PURIFICATION AND CHARACTERISATION

OF ORGANIC COMPOUNDS

Total No.of questions in Purification and characterisation of

organic compound are -

In Chapter Examples.............................................................. 06
Solved Examples ................................................................... 10

Total No. of questions .......................................................... 16

1. PURIFICATION OF ORGANIC COMPOUNDS
The methods to be employed depend on the
physical state of the compound.
1.1 Crystallisation : This method is based on the
differences in the solubility of the organic
compound and its impurities in a solvent.
(a) Preparation of the solution : Organic substance
is powdered and is dissolved in a suitable solvent
by heating. The amount of solvent should be just
sufficient to dissolve the whole of the solid on
heating.
Choice of Solvent. The choice of solvent is very
important in the crystallisation process. The main
conditions of the solvent are:
(i) The organic substance should dissolve in the
solvent upon heating and it should get separated
on cooling.
(ii) The solvent should not dissolve the impurities.
(iii) The solvent should not react chemically with the
substance.
For example, suppose we want to purify sugar
containing an impurity of common salt. This can
be done by treating the mixture with ethanol
around 350 K. The sugar will dissolve whereas
common salt remains insoluble.
(b) Filtration of the solution. The hot saturated
solution is filtered preferably through a fluted filter
paper placed in a glass funnel. The use of the
fluted filter paper makes the filtration rapid. The
jacketer of the hot water funnel is heated from
outside and this keeps the solution hot in the
glass funnel. This will prevent the formation of
crystals during filtration.
(c) Crystallisation. The hot filtration is allowed to
cool slowly and undisturbed in a beaker or in a
crystallising dish. After some time the crystals of
the pure compound are formed.
(d) Separation of the crystals. The crystals formed
are separated from the mother liquor by filtration.
The filtration is normally done by use of Buckner
funnel and a suction pump. This enables the
filtration under reduced pressure and is therefore,
quite fast.
(e) Drying of crystals. The crystals are dried by
pressing between the folds of filter paper and
then placed in a steam of air oven for some time.
The crystals are finally dried over sulphuric acid
or calcium chloride in a desiccator.
1.2 Sublimation : Certain organic solids directly
change from solid to vapour state on heating.
This process is called sublimation. The vapours
on cooling change back to the solid form
Heat
Solid Vapours
Cool
The sublimation process is used f or the
separation of those solids which sublime on
heating from non-volatile solids. The process is
generally used for the purification of camphor,
naphthalene, anthracene, benzoic acid, etc.
containing non-volatile impurities.
1.3 Distillation : This method is used for the
purif ication of liquids which boil without
decomposition and contain non-volatile impurities.
The simple distillation involves its boiling point so
that it is converted into vapours. On cooling the
vapours, pure liquid is obtained.
The distillate contains pure liquid while the
impurities are left behind in the distillation flask
e.g.Ether from ethyl alcohol.
1.4 Fractional Distillation : This process is used to
separate a mixture of two or more miscible liquids
which have boiling points close to each other.
The fractionating column is a long tube provided
with obstructions to the passage of the vapours
moving upwards and liquid moving downwards.
This method may be used to separate a mixture
of acetone (b.p. 330K) and methyl alcohol
(b.p. 338. K).
1.5 Distillation under Reduced pressure (Vaccum
Distillation) : Certain liquids have a tendency to
decompose at a temperature below their boiling
points. Such liquids cannot be purified by ordinary
distillation. Therefore vacuum distillation is used
for liquids which decompose at a temperature
below their normal boiling points.
Ex. glycerol boils with decomposition at 563K.
1.6 Steam distillation : The process of steam
distillation is used for the separation and
purification of liquid which is appreciably volatile
 in steam, from non-volatile components of a
mixture. Thus, the process of steam distillations
is used to purify the substances which
(i) are volatile in steam but are not miscible
with water
(ii) possess sufficiently high vapour pressure at
the boiling point temperature of water (1000C)
(iii) contain non-volatile impurities.
The process of steam distillation can be
applied for the separation of a mixture of
o-nitrophenol and p-nitrophenol. In this
process, water vapours carry along with them
vapours of o-nitrophenol which is more volatile
and they get condensed in the receiver ;
p-nitrophenol with higher b.p. remains in the
distillation flask. The method can also be
used for the purification of impure sample of
aniline.
1.7 Chromatography : This method is based on the
differences in the rates at which the components
of a mixture are adsorbed on a suitable adsorbent.
There are many forms of chromatography such
as column chromatograhy, paper chromatography,
thin layer chromatography (TLC), gas
chromatography, etc. The simplest method is
column chromatography.
Applications of chromatographic method. This
method has been used
(i) To separate ortho and para nitro-anilines.
(ii) To separate blue and red dyes.
(iii) To separate and purify plant pigments and
other natural products.
Types of chromatography :
Based on the principle involved chromatography
is classified into different categories. Two of these
are.
(a) Adsorption chromatography, and
(b) Partition chromatography
(a) Adsorption chromatography :
Adsorption chromatography is based on the fact
that different compounds are adsorbed on an
adsorbent to different degrees. Commonly used
adsorbents are silica gel and alumina, When a
mobile phase is allowed to move over a stationary
phase (adsorbent), the components of the mixture
move by varying distances over the stationary
phase. Following are two main types of
chromatographic techniques based on the
principle of differential adsorption.
(i) Column chromatography, and
(ii) Thin layer chromatography.
Column chromatography:
Solvent
a a
b+c b
Adsorbent c
(stationary phase)
Glass wool
Column chromatography. Different stages of
separation of components of a mixture
Column chromatography involves separation of a
mixture over a column of adsorbent (stationary
phase) packed in a glass tube. The column is
fitted with a stopcock at its lower end. The mixture
adsorbed on adsorbent is placed on the top of
the adsorbent column packed in a glass tube. An
appropriate eluant which is a liquid or a mixture
of liquids is allowed to flow down the column
slowly. Depending upon the degree to which the
compounds are adsorbed, complete separation
takes place. The most readily adsorbed
substances are retained near the top and others
come down to various distances in the column
Thin layer chromatography :
jar
adsorbent coated
on glass plate
sample dot
base line
solvent
Thin layer chromatography
chromatogram being developed
 (b) Partition Chromatography :
solvent
front
spot
y base line
x spot
base line
Developed chromatogram
Thin layer chromatography (TLC) is another type
of adsorption chromatography, which involves
separation of substances of a mixture over a thin
layer of an adsorbent coated on glass plate. A
thin layer (about 0.2 mm thick) of an adsorbent
(silica gel or alumina) is spread over a glass
plate of suitable size. The plate is known as thin
layer chromatography plate or chromaplate. The
solution of the mixture to be separated is applied
as a small spot about 2 cm above one end of
TLC plate. The glass plate is then placed in a
closed jar containing the eluant. As the eluant
rises up the plate, the components of the mixture
move up along with the eluant to different
distances depending on their degree of adsorption
and separation takes place. The ralativ e
adsorption of each component of the mixture is
expressed in terms of its retardation factor
i.e. Rf value
D istance movedby the substance from base line (x)
Rf 
Distance movedby the solvent from base line (y)
The spots of coloured compounds are visible on TLC
plate due to their original colour. The spots of
colourless compounds which are invisible to the
eye but fluoresce, can be detected by putting
the plate under ultraviolet light. Another detection
technique is to place the plate in a covered jar
containing a few crystals of iodine spots of
compounds, which adsorb iodine will show up as
brown spots. Sometimes an appropriate reagent
may also be sprayed on the plate. For example,
Amino acids may be detected by spraying the
plate with ninhydrin solution
card board
chromatography
paper
jar
solvent
card board
chromatography
paper
jar
spot
base line
solvent
Paper chromatography chromatography
paper in two different shapes
Partition chromatography is based on continuous
differential partitioning of components of mixture
between stationary and mobile phases. Paper
chromatography is a type of partition
chromatography. In paper chromatography, a
special quality paper known as chromatography
paper is used. Chromatography paper contains
water trapped in it, which acts as the stationary
phase.
A strip of chromatography paper spotted at the
base with the solution of the mixture is suspended
in a suitable solvent or a mixture of solvents This
solvent rises up the paper by capillary action and
flows over the spot. The paper selectively ratains
different components according to their differing
partition in the two phases. The paper strip so
developed is known as a chromatogram. The
spots of the separated coloured compounds are
visible at different heights from the position of
initial spot on the chromatogram. The spots of
the separated colourless compounds may be
observed either under ultraviolet light or by the
use of an appropriate spray reagent as discussed
under thin layer chromatography.
2. QUALITATIVE ANALYSIS
CaO
CH3CONH2 + NaOH CH3COONa + NH3
The qualitative analysis of an organic compound
acetamide
involves the detection of all the elements present
in it. Limitation : This method has a limitation. A large
2.1 Detection of Carbon and Hydrogen : A small number of organic compounds such as nitro and
amount of the dry and powdered substance is diazo compounds do not liberated ammonia on
mixed with about double the amount of pure and heating with sodalime.
dry copper oxide. The mixture is heated in a well (b) Lassaigne’s method : A small piece of a dry
dried hard glass tube (fig) delivery tube is packed sodium metal is heated gently in a fusion tube
with glass wool containing anhydrous copper till it melts to a shining globule. Then , a small
sulphate (white). When the mixture is heated , amount of organic substance is added and the
the carbon present in the compound is oxidised tube is heated strongly till it becomes red hot.
to carbon dioxide which turns lime water milky. The red hot tube is then cooled and filtered. The
The hydrogen present in the organic compound filtered liquid is known as sodium extract or
is oxidised to water which turns anhydrous copper Lassaigne’s extract.
sulphate in the bulb to blue.
The Lassaigne’s extract is usually alkaline. If not,
it may be made alkaline by adding a few drops
Anhydrous copper sulphate of a dilute solution of sodium hydroxide added to
a part of sodium extract a small amount of a
Organic compound freshly prepared ferrous sulphate solution is
+ and the contents are warmed. A few drops of
Copper oxide
Lime water ferric chloride solution are then added to the
contents and the resulting solution is acidified
with dilute hydrochloric acid. The appearance of
a bluish green or a blue colouration confirms the
fig. Detection of carbon and hydrogen in an presence of nitrogen in the organic compound.
organic compound The following chemical reactions occur during the
test :
C + 2CuO Heat
 CO2 + 2Cu Na + C + N  NaCN
from organic from organic
compound compound
CO2 + Ca(OH)2  
 CaCO3 + H2O FeSO4 + 2NaCN Fe(CN)2 + Na2SO 4
lime water milky Fe(CN)2 + 4NaCN  Na4[Fe(CN)6 ]
Heat
2H + CuO   H2O + Cu sodium ferrocyanide
from organic 3Na4[Fe(CN)6] + 4FeCl3 Fe4[Fe(CN)6]3 + 12NaCl
compound ferric ferrocyanide
(blue colour)
CuSO4 + 5H2O  
 CuSO4 . 5H2O
2.3 Detection of Sulphur : The sulphur in the
anhydrous hydrated copper sulphate
compound reacts with sodium metal to form
copper sulphate (blue) sodium sulphide.
(white) 2Na + S  Na2S
This method is known as copper oxide test. from organic
2.2 Detection of Nitrogen : Nitrogen in an organic compound
compound is detected by the following tests :
The Lassaigne’s extract is divided into two parts
(a) Soda lime test. A pinch of an organic compound and following tests are performed.
is heated strongly with soda lime (NaOH + CaO)
(i) Sodium nitroprusside test. The one portion of
in a test tube. If ammonia gas evolves, it indicates
the extract, a few drops of sodium nitroprusside
nitrogen. are added. The appearance of violet colouration
 indicates sulphur. Na3PO 4  3HNO3  H3PO 4  3NaNO 3
Na2S + Na2 [Fe(CN)5NO]  Na4[Fe(CN)5NO.S] H3PO 4  12(NH4 )2 MoO 4  21HNO3 
sod. nitroprusside violet colouration Ammonium
(ii) Lead acetate test : The other part of the molybdate
Lassaigne’s extract is acidified with acetic acid (NH4 )3 PO 4 .12MoO3  21NH4NO 3  12H2O
and then lead acetate solution is added. Ammonium
Formation of black precipitate confirms the
phosphomolybdate
presence of sulphur.
Examples
Na2S + Pb(CH3COO)2  PbS + 2CH3COONa based on Qualitative analysis
lead acetate black Ex.1 In Lassaigne’s test when both N and S are
present, blood red colour obtained is due to
2.4 Detection of Halogens : the formation of -
Lassaigne’s test. Sodium extract is prepared as (A) Ferric ferrocyanide
already. During fusion , sodium will combine with (B) Ferric sulphocyanide
the halogen (from the organic compound) to form
(C) Ferric cyanide
sodium halide
(D) None Ans.(B)
Na + X Fusion
  NaX (X = Cl, Br, I) Sol. 3 NaCNS + FeCl 3  Fe(CNS)3 + 3NaCI
(i) A white precipitate soluble in ammonium (Red)
hydroxide solution indicates the presence of
chlorine in the organic compound
3. QUANTITATIVE ANALYSIS
NaCl + AgNO3  AgCl + NaNO 3
white ppt. 3.1 Estimation of Carbon and Hydrogen :
(ii) A dull yellow precipitate partially soluble in Principle. A known weight of the given dry
ammonium hydroxide solution indicates the organic compound is heated strongly with dry
presence of bromine in the organic compound. cupric oxide in an atmosphere of air or oxygen
NaBr + AgNO3  AgBr + NaNO 3 free from CO2. The carbon and hydrogen of the
organic compound are oxidised to CO2 and water
dull yellow ppt. vapour as :
(iii) A bright yellow precipitate, completely insoluble C + 2CuO ––––– CO2 + 2Cu
in ammonium hydroxide solution, indicates the (from compound)
presence of iodine in the organic compound.
2H + CuO ––––– H2O + Cu
NaI + AgNO3  AgI + NaNO3 (from compound)
bright yellow ppt Procedure :
Special test for bromine and iodine. Let the mass of organic compound taken = m g
2NaBr + Cl2  2NaCl + Br2 Mass of water formed = m 1 g
(increase in CaCl2 U-tube)
(turns CS2 layer orange)
Mass of carbon dioxide formed = m2 g
2NaI + Cl2  2NaCl + I2 increase in potash tubes)
(turns CS2 layer violet) (a) Percentage of Carbon
We know that 1 mole of carbondioxide (44 g)
Test of phosphorus : contains 1 gram atom of carbon (12g).
The compound is heated with an oxidising agent CO2 C
(sodium peroxide). The phosphorus present in 44 g of CO2 contain C = 12 g
the compound is oxidised to phosphate. The 12
solution is boiled with nitric acid and then treated m2 g of CO 2 contains C = × m2 g
44
with ammonium molybdate. A yellow colouration
12m 2
or precipitate indicates the presence of Hence Percentage of carbon = 44  m × 100
phosphorus.
(b) Percentage of Hydrogen when all the gases except nitrogen are absorbed.
We know that one mole of water (18g) contains The volume of nitrogen produced is measured at
2 gram atom of hydrogen (2g) room temperature and atmospheric pressure.
H2O =2H From the volume of N2 produced, percentage of
18g of H2O contain H = 2g nitrogen in the sample can be calculated.

2
C + 2CuO  CO2 + 2Cu
 m 1 g of H2O contains H = × m1 g 2H + CuO  H2O + Cu
18
2N + CuO  N2 + oxides of nitrogen
2m 1
Percentage of hydrogen = 18  m × 100 Oxides of nitrogen + Cu  CuO + N2
Let the mass of organic compound = w g
Percentage of C
The volume of nitrogen collected = Vcm 3
12 Mass of CO 2 formed Atmospheric pressure (f rom barometer)
= × x 100
44 Mass of compound taken = P mm of Hg
Percentage of H Room temperature = t0C
Aqueous tension at t0C = a mm of Hg
2 Mass of H2 O formed
= × x 100 Pressure of dry nitrogen = (P – a) mm of Hg
18 Mass of compound taken
Let us first convert the volume of nitrogen to
volume at S.T.P.
Examples Experimental conditions S.T.P. conditions
based on Estimation of carbon and hydrogen
P1 = (P – a) mm Hg P2 = 760 mm
Ex.2 On complete combustion, 0.246g of an
organiccompound gave 0.198g of carbon T1 = (273 + t) K T2 = 273
dioxide and 0.1014g of water. Determine the V1 = V cm3 V2 = ?
percentage composition of carbon and
hydrogen in the compound. P1V1 P2 V2
Applying gas equation =
T1 T2
12  0.198  100
Sol. Percentage of carbon =
44  0.246
P1V1T2 (P  a) x V x 273
= 21.95 %  V2 = = = x cm3 (say)
P2 T1 760 (273  t)
2  0.1014  100
Percentage of hydrogen = Now 22400 cm3 of N2 at S.T.P. weight = 28 g
18  0.246
= 4.58 % 28
x cm3 of N2 at S.T.P. will weigh = × xg
22400
3.2 Estimation of Nitrogen :  Percentage of nitrogen
There are two methods for the estimation of
nitrogen Mass of nitrogen
= x 100
(i) Duma’s method (ii) Kjeldahl’s method Mass of organic compound
(i) Duma’s method :
Principle of the method. A known mass of an 28 x x 100
=
organic compound is heated with dry cupric oxide 22400 x w
in an atmosphere of carbon dioxide. The carbon
Examples
and hydrogen are oxidised to carbon dioxide and based on Estimation of Nitrogen
water respectively while nitrogen is set free. If Ex.3 In duma’s method for estimation of nitrogen.,
any oxide of nitrogen is produced during this 0.3g of an organic compound gave 50mL of
process, it is reduced to nitrogen by passing nitrogen collected at 300K temperature and
over a heated copper gauze. The gaseous mixture 715 mm pressure. Calculate the percentage
is collected over an aqueous solution of KOH composition of nitrogen in the compound.
(Aqueous tension at 300K = 15 mm)
Sol. Volume of nitrogen collected at 300K and Normality of acid = N1
715 mm presssure is 50mL Let vol. of standard alkali used for neutralisation
Actual pressure = 715-15 = 700 mm of unused acid = V2 cm 3
Normality of standard alkali = N2
Volume of nitrogen at STP  273  700  50 N1V1
300  760  = N 2V
2
alkali acid
= 41.9 mL Let this volume of v cm 3
22,400 mL of N2 at STP weight = 28g  Vol. of acid used for neutralisation of ammonia
28  41.9 = (V – v) cm 3 of N1 normality
41.9 mL of nitrogen weights = g  Ammonia liberated = (V – v) cm3 of N1 solution
22400
Now,1000 cm 3 of 1N NH3 solution contains
28  41.9  100 nitrogen = 14 g
Percentage of nitrogen =
22400  0.3 (V – v) cm 3 of N1 NH3 solution contains
14 ( V  v ) x N1
= 17.46% nitrogen = g
1000
Percentage of nitrogen
(ii) Kjeldahl’s method : This method cannot be used Mass of nitrogen
for = x 100
Mass of organic compound
(i) Organic compounds containing nitrogen in the 14 (V  v) x N 1 100
ring such as pyridine, quinoline, etc. = ×
1000 w
(ii) Organic compounds containing nitrogen (-NO2)
1. 4 (V  v) x N1
and diazo (-N = N-) groups. =
w
Principle : A known weight of the organic
compound is heated with conc. H2SO 4 so that Examples
based on Estimation of Nitrogen
nitrogen is quantitatively converted into ammonium
Ex.4 During estimation of nitrogen present in an
sulphate. The solution is then heated with excess
organic compound by Kjeldahl’s method, the
of sodium hydroxide. The ammonia gas evolved ammonia evolved from 0.5 g of the compound
is passed into a known but excess volume of in Kjeldahl’s estimation of nitrogen,
standard acid (HCl or H2SO 4). The acid left neutralized 10 mL of 1 M H2SO 4. Find out
unused is estimated by titrating the solution with the percentage of nitrogen in the compound.
standard alkali. From the amount of acid left Sol. 1 M of 10 mL H2SO 4 = 1M of 20mL NH3
unused the amount of acid used for neutralisation 1000mL of 1M ammonia contains 14 g
of ammonia can be calculated. From this nitrogen
percentage of nitrogen can be calculated. 14  20
Conc. H2 SO 4
20 mL of 1M ammonia contains g
C, H, S   CO 2 + H2O + SO 2 1000
nitrogen
(from organic
compound) 14  20  100
Percentage of nitrogen = = 56.0 %
Conc. H SO
1000  0.5
2 4
N     (NH4)2SO 4
(from organic ammonium 3.3 Estimation of Halogens :
compound) sulphate Carius method :
Principle : A known mass of the organic
(NH4)2SO4 + 2NaOH Heat
 substance is heated with fuming HNO 3 in a
Na2SO4 + 2NH3 + 2H2O Carius tube. The silver halide so obtained is
2NH3 + H2SO4  (NH4)2SO 4 separated, washed, dried and weighed. From the
weight of silver halide formed, the percentage of
NH3 + HCl  NH4Cl halogen can be calculated.
X + AgNO 3 AgX
Calculations
Halogen
Let the mass of organic compound = w g
Carbon, hydrogen or sulphur present in the
Volume of standard acid taken = V cm 3 compound will be oxidised to CO2, H2O and
 H2SO4 respectively. precipitated with barium chloride as barium
HNO 3 sulphate. The precipitate is filtered, washed, dried
C + 2O  
 CO 2 and weighed. From the weight of BaSO4 formed,
3 HNO the percentage of sulphur can be calculated. The
2H + O  
  H2O main reactions are :
3HNO
S + H2O + 3O     H2SO 4 S + H2O + 3O HNO 3
 H2SO 4
Calculations : H2SO 4 + BaCl2  BaSO4
Let the mass of organic compound be w g ppt.
Mass of silver halide formed = a g Calculations :
Now, AgX = X Let the mass of organic compound = w g
108 + X parts by weight of silver halide contains Mass of BaSO4 formed = a g
X parts by weight of halogen (X is its atomic
BaSO 4  S
mass)
137 + 32 + 64 = 32
(108 + X) g of silver halide give halogen = X
= 233
a g of silver halide will give halogen
233 g of BaSO4 contain sulphur = 32 g
X
= × ag 32 x a
(108  X) a g of BaSO4 will contain sulphur = g
 Percentage of halogen 233
Percentage of sulphur
Mass of ha log en
= x 100 Mass of sulphur
Mass of organic compound = × 100
Mass of organiccompound
X xa 100 32 a 100
= x = ×
(108  X) w 233 w
Here X is the atomic mass of halogen, e.g. Examples
based on Estimation of Sulphur
Cl = 35.5 , Br = 80 (79.9 exact),
I = 127 (126.9 exact) Ex.6 In sulphur estimation, 0.157 g of an organic
Percentage of halogen compound gave 0.4813 g of barium sulphate.
What is the percentage of sulphur in the
Atomic mass of halogen  Mass of silver halide compound?
= × 100 Sol. Molecular mass of BaSO4 = 137 + 32 + 64
(108  At.mass of halogen)  Mass of organic substance
= 233 g
233 g BaSO4 contains 32 g sulphur
Examples
based on Estimation of Halogens
0.4813 g BaSO4 contains 32  0.4813 g
Ex.5 In Carius method of estimation of halogen, 233
0.15 g of an organic compound gave 0.12 g
of AgBr. Find out the percentage of bromine sulphur
in the compound. 32  0.4813  100
Sol. Molar mass of AgBr = 108 + 80 Percentage of sulphur =
233  0.157
= 188 g mot–1
= 42.10 %
188 g AgBr contains 80 g bromine
80  0.12
0.12 g AgBr contains g bromine
188
80  0.12  100
Percentage of bromine =
188  0.15
= 34.04 %
3.4 Estimation of Sulphur
Sulphur is estimated by Carius method.
Principle : A known mass of the organic
compound is heated with fuming HNO3 in a
sealed tube when sulphur is quantitatively
conv erted into sulphuric acid. It is then
 SOLVED EXAMPLES
Ex.1 Liquid which decompose below their normal Ex.5 A compound which does not give a positive
boiling points can be distilled at lower test in the Lassaigne’s test for ‘N’ is-
temperature by- (A) Glycine (B) Phenyl hydrazine
(A) Increasing the pressure (C) Urea (D) Azobenzene
(B) Decreasing the pressure Ans. (D)
(C) Heating in water bath
(D) Heating in sand bath Ans.(B)
Sol. Azobenzene
Sol. B.pt. gets lowered at low pressure.
does not give positive test in Lassaigne ’s
Ex.2 A bottle containing two immiscible liquids is test for N.
given to you. They may be separated by
Ex.6 Liebig method is used for the estimation of -
using a-
(A) Nirogen
(A) Fractionating coloumn
(B) Sulphur
(B) Separating funnel
(C) Carbon and Hydrogen
(C) Vacuum distillation
(D) Halogens
(D) Steam distillation Ans.(B) Ans. (C)
Sol. Being immiscible liquids, they form different Sol. Liebig method is used for the estimation of
layers. carbon and hydrogen.
Ex.3 In Lassaigne’s test for nitrogen, the blue
colour is due to the formation of - Ex.7 The quantitative determination of halogen in
an organic compound is known as-
(A) Ferric ferrocyanide
(A) Dumas method
(B) Potassium ferrocyanide
(B) Carius method
(C) Sodium ferrocyanide
(C) Kjeldahl method
(D) Sodium cyanide Ans.(A)
(D) Leibig method Ans.(B)
Sol. In Lassaigne’s test substance is heated Sol. The quantitative determination of halogen in
strongly with sodium metal then water extract an organic compound is called as carius
is boilded with alkaline FeSO4 solution and method.
after cooling FeCI3 solution and excess of
HCI is added in it. If prussian blue or green Ex.8 0.2475g of an organic compound gave on
ppt. is obtained then Nitrogen is confirmed- combustion 0.4950g of carbon dioxide and
Na + C + N  NaCN 0.2025 g of water. The percentage of carbon
and hydrogen are-
FeSO4 + 2NaOH  Fe(OH)2 + Na2SO 4 (A) 54.54, 9.09 (B) 52.54, 8.09
6NaCN + Fe(OH)2  Na4[Fe(CN)6] + 2NaOH (C) 120, 5.8 (D) None Ans. (A)
3Na4[Fe(CN)6] + 4FeCl3  Sol. Wt. of organic compound = 0.2475 g
Wt. of CO2 produced = 0.4950 g
Fe 4[Fe(CN)6]3 + 12NaCl
Wt. of H2O produced = 0.2025 g
sodium ferrocyanide prussian blue or green
Percentage of carbon
(ferric ferrocyanide)
12 Wt. of CO 2
Ex.4 In sodium fusion test of organic compounds, = × x 100
44 Wt. of compound
the nitrogen of an organic compound is
converted to- 12 0.4950
(A) Sodamide = × × 100 = 54.54
44 0.2475
(B) Sodium cyanide Percentage of hydrogen
(C) Sodium nitrite Wt. of H2 O
2
(D) Sodium nitrate Ans. (B) = × × 100
18 Wt. of compound
Sol. Na + C + N  fusion
 NaCN 2 0.2025
= × × 100 = 9.09
18 0.2475
Ex.9 0.257 g of an organic substance was heated
Ex.10 0.395 g of an organic compound by Carius
with conc H2SO 4 and then distilled with
method for the estimiation of sulphur gave
excess of strong alkali. The ammonia gas
0.582 g of BaSO4. The percentage of sulphur
evolved was absorbed in 50 ml of N/10 HCl in the compound is-
which required 23.2 ml of N/10 NaOH for
(A) 20.24 (B) 35
neutralisation at the end of the process. The
(C) 40 (D) 45 Ans. (A)
percentage of nitrogen in the compound is-
Sol. Mass BaSO4 = 0.582 g
(A) 14.6 (B) 18.0
We know BaSO4  S
(C) 17.0 (D) 15.5 Ans.(A)
233 32
N 233 g of BaSO4 contain sulphur = 32 g
Sol. Volume of HCl taken = 50ml
10
32
N 0.582 g of BaSO4 contains sulphur = × 0.582
233
Volume of NaOH used for neutralisation
10 Percentage of sulphur
of unused acid = 23.2 ml
Wt. of sulphur
Now N1 V1(NaOH) = N2V2(HCl) = x 100
Wt. of compound
N N
23.2 ml of NaOH 23.2 ml of HCl 32 x 0.582
10 10 = x 100 = 20.24 %
233 x 0.395
N
 Volume of HCl unused = 23.2 ml
10
 Volume of N/10 HCl required f or
neutralization of NH3 = 50 - 23.2 = 26.8 ml
N
26.8 ml of HCl = 26.8 ml of N/10 NH3
10
1000 ml of 1N NH3 solution contains nitrogen
= 14 g
26.8 ml of NH3 solution contains nitrogen
14 x 26.8
=
10 x 1000
Percentage of nitrogen
14 x 26.8 x 100
= = 14.6%
10 x 1000 x 0.257