Additional Topics (Physics & Chemistry)

CHEMISTRY

PRINCIPLES RELATED TO PRACTICAL CHEMISTRY

A. DETECTION OF THE FUNCTIONAL GROUPS IN ORGANIC COMPOUNDS

I. DETECTION OF HYDROXYL GROUP
i. TEST FOR ALCOHOLIC (R–OH) GROUP
Theory
Alcoholic compounds on reaction with ceric ammonium nitrate give a red colouration due to the
formation of a complex.

Distinction between primary, secondary and tertiary alcohols can be done on the basis of iodoform
test and Lucas test. Ethanol and secondary alcohols which contain CH3 – CH(OH)R group (iodoform
reaction) give positive iodoform test. To carry out reaction, potassium iodide and sodium hypochlorite
solutio are added to the compound in the presence of sodium hydroxide solution. Probably sodium
hypochlorite first oxidses potassium iodide into potassium hypoiodite, which oxidises CH3 –CH(OH)R
group to CH3COR group and then iodinates it in the alkaline medium of the reaction mixture by
replacing the α -hydrogen attached to the carbon atom adjacent to carbonyl group by iodine. Iodoform
is formed after cleavage of C – C bond.

Lucas Test
Lucas reagent contains zinc chloride and concentrated hydrochloric acid. This reagent reacts with
primary, secondary and tertiary alcohols at different rates. Tertiary alcohols react almost
instantantaneously, secondary alcohols react in about 1-5 minutes and primary alcohols react very
slowly. The reaction may take 10 minutes to several days.

Alcohols are soluble in Lucas reagent but the formed alkyl halides are not solube. Therefore, formation
of two layers in the reaction medium indicate the occurrence of the reaction.
Primary alcohols - Layers do not separate
Secondary alcohols - Layers separate within 1-5 minutes
Tertiary alcohols - Layers separate immediately
59
 Brilliant STUDY CENTRE

ii. TEST FOR PHENOLIC (AR-OH) GROUP

Theory
The –OH group attached directly to the ring carbon of an aromatic ring is called phenolic –OH group.
Phenols are weakly acidic, therefore they are soluble in NaOH solution but at the same time they are
not sufficiently acidic to be soluble is sodium hydrogen carbonate solution. Phenols give coloured
complex with neutral ferric chloride solution. For example, phenol gives a complex of violet colour as
follows :

Resorcinol, o–, m– and p-cresol give violet or blue colouration, catechol gives green colour which
rapidly darkens. 1 and 2-Naphthol do not give characteristics colours. Phenols condense with phthalic
anhydride in the presence of concentrated H2SO4, Phenol condeses to give phenolphthalein which
gives a dark pink colour with NaOH solution. This is called phthalein dye test.

Colours produced by some other phenolic compounds in phthalein dye test

Compound Colour Compound Colour
Usually blue takes
o-Cresol red Catechol
longer time to appear
m-Cresol bluish - purple
Green fluorescent
p-Cresol No colour Resorcinol
colour of fluorescein
II. DETECTION OF CARBONYL GROUP
O
(ALDEHYDIC AND KETONIC GROUPS ( CHO and C ))

60
 Additional Topics (Physics & Chemistry)

Theory
Both aldehydes and ketones contain carbonyl group (>C = O) and commonly known as carbonyl
compounds. Identification of a aldehydes and ketones is done by two important reactions of carbonyl
group i.e.
i) addition reaction on double bond of > C = O group and
ii) oxidation of carbonyl group
Addition reactions of derivatives of ammonia are important from the point of view of identification of
carbonyl compounds. Addition is generally followed by elimination resulting in the formation of
unsaturated compound.

These reaction are catalysed by an acid or a base and do not occur under strongly acidic or basic
conditions. Each reaction requires an optimum pH for its occurrence. Therefore, maintenance of pH
is very important while carrying out these reactions. As far as oxidation is concerned, aldehydes are
easily oxidised to carboxylic acids while ketones require relatively stronger oxidising agent. Distinction
can be made between these two types of carbonyl compounds on the basis of difference in their
reactivity.
Following tests are performed for the identification of aldehydic and ketonic groups.
i) On reaction with 2, 4-dinitrophenylhydrazine (2, 4-DNP), they form the respective 2, 4-dinitrophenyl
hydrazones.

These two carbonyl compounds (aldehydes and ketones) are distinguished on the basis of tests
using mild oxidising reagents, like Tollen’s reagent and Fehling’s reagent or Benedict’s reagent. Tollen’s
reagent is an alkaline solutions of silver cation complexed with tartarate and citrate ions respectively.
Fehling’s reagent is freshly prepared by mixing equal amounts of Feshling’s solution A and Fehling’
s solution B.Fehling’s reagent deteriorates on keeping while Fehling’s solutions A and B are quite
stable. Fehling’s solution A is an aqueous copper sulphate solution while Fehling’s solution B is an
alkaline solution of sodium potassium tartarate (Rochelle’s salt). The reagent contains Cu2+ ion
complexed with tartarate ions. The structure of the complex is given below :

61
 Brilliant STUDY CENTRE

Benedict modified the original Fehling’s test by using a single solution which is more convenient for
alkaline solution containing a mixture of copper sulphate and sodium citrate (2Na3C6H5O7.11H2O).
Complex formation decreases the cupric ion concentration below that necessary for precipitation of
cupric hydroxide. These two reagents oxidize aldehydes while ketones remain unaffected. The
chemistry of these tests is as follows:

RCHO  2AgNH3 2  2OH 

 2Ag  3NH2  H2O  RCOOH4
From Tollen ' s reagent

RCHO  2Cu2 complexed 5OH 

 RCOO  Cu2O  3H2O
Fehling ' s solution

However, aromatic aldehydes do not give positive Fehling’s test. In Benedict test also, Cu2+ ions are
reduced to Cu+ ions in the same manner as in the case of Fehling’s reagent.
Aldehydes also give pink colour with Schiff’s reagent (the reagent is prepared by decolourising aqueous
solution of p-rosaniline hydrochloride dye by adding sodium sulphite or by passing SO2 gas). Ketones
do not respond to this test.
III. DETECTION OF CARBOXYL GROUP (–COOH)
Theory
Organic compounds containing carboxyl functional groups are caled carboxylic acids.
The term carboxyl, derives its name from the combination of words carbonyl and hydroxyl because
O
carboxylic functional group contains both of these groups( C OH ). These acids turn blue litmus
red and react with sodium hydrogencarbonate solution to produce effervescence due to the formation
of carbon dioxide. This is a test that distinguishes caboxylic acids from phenols.

These react with alcohols in the acidic medium to produces esters.

IV. DETECTION OF AMINO GROUP (–NH2)

Theory
Organic compounds containing amino group are basic in nature. Thus they easily react with acids to
form salts, which are soluble in water. Both, aliphatic and aromatic amines are classified into three
classes namely-primary(–NH2), secondary (–NH–) and tertiary (–N<), depending upon the number of
hydrogen atoms attached to the nitrogen atom. Primary amine has two hydrogen atoms, secondary
has one while tertiary amine has no hydrogen atom attached to nitrogen.
i) Carbylamine test
Aliphatic as well as aromatic primary amines give carbylamine test in which an amine is heated with
chloroform.
62
 Additional Topics (Physics & Chemistry)

iI) Azo dye test

Aromatic primary amines can be confirmed by azo dye test. Primary amine e.g. aniline reacts with
nitrous acid generated in situ by the reaction of sodium nitrite with HCl at 0 - 5oC to produce diazonium
salt. This couples with a-naphthol to give a scarlet red dye, which is sparingly soluble in water.

B. QUALITATIVE ANALYSIS
Analysis always does not mean breaking of substance into its ulitmate constituents. Finding out the
nature of substance and identify of its constituents is also analysis and is known as qualitative analysis.
Qualitative analysis of inorganic salts means the identification of cations and anions present in the
salt of a mixture of salts. Inorganic salts may be obtained by complete or partial neutralisation of acid
with base or vice-versa. In the formation of a salt, the part contributed by the acid is called anion and
the part contributed by the base is called cation. For example, in the salts CuSO4 and NaCl, Cu2+ and
Na+ ions are cations and SO 24  and Cl– ions are anions. Qualitative analysis is carried out on various
scales. Amount of substance and employed in these is different. In macro analysis, 0.1 to 0.5 g of
substance and about 20 mL of solution is used. For semimicro analysis, 0.05 g substance and 1 mL
solution is needed while for micro analysis amount required is very small. Qualitative analysis is
carried out through the reactions which are easily perceptible to our senses such as sight and smell.
Such reactions involve:
a) Formation of a precipitate
b) Change in colour
c) Evolution of gas etc.
Systematic analysis of an inorganic salt involves the following steps :
i) Preliminary examination of solid salt and its solution.
ii) Determination of anions by reactions carried out in solution (wet tests) and confirmatory tests.
iii) Determination of cations by reactions carried out in solution (wet tests) and confirmatory tests.
Preliminary examination of a salt often furnishes important information, which simplifies further course
of analysis. Although these tests are not conclusive but sometimes they give quite important clues for
63
 Brilliant STUDY CENTRE

the presence of certain anions or cations. These tests can be performed within 10-15 minutes. These
involve noting the general appearance and physical properties, such as colour, smell, solubility etc. of
the salt. These are named as dry tests.
Heating of dry salt, blow pipe test, flame tests, borax bead test, sodium carbonate bead test, charcoal
cavity test etc. come under dry tests.
Solubility of a salt in water and the pH of aqueous solutions give important information about the
nature of ions present in the salt. If a solution of the salt is acidic or basic in nature, this means that it
is being hydrolysed in water. If the solution is basic in nature then salt may be some carbonate or
sulphide etc. If the solution shows acidic nature then it may be an acid salt or salt of weak base and
strong acid. In this case it is best to neutralise the solution with sodium carbonate before testing it for
anions.
Gases evolved in the preliminary tests with dil. H2SO4/dil. HCl and conc. H2SO4 also give good
indication about the presence of acid radicals. Preliminary tests should always be performed before
starting the confirmatory tests for the ions.
Theory
Two basic principles of great use in the analysis are :
i) the solubility product and
ii) the common ion effect
When ionic product of a salt exceeds its solubility product, precipitation takes place. Ionic product of
salt is controlled by making use of common ion effect which you have studied in the textbook of
chemistry.
I(a) ANALYSIS OF ANIONS
Preliminary Test with Dilute Sulphuric Acid
In this test the action of dilute sulphuric acid (procedure is given below) on the salt is noted at room
temperature and on warming. Carbonate ( CO32 ) , sulphide (S2–), sulphite ( SO32 ), nitrite ( NO2 ) and
acetate (CH3COO–) react with dilute sulphuric acid to evolve different gases. Study of the characteristics
of the gases evolved gives information about the anions. Summary of characteristic properties of
gases is given below.
Preliminary test with dilute sulphuric acid
Inference
Observations
Gas Evolved Possible Anion
A colourless, odourless gas is evolved with brisk
effervescence, which turns lime water milky. CO2 Carbobate CO32 

Colourless gas with the smell of rotteneggs is

evolved which turns lead acetate paper black. H2S Sulphide (S2-)

Colourless gas with the a pungent smell, like

burning sulphur which turns acidified potassium SO2 Sulphite SO32 
dichromate solution green.
Brown fumes which turn acidified potassium
NO2 Nitrite NO2 
iodide solution containing starch solution blue.
Colourless vapours with smell of vinegar.
CH3COOH vapours Acetate, (CH3COO-)
Vapours turn blue litmus red.

64
 Additional Topics (Physics & Chemistry)

Chemistry of Confirmatory Tests

Confirmatory (wet) tests for anions are performed by using water extract when salt is soluble in water
and by using sodium carbonate extract when salt is insoluble in water. Confirmation of CO23  is done
by using aqueous solution of the salt or by using solid salt as such because sodium carbonate extract
contains carbonate ions. Water extract is made by dissolving salt in water. Preparation of sodium
carbonate extract is given below.
Preparation of sodium carbonate extract
Take 1 g of salt in a porcelain dish or boiling tube. Mix about 3 g of solid sodium carbonate and add
15 mL of distilled water to it. Stir and boil the content for about 10 minutes. Cool, filter and collect the
filtrate in a test tube and label it as sodium carbonate extract.

1. Test for Carbonate ion CO23 

If there is effervescence with the evolution of a colourless and odourless gas on adding dil. H2SO4 to
the solid salt, this indicates the presence of carbonate ion. The gas turns lime water milky due to the
formation of CaCO3

Na 2CO3  H2SO 4 
 Na 2SO 4  H2O  CO 2

Ca OH2  CO2 
 CaCO3  H2O
If CO2 gas is passed in excess through lime water, the milkiness produced disappears due to the
formation of calcium hydrogen carbonate which is soluble in water.

 Ca HCO3 2
CaCO3  CO2  H2O 
2. Test for Sulphide ion [S2–]
a) With warm dilute H2SO4 a sulphide gives hydrogen sulphide gas which smells like rotten eggs. A
piece of filter paper dipped in lead acetate solution turns black on exposure to the gas due to the
formation of lead sulphide which is black in colour.

Na2S  H2SO 4 
 Na2SO 4  H2S

CH3COO2 Pb  H2S  LeadPbS

sulphide
 2CH3COOH
Black precipitate

b) If the salt is soluble in water, take the solution of salt in water make it alkaline with ammonium
hydroxide and add sodium nitroprusside solution. If it is insoluble in water take sodium carboante
extract and add a few drops of sodium nitroprusside solution. Purple or violet colouration due to
the formation of complex compound Na4[Fe(CN)5NOS] confirms the presence of sulphide ion in
the salt.

3. Test for Nitrite ion NO2 

a) On treating a soild nitrite with dil.H2SO4 and warming, reddish brown fumes of NO2 gas are
evolved. Addition of potassium iodide solution to the salt solution followed by freshly prepared
starch solution and acidification with acetic acid produces blue colour. Alternatively, a filter paper
moistened with potassium iodide and starch solution and a few drops of acetic acid turns blue on
exposure to the gas due to the interaction of liberated iodine with starch.

65
 Brilliant STUDY CENTRE

i) 2NaNO 2  H2SO4 
 Na2SO 4  2HNO 2

3HNO 2 
 HNO3  2NO  H2O

2NO  O2 
 2NO2
Brown gas

ii) NO2  CH3COOH 

 HNO2  CH3 COO

2HNO 2  2KI  2CH3COOH 

 2CH3 COOK  2H2O  2NO  I2

I2  Starch 
 Blue complex

b) Sulphanilic acid – 1-napthylamine reagent test (Griss - Ilosvay test). On adding sulphanilic acid
and 1-naphthylamine reagent to the water extract or acidified with acetic acid, sulphanilic acid is
diazotised in the reaction by nitrous acid formed. Diazotised acid couples with 1-naphthylamine
to form a red azo-dye.

NO2  CH3COOH 
 HNO 2  CH3 COO

The test solution should be very dilute. In concentrated solutions reaction does not proceed
beyond diazotisation.

Preliminary Test with Concentrated Suphuric Acid

If no positive result is obtained from dil. H2 SO4 test, take 0.1 g of salt in a test tube and 3-4
drops of conc. H2SO4. Observe the change in the reaction mixture in cold and then warm it.
Identify the gas evolved on heating

66
 Additional Topics (Physics & Chemistry)

Chemistry of Confirmatory Tests

1. Test for Chloride ion [Cl–)
a) If on treatment with warm conc. H2SO4 the salt gives a colourless gas with pungent smell or and
if the gas which gives dense white fumes with ammonia solution, then the salt may contain Cl–
ions and the following reaction occurs.
NaCl  H2SO4 
 NaHSO 4  HCl
Sodium Hydrogen chloride
hydrogen sulphate Colourless gas

HCl  NH3 
 NH Cl4
Ammonium chloride
White fumes

b) If a salt gives effervescence on heating with conc. H2SO4 and MnO2 and a light greenish yellow
pungent gas is evolved, this indicates the presence of Cl– ions.
MnO2  2NaCl  2H2SO 4 
 Na 2SO 4  MnSO 4  2H2O  Cl2
c) Salt solution acidified with dilute HNO2 on addition of silver nitrate solution gives a curdy white
precipitate soluble in ammonium hydroxide solution. This indicates the presence of Cl– ions in
the salt.
NaCl  AgNO3 
 NaNO3  AgCl
Silver chloride
 White precipitate

  AgNH3 2  Cl
AgCl  2NH4OH 
Diammin e silver I
chloride

67
 Brilliant STUDY CENTRE

d) Mix a little amount of salt and an equal amount of solid potassium dichromate (K2Cr2O7) in a test
tube and add conc. H2SO4 to it. Heat the test tube and pass the evolved gas through sodium
hydroxide solution. If a yellow solution is obtained, divide the solution into two parts. Acidify the
first part with acetic acid and then add lead acetate solution. Formation of a yellow precipitate of
lead chromate confirms the presence of chloride ions in the salt. This test is called chromyl
chloride test.

4NaCl  K 2Cr2O7  6H2SO4 

 2KHSO4  2CrO2Cl2  4NaHSO 4  3H2O
(Chromyl
chloride)

CrO2Cl2  4NaOH 
 Na2CrO 4  2NaCl  2H2O

CH3COO2 Pb  Na2CrO 4  PbCrO 4  2CH3COONa

Sodium Lead chromate
chromate ( Yellow precipitate)

Acidify the second part with dilute sulphuric acid add small amounts of amyl alcohol and then
1 mL of 10% hydrogen peroxide solution. On gentle shaking organic layer turns blue. CrO24 ion
formed in the reaction of chromyl chloride with sodium hydroxide reacts with hydrogen peroxide
to form chromium pentoxide (CrO5) (See structure) which dissolves in amyl alcohol to give blue
colour.
CrO24  2H  2H2O 2 
 CrO5  3H2O
Chromium
pentoxide

2. Test for Bromide ion [Br–)

If on heating the salt with conc.H2SO4 reddish brown fumes of bromine are evovled in excess, this
indicates the presence of Br ions. The fumes get intensified on addition of MnO2. Bromine vapours
turn starch paper yellow.

2NaBr  2H2SO 4 
 Br2  SO2  Na2SO 4  2H2O

2NaBr  MnO2  2H2SO 4 

 Na 2SO 4  MnSO 4  2H2O  Br2
a) Add 1 mL of carbon teterachoride (CCl4)/chloroform (CHCl3)** and excess of freshly prepared
chlorine water dropwise to the salt solution in water or sodium carbonate extract neutralised with
dilute HCl. Shake the test tube vigorously. The appearance of an orange brown colouration in
the organic layer due to the dissolution of bromine in it, confirms the presence of bromide ions.

2NaBr  Cl2 
 2NaCl  Br2
b) 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 which dissolves in ammonium
hydroxide with difficulty.

NaBr  AgNO3 
 NaNO3  AgBr
Silver bromide
Pale yellow precipitate

68
 Additional Topics (Physics & Chemistry)

3. Test for Iodide ion [I–)

If on heating the salt with conc.H2SO4 deep violet vapours with a pungent smell are evolved. These
turns starch paper blue and a violet sublimate is formed on the sides of the test tube, it indicates the
presence of I– ions. Some HI, sulphur dioxide, hydrogen sulphide, and sulphur are also formed due to
the following reactions.

2NaI  2H2SO 4 
 Na2SO 4  SO2  2H2 O  I2

I2  Starch solution 
 Blue colour

NaI  H2SO 4 
 NaHSO 4  HI

2HI  H2SO 4 
 2H2O  I2  SO 2

6NaI  4H2SO 4 
 3I2  4H2O  S  3Na2SO 4

8NaI  5H2SO 4 
 4I2  H2S  4Na 2SO 4  4H2O
On adding MnO2 to the reaction mixture, the violet vapours become dense.

2NaI  MnO 2  2H2SO4 

 I2  MnSO 4  Na2SO 4  2H2O
b) 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 and shake the test tube vigorously. Presence of violet
colouration in the organic layer confirms the presence of iodide ions.

2NaI  Cl2 
 2NaCl  I2
Iodine dissolves in the organic solvent and solution becomes violet.
c) Acidify sodium carbonate extract of the salt with dil.HNO3 and add of NH4OH confirms the presence
of iodide ions.

NaI  AgNO3 
 AgI  NaNO3
Silver iodide
Yellow precipitate

4. Test for Nitrate ion NO3 

a) If on heating the salt with conc. H2SO4 light brown fumes are evolved then heat a small quantity
of the given salt with few copper turnings or chips and conc. H2SO4. Evolution of excess of brown
fumes indicates the presence of nitrate ions. The solution turns blue due to the formation of
copper sulphate.

NaNO3  H2SO 4 
 NaHSO 4  HNO3

4HNO3 
 4NO 2  O 2  2H2O

2NaNO3  4H2SO4  3Cu 

 3CuSO4  Na2SO4  4H2O  2NO
Copper sulphate
Blue

2NO  O2 
 2NO2
Brown fumes

69
 Brilliant STUDY CENTRE

b) Take 1 mL of an aqueous solution of the salt and add 2 mL conc. H2SO4 slowly. Mix the solutions
thoroughly and cool the test tube under the tap. Now, add freshly prepared ferrous sulphate
solution along the sides of the test tube dropwise so that it forms a layer on the top of the liquid
already present in the test tuebe. A dark brown ring is formed at the junction of the two solutions
due to the formation of nitroso ferrous sulphate. Alternatively first ferrous sulphate is added and
then concentrated sulphuric acid is added.

NaNO3  H2SO 4 
 NaHSO 4  HNO3

 3Fe2 SO4 3  4H2O  2NO

6FeSO4  3H2SO4  2HNO3 

 Fe NOSO 4
FeSO4  NO 
Nitroso ferrous sulphate
Brown

Test for Sulphate

If no positive test is obtained in previous steps, then tests for the presence of sulphate ions are performed.

Test of Sulphate ions SO24 

a) Aqueous solution or sodium carbonate extract of the salt acidified with acetic acid on addition of
barium sulphate insoluble in conc. HCl or conc. HNO3.

Na2SO 4  BaCl2 
 BaSO 4  2NaCl
Barium sulphate
 Whiteprecipitate

b) Sulphate ions give white precipitate of lead sulphate when aqueous solution or soidum carbonate
extract neutralised with acetic acid is treated with lead acetate solution.

Na2SO4  CH3COO2 Pb 
 PbSO4  2CH3COONa
Lead sulphate
 White precipitate 

I(b) ANALYSIS OF CATIONS

Step - I : Preliminary Examination of the Salt for Identification of Cation
1. Colour Test

Colour Cations Indicated

Light green, Yellow, Brown Fe , Fe3+
2+

Blue Cu2+
Bright green Ni2+
Blue, Red, Violet, Pink Co2+
Light pink Mn2+

2. Dry Heating Test

i) Take about 0.1 g of the dry salt in a clean and dry test tube.
ii) Heat the above test tube for about one minute and observe the colour pf the residue when it is
hot and also when it becomes cold. Observation of changes gives indications about the presence
of cations, which may not be taken as conclusive evidence

70
 Additional Topics (Physics & Chemistry)

Inference from the colour of the salt in cold and on heating

Colour when cold Colour when hot Cations Indicated
Blue White Cu2+
Green Dirty white or yellow Fe2+
White Yellow Zn2+
Pink Blue Co2+
3. Flame Test
The chlorides of several metals impart characteristic colour to the flame because they are volatile in
non-luminous flame. This test is performed with the help of a platinum wire as follows :
i) Make a tiny loop at one end of a plantinum wire.
ii) To clean the loop dip it into concentrated hydrochloric acid and hold it in a non-luminous flame
iii) Repeat step (ii) until the wire imparts no colour to the flame.
iv) Put 2-3 drops of concentrated hydrochloric acid on a clean watch glass and make a paste of a
small quantity of the salt in it.
v) Dip the clean loop of the platinum wire in this paste and introduce the loop in the non-luminous
(oxidising) flame
vi) Observe the colour of the flame first with the naked eye and then through a blue glass and
identify the metal ion

Inference from the colour of the salt in cold and on heating

Colour of the flame Colour of the flame
Inference
observed by naked eye observed through blue glass
Green flame with Same colour as observed
blue centre Cu2+
without glass
Crimson red Purple Sr2+
Apple green Bluish green Ba2+
Brick red Green Ca2+
4. Borax Bead Test
This test is employed only for coloured salts because borax reacts with metal salts to form metal
borates or metals, which have characteristic colours.
i) To perform this test make a loop at the end of the platinum wire and heat it in a flame till it is red
hot.
ii) Dip the hot loop into borax powder and heat it again until borax forms a colourless transparent
bead on the loop. Before dipping the borax bead in the test salt or mixture, confirm that the bead
is transparent and colourless. If it is coloured this means that, the platinum wire is not clean.
Then make a fresh bead after cleaning the wire.
iii) Dip the bead in a small quantity of the dry salt and again hold it in the flame.
iv) Observe the colour imparted to the bead in the non - luminous flame as well as in the luminous
flame while it is hot and when it is cold
v) To remove the bead from the platinum wire, heat it to redness and tap the platinum wire with your
finger.
71
 Brilliant STUDY CENTRE

On heating, borax loses its water of crystallisation and decomposes to give sodium metaborate
and boric anhydride.

Na2B4O7 .10H2O 
 Na2B4O7  10H2O
Borax

Na2B 4O7 
 2NaBO2  B2O3
Sodiummetaborate Boric anhydride

On treatment with metal salt, boric anhydride forms metaborate of the metal which gives different
colours in oxidising and reducing flame. For example, in the case of copper sulphate, following
reactions occur.

CuSO4  B2O3    
Nonlu min ous flame
 Cu BO2 2  SO3
Cupric metaborate
Blue green

Two reactions may take place in the reducing flame :

i) The blue Cu(BO2)2 is reduced to colourless cuprous metaborate as follows:

2Cu BO2 2  2NaBO2  C 

Lumin ous flame
2CuBO2  Na2B4O7  CO
or (ii) Cupric metaborate may be reduced to metallic copper and the bead appears red and
opaque.

2Cu BO2 2  4NaBO2  2C 

Luminous flame
2Cu  2Na2B4O7  2CO
Inference from the borax bead test
Heating in oxidising Heating in reducing
(non-luminous) flame (luminous) flame
Inference
Colour of the salt bead Colour of the salt bead
In cold In hot In cold In hot
Blue Green Red opaque Colourless Cu2+
Reddish brown Violet Grey Grey Ni2+
Light violet Light violet Colourless Colourless Mn2+
Yellow Yellowish brown Green Green Fe2+
5. Charcoal Cavity Test
Metallic carbonate when heated in a charcoal cavity decomposes to give corresponding oxide.
The oxide appears as a coloured residue in the cavity. Sometimes oxide may be reduced to
metal by the carbon of the charcoal cavity.

6. Cobalt Nitrate Test

If the residue in the charcoal cavity is white, cobalt nitrate test is performed.
(i) Treat the residue with two or three drops of cobalt nitrate solution.
(ii) Heat it strongly in non-luminous flame with the help of a blow pipe and observe the colour of the
residue.

72
 Additional Topics (Physics & Chemistry)

On heating, cobalt nitrate decomposes into cobalt (II) oxide, which gives a characteristic colour
with metal oxide present in the cavity.
Thus, with ZnO, Al2O3 and MgO, the following reactions occur.

Wet Tests for Identification of Cations

The cations indicated by the preliminary tests given above are confirmed by systematic analysis
given below. The first essential step is to prepare a clear and transparent solution of the salt. This
is called original solution. It is prepared as follows:
Preparation of Original Solution (O.S.)
To prepare the original solution, following steps are followed one after the other in a systematic order.
In case the salt does not dissolve in a particular solvent even on heating, try the next solvent.
The following solvents are tried:
1. Take a little amount of the salt in a clean boiling tube and add a few mL of distilled water and shake
it. If the salt does not dissolved, heat the content of the boiling tube till the salt completely
dissolves.
2. If the salt is insoluble in water as detailed above, take fresh salt in a clean boiling tube and add a
few mL of dil.HCl to it. If the salt is insoluble in cold, heat the boiling tube till the salt is completely
dissolved.
3. If the salt does not dissolve either in water or in dilute HCl even on heating, try to dissolve it in a few
mL of conc. HCl by heating.
4. If salt does not dissolve in conc. HCl, then dissolve it in dilute nitric acid.
5. If salt does not dissolve even in nitric acid then a mixture of conc. HCl and conc. HNO3 in the ratio
3:1 is tried. This mixture is called aqua regia. A salt not soluble in aqua regia is considered to be
an insoluble salt.
Group Analysis
(I) Analysis of Zero group cation (NH4+ ion)
(a) Take 0.1 g of salt in a test tube and add 1-2 mL of NaOH solution to it and heat. If there is a smell
of ammonia, this indicates the presence of ammonium ions. Bring a glass rod dipped in hydrochloric
acid near the mouth of the test tube. White fumes are observed.
(b) Pass the gas through Nessler’s reagent. Brown precipitate is obtained.
Chemistry of Confirmatory Tests for NH4+ ion
(a) Ammonia gas evolved by the action of sodium hydroxide on ammonium salts reacts with
hydrochloric acid to give ammonium chloride, which is visible as dense white fume.

73
 Brilliant STUDY CENTRE

Separation of all the six groups

74
 Additional Topics (Physics & Chemistry)

Group reagents for precipitating ions

(II) Analysis of Group - I cations

Take a small amount of original solution ( if prepared in hot conc. HCl) in a test tube and add cold
water to it and cool the test tube under tap water. If a white precipitate appears, this indicates the
presence of Pb2+ ions in group –I. On the other hand, if the original solution is prepared in water
and on addition of dil. HCl, a white precipitate appears, this may also be Pb2+.

75
 Brilliant STUDY CENTRE

76
 Additional Topics (Physics & Chemistry)

(IV) Analysis of Group - III cations

77
 Brilliant STUDY CENTRE

78
 Additional Topics (Physics & Chemistry)

2. Test for Nickel ion (Zn2+)

79
 Brilliant STUDY CENTRE

2. Test for Calcium ion(Ca2+)

80
 Additional Topics (Physics & Chemistry)

C. Preparation of some compounds

I Inorganic Compounds
To prepare double salts : ferrous ammonium sulphate (Mohr’s salt) and potash alum.
Theory
When a mixture containing equimolar proportions of potassium sulphate and aluminium sulphate or
ferrous sulphate and ammonium sulphate is crystallised from its solution, a double salt is formed. The
formation of double salt may be shown as follows:

Fe2+ and Al3+ ions undergo hydrolysis, therefore, while preparing aqueous solutions of ferrousulphate
and aluminium sulphate in water, 2-3 mL dilute sulphuric acid is added to prevent the hydrolysis of
these salts.
a) Preparation of Double Salt : Potassium Aluminium Sulphate (Potash Alum)
i) Take 10 mL of distilled water in a 50 mL beaker and heat it to about 40oC. Dissolve 6.6 g of
aluminium sulphate in it and add about 0.4 mL of dilute sulphuric acid.
ii) Weigh 2.4 g of powdered potassium sulphate and transfer it to the above solution.
iii) Heat the solution with constant stirring till potassium sulphate dissolves compeltely.
iv) Allow the solution to cool to room temperature slowly.

81
 Brilliant STUDY CENTRE

v) On cooling, white crystals of potash alum separate out.

vi) Decant the mother liquor and wash the crystals by gently shaking with 1 : 1 cold water and alcohol
mixture.
vii) Filter the crystals, dry these between the folds of a filter paper and note the yield.
b) Preparation of Double Salt : Ammonium Ammonium Sulphate
i) Dissolve 3.5 g of ferrous sulphate and 1.7 g of ammonium sulphate (weighed separately), in 5 mL
of distilled water contained in a 50 mL conical flask by heating. Add about 0.5 mL of dilute sulphuric
acid to the flask and concentrate the solution by heating till the crystallization point is reached.
ii) Allow the mixture to cool to room temperature slowly.
iii) On cooling, light green crystals of ferrous ammonium sulphate separate out.
iv) Decant the mother liquor and wash the crystals by shaking with very small amounts of 1:1 cold
water and alcohol mixture to remove sticking mother liquor.
v) Separate the crystals by filtration wash with alcohol, dry between the folds of a filter paper and
record the yield.
Precautions
a) Cool the solution slowly to get good crystals. Avoid rapid cooling.
b) Do not disturb the solution while cooling.
c) Avoid prolonged heating while preparing crystals of ferrous ammonium sulphate, as it may oxidise
ferrous ions to ferric ions and change the stoichiometry of the crystals.
II. Organic Compounds
a) Acetanilide.
Theory
The replacement of one hydrogen atom of the –NH2 group of aniline by CH3CO– group in the presence
of glacial acetic acid. Gives acetanilide. In the laboratory, acetylation is usually carried out with acetic
anhydride. Acetyl chloride may also be used for the purpose of acetylation if acetic anhydride is not
available. Acetylation with CH3COCl is usually carried out in the presence of pyridine.

Procedure
i) Take 5 mL of aniline in a 100 mL round bottom flask and add acetylating mixture containing 5 mL
acetic acid. Alternatively, you can use 5 mL of acetyl chloride and 5 mL of dry pyridine as the acetylating
mixture.
ii) Fir an air condenser on the mouth of the round bottom flask after adding a few pumice stones and
reflux the mixture gently for 10-15 minutes on a sand ethanol.
iii) Cool the reaction mixture and pour it slowly in 150-200 mL of ice cold water with stirring.
iv) Filter the solid, wash it with cold water and recrystallise a small amount of sample from hot water
containing a few drops of methanol or ethanol.
v) Report the yield and the melting point of the compound.
82
 Additional Topics (Physics & Chemistry)

Precautions
a) Handle acetic anhydride and acetyl chloride carefully as they cause irritation to the eyes and acetyl
chloride also strongly fumes in air.
b) Store acetylchloride under dry conditions.
c) Handle pyridine with extreme caution. Dispense it in an efficient fume cupboard and water disposable
glasses while using it.
d) Distil pyridine before use because it absorbs mioisture and the reaction does not take place under
moist conditions.
e) Wash the solid 2-3 times with cold water till the filtrate is neutral to litmus.
f) Determine the melting point of perfectly dried and recrystallised sample.
ALTERNATIVE METHOD FOR THE PREPARATION OF ACETANILIDE
If acetic anhydride of pyridine is not available then the following method can be used for the preparation
of acetanilide.
Procedure
i) Take 1 mL of aniline in a dry boiling tube, add 1 mL of glacial acetic acid to it and mix the two
thoroughly.
ii) To the above mixture add 1 mL of acetyl chloride in lots (0.3 mL at a time). The mixture becomes
warm. If the boiling tube becomes unbearable to touch, cool it under tap water.
iii) After addition of whole amount of acetyl chloride, heat the mixture for five minutes in a boiling water
bath.
iv) Cool the boiling tube and add ice-cold water  10mL  into the tube with constant stirring.
v) Filter the acetanilide separated as white powder and wash with water fill filtrate is neutral to litmus.
vi) Crystallise the crude acetanilide with hot water. White shining needle shaped are obtained.
vii) Report the yield and melting point of the compound.
Precautions
a) If aniline sample is too much coloured, distill it before carrying out the experiment, because yield is
lowered with impure aniline.
b) Use perfectly dry apparatus.
c) Do not inhale the vapours coming out during the addition of acetylchloride.
b) p-nitroacetanilide.
Theory
p-Nitroacetanilide is prepared by the nitration of acetanilide by using a mixture of conc. nitric acid and
conc. sulphuric acid as nitrating reagent. The mixture of the two acids release nitronium ion NO2  ,
which acts as an electrophile in the reaction.
HNO3  2H2SO 4 
 NO2  H2O  2HSO4
Nitronium ion attacks the benzene ring containing anilide group, mainly at the para position to give p-
nitroacetanilide as a major product. This is an example of aromatic electrophilic substitution reaction.

83
 Brilliant STUDY CENTRE

Procedure
i) Dissolve 2 g of acetanilide in 2 mL of glacial acetic acid taken in a 100 mL beaker.
ii) Add 4 mL of conc. H2SO4 gradually with stirring to the above mixture. The mixture becomes hot and
clear solution is obtained. Cool the reaction mixture in an ice bath maintained at 0-5oC.
iii) Add a cold mixture of 1.0 mL conc. HNO3 and 1.0 mL conc. H2SO4 to the viscous reaction mixture
drop by drop with constant stirring, so that the temperature of the mixture does not rise above 10oC.
iv) Remove the beaker from the ice bath and allow the reaction mixture to attain room temperature.
Let it stand at room temperature for about 30 minutes. Stir the reaction mixture continuously and pour
it on 100 g of crushed ice.
v) Stir the mixture well and filter the compound so obtained.
vi) Wash the compound with cold water and dry it.
vii) Recrystallise a small amount of the pale yellow solid from alcohol. Colourless crystals of
p-nitroacetanilide are obtained. Yellow ortho-nitroacetanilide formed in the small amount remains
dissolved in the mother liquor.
viii) Record the yield and metlting point of the pure compound.
Precautions
a) Do not allow the temperature of the reaction mixture to exceed 10oC during addition of nitrating
mixture.
b) Add mixture of concentrated nitric acid and sulphuric acid into the solution of acetanilide slowly and
carefully.
c) Aniline yellow (p-amino-azobenzene)
Theory
p-aminobenzene can be prepared in a good yield by rearrangement reaction of diazoaminobenzene
with a small quantity of aniline hydrochloride in the presence of aniline as solvent. The chemistry of
this conversion is as follows :

84
 Additional Topics (Physics & Chemistry)

The above reaction is carried out only in weekly acidic conditions.

Procedure
i) Dissolve 3 g of finely powdered diazoaminobenzene in 7 mL of aniline in a 100 mL conical flask.
ii) Add 1.5 g of finely powdered aniline hydrochloride to the above mixture.
iii) Warm the mixture with occasional shaking on a water bath at about 40-45oC, for a period of about
one hour.
iv) Remove the flask from the water bath and allow the reaction mixture to stand at room temperature
for about 30 minutes.
v) Add 9 mL of glacial acetic acid diluted with an equal volume of water and shake the reaction
mixture thoroughly to convert excess aniline to its acetate, which is water-soluble.
vi) Allow the mixture to stand for 15 minutes with occasional stirring.
vii) Filter p-aminoazobenzene, wash with a little cold water and dry between the folds of a filter paper.
viii) Recrystallise a small portion of crude p-aminoazobenzene from carbon tetrachloride.
ix) Report the yield and melting point of p-aminoazobenzene.
Precautions
a) Maintain the temperature of the reaction mixture at about 40-50oC.
b) Wash the crude product with a small volume of water repeatedly.
c) Note the melting point of the perfectly dry sample.
ANALTERNATIVE PROCEDURE FOR PREPARING ANILINE YELLOW
Theory
Aniline yellow can also be prepared by direct diazotisation and coupling as followed for phenyl-azo-
β -naphthol dye. However, coupling of the diazonium salt with aniline or any other aromatic amine is
carried out in a weakly acidic medium.
Procedure
i) Prepare a solution of benzene diazonium chloride using 2 mL of aniline according to the method
described for the preparation of phenyl-azo- β -naphthol dye (see experiment 10.4)
ii) Prepare a solution of 4 mL aniline in 4 mL 1.0 M HCl.
iii) Add the cold solution of aniline hydrochloride slowly into the cold solution of benzene diazonium
chloride.
iv) Filter the yellow compound and dry it between the folds of a filter paper.
v) Recrystallise the small amount of crude sample from carbon tetrachloride and report the yield and
melting point.
d) Iodoform
Theory

85
 Brilliant STUDY CENTRE

Procedure
Mass 5 grams of potassium carbonate K2CO3. Dissolve in 20 mL of distilled water, taken in an
Erlenmeyer flask. Stir the mixture constantly to ensure the potassium carbonate is completely dissolved.
The mixture is then placed in a warm water bath, which is at about 75 to 80 degrees Celsius. Cool the
solution when the reaction is complete. The yellow crystals formed is iodoform. Separate the iodoform
from the mixture by filtration. Wash the iodoform with water. A small sample of the iodoform is
recrystallized from alcohol. Dry the iodoform crystals.
III. Colloids

86
 Additional Topics (Physics & Chemistry)

D. QUANTITATIVE ANALYSIS- TITRATION

Titration is the measurement of the volume of a solution of one reactant that is required to react
completely with a measured amount of another reactant. As both the reactants are taken in the form
87
 Brilliant STUDY CENTRE

of solutions and the titration is the measurement of volume of one solution that must be added to
another solution till the reaction is complete, this method of quantitative analysis is, therefore, called
volumetric analysis. Usually the concentration of one of the solutions is known, (called standard
solution) and it is desired to find the concentration of the other by titration. The apparatus used is
shown in Fig. 8.2. A known volume of the solution is taken in the titration flask (with the help of a
pipette) and the other solution is taken in the burette which is graduated in cc’s and has a stop-clock
at the bottom to control the amount of flow into the flask. The solution to be titrated (taken in the flask)
is called titrate and the solution with which the titration is to be done (taken in the burette) is called the
titrant. The point at which the required volume of one solution has been added to the other to exactly
complete the reaction between the two is called end point or equivalence point.
There are many types of titrations such as redox titrations (involving oxidation and reduction), acid-base
titrations (involving neutraisation), precipitation titrations (titrations (r.g. NaCl vs AgNO3), complexometric
titrations (involving formation of complexes) but here we shall take up a brief discussion of acid-base
titirations in aqueous solutions only.
i) Acid - Base Titration
Theory of Indicates
An indicator is a substance which is used to determine the end point in a titration. In acid base titrations
organic substances are generally used as indicators. They change their colour within a contain pH range.
The colour change and the pH range. The colour change and the pH range of common indicators are
tabulated below.

Indicator pH range Colour change

Methyl orange 3.2 - 4.5 Pink to yellow
Methyl red 4.4 - 6.5 Red to yellow
Litmus 5.5 - 7.5 Red to blue
Phenol red 6.8 - 8.5 Yellow to red
Phenolphthalein 8.3 - 10.5 Coloureless to pink
Theory of acid-base indicators
Ostwald’s theory : According to this theory
a) The colour change is due to ionisation of the acid-base indicator. The unionised form has different colour
than the ionised form.
b) The ionisation of the indicator is largely affected in acids and bases as it is either a weak acid or a weak
base. In case, the indicator is a weak acid, its ionisation is very much low in acids due to common H+ ions
while it is fairly ionised in alkalies. Similarly, if the indicator is a weak base, its ionisation is large in acids and
low in alkalies due to common OH– ions.
Considering two important indicators phenolphthalein (a weak acid) and methyl orange (a weak base),
Ostwald’s theory can be illustrated as follows:
Phenolphthalein : It can be represented as HPh. It ionises in solution to a small extent as :

88
 Additional Topics (Physics & Chemistry)

Applying law of mass action,

The undissociated molecules of phenolphthalein are colourless while Ph– ions are pink in colour. In presence
of an acid, the ionisation of HPh is practically negligible as the equilibrium shifts to left hand side use due to
high concentration of H+ ions. Thus, the solution would remain colourless. On addition of alkali, hydrogen
ions are removed by OH– ions in the form of water molecules and the equilibrium shifts to right hand side.
Thus, the concentration of Ph– ions increases in solution and they impart pink colour to the solution.
Let us derive Henderson’s equation for an indicator

At equivalence point;

Methyl orange : It is a very weak base and can be represented as MeOH. It is ionised in solution to give
Me+ and OH– ions.

Applying law of mass action,

In presence of an acid, OH– ions are removed in the form of water molecules and the above equilibrium
shifts to right hand side. Thus, sufficient Me+ ions are produced which impart red colour to the solution. On
addition of alkali, the concentration of OH– ions increases in the solution and the equilibrium shifts to left

89
 Brilliant STUDY CENTRE

hand side, i.e., the ionisation of MeOH is practically negligible. Thus, the solution acquires the colour of
unionised methyl ornage molecules, i.e., yellow.
This theory also explains the reason why phenolphthalein is not a suitable indicator for titrating a weak base
against strong acid. The OH– ions furnished by a weak base are not sufficient to shift the equilibrium
towards right hand side considerably, i.e., pH is not reached to 8.3. Thus, the solution does not attain pink
colour. Similarly, it can be explained why methyl orange is not a sutiable indicator for the titration of weak
acid with strong base.
Selection of suitable indicator or choice of indicator
The neutralisation reactions are of the following four types :
i) A strong acid versus a strong base.
ii) A weak acid versus a strong base.
iii) A strong acid versus a weak base.
iv) A weak acid versus a weak base.
In order to choose a suitable indicator, it is necessary to understand the pH changes in the above four types
of titrations. The change in pH in the vicinity of the equivalence point is most important for this purpose. The
curve obtained by plotting pH as ordinate against the volume of alkali added as abscissa i known as
neutralisation or titration curve.

ii) Redox Titration- Permanganometry

90
 Additional Topics (Physics & Chemistry)

MOHR’S SALT
AIM : (a) To prepare 250 ml of M/20 solution of Mohr’s
(b) Using this calculate the molarity and strength of the given KMnO4 solution
APPARATUS AND CHEMICALS REQUIRED :- Mohr’s salt, weighing bottle, weight box, volumetric flask,
funnel, distilled water, chemical balance, dilute H2SO4, beakers, conical flask, funnel, burette, pipette,
clamp stand, tile, KMnO4 solution.
THEORY : (a) Mohr’s salt having the formula FeSO4 (NH4)2SO4.6H2O has molar mass 392 gmol–1. It is a
primary standard.
Its equivalent mass is 392/1 = 392 as its n factor is 1 as per the following reaction

Fe 2  Fe 3  e 
PROCEDURE:
1. Weight a clean dry bottle using a chemical balance
2. Add 4.9 g more weights to the pan containing the weights for the weighting bottle
3. Add Mohr’s salt in small amounts to the weighing bottle, so that the pans are balanced.
4. Remove the weighing bottle from the pan
5. Using a funnel, transfer the Mohr’s salt to the volumetric flask
6. Add about 5 ml of dilute H2SO4 to the flask followed by distilled water and dissolve the Mohr’s salt
7. Make up the volume to the required level using distilled water
8. The standard solution is prepared
(B) THEORY
1. The reaction between KMnO4 and Mohr’s salt is a redox reaction and the titration is therefore called
a redox titration.
2. Mohr’s salt is the reducing agent and KMnO4 is the oxidizing agent
3. KMnO4 acts as an oxidising agent in all the mediums; i.e. acidic, basic and neutral medium.
4. KMnO4 acts as the strongest oxidizing agent in the acidic medium and therefore dil. H2SO4 is added
to the conical flask before starting the titration.
Ionic equations involved:-

Reduction half : MnO 4  8H   5e  

 Mn 2  4H 2 O

Oxidation half : 5Fe 2  

 5Fe3  5e 

Overall Equation : MnO 4  8H   5Fe 2  

 Mn 2   5Fe3  4H 2 O
INDICATOR : KMnO4 acts as a self indicator
END POINT : Colourless to light pink (KMnO4 in the burette)
PROCEDURE:
1. Fill the burette with KMnO4 solution
2. Pipette out 10 ml of Mohr’s salt solution into the conical flask

91
 Brilliant STUDY CENTRE

3. Add half test tube of dil. H2SO4

4. Keep a glazed tile under the burette and place the conical flask on it
5. Note down the initial reading of the burette
6. Run down the KMnO4 solution into the conical flask drop wise with shaking
7. Stop the titration when a permanent pink colour is obtained in the solution.
8. This is the end point. Note down the final burette reading
9. Repeat the experiment until three concordant values are obtained.
10.
OBSERVATION TABLE (TO BE PUT UP ON THE BLANK SIDE USING A PENCIL)
Volume of Mohr’s salt solution taken:-

Burette Readings Volum e of KMnO 4

Sl.No
INITIAL FINAL USED (m l)
1 10 18.8 8.8
2 18.8 27.7 8.9
3 27.7 36.5 8.8

Concordant Value = 8.8 mL

Calculations : (To be put up on the blank side using a pencil)
Calculation of amount of Mohr’s salt to be weighed to prepare 100 mL M/20 solution:
Molecular mass of Mohr’s salt - 392 g/mole
1000 cm3 of 1M KMnO4 require 393 g Mohr’s salt
250 cm3 of M/40 KMnO4 require = 392/40g = 4.9 g
Using formula:

N1M1V1  N 2 M 2 V2
Where N1 = 5 (for KMnO4), V1 = 8.8 mL; M1 = ?
N2 = 1 (for Mohr’s salt), V2 = 10 mL, M2 = 1/20 M
M1 = [1*(1/20)*10]/[5*8.8] = 1/88 M = 0.01 M
Strength = M × Molar mass = 158* (1/88) = 1.79 g/L
Result (On ruled side) : The molarity of KMnO4 = 0.01 M and the strength of KMnO4 = 1.79 g/L
OXALIC ACID
AIM : (a) To prepare 100 ml of M/40 solution of oxalic acid.
(b) Using this calculate the molarity and strength of the given KMnO4 solution
Apparatus and chemicals required : Oxalic acid, Weighing bottle, Weight box, Volumetric flask,
Funnel, Distilled water, Chemical balance, Beakers, Conical flask, Funnel, Burette, Pipette, Clamp
stand, Tile, Dilute H2SO4, KMnO4 solution.
92
 Additional Topics (Physics & Chemistry)

Theory : (a) Oxalic acid is a dicarboxylic acid having molar mass 126 gmol–1. It is a primary standard
and has the molecular formula COOH–COOH.2H2O. Its equivalent mass is 126/2 = 63 as its n factor
is 2 as per the following reaction.
COOH –COOH  2CO2 + 2H+ + 2e–
PROCEDURE
1. Weigh a clean dry bottle using a chemical balance
2. Add 3.15g more weights to the pan containing the weights for the weighting bottle
3. Add oxalic acid in small amounts to the weighing bottle, so that the pans are balanced.
4. Remove the weighing bottle from the pan
5. Using a funnel, transfer the oxalic acid to the volumetric flask
6. Add a few drops of distilled water to dissolve the oxalic acid
7. Make up the volume to the required level using distilled water
8. The standard solution is prepared
THEORY
1. The reaction between KMnO4 and oxalic acid is a redox reaction and the titration is therefore called a
redox titration.
2. Oxalic acid is the reducing agent and KMnO4 is the oxidising agent
3. KMnO4 acts as an oxidising agent in all the mediums, i.e. acidic, basic and neutral medium
4. KMnO4 acts as the strongest oxidizing agent in the acidic medium and therefore dil. H2SO4 is added
to the conical flask before starting the titration.
5. The titration between oxalic acid and KMnO4 is a slow reaction, therefore heat the oxalic acid solution
to about 60°C to increase the rate of the reaction.
ionic equations involved:

Reduction half : MnO 4  8H   5e  

 Mn 2   4H 2 O]X 2

Oxidation half : C 2 O 42 

 2CO 2  2e  ] X 5

Overall equation : 2MnO 4  16H   5C 2 O 42 

 2Mn 2   10CO 2  8H 2 O
INDICATOR : KMnO4 acts as a self indicator.
END POINT : Colourless to light pink [KMnO4 in the burette]
PROCEDURE:-
1. Fill the burette with KMnO4 solution
2. Pipette out 10 ml. of oxalic acid solution into the conical flask
3. Add half a test tube of dil. H2SO4 and heat the solution to about 60°C to increase the rate of the
reaction.
4. Keep a glazed tile under the burette and place the conical flask on it
5. Note down the initial reading of the burette

93
 Brilliant STUDY CENTRE

6. Run down the KMnO4 solution into the conical flask drop wise with shaking
7. Stop the titration when a permanent pink colour is obtained in the solution.
8. This is the end point. Note down the final burette reading
9. Repeat the experiment until three concordant values are obtained.
Observation table : (To be put up on the blank side using a pencil)
Volume of Oxalic Acid solution taken = 10 mL

Burette Readings Volume of KMnO4

Sl.No
INITIAL FINAL USED (ml)
1 16 26.5 10.5
2 26.5 36.9 10.4
3 36.9 47.4 10.5

Concordant Value = 10.5 mL

Calculations (To be put up on the blank side using a pencil)
Calculation of amount of oxalic acid to be weighed to prepare 100 ml M/20 solution.
Molecular Mass of Oxalic Acid = 126g/mole
1000 cm3 of 1M oxalic acid require 126g oxalic acid
1000 cm3 of M/40 oxalic acid require = 126/40 g = 3.15g
Using formula
N1M1V1 = N2M2V2
Where N1 = 5 (for KMnO4), V1 = 10.5; M1 = ?
N2 = 2 (for oxalic acid), V1 = 10 ml; M2 = 1/40
M1 = [2*(1/40)*10]/[5*10.5] = 1/105 m = 0.0095 M
Strength = M × Molar maxx = 1.58 * (1/105) = 1.504 g/L
RESULT (ON RULED SIDE)
The Molarity of KMnO4 = 0.0095 M and the strength of KMnO4 = 1.504 g/L

94
 Additional Topics (Physics & Chemistry)

QUESTIONS
PRINCIPLES RELATED TO PRACTICAL CHEMISTRY
1. A phenolic compound gives green colour which rapidly darkens with neutral ferric chloride solution.
The compound is
1) Resorcinol 2) Catechol 3) o-Cresol 4) m-Cresol
2. Match Column-I with Column-II
Column-I (Test) Column-II (Reagents)
a) Tollen’s test p) CuSO4 + Na3C6H5O7
b) Schiff’s test q) CuSO4 + KNaC4H4O6
c) Fehling’s test r) [Ag(NH3)2]NO3]OH–
d) Benedict’s test s) p-Rosaniline hydrochloride + SO2(g)
1) a  r; b  s; c  q; d  p 2) a  s; b  r; c  p; d  q

3) a  s; b  r; c  q; d  p 4) a  p; b  q; c  r; d  s
3. Ceric ammonium nitrate (CAN) reagent is used to test
1) Alcoholic group 2) Phenolic group 3) Aldehydic group 4) Amino group
4. Aniline and Benzylamine can be best distinguished by
1) Carbylamine test 2) Azo dye test 3) CAN test 4) Luca’s test
5. Action of dilute H2SO4 on an inorganic salt gives a colourless gas with the smell of rotten eggs.
Identify the correct statement from the following
1) The gas is SO2 2) The gas turn lead acetate paper black
3) The gas turns lime water milky 4) The gas is non toxic
6. Griss-Ilosvay test is used for the confirmatory test for

1) CH 3 COO  ion 2) S2 ion 3) NO 2 ion 4) NO 3 ion

7. Consider the reactions

NaCl  H 2SO 4 
 X  Ygas
Y  Z 
 Wgas

W is
1) NH3 2) (NH4)2 SO4 3) NH4Cl 4) (NH4)3PO4
8. Presence of yellow precipitate in chromyl chloride test confirms the presence of chloride ion. The
yellow precipitate is
1) CrO2Cl2 2) Na2CrO4 3) PbCl2 4) PbCrO4
9. Which of the following compound is coloured?
1) [Fe(NO)]SO4 2) BaSO4 3) PbSO4 4) AgCl
10. During the preliminary examination of the salt, a bright green colour is observed which indicates
the presence of
1) Fe3+ 2) Cr2+ 3) Mn2+ 4) Ni2+

95
 Brilliant STUDY CENTRE

11. Which of the following is a pair of group-III cations?

1) Pb2+, Cu2+ 2) Al3+, Fe3+ 3) Co2+, Ni2+ 4) Ba2+, Ca2+
12. In group analysis of cations in inorganic salts, group-II cations are precipitated as
1) Chloride 2) Sulphides 3) Hydroxides 4) Carbonates
13. No specific group reagent is required for the precipitation of
1) Ni2+ 2) Pb2+ 3) Mg2+ 4) Mn2+
K  Fe  CN  
14. In the reaction Cu  NH 3 4  SO 4 
CH 3COOH
 
4 6
 X  Chocolate brown precipitate  . Then
oxidation state of counter ion in X is
1) 0 2) +1 3) +2 4) +3
15. ‘Lake test’ is used for the confirmation of
1) Fe3+ 2) Ni2+ 3) Al3+ 4) Mg2+
16. Aqueous solution of which of the following metal ion gives a brilliant red precipitate with DMG?
1) Zn2+ 2) Ni2+ 3) Cu2+ 4) Mg2+

Diazoaminobenzene   X . Then X is

HCl
17. Aniline solvent

1) Iodoform 2) Aniline yellow 3) p-nitroacetanilide 4) Acetanilide

18. Identify a mismatch
Colloid Preparation method
1) Au sol Bredig’s arc method
2) S sol Oxidation
3) Fe(OH)3sol Hydrolysis
4) As2S3 sol Reduction
19. Which of the following titration will have the equivalence point of a pH > 8?
1) HCl and NH3 2) CH3COOH and NH3 3) HCl and NaOH 4) CH3COOH and NaOH
20. Observation table for a permanganometric titration for the estimation of concentration of KMnO4 is
given below

Burette reading
No Volume of KMnO4 used (mL)
Initial Final
1 18 28.2 10.2
2 28.2 38.3 10.1
3 38.3 48.4 10.1

Volume of (M/20) oxalic acid solution = 10 mL

Strength of KMnO4 is
1) 1.504 g/L 2) 3.128 g/L 3) 4.169 g/L 4) 5.088 g/L

96