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Qualitative Analysis
 Chemical Analysis

Qualitative

The resolution of a
chemical compound into
Chemical
its proximate or ultimate
Analysis
parts to determine
its elements.

Quantitative
 Qualitative Analysis of Inorganic Salts

Part contributed Part contributed

by a base by an acid
Identification of
cations and anions
present in salt or
mixture of salts
Basic radicals Acidic radicals
 Qualitative Analysis of Inorganic Salts

Example
O4

−
O4
Cation Anion

Basic Acidic
radical radical
Note!!

Qualitative analysis is carried

out through the reactions
that are easily perceptible
to our senses.

Sight, smell
and more
 Reactions

01 Formation of precipitate

Change in colour 02

03 Evolution of gas
 Steps in Salt Analysis

Preliminary examination of solid

Step 1 Carried out
salt and its solution
in solution

Determination of anions by wet

Step 2 Carried out
test and confirmatory test
in solution

Determination of cations by wet

Step 3
test and confirmatory test

These tests are not conclusive but

sometimes provide important clues.
 Preliminary Tests

These tests involve noting of

general appearances and
physical properties.

Colour and
Solubility
smell
Dry tests
 Dry Tests

Flame test
✓
Borax bead test
✓
Sodium carbonate
bead test
 Sodium Carbonate Bead Test

● A small quantity of Na2CO3 powder is heated in

platinum wire loop in a Bunsen burner till
it forms a white bead.
● This hot bead is dipped into a pinch of
KNO3 powder and then in the sample powder.
● Mn will form a green bead and Cr will
form a yellow bead.
 Analysis of Anions

● Group A: Produces vapour/gas on mixing with

dil. H2SO4/HCl
● Group B: Produces vapour/gas on mixing with
conc. H2SO4/HCl
● Group C: Does not produce any vapour/gas
with any of them
Chemical Analysis

Water extract is
made by dissolving
salt in water.
 Sodium Carbonate Extract

Preparation
Take 1 g of salt in a porcelain dish
or boiling tube. Mix about 3 g of
solid sodium carbonate and add
distilled water to it .

Stir and boil the content for about

10 minutes. Once it cools, filter and
collect the filtrate in a test tube.
 Analysis of Anions

Carbonate (CO32 ─) Chloride (Cl─)

Sulphide (S2─) Test of Bromide (Br─)

Sulphate (SO42─) Iodide (I─)

Nitrate (NO3─)
 Confirmation Test for CO32 ─

Confirmation of CO32 ─ is done by using

aqueous solution of the salt or by using
solid salt as such.

Sodium carbonate extract

contains carbonate ions.
 Confirmation Test for CO32 ─

Take 0.1 g of salt in a test tube, and

01 add dilute sulphuric acid.

CO2 gas is evolved with brisk effervescence,

which turns lime water milky.
02

On passing the gas for some more

03 time, milkiness disappears.
 Confirmation Test for CO32 ─

The evolution of colourless and odourless

2−
gas indicates the presence of CO3

Na2CO3 + H2SO4 Na2SO4 + H2O + CO2

Ca(OH)2 + CO2 CaCO3 + H2O

Milky

CaCO3 + CO2 + H2O Ca(HCO3)2

Soluble in water
 Analysis of Anions

Carbonate (CO32 ─) Chloride (Cl─)

Sulphide (S2 ─) Test of Bromide (Br─)

Sulphate (SO42─) Iodide (I─)

Nitrate (NO3─)
 Confirmation Test for Sulphide

● Presence of sulphide is confirmed by mixing 1 mL of

the water extract with NH4OH or sodium carbonate
extract to make it alkaline.
● On adding a few drops of sodium nitroprusside, the
solution turns purple in color due to formation of the
complex Na4[Fe(CN)5NOS]
 2─
Confirmatory Test of SO4

Aqueous solution or sodium

carbonate extract of the salt
is acidified with acetic acid.
Reaction

Addition of barium chloride Na2SO4 + BaCl2 BaSO4 + 2NaCl

gives a white precipitate of
barium sulphate. Barium sulphate
(white precipitate)

BaSO4 is insoluble in conc.

HCl or conc. HNO3.
 2─
Confirmatory Test of SO4

Sulphate ions give white precipitate of lead

sulphate.When aqueous solution or sodium
carbonate extract is neutralised with acetic
acid and treated with lead acetate solution

Reaction

Na2SO4 + (CH3COO)2Pb PbSO4 + 2CH3COONa

Lead sulphate
(white precipitate)
 Confirmatory Test of NO3 ─

On heating the salt with conc. H2SO4

light brown fumes are evolved

On adding of a small quantity of copper

turnings, the solution turns blue due to
the formation of copper sulphate.
 Confirmatory Test of NO3 ─

The evolution of excess of

brown fumes
indicates the presence of NaNO3 + H2SO4 NaHSO4 + HNO3
nitrate ions.
Copper sulphate (Blue)

The solution turns blue 4HNO3 4NO2 + O2 + 2H2O

due to the formation of
copper sulphate. Brown fumes
 Confirmatory Test of NO3 ─

NaNO3 + H2SO4 NaHSO4 + HNO3

6FeSO4 + 3H2SO4 + 2HNO3 3Fe2(SO4)3 + 4H2O + 2NO

FeSO4 + NO + 5H2O [Fe(H2O)5(NO)]SO4

Pentaaquanitrosoniumiron (I)
sulphate
Brown colour
 Analysis of Anions

Carbonate (CO32 ─) Chloride (Cl─)

Sulphide (S2─) Test of Bromide (Br─)

Sulphate (SO42─) Iodide (I─)

Nitrate (NO3─)
 Confirmatory Test for Chlorides

● Chloride ions are confirmed by chromyl chloride test.

● Mix a small amount of salt and an equal amount of
solid K2Cr2O7 in a test tube and add conc. H2SO4 to it.
● Pass the evolved gas through NaOH solution.
● Acidify the solution with lead acetate. Formation of a
yellow precipitate of lead chromate confirms the
presence of chloride ions.
 Confirmatory Test of Cl−

Acidify the second part with dil.

H2SO4 and add small amounts of
amyl alcohol and then 1 ml of 10%
hydrogen peroxide solution.

On shaking gently, the

organic layer turns blue.
 Confirmatory Test of Cl−

CrO42─ ion formed in the reaction

of chromyl chloride with
sodium hydroxide reacts with
hydrogen peroxide to form
chromium pentoxide.

Chromium pentoxide dissolves in

amyl alcohol to give blue colour.

2−
CrO4 + 2H+ + 2H2O2 CrO5 + 3H2O

Chromium
pentoxide
 Analysis of Anions

Carbonate (CO32 ─) Chloride (Cl─)

Sulphide (S2─) Test of Bromide (Br─)

Sulphate (SO42─) Iodide (I─)

Nitrate (NO3─)
 Confirmatory Test for Bromides

● If the salt, on heating with conc. H2SO4 leads to

evolution of reddish brown fumes, then
bromide ion may be present.
● The fumes are intensified by addition of MnO2.
● On adding CHCl3 and Cl2 and shaking the tube
vigorously, if the organic layer shows orange
coloration, then bromide ion is present.
 Confirmatory Test of Br−

Acidify the sodium carbonate extract of the

salt with dil. HNO3. Add silver nitrate (AgNO3)
solution and shake the test tube.

A pale-yellow precipitate is obtained

that dissolves in ammonium
hydroxide with difficulty.

NaBr + AgNO3 NaNO3 + AgBr

Silver bromide
Pale yellow precipitate
 Analysis of Anions

Carbonate (CO32 ─) Chloride (Cl─)

Sulphide (S2─) Test of Bromide (Br─)

Sulphate (SO42─) Iodide (I─)

Nitrate (NO3─)
 −
Confirmatory Test of I

Acidify sodium carbonate extract

of the salt with dil. HNO3 and add
AgNO3 solution.

Appearance of yellow precipitate

insoluble in excess NH4OH confirms
the presence of iodide ions

NaI + AgNO3 NaNO3 + Agl

Silver iodide
Yellow precipitate
 −
Confirmatory Test of I

Add 1 mL of CHCl3 or CCl4 and chlorine

water in excess to the salt solution in water
or sodium carbonate extract neutralised
with dil.HCl

shake the test tube

vigorously.

Violet colouration in organic layer

confirms the presence of iodide ions
 Steps in Salt Analysis

Preliminary examination
01 of solid salt and its solution.

Determination of anions by wet

test and confirmatory test. 02

Carried in Determination of cations by

solution
03 wet test and confirmatory test.
 Classification of Cations

Zero
Group Group-I Group-II Group-III Group-IV Group-V Group-VI
goup
Cd2+, Sn2+,
Sb3+, Pb2+, Zn2+,
Ag+, Pb2+ , Hg2+, Bi3+, Al3+, Fe3+, Ba2+, Sr2+,
Cations NH4+ Mn2+, Mg2+
Hg22+ Cr3+ Ca2+
Cu2+, As3+ Co2+, Ni2+
, Sn4+

H2S in
H2S gas NH4OH (NH4)2CO3
the
Group Dilute in the in the in the
None presence None
reagent HCl presence presence presence
of
of Dil. HCl of NH4Cl of NH4OH
NH4OH
 Classification of Cations

● The order of adding reagents for group I and II is: dil.HCl

followed by H2S gas.
● For group III the reagent is NH4OH in presence of NH4Cl
● H2S in the presence of NH4OH is used for group IV
● For group V, (NH4)2CO3 in the presence of NH4OH is used.
● There is no reagent for group VI.
Note!!

Precipitation of Group II ions takes

place because they have lower Ksp
values. Hence at low conc. of
sulphide ions, they get precipitated.
 Some Mnemonics

● Mnemonic for group I : AAJ HOGI PROBLEM

● Mnemonic for group IIA : PUNJABI KUDI HOGI KAID
● Mnemonic for group IIB : ASSI SAB TANA TAN
● Mnemonic for group I : AAJ HOGI PROBLEM
● Mnemonic for group IIA : PUNJABI KUDI HOGI KAID
● Mnemonic for group IIB : ASSI SAB TANA TAN
Steps Involved in Examination of Cations

Preliminary examination of the

01 salt for identification of cation

Wet tests for the

confirmation of cations 02
 Preliminary Examination

Colour test

Dry heating test

Identification of
cations by
Flame test

Borax bead test

 Colour Test

Cations
Colour
indicated

Light green,
Fe2+, Fe3+
yellow, brown

Blue Cu2+, Sr2+, Ca2+

Bright Green Ni2+

Blue, red,
Co2+
violet, pink

Light Pink Mn2+

 Dry Heating Test

Take about 0.1 g of the dry salt

in a clean and dry test tube.

Heat the above test tube for

about one minute and observe
the colour of the residue
when it is hot and also
when it gets cold.
 Dry Heating Test

Cations
Colour when Cold Colour when hot
indicated

Blue White Cu2+

dirty white
Green Fe2+
or yellow

White yellow Zn2+

Pink Blue Co2+

 Flame Test

Take a glass rod and dip in the

solution of the salt

Heat the above glass rod on a

Bunsen burner and observe the
color of the flame
 Flame Test

Colour of the flame

Colour of the flame
observed through Inference
observed by naked eye
blue glass

Green flame Same colour as

Cu2+
with blue centre observed without glass

Crimson red Purple Sr2+

Apple green Bluish green Ba2+

Brick red Green Ca2+

 Borax Bead Test

● On heating, borax loses its water of crystallisation.

● It then decompose to give sodium metaborate and
boric anhydride.
● On treatment with a metal salt, boric anhydride forms
metaborate of the metal which shows different colors.
 Steps Involved in Examination of Cations

Preliminary examination of the

01 salt for identification of cation

Wet tests for the

confirmation of cations 02
The first essential
step is
to prepare a clear
and transparent
solution of salt called
Original solution .
 Preparation of Original Solution

Take a little amount of the salt in a clean boiling tube and add
01 a few mililitres of distilled water, shake it. Heat the contents of
the boiling tube till all the salt is completely dissolved.

If the salt is insoluble in water, take fresh salt in a clean boiling

02 tube and add few mililitres of dil. HCl to it. If the salt is insoluble
in cold, heat the boiling tube until all the salt is dissolved.
 Preparation of Original Solution

If the salt does not dissolve either in water or in dil. HCl even on
03 heating. Try to dissolve the salt in few mL of conc. HCl by heating

If the salt does not dissolve in conc. HCl, then dissolve it in dilute
04 nitric acid. If the salt does not dissolve even in nitric acid then try
to dissolve it in mixture of conc. HCl and conc. HNO3 (3:1 ratio)

In general, a salt not soluble in aqua regia

is considered as an insoluble salt.
 Analysis of Zero Group Cation

● Take 0.1 g of salt in a test tube and add 1-2 mL of NaOH

solution to it and heat. If smell of ammonia is detected,
we can predict the presence of ammonium ions.
● To confirm the presence of ammonium ions, the
evolved gas, on passing through HCl give dense white
fumes of ammonium chloride.
● For further confirmation, the gas evolved is passed
through Nesslers reagent which gives a brown
precipitate if ammonium ion is present.

2K2HgI4 + NH3 + 3KOH HgO.Hg(NH2)I + 7KI + 2H2O

Note!!

For the analysis of

cations belonging to
groups I-VI, the
cations are
precipitated from
original solution by
using the group
reagents.
 Original solution
Dil. HCl

Precipitate, If no precipitate
Group I is formed

Hg22+, Ag+, Pb2+ as Pass H2S gas

chloride

If no precipitate, take
Precipitate, Group II
original solution

(Pb2+, As3+, Cu2+) as sulphide

 Heat (O.S) with conc.
HNO3, cool and add
solid NH4Cl + NH4OH
solution in excess

Precipitate, Group III If no precipitate

(Al3+, Cr3+, Fe3+)

as hydroxides Pass H2S gas
 Pass H2S gas

If no precipitate, take
Precipitate, Group IV
original solution

(Zn2+, Mn2+, Ni2+, Add NH4OH and

Co2+) as sulphides solid (NH4)2CO3

Precipitate, Group V If no precipitate,

take original
solution to test
(Ba2+, Sr2+, Ca2+)
Group VI, Mg2+
as carbonates
Tests for Group I
● Pb2+ can be confirmed by a yellow precipitate
of PbI2 on addition of KI.
● It can also be confirmed by a yellow precipitate
of PbCrO4 on addition of potassium chromate.
● The yellow precipitate (PbCrO4) is soluble
in hot NaOH solution.
● A white precipitate of lead sulphate (PbSO4)
is formed on addition of alcohol followed by dil. H2SO4
 Tests for Group I

● Pb2+ can be confirmed by a yellow precipitate

of PbI2 on addition of KI.
● It can also be confirmed by a yellow precipitate
of PbCrO4 on addition of potassium chromate.
● The yellow precipitate (PbCrO4) is soluble
in hot NaOH solution.
● A white precipitate of lead sulphate (PbSO4)
is formed on addition of alcohol followed by dil. H2SO4
Confirmatory Tests For Pb2+ Ions

Sodium hydroxide solution

A white precipitate is formed which

is soluble in excess of the reagent

─
Pb2+ + 2OH Pb(OH)2

─ 2─
Pb(OH)2 + 2OH [Pb(OH)4]
Confirmatory Tests For Pb2+ Ions

Ammonia solution

With ammonia solution, Pb2+ gives a

white precipitate of lead hydroxide

+
Pb2+ + 2NH4OH Pb(OH)2 + 2NH4
 Confirmatory Tests For Hg22+ Ions

Ammonia solution

A mixture of mercury metal (black

precipitate) and basic mercury (II) amido
chloride (white precipitate) is formed

2Hg2Cl2 + 4NH4OH HgO.Hg(NH2)Cl + 2Hg + 3NH4Cl + 3H2O

 Confirmatory Tests For Hg22+ Ions

White ppt of Hg2Cl2 after dissolution

in aqua regia gives HgCl2

Potassium Iodide test:

Stannous Chloride test:
Scarlet/red precipitate is
White precipitate is formed
formed which is soluble in
which finally turns to black
excess of the reagent

2HgCl2 + SnCl2 Hg2Cl2 + SnCl4 HgCl2 + 2KI HgI2 + 2KCl

Hg2Cl2 + SnCl2 2Hg + SnCl4 HgI2 + 2KI(excess) K2[HgI4]

Confirmatory Tests For Ag+ Ions

Potassium iodide solution

A bright yellow precipitate is

formed which is insoluble in dilute
ammonia but partially soluble in
concentrated ammonia

─
Ag+ + I AgI

AgI + 2NH3 [Ag(NH3)2]+ + I ─

Confirmatory Tests For Ag+ Ions

Potassium Chromate solution

Red precipitate is formed which is

soluble in dilute HNO3 and in
ammonia solution

2─
2Ag+ + CrO4 Ag2CrO4
 Tests for Group II

● When group I is absent, in the same test tube, add

excess
of water and warm the test tube and pass H2S
● Precipitate formation indicates presence of group II
● A black precipitate indicates presence of Cu2+/Pb2+ ions
● A yellow precipitate indicates presence of As3+ ions
● Adding excess of yellow ammonium sulphide to the OS,
results in an insoluble precipitate indicates the
presence of group II A (Cu2+/Pb2+) and soluble
precipitate indicates the presence of group II B (As3+)
Confirmatory Tests For Cu2+ Ions

Sodium hydroxide in cold solution

A white precipitate is formed which

is soluble in excess of the reagent

─
Cu2+ + 2OH Cu(OH)2

Heat
Cu(OH)2 CuO (red) + H2O
 Tests for Group III

Original Solution

Add 2-3 drops of conc. HNO3, heat, add small

amount of NH4Cl(s) and excess of NH4OH

Brown Precipitate

Group III present

Gelatinous white Brown

Precipitate Precipitate

Al3+ Present Fe3+ Present

 Confirmatory Tests For Cr3+ Ions

A yellow solution of Na2CrO4

gives the following reactions

Barium chloride solution

Lead acetate solution Yellow precipitate is formed
Yellow precipitate of lead owing to the formation of
chromate is formed. barium chromate which is
insoluble in acetic acid

2─ 2─
CrO4 + Pb2+ PbCrO4 CrO4 + Ba2+ BaCrO4
 Tests for Group IV

Original Solution
(from the previous group test)
Pass H2S gas
White Black Flesh-coloured
Precipitate Precipitate Precipitate

Zn2+ Ions Ni2+ /Co2+ Ions Mn2+ Ions

Gives white Gives white ppt Gives black ppt of NiCl2

ppt with with NaOH which with HCl which dissolves
NaOH which on oxidation gives in aqua regia. When
is soluble in brown hydrated DMG is added to NiCl2 in
excess NaOH manganese dioxide presence of NH4OH, a
deep red ppt is obtained
 Tests For Zn2+ Ions

When potassium ferrocyanide is added to the

solution after neutralisation by NH4OH

A white precipitate of variable composition is

formed. If excess reagent is added, the
composition of precipitate is K2Zn3[Fe(CN)6]2

3Zn2+ + 2K+ + 2[Fe(CN)6]4- K2Zn3[Fe(CN)6]2

 Tests For Mn2+ Ions

On boiling a dilute solution of Mn2+ with PbO2 and a

little conc. HNO3 and allowing the suspended solid
containing unattacked PbO2 to settle,

The supernatant liquid acquired a violet-red

(or purple) colour due to permanganic acid.

─
5PbO2 + 2Mn2+ + 4H+ 2MnO4 + 5Pb2+ + 2H2O
 Analysis of Group IV Cations

Tests for cobalt

ions (Co2+) Cobalt sulphide dissolves in aqua regia
in the same manner as nickel sulphide.

When the aqueous solution of the

residue obtained after treatment with
aqua regia is treated with

Strong solution of potassium nitrite after

neutralisation with NH4OH and the
solution is acidified with CH3COOH
 Tests for Co2+ Ions

A yellow precipitate of the complex

of cobalt named potassium
hexanitritocobaltate (III) is formed.

Reaction
CoS + HNO3 + 3HCl CoCl2 + NOCl + S + 2H2O

CoCl2 + 7KNO2 + 2CH3COOH K3[Co(NO2)6] + 2KCl + 2CH3COOK + NO + H2O

Potassium hexanitritocobalt(III)
(Yellow precipitate)
 Analysis of Group V Cations

Take original solution and add small amount of

solid NH4Cl and an excess of NH4OH solution
followed by solid ammonium carbonate (NH4)2CO3

White precipitate indicates the

presence of group V cations
 Analysis of Group V Cations

Dissolve the white precipitate by

boiling with dilute acetic acid

And divide the solution into 3 parts,

one each for Ba2+, Sr2+ and Ca2+ ions

Preserve a small amount of

precipitate for flame test
Note!!

The Group V cations are

precipitated as their carbonates
which dissolve in acetic acid
due to the formation of
corresponding acetates.
 Test For Ba2+ Ions

Potassium chromate (K2CrO4) solution

gives a yellow precipitate of barium
chromate when the solution of fifth group
precipitate in acetic acid is treated with it

BaCO3 + 2CH3COOH (CH3COO)2Ba + H2O + CO2

(CH3COO)2Ba + K2CrO4 BaCrO4 + 2CH3COOK

Barium chromate
(yellow precipitate)
Flame Test For Ba2+ Ions

A grassy green colour

of the flame confirms the
presence of Ba2+ ions.
 Test For Sr2+

Solution of V group precipitate

in acetic acid gives a white
precipitate of strontium
sulphate with ammonium
sulphate (NH4)2SO4

SrCO3 + 2CH3COOH (CH3COO)2Sr + H2O + CO2

(CH3COO)2Sr + (NH4)2SO4 SrSO4 + 2CH3COONH4

Strontium sulphate
(white precipitate )
Flame Test For Sr2+ Ions

A crimson red flame

confirms the presence
of Sr2+ ions.
 Test For Ca2+ Ions

Solution of V group precipitate

in acetic acid gives a white
precipitate with ammonium
oxalate solution.

CaCO3 + 2CH3COOH (CH3COO)2Ca + H2O + CO2

(CH3COO)2Ca + (NH4)2C2O4 (COO)2Ca + 2CH3COONH4
Ammonium Calcium oxalate
oxalate (white precipitate)
 Flame Test For Ca2+ Ions

Perform the flame test as

mentioned above. Calcium
imparts brick red colour to the
flame, which looks greenish-yellow
through blue glass.
 Test For Mg2+ Ions

If group V is absent, the solution may contain

magnesium carbonate, which is soluble in water
in the presence of ammonium salts because the
equilibrium is shifted towards the right-hand side.

+ 2− −
NH4 + CO3 NH3 + HCO3
 Test For Mg2+ Ions

The concentration of
carbonate ions required to produce
a precipitate is not attained.

Indicates the
presence of When disodium hydrogenphosphate solution
Mg2+ ions is added and the inner walls of the
test tube are scratched with a glass rod,

A white crystalline precipitate of

magnesium ammonium
phosphate is formed
 Test For Mg2+ Ions

Reaction

Mg2+ + Na2HPO4 + NH4OH Mg(NH4)PO4 + 2Na+ + H2O

Magnesium ammonium
phosphate
(White precipitate)
 Test For Mg2+ Ions

Ammonia solution

A white gelatinous precipitate

is formed

+
Mg2+ + 2NH4OH Mg(OH)2 + 2NH4
 Test For Mg2+ Ions

Titan yellow (a water soluble

yellow dyestuff)

It is adsorbed by Mg(OH)2 producing a

deep red colour or precipitate

Dissolve the precipitate in dil. HCl

(minimum quantity) and to 1 drop of NaOH
solution (2M) followed by 1 drop of titan
yellow solution a deep red colour solution
or precipitate is obtained
 Practical
Organic
Chemistry
Elements Present in an Organic Compound

Elements
necessary for
an organic
compound

C
 Elements Present in an Organic Compound

An organic
compound may O
possess

X X : Halogens
 Detection of Element

Carbon and
Nitrogen Sulphur Halogens Phosphorous
Hydrogen
Detection of Carbon and Hydrogen

Method for the detection of C and H

is also known as Liebig's Method
 Organic compound

Δ CuO (Cupric oxide)

CO2 H2O

Ca(OH)2 Anhydrous CuSO4 (white)

CaCO3 CuSO4.5H2O
(Milky) (Blue)

CO2 Blue vitriol

CaHCO3
Milkiness disappears
since it is water soluble
 Detection of Carbon and Hydrogen

While heating, the carbon present in

the compound is oxidised to CO2.

From the organic Δ

C + 2CuO CO2 + 2Cu
compound

Δ
CO2 + Ca(OH)2 CaCO3 + H2O

(Lime water)

Precipitate
Milky/Turbid
 Detection of Carbon and Hydrogen

Hydrogen present in the compound

is oxidised to H2O.

From the organic Δ

compound 2H + CuO H2O + Cu

Δ
CuSO4 + 5H2O CuSO4.5H2O

(Anhydrous)
Copper(II)sulphate
Pentahydrate
Blue vitriol
 Detection of Element

Carbon and
Nitrogen Sulphur Halogens Phosphorous
Hydrogen

Done by Lassaigne’s test

 Lassaigne’s Test

Lassaigne’s test can be carried

out with the help of sodium
fusion extract.

The elements present in a

compound are converted from
covalent to ionic form by fusing
the organic compound with
Sodium (Na) metal.
 Lassaigne’s Test

● Lassaigne’s extract is prepared by heating a small

piece of sodium in a fusion tube. The organic sample
is added to this heated sodium.
● The tube is then dropped in water to prepare the
extract.
● The elements in organic compounds like C, N, S, X are
converted into ionic sodium salts.
 Detection of Nitrogen

● The sodium fusion extract is heated with Iron (II)

sulphate (FeSO4) and then acidified with conc.
sulphuric acid.
● Lassaigne extract (having NaCN) is heated with Iron(II)
sulphate to form sodium hexacyanoferrate (II).
● On heating with concentrated sulphuric acid, some
Fe(II) ions are oxidised to Fe(III).
● Fe(III) reacts with Sodium hexacyanoferrate(II) to
produce prussian blue colour of iron(III)
hexacyanoferrate(II) which confirms the presence of
N.
 Detection of Element

Carbon and
Nitrogen Sulphur Halogens Phosphorous
Hydrogen
 Test for Sulphur

Detection of Sulphur

Lead acetate Sodium

test nitroprusside test
 Lead Acetate Test

Lassaigne extract (having Na2S)

is acidified with acetic acid and
lead acetate (Pb(CH3COO)2)
is added to it.

S2 ─ ＋ Pb2＋ PbS

Black Precipitate

Indicates the
presence of S
 Test for Sulphur

Detection of Sulphur

Lead acetate Sodium

test nitroprusside test

On treating the Lassaigne extract

(Na2S) with sodium nitroprusside,
the appearance of violet colour
indicates the presence of Sulphur.
 Test for Nitrogen and Sulphur

● If both nitrogen and sulphur are present in an organic

compound, Sodium thiocyanate is formed.
● If sodium fusion is carried out with an excess of
sodium, then the sodium thiocyanate formed is
further decomposed to yield cyanide and sulphide.
 Detection of Element

Carbon and
Nitrogen Sulphur Halogens Phosphorous
Hydrogen
 Test for Nitrogen and Sulphur

● The sodium fusion extract (having NaX) is acidified

with nitric acid and then treated with silver nitrate
(AgNO3).
● White curdy precipitate soluble in NH4OH indicates
presence of Cl.
● Pale yellow precipitate sparingly soluble in NH4OH
indicates presence of Br.
● Yellow precipitate insoluble in NH4OH indicates
presence of I.
 Detection of Functional Groups

Amino groups
Detection of
Alcoholic (OH ─) Functional
Groups Carboxyl(COOH)

Phenolic (OH ─) Carbonyl

(Ketone)
Carbonyl
(aldehyde)
 Detection of Alcoholic OH-

Ceric Ammonium
Test (CAN)

Detection of
Lucas Test
Alcohols by

Iodoform Test
 Ceric Ammonium Test (CAN)

Alcohol on reaction with ceric ammonium nitrate

give a red colour complex.

(NH4)2[Ce (NO3)6] + 3ROH [Ce (NO3)4 (ROH)3] + 2NH4NO3

Ceric Ammonium
Nitrate(CAN)
Red Complex
 Lucas Test

Alcohols are soluble in Lucas reagent but the formed alkyl

halides are not soluble. Therefore, formation of two layers in the
reaction medium indicate the occurrence of the reaction

RCH2OH (1°) + HCl ZnCl2 No reaction, Layers do not seperate

R2CHOH (2°) + HCl ZnCl2 R2CHCl + H2O, Layers separate within 1-5 mins

R3COH (3°) + HCl ZnCl2 R3CCl + H2O, Layers separate immediately

 Lucas Test

Lucas test is applicable to only those alcohols which are soluble

in the reagent because the test is based on separation of alkyl
halides as separate layer.
 Iodoform Test

Ethanol and secondary alcohols which contain CH3—CH(OH)R

group (iodoform reaction) give positive iodoform test.

NaOH
KI + NaClO NaOI

NaOI NaOI NaOH

RCH3CH2OH CH3CHO CI3CHO CHI3 + HCOONa
 Test for Phenols

Phenols are weakly acidic, therefore they are soluble in NaOH

solution but at the same time they are not sufficiently acidic to
be soluble in sodium hydrogencarbonate solution(NaHCO3).

With Ferric Chloride Solution

Phenols give coloured complex with neutral ferric chloride solution.

6C6H5OH + FeCl3 [Fe (C6H5O)6]3- + 3HCl + 3H+

Violet complex
 Test for Phenols

Compound Colour given in FeCl3 solution

o-Cresol red

m-Cresol bluish-purple

p-Cresol No colour

Usually, blue takes

Catechol
longer time to appear

Resorcinol Green fluorescent colour of fluorescein

Tollen’s Test
 Tollen’s Test

_
RCHO + 2[Ag(NH3)2 ]+ + 3OH

_
RCOO + 2Ag↓ + 2H2O + 4NH3
 Fehling’s Test

Fehling’s
test
Fehling’s Test

_
+
_
+
 Fehling’s Test

_
RCHO RCOO

2Cu2+ Cu2O↓
 Benedict’s Test

2– _
RCHO Cu(Citrate)2 5OH

_
RCOO Cu2O ↓ 3H2O
Comparison of Tollens’ and Fehling’s
Tests

✔ ✔

✔
 Schiff’s Reagent

Schiff’s
Reagent
 Test for Carboxylic Acids

▪ Carboxylic acids turn blue litmus into red.

▪ They react with sodium hydrogencarbonate solution to
produce effervescence due to the formation of carbon dioxide.

This is a test that distinguishes carboxylic acids from phenols.

RCOOH + NaHCO3 → RCOONa + H2O + CO2

▪ These react with alcohols in the acidic medium to produce

esters.

Sweet smell of the substance formed indicates the presence of

carboxyl function in the compound.
Conc. H2SO4
RCOOH + R’OH RCOOR' + H2O
Δ
 Test for Amino Group

▪ Carbylamine Test

Aliphatic as well as aromatic primary amines give this test in

which an amine is heated with chloroform.

An obnoxious smell of carbylamine confirms the presence of

primary amino group in the compound.

Δ
RNH2 + CHCl3 + 3KOH → RNC + 3KCl + 3H2O
 Test for Amino Group

▪ Azo dye Test

This test confirms the presence of aromatic primary amines.

Primary amine e.g. aniline reacts with nitrous acid generated in
situ by the reaction of sodium nitrite with HCl at 0–5°C to
produce diazonium salt.

NaNO2 + HCl NaCl

2 H2O
 Test for Amino Group

BDC couples with β-naphthol to give a scarlet red dye, which

is sparingly soluble in water.

BDC + β-naphthol → β-naphthol azo-dye

 Preparation of Acetanilide

The replacement of one

hydrogen atom of the — NH2
group of aniline by CH3CO–
group in the presence of glacial
acetic acid.

Generally done by Acetic

anhydride but in absence of
acetic anhydride, acetylation
with CH3COCl is usually
carried out in the presence of
pyridine.
 Preparation of p-Nitroacetanilide

p-Nitroacetanilide is prepared
by the nitration of acetanilide
by using a mixture of conc.
nitric acid and conc. sulphuric
acid as nitrating reagent.

HNO3 + 2H2SO4 → NO2+ + H3O + + 2HSO4-

 Preparation of Aniline

Aniline is prepared by the reduction of nitro compounds.

Preparation of Aniline by
Catalytic Hydrogenation

H2, Pd
Preparation of Aniline by Treatment
with Acid

M + HCl

Sn Fe
Preparation of Aniline by Treatment
with Acid
Preparation of Aniline by Electrolytic
Reduction
 Preparation of Iodoform

Iodoform
reaction
Preparation of Iodoform
Preparation of Inorganic Compounds

Mohr’s Salt
FeSO4.(NH4)2SO4.6H2O

Preparation
of

Potash Alum
K2SO4. Al2(SO4)3. 24H2O
 Preparation of Mohr’s Salt

Equimolar mixture containing ferrous

sulphate and ammonium sulphate is
crystallised from its solution, we
obtain a double salt called Mohr’s salt.

FeSO4 + (NH4)2SO4 + 5H2O FeSO4.(NH4)2SO4.6H2O

Ferrous ammonium sulphate

(Mohr’s salt)
2-3 drops of
dil H2SO4
 In a conical flask, add 3.5 g of Add 0.5 ml of
ferrous sulphate + dil H2SO4 in
1.5 g of ammonium sulphate in 5 order to avoid
ml distilled water hydrolysis of
Procedure in Fe2+ ions

preparation Δ

of Mohr’s After dissolution, allow the mixture to

coo slowly to the room
Salt temperature(Light green crystals of
ferrous ammonium sulphate seperates
out on cooling)

Decant the mother liquor and wash

crystals by 1:1 cold water and alcohol
mixture

Filter the crystals, wash with

alcohol and dry
 Preparation of Potash Alum

Equimolar proportions of potassium

sulphate and
aluminium sulphate is crystallised
from its solution, a double salt called
Potash Alum is obtained.

K2SO4 + Al2(SO4)3 + 24H2O K2SO4.Al2(SO4)3.24H2O

Potash Alum
 In a 50 ml beaker, add 10 ml Add 0.4 ml of dil
distilled water and heat to 40℃. H2SO4 in order to
To this, add 6.6 g aluminium avoid hydrolysis of
sulphate + 2.4 g of powdered Al3+ ions
potassium sulphate
Procedure in
Heat slowely with continuous stirring
preparation till all potassium sulphate dissolves
of Potash
Alum Allow the mixture to coo slowly to the
room temperature(White crystals of
potash alum seperates out on cooling)

Decant the mother liquor and wash

crystals by 1:1 cold water and alcohol
mixture

Filter the crystals, wash with

alcohol and dry
 Chemical Analysis

Detection of Amount of
elements/funct Qualitative Quantitative substance in
ional groups solution

Gravimetric Titrimetric

Measurement Only volume

of mass and measurement
volume
 Terms in Titrimetric Analysis

Standard Solution
▪ The solution with accurate concentration It is usually
▪ Its volume which reacts quantitatively added from
with solution of a substance of unknown burette
concentration, is determined.

Titrand
Titrant The substance dissolved in
The reagent of known the solution of unknown
concentration concentration (being
titrated)
 Terms in Titrimetric Analysis

Titration
The process of adding the standard
Solution (titrant) to the solution of unknown
concentration (titrand) until the reaction is
just complete is called titration.

End Point
• At the completion of the reaction, the
Equivalence Point indicator shows a visible change e.g.
The point at which (colour change or turbidity) at this point.
reaction is completed • For an ideal titration, end point and
equivalence point should coincide but
generally there occurs a small difference
called titration error.
 Acid - Base Titration

Out of an acid & a base solution,

taking a known volume
of one of them in a flask & taking the
other in a burette
& finding its volume required for
complete neutralization.
 Acid - Base Titration

Equivalence point is achieved when

stoichiometrically equivalent amount
of acid & base have combined

pH calculation at equivalence point can

be done according to the nature of species
formed at equivalence point
 Indicators

Substances which indicate the end-point of a

titration generally by changing their colour

Indicators are either weak organic acids or weak

organic bases having characteristically different
colours in their ionised & unionised forms.
 Indicators

Phenolphthalein Methyl orange

Common
acid-base
indicators
 Indicators

_
HIn (aq) ⇌ H+ (aq) + In (aq)

_
[H+][In ]
KIn = [HIn]

KIn [HIn]
[H+] = _
[In ]
 Indicators

KIn [HIn]
[H+] = _
[In ]

Taking logarithm on both the sides and multiplying by (-1),

[HIn]
- log [HIn]
-log [H+] = -log KIn + - log [In_-]
[In ]

_
[HIn]
[In ]
pH = pKIn + log
log [In-]
[HIn]
 Example

Phenolphthalein is a weak acid;

HPh(aq) + H2O(l) ⇌ H3O+(aq) + Ph (aq)

Colourless Pink
 Example

Methyl orange is a weak base;

MOH(aq) + H2O(l) ⇌ OH (aq) + M+(aq)

Yellow Red
 pH Range of Indicator

pH range between which the indicator changes its colour.

14 14

10.0
8.3

4.
4
3.1

0.0 0.0

Methyl Orange Phenolphthalein

 Redox Titration

The titrations involving redox reaction are

called redox titrations.

Indicator in Redox Titration

▪ Unlike indicators in acid-base titration which are

sensitive to change in pH, indicators in redox
titration are sensitive to oxidation potential.

▪ These indicators have an oxidation potential

intermediate between the values for the solution
of titrant and titrand and these show sharp
readily detectable colour change.
 Titrating Oxalic acid vs KMnO4

Potassium permanganate
Oxalic Acid acts as acts as a powerful
reducing agent. oxidising agent. It also acts
as self-indicator.

• This process is carried out in acidic medium (dil H2SO4 is used).

• Nitric acid can not be used because it acts as oxidising agent.
• HCl is also not used because it reacts with KMNO4 and produce
Cl2 which acts as an oxidising agent.

2KMnO4 + 16 HCl 2KCl + 2 MnCl2 + 5Cl2+ 8H2O

 Titrating Oxalic acid vs KMnO4

+7 +2
Reduction Half MnO4- + 5e- + 8H+ Mn2+ + 4H2O × 2

+3 +4
Oxidation Half C2O4 2- 2CO2 + 2e- × 5

Net Equation 2MnO4- + 5C2O42- + 16H+ 2Mn2+ + 10CO2 + 8H2O

 Titrating Oxalic acid vs KMnO4

Colour of KMNO4 is discharged due to reduction

by oxalic acid but when all oxalate ions
consumed, addition of little excess of unreacted
KMNO4 shows pink colour at end point.

As the reaction takes place at a higher

temperature, warming of oxalic acid (50-60 ℃)
solution with H2SO4 is essential.

During the titration, first mangnous sulphate is

formed which catalyses reduction of KMNO4.
Thus in the beginning, reaction is slow but with
time, its rate increases.
 Titrating Mohr’s Salt vs KMnO4

Ferrous ammonium Potassium permanganate

sulphate acts as reducing acts as a powerful
agent. oxidising agent.

+7 +2
Reduction Half MnO4 + - 5e- + 8H+ Mn2+ + 4H2O

+2 +3
Oxidation Half Fe2+ Fe3+ + e- × 5

Net Equation MnO4- + 5Fe2+ + 8H+ Mn2+ + 5 Fe3+ + 4H2O

 Titrating Oxalic acid vs KMnO4

In this reaction, heating ferrous ammonium sulphate

is not required as reaction rate is high even at room
temperature and heating may oxidise ferrous ions
into ferric ions by oxygen in air.
So, error may comes if the reaction mixture is heated.
 Enthalpy of solution of CuSO4

Calorimeter
The vessel in which measurement of
heat changes is carried out.
Calorimeter Constant
The sum of heat absorbed
The sum of enthalpy changes taking place in
by calorimeter, stirrer and
the calorimeter (loss and gain of energy)
thermometer for each
must be zero(Conservation of energy)
unit of temperature
change.
Let, initial temperature of 100 ml water
taken in calorimeter = t1 ℃
mass of powdered copper sulphate = w1 g
After dissolution of copper sulphate,
temperature of solution = t2 ℃
 Enthalpy of solution of CuSO4

Total mass of solution = (100 + w1) g,

assuming density of water 1 g/ml

Change in temperature = (t2 - t1 ) ℃

Enthalpy change of the calorimeter = w (t2 - t1 )

where, w= calorimeter constant

Enthalpy change of the solution = [(100 + w1) (t2 - t1 )] 4.184 J

Total enthalpy change of the calorimeter

= w (t2 - t1 ) + [(100 + w1) (t2 - t1 )] 4.184 J
 Enthalpy of solution of CuSO4

Heat liberated on dissolution of 1 g copper sulphate

w (t2 - t1 ) + [(100 + w1) (t2 - t1 )] 4.184 J
=
w1

Molar mass of copper sulphate = 249.5 g

w (t2 - t1 ) + [(100 + w1) (t2 - t1 )] 4.184

× 249.5 J/mol
Hence, ΔsolH of CuSO4.5H2O = w1
 Enthalpy of neutralisation of
Strong Acid vs Strong Base

Enthalpy of neutralisation
The amount of heat liberated when 1 mol of H+
ions furnished by acid combine with 1 mol of OH–
ions furnished by base to form water.

H+(aq) + OH-(aq) H2O(l), ΔneutH

From Acid From Base

ΔneutH= 57 kJ/mol, if both (acid and base) are strong.

For weak acids and bases, some part of the heat
liberated is used to ionize weak acid or weak base or
both and hence ΔneutH< 57 kJ/mol.
 Preparation of

Lyophilic Sol Lyophobic Sol

Egg Albumin Starch/gum Ferric hydroxide or, Arsenious

Sol Sol Aluminium hydroxide Sulphide Sol
Preparation of Egg Albumin Sol

Prepare 100 mL of 5% (w/v) solution

of NaCl in water in a beaker.

Break one egg in a porcelain dish

and pipette out the
albumin and pour it in the NaCl
solution.

Stir well to ensure that the sol

is well prepared.
 Preparation of Starch/gum Sol

Take 100 mL of distilled water with the

help of a measuring cylinder and transfer
it to a beaker and boil it.

Make a paste of 500 mg starch or gum in hot

water and transfer this paste to 100 mL of
boiling water with constant stirring

Keep water boiling and

stirring for 10 minutes after
addition of paste.
 Preparation of Ferric hydroxide or,
Aluminium hydroxide Sol

Take 100 mL of distilled water, boil it and

add 2 g of ferric chloride or,
aluminium chloride and stir it well.

In another beaker, take 100 mL of distilled

water, boil it and add 10 ml of previously
prepared ferric chloride or,
aluminium chloride solution drop by drop.

Keep water boiling till

brown/white sol is obtained.
Preparation of Arsenious Sulphide Sol

Take 100 mL of distilled water, add 0.2 g of

arsenious oxide to it and boil.

Cool and filter the solution.

Pass hydrogen sulphide (H2S) gas

through the filtered solution till it
smells of H2S

Expel H2S gas from the sol by

slow heating and filter it.
 Kinetic study of the reaction of I- with H2O2

2I-(aq) + H2O2 (l) + 2H+ (aq) I2 (g) + 2H2O(l)

The time duration in

To the above reaction mixture, sodium Consumption of a
thiosulphate in presence of starch solution fixed amount of the
as indicator is added, I2 again converts to I- thiosulphate ions is
reproducible.

I2 (g) + 2 S2O32- (aq) S4O62- (aq) + 2I-(aq)

Since the time for the
appearance of colour
is noted, the reaction
After complete consumption of thiosulphate ions, is also called a clock
I2 (g) produced in thereaction of H2O2 with I- forms reaction.
intense blue colour complex with starch.