QUALITATIVE ANALYSIS

INORGANIC ANALYSIS
Qualitative analysis is an analytical method used to determine the elements or groups present in a
sample. It does not determine the actual amount of such elements or groups.
The aim of qualitative inorganic analysis is to determine the metallic radical (cations) and acidic
radicals (anions) present in an unknown inorganic substance, the methods used in the
determination of these radicals are as follows:
A. Preliminary Investigation
B. test for acidic radicals
C. test for metallic radicals

A. Preliminary Investigation
This involves
i) Physical Properties
ii) Action of Heat on substance
iii) Flame test

i) Physical properties
The unknown substance should be carefully examined noting the colour, smell and also
whether it is crystalline, amorphous or deliquescent. The following table gives a rough
guide.

Table 1: physical properties of some inorganic salts

Observation Inference
Blue substance Indicates the presence of copper (II) salt
Black substance Indicates the presence of an oxide or a sulphide
Yellow substance Indicate the presence of lead (II) or iron (III) salt
Green substance Indicates the presence of iron (II) or copper (II) salt
Substance sublimes Most probably an ammonium halide e.g. (NH4CI)
Substance is deliquescent Probably chloride or nitrate is present
Deep pink (not visible solution) Manganese salt present
Sample is white Na+, Ca2+, AI3+, Zn2+, and Pb2+ salts

ii) Action of Heat on Substance

Most substances when heated give off one or more gases. The gas if identified, can give a clue as
to the type of substance being heated. E.g. if ammonia gas is given off on a substance, that
compound is most likely an ammonium compound
(NH4)2CO3(g) → NH3(g) + H2O + CO2(g)
NH4CI → NH3(g) + HCI
Ammonia can be identified by its smell and effect on litmus. Some substances give off water
when heated they are most likely hydrated salts (which gave off their water of crystallization on
heating) or a hydrogen carbonate, or a hydroxide
e.g

CuSO4.5H2O → CuSO4 + 5H2O

(blue) (white)

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 Cu(OH)2 → CuO + H2O
(blue) (black)

2NaHCO3(s) → Na2CO3(s) + H2O + CO2(g)

The following substances when heated do not decompose but a change in colour is observed:
A zinc salt (e.g. ZnO) is yellow when heated and white when cold.
A lead salt (e.g. PbO) is reddish brown when hot and yellow when cold.
A few substances when heated sublime i.e. changes from a solid to gaseous state. ammonium
halides such as NH4CI, NH4I, NH4Br are very good examples
NH4CI → NH3(g) + HCI
(solid) (gas) (gas)

Table 2: colour changes when some substances are heated

Substance Colour before heating Colour after heating
CuSO4.5H2O Blue White
CuCI2.2H2O Blue Brown
FeCI3 Yellow Black
Pb(NO3)2 Yellow Reddish brown
Zn(NO3)2 White Yellow
ZnO, ZnCO3 White Yellow
PbO Yellow Reddish brown

iii) Flame Test

Pour some concentrated hydrochloric acid into a watch glass and dip platinum or a nichrome
wire into it. Hold the wire in a hot flame until it is colourless. Repeat this process. Moisten the
wire by dipping it into concentrated hydrochloric acid, dip it into the unknown solid, heat
strongly and observed colour changes.

Table 3: Flame Colour of Some Cations

Colour Cation
A Brilliant or golden yellow Sodium ions, Na+
B Lilac Potassium ions, K+
C Brick-red Calcium ions, Ca2+
D Bluish green or dark green Copper (II) ions, Cu2+
E Pale or light blue Lead (II) ions, Pb2+
F Yellowish green Barium ions, Ba2+
G Silver-white Aluminium Al3+
H Gold Iron (II)
I Orange-brown Iron (III)

B. IDENTIFICATION OF ACIDIC RADICALS (ANIONS)

Test for Acidic Radicals
The action of heat, dilute hydrochloric acid or concentrated tetraoxosulphate (VI) acid on a
substance gives an indication as to the acidic radicals present. This may involve the following:

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i) The Action of Heat
Heat a little of the dry substance in a test tube until no further change is seen. Note the state of
the residue and its colour. The following observation gives a guide.

Table 4: Action of Heat on Some Inorganic Samples

Observation Inference
Colourless, odourless gas, rekindles a Oxygen from oxides present
glowing splint
Colourless, odourless gas, turns lime water CO2(g) from carbonate and hydrogen
milky carbonates
Liquid, condenses on sides of test tube and Water of crystallization from salt
turns anhydrous copper (II) tetraoxosulphate
(VI) blue.
Reddish brown fumes. Dark red substance Nitrogen (IV) oxide from lead salt
when hot and yellow when cold

ii) Action of Dilute Hydrochloric Acid (HCI)

To the dry substance in a test tube, add some dilute hydrochloric acid and warm if no reaction
occurs but do not heat strongly.

Table 5: Action of dilute hydrochloric acid (HCI) on some samples

Observation Inference
If a reddish-brown gas is given off Gas is nitrogen (IV) oxide which indicates
presence of trioxonitrate (V) or dioxonitrate
(III) ion
If a colourless, pungent gas which turns The gas is sulphur (IV)oxide from sulphate
acidified potassium heptaoxodichromate which indicates the presence of
(VI) paper green trioxosulphate (IV)
If gas smells of rotten eggs and blackens leads Gas is hydrogen sulphide which indicates the
(II) ethanoate paper presence of sulphate ion
If gas turns lime water milky Gas is carbon (IV) oxide which indicates the
presence of HCO3- or CO32-

iii) Action of concentrated tetraoxosulphate (VI) acid on some samples

To the dry substance, add a little concentrated tetraoxosulphate (VI) acid and warm gently, if no
reaction occurs. Take careful observation, this acid is very corrosive. DO NOT BOIL

Table 6: Action of concentrated tetraoxosulphate (VI) acid on some samples

Observation Inference
If gas turns lime water milky Gas is CO2, indicating presence of HCO3- or
CO32-
Violent acid vapour accompanied by pungent Hydrogen iodide or iodine indicating the
smell. Odour of H2S presence of iodide ion
If reddish brown fumes which become deep Gas is nitrogen (IV) oxide, indicating the
brown on addition of copper turnings are presence of trioxonitrate (V) ion

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observed. Blue litmus turned red
If a colourless pungent gas fumes in air The gas is hydrogen chloride indicating the
bleaches litmus paper presence of a chloride
If a yellowish green gas is evolved, bleaches The gas is chlorine indicating the presence of
litmus paper and turns starch iodide paper chloride ion
blue
Brown fumes which deepen in the presence of NO2 from nitrate
copper turnings

iv) Confirmatory Tests for Acidic Radicals

A single test is usually not enough to give a true identity of an ion. A single test may suggest the
presence of several possible ions – this is reported as “suspected”. For example, a colourless gas
that has a strong irritating smell can be HCl of SO2, further text with litmus paper will show that
both gases also turn blue litmus paper to red. At this point, the inferred report is “suspected”.
Further test with liquid ammonia will distinguish both gases as only HCl will give a white fume.
This confirms HCl and finally reported as – “confirmed”.

Table 7 : Confirmatory Tests for Acidic Radicals

Test Observation Inference
1. Trioxonitrate (V) ion
(NO3-)
(a) To a solution of the
substance add a little freshly
A brown ring is formed at
prepared iron (II)
the junction of the two NO is formed
tetraoxosulphate (VI)
layers (solution)
solution and shake until it
dissolves.
NB: ferrous ammonium
Carefully pour cold
sulphate can also be used
concentrated H2S04 acid NO3- Confirmed
instead of freshly prepared
down the side of test tube.
FeSO4 solution
This should form a separate
layer at the bottom. Do not
shake the test tube while
adding the acid
(b) add copper turnings and Fumes of nitrogen (IV) oxide
Deep brown fumes are
concentrated H2SO4 acid to gas, confirming the presence of
given off
the dry substance and warm a trioxonitrate (V) ion NO3-
2. Tetraoxosulphate ion
(SO42-)
To a little of the solution A white precipitate which is White precipitate is barium
add dilute hydrochloric acid insoluble in excess HCI acid tetraoxosulphate (VI)
followed by barium chloride is formed confirming the presence of

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solution tetraoxosulphate (VI) ion SO42-

3. Trioxosulphate (IV)
(SO32-)
a) To a solution of a MnSO3 is colourless. Presence
substance, add KMnO4 and Solution becomes colourless of trioxosulphate (IV) ion is
dilute H2SO4 solution confirmed (SO32-)
b) To little of the
solution, add few drops of
chlorine water (chlorine
Solution becomes colourless Presence of trioxosulphate (IV)
water is a mixture of CI2
and water to give colourless
chlorate acid)
c) To the solution add
White ppt soluble in excess
barium chloride solution White ppt. is BaSO3
HCI acid
and HCI
d) To the solution add
KMnO4 solution turns
few drops of dilute H2SO4 SO32- ion confirmed
colourless
then few drops of KMnO4
e) To solution, add
Solution changes from
potassium chromate SO32- confirmed
orange to green
solution
4. Sulphide ion (S2-)
a) To a solution of the Cloudiness is due to sulphur
substance add KMnO4 and Solution becomes cloudy being precipitated. Sulphide is
dilute H2SO4 solution confirmed
b) If the solution is soluble
in water, add silver nitrate A black precipitate is The black ppt. is PbS .
solution or Pb(NO3)2 or lead formed Sulphide ion is confirmed
(II) ethanoate Pb(CH3COO)2
5. Halide ions (X-)
A white precipitate which is
a) To a solution of the
soluble in NH3 solution is
substance, add dilute HNO3 White ppt. is AgCI confirming
formed. (Soluble ppt.
and AgNO3 solution. Then the presence of CI- ion
darkens on exposure to
add ammonium hydroxide
light)
A pale-yellow precipitate
Pale yellow ppt is AgBr
which is sparingly soluble
confirming the presence of Br-
in ammonium hydroxide is
ion
formed
A yellow ppt which is
Yellow ppt is AgI which
insolube in ammonia
confirms the presence of I- ion
solution is formed
b) To dry the substance, A greenish gas evolved, Gas is chlorine which confirm
add manganese (IV) oxide which bleaches moist litmus the presence of chloride ion

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powder and heat paper
6. Nitrite ion (NO2)
To solution of the
substance, add freshly
prepared iron (II) sulphate A brown solution is formed Nitrite ion (NO2-) is confirmed
FeSO4 or Ammonium
ferrous sulphate
7. Carbonate (CO32-)
White precipitate is formed
These are mostly insoluble.
and a colourless gas which
To the substance add 2 The gas is CO2 from (CO32-)
turns lime water milky is
Molar HCI
evolved
8. Bicarbonate (HCO3-)
To the solution add MgSO4
Form white precipitate. CO2
solution. Only the alkali
gas is evolved on warming A bicarbonate is confirmed
metals have solid
and no ppt. when cold. It is HCO3-
bicarbonate and they are
also neutral to litmus
soluble in water

C. IDENTIFICATION OF METALLIC RADICALS (CATIONS)

Test for Metallic Radicals
A metallic radical can be identified from the colour and solubility of the precipitate it forms with
NaOH or NH4OH solution

A. With NaOH
To a solution of the substance, add a little NaOH and note colour of precipitate formed. Add
excess NaOH, shake well and observe if precipitate is soluble or insoluble

Table 8: Test Using NaOH

Observation Inference
If the precipitate is light-blue or pale-blue and The pale blue ppt. is Cu(OH)2
insoluble in excess sodium hydroxide Cu2+ is present
Cu2++ 2NaOH → Cu(OH)2 + 2Na+
If the precipitate is dark green and insoluble The green ppt. is Fe(OH)2
in excess NaOH Fe2+ is present
Fe2++ 2NaOH → Fe(OH)2 + 2Na
Turns brown on standing Fe2+ oxidizes to Fe3+
If there is a brown or black precipitate, The brown or black ppt is AgOH
insoluble in excess NaOH solution Ag+ is present
Ag+ + NaOH → Na+ + AgOH
If the precipitate is reddish brown and The reddish brown ppt. is Fe(OH)3
insoluble in excess sodium hydroxide Fe3+ is present
Fe3+ + 3NaOH → Fe(OH)3 +3Na+
If the precipitate is dirty white and insoluble The dirty white ppt. is Ca(OH)2

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in excess sodium hydroxide Ca2+ is present
Ca2+ 2NaOH → Ca(OH)2 + 2Na+
If the precipitate is white gelatinous and The white gelatinous ppt. may be Pb(OH)2
soluble in excess sodium hydroxide Al (OH)3 or Zn(OH)2
Pb2+, Al3+ or Zn2+ may be present

If no visible reaction, chocking or irritating The gas is NH3 from NH4+

smell gas is evolved. Turns red litmus paper NH4+ + NaOH → Na+ + NH4OH
blue

B. Test using ammonia solution (NH3)

To a solution of the substance, add a little ammonium hydroxide and note the colour of
precipitate formed. Add excess of it, shake and observe if precipitate is soluble or insoluble.

Table 9: Test Using NH4OH

Observation Inference
Reddish brown and insoluble in The reddish brown ppt. is Fe(OH)3
excess ammonium hydroxide Fe3+ is present
Fe3+ + 3NH4OH → Fe(OH)3 + NH4+
If the precipitate is dirty green The green ppt. is Fe(OH)2
and insoluble in excess Fe 2+ is present
ammonium hydroxide Fe2++ 2NH4OH → Fe(OH)2 + 2NH4+
If the precipitate is white and Pb2+ or Al3+ ion is present
insoluble in excess ammonium Pb2+ + 2NH4OH → Pb(OH)2 + 2NH4+
hydroxide Al3+ + 2NH4OH → Al(OH)3 + 3NH4+
If the precipitate is white The white ppt. is Zn(OH)2
gelatinous precipitate and Zn2+ ion is present
soluble in excess ammonium Zn2+ + 2NH4OH → Zn(OH)2 + 2NH4+
hydroxide On addition of excess NH4OH, soluble Zn(OH)2
dissolves to form colourless Zn(NH3)4(OH)2
Zn(OH)2 + 4NH2OH → Zn(NH3)4(OH)2 + 4H2O
If a light or pale blue ppt. which The pale blue ppt. is Cu(OH)2
is soluble in excess ammonium Cu2+ is present
to give a deep blue solution Cu2+ + 2NH4OH → Cu(OH)2 + 2NH4+
On addition (in drops) of excess hydroxide soluble deep
blue Cu(NH3)4(OH)2 is formed.
Cu(OH)2 + 4NH4OH → Cu(NH3)4(OH)2 + 4H2O
If a green ppt which is insoluble Precipitate is Fe(OH)2
in excess in ammonium Fe2+ is present
hydroxide
If a reddish brown ppt insoluble Precipitate is Fe(OH)3
in excess ammonium hydroxide Fe3+ is present
If no precipitate or no visible Ca2+, Ba2+, NH4+, Na+ or K+ ions are present
reaction is formed

CONFIRMATORY TESTS FOR METALLIC RADICALS

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A single test is usually not enough to give a true identity of an ion. A single test may suggest the
presence of several possible ions – this is reported as “suspected”. For example, if NaOH is
added to a sample and a white ppt appears, this ppt may be Al3+, Zn2+ or Pb2+. To confirm which
of these ions is present, a further test is need e.g., if the ppt dissolves on addition of excess
NaOH, then Zn2+ being the only cation (amongst these) that is soluble in excess NaOH is then
reported as “confirmed”.

The following are some test that can be carried out for some metallic radicals

Test Observation Inference

1. Copper Cu2+) The black precipitate is copper
To a solution of the salt A black precipitate sulphide (CuS)
(a) Add dilute HCl acid is formed Cu2+ → + H2S CuS + 2H+
and hydrogen sulphide Copper ion is confirmed
(b) Add ethanoic acid and A reddish-brown The reddish brown is Cu2[Fe(CN)6]
two drops of precipitate is Cu2+ is confirmed
hexacyanoferrate formed
(i) K4[Fe(CN)6]
(c) Add Kl solution A brown The brown precipitate is CuI2
precipitate and Cu2+ + 4l- → Cul2
precipitate are
formed
2. Iron(II) Fe2+ The dark blue ppt. is
(a) To a solution of the salt, A dark blue ppt. is Fe3 [Fe(CN)6]
add potassium formed 3Fe2+ + K3[Fe(CN)6] →
hexacyanoferrate (III), Fe3 Fe(CN6 ) + 6K+
K3[Fe(CN)6] Fe2+ Confirmed
(b) To the solution of the Fe2+ oxidizes to Fe3+
substance, add a few The solution turns Fe2+ confirmed
drops of conc. HNO3 brown
acid and boil for a while
3. Fe3+ Blood red colouration is Fe(SCN)3
To a solution of the A blood red Fe3+ is confirmed.
substance, colouration is KSCN + Fe3+ → Fe(SCN)3
(a) Add potassium formed
thiocyanate solutions
(b) Add K3[Fe(CN)6] A brown The brown precipitate is Fe[Fe(CN)6].
solution precipitate is Fe3+ is confirmed.
formed Fe3+ + K3[Fe(CN)6] →
Fe [Fe(CN)6] + 3K+

4. Ca2+
To the solution of the A white ppt. is The white ppt. is CaCO3
substance, formed (NH4)2CO3 + Ca2+ → CaCO3 + 2NH4+
(a) Add (NH4)2CO3
A milky or a white Ca2+ + H2SO4 → CaSO4 + 2H+

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 (b) Add dilute H2SO4 ppt. which later Ca2+ is confirmed from CaSO4
gives a white ppt.
A yellow The yellow precipitate is PbI2
5. Lead (Pb ) 2+
precipitate is Pb2+ + I- → PbI2
To a solution of the salt, formed
(a) Add KI (potassium Pb2+ is confirmed
iodide) solution A yellow ppt. The yellow ppt. is PbCrO4
which is soluble in Pb2+ + PbCrO4 → PbCrO4 + K
(b) Add K2CrO4 excess K2CrO4 is Pb2+ is confirmed
formed

6. Zinc (Zn2+) A white precipitate Zn2+ ion is confirmed

To a solution of the salt,
add a little NH4OH, shake,
then add more hydroxide,
shake and observe.
H2S or K4[Fe(N)6] can also
be added.
is formed which Zn2+ + 2NH4OH → Zn(OH)2 +
dissolves on 2NH4+
addition of excess On addition of excess NH4OH soluble
hydroxide Zn(OH)2 dissolves to form colourless
Zn(OH3)4(OH)2
Zn(OH)2 + 4NH4OH →
Zn(NH3)4(OH)2 + 4H2O

7. Aluminium AI3+ The white precipitate is AI(OH)3

(a) To a solution of the A white precipitate AI3+ + 3NH4OH → AI(OH)3 +
salt, add few drops of is formed 3NH4+
ammonia solution then AI3+ is confirmed
add NH4CI solution A white gelatinous AI3+ confirmed
(b) To the solution of the precipitate is
salt, add few drops of formed
2M HCI followed by
one drop of litmus
solution
(c) To the solution of the
sample, add few drops
of alizarin solution The alizarin dye is
then add ammonia completely taken- AI3+ confirmed
solution up and the ppt. is
coloured pink
8. Silver ion (Ag+) A white ppt. is Silver ion (Ag+) is confirmed.
To the solution of the salt, formed soluble in Ag+ + HCI → AgCI + H+
add dilute HCI then add NH4OH and
ammonia dissolve on
exposure to light
9. Sodium ion (Na+) A yellow Sodium ion (Na+) is confirmed
To the solution of the precipitate is
substance, add few drops of formed
Zinc uranyl acetate solution
10. Magnesium (Mg2+) A colourless Mg2+ is confirmed

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To the solution of the crystal is formed
substance, add solid NH4Cl
then phosphate solution
11. Sn2+ White precipitate Sn2+ convert Hg2+ to Hg+ as Hg2CI2 turn
(a) Solution of the which turns grey grey then black
sample + H2S + then black brown
Conc. HCI + HgCI2 precipitate Sn2+ confirmed
(b) Solution of the
sample + H2S until
saturation Sn2+ confirmed
12. Ba2+ Yellow precipitate, The yellow precipitate is BaCrO4
Sample solution + K2CrO4 insoluble in excess Ba2+ present
in drops then in excess + K2CrO4 insoluble
warm on warming

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ORGANIC ANALYSIS

Action of Heat or Ignition Test

Table 11: Observation and inference that can be drawn from the ignition test
Possible observations Inference
If inflammable
(i) Sooty luminous flame or smoky flame Compound with high carbon content e.g.
aromatic compound or highly unsaturated
hydrocarbon
(ii) Non luminous blue flame or non-
sooty or smoky flame Compound with low carbon content e.g.
Aliphatic saturated compounds
(iii) Does not burn readily but produces a
smoky flame on burning It may be halogen compounds
(iv) Burns rapidly
Carbohydrate present

Solubility
The table below shows the common inference that may be drawn when organic compounds are
dissolved in various reagents. A portion of the sample is treated with:
Test Observation Inference
(a) Hot or cold water If it dissolves to give a Low molecular mass alcohol,
neutral solution (soluble) carbonyl compounds, amides,
carbohydrate
If it dissolve to give an acidic Carboxylic acids and its salt,
solution and turns blue litmus salts of amine with strong
paper red acid are present
If it dissolve to give a basic Amines and salts of
solution carboxylic acids with strong
base are present
(b) Saturated NaHCO3 (i) If soluble with Carboxylic acid present
solution effervescence
(II) if insoluble phenol, amide, ester,
hydrocarbon is likely present
(c) Dilute NaOH Solution turning blue litmus Acidic substance present e.g
solution paper red phenol, carboxylic acid,
alcohols, sulphoamide
(SO3NHR) etc
Insoluble Basic substance e.g amine
and salt of carboxylic acid
with strong base present

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Dilute HCI + heat if Soluble turning red litmus Basic compound present i.e
necessary blue compound containing N e.g
amine

THE GENERAL CLASSIFICIAITON TEST

Test for Unsaturation
Bromine water
Add 2cm3 of CCI4 to 2 drops (or 0.1g) of the compound and shake to dissolve. Now add 2%
solution of bromine in CCI4 drop wise with shaking.
The discharge of colour of the bromine without the evolution of gas (HBr) indicates that the
tested compound is saturated.

(a) KMnO4 (Beayers test)

To about 2 drops or 0.1g of the compound dissolved in 2cm3 of eater or acetone (if insoluble in
water) add 2% KMnO4 solution, if the colour of KMnO4 changes from purple to colourless and
brown colour ppt. (MnO2) appears. Aldehydes and alcohols also give positive result, then the
compound is unsaturated but if there is no change in colour i.e solution remains pink then the
compound is saturated.

CONFIRMATORY TEST FOR FUNCTIONAL GROUPS

ALCOHOLS (ALKANOLS)
(i) Sodium test: (carry out this reaction with extreme care) add a small amount of freshly cut
sodium metal with care to about 1cm3 of anhydrous liquid containing the alcohol
functionality in dry test tube
Note: hold the test tube away from you (arm stretch) and do not pour the reaction mixture into
the sink or dust bin
A vigorous effervescence with the evolution of hydrogen gas, which is colourless, odourless and
has no effect on litmus paper indicating the presence of alcohol
Na(s) + CH3CH2OH → CH3CH2ONa + 1/2H2
Sodium ethoxide

(ii) Add about 2cm3 of ethanoic acid and a few drops of concentrated H2SO4 to about 2cm3 of
the dissolve substance in a test-tube. Boil the mixture if a characteristic pleasant fruit
smell called ester is formed alcohol functionality is present.
ROH+R1COOH → R1COOR + H2O
(iii) Place about 1cm3 of Ceric nitrate (Ceric ammonium nitrate, (NH4)2(Ce(No3)6, reagent in
a test tube and add 3cm3 of distilled water, mix thoroughly. A colour change from
yellow to red indicates an alcohol
NH4)2(Ce(NO3)6 + ROH → (NH4)2(Ce(NO3)5OR + HNO3
(iv) Dissolve 0.5g of sodium dichromate in a few drops of water, add an equal number of
drops of concentrated H2SO4 and a little of the unknown compound and warm gently.
Pass the gas evolved into the top of schiff’s reagent in a test tube but not directly into the
reagent. When enough gas has been collected shake it up with reagent.
If dichromate turns green and schiff’s reagent turns pink, the tested compound is a
primary alcohol. If only dichromate turns green and vapour has no effect on schiff’s

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 reagent the compound is secondary alcohol. Tertiary alcohol has no effect or both
reagents (dichromiate and schiff’s reagent).
H H OH
CrO3 2- CrO3 2-
R C OH R C R C
Oxidation Oxidation
O O
H
1o Alcohol Aldehyde Pink colour with Schiff reagent
H
O
CrO3 2- CrO3 2-
R C OH R C No Oxidation
Oxidation Oxidation
R R
No Pink colour with Schiff reagent
2o Alcohol Ketone

R
CrO3 2-
R C OH No Oxidation No Pink colour with Schiff reagent
Oxidation
R
o
3 Alcohol
Oxidation is indicated by dicromate with a colour change from orange to green

V) Place about 1cm3 of ethanol (or benzoyl) chloride reagent in a test and add 3cm3 of distilled
water, mix thoroughly and add 3 drops of 0.5g of the test compound (if it is water soluble).
Shake the mixture thoroughly. If liberation of an acidic gas (the gas bleaches litmus paper)
which forms a white dense fume with ammonia solution (with the separation of an oily layer).
This confirms the presence of an alcohol group.
ROH + CH3COCI → RCOOCH3 + HCI

1. ALDEHYDES AND KETONES

Common test
(i) If the substance is in solid state, dissolve in methanol and add few drops of 2.4
dinitrophenylhydrazine reagent to about 1cm3 of the solution of the substance and methanol. A
yellow precipitate formed within a few minutes indicate the presence of an aldehyde or ketone
NO2 NO2
H2SO4 ---NH—N=C
C=O NO2-- --NHNH2 Alcohol NO2---
Aldehyde OR 2.4 dinitrophenylhydrazine
ketone 2,4-dinitrophenylhydrazone

(ii) Iodoform Test (for methylketone CH3CO)

To four drops (0.1g) of the compound in a test tube add 2cm3 of dioxane and shake to dissolve.
Then add 1cm3 of 10% KI solution followed by 5cm3 of freshly prepared sodium hypochloric
solution and shake vigorously to ensure thorough mixing, yellow precipitate of triidomethane
(iodoform) CHI3 indicates the presence of a methylketone or aldenyde .

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 RCOCH3 + 3I2 + 3NaOH → RCOCI3 +3NaI + 3H2O
Methylketone

RCOCI3 + NaOH → RCOONa + CHI3

Sodium carboxylate lodoform (yellow)

(iii) Sodium nitroprusside test (for methylketones CH3CO)

To few drops of the compound add 1 ml of sodium nitroprusside (Na[Fe(CN)5NO].2H3O)
solution and excess of 30% sodium hydroxide solution, a red colour complex is a positive test.

(iv) Sodium hydrogen sulphite test

Add 2cm3 of the reagent into a test tube containing the carbonyl compound, ketone and aldehyde
give adduct. Heat is evolved and a crystalline precipitate of the hydrogen sulphite adduct
separately readily.
The adduct is the white precipitate formed

Test to differentiate between aldehyde and ketone

(i) Silver mirror (Tollen’s test)
Add 1-2 drops of dilute NaOH to about 2cm2 of AgNO3 then add ammonia solution until the
precipitate formed just dissolved. Add about 1-2cm3 of the unknown organic substance to the
prepared tollen’s reagent and warm on a water bath. Do not shake the test tube. A mirror of
metallic silver is found on the wall of the test tube which shows the presence of an aliphatic
aldehyde
RCHO + 2Ag(NH3)2OH → RCOONH4 + 2Ag+ H2O + 3NH3
(silver mirror)
(ii) Fuchsin Reagent Test
To about 2cm3 of schiff’s reagent add 2 drops or 0.1g of the unknown substance production of
pink colour indicates the presence of aldehyde but ketone have no effect (aliphatic aldehydes).

(iii) Fehling’s test

To about 2cm3 of fehling solution A, add Fehling’s solution B until precipitate first formed just
dissolved.
Add the compound and boil. The solution turns green and a fine yellow or red precipitate
separates either immediately or on standing if an aldehyde is present
RCHO + 2Cu2+ + NaOH + H2O → RCOONa + CO2 + 4H+

2. CARBOXYLIC ACID
(i) To about 2-3 drops of solution of the organic substance in water in a test tube, add saturated
solution of aqueous sodium hydrogen carbonate in drops till in excess. An effervescence which
evolved a colourless odourless gas and acidic to litmus occurs. The gas also turns lime water on a
glass rod milky indicating that the gas is CO2
RCOOH + NaHCO3 → RCOONa + CO2 + H2O
Hence, – COOH group is present
(II) Add about 2cm3 of ethanol and a few drops of concentrated H2SO4 to about 2cm3 of the
substance in a test tube. Boil the mixture, if a characteristic pleasant fruity smell substance called

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ester is formed, carboxylic acid group is present

3. PHENOL
(i) Ferric chloride test: to a solution of the compound, in about 1cm3 of water or
alcohol, add few drops of ferric chloride (FeCI3). A violet or blue colouration
indicates the presence of phenol
(ii) Bromine water test: –to a solution of the compound add a drop of bromine water. A
distinct change in colour to white indicates that phenol is present in the compound.
NB: Phenol is readily soluble in NaOH but slightly soluble in water.

4. ESTER
This is a neutral compound insoluble in water, acidic or cold alkaline solution. It has a sweet
smell.
(i) To small amount of the compound in a test tube, add 1cm3 of 0.5M hydroxylamine
hydrochloride in 95% ethanol. Then add 0.5cm3 of 5M HCI. If the solution becomes
cloudly, add FeCI3 until the colour fully developed in the solution. Magenta or deep
red indicates the present of ester.
(ii) To small amount of the compound add 2 drops of dilute NaOH
(2 moldm-3) and 2 drops of phenolphthalein then shake the test tube before boilding
for a while on a water bath. The disappearance of the pink colour of the
phenolphthalein indicates the presence of an ester.
5. AMINE
(i) Nitrous test
Iced-cold concentrated HCI acid is used (HCI). Add about 1cm3 or 0.5 of the compound to the
ice cold conc. HCI and add about 2cm3 of sodium nitrite (NaNO2) solutions drop wise.
If a separate yellow oily layer is formed, secondary amines (aliphatic or aromatic) are present.
There is no reaction with tertiary amine but they form a soluble salt. The reaction mixture gives
an immediate positive test on the starch-iodide paper for nitrous acid
If the ice-cold solution does not react as in the above reaction, then perform test below for
aromatic amine:
Pour about 2cm3 of the ice-cold solution into a test tube and add 1cm3 of previously prepared
solution of b-naphthol in 10% NaOH. A deep orange to red coloration indicates an aromatic
primary amine.
To secondary aliquot of the ice-cold amine hydrochloric acid solution, add 1cm3 20% NaOH
solution. If the original red or orange colouration turns green, then an aromatic tertiary amine is
present. Aromatic amines reacts with nitrous acid to form the orange coloured hydrochloride salt
of the C-nigrosoamine. Treating the solution with base liberates the blue or green C-
nitrosoamine.
(ii) Sulphonyl chloride test (Hinsberg test)
Add about 5cm3 10% of the solution of the compound and 1cm3 P – toluene Sulphonyl Chloride
(or benzyi sulphonyl chloride) to about 1cm3 of the compound. Cover with stopper and shake
vigorously. When the colour of sulphonyl chloride has disappeared, add HCI and examine the
product.
If a precipitate is formed, dilute with about 10cm3 of water and shake. A soluble ppt. indicates
primary amines while an insoluble precipitate indicates secondary amines.

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 6. AMIDES
Add about 2cm3 of dilute NaOH solution to the solution of the compound in a test tube and boil
for a while if a gas which is colourless with a pungent and irritating smell is evolved. It also turns
red litmus paper blue and produces a white dense fume of NH4CI with concentrated HCI, then an
amide is present
The gas is NH3 indicating the presence of an amide.
RCONH3 + NaOH → RCOON3 + NH3

NH3 + HCI → NH4CI

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 EXPERIMENT ONE
SALT ANALYSIS
a. Sample C is a metal, carry out the following tests on sample C. Record your observations
and draw your inference.
Put C in a test tube and add dilute hydrochloric acid. Test the gas evolved with litmus papers (red
and blue) and a lighted splinter.
b. Sample D is an Inorganic salt. Add MnO2 to sample D in a test tube and heat strongly. Test
the gas evolved with litmus paper (red and blue) and glowing splinter. Record your
observations and your inference.
c. Sample E is an inorganic salt. Carry out the following tests on the sample:
i. Divide the sample into two portions and to the first portion add concentrated
tetraoxosulphate (VI) acid. Test the gas evolved with litmus paper (blue and red) and with a
glass rod dipped in NH3(aq) or AgNO3 solution.
ii. Add water to the second portion in a test tube. Add dilute hydrochloric acid and AgNO3
solution followed by excess NH3(aq).
Write your observation and draw your inferences from your result and identify the anion in
sample E.
d. Sample J: Divide sample J into two parts. Heat the first part strongly in a test tube. Test any
gas(es) evolved with litmus papers and lime water.
i. To the second part add dilute hydrochloric acid and divide the resulting solution into two
portions
ii. To the first portion, add aqueous sodium hydroxide in drops and then in excess
iii. To the second portion, add aqueous ammonia in drops and then in excess
Record your observations and draw your inferences.

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 EXPERIMENT TWO
K is a mixture of two salts, carry out the following exercise on K. Record your observation and
identify any gas(es) evolved.
A. Put K in a test tube and add about 5cm3 of water. Stir thoroughly and then filter.
Divide the filtrate into 3 portions
i. To the first portion add sodium hydroxide solution in drops and in excess.
ii. To the second portion add NH3(aq) in drops and then in excess.
iii. Acidify the 3rd portion with dil. HNO3 followed by few drops of AgNO3
solution. Then add NH3(aq) in drops and in excess
B. To the residue, add dilute HNO3, identify any gas liberated
C. Divide the resulting solution from B into two portions
i. To the first portion add NaOH(aq) in drops and in excess
ii. To the second portion add NH3(aq) in drops and in excess
iii. From your results name the filtrate and the residue

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 EXPERIMENT THREE
A. Sample D is an inorganic salt. Add water to the sample followed by a little freshly prepared
FeSO4 solution. With the test tube in the slanting position carefully pour concentrated H2SO4
down the test tube. From your observation, and inferences identify the anion in the sample D.
B. Give the reason for the following:
i. Using just a small quantity of indicator during acid base titrations
ii. Obtaining at least two sets of readings for the titration experiment
C. M is a mixture of NaCl, NH4Cl and PbSO4. Describe how you would obtain each
component in a pure state.

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 EXPERIMENT FOUR
You are provided with two samples labelled H and K. Carry out the following tests on them and
record your observations
a) Sample H
Take 2g of sample H and add 2mL of distilled water to sample H and record your observation.
Divide your sample into 3 portions and carry out the following analyses
To the first portion, add 0.5mL of ethanol followed by 5 drops of 2,4-dinitrophenylhydrazine
To the second portion, add 0.5mL of 10% NaOH followed by 6 drops of I2/KI mixture with
shaking
To the third portion add 6 drops of I2/KI solution
b) Sample K
Add 2mL of distilled water to 1g of sample K and record your observation. Divide sample K into
three portions
To the first portion, add 0.5mL of ethanol followed by 5 drops of 2,4-dinitrophenylhydrazine
To the second portion, add 0.5mL of 10% NaOH followed by 6 drops of I2/KI mixture with
shaking
To the third portion add 2mL of Fehlings/Tollens reagent.

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 EXPERIMENT FIVE
You are provided with two samples labelled P and Q. Carry out the following analyses on then.
Add 5 drops of each sample into separate test tubes.
a) To the first test tube, add 1 mL of distilled water followed by 0.5 mL of 10% NaOH.
b) Add 8 drops of I2/KI mixture while shaking.
c) To the second test tube, add 4 drops of ethanol, followed by 5 drops of 2,4-
dinitrophenylhydrazine.
d) Record your observations and draw possible conclusions
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 EXPERIMENT SIX
You are provided with three organic liquids A, B and C, you are to determine the functional
group present in each. Record your observation and inference in each step.

Test 1: Add 1 mL of each sample to separate test tubes and add 1 mL of 2,4-DNP
Test 2: Add 1 mL of each sample to separate test tubes and add 1 mL of Tollen’s reagent
Test 3: Add 1 mL of each sample to separate test tubes and add 1 mL of potassium dichromate
solution.
Test 4: Add 1 mL of each sample to separate test tubes and add 1 mL of iodine solution followed
by 1 mL of NaOH solution
Test 5: Add 1 mL of each sample to separate test tubes and add 1 mL of KMnO4 followed by 1
mL of NaHCO3 solution

Questions
1. State the functional group present in A, B and C
2. Write the structural formula of A, B and C if the contain 3 carbon atoms.
3. Write an equation to show the reaction occurring in Test 3.
4. What gas is evolved on Test 5
What gas is evolved in Test 3

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 EXPERIMENT SEVEN
State what you would see on
i. Bubbling SO2 into acidified KMnO4 Solution
ii. Mixing Zinc dust with CuSO4 solution
iii. Adding conc. HNO3 to freshly prepared FeSO4 solution.
iv. List two substances in each case that would be added to dilute H2SO4 to produce
a. H2(g) b. ZnSO4(aq)

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 EXPERIMENT EIGHT
D is a mixture of two inorganic salts. Perform the following tests on D and record your
observations and inference in the table below.
a) Put 5g of D in a test tube and add 15 ml of distilled water. Stir and filter. Test the filtrate
with litmus paper.
b) (i) to 2 ml of the filtrate, add few drops of 2M HNO3, followed by 0.5M AgNO3.
(ii) Add excess 2M NH3 solution in excess
c) To the residue, add 5 ml of 2M HNO3 in drops. Divide the portion into two
(i) To the first portion, add 2M NH3 solution in drops and then in excess
(ii) to the second portion add 2M HCl solution.

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 EXPERIMENT NINE
You are provided with three organic liquids labelled A, B, C. Perform the following tests to
determine the functional group present. Perform each test with fresh samples
Test 1: add 1 ml of each to different test tubes and add 1 ml of 2,4-DNP
Test 2: add 1 ml of each to different test tubes and add 1 ml of tollens reagent
Test 3: add 1 ml of each to different test tubes and add 1 ml of potassium dichromate solution
followed by NaHCO3.
Test 4: add 1 ml of each to different test tubes and add 1 ml of iodine followed by 1 ml of NaOH

Questions:
a) State the functional group present in A, B, C
b) Write the structure of A, B and C with the least number of carbon atom(s).
c) Name the two types of reactions occurring in Test 3 with potassium dichromate
d) Write an equation each to represent the reactions listed in (c)

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 EXPERIMENT TEN
Q is a mixture of two inorganic salts. Carry out the following tests on sample Q, record you tests,
observations and give inferences.

Transfer 1.0 g of Q into a boiling tube and add 5 mL of distilled water. Stir and allow to settle,
then filter and keep the filtrate.

a) To a small portion of the filtrate in a test tube, add small amount of ammonia in drops and
then in excess
b) To the precipitate in (a), add 6M HCl, followed by K3Fe(CN)6
c) To another portion of the filtrate, add HNO3, then AgNO3.
d) To the resulting mixture in (c), add excess ammonia solution
e) To another portion of the filtrate, add 2M HCl, then Barium chloride
f) To the resulting mixture in (e), add excess 2M HCl
g) To another portion of the filtrate, add barium chloride followed by 2M HCl.

Questions
i) Write an equation for the reaction occurring in (a)
ii) Write an equation for the reaction occurring in (b) with HCl
iii) Write an equation for the reaction occurring in (d)
iv) Write an equation for the reaction occurring in (g)
v) What type of reaction is occurring in (ii) above?

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