Qualitative Analysis

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Chem Lectures

Qualitative Analysis

Learning Outcomes
1. To describe the use of aqueous sodium hydroxide and aqueous ammonia to identify the following aqueous cations:
Al3+, NH4+, Ca2+, Cu2+, Fe2+, Fe3+, Zn2+.
2. To describe tests to identify the following anions: CO32, Cl, I, NO3 SO42.
3. To describe tests to identify the following gases: NH3, CO2, Cl2, H2, O2, SO2.

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 Qualitative Analysis

1. What Physical Tests Can be Used to Identify Substances?

 Tests which can be used to identify a substance includes:

- Colour
- Smell
- Solubility in water
- pH
- Redox nature
- Action of heat

 A few common terms will be used throughout:

(1) Precipitate: The insoluble salt which forms during the reaction is known as the precipitate
(ppt). We use the colour and solubility of the ppt in dilute H2SO4/ dilute NaOH to determine
the presence/ absence of certain metal ions.

(2) Add reagent (e.g., dilute NaOH, dilute HCl, etc): This means to add the reagent dropwise
(up to 3 drops) and to observe the solution closely for signs of ppt formation or
effervescence.

(3) Effervescence: This refers to the 'fizzing' or 'bubbling' that is observed, indicating that a gas
has evolved. The gas evolved can tell us the identity of some common anions. Sometimes,
you will need to smell the gas to determine the identity of the gas. to do this, waft the gas
towards your nose. Do not inhale directly.

(4) Excess reagent: This means to add additional drops of a reagent, dropwise, observing
after each drop. Do not add a large volume all at once, as you may miss some critical
observations.

(5) Leave to stand: This means to leave the mixture in the test tube to stand in air for a few
minutes. During this period, observe frequently for any changes. However, do not stare at
the test tube continuously.

(6) Test for gas: Waft (sweep) the gas gently to your nose by making sweeping motions above
the test tube. Do not inhale directly from the test tube!

 The following tables contain description of tests which you will need to memorise.

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 Identifying Cations
Add NaOH(aq)
To a portion of an aqueous
solution containing the
Cation
unknown, add:
Present
a) 2-3 drops of NaOH(aq).
b) followed by excess
NaOH(aq).
Na+, K+ a) No precipitate forms.
Sodium ion, b) No precipitate forms.
potassium
ion
NH4+ a) No precipitate forms.
Ammonium b) On heating, a
ion colourless, pungent gas
evolves, which turns
moist red litmus paper
blue. NH3(g) is evolved.
Zn2+ a) White precipitate forms.
Zinc ion b) Precipitate dissolves in
excess NaOH(aq) to
give a colourless
solution.
Pb2+ a) White precipitate forms.
Lead ion b) Precipitate dissolves in
excess NaOH(aq) to
give a colourless
solution.
Ionic Equation
- a) No precipitate formed.
NH4+ + OH  NH3 + H2O
Zn2+(aq) + 2OH(aq)  Zn(OH)2(s)
white ppt
Pb2+(aq) + 2OH(aq)  Pb(OH)2(s)
white ppt
Pb(OH)2(s) + 2OH(aq) Ý
Pb(OH)42(aq)
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Qualitative Analysis
Add NH3(aq)*
To a portion of an aqueous
solution containing the
unknown, add: Ionic Equation
a) 2-3 drops of NH3(aq).
b) followed by excess
NH3(aq).
-
b) No precipitate formed.
- -
a) White precipitate forms. Zn2+(aq) + 2OH(aq)  Zn(OH)2(s)
b) Precipitate dissolves in white ppt
excess NH3(aq) to give
a colourless solution. Zn(OH)2(s) + 4NH3(aq) Ý
Zn(NH3)42+(aq) + 2OH(aq)
a) White precipitate forms. Pb2+(aq) + 2OH(aq)  Pb(OH)2(s)
b) Precipitate is insoluble white ppt
in excess NH3(aq).
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Add NaOH(aq)
To a portion of an aqueous
solution containing the
Cation
unknown, add:
Present
a) 2-3 drops of NaOH(aq).
b) followed by excess
NaOH(aq).
Al3+ a) White precipitate forms.
Aluminium b) Precipitate dissolves in
ion excess NaOH(aq) to
give a colourless
solution.
Ca2+ a) White precipitate forms.
Calcium ion b) Precipitate is insoluble
in excess NaOH(aq).
Cu2+ a) Blue precipitate forms.
Copper(II) b) Precipitate is insoluble
ion in excess NaOH(aq).
Fe2+ a) Green precipitate
Iron(II) ion forms, which turns
brown on standing in
air.
b) Precipitate is insoluble
in excess NaOH(aq)
Fe3+ a) Reddish-brown
Iron(III) ion precipitate forms.
b) Precipitate is insoluble
in excess NaOH(aq)
Ionic Equation
Al3+(aq) + 3OH(aq)  Al(OH)3(s)
white ppt
Al(OH)3(s) + OH(aq) 
Al(OH)4(aq)
Ca2+(aq) + 2OH(aq)  Ca(OH)2(s)
white ppt
Cu2+(aq) + 2OH(aq)  Cu(OH)2(s)
blue ppt
Fe2+(aq) + 2OH(aq)  Fe(OH)2(s)
green ppt
On standing in air: 4Fe(OH)2 +
O2(g) + 2H2O(l)  4Fe(OH)3(s)
Fe3+(aq) + 3OH(aq)  Fe(OH)3(s)
reddish-brown ppt
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Qualitative Analysis
Add NH3(aq)*
To a portion of an aqueous
solution containing the
unknown, add: Ionic Equation
a) 2-3 drops of NH3(aq).
b) followed by excess
NH3(aq).
a) White precipitate forms. Al3+(aq) + 3OH(aq)  Al(OH)3(s)
b) Precipitate is insoluble white ppt
in excess NH3(aq).
a) No precipitate forms. -
b) -
a) Blue precipitate forms. Cu2+(aq) + 2OH(aq)  Cu(OH)2(s)
b) Precipitate dissolves in blue ppt
excess NH3(aq) to form
a dark blue solution. Cu(OH)2(s) + 4NH3(aq) Ý
Cu(NH3)42+(aq) + 2OH(aq)
a) Green precipitate forms, Fe2+(aq) + 2OH(aq)  Fe(OH)2(s)
which turns brown on green ppt
standing in air.
b) Precipitate is insoluble On standing in air: 4Fe(OH)2 +
in excess NaOH(aq) O2(g) + 2H2O(l)  4Fe(OH)3(s)
a) Reddish-brown Fe3+(aq) + 3OH(aq)  Fe(OH)3(s)
precipitate forms. reddish-brown ppt
b) Precipitate is insoluble
in excess NaOH(aq)
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 Qualitative Analysis
* Do not attempt to test for NH3(g) when you add NH3(aq).

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 Qualitative Analysis
3. Identifying Gases

(a) Litmus Paper Test

Characteristics
Gas (b) Confirmatory Test - in some cases, the Observation
(colour, smell)
litmus paper test is also the confirmatory test
H2 Colourless, odourless a) Place pieces of moist red and blue litmus a) Does not change the colour of moist
Hydrogen papers near to the gas. litmus paper.
b) Insert a lighted splint. b) Lighted splint is extinguished with a pop
sound.
O2, Colourless, odourless a) Place pieces of moist red and blue litmus a) Does not change the colour of moist
Oxygen papers near to the gas. litmus paper.
b) Insert a glowing splint into the gas. b) Glowing splint is rekindled.
H2O Colourless, odourless a) Place pieces of moist red and blue litmus a) Neutral to moist litmus paper.
Water vapour papers near to the gas.
b) Place a piece of anhydrous cobalt(II) chloride b) Anhydrous CoCl2 paper turns from blue
(CoCl2) paper. to pink.
CO2 Colourless, odourless a) Place a piece of moist blue litmus paper near a) Moist blue litmus paper turns red.
Carbon dioxide to the gas.
(acidic gas) b) Pass the gas evolved into limewater. b) White precipitate forms. (Precipitate
dissolves when excess gas is bubbled
into the mixture.)
Cl2 Pale yellow, pungent a) Place a piece of moist blue litmus paper near a) Moist blue litmus paper turns red and
Chlorine to the gas. then is bleached.
(acidic gas) b) Place a piece of moist starch-potassium iodide b) Moist starch-potassium iodide paper
paper near to the gas. turns blue-black.
SO2 Colourless, pungent a) Place a piece of moist blue litmus paper near a) Moist blue litmus paper turns red.
Sulfur dioxide to the gas.
(acidic gas) b) Use a piece of filter paper dipped in acidified b) Acidified KMnO4 paper turns from purple
aqueous potassium manganate(VII) (KMnO4). to colourless.
NH3 Colourless, pungent a) Place a piece of moist red litmus paper near to a) Moist red litmus paper turns blue.

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 Qualitative Analysis

(a) Litmus Paper Test

Characteristics
Gas (b) Confirmatory Test - in some cases, the Observation
(colour, smell)
litmus paper test is also the confirmatory test
Ammonia the gas.
(alkaline gas) b) Dip a glass rod into concentrated hydrochloric b) Dense white fumes (of ammonium
acid and place in the gas. chloride) forms.
HCl Colourless, pungent a) Place a piece of moist blue litmus paper near a) Moist blue litmus paper turns red.
Hydrogen to the gas.
chloride b) Dip a glass rod into concentrated aqueous b) Dense white fumes of ammonium
(acidic gas) ammonia and place in the gas. chloride formed.
NO2 Brown, pungent a) Place a piece of moist blue litmus paper near a) Moist blue litmus paper turns red.
Nitrogen dioxide to the gas.
(acidic gas)
I2 Violet/ purple, pungent a) Place a piece of moist blue litmus paper near a) Moist blue litmus paper turns red.
Iodine to the gas.
(acidic gas) b) Place a piece of filter paper dipped in starch b) Moist starch paper turns blue-black.
solution near to the gas.

Note

 If the gas has to be bubbled through a test solution, e.g., carbon dioxide into limewater, place a thumb over the mouth of the test tube after
addition of reagent. Use a dropper to suck up the air and bubble it directly into a test tube of the test reagent.

 How do we know if there will be any gas? We must first know what reagents when added could result in gas production, e.g., dilute acids.
The dropper, limewater, moist litmus paper etc, will all need to be prepared first in advance.

 Don't test for NH3(g) when you add NH3(aq). It will obviously be present, because you added it in!

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4. Identifying Anions
Anion Test
CO32 To a portion of an aqueous
solution containing the
unknown, add dilute HCl or
dilute H2SO4.
To a portion of an aqueous
solution containing the
unknown, add Ba(NO3)2(aq)
or BaCl2(aq), followed by
dilute HNO3 or HCl.
NO3 Add an equal volume of
Nitrate NaOH(aq) to a portion of the
aqueous solution of the
unknown compound. Add a
small spatula full of
Devarda's alloy/ few strips of
aluminium foil. Warm gently.
Cl To a portion of an aqueous
chloride solution containing the
unknown, add dilute HNO3.
Followed by 2-3 drops of
AgNO3(aq), followed by
excess NH3(aq).
Qualitative Analysis
Observation Ionic Equation
Effervescence observed. Colourless, odourless CO32(aq) + H+(aq)  H2O(l) + CO2(g)
gas evolves. Gas turns moist blue litmus paper effervescence
red, and forms a white precipitate in limewater.
Carbon dioxide gas is evolved. CO2(g) + Ca(OH)2(aq)  CaCO3(s) + H2O(l)
white ppt

White precipitate forms. Precipitate dissolves in Ba (aq) + CO3 (aq)  BaCO3(s)
2+ 2
excess dilute HNO3 or HCl. white ppt
Effervescence observed. Colourless, odourless
gas evolves. Gas turns moist blue litmus paper
red, and forms a white precipitate in limewater.
Carbon dioxide gas is evolved.
Colourless, pungent gas evolves. Gas turns 3NO3(aq) + 8Al(s) + 18H2O(l) + 5OH-(aq) 
moist red litmus paper red. NH3(g) is evolved. 8[Al(OH)4](aq) + 3NH3(g)
(Acid is added to remove any CO32 which might
be present, in case a false positive is given.
AgNO3(aq) also reacts with CO32 to give a
white precipitate.)
White precipitate forms. Precipitate dissolves in Ag+(aq) + Cl(aq)  AgCl(s)
excess NH3(aq) to form a colourless solution. white ppt
AgCl(s) + 2NH3(aq)  [Ag(NH3)2]+(aq) + Cl-(aq)
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Anion Test
To a portion of an aqueous
solution containing the
unknown, add dilute HNO3.
Followed by 2-3 drops of
Pb(NO3)2(aq).
Warm the resultant solution
gently and leave to cool.
I To a portion of an aqueous
iodide solution containing the
unknown, add dilute HNO3.
Followed by 2-3 drops of
AgNO3(aq), followed by
excess NH3(aq).
To a portion of an aqueous
solution containing the
unknown, add dilute HNO3.
Followed by 2-3 drops of
Pb(NO3)2(aq).
Warm the resultant solution
gently and leave to cool.
Qualitative Analysis
Observation Ionic Equation
(Acid is added to remove any CO32 which might
be present, in case a false positive is given.
AgNO3(aq) also reacts with CO32 to give a
white precipitate.)
White precipitate forms. Pb2+(aq) + 2Cl(aq)  PbCl2(s)
white ppt
Precipitate dissolves upon warming, and
reappears as white crystals on cooling.
(Acid is added to remove any CO32 which might
be present, in case a false positive is given.
AgNO3(aq) also reacts with CO32 to give a
white precipitate.)
Yellow precipitate forms. Precipitate insoluble Ag+(aq) + I(aq)  AgI(s)
in excess NH3(aq). yellow ppt
AgCl(s) + 2NH3(aq)  [Ag(NH3)2]+(aq) + Cl-(aq)
(Acid is added to remove any CO32 which might
be present, in case a false positive is given.
AgNO3(aq) also reacts with CO32 to give a
white precipitate.)
Yellow precipitate forms. Pb2+(aq) + 2I(aq)  PbI2(s)
yellow ppt
Precipitate dissolves upon warming, and
reappears as yellow crystals on cooling.
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 Qualitative Analysis

Anion Test Observation Ionic Equation

SO42 To a portion of an aqueous (Acid is added to remove any CO32 which might SO42(aq) + Ba2+(aq)  BaSO4(s)
sulfate solution containing the be present, in case a false positive is given. white ppt
unknown, add dilute HNO3. AgNO3(aq) also reacts with CO32 to give a
white precipitate.)

Followed by 2-3 drops of White precipitate forms.

Ba(NO3)2.

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 Qualitative Analysis

5. Summary of Tests

NaOH(aq)

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

White ppt Blue ppt Reddish

No precipitate forms insoluble in xs White ppt soluble in insoluble in xs brown ppt
NaOH(aq) xs NaOH(aq) NaOH(aq) insoluble in xs
NaOH(aq)
NH3 gas evolved
on warming Green ppt.
Turns reddish
brown on
standing in air.

NH3(aq)

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

White ppt Blue ppt Reddish

No precipitate forms soluble in White ppt soluble in brown ppt
xs NH3(aq) insoluble in xs NH3(aq)
xs NH3(aq) to form a
dark blue
solution Green ppt
insoluble.
Turns reddish
brown on
standing

Dilute acid, HCl, H2SO4

Effervescence observed No effervescence observed

H2 CO2 SO2

Metal CO32- SO32-

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 Qualitative Analysis

Add BaCl2(aq)/dil HCl

White ppt, No ppt

SO42
To new sample, add
AgNO3(aq)/dil HNO3

No ppt White ppt, Yellow ppt

insoluble
To new sample, add NaOH(aq), in acid
Al foil/ Devarda’s alloy, warm
gently
NH3 evolved CI I

NO3

Characteristics
Gas Observation
(colour, smell)
H2 Colourless, odourless Lighted splint is extinguished with a pop sound.
Hydrogen
O2, Colourless, odourless Glowing splint is rekindled.
Oxygen
H2O Colourless, odourless Anhydrous CoCl2 paper turns from blue to pink.
Water vapour
CO2 Colourless, odourless Moist blue litmus paper turns red.
Carbon dioxide White precipitate forms.
Cl2 Pale yellow, pungent Moist blue litmus paper turns red and then is bleached.
Chlorine Moist starch-potassium iodide paper turns blue-black.

SO2 Colourless, pungent Moist blue litmus paper turns red.

Sulfur dioxide Acidified KMnO4 paper turns from purple to colourless.
NH3 Colourless, pungent Moist red litmus paper turns blue.
Ammonia Dense white fumes (of ammonium chloride) forms with
concentrated HCl.
HCl Colourless, pungent Moist blue litmus paper turns red.
Hydrogen chloride Dense white fumes of ammonium chloride formed.
NO2 Brown, pungent Moist blue litmus paper turns red.
Nitrogen dioxide
I2 Violet/ purple, pungent Moist blue litmus paper turns red.
Iodine Moist starch paper turns blue-black.

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