Anion analysis

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Chloride Cl- Links

AgCl, PbCl2, Hg2Cl2 and CuCl are insoluble in water. Inorganic analysis
introduction
Concentrated sulphuric acid liberates steamy acidic fumes of Preliminary tests
HCl from solid chlorides: Cation analysis

NaCl(s) + H2SO4(l) " NaHSO4(s) + HCl(g)

Silver nitrate solution added to a solution of a chloride that has Ions

been acidified (test with blue litmus paper) with dilute nitric acid
gives a white precipitate of silver chloride. The precipitate is readily
soluble in dilute ammonia or in sodium thiosulphate solution: chloride
bromide
iodide
Ag+(aq) + Cl- (aq) " AgCl(s) sulphite
sulphate
AgCl(s) + 2NH3(aq) " [Ag(NH3)2]+(aq) + Cl- (aq) nitrate
carbonate
hydrogen carbonate
AgCl(s) + 2S2O32- (aq) " [Ag(S2O3)2]3- (aq) + Cl- (aq)
ethanoate
ethanedioate
Acidification with nitric acid is necessary to eliminate carbonate or chromate(VI)
sulphite, both of which interfere with the test by giving spurious dichromate(VI)
precipitates.

Concentrated solutions of sulphates can give a precipitate of silver

sulphate in this test; its appearance is wholly different from AgCl.
The latter is truly white; the sulphate is a pearly white, rather like
pearlescent nail varnish.

Bromide Br-

AgBr, PbBr2, Hg2Br2 and CuBr are insoluble in water.

Concentrated sulphuric acid gives a mixture of hydrogen

bromide, bromine and sulphur dioxide with solid bromides; the HBr
produced is oxidised by sulphuric acid. The mixture evolves
steamy brownish acidic fumes:

NaBr(s) + H2SO4(l) " NaHSO4(s) + HBr(g)

2HBr + H2SO4 " Br2 + SO2 + 2H2O

Silver nitrate solution added to a solution of a bromide that has

been acidified (test with blue litmus paper) with dilute nitric acid
gives a cream precipitate of silver bromide. The precipitate is
readily soluble in concentrated ammonia:

Ag+(aq) + Br- (aq) " AgBr(s)

AgBr(s) + 2NH3(aq) " [Ag(NH3)2]+(aq) + Br- (aq)

Acidification with nitric acid is necessary to eliminate carbonate or

sulphite, both of which interfere with the test by giving spurious
precipitates.

Oxidising agents oxidise bromide to bromine, which is yellow or

orange in aqueous solution. Bromine can be extracted from the
solution by shaking with an immiscible organic solvent, for
example hexane, the organic layer then turning orange.

A suitable oxidising agent is sodium chlorate(I); this is added to the

test solution, followed by a little dilute hydrochloric acid and a few
cm 3 of hexane:

OCl- (aq) + 2H+(aq) + 2Br- (aq) " Br2(aq) + Cl- (aq) + H2O(l)

Iodide I-

AgI, PbI2, Hg2I2 and CuI are insoluble in water.

Concentrated sulphuric acid gives a mixture of hydrogen

Concentrated sulphuric acid gives a mixture of hydrogen
iodide, iodine, hydrogen sulphide, sulphur and sulphur dioxide
when added to solid iodides; the HI produced is oxidised by
sulphuric acid. The mixture evolves purple acidic fumes, turns to a
brown slurry, and is a mess:

NaI(s) + H2SO4(l) " NaHSO4(s) + HI(g)

2HI + H2SO4 " I2 + SO2 + 2H2O

6HI + H2SO4 " 3I2 + S + 4H2O

8HI + H2SO4 " 4I2 + H2S + 4H2O

There are no state symbols in these equations because the

mixture is such a mess, and is more sulphuric acid than water.

Silver nitrate solution added to a solution of an iodide that has

been acidified (test with blue litmus paper) with dilute nitric acid
gives a yellow precipitate of silver iodide. The precipitate is
insoluble even in concentrated ammonia:

Ag+(aq) + I- (aq) " AgI(s)

Acidification with nitric acid is necessary to eliminate carbonate or

sulphite, both of which interfere with the test by giving spurious
precipitates.

Oxidising agents oxidise iodide to iodine, which is yellow or

orange in aqueous solution. Iodine can be extracted from the
solution by shaking with an immiscible organic solvent, for
example hexane, the organic layer then turning purple.

A suitable oxidising agent is sodium chlorate(I); this is added to the

test solution, followed by a little dilute hydrochloric acid and a few
cm 3 of hexane:

OCl- (aq) + 2H+(aq) + 2Ir- (aq) " I2(aq) + Cl- (aq) + H2O(l)

Lead ethanoate or lead nitrate solutions give a bright yellow

precipitate of lead(II) iodide with iodides:

Pb2+(aq) + 2I- (aq) " PbI2(s)

The colour of lead(II) iodide comes from interactions in the lattice;

dissolving the salt in boiling water gives a colourless solution which
deposits glittering yellow plates on cooling.

Solutions of copper(II) salts give a brown mixture containing

iodine and copper(I) iodide when added to solutions of iodides.
Addition of sodium thiosulphate solution decolourises the iodine
and leaves pinkish-cream copper(I) iodide as a precipitate.

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

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

This reaction is the basis for the volumetric estimation of copper;

the iodine liberated from a known amount of a copper(II) solution
is titrated with standard sodium thiosulphate solution.

Sulphite SO 32-

Sulphurous acid is considerably stronger than carbonic acid, so

sulphites do not give the effervescence that is characteristic of
carbonates when dilute acid is added.

Dilute hydrochloric acid on warming with a sulphite evolves

sulphur dioxide; this turns acidified potassium dichromate(VI)
solution (or paper) green:

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

Barium chloride solution gives a white precipitate of barium

sulphite; addition of dilute hydrochloric acid causes the precipitate
to dissolve without effervescence:

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

Sulphate SO 42-

BaSO4, SrSO4 and PbSO4 are insoluble; CaSO4 is sparingly soluble.

Barium chloride solution added to the test solution acidified with

Barium chloride solution added to the test solution acidified with
dilute hydrochloric acid gives a white precipitate of barium
sulphate:

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

HSO4- does the same thing with barium ions; however the original
test solution would then be very acidic, so that should be tested for.

The addition of HCl destroys any carbonate or sulphite ions present

so prevents the spurious positive result due to the precipitation of
these barium salts. Barium nitrate solution can be used instead of
barium chloride.

18.2 Lead ethanoate solution gives a precipitate of white lead

sulphate:

Pb2+(aq) + SO42- (aq) " PbSO4(s)

Nitrate NO 3-

Since all nitrates are water soluble, there is no precipitation

reaction for this ion.

Solid nitrates decompose on heating; those of group 1

(except Li) give the nitrite and oxygen;

2NaNO3(s) " 2NaNO2(s) + O2(g)

All others give the metal oxide, nitrogen dioxide, and oxygen. A
brown gas is emitted that re-lights a glowing splint:

2Pb(NO3)2(s) " 2PbO(s) + O2(g) + 2NO2(g)

Nitrate ions are reduced to ammonia by boiling with aluminium

or with Devardas Alloy in sodium hydroxide solution. Devardas
Alloy contains aluminium, zinc and copper. Since ammonium ions
also give ammonia with NaOH, the test solution must be boiled with
NaOH and the vapour tested for ammonia; if present heating must
continue until all the ammonia has gone. The mixture is then
cooled, Devardas Alloy (or a piece of aluminium foil) added, and
the mixture re-heated. A gas that turns moist red litmus paper blue
indicates nitrate in the original solution:

3NO3- (aq) + 8Al(s) + 18H2O(l) + 21 OH- (aq) " 8[Al(OH)6]3- (aq) +

3NH3(g)

Not an equation to be remembered!

Carbonate CO 32-

Only the alkali metal and ammonium carbonates are water soluble.
Some carbonates (e.g. zinc, copper(II)) are basic carbonates and
contain a proportion of the hydroxide in their structure.

Heating decomposes all but the alkali and alkaline earth metal
carbonates (at Bunsen temperatures) giving the oxide and carbon
dioxide:

CuCO3(s) " CuO(s) + CO2(g)

Dilute hydrochloric acid gives vigorous effervescence with

carbonates, evolving carbon dioxide:

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

Bicarbonates also give this effervescence. The reaction of

carbonates with acid is exothermic; bicarbonates react
endothermically.

Hydrogen carbonate (bicarbonate) HCO 3-

Only the alkali metal and ammonium bicarbonates are obtainable

as solids; group 2 bicarbonates exist only in solution.

Calcium chloride solution on addition to a bicarbonate solution

gives no precipitate since calcium bicarbonate is soluble; this
distinguishes it from carbonate, which does give a precipitate. On
heating the calcium chloride/bicarbonate mixture a white
precipitate appears since the bicarbonate decomposes to
precipitate appears since the bicarbonate decomposes to
carbonate:

Ca2+(aq) + 2HCO3- (aq) " CaCO3(s) + CO2(g) + H2O(l)

Ethanoate CH3COO -

Ethanoates on heating with dilute hydrochloric acid give ethanoic

acid, recognisable by its vinegary smell.

Neutral iron(III) chloride solution added to neutral solutions of

ethanoate ion give a deep red colouration owing to formation of
iron(III) ethanoate.

Ethanedioate C2O 42-

Concentrated sulphuric acid added to a solid ethanedioate salt

gives a mixture of carbon monoxide and carbon dioxide from
dehydration of the ethanedioic acid formed:

HOOC-COOH " H2O + CO2 + CO

Potassium manganate(VII) solution acidified with dilute

sulphuric acid added to a solution of an ethanedioate causes the
purple colour to disappear:

2MnO4- (aq) + 5C2O42- (aq) + 16H+(aq) " 2Mn2+(aq) + 10CO2(g) +

8H2O(l)

Calcium chloride solution added to a solution of an ethanedioate

gives a white precipitate of calcium ethanedioate:

Ca2+(aq) + C2O42- (aq) " CaC2O4(s)

The precipitate dissolves readily in dilute hydrochloric acid.

Chromate(VI) CrO 42- and dichromate(VI)

Cr2O 72-

These ions are related through the equilibrium

Cr2O72- (aq) + 2OH- (aq) D 2CrO42- (aq) + H2O(l)

In alkaline solution the yellow chromate(VI) dominates, in acidic

solution orange dichromate(VI). All dichromate(VI) salts are
soluble; addition of dichromate(VI) ions to solutions of ions of
metals which have insoluble chromate(VI) salts leads to the
precipitation of chromates. This means that the only dichromates
that can exist are those of group 1 metals, ammonium,
magnesium, calcium and strontium.

Barium chloride solution added to a chromate(VI) or

dichromate(VI) solution precipitates bright yellow barium
chromate(VI):

Ba2+(aq) + CrO42- (aq) " BaCrO4(s)

The addition of a heavy metal ion to potassium dichromate

solution precipitates the chromate and therefore moves the
equilibrium to the right hand side. If the chromate is sparingly
soluble (e.g. strontium) the supernatant liquid will remain yellow.
Very insoluble chromates, such as lead, remove all the colour
from the supernatant liquid.

Dichromate(VI) ion solution in sulphuric acid is an

oxidising agent; oxidation is shown by the solution turning from
orange to green (Cr(III)). The following can be oxidised:

(a) iron(II) to iron(III):

Cr2O72- (aq) + 14H+(aq) + 6Fe2+(aq) " 2Cr3+(aq) + 7H2O(l) +

6Fe3+(aq)

(b) iodide to iodine (the solution turns murky greenish-brown):

Cr2O72- (aq) + 14H+(aq) + 6I- (aq) " 2Cr3+(aq) + 7H2O(aq) +

3I2(aq)

(c) sulphite to sulphate:

 Cr2O72- (aq) + 8H+(aq) + 3SO32- (aq) " 2Cr3+(aq) + 4H2O(l) +
3SO42- (aq)

(d) nitrite to nitrate:

Cr2O72- (aq) + 8H+(aq) + 3NO2- (aq) " 2Cr3+(aq) + 4H2O(l) +

3NO3- (aq)

(e) hydrogen peroxide reacts with acidified dichromate(VI)

solutions to give a blue compound that rapidly turns green and
evolves oxygen. The blue compound can be extracted into an
organic solvent such as butan-1-ol. The blue compound is
CrO5, which contains a peroxy structure. It is covalent, and is
stable in organic solvents though not in water.

Cr2O72- (aq) + 8H+(aq) + 3H2O2 (aq) " 2Cr3+(aq) + 7H2O(l) + 3

O2(g)

Alcohols are oxidised by acidified potassium dichromate(VI)

solution. Primary alcohols give aldehydes and then acids,
secondary alcohols give ketones. Ethanol can be used to test for
dichromate(VI) ions, therefore, the solution turning green and the
apple smell of ethanal being evident.

JRG Beavon 2007