Qualitative Analysis

Qualitative analysis relies on observations rather than measurements, and is

often carried out simply on a test-tube scale. In this topic we will look at the
tests used to identify:
Carbonate ions,
CO32Sulphate ions,
SO42Halide ions,
Cl-, Br - and IAmmonium ions,
NH4+
It is necessary to avoid false positives caused by interfering ions, so it is
necessary to perform tests on unknown compounds in a sequence that
minimizes the chances of this. When testing an unknown substance that
contains one of these negatively-charged ions (anions), the sequence of tests
should be:
i) Test for carbonate ions
Test: Add dilute nitric acid to the solid unknown, or to a solution containing the
unknown.
Result: The absence of fizzing shows carbonate is not present. If fizzing is
seen, the gas being produced should be bubbled through limewater (calcium
hydroxide solution) to show that it is carbon dioxide: the limewater will turn
cloudy.
Ionic equation:
e.g. full equation:

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

2HNO3(aq) + Na2CO3(s) 2NaNO3(aq) + CO2(g) + H2O(l)

Limewater test:

Ca(OH)2(aq) + CO2(g) CaCO3(s) + H2O(l)

Interference:
Few other ions cause fizzing on the addition of an acid, although
hydrogencarbonate ions would also cause carbon dioxide to be produced.
Using nitric acid prevents ions being introduced that would interfere with
subsequent tests. Sulphuric acid would introduce sulphate ions, while
hydrochloric acid would introduce chloride ions.
ii) Test for sulphate ions
Test: add a solution containing barium ions, Ba2+(aq) to a solution containing
the unknown. Barium nitrate or barium chloride solution would be suitable.
Result: A white precipitate indicates the presence of sulphate ions, which
have reacted with the barium ions to form insoluble barium sulphate.
Ionic equation:

Ba2+(aq) + SO42-(aq) BaSO4(s)

Full equation: e.g. Na2SO4(aq) + Ba(NO3)2(aq) BaSO4(s) + 2NaNO3(aq)

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Interference:
Barium carbonate is also insoluble, and so the presence of carbonate ions
would interfere with this test and give a false positive. Before the test for
sulphate ions is carried out, carbonate ions should be removed by acidifying
the solution (which is what is done in the test for carbonate ions). It is
important that sulphuric acid is not used to do this, as sulphate ions will be
introduced giving a false positive result.
Barium chloride should not be used for this test if a test for halide ions is to be
performed subsequently, as chloride ions will be added.
iii) Test for halide ions
Test: add a solution containing silver ions to a solution containing the
unknown. Silver nitrate would normally be used.
Results: a precipitate of the silver halide is produced if silver ions are present.
The colour of the precipitate indicates which halide ion was in the unknown.
Chloride ions: white precipitate Ag+(aq) + Cl-(aq) AgCl(s)
Bromide ions: cream precipitate Ag+(aq) + Br -(aq) AgBr(s)
Iodide ions: yellow precipitate
Ag+(aq) + I-(aq) AgI(s)
Further test with ammonia
These colours can be difficult to tell apart as they are not very different, but a
further test can be used to tell the precipitates apart. This is based on
differences in their solubilty in ammonia:
Silver chloride precipitate
Silver bromide precipitate
Silver iodide precipitate

Soluble in dilute ammonia solution, NH3(aq)

Soluble in concentrated ammonia solution NH3(aq)
Insoluble in ammonia solution

Interference:
Note that both silver carbonate and silver sulphate are insoluble and so the
presence of sulphate ions or carbonate ions would interfere with this test
causing a false positive. It is therefore advisable to test for these ions first and
show that they are not present before performing the test for halide ions.
The use of hydrochloric acid in the test for carbonate ions, or the use of
barium chloride in the test for sulphate ions would introduce chloride ions
which would give a false positive result.
Testing a mixture of ions
It is possible that an unknown might contain more than one of these anions to
be identified.
1. Perform the test for carbonate ions by adding dilute nitric acid. Fizzing
indicates the presence of carbonate ions, and also destroys them,
removing them from the mixture. Nitric acid should be added until there is
no more fizzing, to ensure there is no remaining carbonate present.

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2. Perform the test for sulphate by adding barium nitrate solution to the
mixture left after the carbonate test. If sulphate is present, a white
precipitate will be formed. This can then be removed by filtering.
3. The tests for halide ions can be carried out by adding silver nitrate solution
to the solution remaining after filtering off any barium sulphate precipitate.
Colour, and the solubility in ammonia solution, can then be used to identify
which halide ion.
It is difficult to identify which halide ions are present in a mixture containing
two or more halide ions, and we are not required to be able to explain how
to do this.
iv) Test for ammonium ions
Identifying the presence of NH4+ ions in a salt, as opposed to metal ions,
requires no sequence of tests as there are no interfering ions.
Test:
Add a few drops of sodium hydroxide solution to a solution of the unknown,
and warm the mixture. Hold a piece of damp pink litmus paper, or universal
indicator paper, near the top of the tube.
Result:
If the pink litmus or the universal indicator paper turns blue, ammonia gas is
being given off, which has been formed from ammonium ions present in the
unknown.
Ionic equation:

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

e.g. full equation (NH4)2SO4(aq) + 2NaOH(aq) Na2SO4(aq) + 2NH3(g) + 2H2O(l)

The indicator paper must be damp so that the ammonia gas can dissolve on
the surface of the paper, forming an alkaline ammonium hydroxide solution. It
is the hydroxide ions that turn the pink litmus paper blue.
NH3(g) + H2O(l) NH4+(aq) + OH-(aq)
You may also be able to smell the distinctive sharp smell of ammonia gas
during this test.

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