloric acid or concentrated sulphuric acid.
In solutions, anions can be tested as shown in the table below.
To test with Silver nitrate add excess nitric acid to solution to decompose any sulphite or carbonate and then add the silver nitrate followed
by aqueous ammonia. To test with Barium chloride add aqueous barium nitrate or chloride and then add excess nitric acid to any precipitate.
Anions

Heat

Hydrogencarbonate/ Carbon dioxide,


bicarbonate - HCO3- CO2 and H2O
evolved.

Carbonate CO32-

Solid
Dilute HNO3/
Dilute HCl
Carbon dioxide, CO2
evolved.

Conc. H2SO4,
heated.

Barium Chloride,
(BaCl2) + HNO3

Aqueous Solutions
Silver Nitrate,
(AgNO3) +
Ammonia solution,
(NH3 (aq))

Lead Nitrate,
Pb(NO3)2

Carbon dioxide,
CO2 evolved.

H+(aq) + HCO32-(aq)
2HCO3- CO32-(s) + H2O(I) + CO2 (g)
H2O(l) + CO2 (g)

H+(aq) + HCO32-(aq)
H2O(I) + CO2 (g)

Carbon dioxide
forms a white
precipitate with lime
water.

Carbon dioxide forms


a white precipitate
with lime water.

Carbon dioxide
forms a white
precipitate with lime
water.

CaOH2 (aq) + CO2(g)


CaCO3(s) + H2O(l)

CaOH2 (aq) + CO2(g)


CaCO3(s) + H2O(l)

CaOH2 (aq) + CO2(g)


CaCO3(s) + H2O(l)

Those of metals
below Calcium in the
series decompose to
give oxide and
Carbon dioxide,
CO2 (g)

Carbon dioxide
evolved.

Carbon dioxide
evolved.

White precipitate.
Soluble in excess
HNO3. CO2 (g) evolved.

White precipitate.
Soluble in nitric acid.

2H+(aq) + CO32-(s)
H2O (l) + CO2 (g)

2H+(aq) + CO32-(s)
H2O (l) + CO2 (g)

Ba2+(aq) + CO32-(aq)
BaCO3 (s)

Pb2+(aq) + CO32-(aq)
PbCO3 (s)

CHM-CAPE-QA-01

Anions

Carbonate CO32-

Heat

CO32- O2-(s) +
CO2(g)

Solid
Dilute HNO3/
Dilute HCl
Test CO2 with
limewater.

Conc. H2SO4,
heated.

Barium Chloride,
(BaCl2) + HNO3

Aqueous Solutions
Silver Nitrate,
(AgNO3) +
Ammonia solution,
(NH3 (aq))

Lead Nitrate,
Pb(NO3)2

Test CO2 with


limewater.

Test CO2 with


limewater.
Chloride Cl-

Bromide Br-

Hydrogen chloride,
HCl(g) evolved.
Some Cl2 (g) if a
strong enough
oxidising agent is
present.

White precipitate.
Soluble in dilute and
conc. NH3 (aq) forming
the diamine silver (I)
ion, [Ag(NH3)2]+ (aq)

H+(aq) + Cl-(s)
HCl (g)

Ag+(aq) + Cl-(aq)
AgCl(s) , white

2Cl-(aq) Cl2 (g) +


2e-

AgCl(s) + 2NH3 (aq)


[Ag(NH3)2]+ (aq) + Cl-(aq)

Br2 (l) and HBr (g)


evolved.

Cream precipitate.
Soluble in conc. NH3(aq)
but insoluble in dil.
NH3(aq).

White precipitate.
Soluble on heating,
re-precipitates on
cooling.

Ag+(aq) + Br-(aq)
AgBr(s) , cream

Pb2+(aq) + 2Br-(aq)
PbBr2 (s) , white

H+(aq) + Br-(s)
HBr (g)
2Br-(aq) Br2 (g) +
2e-

White precipitate.
Soluble on heating,
re-precipitates on
cooling.
Pb2+(aq) + 2Cl-(aq)
PbCl2 (s) , white

CHM-CAPE-QA-01

Anions

Heat

Solid
Dilute HNO3/
Dilute HCl

Iodide I-

Conc. H2SO4,
heated.

Barium Chloride,
(BaCl2) + HNO3

Aqueous Solutions
Silver Nitrate,
(AgNO3) +
Ammonia solution,
(NH3 (aq))

HI (g), SO2 (g) , I2 (g)


and
H2S (g) formed.

Yellow precipitate.
Insoluble in dilute and
conc. NH3 (aq)

2I-(aq)

Ag+(aq) + I-(aq)

I2 (aq) + 2e

Sulphate SO42-

Add excess dilute HNO3


(aq) making the solution
to be tested acidic. This
removes any
contaminating
carbonates present.
Then add the BaCl(aq) or
Ba(NO3)2 (aq).

AgI(s) ,

Lead Nitrate,
Pb(NO3)2

Bright Yellow
precipitate.
Pb2+(aq) + I-(aq)
PbI2(s)
White precipitate.
Insoluble in dilute
HNO3 (aq).
Pb2+(aq) + SO42-(aq)
PbSO4 (s)

White precipitate.
Insoluble in acid.
Ba2+(aq) + SO42-(aq)
BaSO4 (s)
Sulphite SO32Sulphites are more
thermally unstable
than the sulphates
and can be tested
using heat.

SO2 (g) evolved.

SO2 (g) evolved.

2H+(aq) + SO32-
H2O(l) + SO2 (g)

SO2 (g) is colourless.


It turns acidified
potassium
dichromate (VI),
Cr2O72-/H+ from
orange to green.

White precipitate.
Soluble in acid (SO2
evolved)

White precipitate.
Soluble in dilute
HNO3.

Ba2+(aq) + SO32-(aq)
BaSO3 (s)

Pb2+(aq) + SO32-(aq)
PbSO3(s)

CHM-CAPE-QA-01

Anions

Heat

Chromate CrO42-

Solid
Dilute HNO3/
Dilute HCl

Conc. H2SO4,
heated.

Add dil. H2SO4 to


the solution.
Colour changes
from yellow to
orange due to the
formation of the
dichromate ion,
CrO72-(aq).
CrO42-(aq) + 2H+(aq)
CrO72-(aq) + H2O(l)

Nitrate NO3-

Nitrates high in the


reactivity
series
decomposes to give
the nitrite and
oxygen gas.
Eg: NaNO3
NaNO3 (s)
NaNO2(s) + O2(g)
Nitrates low in the
reactivity series
decomposes to give
the oxide, nitrogen

Warm with conc.


H2SO4. NO2(g) and
HNO3(aq) produced.
HNO3(aq) + NO3-(s)
HNO3 (aq) +
HSO4-(aq)
Add a small piece of
Cu. Solution turns
blue and brown
fumes of NO2(g)
evolves.

Barium Chloride,
(BaCl2) + HNO3

Aqueous Solutions
Silver Nitrate,
(AgNO3) +
Ammonia solution,
(NH3 (aq))

Lead Nitrate,
Pb(NO3)2

CHM-CAPE-QA-01
dioxide and oxygen
gas.
Eg: Cu(NO3)2
Cu(NO3)2 (s)
CuO(s) + O2(g) +
NO2(g)

4H+(aq)

2NO3- (aq) +

+
Cu(s) Cu2+(aq) +
4NO2(g) + 2H2O(l)