IDENTIFICATION OF CATIONS

Cations can be identified in using one of three ways:

1. Reaction with sodium hydroxide

2. Reaction with aqueous ammonia
3. Reaction with sodium carbonate

1) REACTIONS WITH SODIUM HYDROXIDE

This is another main test to test for the presence of cations. Sodium hydroxide
dissociates fully into solution, producing OH- ions:

NaOH(s)  Na+(aq) + OH-(aq)

OH- ions readily combine with any metal cation in preference to other anions. Also OH -
ions usually form insoluble salts (precipitates) when combined with most cations.
Hence the products can be easily discerned.

POINTS TO NOTE:

1. Usually the ionic equation to represent the reaction involves the cation
combining with OH-

For example: Na+(aq) + OH-(aq)  NaOH(aq)

Cu2+(aq) + 2OH-(aq)  Cu(OH)2(s)

2. You will have to remember the solubility rules in order to determine whether the
salts formed are soluble or insoluble. All group I metals and NH4+ salts are
soluble. The rest are insoluble.
3. Sodium hydroxide can be added firstly dropwise and then in excess. Dropwise
addition determines whether a precipitate forms or not and its colour. Addition
in excess determines whether or not the precipitate is soluble/ insoluble in excess
sodium hydroxide. Most precipitates are insoluble in excess. The ones that are
soluble in excess form complexes with the metals (see Transition Metals). The
cations which give precipitates that are soluble in excess are:

 Al(OH)3(s) + OH-(aq)  Al(OH4)-(aq)

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  Cr(OH)3(s) + OH-(aq)  Cr(OH)4-(aq)
 Pb(OH)2(s) + 2OH-(aq)  Pb(OH)42-(aq)
 Zn(OH)2(s) + 2OH-(aq)  Zn(OH)42-(aq)

2) REACTIONS WITH AQUEOUS AMMONIA

Ammonia gas can dissolve easily in water and then dissociate into its ions.

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

Aqueous ammonia in water is a weak base, so it only partially ionizes in solution.

Therefore, the amount of precipitation expected would be less than if sodium hydroxide
is used. Aqueous ammonia is usually used as a confirmatory test after sodium
hydroxide is used.

POINTS TO NOTE

1. The equations to show the formation of the precipitate follows the same format
as with sodium hydroxide. The cation of the unknown salt combines with OH - to
form a salt which may be soluble or insoluble.

2. Some precipitates will be soluble in excess aqueous ammonia. In this case, they
form complexes with ammonia and ligand displacement reactions occur.
 Cu(OH)2(s) + 4NH3(aq)  Cu(NH3)42+(aq) + 2OH-(aq)
 Zn(OH)2(s) + 4NH3(aq)  Zn(NH3)42+(aq) + 2OH-(aq)

3) REACTIONS WITH CARBONATES

Soluble carbonates, such as sodium or potassium carbonate, can also be used to

determine the presence of cations. This is because most carbonate salts are insoluble and
therefore their colours can be determined.

POINTS TO NOTE:

1. The ionic equation involves the combination of the cation of the salt with the
carbonate anion. For example:

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 2Na+(aq) + CO32-(aq)  Na2CO3(aq)
Ca2+(aq) + CO32-(aq)  CaCO3(s)

The solubility of the salts formed can be determined using the solubility rules.
2. Some precipitates decompose on heating. When they do, carbon dioxide is
evolved:
 Al2(CO3)3(s) + 2H2O(l)  2Al(OH)3(s) + 3CO2(g)
 CuCO3(s)  CuO(s) + CO2(g)
 Fe2(CO3)3(s) + 3H2O(l)  2Fe(OH)3(s) + 3CO2(g)

IDENTIFICATION OF GASES
Testing for gases is usually a confirmatory test for the presence of certain anions. Below
are the tests for certain gases:

 O2(g) – hold a glowing splint in the gas. Oxygen is a gas that supports
combustion, so the splint would relight.

 H2(g) – hold a glowing splint in the gas. Hydrogen is an explosive gas. It would
relight the glowing splint with a ‘popping’ sound.

 CO2(g) – bubble the gas through limewater. A white precipitate forms in the
limewater:
Ca(OH)2(aq) + CO2(g)  CaCO3(s) + H2O(l)

 Cl2(g) – chlorine is an acidic gas as well as a bleaching agent. It would turn

moist blue litmus paper red and then white (bleaching it). Chlorine also has an
irritating smell.

 NO2(g) – nitrogen dioxide is an acidic gas. It would turn moist blue litmus
paper red. It is also a reddish-brown gas.

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  SO2(g) – Sulphur dioxide is a reducing agent. If the gas is bubbled through
acidified potassium dichromate, it changes its colour from orange to green.
Sulphur dioxide also has an irritating smell.

 HCl(g) – this gas has an irritating smell. Exposing HCl(g) to ammonia gas
would form dense white fumes of ammonium chloride:
HCl(g) + NH3(g)  NH4Cl(g)

 NH3(g) – ammonia is a basic gas. It would therefore turn moist red litmus paper
blue. NH3(g) also has a pungent smell.

IDENTIFICATION OF ANIONS
Carbonates:

 Add an acid to the carbonate, so it releases CO2(g)

CO32-(aq) + 2H+(g)  CO2(g) + H2O(l)
 Then test for CO2(g) by bubbling through lime water. A white precipitate
would form.

Nitrates:

Nitrates can be tested for in 2 ways:

1. Warm with 2cm3 of conc. H2SO4. Then add some copper turnings:
Cu(s) + 2NO3-(aq) + 4H+(aq)  Cu2+(aq) + 2NO2(g) + 2H2O(l)
Brown fumes of NO2(g) can be observed. NO2(g) would also turn moist blue
litmus paper red.
2. Add NaOH(aq) followed by either zinc powder or aluminium powder:
NO3-(aq) + 4Zn(s) + 7OH-(aq)  6H2O(l) + NH3(g) + 4Zn(OH)42-(aq)
 Test for NH3(g) by holding moist red litmus paper over gas. It would turn
blue. Also NH3(g) has a pungent smell.

Sulphates:

 Add nitric acid to remove any contaminating anions that may be present.
 Then add BaCl2(aq) or Ba(NO3)2(aq):

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 Ba2+(aq) + SO42-(aq)  BaSO4(s) - a white precipitate forms

Sulphites:
1. If the sample is solid, then heat it. Test for SO2(g) by bubbling through acidified
potassium dichromate. It would turn from orange to green.
2. If the sample is in a solution, then add HCl(aq) and heat:
SO32-(aq) + 2H+(aq)  SO2(g) + H2O(l)
 Test for SO2(g) by bubbling through acidified potassium dichromate. It would
turn from orange to green.

Halides:

1. Add nitric acid to remove any contaminating anions that may be present. Then
add silver nitrate followed by aqueous ammonia:

 Cl-(aq) – a white precipitate forms:

Ag+(aq) + Cl-(aq)  AgCl(s)
White precipitate is soluble in aqueous ammonia:
AgCl(s) + 2NH3(aq)  [Ag(NH3)2]Cl(aq)

 Br-(aq) – a cream precipitate forms:

Ag+(aq) + Br-(aq)  AgBr(s)

Cream precipitate is slightly soluble in aqueous ammonia.

 I-(aq) – a yellow precipitate forms:

Ag+(aq) + I-(aq)  AgI(s)

Yellow precipitate is insoluble in aqueous ammonia.

2. Add nitric acid to remove any contaminating anions. Then add lead nitrate and
warm gently.

 Cl-(aq) – white precipitate forms which dissolves upon heating:

Pb2+(aq) + 2Cl-(aq)  PbCl2(s)

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  Br-(aq) – white/cream precipitate forms which dissolves upon heating:
Pb2+(aq) + 2Br-(aq)  PbBr2(s)

 I-(aq) – yellow precipitate forms which does not dissolve upon heating:
Pb2+(aq) + 2I-(aq)  PbI2(s)

Chromates:
 Add dilute sulphuric acid:
2CrO4-(aq) + 2H+(aq)  Cr2O72-(aq) + H2O(l)
Colour changes from yellow to orange.

 Add a drop of dilute hydrogen peroxide. A blue colour forms which quickly
turns green.