Test For Functional Groups

Aim
To identify the functional group present in an organic Compound.

.Test For unsaturation

Theory
Organic compounds containing > C = C < and / or – C ≡ C – bonds are
called unsaturated compounds.
These compounds undergo an additional reaction with bromine water or the
solution of bromine in carbon tetrachloride, chloroform or glacial acetic acid.
Addition of bromine to an alkene results in the formation of vicinal
dibromide. The reddish orange color of the solution of bromine in carbon
tetrachloride disappears on reaction with an alkene.
The reaction is as follows :
Br H
H C = CH + Br H C CH
H Br
(colourless)

Alkenes decolourise the neutral/alkaline KMnO4 solution and vicinal glycols

are formed (Bayer’s test). Reaction takes place as follows :

OH
- -
3CH = CH + 4H O + 2MnO4 3CH CH + 2OH + 2MnO
(purple) OH

Both the above reactions are used as tests for unsaturation.

Material Required:
• Test tubes : Two
• Test tube holder : One
• Potassium hydroxide solution : -2 mL
• Carbon tetrachloride/chloroform : 2 mL
• Bromine water/solution of bromine
in CCl4 or chloroform : 2 mL
• Potassium permanganate solution : As per need
• Compound to be tested : As per need
Procedure
A) Bromine Water Test
Dissolve 0. g or 5 drops of organic compounds in 2 mL of carbon
tetrachloride in a test tube and add %2solution of bromine in carbon
tetrachloride or bromine water drop by drop with continuous shaking.
Decolourization of bromine solution indicates the presence of
unsaturation in organic compound.
B) Bayer’s test
Dissolve 30-25 mg of organic compound in 2 mL of water or acetone
(free of alcohol) and add % potassium permanganate solution containing
equal volume of % sodium carbonate solution. The discharge of the
color of more than one drop of potassium permanganate indicates the
presence of unsaturation in the organic compound. Carrying out the
reaction under alkaline conditions removes the possibility of confusion
due to substitution in aromatic compounds.

Note:
i) Unsaturation in an organic compound is confirmed only when both of
the above tests are positive.
ii) In place of CCl any other solvent such as CHCl /dioxane and even
water can be used to dissolve the organic compound for carrying out
the reaction.

2.Test For Alcoholic (R–OH) Group:

Theory
Alcoholic compounds on reaction with ceric ammonium nitrate complex give
a red colouration due to the formation of a complex.

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

Ceric ammonium nitrate Red 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 solution
are added to the compound in the presence of sodium hydroxide solution.
Probably sodium hypochlorite first oxidized potassium iodide into potassium
hypoiodite, which oxidizes 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.
Potassium Potassium
hypoiodite hypoiodite NaOH
CH CH OH CH CHO C CHO CH + HCOONa
Lucas Test
Lucas reagent contains zinc chloride and concentrated hydrochloric acid.

rates. Tertiary alcohols react almost instantaneously,secondary alcohols react

in about 5- minutes and primary alcohols react very slowly.
The reaction may take 0 minutes to several days.

ZnCl
RCH OH + HCl No reaction ⁄ Slow reaction
ZnCl
R CHOH + HCl R CHCl + H O
ZnCl
R3COH + HCl R3CCl + H O

Alcohols are so luble in Lucas reagent but the formed alkyl halides are not
soluble. Therefore, formation of two layers in the reaction medium indicates
the occurrence of the reaction.
Primary alcohols – Layers do not separate
Secondary alcohols – Layers separate within 5- minutes
Tertiary alcohols – Layers separate immediately.

Material Required:
• Test tube holder : One
• Test tubes : As per need
• Ceric ammonium nitrate
solution : As per need
• Sodium hydroxide : As per need
• Iodine solution : As per need
• Lucas reagent : As per need
• Dioxan : As per need

Procedure
A) Ceric ammonium nitrate test
Take mL solution of organic compound dissolved in a suitable solvent.
Add a few drops of ceric ammonium nitrate solution. Appearance of red
color shows the presence of alcoholic – OH group.

Note:
The red color disappears after keeping the reaction mixture for
sometime. The colour also disappears if excess of ceric ammonium
nitrate solution is added. Therefore,use of excess of ceric ammonium
nitrate solution should be avoided.
B) Iodoform test
First method
Take 0.2 mL of the compound in a test tube, add 0 mL of %10 aqueous
KI solution and 0mL of freshly prepared NaOCl solution.
Warm gently; yellow crystals of iodoform separate.

Second method
Dissolve 0. g or 4 to 5 drops of compound in 2mL of water. If it doesn’t
dissolve, add dioxane drop by drop to get a homogeneous solution.
Add 2 mL of %5 sodium hydroxide solution followed by potassium
iodide-iodine reagent* dropwise with continuous shaking till a definite
dark colour of iodine persists. Allow the reactants to remain at room
temperature for 3-2 minutes.
If no iodoform separates, warm the reaction mixture in a water bath at
°60C. Add more drops of potassium iodide–iodine reagent. If colour of
iodine disappears continue addition of reagent till the colour of iodine
persists even after two minutes of heating at °60C.
Remove excess iodine by adding a few drops of sodium hydroxide
solution with shaking.
Dilute the mixture with equal volume of water and keep it at room
temperature for 15-10 minutes. A yellow precipitate of iodoform is
obtained if test is positive.

C) Lucas test
Take 1 mL of compound in a test tube. Add 10 mL of Lucas reagent layer.
Shake well and note the time for the separation of two distinct layers.

Note:
Lucas test is applicable to only those alcohols which are solublein the
reagent because the test is based on separation of alkyl halides as
separate layer.

3.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 weaklyacidic,therefore they are

to be soluble is sodium hydrogencarbonate solution. Phenols give coloured

complex with neutral ferric chloride solution. For example, phenol gives
acomplex of violet colour as follows :

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

(Violet complex)
Resorcinol, o–, m– and p–cresol give violet or blue colouration,catechol gives
green colour which rapidly darkens.
and 2–Naphthol do not give characteristics colours. Phenols condense with
phthalic anhydride in the presence of concentrated H SO , Phenol condeses
to give phenolphthalein which gives a dark pink colour with NaOH solution.
This is called phthalein dye test.
OH
OH
OH
CO
Conc. H SO
+ O
CO C O
CO

NaOH

-O -O
O O
OH
Excess NaOH
C C

COO- COO-

(Colourless) (Pink)

Compound Colour Compound Compound

O – Cresol Red Catechol Usually blue takes
longer time to appear
m – Cresol Bluish purple Resorcinol Green fluorescent
colour of fluorescein
p – Cresol No colour

Material Required:
• Test tube holder : One
• Test tubes : As per need
• Blue litmus paper
• Ferric chloride solution
• Conc. sulphuric acid
• Sodium hydroxide
• Phthalic anhydride
• Organic compoundcontaining phenolic – OH group
Procedure
A) Ferric chloride test
Take 2 mL of aqueous or alcoholic solution of the organic compound in
a test tube, add neutral ferric chloride solutiondropwise and note the
colour change.
Appearance of a blue,green, violet or red colour indicates the presence
of phenolic –OH group.
B) Phthalein dye test
Take 0. g of organic compound and 0. g of phthalic anhydride in a clean
dry test tube and add 2- drops of conc. H SO .
Heat the test tube for about minute in an oil bath. Cool and pour the
reaction mixture carefully into a beaker containing 5 mL of dilute
sodium hydroxide solution. Appearance of pink, blue, green, red etc.
colours indicates the presence of phenolic –OH group in the compound.
However, the colour disappears on addition of large excess of sodium
hydroxide solution.
Note:
i) Neutral ferric chloride solution is prepared by adding dilute sodium
hydroxide solution to ferric chloride solution drop by drop till a small
but permanent brown precipitate appears.
Solution is filtered and the clear filtrate is used for the test.
ii) Some phenols like 2,4,6 –trinitrophenol and 2,4 –dinitrophenol, which
contain electron withdrawing groups are strong acids and dissolve even
in sodium hydrogencarbonate solution.

3.Test for Aldehydic And Ketonic Groups:

Theory
Both aldehydes and ketones contain carbonyl group (>C = O) and compound
are commonly known as carbonyl compounds. Identification of 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.
OH
-H O
>C = O + RNH2 C >C = NR
NHR

(R = alkyl, aryl or C6H5NH etc.)

These reactions are catalysed by an acid or a base and do not occur under
strongly acidic or basic conditions. Each reactionrequires 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 agents.
Distinction can be made between these two types of carbonyl compounds

Following tests are performed for the identification of aldehydic and ketonic
groups:
(i) On reaction with -2,4dinitrophenyl hydrazine (-2,4DNP), they form the
respective 2,4–dinitrophenyl hydrazones.
NO NO

>C = O + H N – NH >C = N – NH

NO NO

2,4 - Dinitrophenyl hydrazine

of carbonyl compound

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 solution of silver cation complexed with
ammonia, and Fehling’s and Benedict’s reagents are alkalinesolutions
containing cupric ions complexed with tartarate and citrate ions respectively.
Fehling’s reagent is freshly prepared bymixing equal amounts of Fehling’s
solution A and Fehling’s solution B. Fehlings 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 Cu+2 ion complexed with tartarate ions.
The structure of the complex is given below :

O C O O C O

H Cu H
H C O O C H
H C O O C H
H Cu H

O C O O C O

Copper tartarate complex

Benedict modified the original Fehling’s test by using a single solution which
is more convenient for the test. Benedict’s solution is more stable than
Fehling’s reagent and can be stored for a longtime.
It is an alkaline solution containing a mixture of copper sulphate and sodium
citrate (2Na C6H5O7 . H2O).
Complex formation decreases the cupric ion concentration below that
necessary for precipitation of cupric hydroxide. These two reagents oxidize

The chemistry of these tests is as follows:

RCHO + 2[Ag(NH3 )2]+ + 2OH- 2Ag + 3NH3 + H2O + RCOONH4

From Tollen’s reagent

RCHO + 2Cu+2 (complexed) + 5OH- RCOO- + Cu2O + 3H2O

Fehling’s solution

However, aromatic aldehydes do not give positive Fehling’s test.In Benedict

test also, Cu+2 ions are reduced to Cu+ ions in the same manner as in the
case of Fehling’s reagent.

by decolourising aqueous solution of p–rosaniline hydrochloride dye by

adding sodium sulphite or by passing SO gas).
Ketones do not respond to this test.

Material Required:
• Beaker (250 mL) : One
• Test tube holder : One
• Test tubes : As per need

• Fehling’s solutions A and B : As per need

• Silver nitrate : As per need
• Dilute ammonium hydroxide solution : As per need
• 2,4 - Dinitrophenyl-hydrazine reagent : As per need

Procedure
A) Test given by both aldehydes and ketones
-2,4Dinitrophenylhydrazine test (-2,4DNP test):-
Take 3-2 drops of the liquid compound in a test tube or in case ofsolid
compound, dissolve a few crystals of it in 3-2 mL alcohol. Add a few
drops of an alcoholic solution of -2,4dinitrophenylhydrazine. Appearance
of yellow, orange or orange-red precipitate confirms the presence of
carbonyl group.If precipitate does not appear at room temperature,
warm the mixture in a water bath for a few minutes and cool.
A) Tests given by aldehydes only

given by aldehydes only.

Take 4-3 drops of the liquid compound or dissolve a few crystals of

Appearance of pink colour indicates the presence of an aldehyde.

Fehling’s test -
Take nearly mL of Fehling’s solution A and mL of Fehling’s solution B in
a clean dry test tube. To this add 3-2 drops of the liquid compound or
about 2 mL of the solution of the solid compound in water or alcohol.
Heat the content of the test tube for about 2 minutes in a water bath.
Formation of brick red precipitate of copper (I) oxide indicates the
presence of an aldehyde.This test is not given by aromatic aldehydes.
Benedicts test -
Add 5 drops of the liquid compound or the solution of the solid organic
compound in water or alcohol to 2 mL Benedict’s reagent.Place the test
tube in boiling water bath for 5 minutes. An orange-red precipitate
indicates the presence of an aldehyde.
Tollen’s test -
(i) Take mL of freshly prepared (~ 2 %) silver nitrate solutionin a test
tube. Add 2- drops of sodium hydroxide solution to it and shake, a
dark brown precipitate of silver oxide appears.
Dissolve the precipitate by adding ammonium hydroxide solution
drop-wise.
(ii) To the above solution, add an aqueous or an alcoholic solution of the
organic compound.
(iii) Heat the reaction mixture of step (ii) in a water bath for about five
minutes. Formation of a layer of silver metal on the inner surface of
the test tube which shines like a mirror, indicates the presence of an
aldehyde.

3.Test for Carboxyl Group (— COOH) —

Theory
Organic compounds containing carboxyl functional groups are called
carboxylic acids. The term carboxyl, derives its name from the combination
of words carbonyl and hydroxyl because carboxylic functional group contains
both of these groups. These acids turn blue litmus red and react with sodium

of carbondioxide.
This is a test that distinguishes carboxylic acids from phenols.
RCOOH + NaHCO RCOONa + H2O + CO2
These react with alcohols in the acidic medium to produce esters.
 Conc. H2SO
RCOOH + R’OH RCOOR’ + H2O
Carboxylic Alcohol Ester
acid

Material Required:
• Test tube holder : One
• Glass rod : One
• Test tubes : As per need
• Blue litmus paper/solution : As per need
• Ethyl alcohol : As per need
• Sodium hydrogen
carbonate solution : As per need

Procedure
A) Litmus test
Put a drop of the liquid compound or a drop of the solution of the
compound with the help of a glass rod on a moist blue litmus paper.
If the blue colour of the litmus paper changes to red, the presence of
either a carboxylic group or a phenolic group is indicated.
B) Sodium hydrogencarbonate test
Take 2 mL of saturated aqueous solution of sodium hydrogencarbonate
in a clean test tube. Add a few drops of the liquid compound or a few
crystals of solid compound to it.

carboxyl group.
C) Ester test
Take about 0. g compound in a test tube, add mL ethanol or methanol
and 3-2 drops of concentrated sulphuric acid. Heat the reaction mixture
for -0 5 minutes in a hot water bath at about °50C. Pour the reaction
mixture in a beaker containing aqueous sodium carbonate solution to
neutralise excess sulphuric acid and excess carboxylic acid.
Sweet smell of the substance formed indicates the presence of carboxyl
function in the compound.
3.Test for 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.

R−NH2 + CHCl3 + 3KOH RNC + 3KCl + 3H2O

(R = alkyl or aryl group) (Carbylamine)

(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 °5–0C to produce diazonium salt.
This couples with β-naphthol to give a scarlet red dye, which is sparingly
soluble in water.
NaNO + HCl
NH2 N+ NCl¯

Benzene diazonium chloride

HO HO

N+ NCl¯ + N=N

ß-Naphthol β - Naphthol azo-dye

(Scarlet red)

Material Required:
• Test tubes : As per need
• Test tube holder : One
• Bunsen burner : One
• Chloroform
• Potassium hydroxide
• Sodium nitrite solution
• Aniline
• β-Naphthol
• Dilute hydrochloric acid
• Sodium hydroxide solution
• Ice
Procedure
A) Solubility test
Take 1 mL of given organic compound in a test tube and add a few drops
of dilute HCl to it. Shake the contents of the test tube well. If the
organic compound dissolves, it shows the presence of an amine.
C6H5NH + HCl +
C6H5NH Cl-
(Anilium chloride soluble in water)

B) Carbylamine test
Take 3-2 drops of the compound in a test tube and add 3-2 drops of
chloroform followed by addition of an equal volume of 0.5 M alcoholic
potassium hydroxide solution. Heat the contents gently. An obnoxious
smell of carbylamine confirms the presence of primary amino group in
the compound.

B) Azo Dye Test

(i) Dissolve nearly 0.2 g of the compound in 2mL of dilute hydrochloric
acid in a test tube. Cool the content of the test tube in ice.
(ii) To the ice cooled solution add 2 mL of %2.5 cold aqueous sodium
nitrite solution.
(iii) In another test tube, dissolve 0.2 g of β-naphthol in dilute sodium
hydroxide solution.
(iv) Add diazonium chloride solution prepared in step (ii) into the cold
β-naphthol solution slowly with shaking. The formation of a scarlet
red dye confirms the presence of aromatic primary amine.
 Titrimetric Analysis
KMnO vs Oxalic acid Experiment -

Aim
To determine the concentration/molarity of KMnO solution by titrating it
against a 0.1 M standard solution of oxalic acid.

Theory
In the present experiment, potassium permanganate acts as a powerful
oxidising agent. Although KMnO acts as an oxidising agent in alkaline
medium also, for quantitative analysis mostly acidic medium is used.
The oxidising action of KMnO in the acidic medium can be represented by
the following equation:

+
MnO4 + 8H + 5e +
Mn + 4H O
The acid used in this titration is dilute sulphuric acid. Nitric acid is not used
as it is itself an oxidising agent and hydrochloric acid is usually avoided
because it reacts with KMnO according to the equation given below to
produce chlorine and chlorine which is also an oxidising agent in the aqueous
solution.

2KMnO4 + 6HCl 2KCl + 2MnCl + 5Cl + 8H O

Since, oxalic acid acts as a reducing agent, it can be titrated against potassium
permanganate in the acidic medium according to the following equation:

Reactions of oxalic acid

A. Chemical equations

Reduction half reaction :

2KMnO4 + 3H2 SO4 K2 SO4 + 2Mn2 SO4 + 3H2 O + 5 [O]

Oxidation half reaction :

H2 C2 O4 + [O] 60 C 2CO2 + H2 O] x 5

2KMnO4 + 3H2 SO4 + 5H2 C2O4 K2 SO4 + 2MnSO4 + 8H2 O + 10 CO2

B. Ionic equation Reduction half reaction

Reduction half reaction :

MnO4 + 5e + 8H+ Mn+2 + 4H2 O] x 2
Oxidation half reaction :
C2O4 2CO2 + 2e ] x 5

2
2MnO4 + 5C2O4 + 16H+ 2Mn2+ + 10CO2 + 8H2O

In these equations,
_ 2
+2
MnO4 is reduced to Mn and C2O4 is oxidised to CO2.The oxidation
2
number of carbon in C2O4 changes from 3+ to 4+. In these titrations,
potassium permanganate acts as a selfindicator.
Initially colour of potassium permanganate is discharged due to its reduction
by oxalic acid. After complete consumption of oxalate ions, the end point is
indicated by the appearance of a light pink colour produced by the addition
of a little excess of unreacted potassium permanganate.

Further, during the titration of oxalic acid against potassium permanganate,

warming of oxalic acid solution (°60–°50C) along with dilute H SO is
required.

This is essential because the reaction takes place at higher temperature.

During the titration, first manganous sulphate is formed which acts as a
catalyst for the reduction of KMnO by oxalic acid.

Therefore, in the beginning the reaction rate is slow and as the reaction
proceeds, the rate of the reaction increases.

Material Required:
• Measuring flask (250 ml) : One
• Burette (50 ml) : One
• Burette stand : One
• Pipette : One
• Conical flask : One
• Funnel : One
• Weighing bottle : One
• Glazed tile(white) : One
• Burner : One
• Wire gauze : One
• Chemical balance : One
• Oxalic acid : As per need
• Potassium permanganate solution : As per need
• 1.0 M Sulphuric acid : As per need
Procedure
A) Preparation of 0. M standard solution of oxalic acid Prepare 0. M oxalic
acid solution as mentioned in experiment 2. (Unit 2, Class XI,
Laboratory Manual)

B) Titration of oxalic acid solution against potassium permanganate solution.

i) Rinse and fill a clean burette with potassium permanganate solution.
Remove the air bubble, if any, from the nozzle of the burette by
releasing some solution through it.
The burette used in the permanganate titration must have a glass stop
cock as rubber is attacked by permanganate ions.
ii) Take 0ml of 0. M oxalic acid solution in a conical flask and add half of
the test tube full (≈5ml) of 0. M H SO to it to prevent the formation
of any precipitate of manganese dioxide during the course of the
titration.
iii) Heat the oxalic acid solution upto °60 –°50C before titrating it with
potassium permanganate solution taken in the burette. To increase the
visibility of the colour change, place the conical flask containing the
solution to be titrated over a white glazed tile kept below the nozzle
of the vertically fitted burette.
iv) Note the initial reading of the volume of permangana te solution in the
burette and add it in small volumes to the hot oxalic acid solution
while swirling the contents of the flask gently. The violet colour of
permanganate solution is discharged on reaction with oxalic acid.
The end point is indicated by the appearance of permanent light pink
colour due to a slight excess of permanganate solution.
v) Repeat the titration till three concordant readings are obtained. Since
the solution of KMnO is of dark colour, the upper meniscus should
be considered for noting the burette readings.
vi) Record the readings as shown in observation Table 6. and calculate
the strength of potassium permanganate solution in mols/litre.

Table 6. :
Titration of potassium permanganate solution against
standard oxalic acid solution

Burette readings Volume (V) of KMnO4

S1. Volume of Oxalic
acid in ml used
No. Initial (x) Final (y) V=(y-x) ml
Calculations
The strength of the unknown solution in terms of molarity may be
determined by the following equation.
a M V =a M V (6. )

For oxalic acid, us potassium permanganate titration:

a = 2, (the number of electrons lost per formula unit of oxalic acid in a
balanced equation of half cell reaction)
a = 5, (the number of electrons gained per formula unit of potassium
permanganate in the balanced equation of half cell reaction)

M and M are the molarities of oxalic acid and potassium permanganate

solutions used in the titration.
V and V are the volumes of oxalic acid and potassium permanganate
solutions.

On putting the value of a and a in equation 6.1 we get Oxalic acid

KMnO4
2M V = 5M V
M = 2M V
5 V (6.2)
We can calculate the molarity of potassium permanganate solution by using
equation 6.2. Strength of the solution is given by the following equation:

Strength = Molarity x Molar mass

Result
(i) Molarity of KMnO solution is .....................
(ii) Strength of KMnO solution is .....................

Precautions
a) Always rinse the burette and the pipette with the solutions to be taken
in them.
b) Never rinse the conical flask with the experimental solutions.
c) Remove the air gaps if any, from the burette.
d) Never forget to remove the funnel from the burette before noting the
initial reading of the burette.
e) No drop of the liquid should hang at the tip of the burette at the end
point and while noting reading.
f) Always read the upper meniscus for recording the burette reading in the
case of all coloured solutions.
g) Never use pipette and burette with a broken nozzle.
h) Lower end of the pipette should always remain dipped in the liquid while
sucking the liquid.
 i) Do not blow out the last drop of the solution from the jet end of the
pipette.
j) The strength of the solution must be calculated up to the fourth decimal
place.
k) Do not forget to heat the mixture of oxalic acid and H SO solutions
between °60–°50C while titrating it against potassium permanganate.

Aim
To determine the concentration/molarity of KMnO solution by titrating it
against standard solution of ferrous ammonium sulphate.

Theory
Like oxalic acid, ferrous ammonium sulphate also acts as a reducing agent in
the titration against potassium permanganate. The reaction which takes place
is given below :

A. Chemical equations

Reduction half reaction :

2KMnO4 + 3H2 SO4 K2 SO4 + 2Mn2 SO4 + 3H2 O + 5 [O]

Oxidation half reaction :

2Fe SO4 (NH4)2 SO4 . 6H2 O + H2 SO4 + [O] Fe2 (SO4) + 2(NH4)2SO4
3
+ 13H2 O] x 5

2KMnO4 + 8H2 SO4 + 10Fe SO4 (NH4)2 SO4 . 6H2 O K2 SO4 + 2Mn SO4 + 5Fe2 (SO4)
3
+ 10(NH4)2SO4 + 68H2 O

B. Ionic equation Reduction half reaction

Reduction half reaction : MnO4 + 5e + 8H+ Mn+2 + 4H2 O

Oxidation half reaction : Fe+2 Fe+3
+e ]x5

MnO4 + 5Fe+2+ 8H+ Mn2+ + 5Fe+3 + 4H2O

The oxidation number of iron in Mohr’s salt is 2+. Iron is oxidised during the
reaction and its oxidation number changes from 2+ to 3+.
In this titration heating of ferrous ammonium sulphate solution is not
required because reaction rate is very high even at room temperature.
Also, at high temperatures, ferrous ions may be oxidised to ferric ions by
oxygen of air and error may be introduced in the experiment.
 Material Required:
• Measuring flask (250 ml) : One
• Burette (50 ml) : One
• Burette stand : One
• Pipette : One
• Conical flask : One
• Funnel : One
• Weighing bottle : One
• Glazed tile(white) : One
• Potassium permanganate solution : As per need
• Dilute Sulphuric acid : As per need
• Ferrous ammonium sulphate : As per need

Procedure
A) Preparation of 0.05M, standard solution of ferrous ammonium sulphate.
i) Weigh 4.9000 g of ferrous ammonium sulphate and transfer it into a
250 ml measuring flask through a funnel.
ii) Transfer the solid sticking to the funnel with the help of distilled water
into the flask and add dilute H SO into the flask drop wise to get the
clear solution.
iii) Shake the flask till the substance dissolves and make the solution upto
the mark.
[Molar mass of FeSO (NH )2SO . 6H2 O = 392 gmol- ]

B) Titration of ferrous ammonium sulphate against potassium permanganate

solution.
i) Rinse and fill the clean burette with potassium permanganate solution.
Remove air bubbles if any, from the burette tip by releasing some
solution through it.
ii) Take 10 mL of 0.05M ferrous ammonium sulphate solution in a conical
flask and add half test tube (≈ 5 mL) full of (1.0M) H SO to it.
iii) Titrate the above solution with potassium permanganate solution till
the colour of the solution changes to permanent pink. Swirl the
content of the flask during the titration.
iv) Repeat the titration, until three concordant readings are obtained.
v) Record the readings as shown in observation Table 6.2 and calculate
the strength of potassium permanganate solution in mols/litre.
 Table 6.2:
Titration of potassium permanganate solution against
standard ferrous ammonium sulphate solution

Volume of ferrous Burette readings

S1. ammonium sulphate Volume (V) of KMnO4
No. solution used for each used
Initial (x) Final (y) V=(y-x) ml
titration in ml

Calculations
The strength of the unknown solution in terms of molarity may be
determined by the following equation.
a M V =a M V

M and M are the molarities of ferrous ammonium sulphate and potassium

permanganate solutions and V and V are volumes of ferrous ammonium
sulphate and potassium permanganate solutions, respectively.

a = , (the number of electrons lost per formula unit of ferrous ammonium

sulphate in the half cell reaction)
a = 5, (the number of electrons gained per formula unit of potassium
permanganate in a half cell reaction)

Strength can be calculated by the formula given below:

Strength = Molarity x Molar mass

Result
The strength of the given potassium permanganate solutions is .................g/L.

Precautions
a) Always use a fresh sample of ferrous ammonium sulphate to prepare its
standard solution.
b) Never rinse the conical flask with the experimental solutions.
c) Remove the air gaps if any, from the burette.
d) Never forget to remove the funnel from the burette before noting the
initial reading of the burette.
e) No drop of the liquid should hang at the tip of the burette at the end
point and while noting reading.
f) Always read the upper meniscus for recording the burette reading in the
case of all coloured solutions.
g) Never use pipette and burette with a broken nozzle.
h) Lower end of the pipette should always remain dipped in the liquid while
sucking the liquid.
i) Do not blow out the last drop of the solution from the jet end of the
pipette.
j) The strength of the solution must be calculated up to the fourth decimal
place.
k) Do not forget to heat the mixture of oxalic acid and H SO solutions
between °60–°50C while titrating it against potassium permanganate.
 Detection and Systematic
Analysis of Cation
Step - 1 :
Preliminary Examination of the Salt for
Identification of Cation
1. Colour Test:
Observe the colour of the salt carefully, which may provide useful
information about the cations. Table 1 gives the characteristic colours of the
salts of some cations.

Colour Cations Indicated

Light green, Yellow, Brown Fe2+ , Fe3+

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

Table 1: Characteristic colours of some metal ions

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
of 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 (see Table)

Colour when cold Colour when hot Inference

Blue White Cu2+

Green Dirty white or yellow Fe2+
White Yellow Zn2+
Pink Blue Co2+

Table 2: Inferences from the colour of the salt in cold and on heating.

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 platinum wire.
(ii) To clean the loop dip it into concentrated hydrochloric acid and hold it
in a non-luminous flame. (Fig.)
(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 (Fig.).
(vi) Observe the colour of the flame first with the naked eye and then
through a blue glass and identify the metal ion with the help of Table
given below:

Platinum wire Platinum

loop
(a) Paste

(d)
(b)

(c)
(e)
Platinum loop

Fig. 1: Performing Flame test

Colour of the flame Colour of the flame Inference

observed by naked eye observed through
blue glass

Green flame with blue Same colour as observed Cu2+

centre without glass
Crimson red Purple Sr2+
Apple green Bluish Green Ba2+
Brick red Green Ca2+

Table 3: Inference from the flame test

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 (Fig.).
(v) To remove the bead from the platinum wire, heat it to redness and
tap the platinum wire with your finger. (Fig.).

(a) Heating in (b) Heating in

reducing flame oxidising flame
Fig. 2: Borax bead test

Borax bead

Fig. 3: Removing borax bead

Heating in oxidising Heating in redusing

(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 Sr2+
Light violet Light violet Colourless Colourless Ba2+
Yellow Yellowish brown Green Green Ca2+

Table 4: Inference from borax bead Test

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. The test may be performed as follows:
(i) Make a small cavity in a charcoal block with the help of a charcoal
borer. Do not apply pressure otherwise it will crack [Fig. 4 (a)].
(ii) Fill the cavity with about 0.2 g of the salt and about 0.5 g of anhydrous
sodium carbonate.
(iii) Moisten the salt in the cavity with one or two drops of water, otherwise
salt/mixture will blow away.
(iv) Use a blowpipe to heat the salt in a luminous (reducing) flame and
observe the colour of oxide/ metallic bead formed in the cavity both
when hot and cold [ Fig. 5 ( b)]. Obtain oxidising and reducing flame as
shown in Fig. 5: a and b.
(v) Always bore a fresh cavity for testing the new salt.

(a) Making charcoal cavity (b) Heating salt in the cavity

Fig. 4: Charcoal cavity test - step 1

Air Air

(a) Oxidising flame (b) Reducing flame

Fig. 5: Obtaining oxidising and reducing flame

When test is performed with CuSO4 , the following change occurs:
Heat
Cu SO4 + Na2 CO3 Cu2 CO3 + Na 2 SO4

Heat
CuCO3 CuO + CO2

Heat
CuO + C Cu + CO
Red colour

In case of ZnSO4 :
Heat
Zn SO4 + Na2 CO3 Zn CO3 + Na 2 SO4

Heat
ZnCO3 ZnO + CO2

The metal ion can be inferred from Table

Observations Inference

Yellow residue when hot and grey metal when cold Pb2+
White residue with the odour of garlic As3+
Brown residue Cd2+
Yellow residue when hot and white when cold Zn2+

Table 5: Inference from the charcoal cavity test

5. 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.

On heating, cobalt nitrate decomposes into cobalt (II) oxide, which gives a
characteristic colour with metal oxide present in the cavity.
Thus, with ZnO, Al2 O3 and MgO, the following reactions occur.

Heat
2Co( NO3)2 2CoO + 4Na 2 + O2

CoO + ZnO CoO. ZnO

Green

CoO + MgO CoO. MgO

Pink

CoO + Al2O3 CoO. Al2O3

Blue
Step - 2 :
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:

1. 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.

2. Group Analysis:
(I) Analysis of Zero group cation (NH4+)
(a) Take 0.1g 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+ :

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.
(NH4)2 SO4 + 2NaOH NH2 SO4 + 2NH3 + 2H2 O
NH3 + HCl NH4 Cl

On passing the gas through Nessler’s reagent, a brown colouration or a

precipitate of basic mercury(II) amido-iodine is formed.

2K2HgI4 + NH3 + 3KOH HgO.Hg(NH2)I + 7KI + 2H2 O

For the analysis of cations belonging to groups I-VI, the cations are
precipitated from the original solution by using the group reagents
(see Table) according to the scheme shown in the flow chart given below:
The separation of all the six groups is represented as below:

Original Solutions
Dil HCl

Precipitate, Group I If no precipitate is formed

(Pb2+) as Chloride Pass H2 S gas

Precipitate, Group II If no precipitate, take original solution

2+ 2+ 3+
(Pb , Cu , As ) Heat (0.S.) with conc. HNO3 ,
as sulphate cool and add solid NH4 CI + NH4 OH
solution in excess

Precipitate, Group III If no precipitate

( Fe3+ , Al3+ ) Pass H2 S
as hydroxides

Precipitate, Group IV If no precipitate take original solution

( Co2+ , Ni2+ , Mn2+ , Zn2+ ) Add NH4 OH and solid (NH4 )2 CO3
as sulphides

Precipitate, Group V If no precipitate take original solution

to test Group VI, Mg2+
( Ba2+ , Sr2+ , Ca2+ )
as carbonates

Flow Chart
 Group Cation Group Reagent

Group zero NH4+ None

Group - I Pb2+ Dilute HCl
Group - II Pb2+, Cu2+, As3+ H2 S gas in presence of dil.HCl
Group - III Al3+ , Fe3+ NH4OH in presence of NH4Cl
Group - IV Co2+, Ni2+, Mn2+ , Zn2+ H2 S in presence of NH4OH
Group - V Ba2+, Sr2+, Ca2+ (NH4)2CO3 in presence of
NH4OH
Group - VI Mg2+ None

Table 6: 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+.
Confirmatory tests are described below in Table

Experiment Observations

Dissolve the precipitate in hot water A yellow precipitate is obtained

and divide the hot solution into three which is soluble in NaOH and
parts. insoluble in ammonium acetate
1. Add potassium iodide solution to solution.
the first part. A white precipitate is obtained
2. To the second part add potassium
chromate solution. which is soluble in ammonium
3. To the third part of the hot acetate solution.
solution add few drops of alcohol
and dilute sulphuric acid.

Table 7: Confirmatory tests for Group-I cation (Pb2+)

Chemistry of Confirmatory Tests of Pb2+ ions :

Lead is precipitated as lead chloride in the first group.
The precipitate is soluble in hot water.
1. On adding potassium iodide (KI) solution, a yellow precipitate of lead
iodide is obtained which confirms the presence of Pb2+ ions

PbCl2 + 2KI PbI2 + 2KCl

This yellow precipitate (PbI2 ) is soluble in boiling water and reappears on

cooling as shining crystals.
2. On addition of potassium chromate (K2 CrO4 ) solution a yellow
precipitate of lead chromate is obtained. This confirms the presence of
Pb2+ ions.

PbCl2 + K2 CrO4 PbCrO4 + 2KCl

The yellow precipitate (PbCrO4 ) is soluble in hot NaOH solution.

PbCrO4 + 4NaOH Na2 [Pb(OH)4 ] + Na2 CrO4

Sodium tetra
hydroxoplumbate (II)

3. A white precipitate of lead sulphate (PbSO4 ) is formed on addition of

alcohol followed by dil. H2 SO4

PbCl2 + H2 SO4 PbSO4 + 2HCl

(White
precipitate)

Lead sulphate is soluble in ammonium acetate solution due to the formation

of tetraacetoplumbate(II) ions. This reaction may be promoted by addition of
few drops of acetic acid.

PbSO4 + 4CH3 COONH4 (NH4 )2 [Pb(CH3 COO)4 ] + (NH4 )2 SO4

(III) Analysis of Group-II cations

If group-I is absent, add excess of water to the same test tube.
Warm the solution and pass H2 S gas for 1-2 minutes (Fig.).

Shake the test tube. If a precipitate appears, this indicates the presence of
group-II cations.
Pass more H2 S gas through the solution to ensure complete precipitation
and separate the precipitate.

If the colour of the precipitate is black, itindicates the presence of Cu2+ or

Pb2+ ions.
If it is yellow in colour, then presence of As3+ ions is indicated.

Take the precipitate of group-II in atest tube and add excess of yellow
ammonium sulphide solution to it. Shake the test tube. If the precipitate is
insoluble, group II-A (copper group) is present.

If the precipitate is soluble, this indicates the presence of group-II B

(arsenic group).
Confirmatory tests for the groups - II A and II B are given in Table.
 Rubber
cork
Stop cock

H2S
Gas
H2S Gas
Iron
sulphide

Sulphuric
acid

Fig. Kipp’s apparatus for preparation of H2S gas

Black precipitate of GroupII A ions If a yellow precipitate soluble

(Pb2+, Cu2+) insoluble in yellow ammonium in yellow ammonium sulphide
sulphide is formed. is formed then As3+ ion is
present.
Boil the precipitate of GroupII A with Acidify this solution with
dilute nitric acid and add a few drops of dilute HC1. A yellow
alcohol and dil. H2 SO4 . precipitate is formed. Heat
the precipitate with
White precipitate If no precipitate concentrated nitric acid and
confirms the Apresence is formed, add add ammonium molybdate
of Pb2+ ions. Dissolve excess of solution.
the precipitate in ammonium A canary yellow precipitate
ammonium acetate hydroxide is formed.
solution. Acidify with solution. A blue
acetic acid and divide solution is
the solution into two obtained, acidify
parts. it with acetic
(i) To the first part add acid and add
potassium chromate potassium
solution, a yellow ferrocyanide
precipitate is formed. solution.
(ii)To the second part, A chocolate
add potassium iodide brown
solution, a yellow precipitate is
precipitate is formed. formed.

Table 8: Confirmatory tests for Group-II A and II B cations

Group-II A (Copper Group)
Chemistry of Confirmatory Tests for NH4+ :
1. Test for Lead ion (Pb2+)
Lead sulphide precipitate dissolves in dilute HNO3 . On adding dil. H2 SO4
and a few drops of alcohol to this solution a white precipitate of lead
sulphate appears.This indicates the presence of lead ions.

3PbS + 8HNO3 3Pb(NO3 )2 + 2NO + 4H2 O + 3S

Pb(NO3 )2 + H2 SO4 PbSO4 + 2HNO3

The white precipitate dissolves in ammonium acetate solution on boiling.

When this solution is acidified with acetic acid and potassium chromate
solutionis added, a yellow precipitate of PbCrO4 is formed.
On adding potassium iodide solution, a yellow precipitate of lead iodide
is formed.

PbSO4 + 4CH3 COONH4 (NH4 )2 [Pb(CH3 COO)4 ] + (NH4 )2 SO4

Pb2+ + CrO 2 - PbCrO
4 4
(Yellow precipitate)

Pb2+ + 2I - PbI2
(Yellow precipitate)

2. Test for Copper ion (Cu2+)

(a) Copper sulphide dissolves in nitric acid due to the formation of copper
nitrate.

3CuS + 8HNO3 3Cu(NO3 )2 + 2NO + 3S + 4H2 O

On heating the reaction mixture for long time, sulphur is oxidised tosulphate
and copper sulphate is formed and the solution turns blue. A small amount
of NH4 OH precipitates basic copper sulphate which is solublein excess of
ammonium hydroxide due to the formation of
tetraamminecopper (II) complex.

S + 2HNO3 H2 SO4 + 2NO

2-
2Cu2+ + SO4 + 2NH3 +2H2 O Cu(OH)2 .CuSO4 + NH4+
Cu(OH)2 CuSO4 + 8NH3 2[Cu(NH3 )4 ]SO4 + 2OH- + SO42 -

The blue solution on acidification with acetic acid and then adding potassium
ferrocyanide [K4Fe(CN)6] solution gives a chocolate colouration due to the
formation of copper ferrocyanide i.e.Cu2 [Fe(CN)6 ].

[Cu(NH3 )4 ]SO4 + 4CH3 COOH CuSO4 + 4CH3 COONH4

2CuSO4 + K4 [Fe(CN)6 ] Cu2 [Fe(CN)6 ] +2K2 SO4

Group-II B (Arsenic Group)
Chemistry of Confirmatory Tests for NH4+ :
1. Test for Lead ion (Pb2+)
group- II precipitate dissolves in yellow ammonium sulphide and the colour
of the solution is yellow, this indicates the presence of As3+ ions.
Ammonium thioarsenide formed on dissolution of As2 S3 decomposes with
dil. HCl, and a yellow precipitate of arsenic (V) sulphide is formed which
dissolves in concentrated nitric acid on heating due to the formation of
arsenic acid. On adding ammonium molybdate solution to the reaction
mixture and heating, a canary yellow precipitate is formed. This confirms
the presence of As3+ ions.
As2 S3 + 3(NH4 )2 S2 2(NH4 )3 As S4 + S
(Yellow ammonium
sulphide)
2(NH4 )3 AsS4 + 6HCl As2 S5 + 3H2 S + 6NH4 Cl

3As2 S5 + 10HNO3 + 4H2 O 6H3 AsO4 + 10NO + 15S

(Arsenic acid)

H3 AsO4 + 12(NH4 )2 MoO4 + 21HNO3 (NH4 )3 [As(Mo3 O10 )4 ]

(Arsenic (Ammonium + 21NH4 NO3 + H2 O
acid) molybdate) (Ammonium arsinomolybdate
yellow precipitate)

(IV) Analysis of Group-III cations

If group-II is absent, take original solution and add 2-3 drops of conc. HNO3
to oxidise Fe2+ ions to Fe3+ ions. Heat the solution for a few minutes.
After cooling add a small amount of solid ammonium chloride (NH4Cl) and
an excess of ammoniumhydroxide (NH4OH) solution till it smells of
ammonia. Shake the test tube. If a brown or white precipitate is formed, this
indicates the presence of group-III cations.
Confirmatory tests of group-III cations are summarised in Table Observe the
colour and the nature of the precipitate. A gelatinous white precipitate
indicates the presence of aluminium ion (Al3+). If the precipitate is brown in
colour, this indicates the presence of ferric ions (Fe3+).

Brown Precipitate Fe3+ White precipitate Al3+

Dissolve the precipitate in dilute Dissolve the white precipitate in dilute
HCl and divide the solution into HCl and divide into two parts.
two parts. (a) To the first part add sodium hydrox
(a) To the first part add potassium -ide solution and warm. A white
ferrocyanide solution [Potasium gelatinous precipitate soluble in
hexacyanoferrate (II)]. A blue excess of sodium hydroxide solution.
precipitate/colouration appears. (b) To the second part first add blue
(b) To the second part add litmus solution and then ammonium
potassium thiocyanate solution. hydroxide solution drop by drop
A blood red colouration along the sides of the test tube. A
appears. blue floating mass in the colourless
solution is obtained.
Table 9: Confirmatory test for Group-III cations
Chemistry of confirmatory tests of Group-III cations
When original solution is heated with concentrated nitric acid, ferrous ions are
oxidised to ferric ions.

2FeCl2 + 2HCl + [O] 2FeCl3 + H2 O

1. Test for Aluminium ions (Al3+)

(a) When the solution containing aluminium chloride is treated with sodium
hydroxide, a white gelatinous precipitate of aluminium hydroxide is
formed which is soluble in excess of sodium hydroxide solution due to
the formation of sodium meta aluminate.

AlCl3 + 3NaOH Al(OH)3 + 3NaCl

Al(OH)3 + NaOH NaAlO2 + 2H2 O
(White gelatinous
precipitate)
(b) In the second test when blue litmus is added to the solution, a red
colouration is obtained due to the acidic nature of the solution.
On addition of NH4 OH solution drop by drop the solution becomes
alkaline and aluminium hydroxide is precipitated. Aluminium hydroxide
adsorbs blue colour from the solution and forms insoluble adsorption
complex named ‘lake’. Thus a blue mass floating in the colourless solution
is obtained. The test is therefore called lake test.

2. Test for ferric ions (Fe3+)

Reddish brown precipitate of ferric hydroxide dissolves in hydrochloric acid
and ferric chloride is formed.

Fe(OH)3 + 3HCl FeCl3 + 3H2 O

(a) When the solution containing ferric chloride is treated with potassium
ferrocyanide solution a blue precipitate/colouration is obtained.
The colour of the precipitate is Prussian blue. It is ferric ferro-cyanide.
The reaction takes place as follows:

4FeCl3 + 3K4 [Fe(CN)6 ] Fe4 [Fe(CN)6 ]3 + 12KCl

If potassium hexacyanoferrate (II) (i.e. potassium ferrocyanide) is added in

excess then a product of composition KFe[Fe(CN)6 ] is formed.
This tends to form a colloidal solution (‘soluble Prussian blue’) and cannot
be filtered.

FeCl3 + K4 [Fe(CN)6 ] KFe[Fe(CN)6 ] + 3KCl

(b) To the second part of the solution, add potassium thiocyanate

(potassium sulphocyanide) solution. The appearance of a blood red
colouration confirms the presence of Fe3+ ions.
(V) Analysis of Group-IV cations
If group-III is absent, pass H2 S gas in the solution of group-III for a few
minutes. If a precipitate appears (white, black or flesh coloured), this
indicates presence of group-IV cations. Table gives a summary of
confirmatory tests of group-IV cations.

White Precipitate White Precipitate Black Precipitate

Zn2+ Mn2+ Ni2+ , Co2+
Dissolve the precipitate Dissolve the Dissolve the precipitate in
in dilute HCl by boiling. precipitate in dilute aqua regia. Heat the
Divide the solution into HCl by boiling, solution to dryness and
two parts. then add sodium cool. Dissolve the residue
(a) To the first part add hydroxide solution in water and divide the
sodium hydroxide in excess. A white solution into two parts.
solution. precipitate is formed (a) To the first part of the
A whiteprecipitate which turns brown solution add ammonium
solublein excess of on keeping. hydroxide solution till it
sodiumhydroxide becomes alkaline. Add
solution confirms a few drops of dimethyl
theions presence of glyoxime and shake the
Zn2+ions. test tube. Formation of
(b) Neutralise the a bright red precipitate
second part with confirms the presence
ammonium hydroxide of Ni2+ ions.
solution and add (b) Neutralise the second
potassium part with ammonium
ferrocyanide solution. hydroxide solution.
A bluish white Acidify it with dilute
precipitate appears. acetic acid and add
solid potassium nitrite.
A yellow precipitate
confirms the presence
of Co2+ ions.
Table 10: Confirmatory test for Group-IV cations

Chemistry of confirmatory tests of Group–IV cations

Fourth group cations are precipitated as their sulphides. Observe the colour
of the precipitate. A white colour of the precipitate indicates the presence
of zinc ions, a flesh colour indicates the presence of manganese ions and a
black colour indicates the presence of Ni2+ or Co2+ ions.
1. Test for Zinc ion (Zn2+)
Zinc sulphide dissolves in hydrochloric acid to form zinc chloride.

ZnS + 2HCl ZnCl2 + H2 S

(a) On addition of sodium hydroxide solution it gives a white precipitate of
zinc hydroxide, which is soluble in excess of NaOH solution on heating.
This confirms the presence of Zn2+ ions.
ZnCl2 + 2NaOH Zn(OH)2 + 2NaCl
Zn(OH)2 + 2NaOH Na2 ZnO2 + 2H2 O
Sodium Zincate
(b) When potassium ferrocyanide K4 Fe(CN)6 solution is added to the
solution after neutralisation by NH4 OH solution, a white or a bluish
white precipitate of zinc ferrocyanide appears.

2ZnCl2 + K4 [Fe(CN)6 ] Zn2 [Fe(CN)6 ] + 4KCl

(Zinc ferrocyanide)

2. Test for Zinc ion (Mn2+)

Manganese sulphide precipitate dissolves in dil. HCl on boiling. On addition
of NaOH solution in excess, a white precipitate of manganese hydroxide is
formed which turns brown due to atmospheric oxidation into hydrated
manganese dioxide..

MnS + 2HCl MnCl2 + H2 S

MnCl2 + 2NaOH Mn(OH)2 + 2NaCl
(White precipitate)
Mn(OH)2 + [O] MnO(OH)2
Hydrated manganese dioxide
(Brown colour)

3. Test for Zinc ion (Ni2+)

The black precipitate of nickel sulphide dissolves in aqua regia and the reaction
takes place as follows:

3NiS + 2HNO3 + 6HCl 3NiCl2 + 2NO + 3S + 4H2 O

After treatment with aqua regia nickel-chloride is obtained which is soluble

in water. When dimethyl glyoxime is added to the aqueous solution of nickel
chloride, made alkaline, by adding NH4 OH solution, a brilliant red
precipitate is obtained.
H
O O

H3C N N CH3
H3 C – C = N – OH C C
Ni + 2NH4 Cl + 2H2 O
NiCl2 + 2NH4 OH + H3 C – C = N – OH C C
N N
H3C CH3

O O
H
Complex of red colour
(Stable form of complex)
4. Test for Cobalt ion (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 a strong solution of potassium nitrite after
neutralisation with ammonium hydroxide and the solution is acidified with
dil. acetic acid, a yellow precipitate of the complex of cobalt named
potassium hexanitritocobaltate (III) is formed.
CoS + HNO3 + 3HCl CoCl2 + NOCl + S + 2H2 O

CoCl2 + 7KNO2 + 2CH3 COOH K3 [Co(NO2 )6 ] + 2KCl + 2CH3 COOK + NO + H2 O

Potassium
hexanitritocobaltate(III)
(Yellow precipitate)

(VI) Analysis of Group- V cations

If group-IV is absent then take original solution and add a small amount
of solid NH4 Cl and an excess of NH4 OH solutionfollowed by solid
ammonium carbonate (NH4 )2 CO3 . If a white precipitate appears, this
indicates the presence of group–V cations. Dissolve the white
precipitate by boiling with dilute acetic acid and divide the solution into
three parts one each for Ba2+, Sr2+ and Ca2+ ions.
Preserve a small amount of the precipitate for flame test. Summary of
confirmatory tests is given in Table:

Dissolve the precipitate by boiling with dilute acetic acid and

divide the solution into three parts one each for
Ba2+, Sr2+ and Ca2+ ion
Ba2+ ions Sr2+ ions Ca2+ ions
(a) To the first part (a) If barium is absent, (a) If both barium and
add potassium take second part of strontium are absent,
chromate solution. the solution and add take the third part of
A yellow precipita ammonium sulphate the solution. Add
-te appears. solution. Heat and ammonium oxalate
scratch the sides of solution and shake well.
(b) Perform the flame the test tube with a A white precipitate of
test with the glass rod and cool. calcium oxalate is
preserved A white precipitate obtained.
precipitate. is formed.
A grassy green (b) Perform the flame test
flame is obtained. (b) Perform the flame with the preserved
test with the precipitate. A brick red
preserved precipitate. flame, which looks
A crimson-red flame greenish-yellow through
confirms the presence blue glass, confirms the
of Sr2+ ions. presence of Ca2+ ions.

Table 11: Confirmatory test for Group–V cations

Chemistry of confirmatory tests of Group– V cations

The Group–V cations are precipitated as their carbonates which dissolve in
acetic acid due to the formation of corresponding acetates.

1. Test for Barium ion (Ba2+)

(a) Potassium chromate (K2 CrO4 ) solution gives a yellow precipitate of
barium chromate when the solution of fifth group precipitate in acetic
acid is treated with it.
 BaCO3 + 2CH3 COOH (CH3 COOH)2 Ba + H2 O + CO2

(CH3 COO)2 Ba + K2 CrO4 BaCrO4 + 2CH3 COOK

Barium chromate
(Yellow precipitate)

(b) Flame test : Take a platinum wire and dip it in conc. HCl. Heat it strongly
until the wire does not impart any colour to the non-luminous flame.
Now dip the wire in the paste of the (Group–V) precipitate in conc. HCl.
Heat it in the flame. A grassy green colour of the flame confirms the
presence of Ba2+ ions.

2. Test for Strontium ion (Sr2+)

(a) Solution of V group precipitate in acetic acid gives a white precipitate of
strontium sulphate with ammonium sulphate, (NH4 )2 SO4 , solution on
heating and scratching the sides of the test tube with a glass rod.
SrCO3 + 2CH3 COOH (CH3 COOH)2 Sr + H2 O + CO2

(CH3 COO)2 Sr + [NH4 ]2 SO4 SrSO4 + 2CH3 COONH4

Strontium sulphate
(White precipitate)

(b) Flame test : Perform the flame test as given in the case of Ba2+.
A crimson red flame confirms the presence of Sr2+ ions.

3. Test for Calcium ion (Ca2+)

(a) Solution of the fifth group precipitate in acetic acid gives a white
precipitate with ammonium oxalate solution.
CaCO3 + 2CH3 COOH (CH3 COO)2 Ca + H2 O + CO2

(CH3 COO)2 Ca + [NH4 ]2 C2 O4 (COO)2 Ca + 2CH3 COONH4

Ammonium Calcium oxalate
oxalate (White precipitate)

(b) Flame test : Perform the flame test as mentioned above. Calcium imparts
brick red colour to the flame which looks greenish-yellow through blue glass.

(VII) Analysis of Group- VI cations

If group–V is absent then perform the test for Mg2+ ions as given below.

Chemistry of Confirmatory Tests of Group–VI cations

1. Test for Magnesium ion (Mg2+)

(a) 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- -
NH + CO
4 3 NH3 + HCO3
The concentration of carbonate ions required to produce a precipitate is
not attained. When disodium hydrogenphosphate solution 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 which
indicates the presence of Mg2+ ions.

Mg2+ + Na2 HPO4 Mg[NH4 ]PO4 + NH4 OH + 2Na+ + H2 O

Magnesium ammonium
phosphate
(White precipitate)

Note down the observations and the inferences of the qualitative analysis in
tabular form.
 Systematic Analysis and
Detection of Anion
Aim
To detect one cation and one anion in the given salt from the following ions:
Cations -
Pb+2, Cu+2,As+3,Al+3,Fe+3,Mn+2,Ni+2,Zn+2,Co+2,Ca+2,Sr+2,Ba+2,Mg+2,NH+4
Anions :
2- -2 2- 2- - - - - - 3- 2- -
CO3 , S , SO3 , SO4 , NO2, NO3, Cl , Br , I ,PO4 ,C2O4 ,CH3COO

Theory
Two basic principles of great use in the analysis are:
(i) the Solubility product; and

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

Material Required:
• Boiling tube : As per need
• Test tubes : As per requirement
• Measuring cylinder : One
• Test tube stand : One
• Test tube holder : One
• Delivery tube : One
• Corks : As per need
• Filter paper : As per need
• Reagents : As per need

Systematic Analysis of Anions

Step 0
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 , sulphide , sulphite,, nitrite , and acetate react with dilute

gases evolved gives information about the anions. Summary of characteristic

properties of gases is given in Table given below:
 Observations Gas evolved Possible Anion
A colourless, odourless gas CO Carbonate (CO32 -)
is evolved with brisk
lime water milky.
Colourless gas with the H S Sulphide (S2-)
smell of rotten eggs is
evolved which turns lead
acetate paper black

Colourless gas with a SO Sulphite (SO32 -)

pungent smell, like burning
sulphur which turns
acidified potassium
dichromate solution green.
Brown fumes which turn NO Nitrite (NO2- )
acidified potassium iodide
solution containing starch
solution blue.

Colourless vapours with CH3COOH Vapours Acetate (CH3COO-)

smell of vinegar. Vapours
turn blue litmus red.

Procedure
(a) Take 0. g of the salt in a test tube and add –2mL of dilute sulphuric acid.
Observe the change, if any, at room temperature. If no gas is evolved,
warm the content of the test tube. If gas is evolved test it by using the
apparatus shown in fig. and identify the gas evolved (See Table )

Reagent
Boiling
tube

Confirmatory tests for CO32-, S2-, SO32-, NO2- and CH3COO-

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 CO32- 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 g of salt in a porcelain dish or boiling tube.
Mix about 3g of solid sodium carbonate and add 5mL of distilled water to it.
Stir and boil the content for about 0 minutes. Cool, filter and collect the
filtrate in a test tube and label it as sodium carbonate extract. Confirmatory
tests for acid radicals, which react with dilute sulphuric acid are given below
in Table

Anion Confirmation test

Carbonate (CO32 -) Take 0. g of salt in a test tube, add dilute sulphuric

acid. CO
which turns lime water milky. On passing the gas
for some more time, milkiness disappears.

Sulphide (S2-) Take mL of water extract and make it alkaline by

adding ammonium hydroxide or sodium carbonate
extract. Add a drop of sodium nitroprusside
solution. Purple or violet colouration appears.

Sulphite (SO32 -) (a) Take mL of water extract or sodium carbonate

extract in a test tube and add barium chloride
solution. A white precipitate is formed which
dissolves in dilute hydrochloric acid and sulphur
dioxide gas is also evolved.
(b) Take the precipitate of step (a) in a test tube and
add a few drops of potassium permanganate
solution acidified with dil.H SO
Colour of potassium permanganate solution
gets discharged.

Nitrite (NO2- ) (a) Take mL of water extract in a test tube.

Add a few drops of potassium iodide solution
and a few drops of starch solution, acidify with
acetic acid. Blue colour appears.
Acidify mL of water extract with acetic acid.
Add 3-2 drops of sulphanilic acid solution follow
-ed by 3-2 drops of -1naphthylamine reagent.
Appearance of red colour indicates the presence
of nitrite ion.

Acetate (CH3COO-) (a) Take 0. g of salt in a china dish. Add mL of

ethanol and 0.2 mL conc.H SO and heat. Fruity
odour confirms the presence of acetate ion.
(b) Take 0. g of salt in a test tube, add 2- mL
distilled water, shake well filter if necessary.
Add to 2mL neutral** ferric chloride solution
to the filtrate.
Deep red colour appears which disappears on
boiling and a brown-red precipitate is formed.

Table 2
Chemistry of Confirmatory Tests
. Test for Carbonate ion [CO32-]

on adding dil. H SO to the solid salt, this indicates the presence of carbona
-te ion. The gas turns lime water milky due to the formation of CaCO3

Na2CO3 + H2SO4 Na2SO4 + H2O + CO2 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.
CaCO3 + CO2 + H2O Ca(HCO3)2

2. Test for Sulphide ion [S2-]

(a) With warm dilute H SO 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.

Na2 S + H2 SO4 Na2 SO4 + H2 S

(CH3COO)2 Pb + H2S PbS + 2CH3COOH

Lead Suphide
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 carbonate 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.

Na2 S + Na2 [Fe(CN)5NO] Na4 [Fe(CN)5NOS]

(Sodium Nitroprusside) (Purple Colour Complex)

3. Test for Sulphite ion [ SO32 - ]

(a) On treating sulphite with warm dil. H SO , SO gas is evolved which is

Na2 SO3 + H2 SO4 Na2 SO4 + H2 O + SO2

The gas turns potassium dichromate paper acidified with dil. H SO ,
green
K2Cr2O7 + H2 SO4 + 3SO2 K2 SO4 + Cr2 (SO4 )3 + H2 O
(Chromium sulphate)
(b )An aqueous solution or sodium carbonate extract of the salt produces a
white precipitate of barium sulphite on addition of barium chloride
solution.
Na2 SO3 + BaCl2 2NaCl + BaSO3
This precipitate gives following tests.

(i) This precipitate on treatment with dilute HCl, dissolves due to decom
-position of sulphite by dilute HCl. Evolved SO2 gas can be tested.
BaSO3 + 2HCl BaCl2 + H2O + SO2

(ii)Precipitate of sulphite decolourises acidified potassium permanganate

solution.
BaSO3 + H2 SO4 BaSO4 + H2O + SO2

2KMnO4 + 3H2 SO4 K2SO4 + 2MnSO4 + 3H2O + 5[O]

SO2 + H2 O + [O] H2SO4

-
4. Test for Nitrite ion [ NO2 ]
(a) On treating a solid nitrite with dil. H SO and warming , reddish brown
fumes of , NO 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.

(i) 2NaNO2 + H2 SO4 Na2 SO4 + 2HNO2

3HNO2 HNO3 + 2NO + H2O
2NO + O2 2NO2 (Brown gas)
HNO2 + CH3COO-
-
(ii) NO2 + CH3COOH
2HNO2 + 2KI + 2CH3COOH 2CH3COOK + 2H2O + 2NO + I2
I2 + Starch Blue complex

(b) Sulphanilic acid — -1naphthylamine reagent test (Griss-Ilosvay test)

On adding sulphanilic acid and -1naphthylamine 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
-1naphthylamine to form a red azo-dye. The test solution should be very
dilute. In concentrated solutions reaction does not proceed beyond
diazotisation.
4. Test for Acetate ion [ CH3COO- ]
(a) If the salt smells like vinegar on treatment with dil. H SO , this indicates
the presence of acetate ions. Take 0. g of salt in a china dish and add mL
of ethanol.
Then add about 0.2 mL of conc. H SO and heat. Fruity odour of ethyl
acetate indicates the presence of CH COO- ion.

2CH3COONa + H2 SO4 Na2 SO4 + 2CH3COOH

CH3COOH + C2H5OH CH3COOC2 H5 + H2O

(b) Acetate gives deep red colour on reaction with neutral ferric chloride
solution due to the formation of complex ion which decomposes on
heating to give Iron (III) dihydroxyacetate as brown red precipitate.

6CH3COO- + 3Fe+3 + 2H2 O [Fe3(OH)2 (CH3COO)6 ]+ + 2H+

[Fe3(OH)2 (CH3COO)6 ]+ + 4H2O 3[Fe(OH)2 (CH3COO)] + 3CH3COOH + H+

Iron (III) dihydroxyacetate
(Brown-red precipitate)

Step 02
Preliminary Test with Concentrated Suphuric Acid

If no positive result is obtained from dil. H SO test, take 0. g of salt in a

test tube and 4-3 drops of conc.H SO . Observe the change in the reaction
mixture in cold and then warm it. Identify the gas evolved on heating.

Table 3

Anion Gas/ Vapours Possible Anions

Evolved
A colourless gas with pungent HCl Chloride (Cl -)
smell, which gives dense white
fumes when a rod dipped in
ammonium hydroxide is brought
near the mouth of the test tube.
Reddish brown gas with a Br2 vapours Bromide (Br-)
pungent odour is evolved.
Intensity of reddish gas increases
on heating the reaction mixture
after addition of solid MnO to
the reaction mixture. Solution
also acquires red colour.
Violet vapours, which turn starch I2 vapours Iodide (I-)
paper blue and a layer of violet
sublimate is formed on the sides
of the tube. Fumes become
dense on adding MnO to the
reaction mixture.
 Brown fumes evolve which become NO2 -
Nitrate (NO ) 3
dense upon heating the reaction
mixture after addition of copper
turnings and the solution acquires
blue colour.

Colourless, odourless gas is evolved CO and CO2 2-

Oxalate (C2O4 )
which turns lime water milky and
the gas coming out of lime water
burns with a blue flame, if ignited.

Confirmatory tests for the anions which react with concentrated sulphuric
- - - - 2-
acid are given in Table Confirmatory tests for Cl , Br , I , NO3 and C2O4

Table 4
Anion Confirmatory Test
-
Chloride (Cl ) (a) Take 0. g of salt in a test tube, add a pinch of
manganese dioxide and 4-3 drops of conc.
sulphuric acid. Heat the reaction mixture.
Greenish yellow chlorine gas is evolved which
is detected by its pungent odour and bleaching
action.
(b) Take mL of sodium carbonate extract in a test
tube, acidfy it with dil. HNO3 or take water
extract and add silver nitrate solution. A curdy
white precipitate is obtained which is soluble in
ammonium hydroxide solution.
(c) Take 0. g salt and a pinch of solid potassium
dichromate in a test tube, add conc. H SO ,
heat and pass the gas evolved through sodium
hydroxide solution. It becomes yellow.
Divide the solution into two parts. Acidify one
part with acetic acid and add lead acetate
solution. A yellow precipitate is formed.
Acidify the second part with dilute sulphuric
acid and add mL of amyl alcohol followed by
mL of %0 hydrogen peroxide. After gentle
shaking the organic layer turns blue.
-
Bromide (Br ) (a) Take 0. g of salt and a pinch of MnO2 in a test
tube. Add 4-3 drops conc.sulphuric acid and
heat. Intense brown fumes are evolved.
(b) Neutralise mL of sodium carbonate extract
with hydrochloric acid (or take the water
extract). Add mL carbon tetrachloride (CCl4 )
/chloroform (CHCl3 )/ carbon disulphide.
Now add an excess of chlorine water dropwise
and shake the test tube. A brown colouration
in the organic layer confirms the presence of
bromide ion.
(c) Acidify mL of sodium carbonate extract with
dil. HNO3 (or take mL water extract) and
add silver nitrate solution. A pale yellow

hydroxide solution is obtained.

 Iodide (I-) (a) Take mL of salt solution neutralised with HCl
and add mL chloroform/carbon tetrachloride/
carbon disulphide. Now add an excess of
chlorine water drop wise and shake the test
tube.
A violet colour appears in the organic layer.
(b) Take mL of sodium carbonate extract acidify
it with dil. HNO3 (or take water extract).
Add, silver nitrate solution. A yellow precipitate
insoluble in NH4OH solution is obtained.

Nitrate (NO3-) (a) Take mL of salt solution in water in a test

tube. Add 2mL conc. of H SO and mix
thoroughly. Cool the mixture under the tap.
Add freshly prepared ferrous sulphate along the
sides of the test tube without shaking.
A dark brown ring is formed at the junction of
the two solutions.

Oxalate (C2O42 -) (a) Take mL of water extract or sodium carbonate

extract acidified with acetic acid and add calcium
chloride solution. A white precipitate insoluble
in ammonium oxalate and oxalic acid solution
but soluble in dilute hydrochloric acid and dilute
nitric acid is formed.
(b) Take the precipitate from test (a) and dissolve it
in dilute H SO . Add very dilute solution of
KMnO and warm. Colour of KMnO solution
is discharged. Pass the gas coming out through
lime water. The lime water turns milky.
Table 4

Chemistry of Confirmatory Tests

–
. Test for Chloride ion [Cl ]
(a) If on treatment with warm conc. H SO 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 + H2 SO4 NaHSO4 + HCl
HCl + NH3 NH4Cl

(b) H SO and MnO and

a light greenish yellow pungent gas is evolved, this indicates the presence
of Cl– ions.

MnO2 + 2NaCl + 2H2 SO4 Na2SO4 + MnSO4 + 2H2O + Cl2

(c) Salt solution acidified with dilute HNO3 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
AgCl + 2NH4OH [Ag(NH3 )2 ] Cl + 2H2O

(d) Mix a little amount of salt and an equal amount of solid potassium
dichromate (K Cr O7) in a test tube and add conc. H SO4 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 + K2Cr2O7 + 6H2SO4 2KHSO4 + 2CrO2Cl2 + 4NaHSO4

(Chromyl chloride) + 3H2O

CrO2Cl2 + 4NaOH Na2CrO4 + 2NaCl + 2H2O

(CH3COO)2Pb + Na2CrO4 PbCrO4 + 2CH3COONa

Acidify the second part with dilute sulphuric acid and add small amounts
of amyl alcohol and then mL of %10 hydrogen peroxide solution.
On gentle shaking organic layer turns blue. C2O42 - 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.

2-
C2O4 + 2H+ + 2H2O2 CrO5 + 3H2O
(Chromium pentoxide)

2. Test for Bromide ion [Br– ]

If on heating the salt with conc.H SO reddish brown fumes of bromine
are evolved in excess, this indicates the presence of Br- ions. The fumes
get intensified on addition of MnO . Bromine vapours turn starch paper
yellow.
2NaBr + 2H2 SO4 Br2 + SO2 + Na2 SO4 + 2H2O
2NaBr + MnO2 + 2H2 SO4 Na2 SO4+ MnSO4 + 2H2O + Br2

(a) Add mL of carbon tetrachloride (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

NaBr + AgNO3 NaNO3 + AgBr

(Silver bromide - Pale yellow precipitate)

3. Test for Iodide ion [I– ]

(a) If on heating the salt with conc. H2 SO4 , 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 + 2H2 SO4 Na2 SO4 + SO2 + 2H2 O + I2

I2 + Starch Blue colour
NaI + H2 SO4 NaHSO4 + HI
2HI + H2 SO4 2H2O + I2 + SO2
6NaI + 4H2 SO4 3I2 + 4H2O + S + 3Na2 SO4
8NaI + 5H2 SO4 4I2 + H2 S + 4Na2 SO4 + 4H2O

On adding MnO2 to the reaction mixture, the violet vapours become

dense.
2NaI + MnO2 + 2H2 SO4 I2 + MnSO4 + Na2 SO4 + 2H2O

(b) Add 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

(c) Iodine dissolves in the organic solvent and the solution becomes violet.
Acidify sodium carbonate extract of the salt with dil.HNO3 and add
AgNO3 solution. Appearance of a yellow precipitate insoluble in excess
of NH4OH confirms the presence of iodide ions.

NaI + AgNO3 AgI + NaNO3

Silver iodide
(Yellow precipitate)
 –
4. Test for Iodide ion [NO3 ]
(a) If on heating the salt with conc. H2 SO4 light brown fumes are evolved
then heat a small quantity of the given salt with few copper turnings or
chips and conc. H SO4. Evolution of excess of brown fumes indicates
the presence of nitrate ions. The solution turns blue due to the
formation of copper sulphate.

NaNO3 + H2 SO4 NaHSO4 + HNO3

4HNO3 4NO2 + O2 + 2H2O
2NaNO3 + 4H2 SO4 + 3Cu 3CuSO4 +Na2 SO4+ 4H2O + 2NO
2NO + O2 2NO2
(Brown fumes)
(b) Take mL of an aqueous solution of the salt and add 2mL conc. H SO4
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 tube. A dark brown ring is formed at the
junction of the two solutions due to the formation of nitroso ferrous
sulphate (Fig.). Alternatively first ferrous sulphate is added and then
concentrated sulphuric acid is added.

FeSO4

Dark brown ring

Fig. 2

Formation of Dark Brown Ring

NaNO3 + H2 SO4 NaH SO4+ HNO3
6 FeSO4 + 3H2 SO4 + 2HNO3 3Fe2(SO4 )3 + 4H2O + 2NO
FeSO4 + NO [Fe(NO)]SO4
Nitroso ferrous sulphate
(Brown)

5. Test for Oxalate ion [C2O42 – ]

If carbon dioxide gas along with carbon monoxide gas is evolved in the
preliminary examination with concentrated sulphuric acid,this gives
indication about the presence of oxalate ion.

(COONa)2 + Conc. H2 SO4 Na2 SO4 + H2O +CO2 + CO

Oxalate is confirmed by the following tests:

(a) Acidify sodium carbonate extract with acetic acid and add calcium
chloride solution. A white precipitate of calcium oxalate, insoluble in
ammonium oxalate and oxalic acid solution indicates the presence of
oxalate ion.

CaCl2 + Na2C2O4 CaC2O4 + 2NaCl

Calcium oxalate
(White precipitate)

(b) KMnO4 test

Filter the precipitate from test (a). Add dil.H2SO4 to it followed by dilute
KMnO4 solution and warm. Pink colour of KMnO4 is discharged:

CaC2O4 + H2SO4 CaSO4 + H2C2O4

Calcium Oxalic
sulphate acid

2KMnO4 + 3H2SO4 + 5H2C2O4 2MnSO4 + K2SO4 + 8H2O + 0CO2

Pass the gas evolved through lime water. A white precipitate is formed
which dissolves on passing the gas for some more time.

Step 03
Test for Sulphate and Phosphate

If no positive test is obtained in Steps-I and II, then tests for the presence of
sulphate and phosphate ions are performed. These tests are summarised in
Table - Confirmatory tests for Sulphate and Phosphate.

Table 5
Ion Confirmatory Test

Sulphate (SO42 -) (a) Take mL water extract of the salt in water

or sodium carbonate and after acidifying with
dilute hydrochloric acid add BaCl2 solution.
White precipitate insoluble in conc. HCl or
conc. HNO3 is obtained.
(b) Acidify the aqueous solution or sodium
carbonate extract with acetic acid and add lead
acetate solution.
Appearance of white precipitate confirms the
presenceof SO42 - ion.

Phosphate (PO43-) (a) Acidify sodium carbonate extract or the

solution of the salt in water with conc. HNO3
and add ammonium molybdate solution and
heat to boiling. A canary yellow precipitate is
formed.
Chemistry of Confirmatory Tests
. Test for Sulphate ion [ SO42 - ]
(a) Aqueous solution or sodium carbonate extract of the salt acidified with
acetic acid on addition of barium chloride gives a white precipitate of
barium sulphate insoluble in conc. HCl or conc. HNO3

Na2 SO4 + BaCl2 BaSO4 + 2NaCl

Barium sulphate
(White precipitate)

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

Na2 SO4 + (CH3COO)2 Pb PbSO4 2+CH3 COONa

2. Test for Phosphate ion [ PO43 - ]

(a) Add conc. HNO3 and ammonium molybdate solution to the test
solution containing phosphate ions and boil.
A yellow colouration in solution or a canary yellow precipitate of
ammonium-phosphomolybdate,

(NH4)3 [P (Mo3O 0 )4 ] is formed. Each oxygen of phosphate has been

replaced by Mo3O 0 group.

Na2HPO4 + 2(NH4)2MoO4 (NH4)3 [P (Mo3O 0 )4 ] + 2NaNO3

MoO4 + 23 HNO3 + 2 NH4NO3 + 2H2O