QUALITATIVE ANALYSIS NOTES

It will be assumed that candidates will be familiar with

(i)the reactions of the following cations:
NH4+; Mg2+; Al3+; Ca2+; Cr3+; Mn2+; Fe2+; Fe3+; Cu2+; Zn2+; Ba2+;

(ii)the reactions of the following anions:

CO3 ; NO3 ; NO2 ; SO4 ; SO3 ; Cl ; Br ;
2– – – 2– 2– – – I– ;

(iii)tests for the following gases: NH3; CO2; Cl2; H2; O2; SO2,
as detailed in the qualitative analysis notes which will be included with the
question paper and are reproduced at the end of the section.

The substances to be investigated may contain ions not included in the above list:
in such cases, candidates will not be expected to identify the ions but only to draw
conclusions of a general nature.
1 SALT ANALYSIS THEORY
 SOME DOS AND DON’TS
1. Appearance of filtrates should be always described.
2. Do not use the words ‘cloudy’, ‘milky’, ‘creamy’, ‘muddy’ or ‘buff’ to describe
precipitates. Do not mention the ‘texture’ of precipitates.
3. Do not use the word ‘clear’ to describe colourless solutions.
4. There are no black solutions or white solutions! DO NOT describe white
precipitate described as a white solution or a cloudy solution. The appearance
of a white colour throughout the solution indicates the formation of a fine
white precipitate that is held in suspension.
5. When an acid is added to the sample and no visible change occurs record in
the observation column “no gas evolved / no precipitate formed”

2 SALT ANALYSIS THEORY

 SOME DOS AND DONTS
6. If the solution is already coloured, any precipitate formed should be allowed to
settle down before recording the colour of the precipitate.
7. Two reagents added together to the sample may react to give an observation,
which has nothing to do with the sample given. While testing for nitrate addition
of aluminium powder and sodium hydroxide will liberate hydrogen irrespective
of whether nitrate is present or not. This is an irrelevant observation. Identifying
the presence of ammonia should be the main concern and not the liberation of
any (or hydrogen) gas.
8. Reagents should be added drop-wise. If not proper observations cannot be
made.
9. If a reaction is exothermic – warming of the tube – report it

3 SALT ANALYSIS THEORY

 HALIDES: Cl ,
– Br , I
– –

Test 1 - Reagents Ag+(aq) [AgNO3] followed by NH3(aq)

gives white ppt. with Ag+ (aq)

Cl –
soluble in NH3 (aq) ;

–
gives cream ppt. with Ag+ (aq)
Br
partially soluble in NH3 (aq);

gives yellow ppt. with Ag+(aq)

I –
insoluble in NH3 (aq);

4 SALT ANALYSIS THEORY

 SULFATE AND SULFITE (SO4 2–, SO3 2–)

Test 1 - Reagents Ba2+(aq) followed by H+(aq)

BaCl2 (aq) followed by dil. HCl or Ba(NO3)2 (aq) followed by dil. HNO3

gives white ppt. with Ba2+ (aq)

SO42–
insoluble in H+ (aq) ;

gives white ppt. with Ba2+ (aq)

SO32–
soluble in H+ (aq);

Note: a white ppt. might appear coloured if its masked by a coloured solution (due
to a transitional metal ion).

5 SALT ANALYSIS THEORY

 SULFATE AND SULFITE (SO4 2–, SO32–)

In the case of a coloured solution the ppt. must either be filtered to be

observed.

Alternatively, the mixture can be decanted or the ppt. allowed to settle

before its colour is observed.

Other tests:

Sulfite (SO32–) gives a pungent gas when an acid is added.

Sulfates (SO42–) also give a white ppt with Pb2+

6 SALT ANALYSIS THEORY

 NITRATE AND NITRITE (NO3 NO2 –, –)

Both give off NH3 gas when warmed with Al and NaOH.
(reduction of NO2–, NO3– to NH3)

NO2– gives brown gas when an acid is added

(smells bleachy)

7 SALT ANALYSIS THEORY

 CO3 2–

Mostly will be supplied as a solid

The only anion in the list that gives an effervescence with dil. Acids

CO32 – + 2H+ → CO2 + H2O

8 SALT ANALYSIS THEORY

 Cu 2+

Reagent Observation

blue ppt.
NaOH
insoluble in excess

pale blue ppt. soluble in excess

NH3
giving dark blue solution

9 SALT ANALYSIS THEORY

 Cr 3+

Reagent Observation

grey-green ppt.
NaOH soluble in excess
giving dark green solution

grey-green ppt.
NH3
insoluble in excess

10 SALT ANALYSIS THEORY

 GROUP 2 - Mg ,
2+ Ca ,
2+ Ba2+

The solubility of the hydroxides increases down the group

• Mg(OH) 2 is a white solid insoluble in both NaOH (aq) and NH3 (aq)

• Ca(OH) 2 is a white solid insoluble in NaOH (aq) but soluble in NH3 (aq)

• Ba(OH) 2 is a white solid soluble in both NaOH (aq) and NH3 (aq)

11 SALT ANALYSIS THEORY

 GROUP 2 - Mg ,
2+ Ca ,
2+ Ba2+

NaOH (aq) is a strong base and hence has a very high concentration of OH– ions

While NH3 (aq) is a weak base and hence has a low concentration of OH– ions

• Mg(OH) 2 being least soluble forms a ppt. with both.

• Ba(OH) 2 being most soluble does not form a ppt. with either.

• Ca(OH) 2 sometimes will form ppt. if the concentration of the two bases are high.

12 SALT ANALYSIS THEORY

 Al3+ Zn 2+

Observation with
Reagent
Al3+ Zn2+

white ppt. white ppt.

NaOH
soluble in excess soluble in excess

white ppt. white ppt.

NH3
insoluble in excess soluble in excess

13 SALT ANALYSIS THEORY

 AMMONIUM - NH4 +

• The only cation to give NH3 gas (pungent) on warming with strong alkalis
NH4+ + OH- → NH3 + H2O

•Forms no ppt.

14 SALT ANALYSIS THEORY

 Fe 2+ Fe 3+

Reagent Fe2+ Fe3+

green ppt. turning brown

red-brown ppt.
NaOH on contact with air
insoluble in excess
insoluble in excess

green ppt. turning brown

red-brown ppt.
NH3 on contact with air
insoluble in excess
insoluble in excess

15 SALT ANALYSIS THEORY

 Fe 2+ Fe 3+

Fe2+ can be oxidised to Fe3+ on contact with air.

Hence the green Fe(OH)2 turns brown Fe(OH)3 on standing due to oxidation with
the oxygen in air.

Fe(OH)2 → Fe(OH)3
+2 +3
green red-brown

16 SALT ANALYSIS THEORY

 Mn 2+

Reagent Observation

off-white ppt. rapidly turning

NaOH brown on contact with air
insoluble in excess

off-white ppt. rapidly turning

NH3 brown on contact with air
insoluble in excess

17 SALT ANALYSIS THEORY

 Mn 2+

Mn2+ can be oxidised to Mn3+ on contact with air.

Hence the white/off-white Mn(OH)2 turns brown Mn(OH)3 (Mn3+) on standing due
to oxidation with the oxygen in air.

Mn(OH)2 → Mn(OH)3
+2 +3
off-white brown

Heating it more will oxidise it to MnO2 (Mn: +4 oxidation state)

18 SALT ANALYSIS THEORY

 GAS TESTS
GAS TEST & TEST RESULT

ammonia, NH3 turns damp red litmus paper blue

carbon dioxide, CO2 gives a white ppt. with limewater (ppt. dissolves with excess CO2)

chlorine, Cl2 bleaches damp litmus paper

hydrogen, H2 pops’ with a lighted splint

oxygen, O2 relights a glowing splint

19 SALT ANALYSIS THEORY