173

Chapter 18
Qualitative inorganic analysis
Learning objectives
■ Describe tests to identify specified anions, cations and gases.
■ Explain the basis of each test.
■ Interpret the results of reported tests.

Introducing inorganic analysis Identification of cations

Qualitative inorganic analysis seeks to identify the
elements found within inorganic compounds through the
use of various reagents. The primary focus in this chapter
is identifying ions in aqueous solutions. The general
procedure is that the unknown solution, when treated
with a certain reagent, is converted into a new compound
that has a characteristic and diagnostic colour, solubility or
other visible change. Reagents should be added gradually
until no further change is observed. Some reactions
liberate gases and confirmatory tests for these gases should
be performed.
You are required to know how to test for and identify the
ions and gases listed in Table 18.1.
Cations are usually identified using two main reagents:
aqueous sodium hydroxide and aqueous ammonia (Table
18.2).
In some instances, aqueous sodium carbonate is used
as a reagent to precipitate insoluble carbonates. A white
precipitate is produced in all instances of cations listed in
Table 18.2, except for Cr3+ (green), Mn2+ (pink), Fe2+ (green),
Fe3+ (brown) and Cu2+ (blue). NH3(g) is evolved with NH4+.
The precipitates are formed during the general reaction:
Mn+(aq) + nOH−(aq) → M(OH)n(s)
where ‘M’ represents the metal atom and ‘n’ represents the
size of the charge on the cation.

Table 18.1 Cations, anions Table 18.2 Summary of reactions of cations with NaOH(aq) and NH3(aq)
and gases to be identified
Reaction with NaOH(aq) Reaction with NH3(aq)
Cations Anions Gases Mg2+ white ppt; insoluble in excess NaOH(aq) white ppt; insoluble in excess NH3(aq)
Mg2+ CO32− CO2 Ca2+ white ppt; insoluble in excess NaOH(aq) no reaction
Al3+ NO3− H2 Ba2+ white ppt from concentrated solutions only no reaction
Ca2+ SO42− HCl Al3+ white ppt; soluble in excess NaOH(aq) to form the complex Al(OH)4−(aq) white ppt; sparingly soluble in excess NH3(aq)
Cr3+ SO32− H2S Pb2+ white ppt; soluble in excess NaOH(aq) to form the complex Pb(OH)42−(aq) white ppt; insoluble in excess NH3(aq)
Mn2+ Cl− NH3 grey-green ppt; soluble in excess NaOH(aq) to give a dark green solution
Cr3+ grey-green ppt; insoluble in excess NH3(aq)
Fe2+ Br− NO2 containing Cr(OH)4−(aq)
white ppt which rapidly turns light brown;
Fe3+ I− O2 Mn2+ white ppt which rapidly turns light brown; insoluble in excess NaOH(aq)
insoluble in excess NH3(aq)
Cu2+ CrO42− SO2 dirty green ppt which changes to brown in air; insoluble in excess dirty green ppt which changes to brown in
Fe2+
Zn 2+
Cl2 NaOH(aq) air; insoluble in excess NH3(aq)
Ba2+ Br2 / HBr Fe3+ red-brown ppt; insoluble in excess NaOH(aq) red-brown ppt; insoluble in excess NH3(aq)
Pb2+ I2 pale blue ppt soluble in excess NH3(aq) to
pale blue ppt; insoluble in excess NaOH(aq); ppt turns black on heating
Cu2+ give a deep-blue solution containing the
NH4+ Cu(OH)2(s) → CuO(s) + H2O(l)
complex ion Cu(NH3)42+(aq)
white ppt; soluble in excess NaOH(aq) to form the complex ion white ppt; soluble in excess NH3(aq) to form
Zn2+
[Zn(OH)4]2−(aq) the complex ion [Zn(NH)3]42+(aq)
solution remains colourless; on heating, pungent colourless ammonia
NH4+ gas evolved which turns moist red litmus blue –
NH4+(aq) + OH− → NH3(g) + H2O(l)
’ppt’ is used as the abbreviation for precipitate; Al3+ can be distinguish from Pb2+ by the insolubility of the lead(II) halides or the
flame test.
174 Unit 1 Module 3 Chemistry of the elements

The information in Table 18.2 add NaOH(aq) add excess

is also provided in the form white
drop by drop NaOH(aq)
precipitate
of flow charts in Figures 18.1 does not
dissolve Ca2+
and 18.2. You can follow these Cation in white precipitate
yellow
aqueous possibly
flow charts when detecting solution Zn2+, Pb 2+, Ca2+, Al 3+
precipitate
possibly Pb 2+
cations. precipitate
no
blue precipitate dissolves
precipitate
Cu2+ possibly
Flame tests Zn2+, Pb2+ or Al 3+
Zn2+
no precipitate
red-brown add Kl(aq) to a possibly
When some metal ions precipitate Zn 2+ , Al 3+
fresh sample
Fe 3+
are heated in a colourless of solution white
flame, the ions become precipitate
add excess NH3(aq)
green precipitate Al 3+
excited causing them to darkening in colour no smell of to a fresh sample
on standing Fe2+ ammonia of solution
emit visible light. This light +
Na or K
+

emission is responsible for no precipitate

the characteristic colour that possibly
+ + +
NH4 , Na , K
the respective ion turns the
smell of ammonia,
flame. Therefore, burning a add excess red litmus turns
+
NaOH(aq) then heat blue NH4
substance in a flame test is
a technique used to visually
determine the presence of Figure 18.1 Tests for cations using aqueous sodium hydroxide.
certain metal ions.
add NH3(aq) add excess
The procedure for performing drop by drop NH3(aq) and stir
white
precipitate does yellow
a flame test is as follows: not dissolve precipitate Pb 2+
Pb 2+ or Al 3+
Cation in white precipitate
■ clean a platinum wire by
aqueous possibly
dipping it repeatedly into solution Zn2+, Pb 2+, Al 3+ white precipitate
soluble in add excess Kl(aq)
conc. hydrochloric acid excess to a fresh sample
blue precipitate NH3(aq) Zn2+ of solution
and heating it until the possibly Cu 2+
flame remains colourless precipitate
add excess
(alternatives to platinum NH3(aq) and stir dissolves to give
a deep blue
wire include wooden red-brown solution Cu 2+
splints and the tip of a lead precipitate
possibly Fe3+
pencil); precipitate does
not dissolve
■ dip the end of the wire green precipitate
Fe 3+

into the acid and then into possibly Fe 2+

precipitate does
the sample of the element not dissolve but
no precipitate darkens on
or compound to be tested; Ca 2+, NH4+, Na+ , K + exposure to air
■ heat the wire in the Fe 2+
add excess
colourless flame and NH3(aq) and stir
observe any flame colour
which is produced. Figure 18.2 Tests for cations using aqueous ammonia.

ITQ 1
(a) State what is observed when aqueous ammonia is added
drop-wise to a solution of copper(II) nitrate until the ammonia
is present in excess.
(b) Write a balanced equation to represent the overall reaction.
ITQ 2
(a) Using NaOH(aq) and NH3(aq) only, describe how these
reagents can be used to distinguish between Ca2+(aq),
Zn2+(aq) and Al3+(aq) ions.
(b) Write balanced equations to represent the reactions between:
(i) Ca2+(aq) and NaOH(aq)
(ii) Al3+(aq) with excess ammonia solution
 Chapter 18 Qualitative inorganic analysis 175

Sodium is a contaminant in many compounds and its Nitrate(V), NO3−

spectrum tends to dominate over others. To alleviate this
Four tests are available.
problem, flame colours are often viewed through cobalt
blue glass to filter out the yellow flame colour of sodium ■ Add conc. H2SO4: on warming, HNO3(g) and red-
and hence allow for easier viewing of other metal ions. brown NO2(g) are given off. The HNO3(g) formed
Some characteristic flame colorations are given in Table undergoes thermal decomposition to produce NO2(g)
18.3. and O2(g).
Table 18.3 Flame tests NO3−(s) + H2SO4(l) → HNO3(g) + HSO4−(aq)
Colour of flame Illustration of colour Inference 4HNO3(g) → 2H2O(l) + 4NO2(g) + O2(g)
lilac (purple through blue K+
■ Add conc. H2SO4 in the presence of Cu: NO2(g) and
glass)
HNO3(g) are liberated. The HNO3(g) reacts with Cu to
produce NO2(g) and the resulting solution is green-
blue in colour due to the presence of Cu2+(aq) ions.
bright yellow (invisible Na+
through blue glass) 4HNO3(g) + Cu(s) → Cu(NO3)2(aq) + 2NO2(g) + 2H2O(l)
■ Add powdered Al or Zn (reducing agents) and
NaOH(aq): on heating, NH3(g) is given off. The
brick-red Ca2+ NO3−(aq) ions are reduced by Al/Zn.
NO3−(s) + 3Al(s) + 3OH−(aq) + 6H2O(l) →
3[Al(OH)4]−(aq) + NH3(g)

yellow-green Ba2+ NO3−(s) + 4Zn(s) + 7OH−(aq) + 6H2O(l) →

4[Zn(OH)4]2−(aq) + NH3(g)
■ Add iron(II) sulfate and conc. H2SO4: crystals of FeSO4
are mixed with the nitrate solution and then conc.
blue-green Cu2+ H2SO4 is gently added to the mixture such that the
H2SO4 forms a layer above the aqueous solution. A
brown ring forms at the junction of the two liquids
owing to the presence of Fe(NO)SO4; this test is
known as the brown ring test. The NO3− ion is reduced
Identification of anions by iron(II) which is oxidized to iron(III) and forms a
nitrosyl complex.
We shall now describe the reactions of some anions with
NO3−(aq) + 3Fe2+(s) + 4H+(aq) →
different reagents.
NO(g) + 3Fe3+(aq) + 2H2O(l)
Carbonates, CO32− NO(g) + FeSO4(s) → Fe(NO)SO4(s)
Two tests are available.
Sulfate(VI), SO42−
■ Add dilute HCl or conc. H2SO4: CO2(g) is liberated with
Two tests are available.
effervescence. Carbonates of the cations Pb2+, Ca2+ and
Ba2+ do not react with H2SO4 as these cations form ■ Add Ba2+(aq)/H+(aq): a white precipitate of BaSO4(s) is
insoluble sulfates. formed. It is soluble in warm conc. HCl.
CO32−(s) + 2H+(aq) → H2O(l) + CO2(g) Ba2+(aq) + SO42−(aq) → BaSO4(s)
■ Add Ba2+(aq) or Ca2+(aq) followed by dilute acid: a This test is carried out in an acidified medium to
white precipitate of BaCO3(s) or CaCO3(s) is formed. inhibit the precipitation of carbonate and sulfate(IV)
The precipitate is soluble in dilute acid with the (sulfite).
liberation of CO2(g). ■ Add Pb2+(aq): a white precipitate of PbSO4(s) is formed
M2+(aq) + CO32−(aq) → MCO3(s) which is soluble in hot conc. H2SO4.
Ba2+ ions can be obtained from BaCl2(aq) and Pb2+(aq) + SO42−(aq) → PbSO4(s)
Ba(NO3)2(aq); Ca2+ ions can be obtained from CaCl2(aq). Pb2+ ions can be obtained from lead(II) ethanoate.
176 Unit 1 Module 3 Chemistry of the elements

Sulfate(IV) (sulfite), SO32− Iodides, I−

Three tests are available Three tests are available.
■ Add dilute HCl or conc. H2SO4: SO2(g) is evolved on ■ Add AgNO3(aq) followed by NH3(aq): a yellow or
warming. cream precipitate of AgI(s) is formed which is insoluble
SO32−(aq) + 2H (aq) → SO2(g) + H2O(l)
+ in NH3.
■ Add Ba2+(aq): a white precipitate of BaSO3(s) is
Ag+(aq) + I−(aq) → AgI(s)
formed which is readily soluble in dilute HCl with the ■ Add conc. H2SO4: iodine is formed as a black or violet
liberation of SO2(g). precipitate. On warming, violet vapours of iodine are
2+
Ba (aq) + SO32−(aq) → BaSO3(s) evolved. HI is initially formed, but is oxidized to iodine.
■ Add AgNO3(aq): a white precipitate of Ag2SO3(s) is
H2SO4(l) + I−(s) → HI(g) + HSO4−(aq)
formed which turns from grey to black on warming as 2HI(g) + [O] → I2(s) + H2O(l)
a result of the decomposition to silver. ■ Add Pb2+(aq): a yellow precipitate of PbI2(s) is formed
+
2Ag (aq) + SO32−(aq) → Ag2SO3(s) which is soluble in excess of the iodide solution.
Pb2+(aq) + 2I−(aq) → PbI2(s)
Chlorides, Cl−
PbI2(s) + 2I−(aq) → [PbI4]2−(aq)
Three tests are available
■ Add AgNO3(aq) followed by NH3(aq): a white Chromate(VI), CrO42−
precipitate of AgCl(s) is formed which is soluble in NH3 Three tests are available.
to form Ag(NH3)2+(aq).
■ Add AgNO3(aq): a red-brown precipitate of Ag2CrO4(s)
Ag+(aq) + Cl−(aq) → AgCl(s)
is formed which is soluble in NH3.
■ Add conc. H2SO4: the pungent, colourless hydrogen
2Ag+(aq) + CrO42−(aq) → Ag2CrO4(s)
chloride gas is evolved.
■ Add Ba2+(aq): a pale yellow precipitate of BaCrO4(s) is
H2SO4(l) + Cl−(s) → HCl(g) + HSO4−(aq)
formed which is soluble in strong acids.
■ Add Pb2+(aq): a white precipitate of PbCl2(s) is formed
Ba2+(aq) + CrO42−(aq) → BaCrO4(s)
which dissolves on heating and re-precipitates on
cooling. ■ Add Pb2+(aq): a yellow precipitate of PbCrO4(s) is
formed.
Pb2+(aq) + 2Cl−(aq) → PbCl2(s)
Pb2+(aq) + CrO42−(aq) → PbCrO4(s)
Bromides, Br−
Flow charts
Three tests are available
The identification of anions is provided in a different form
■ Add AgNO3(aq) followed by NH3(aq): a white or cream
in Figures 18.3–18.6.
precipitate of AgBr(s) is formed which is partially
soluble in NH3.
Ag+(aq) + Br−(aq) → AgBr(s)
■ Add conc. H2SO4: red-brown vapours of Br2(g) and ITQ 3 Two solutions, labelled X and Y, contain either chloride
HBr(g) are seen. The HBr(g) that is formed is oxidized or bromide ions. Describe how AgNO3 followed by NH3(aq) can
to Br2(g). be used to identify the ion in each solution. Write the balanced
equations for the reactions occurring.
H2SO4(l) + Br−(s) → HBr(g) + HSO4−(aq)
■ Add Pb2+(aq): a white precipitate of PbBr2(s) is formed.
ITQ 4
This precipitate dissolves on heating and re-precipitates
(a) Describe what you would see when an aqueous solution of
on cooling. silver nitrate is added to a solution containing iodide ions
Pb2+(aq) + 2Br−(aq) → PbBr2(s) followed by aqueous ammonia.
(b) Write balanced equations for the reactions occurring in part (a).
(c) List and explain the observations when conc. H2SO4 is added
to solid potassium iodide.
 Chapter 18 Qualitative inorganic analysis 177

heat the solid: is gas given off?

no
gas
Cl
– –
Br I
– 2–
SO4 Testing for gases
As we have seen in several of the reactions encountered,
CO2 SO2 NO2 O2
gases can be produced in some tests. Confirmatory tests for
these gases should be performed when they are generated
CO32– SO32– NO3– (Na + )NO3–
in the test. When a gas needs to be tested with materials
Figure 18.3 Testing for anions; heating the solid. such as moist litmus paper and splints, the material should
be placed at the mouth of the test tube where the gas is
escaping.
dilute acid on the solid: is gas given off?

Carbon dioxide, CO2

CO2 SO2
■ Colourless, odourless.
■ When bubbled through lime water (Ca(OH)2(aq)), the
CO32– SO32–
mixture turns milky. The milky appearance is due to
Figure 18.4 Testing for anions; adding dilute acid. the formation of a solid precipitate of CaCO3.
Ca(OH)2(aq) + CO2(g) → CaCO3(s) + H2O(l)
acidified (HNO3) aqueous silver nitrate with
a solution of the sample Hydrogen, H2
■ Colourless, odourless.
white cream yellow
precipitate precipitate precipitate ■ ‘Pops’ with lighted splint or may burn with a blue
darkens in
the light flame. H2(g) is recognized by the ‘pop’ when it burns.
This ‘pop’ is the sound of a small explosion since H2 is
Cl – Br – I– extremely flammable.
Figure 18.5 Testing for anions; adding AgNO3(aq)/H+(aq).
Hydrogen chloride, HCl
■ Colourless, pungent.
acidified (HCl) aqueous barium chloride with
a solution of the sample
■ HCl(g) is an acidic gas; it dissolves in water to form
hydrochloric acid, HCl(aq).
white precipitate
■ Fumes in moist air; turns moist blue litmus red; fumes
with NH3(g). The fumes are due to the formation of
2–
NH4Cl.
SO4
HCl(g) + NH3(g) → NH4Cl(g)
Figure 18.6 Testing for anions; adding BaCl2(aq)/H+(aq).
Hydrogen sulfide, H2S
■ Colourless, odour of rotten eggs.
■ Turns Pb2+ ions black due to the formation of PbS.

ITQ 5 Ammonia, NH3

Two calcium salts D and G were heated and the following results ■ Colourless, pungent.
were obtained:
■ Turns moist red litmus blue; fumes with HCl(g).
Compound D decomposed to give a gas which formed a white
ppt when bubbled into Ca(OH)2(aq). ■ Ammonia is an alkaline gas.
Compound G decomposed to give two gases. One was brown
and turned blue litmus red and the other rekindled a glowing Nitrogen dioxide, NO2
splint. ■ Red-brown, pungent.
(a) Identify the gases evolved in heating compounds D and G.
■ Turns moist blue litmus red.
(b) Deduce the molecular formulae of D and G.
178 Unit 1 Module 3 Chemistry of the elements

Oxygen, O2
■ Colourless, odourless.
■ Relights a glowing splint.
■ Oxygen is the only gas which supports burning and
hence will relight a glowing splint.

Sulfur dioxide, SO2

■ Colourless, choking odour.
■ Turns moist blue litmus red.
■ Turns KMnO4/H+ colourless.
■ Turns K2Cr2O7/H+ green.
■ SO2(g) is an acidic, reducing gas.

Chlorine, Cl2
■ Pale yellow-green, pungent, choking odour.
■ Bleaches moist blue litmus.
■ Cl2(g) has a bleaching effect.

Bromine, Br2/HBr
■ Red-brown, pungent.
■ Moist blue litmus turns red then bleached; fumes in
moist air.
■ Br2(g) has a bleaching effect.

Iodine, I2
■ Violet-black solid and violet vapours.
■ Bleaches moist litmus.
■ Turns starch/iodide paper blue-black.