Qualitative Analysis

•Cations
•Anions
•Gases
OBJECTIVES
By the end of the topic, you should be
able to:
 describe the use of aqueous sodium
hydroxide and aqueous ammonia to identify
the following aqueous cations: aluminium,
ammonium, calcium, copper(II), iron(II),
iron(III), lead(II) and zinc (formula of complex
ions are not required)
OBJECTIVES
describe tests to identify the following anions:
 carbonate (by the addition of dilute acid and
subsequent use of limewater);
 chloride (by reaction of an aqueous solution with
dilute nitric acid and aqueous silver nitrate);
 iodide (by reaction of an aqueous solution with
dilute nitric acid and aqueous lead(II) nitrate);
 nitrate (by reduction with aluminium and aqueous
sodium hydroxide to ammonia and subsequent use
of litmus paper) and
 sulfate (by reaction of an aqueous solution with
dilute nitric acid and aqueous barium nitrate)
OBJECTIVES
describe tests to identify the following gases:
 ammonia (using damp red litmus paper);
 carbon dioxide (using limewater);
 chlorine (using damp litmus paper);
 hydrogen (using a burning splint);
 oxygen (using a glowing splint) and
 sulfur dioxide (using acidified potassium
manganat (VII))
What is Qualitative Analysis (QA)?

identification of chemical species

present in a substance or the
chemical composition of a mixture
through chemical tests and
observations.
 Look out for:
a)colour (either of the residue, liquid,
solution, gas or precipitate)
b)solubility (of precipitate in excess of the
reagent)
c)observations made with specific tests,
like using wooden splint, litmus papers etc.
(usually for gaseous products)
 Mix and match!
The analysed substance, (the unknown
ionic compound) can be identified by
matching the properties observed with
those that you are learning next.
 Test for Cations
• Cations can be identified using aqueous
sodium hydroxide and aqueous ammonia
as they both dissociate in water to produce
hydroxide ions.
• NH3 (aq) + H2O (l) ⇌ NH4+ (aq) + OH- (aq)
 Test for Cations
• All cations (except NH4+ and Group I ions
such as Na+ & K+) form a precipitate with
these alkalis.
• Mn+(aq) + OH- (aq)  M(OH)n (s)
cation + hydroxide ion  precipitate

where n is the charge of the metal

 Recall: Precipitation Reaction

Precipitate
• positive and negative ions of the two substances in
solution are mutually interchanged.
• One of the products formed is usually insoluble.
• Example:
CaCl2(aq)+ 2NaOH (aq) --> Ca(OH)2(s) + 2NaCl (aq)
precipitate
 Proper procedural skills:
Preparation of Sample solution:
1. Place about 5 cm3 of sample solution into the test tube which should
just cover the bottom hemisphere of the test tube.
2. For solids sample, they are to dissolve it with distilled water to form
a solution. Likewise, it should too be just 5cm3.

Test Procedures:
1. Record observations on the initial colour of the sample solution.
2. Add drop by drop of reagent to the sample solution.
3. Shake the mixture.
4. Make observations (any ppt formed, colour of solution?) and
record them.
5. For excess addition of reagent, add 1cm3 height portion of the
reagent.
6. Shake the mixture.
7. Repeat steps 5 and 6 until the test tube is ¾ filled.
8. For ammonium sample solutions, see next slide.
moist red litmus paper turn blue

For ammonium salts

after the addition of aq.
NaOH, warm the test
tube and test the gas with
damp red litmus paper.

NH3 gas which is

evolved would turn damp
red litmus blue.
 WHAT to observe and HOW to record
your Observations
• If a precipitate is formed, record its colour.
 E.g. A white precipitate is obtained.
• If there seems to be no reaction, record as: No
visible reaction
• When you are asked to add more reagent until
in excess, record what happens to the
precipitate.
 E.g. The white precipitate dissolves to form a
colourless solution.
 E.g. The white precipitate is insoluble in excess
reagent.
 Test on Cations – Ca2+
Cation Addition of Observation Ionic equations
alkalis
Ca2+ • Add dilute • White precipitate Ca2+ (aq) +
sodium formed, 2OH- (aq)
hydroxide insoluble in Ca(OH)2 (s)
dropwise. excess aqueous
Then add sodium
excess hydroxide.
aqueous
sodium
hydroxide. • No visible
• Add aqueous reaction.
ammonia. Solution remains
colorless.
 A colourless
solution of Ca2+

Before the
addition of
NaOH
After aq. NaOH
is added, a
white precipitate
is formed which
is insoluble in
excess NaOH.
A colourless solution of Ca2+
Before the addition of aq.
ammonia

No visible change of Ca2+

After the addition of aq.
ammonia
Why does Ca2+ ions form a precipitate with
aqueous sodium hydroxide but not with aqueous
ammonia?
• Calcium hydroxide is slightly soluble in water
and would require a high concentration of
hydroxide ions to react with it to form a
precipitate. Hence, since
• sodium hydroxide is a strong alkali, the
calcium ions react with the high concentration
of hydroxide ions to form a precipitate.
• Aqueous ammonia being a weak alkali do not
have sufficient hydroxide ions and thus, no
precipitate is seen.
 Test on Cations – NH4+
NH4+ • Add dilute • No visible reaction. NH4+ (aq) + OH (aq)
sodium Solution remained 
hydroxide colourless. H2O (l) + NH3 (g)
dropwise until
in excess.
• Warm the • On warming, a
solution gently colourless and
pungent gas
evolved, turned
moist red litmus
paper blue.
• Add aqueous • No visible reaction.
ammonia • Solution remained
dropwise until colourless.
in excess.
video on NH4+ with aqueous
NaOH

https://www.youtube.com/watch?v=b28pw1q2qdo
 Test on Cations – Cu2+
Cu2+ •Add dilute •Blue precipitate •Cu2+ (aq) + 2OH-
sodium hydroxide formed, insoluble (aq) Cu(OH)2 (s)
dropwise until in in excess aqueous
excess. sodium hydroxide.
•Blue precipitate •Cu(OH)2 (s) 
turns black on CuO (s) + H2O (l)
heating.

•Add aqueous •Light blue

ammonia precipitate formed, •Cu2+ (aq) + 2OH-
dropwise until in soluble in excess (aq)  Cu(OH)2 (s)
excess. aqueous ammonia •Cu(OH)2 + 4NH3
to give a deep blue (aq)
solution. •[Cu(NH3)4]2+ (aq) +
•2OH- (aq)
 A blue solution of Cu2+
Before the addition of aq.
NaOH

After aq. NaOH is

added, a blue
precipitate is formed
which is insoluble in
excess NaOH.
A blue solution of Cu2+
Before the addition of
aqueous ammonia

After aq. NaOH is

added, a light blue
precipitate is formed
which is soluble in
excess aq. ammonia
to form a deep blue
solution.
 Test on Cations – Fe2+
Fe2+ • Add dilute • Green precipitate • Fe2+ (aq) + 2OH-
sodium formed, insoluble (aq) Fe(OH)2 (s)
hydroxide in excess aqueous
dropwise until sodium hydroxide.
in excess. • On standing, dirty-
green precipitate
turned reddish- • Fe(OH)2 oxidized in
brown. air to become
Fe(OH)3
• Green precipitate
• Add aqueous formed, insoluble
ammonia in excess aqueous
dropwise until • Fe2+ (aq) + 2OH-
ammonia.
(aq) Fe(OH)2 (s)
in excess. • On standing, dirty-
green precipitate
• Fe(OH)2 oxidized in
turned reddish-
brown. air to become
Fe(OH)
 A pale green solution of
Fe2+ Before the addition of
aq. NaOH/ aq.NH3

After aq. NaOH/ aq.

NH3 is added, a green
precipitate is formed
which is insoluble in
excess aq.NaOH/ NH3.
 Test on Cations – Fe3+
Fe3+ • Add dilute • Reddish-brown • Fe3+ (aq) + 3OH-
sodium precipitate (aq) Fe(OH)3
hydroxide formed, (s)
dropwise until insoluble in
in excess. excess aqueous
sodium
hydroxide.

• Add aqueous • Reddish-brown • Fe3+ (aq) + 3OH-

ammonia precipitate (aq) Fe(OH)3
dropwise until formed, (s)
in excess. insoluble in
excess aqueous
ammonia.
A yellow solution of Fe3+
Before the addition of aq.
NaOH/ aq.NH3

After aq. NaOH/ aq.

NH3 is added, a
reddish-brown
precipitate is formed
which is insoluble in
excess aq.NaOH/ NH3.
 Test on Cations – Al3+
Al3+ • Add dilute • White precipitate • Al3+ (aq) + 3OH-
sodium formed, soluble (aq) Al(OH)3
hydroxide in excess (s)
dropwise aqueous sodium
until in hydroxide to give Al(OH)3 + 3OH-
excess. a colourless (aq)
solution. [Al(OH)4]- (aq)
(aluminate ion)

• Add • White precipitate • Al3+ (aq) + 3OH-

aqueous formed, insoluble (aq) Al(OH)3
ammonia in excess (s)
dropwise aqueous
until in ammonia.
excess.
 A colourless solution of
Al3+ Before the addition of
NaOH

After aq. NaOH is

added, a white
precipitate is formed
which is soluble in
excess NaOH to form
a colourless solution.
 A colourless solution of
Al3+ Before the addition of
aq. ammonia

After aq. NH3 is added,

a white precipitate is
formed which is
insoluble in excess
NH3.
 Test on Cations – Pb2+
Pb2+ • Add dilute • White precipitate • Pb2+ (aq) + 2OH-
sodium formed, soluble in (aq) Pb(OH)2
hydroxide excess aqueous (s)
dropwise until sodium hydroxide • Pb(OH)2 + 2OH-
in excess. to give a (aq)
colourless [Pb(OH)4]2- (aq)
solution. (plumbate ion)

• Add aqueous • White precipitate • Pb (aq) + 2OH

2+ -

ammonia formed, insoluble (aq) Pb(OH)2

dropwise until in excess (s)
in excess. aqueous
ammonia.
 A colourless solution of
Pb2+ Before the addition of
NaOH

After aq. NaOH is

added, a white
precipitate is formed
which is soluble in
excess NaOH to form
a colourless solution.
 A colourless solution of
Pb2+ Before the addition of
aq. ammonia

After aq. NH3 is added,

a white precipitate is
formed which is
insoluble in excess
NH3.
 Test on Cations – Zn2+
Zn2+ •Add dilute •White precipitate •Zn2+ (aq) + 2OH-
sodium formed, soluble in (aq) Zn(OH)2(s)
hydroxide excess aqueous •Zn(OH)2 (s) + 2OH
dropwise until in sodium hydroxide to (aq) [Zn(OH)4]2- (aq)
excess. give a colourless (zincate ion)
solution.

•Add aqueous •White precipitate •Zn2+ (aq) + 2OH-

ammonia formed, soluble in (aq) Zn(OH)2 (s)
dropwise until in excess aqueous •Zn(OH)2 (s) + 4NH3
excess. ammonia to give a (aq)
colourless solution. [Zn(NH3)4]2+ (aq) +
2OH- (aq)
 A colourless solution of
Zn2+ Before the addition of
NaOH/ aq. NH3

After aq. NaOH/ aq.

NH3 is added, a white
precipitate is formed
which is soluble in
excess aq. NaOH/ aq.
NH3 to form a
colourless solution.
Which observations mirror
that of Pb2+ ?
Al3+

How to differentiate them

then?
 To differentiate Pb2+ and Al3+, do EITHER
of the following:
Catio Test Observation Ionic equations
n
Pb2+ Add aqueous Yellow precipitate formed. Pb2+ (aq) + 2I- (aq)
Al3+ potassium No visible change.  PbI2 (s)
iodide. Colourless solution ---
remains.

Pb2+ Add dilute White precipitate formed. Pb2+ (aq) + SO42- 

Al3+ sulfuric No visible change. PbSO4 (s)
acid Colourless solution ---
remains.

Pb2+ Add dilute White precipitate formed. Pb2+ (aq) + 2CI- (aq)
Al3+ hydrochlori No visible change.  PbCl2 (s)
c acid Colourless solution ---
remains.
Summary of white ppt
Summary of coloured ppt
 CHECK FOR UNDERSTANDING (CATIONS)
Using aqueous
sodium hydroxide
NaOH (aq)

No precipitate formed Precipitate formed

Na+ Colourless, White precipitate Coloured precipitate

pungent gas formed, insoluble in
K+ evolved upon
formed
excess aqueous
heating, sodium hydroxide

Gas is ammonia
Precipitate
Precipitate soluble
insoluble in excess Blue Reddish
in excess to give a
aqueous sodium green -brown
colourless solution
NH4+ hydroxide

Cu2+
Zn2+ Ca2+ Fe2+ Fe3+
Al3+
Pb2+
oxidises in air
 CHECK FOR UNDERSTANDING (CATIONS)
Using aqueous ammonia
NH3 (aq)

No precipitate formed Precipitate formed

Ca2+ Na+
White precipitate formed
K+, NH4+ Coloured precipitate formed

Precipitate soluble in Precipitate insoluble Precipitate soluble Precipitate insoluble in

excess to give a in excess aqueous in excess to form a excess aqueous ammonia
colourless solution ammonia deep blue solution

Al3+ Blue Reddish

Zn2+ green
Pb2+ -brown

Cu2+
+ H2SO4/HCl  Pb2+: white ppt: PbSO4 / PbCl2 Fe2+ Fe3+
 Al3+: colourless solution: no visible reaction
+ KI  Pb2+: yellow ppt: PbI2
 Al3+: colourless solution: no visible reaction oxidises in air
 TEST FOR ANIONS
Anions Test
Add any dilute acid
Bubble the gas given off into
limewater (aqueous calcium
hydroxide).
CO32-
Add dilute nitric acid, then
Cl- (a) add aqueous silver nitrate.
Add dilute nitric acid, then
(a) add aqueous silver nitrate.
(b) add aqueous lead(II) nitrate.
I-
Test Result
Effervescence of colourless gas is
observed. White precipitate is
formed when the colourless gas
was bubbled into limewater.
Gas is carbon dioxide.
ionic equation:
CO32-(aq) + 2H+(aq)
 CO2(g) + H2O(l)
(a) White precipitate is formed.
Ionic Equation:
Ag+ (aq) + Cl- (aq)  AgCl (s)
(a) Pale yellow precipitate is
formed.
Ionic Equation:
Ag+ (aq) + I- (aq)  AgI (s)
(b) (Bright) Yellow precipitate is
formed.
 TEST FOR ANIONS
Anions Test
Add aqueous sodium hydroxide
(until solution is alkaline) and
NO3-
aluminium foil / Devarda’s
alloy^, warm gently.
Add with dilute nitric acid, then
SO42- add aqueous barium nitrate.
Test Result
Effervescence of colourless gas is
observed. Moist red litmus paper
turned blue. The colourless gas
produced is ammonia gas.
White precipitate is formed.
Ionic Equation:
Ba2+ (aq) + SO4- (aq)  BaSO4 (s)

What is Devarda’s alloy?

• Alloy made up of aluminium, copper and zinc
• Acts as a reducing agent to reduce nitrates into
ammonia under alkaline conditions
 Q3) Why do we need to acidify the solutions
when testing for chlorides, sulfates and
iodides?

• Carbon dioxide gas in the air can dissolve into the

solutions. Hence, this is to remove any carbonate
ions present in the sample.
• Any carbonate ions present would react with
aqueous silver / lead(II) / barium ions to form a
white precipitate (silver carbonate, lead(II)
carbonate or barium carbonate) thus giving
misleading results.
Missing bottle labels

sodium carbonate AgNO3 acidified by HNO3, white precipitate formed

sodium chloride NaOH, Al powder, warm,

NH3 gas: pungent odour which turns red litmus
blue

sodium nitrate BaCl2 acidified with dilute HCl: white precipitate

formed

+dilute HCl, effervescence, CO2 forms white

sodium sulfate preciptate with limewater

Task: Match the correct reagents to identify

the anions present.
 When to test for gases?
whenever
• the solution/solid sample is warmed or
heated
• effervescences/bubbles is observed
Gases Tests Observations Equations

H2 Insert • Bubbles of a Reaction of Acid + metal

lighted/burning colourless gas is (except Cu, Ag, Pb)
splinter into seen. 2HCl + Mg  MgCl2 + H2
mouth of test- • Gas evolved,
tube. extinguished lighted
splinter with a ‘pop’
sound.
O2 Insert glowing • Gas evolved relight 1) Decomposition of
splinter into glowing splinter. hydrogen peroxide
test-tube. H2O2  2H2O + O2
2) Thermal decomposition of
metal nitrates:
2Cu(NO3)2  2CuO + NO2 +
O2

CO2 Bubble gas • Bubbles of a Reaction of acid + metal

through lime colourless gas is carbonate
water (aqueous seen. 2HNO3 + CaCO3 
calcium • Gas evolved forms a Ca(NO3)2 +CO2 + H2O
hydroxide) white precipitate
with limewater.
Cl2 Place a moist blue A choking yellowish- Reaction with chlorate (I)
litmus paper at green gas evolved, solution:
mouth of test-tube. turned moist blue litmus ClO- + Cl- + 2H+  Cl2 + H2O
paper to red then to
colourless. Cl2 (g) + H2O (l) HClO
(aq) + HCl (aq)

SO2 Place a strip of filter Orange acidified Cr2O72- (aq) + 3SO2 (g) + 2H+ (aq)
paper soaked in potassium dichromate(VI)  3SO42- (aq) + 2Cr3+ (aq) + H2O
*acidified potassium solution turns green (l)
dichromate (VI)/ Or 2MnO4- (aq) + 5SO2 (g) + 2H2O(l)
acidified potassium Purple acidified  5SO42- (aq) + 2Mn2+ (aq) + 4H+
manganate (VII) potassium (aq)
solution in the mouth manganate(VII) solution
of the test-tube. turns colourless.
*acidified with dilute
sulfuric acid

NH3 Place a moist red Upon warming the 1) Reaction of alkali +

litmus paper at mixture, a pungent and ammonium salt:
mouth of test-tube. colourless gas turns OH-(aq) + NH4+ (aq)  NH3 (g)
moist red litmus paper + H2O (l)
blue. (NH4+ ion is present)
2) Reaction of NaOH +
Devarda’s alloy/Al/Zn:
- -
 Think about this…

Q:If moist red litmus paper turns blue, what

is produced? what ion would be present?
A: Ammonia gas
Q: What ion would be present?
A: Either nitrate or ammonium ion
How to know if it is nitrate or ammonium ion?
• It is ammonium ion, if only aqueous
sodium hydroxide is added and warmed.
• It is nitrate ion, if aqueous sodium
hydroxide and aluminium powder/devarda’s
alloy is added
and warmed.
Q4) Explain with an aid of an equation, why the litmus
paper should be moist when testing for ammonia gas?

• The water on the litmus paper allows the

ammonia gas to hydroxide ions and form
hydroxide ions which will turn the red
litmus paper blue.
• Equation:
OH-(aq) + NH4+(aq) ⇌ NH3(g) +
H2O(l)
Q5) Explain with an aid of an equation, why the litmus
paper should be moist when testing for chlorine gas?
• The water on the litmus paper reacts with the chlorine
gas to form hydrochloric acid(HCl) and hypochlorus
acid (HClO).
• Equation:
Cl2 (g) + H2O (l)  HClO (aq) + HCl (aq)
• The acids dissociate in water to produce hydrogen ions
that will turn the blue litmus paper red.
• The chlorate(I) ions (ClO-) bleaches the litmus paper.
 Colours & odour of gases
GAS COLOUR ODOUR
H2 Colourless Odourless
O2 Colourless Odourless
CO2 Colourless Odourless
H2O
Colourless Odourless
vapour
NH3 Colourless Pungent
SO2 Colourless Pungent, burning sulfur smell
Colourless/white
HCl Pungent
fumes
Cl2 Pale yellowish-green Choking
NO brown Pungent
 Colours of Metals
metal chemical formula colour

aluminium Al silvery-grey
foil/powder
zinc granules/powder Zn silvery-grey

iron wire/iron powder Fe silvery-grey

copper strip Cu pink/pinkish-brown

magnesium strips Mg silvery-grey

silver granules Ag silvery

gold foil Au yellow

All metals are silvery-grey in colour except copper, silver and gold.
 compounds in solid form in aqueous form (if they
of dissolve)
Group I, II & III
white colourless
& NH4+
white [PbCl2 PbBr2, Pb(OH)2,
& PbSO4]
Pb2+ colourless [Pb(NO3)2]
yellow [PbI2], yellow/red
[PbO]
black [CuO]
blue [Cu(NO3)2 & CuSO4]
Cu2+ green [CuCO3]
bluish-green [CuCl2]
blue [Cu(OH)2]
Fe2+ green pale green
Fe3+ yellow reddish-brown
white [AgCl, Ag2SO4]
Ag+ pale yellow [AgBr] colourless [AgNO3]
yellow [AgI]
yellow when hot & white
Zn2+ colourless
when cold [ZnO]
 Practice Question 1
contains nitrate ions
Warm with
aluminium powder
B: nitric acid and excess
Warm with Al
aqueous
powder sodium
and
Black solid A Aqueous solution B turns excess
hydroxide
NaOH
Universal Indicator red
A: copper(II)
oxide E: ammonia gas
Mixing A and B
Colourless gas E
A- copper(II) oxide
Blue C: copper(II) turns damp red
B- nitric acid solution C nitrate litmus paper blue
C- copper(II) nitrate
D-aqueous ammonia
E- ammonia gas Mixing C in
excess of D Aqueous solution D turns
Universal Indicator blue Warm D

D: aqueous ammonia
Dark blue
solution contains copper(II) ions
 Practice Question 2
Compound G Black solid J

Q: iron(II) J: iron(II) oxide

carbonate Add dilute sulfuric acid Add dilute sulfuric acid

M: iron(II) sulfate
contains sulfate ions
Colourless Green salt
White solid Q
gas L gives a solution M Add barium chloride
solution
white ppt with Add Q: barium sulfate
limewater aqueous
ammonia
G- iron(II) carbonate
L: carbon dioxide
J - iron(II) oxide
Green solid R
L – carbon dioxide
contains iron(II) ions M – Iron(II) sulfate
R – iron(II) hydroxide
R: iron(II) hydroxide
Q – barium sulfate
b) Write the ionic equation with state
symbols for the formation of R from M.
• Fe2+ (aq) + 2OH- (aq) Fe(OH)2 (s)
c) Write the chemical equation for the
formation of the white precipitate from L.
• Ca(OH)2 + CO2  CaCO3 + H2O
d) Write the ionic equation with state
symbols for the formation of Q from M.
• Ba2+ (aq) + SO4- (aq)  BaSO4 (s)