QUALITATIVE ANALYSIS FOR CAPE CHEMISTRY

QUALITATIVE ANALYSIS
The primary objective of qualitative analysis is the identification of the constituents of a substance, be it a single solid or a mixture of
solid substances, a solution, a gas or a mixture of gases. This identification usually involves the conversion of the unknown into some
other compound which can be identified by its known characteristic properties. For example an unknown compound can identified as
being a sulphate if it produces, on reaction with a mixture of barium chloride solution and hydrochloric acid, a white precipitate. The
reactions carried out are called tests.
Tests may be divided into preliminary and confirmatory. Preliminary gives an indication of what may be present where as confirmatory
as the name suggests, confirms what was indicated to be present.
Preliminary Tests
Some preliminary tests are listed below:
NB. Some preliminary tests may serve as confirmatory tests.
(1) Appearance
Note the colour
Appearance

Deductions

White solid or colourless solution

Probable absence of transition elements

Coloured solid or coloured solution

Probable presence of transition elements

Black solid

Probable presence of a sulphide or oxide

Text Frank Weise, 2009. All rights reserved.

QUALITATIVE ANALYSIS FOR CAPE CHEMISTRY

2

Some characteristic colours of aqueous solutions of ions containing transition elements:

Ion

Colour

Cr3+(aq)

Green, blue green or pale violet

CrO42-(aq)

yellow

Cr2O72-(aq)

orange

Cu2+(aq)

Blue, blue green or green

Fe2+(aq)

Pale green, pale blue green

Fe3+(aq)

Yellow brown, brown

Mn2+(aq)

Very pale pink

Ni2+(aq)

green

Text Frank Weise, 2009. All rights reserved.

QUALITATIVE ANALYSIS FOR CAPE CHEMISTRY

3

The underlined are the more common colours.

(2) Flame Tests
Flame tests are carried out using nichrome wire ( cleaned with conc. HCl ). It identifies the presence of cations.
The cleaned wire is dipped into the solid sample, then placed in the flame. A characteristic colour of the flame is observed. Some
are listed in the table below:

Cation

Colour of Flame

Cu2+

Bright green

Na+

yellow

Ca2+

Brick red

Ba2+

Yellow green

K+

lilac

(3) Action of Heat ( on solids )

Observation(s)

Inference(s)

Liquid (water) condenses at top of tube which either turns

Solid is a hydrate or contains water of crystallization

Text Frank Weise, 2009. All rights reserved.

QUALITATIVE ANALYSIS FOR CAPE CHEMISTRY

4

a) blue CoCl2 paper pink

b) white anhydrous CuSO4 blue
when GENTLY heated.
When STRONGLY heated:
Colourless, odourless gas (CO2) is evolved which turns lime water

Solid is a carbonate or a bicarbonate

milky.
Colouless, pungent gas (NH3) which turns moist red litmus blue or
form dense white fumes with HCl(g)
Colourless, choking odour gas (SO2 ) which turns orange

Solid contains NH4+ ion

Solid contains either S2-, SO32-, or SO42- ion

H+/K2Cr2O7(aq) green or purple H+/KMnO4(aq) colourless

Reddish brown, pungent odour gas (NO2) which turns moist blue

Solid contains NO3- ion

litmus red
Purple vapour

No reaction ( recorded as no visible change)

Text Frank Weise, 2009. All rights reserved.

Iodine I2.

Solid is an ionic compound with high lattice energy

QUALITATIVE ANALYSIS FOR CAPE CHEMISTRY

5

Purple black solid formed (I2) on the cooler parts of the tube

Solid contains iodide (I-) ion

(4) Action of dilute HCl

Observation(s)

Inference(s)

Effervescence, gas (CO2) is evolved which turns lime water milky.

Substance contains CO32- .

Colourless, choking odour gas (SO2 ) which turns orange

Substance contains SO32-.

H+/K2Cr2O7(aq) green or purple H+/KMnO4(aq) colourless

Reddish brown, pungent odour gas (NO2) which turns moist blue

Substance contains NO2-.

litmus red.

(5) Action of conc. H2SO4 ( on solids)

Observation(s)

Inference(s)

Colourless, lachrymatory gas (HCl) which either

Solid contains chloride (Cl-) ion

a) fumes in moist air

Text Frank Weise, 2009. All rights reserved.

QUALITATIVE ANALYSIS FOR CAPE CHEMISTRY

6

b) turns moist blue litmus red or

c) forms dense white fumes with ammonia gas
Red brown gas (Br2) which turns moist blue litmus red then

.
Solid contains bromide (Br-) ion

bleaches it.
Purple vapour (I2(g)) which bleaches litmus and which turns
starch solution dark blue.

Solid contains iodide (I-) ion

(6) Action of conc. HCl ( on solids)

Observation(s)

Inference

Greenish yellow gas (Cl2) which bleaches litmus

Solid contains PbO2.

Confirmatory Tests
For some common anions
Anion

Test

Observation

SO32-

Add acid followed by KMnO4

Colour change from purple to colourless

Add Iodine solution

Colour change from brown to colourless

Add conc. H2SO4 then warm.

Reddish brown gas (NO2)

NO3-

Text Frank Weise, 2009. All rights reserved.

QUALITATIVE ANALYSIS FOR CAPE CHEMISTRY

7

PO43-

Add HNO3 followed by ammonium molybdate

Yellow precipitate

solution.

For some cations

Cation

Test

Observation

Pb2+

Add dilute HCl(aq)

White ppt., soluble on heating.

Add K2CrO4(aq)

Yellow ppt., soluble in dilute HNO3(aq)

Add potassium hexacyanoferrate(II) soln.

Pale blue ppt.

Add potassium hexacyanoferrate(III) soln

Dark blue ppt.

Add potassium hexacyanoferrate(II) soln.

Dark blue ppt.

Add Ammonium thiocyanate solution

Light red solution

Fe2+

Fe2+

Reactions of cations with NaOH(aq), NH3(aq) and Na2CO3(aq)

The cations of concern: Cr3+, Al3+,Pb2+,Zn2+ , Ba2+,Ca2+,Mg2+ ,Mn2+, Fe2+, Fe3+, Ni2+,NH4+,Cu2+.
Introduction:
The reactions of the cations with these reagents will form
Text Frank Weise, 2009. All rights reserved.

QUALITATIVE ANALYSIS FOR CAPE CHEMISTRY

8

a)

hydroxides in the case of NaOH(aq) and NH3(aq) &

b)

carbonates in the case of Na2CO3(aq)

A precipitate will form if the compounds formed are insoluble in water. It is therefore important to understand and memorize the
solubility of hydroxides and carbonates.
Only group I hydroxides ( these include for sodium and potassium) and hydroxides of barium and strontium of group II are soluble.
Only the carbonates of group I ( these include for sodium and potassium) and ammonium carbonate are soluble.
Some insoluble hydroxides are amphoteric (i.e. they can react with both acids and bases). These will react with excess strong
bases to form soluble salts i.e. they will dissolve in the excess alkali to form solutions. Examples of ions that will form amphoteric
hydroxides are Cr3+, Al3+,Pb2+,Zn2+.
Some insoluble hydroxides will form more stable soluble complexes with excess ammonia molecules in solution. Examples of ions
whose hydroxides will form stable soluble complexes with excess aqueous ammonia are Cu 2+, Zn2+ and Ni2+.
Precipitates and solutions which are coloured usually contain a transition element, so the ions that may be inferred are Cr3+, Mn2+,
Fe2+, Fe3+, Ni2+ and Cu2+.
Precipitates which are white and solutions which are colourless usually contain no transition elements, so one can infer the absence
of Cr3+, Mn2+, Fe2+, Fe3+, Ni2+ and Cu2+.
Carbonate precipitates are usually formed with either of the following:
a)

No further change. Examples include those formed from Pb2+, Zn2+, Ba2+,Ca2+, and Mg2+.

Text Frank Weise, 2009. All rights reserved.

QUALITATIVE ANALYSIS FOR CAPE CHEMISTRY

9

b)

Effervescence as CO2 is evolved. Usually the reactions of small cations with large charges will cause this. The solutions
of these ions are acidic. Examples include Fe3+ and Al3+.

c)

The carbonates formed turned black on heating. Recall that some carbonates decompose on heating to form the oxide
and carbon dioxide. It is the oxide formed which is black. Examples include those formed from Cu 2+ and Ni2+.

Cation
Pb2+

Effect of NaOH(aq)
White ppt.; soluble in excess to form colourless solution.

White ppt.; insoluble in excess

Pb(OH)2(s) + 2OH-(aq)Pb(OH)42-(aq)

Pb2+(aq) + 2OH-(aq). Pb(OH)2(s)

white
Al3+

Plumbate ion (or leadate ion)

white

White ppt.; soluble in excess to form colourless solution.

White ppt.; insoluble in excess

Al(OH)3(s) + OH-(aq)Al(OH)4-(aq)
white

Al3+(aq) + 3OH-(aq). Al(OH)3(s)

Aluminate ion
Zn2+

Effect of NH3(aq)

white

White ppt.; soluble in excess to form colourless solution.

White ppt.; soluble in excess

Zn(OH)2(s) + 2OH-(aq)Zn(OH)42-(aq)

Zn(OH)2(s) + 4NH3(aq). Zn(NH3)42+(aq) + 2OH-(aq)

white

zincate ion

Tetrammine zinc (II)

ion
( Stable complex)

Text Frank Weise, 2009. All rights reserved.

QUALITATIVE ANALYSIS FOR CAPE CHEMISTRY

10
Cr3+

Grey green ppt.; soluble in excess to form green solution.

Grey green ppt.; insoluble in excess

Cr(OH)3(s) + OH-(aq)Cr(OH)4-(aq)

Cr3+(aq) + 3OH-(aq). Cr(OH)3(s)

grey green

Mg2+

Cation

Ca2+

green

Grey green

White ppt.; insoluble in excess.

White ppt.; insoluble in excess.

Mg2+(aq) + 2OH-(aq). Mg(OH)2(s)

Mg2+(aq) + 2OH-(aq). Mg(OH)2(s)

Effect of NaOH(aq)

White ppt.; insoluble in excess.

Ca2+(aq) + 2OH-(aq). Ca(OH)2(s)
white

Text Frank Weise, 2009. All rights reserved.

Effect of NH3(aq)

No ppt. [OH-] furnished by NH3(aq) is insufficient to cause the product of

the ion concentrations,[Ca2+][OH-]2, to exceed Ksp(Ca(OH)2), so no
precipitation.

QUALITATIVE ANALYSIS FOR CAPE CHEMISTRY

11
Ba2+

White ppt.; insoluble in excess ONLY with concentrated

NaOH(aq).

No ppt..

Ba2+(aq) + 2OH-(aq). Ba(OH)2(s)

White
Reason: Ba(OH)2 is quite soluble in water. However in
concentrated NaOH(aq), the product of the ion
concentration,[Ba2+][OH-]2, is EXCEEDS the Ksp(Ba(OH)2),
so precipitation occurs

Cu2+

Light blue ppt.; insoluble in excess.

Light blue ppt.; soluble in excess forming a dark blue solution.

Cu2+(aq) + 2OH-(aq). Cu(OH)2(s)

Cu(OH)2(s) + 4NH3(aq) Cu(NH3)42+(aq) + 2OH-(aq)

blue

light blue

light blue

( Turns black on standing the suspension)

Cu(OH)2(s) CuO(s) + H2O(l)

Cation

Effect of NaOH(aq)

Text Frank Weise, 2009. All rights reserved.

dark blue
Tetraammine copper (II) ion
( stable complex )

Effect of NH3(aq)

QUALITATIVE ANALYSIS FOR CAPE CHEMISTRY

12

Ni2+

Pale green ppt.; insoluble in excess.

Pale green ppt.; soluble in excess to form a green solution.

Ni2+(aq) + 2OH-(aq). Ni(OH)2(s)

Ni(OH)2(s) + 6NH3(aq) Ni(NH3)62+(aq) + 2OH-(aq)

green

pale green

pale green

green
hexaammine nickel(II) ion
(stable complex)

NH4+

No ppt. Ammonia is produced on heating.

Not applicable

Fe2+

Dirty green ppt.; insoluble in excess

Dirty green ppt.; insoluble in excess

Fe2+(aq) + 2OH-(aq) Fe(OH)2(s)

Fe2+(aq) + 2OH-(aq) Fe(OH)2(s)

green

green

Fe3+

Mn2+

dirty green

dirty green

( Turns red-brown on exposure to air; oxidized to Iron (III))

( Turns red-brown on exposure to air; oxidized to Iron (III))

Red-brown ppt.; insoluble in excess

Red-brown ppt.; insoluble in excess

Fe2+(aq) + 2OH-(aq) Fe(OH)2(s)

Fe2+(aq) + 2OH-(aq) Fe(OH)2(s)

pale green

pale green

dirty green

Off white ppt. ;insoluble in excess. Precipitate turns light

brown on exposure to air ; it is oxidized to manganese (III).

Text Frank Weise, 2009. All rights reserved.

dirty green

Off white ppt. ;insoluble in excess. Precipitate turns light brown on

exposure to air ; it is oxidized to manganese (III).

QUALITATIVE ANALYSIS FOR CAPE CHEMISTRY

13
Mn2+(aq) + 2OH-(aq) Mn(OH)2(s)

Mn2+(aq) + 2OH-(aq) Mn(OH)2(s)

pink

pink

off white

Cation

off white

Effect of Na2CO3(aq)

Pb2+
Zn2+

All forms a white ppt. with no other change.

Ba2+

General equation:

M2+(aq) + CO32-(aq) MCO3(s)

Ca2+

white

Mg2+
Al3+

White ppt., effervescence, evolution of CO2

Al3+(aq) + CO32-(aq) Al2CO3(s)
white
CO32-(aq) + H+(aq) H2O(l) + CO2(g)
( from Al3+(aq) )

Text Frank Weise, 2009. All rights reserved.

QUALITATIVE ANALYSIS FOR CAPE CHEMISTRY

14

Fe3+

Red-brown ppt., effervescence, evolution of CO2.

Fe3+(aq) + CO32-(aq) Fe2CO3(s)
Yellow-brown

Red-brown

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

( from Fe3+(aq) )

Fe2+

Dirty-green ppt. with no other change.

Fe2+(aq) + CO32-(aq) FeCO3(s)
green

Cr3+

dirty-green

Cr3+(aq) + CO32-(aq) Cr2CO3(s)

green

Cu2+

dirty-green

Light-blue ppt.; turns black on heating.

Cu2+(aq) + CO32-(aq) CuCO3(s)
blue
CuCO3(s)

Text Frank Weise, 2009. All rights reserved.

light-blue
CuO(s) + CO2(g)

QUALITATIVE ANALYSIS FOR CAPE CHEMISTRY

15

black

Ni2+

Light-green ppt.; turns black on heating.

Ni2+(aq) + CO32-(aq) NiCO3(s)
green
NiCO3(s)

light-green
NiO(s) + CO2(g)
black

Text Frank Weise, 2009. All rights reserved.