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QUALITATIVE ANALYSIS NOTES

Tests for Cations (Positive Ions):

Cations are identified based on their reactions with 2 reagents: aqueous sodium hydroxide and
aqueous ammonia. The colour of the precipitates (ppt) formed and their solubility in excess of
the reagent serves as a useful guide for the identification of cations in aqueous solutions.

Observations:
Identity of
Cation Reaction with aqueous sodium Reaction with aqueous ammonia precipitate
hydroxide

White precipitate formed, soluble in White precipitate formed, insoluble


Aluminium hydroxide
Al3+ excess aqueous sodium hydroxide to in excess aqueous ammonia.
Al(OH)3
give a colourless solution.

White precipitate formed, insoluble Calcium hydroxide


Ca2+ No visible reaction.
in excess aqueous sodium hydroxide. Ca(OH)2

Blue precipitate formed, insoluble in Blue precipitate formed, soluble in


Copper(II) hydroxide
Cu2+ excess aqueous sodium hydroxide. excess aqueous ammonia to give a
Cu(OH)2
dark blue solution.

Dirty-green precipitate formed, Dirty-green precipitate formed,


insoluble in excess aqueous sodium insoluble in excess aqueous
Iron(II) hydroxide
Fe2+ hydroxide. Dirty-green precipitate ammonia. Dirty-green precipitate
Fe(OH)2
turns reddish-brown on standing in turns reddish-brown on standing in
air. air.

Reddish-brown precipitate formed, Reddish-brown precipitate formed,


Iron(III) hydroxide
Fe3+ insoluble in excess aqueous sodium insoluble in excess aqueous
Fe(OH)3
hydroxide. ammonia.

White precipitate formed, soluble in White precipitate formed, insoluble


Lead(II) hydroxide
Pb2+ excess aqueous sodium hydroxide to in excess aqueous ammonia.
Pb(OH)2
give a colourless solution.

White precipitate formed, soluble in White precipitate formed, soluble


Zinc hydroxide
Zn2+ excess aqueous sodium hydroxide to in excess aqueous ammonia to give
Zn(OH)2
give a colourless solution. a colourless solution.

On warming, a colourless, pungent


gas evolved which turned moist red
NH4+ No visible reaction. -
litmus paper blue. The gas is
ammonia.

Na+ No visible reaction. No visible reaction. -


K+ No visible reaction. No visible reaction. -
Note: To distinguish between Al3+ and Pb2+, add aqueous potassium iodide (KI).
If Pb2+ is present, a bright yellow ppt is formed. This ppt is PbI2.

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Tests for Anions (Negative Ions):

Anions are identified based on their reactions with specific reagents.

Anion Test Observations Identity of precipitate


Add aqueous sodium hydroxide.
A colourless, pungent gas evolved
- Then add a little aluminium
NO3 which turned moist red litmus paper -
powder or Devardas alloy.
blue. The gas is ammonia.
Warm.

Brisk effervescence. A colourless,


A white precipitate is
odourless gas evolved which gives a
obtained because of the
CO32- Add any dilute acid. white precipitate with limewater
calcium carbonate
(calcium hydroxide). The gas is
(CaCO3) formed.
carbon dioxide.

Add dilute nitric acid. Silver chloride


Cl- A white precipitate is formed.
Add aqueous silver nitrate. AgCl

Add dilute nitric acid. Lead(II) iodide


I- A yellow precipitate is formed.
Add aqueous lead(II) nitrate. PbI2

Add dilute nitric acid.


A white precipitate is formed.
Add aqueous barium nitrate.
2- Barium sulfate
SO4
BaSO4
Add dilute hydrochloric acid.
A white precipitate is formed.
Add aqueous barium chloride.

Note:
The purpose of adding dilute nitric acid before adding the specific reagents is to prevent the
precipitation of CO32- ions (i.e. to eliminate the possible presence of CO32- ions) and at the
same time, not interfere with the test (because nitrates ions do not form precipitates as nitrate
compounds are soluble in water).

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Tests for Gases:

Gas Colour & Odour Test Observations

Colourless gas with Place a piece of moist red litmus


Ammonia Red litmus paper turns blue.
a pungent smell paper in the gas.

Carbon Colourless and Bubble the gas through aqueous


White precipitate is formed.
dioxide odourless gas calcium hydroxide (limewater).

Greenish-yellow gas Place a piece of moist blue Blue litmus paper turns red, and is
Chlorine
with a pungent smell litmus paper in the gas. then bleached.

Colourless and Place a lighted wooden splint Lighted splint is extinguished with a
Hydrogen
odourless gas near the gas. `pop sound.

Colourless and Place a glowing wooden splint


Oxygen Glowing splint is relighted.
odourless gas near the gas.

Place a drop of acidified


potassium manganate(VII) Acidified purple potassium
Sulphur Colourless gas with
solution on a piece of filter manganate(VII) solution is
dioxide a pungent smell
paper, and then place it in the decolourised.
gas.

Tests for Water or Water Vapour:

There are 2 chemical tests to detect the presence of water or water vapour:

1. Use anhydrous copper(II) sulphate


Water will change the colour of anhydrous copper(II) sulphate from white to blue.

2. Use dry cobalt(II) chloride paper


Water will change the colour of dry cobalt(II) chloride paper from blue to pink.

Note that these 2 tests only show the presence of water. They cannot be used to test for the
purity of water.

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SUMMARY (CATIONS)

Concept Map 1: Reaction with aqueous sodium hydroxide

Salt solution

aqueous sodium
hydroxide

White ppt: Blue ppt: Dirty-green ppt: Reddish-brown ppt: No ppt:


Al3+, Ca2+, Pb2+, Zn2+ Cu2+ Fe2+ Fe3+ NH4+, Na+, K+

Excess aqueous
sodium hydroxide Warm

Ammonia produced:
NH4+
White ppt soluble: White ppt insoluble:
Al3+, Pb2+, Zn2+ Ca2+

Concept Map 2: Reaction with aqueous ammonia

Salt solution

aqueous ammonia

White ppt: Blue ppt: Dirty-green ppt: Reddish-brown ppt: No ppt:


Al3+, Pb2+, Zn2+ Cu2+ Fe2+ Fe3+ Ca2+, NH4+, Na+, K+

Excess aqueous
ammonia

White ppt soluble: White ppt insoluble: Blue ppt soluble:


Zn2+ Al3+, Pb2+ Cu2+

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SUMMARY (ANIONS)

1. Test for carbonate (CO3 2-)

dilute acid

carbonate

carbon dioxide gas

2. Test for nitrate (NO3 -)

sodium hydroxide and aluminium powder (Devardas alloy)

nitrate
warm
ammonia gas

3. Test for chloride (Cl - )

acidified silver nitrate

chloride

white precipitate

4. Test for iodide ( I- )

acidified lead (II) nitrate

iodide

yellow precipitate

5. Test for sulfate ( SO42- )

acidified barium nitrate / barium chloride

sulfate

white precipitate

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IONIC EQUATIONS (CATIONS)

Add aqueous sodium


hydroxide/aqueous ammonia:
Cation Ionic Equation:
Colour of Identity of precipitate
precipitate

Al3+ White Aluminium hydroxide Al3+ (aq) + 3OH- (aq) Al(OH)3 (s)

Ca2+ White Calcium hydroxide*

Cu2+ Blue Copper(II) hydroxide

Fe2+ Dirty-green Iron(II) hydroxide

Fe3+ Reddish-brown Iron(III) hydroxide

Pb2+ White Lead(II) hydroxide

Zn2+ White Zinc hydroxide

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

* For the calcium ion (Ca2+), very little or no precipitate is formed with aqueous ammonia.

Note:

For the ammonium ion (NH4+), ammonia gas (NH3) is evolved when warmed with aqueous
sodium hydroxide.

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IONIC EQUATIONS (ANIONS)

Identity of
Anion Test: Ionic Equation:
precipitate

Aqueous sodium
-
NO3 hydroxide +
- -
Aluminium powder
(with warming)

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

Cl- Dilute nitric acid + Silver


Silver nitrate chloride

I- Dilute nitric acid + Lead(II)


Lead(II) nitrate iodide

Dilute nitric acid +


Barium nitrate
Barium
SO42-
sulfate
Dilute hydrochloric
acid + Barium
chloride

Note:

For the nitrate ion (NO3-), ammonia gas (NH3) is evolved when warmed with aqueous sodium
hydroxide and aluminium powder.

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PRECIPITATION ILLUSTRATION (CATIONS)

To illustrate how a precipitation reaction takes place for cations, consider the following model
for the test for Cu2+ ions.

Cu2+
+
Xm- Cu2+ OH-
OH-
Xm- Cu2+ Xm- OH- Na+ OH-

Xm- Cu2+ Na+ OH- Na+


Cu2+

Test solution Reagent

Xm- Na+ Xm-


Na+
spectator ions
m-
Na + X Xm-

OH- Cu2+ OH- Cu2+ OH-


precipitate (ppt)
Cu2+ OH- Cu2+ OH- Cu2+

1. Suppose the above test solution is copper(II) nitrate, can you work out the ionic equation
for the precipitation reaction?

2. Suppose the above test solution is copper(II) sulfate, can you work out the ionic equation
for the precipitation reaction?

8
PRECIPITATION ILLUSTRATION (ANIONS)

To illustrate how a precipitation reaction takes place for anions, consider the following model
for the test for Cl- ions.

Cl-
+
Yn+ Cl- Ag+
Ag+
Yn+ Cl- Yn+ Ag+ NO3- Ag+

Yn+ Cl- NO3- Ag+ NO3-


Cl-

Test solution Reagent

Yn+ NO3- Yn+


spectator ions
NO3-
NO3- Yn+ Yn+

Cl- Ag+ Cl- Ag+ Cl-


precipitate (ppt)
Ag+ Cl- Ag+ Cl- Ag+

1. Suppose the above test solution is potassium chloride, can you work out the ionic equation
for the precipitation reaction?

2. Suppose the above test solution is hydrochloric acid, can you work out the ionic equation
for the precipitation reaction?