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Methods of Purification of Organic  Crystallisation is based on the difference in

solubilities of the compound and impurities in a


Compounds : suitable solvent.
Organic compounds obtained either from natural  The principle involved in this method is impure
source (or) synthesized in laboratory contaminated compound dissolved in a solvent is sparingly soluble
with impurities. at low temperature, but appreciably soluble at high
Various methods are used for removal of impurities temperature.
from an organic compound depends on the nature  Insoluble impurities are removed by filtration in hot
of compound and type of impurities present in it. condition.
The following methods are commonly used for  If a compound is highly soluble in one solvent and
purification very little soluble in another solvent, then crystallisation
1) Sublimation 2) Crystallisation is carried out by using mixture of these solvents.
3) Distillation  Impurities, which impart colour are removed by
4) Solvent extraction (differential extraction) adsorbing over activated charcoal.
5) Chromatography.  Repeated crystallisation is required if organic
Note: Most of the pure compounds contains sharp compound contains impurities of comparable
Melting point & Boiling points. solubilities.
Sublimation :  The process of separation of different components
“The process of conversion of solid sublimate to of a mixture by repeated crystallisation is called
vapour state directly by heating without passing fractional crystallisation.
through liquid state is called sublimation”.  Fractional crystallisation is used for separation of
two or more soluble substances which have different
solid vapour
solubilities in the same solvent.
 This method is used for purification of solids
 Most commonly used solvents for crystallisation are
 Sublimation process is used for separation of sublimable
water, alcohol, ether, chloroform, carbontetrachloride,
volatile compounds from non sublimable impurities.
acetone, benzene, petroleum ether.
 Sublimation is generally used for purification of
 Sugar having an impurity of common salt can be
camphor, napthalene, Anthracene, Benzoic acid,
crystallised from hot ethanol, since sugar dissolves
phthalic anhydride, Anthraquinone, Indigo, Iodine,
in hot ethanol but common salt does not.
HgCl2, solid SO2.
 Fractional crystallisation can be used to separate a
Crystallisation : mixutre of KClO3 (less soluble) and KCl (more
 It is used for purification of solid organic soluble).
compounds.
GENERAL ORGANIC CHEMISTRY 185
EX.1: How is ethyl alcohol purified from
Distillation :
methylated spirit.
 Distillation in an important method used to separate Sol. Methylated spirit is ethyl alcohol contaminated
i) Volatile liquids from non volatile impurities. mainly with methyl alcohol.
ii) Liquids having sufficient difference in boiling points. Ethyl alcohol is purified by fractional distillation since
Simple Distillation : the difference in boiling point is less.
This process is used for purification of liquids which Distillation Under Reduced Pressure
does not undergo decomposition at their boiling points.
(Vacuum Distillation) :
 The vapourisation of a liquid by heating and
 This method is used to purify liquids having very
subsequent condensation of vapours by cooling is
high boiling points, which decompose at or below
known as distillation.
their boiling points.
 Liquid mixture is taken in a round bottom flask and
 These liquids are made to boil at a temperature lower
heated carefully, the vapour component with lower
than their normal boiling point by reducing pressure on
boiling point distills first, the vapour formed is
their surface with the help of vacuum pump.
condensed by using condenser and the liquid is
 Glycerine H2O2, formaldehyde are purified by
collected in a receiver. The vapours of component
vacuum distillation.
with higher boiling point distills latter.
 Glycerol can be separated from spent-lye in soap
 The liquids that have boiling point difference greater
industry by using vacuum distillation.
than 400C can be purified by this method.
 Sugar cane juice is concentrated in sugar industry
Eg:
by evaporation under reduced pressure which
i) Chloroform (B.P. 334 K) & Aniline (B.P. 457 K)
saves lot of fuel.
ii) Ether (B.P. 308 K)& Toluene (B.P. 384 K)
iii) Benzene (B.P. 353 K)& Aniline(B.P. 475 K) Steam Distillation :
Fractional Distillation :  This method is used for separation and purification
of organic compounds (solids or liquids) which
 Fractional distillation is used if the difference in
i) are steam volatile
boiling point of two liquids is less than 400 C . ii) are insoluble in water.
 Vapours of liquid mixture are passed through iii) Posess high vapour pressure (10-15 mm of Hg
fractionating column before condensation,which is at 373 K)
fitted over mouth of the round bottom flask. iv) Contains non valatile impurities.
 Vapours of liquid with higher boiling point condense  Steam distillation is based on Dalton’s law of partial
before the vapours of liquid with lower boiling point, pressure i.e., P = P1 + P2. where P = Atmospheric
the vapours raising up in the fractionating column is pressure
richer in more volatile component. P1 = Vapour pressure of organic liquid
 Fractionating column provides many surfaces for P2 = Vapour pressure due to water.
heat exchange between ascending vapours and  Compounds which can be purified by steam
descending condensed liquid. distillation are aniline, nitrobenzene, bromobenzene,
 Each successive condensation and vapourisation unit o-nitrophenol, o-hydroxy benzaldehyde
in the fractionating column is called a theoritical plate. (salicylaldehyde), o-hydroxy acetophenone,
 Liquids forming a constant boiling mixture turpentine oil, essential oils.
(azeotropic mixture) can not be separated by this EX.2: Mention about the purification of (a) aniline
method. and (b) naphthalene
 Fractional distillation is used to separate different Sol. a)Aniline can be purified by steam distillation because
fractions of crude oil in petroleum industry. it is immiscible with water and steam volatile.
 This method is used for separation of mixture of b) Naphthalene can be purified by sublimation
acetone (B.P. 330K) and methyl alcohol (B.P. 338K) because it changes on heating directly to vapour state
 Mixture of benzene and toluene can be separated and on cooling, it changes back into solid form.
by fractional distillation.

186 GENERAL ORGANIC CHEMISTRY


“Chroma’’ means colour and “graphy’’ means
Solvent Extraction (Differential Extraction) :
writing.
 Definition: The process of isolating an organic  This method was first used for separation of
compound from its aqueous solution by shaking coloured substances found in plants.
with a suitable solvent is called differential extraction.  This method was described by Tswett.
It is also called solvent extraction  This Technique consists of two phases one is
 When an organic compound is present in an stationary phase of large surface area while the
aqueous medium, then it is separated by shaking it second is moving phase which is allowed to move
with an organic solvent in which it is more soluble slowly over the stationary phase.
than in water.  Stationary phase is either liquid or solid, while
 Solvent should be immiscible with water and organic moving phase may be liquid or gas.
compound to be separated should be highly soluble  The technique of chromatography is based on the
in it. rates at which the components of the mixture moves
 Organic solvent and aqueous solution are immiscible through a porous medium (called stationary phase)
with each other, so they can form two distinct layers under the influence of some solvent (or) gas (called
which can be separated by separatory funnel. mobile phase).
 Organic solvent is distilled or evaporated to get  Mixture of substances is applied on a stationary
organic compound. phase which may be solid or liquid. A pure solvent,
 If organic compound is less soluble in organic a mixture of solvents or a gas is allowed to move
solvent then large quantity of solvent is required to slowly over the stationary phase, the components
extract small quantity of compound, which is said of the mixture get gradually separated from one
to be continuous extraction. another.
 Benzoic acid can be extracted from its aqueous  Recovery of separated substances by using suitable
solution using benzene as solvent. solvent is known as elution. The solvent used is
 Ether is a better solvent in differential extraction known as eluant.
due to :
i) its less polarity ii) least reactivity S. Chromatography Stationary Mobile
iii) less boiling point No. Process Phase Phase
iv) higher solubility of organic compounds 1. Column
Separation by Chemical Methods : chromatography Solid Liquid
(Adsorption)
 It is used for mixture of substances which are
chemically different. 2. Liquid-liquid
Eg: 1) Separation of acidic and basic compounds partition Liquid Liquid
of coal-tar. chromatography

2) HC CH
ammonical dil.
CuC CCu HCl HC CH 3. Paper Liquid Liquid
(impure) Cu Cl
2 2 (red ppt.) (pure) chromatography
Ca(OH)2 conc. 4. Thin layer Liquid(or) Liqid
3) Pyroligneous Ca(OH) Calcium CH3OOH
HCl chromatography solid
Acid acetate
(from wood distillation industry) (TLC)
4) CH3OH Methyl oxalate NaOH(aq) CH3OH 5. Gas-liquid Liquid Gas
(Impure) (Crystalline) (pure) chromatography
(GLC)
Chromatography :
6. Gas-solid
 This method is used for separation of mixtures into chromatography Solid Gas
their components, purification of compounds and (GSC)
also to test the purity of compounds.
7. Ionic change Solid Liquid
 Chromatography is obtaind from the greek word chromatography

GENERAL ORGANIC CHEMISTRY 187


 Based on the principle involved chromatography
is classified in to
a) Adsorption chromatography and
b) partition chromatography.
a. Adsorption Chromatography :
 Adsorption chromatography is based on the fact Y
that different compounds are adsorbed on an X
adsorbent to different degrees.
 Commonly used adsorbents are sillica gel, alumina,
magnesium oxide, cellulose powder, activated (base line)
animal charcoal.
 When a mobile phase is allowed to move over
stationary phase, the components of the mixture
Distance moved by the substance from base line (x)
move by varying distances over stationary phase. Rf 
Distance moved by the solvent from base line (y)
 There are two main types of chromatographic
 The spots of coloured compounds are visible on
techniques based on principle of differential
TLC plate due to their original colour.
adsorption
 The colourless compound which fluroscene are
(i) Column chromatography and
detected with ultraviolet light
(ii) Thin layer chromatography (TLC)
 Spots of compounds are even detected by allowing
i) Column Chromatography
them to adsorb iodine, will show up as brown
 It involves separation of a mixture over a column
spots.
of adsorbent packed in a glass tube, which is fitted
 Some times an appropriate reagent is sprayed on
with stop cock at its lower end.
the plate.
 The mixture to be adsorbed on the adsorbent is
Eg: Amino acids are detected by spraying the plate
placed at the top of the stationary phase.
with ninhydrin solution.
 An appropriate eluant, which is a liquid or a mixture
of liquids is allowed to flow down the column slowly. Partition Chromatography :
 The most readily adsorbed substances are retained  Partition chromatography is based on continuous
near the top and others come down to various differential partitioning of components of a mixture
distances in the column. between stationary and mobile phases.
ii) Thin Layer Chromatography (TLC)  Paper chromatography is a type of partition
 It involves separation of substances of a mixture over chromatography.
a thin layer of an adsorbent coated on glass plate.  In paper chromatography a special quality paper
 The glass plate is coated with adsorbent (ex: silica known as chromatography paper is used.
gel, alumina) as a thin layer (about 0.2mm thick) is  In Chromatography paper, cellulose helps as inert
called chromatography plate or chroma plate . support, and water absorbed from air on to
 The solution of mixture to be separated is applied hydroxyl groups of cellulose acts as stationary
as small spot about 2cm above from one end of phase.
the TLC plate.  The chromatography paper spotted with the
 The glass plate is placed in a closed jar containing solution of mixture at the base is suspended in a
the eluant, as the eluant rises up, the components suitable solvent or mixture of solvents, this solvent
of the mixture move up along the eluant to different (s) acts as mobile phase.
distances depending on their degree of adsorption  The solvent rises up the paper by capillary action
and separation takes place. and flows over the spot.
 The relative adsorption of each component of the  The paper selectively retains different components
mixture is expressed in terms of its retardation according to their differing partition in the two
phases. The paper strip so developed is called
factor i.e, R f value. chromatogram.

188 GENERAL ORGANIC CHEMISTRY


 The spots of the separated coloured compounds  Water vapours turn anhydrous copper sulphate in
are visible at different heights from the position of to blue.
initial spot on the chromatogram. CuSO  5 H 2O  CuSO4 .5H 2O
4
 The spots of the separated colourless compounds anhydrous hydrated
 colour less   blue 
may be observed either under ultraviolet light or
by the use of appropriate spraying agent. Detection of Nitrogen, Sulphur
Additional Information : Halogens & Phosphorus :
Applications of Chromatography :  Nitrogen, sulphur, halogens and phosphorus
I) i) In Chemical Industry column chromatography present in an organic compound are detected
is used for separation of required components by Lassaigne’s test.
obtained after synthesis.  Organic compounds are fused with dry sodium in
ii) TLC is useful for monitoring large scale column fusion tube and fused mass after extraction with
chromatography. water is boiled and filtered, the filtrate is called
II) Pharmaceutical industry : Chromatography is sodium fusion extract.
used for separation of chiral compounds to  During prepartion of sodium fusion extract covalent
obtained pharmaceutically active optical isomer. compound is converted into ionic compound.
III) Food Industry : Chromatography techniques are  The following reactions takes place
used for quality control in food industry. It is used 
Na  C  N   NaCN
to determine presence and to separate additives, 
flavours etc. It is also used to detect presence of 2Na  S   Na2 S
contaminents like mould, bacteria in food. 
2 Na  X 2   2 NaX (X=Cl,Br or I)
IV) Environment - Testing Lab : Presence and
quality of pollutants in air and drinking water can Test for Nitrogen :
be determined by chromatography technique. Sodiumfusion extract is boiled with freshly
V) Diagnostic Technique : Presence of certain drugs prepared ferrous sulphate ( FeSO4 )solution and
and the marker compounds for medical diagnosis
then acidified with concentrated sulphuric acid. The
in blood and urine are determined.
formation of prussian blue colour confirms the
Qualitative Analysis of Organic presence of nitrogen.
Compounds (Detection of Elements) : 2 NaCN  FeSO4  Fe(CN )2  Na2 SO4
 The qualitative analysis of an organic compound Fe(CN )2  4 NaCN  Na4 [ Fe(CN )6 ]
involves detection of all elements present in it.
sodium hexacyano ferrate(II)
Detection of Carbon and Hydrogen : On heating with concentrated sulphuric acid some
 Carbon and hydrogen are detected by heating the Iron(II) ions are oxidised to Iron(III)
compound with cupric oxide (CuO). ion, which reacts with sodium hexacyano ferrate(II)
 Carbon present in the compound is oxidised to to produce Iron (III)
carbondioxide, which turns lime water milky. hexacyanoferrate(II) (ferric ferrocyanide) which is
 Hydrogen present in the compound is converted in prussian blue in colour.
to water, which turns anhydrous copper sulphate 3 Na4 [ Fe(CN )6 ]  2 Fe2 ( SO4 )3
into blue.
 Fe4 [ Fe(CN )6 ]3  6 Na2 SO4
C  2CuO  2Cu  CO2

ferricferrocyanide (prussianblue)
H 2  CuO  Cu  H 2O  This test fails in case of diazo compounds.

 If the amount of nitrogen present is less, then
 Carbondioxide turns lime water milky.
prussian blue is present in collodial form and the
Ca(OH )2  CO2  CaCO3  H 2O solution looks green.
(milky)

GENERAL ORGANIC CHEMISTRY 189


EX.3: Hydrazine does not give Lassaigne’s test. NaCl  AgNO3  AgCl   NaNO3
Why ?
(white ppt)
Sol. In the Lassaigne’s test, nitrogen is converted to
cyanide by combining with carbon of the AgCl  2 NH 4OH  [ Ag ( NH3 )2 ]Cl  2H 2O
compound. Hydrazine does not contain carbon and (soluble complex)
hence cyanide cannot form. ii) Yellowish precipitate, sparingly soluble in
EX.4: Why diazonium salts do not show positive ammonium hydroxide indicates presence of bromine
Lassaigne’s test for nitrogen ? NaBr  AgNO3  AgBr   NaNO3
Sol. Diazonium salts are unstable and lose nitrogen as
yellowish ppt
N 2 gas on heating. Hence during fusion, no sodium iii) Yellow precipitate, insoluble in ammonium
cyanide is formed in Lassaigne’s extract due to the hydroxide indicates presence of Iodine.
loss of nitrogen. NaI  AgNO 3  AgI   NaNO3
Test for Sulphur : yellow
a) Sodium fusion extract is acidified with acetic acid precipitate
and lead acetate is added to it, a black precipitate  Nitrogen and sulphur are also present in the
of lead sulphide is formed, which indicates compound, the sodiumfusion extract is boiled with
presence of sulphur. concentrated nitric acid to decompose sodium
Na2 S  (CH 3COO ) 2 Pb  PbS  2CH 3COONa cyanide & sodium sulphide formed during
black Lassaigne’s test , otherwise they interfere with silver
b) Sodium fusion extract is treated with freshly nitrate test for halogens.
prepared sodium nitroprusside, appearance of NaCN  HNO3  NaNO3  HCN 
violet colour (purple) indicates presence of sulphur. Na2 S  2 HNO3  2 NaNO3  H 2 S 
Na2 S  Na2 [ Fe(CN )5 NO ]  Na4 [ Fe(CN )5 NOS ]
 If NaCN and Na2 S are not decomposed, then
(sodium nitro prusside) (violet)
 In case both nitrogen and sulphur are present in an white and black precipitates of AgCN and Ag 2 S
organic compound sodium thiocyanate is formed, are formed respectively with silver nitrate solution.
which gives blood red colour with neutral FeCl3 Beilstein’s Test :
solution. A copper wire flattened at one end is heated in an
oxidising flame of Bunsen burner. The heating is
Na  C  N  S  NaSCN
continued till it does not impart blue colour flame.
3NaSCN  FeCl3  Fe( SCN )3  3NaCl The hot end of copper wire is now touched with
(blood red) the organic substance and is once again kept in
(or) flame, the appearance of green or blue colour
Fe 3  SCN   [ Fe( SCN )]2 indicates the presence of halogens in the organic
compound.
(blood red)
Limitations :
 If sodium fusion is carried out with excess of sodium,
a) Substances such as urea, thiourea do not contain
the thiocyanate decomposes to yield cyanide and
halogens but gives this test.
sulphide, these ions gives their usual tests.
b) It does not tells which halogen is present in
NaSCN  2 Na  NaCN  Na2 S organic compound.
Test for Halogens : Chlorine Water Test for Bromine and
 Sodiumfusion extract is acidified with nitric acid and Iodine :
then treated with silver nitrate solution.  Both AgBr and AgI are yellow precipitates, it is
i) White precipitate, soluble in ammonium
a littile bit difficult to identify given halogen in bromine
hydroxide indicates presence of chlorine.
or iodine, to confirm it chlorine water test is used.

190 GENERAL ORGANIC CHEMISTRY


 Sodium fusion extract is acidified with dilute
Quantitative Analysis :
H 2 SO4 (or) HNO3 , to this 1(or) 2ml of It involves the estimation of percentage composition
chloroform (or) Carbon tetrachloride is added and of various elements by suitable methods.
then excess of chlorine water is added with constant
shaking. Estimation of Carbon and Hydrogen :
i) If chloroform (or) carbon tetrachloride layer  Carbon and hydrogen are estimated by Liebig’s
becomes yellow (or) brown indicates presence of combustion method.
bromine.  A known mass of an organic compound is burnt in
the presence of excess of oxygen
2 NaBr  Cl2  2 NaCl  Br2
(free from CO2) and Cupric oxide (CuO)
Br2 dissolves in chloroform (or)  Carbon and hydrogen present in the compound are
carbontetrachloride gives yellow (or) brown colour. oxidised to CO2 and H2O respectively
ii) If chloroform (or) carbon tetra chloride layer
 y y
becomes violet indicates presence of iodine. C x H y   x   O2  
 xCO2  H 2O
 4 2
2 NaI  Cl2  2 NaCl  I 2
 CO2 and H2O produced are weighed by absorbing
I 2 dissolves in chloroform (or) carbontetrachloride in concentrated solution of potassium hydroxide
gives violet colour. and anhydrous calcium chloride (or) magnesium
 Presence of NaCN (or) Na2 S in sodium fusion perchlorate respectively
extract does not interfere in this test. 12 weight of CO2 formed
%C    100
44 weight of organic Compound
Test for Phosphorus :
The compound is heated with oxidising agent 2 weight of H 2O formed
%H    100
(sodium peroxide) or with fusion mixture (sodium 18 weight of organic Compound
carbonate and potassium nitrate) phosphorus EX.5: On complete combustion, 0.246g of an
present in the compound is oxidised to sodium organic compound gave 0.198g of carbon
phosphate. The solution is boiled with nitric acid dioxide and 0.1014g of water. Determine the
and then treated with ammonium molybdate, a percentage composition of carbon and
canary yellow (ammonium phospho molybdate) hydrogen in the compound.
precipitate formation (or) yellow colouration 12  0.198  100
indicates presence of phosphorus. Sol. % of carbon =  21.95
44  0.246
2 P  5 Na2O2  2 Na3 PO4  2 Na2O
 2  0.1014  100
% of hydrogen =  4.58
Na3 PO4  3HNO3  H 3 PO4  3NaNO3 18  0.246
H 3 PO4  12( NH 4 ) 2 MoO4  21HNO3  Estimation of Nitrogen :
( NH 4 )3 PO4 .12MoO3  21NH 4 NO3  12 H 2O Nitrogen present in organic compound is estimated by
a) Dumas method b) Kjeldahl’s method
(ammonium phospho molybdate)
Dumas Method :
Test for Oxygen :  In this method nitrogen present in the organic
 There is no direct test for oxygen. compound is converted in to N2(molecular
 If organic compound is heated in a dry test tube in nitrogen)
nitrogen atmosphere, if water droplets are formed  A weighed amount of organic compound is heated
on the walls of the test tube indicates presence of with cupric oxide in an atmosphere of
oxygen. carbondioxide
 Presence of oxygen can be known by testing  Carbon and hydrogen present in the compound are
functional groups containing oxygen. oxidised to CO2 and H 2O , while N 2 is set free.
Eg: –OH, –COOH, –CHO, –NO2 etc

GENERAL ORGANIC CHEMISTRY 191


 Some oxides of nitrogen formed are reduced to % of nitrogen =
free nitrogen by passing over heated copper gauze 28 vol.of N 2 at STP
  100
 y 22400 wt.of organic compound
C x H y N z   2 x   CuO 
 2 28 41.9
=   100  17.46
y z  y 22400 0.3
xCO2  H 2O  N 2   2 x   Cu
2 2  2 22400 ml of dinitrogen at STP weigh = 28g

 Oxides of nitrogen + Cu  N 2  CuO 28  41.9


41.9 ml dinitrogen at STP weight = g
22400
 The mixture of gases produced is collected over
caustic potash solution (KOH solution) which 28  41.9
0.3 g of organic compound contains g
absorbs CO2. 22400
 Nitrogen is collected in the upper part of nitro meter.
of N 2
28 Volume of nitrogen in ml at STP
%N    100 100 g of organic compound contain
22400 Weight of organic compound
28  41.9 100
EX.6: 0.25g of an organic compound gave 30cm 3   17.46
22400 0.3
of moist dinitrogen at 288 K and 745 mm
presure. Calculate the percentage of nitrogen. percentage of nitrogen = 17.46
(Aqueous tension at 288K=12.7mm) Kjeldahl’s Method :
Sol. Mass of the substance = 0.25g  In this method nitrogen present in the organic
Volume of moist dinitrogen = 30cm 3 compound is converted in to ammonia (NH3)
 A known mass of organic compound containing
Temperature = 288K
nitrogen is heated with concentrated sulphuric acid
Pressure = 745 -12.7 = 732.3mm
in presence of K2SO4 and CuSO4 then nitrogen
Volume of dinitrogen at STP :
present in the compound is converted in to
PV T 732.3  30  273 ammonium sulphate.
V2  1 1
 2   27.4cm3
T1 P2 288  760  Organic compound + H 2 SO4   NH 4 2 SO4
Percentage of nitrogen in organic compound =  The resulting solution is distilled with excess of
28 vol.of N2 at STP sodium hydroxide
 100
22400 wt.of organiccompound  NH 4 2 SO4  2 NaOH  Na2 SO4  2 NH 3  2H 2O
 Ammonia evolved is absorbed in a known but
28 27.4
  100  13.6 excess volume of standard HCl (or)
22400 0.25 H2SO4solution.
EX.7: 0.3g of an organic compound gave 50ml.  The acid left unreacted is estimated by titration
nitrogen at 270C and 715mm pressure. If the against standard solution of sodium hydroxide.
aqueous tension at 270C is 15mm, calculate Percentage of Nitrogen =
the percentage compoistion of nitrogen in the
14 VN
compound.   100
1000 wt. of organic compound
Sol. Mass of the substance = 0.3g
Volume of the moist dinitrogen=50ml 1.4  V  N
%N 
Temperature = 27 0 C = 27+273 = 300K Weight of organic compound
Pressure = 715 - 15 = 700mm Where V = Volume of acid in ml neutralised by
Volume of dintrogen at STP : ammonia
PV
1 1 T 700  50  273 N = Normality of acid.
v2   2   41.9ml
T1 P2 760  300  This method is simpler and more convenient
 It is mainly used to find percentage of nitrogen

192 GENERAL ORGANIC CHEMISTRY


present in food stuffs, soils, fertilizers and various m. eq of H 2 SO4 unused = 20 - 15.4 = 4.6
agricultural products.
% of nitrogen =
 This method is not applicable to compounds
containing nitro (-NO2), Nitroso (NO), azo group 1.4  m.eq. of H 2 SO4 unused 1.4  4.6
  12.88
O
wt.of organic compound 0.5
  
  N  N  
  N  N   , azoxy compounds   Estimation of Halogens Carius Method :
   A weighed amount of an organic compound is
heated with fuming nitric acid in the presence of
silver nitrate contained in a hard glass tube known
and nitrogen present in the ring (pyridine , as carius tube.
N  Carbon and hydrogen present in the compound is
converted in to CO2 and H2O.
 Halogen present in the organic compound is
quinoline ) because nitrogen converted in to silver halide.
N  The precipitate is washed, dried and weighed.
present in these compounds is not quantitatively Percentage of halogen =
converted in to ammonium sulphate. Atomicweightof halogen Weightof silverhalide formed
EX.8: In Kjeldahl’s estimation of nitrogen, the  100
Mwtof
. silverhalide Weightof organiccompound
ammonia evolved from 0.5g of an organic
35.5 wt. of AgCl formed
compound neutralised 10ml of 1M H 2 SO4 . %Cl    100
143.5 Wt. of organic compound
Calculate the percentage of nitrogen in the
compound. 80 wt. of AgBr formed
% Br   100
Sol. 10 ml of 1M H 2 SO4 = 20ml of M NH 3 188 Wt. of organic compound
1000 ml of 1M ammonia contains 14g nitrogen 127 Wt. of AgI formed
%I   100
14  20 235 Wt. of organic compound
20 ml of 1M ammonia contains g N2
1000 EX.10: In Carius method, 0.1890g of an organic
14  20 100 compound gave 0.2870g of silver chloride.
% of nitrogen =  56.0 Calculate the percentage of chlorine in the
1000  0.5
compound.
EX.9: In Kjeldahl’s estimation of nitrogen, the
Sol. Weight of subtance = 0.1890g
ammonia obtained from 0.5g of an organic
Weight of silver chloride = 0.2870g
substance was passed into 100cm 3 of
M weigh of AgCl  35.5  100
H 2 SO4 . The excess of acid required % of chlorine = weight of subtance 143.5
10
M 0.2870  35.5  100
154 cm3 of NaOH for neutralisation.   37.8
10 0.1890  143.5
calculate the percentage of nitrogen in the
EX.11: One gram of a bromoalkane on heating
compound.
with excess silver nitrate in Carius tube
Sol. m eq. of H 2 SO4 taken = molarity x basicity x method gave 0.94g of yellow precipitate. What
volume (ml) is the percent weight of halogen ?
1 Sol. Weight of subtance = 1g Yellow precipitate is
=  2  100  20 AgBr ; Weight of AgBr = 0.94g
10
1 0.94  80  100
m.eq of NaOH =  1154  15.4 % of Bromine =  40
10 1188

GENERAL ORGANIC CHEMISTRY 193


EX.12: In carius method of estimation of halogen.  Phosphoric acid is precipitated as magnesium
0.15g of an organic compound gave 0.12g of ammonium phosphate (Mg NH4 PO4), by addition
AgBr. Find out the percentage of bromine in of magnesia mixture (MgCl2 + NH4OH + NH4Cl)
the compound.  Magnesium ammonium phosphate is washed, dried
80  0.12  100 and it is heated strongly to get magnesium
Sol. % of bromine =  34.04
188  0.15 pyrophosphate  Mg2 P2O7  .
Magnesia m i x ture
Estimation of Sulphur Carius method: H PO
3 4   Mg NH 4 PO4
 Phosphoric acid   Magnesium ammonium phosphate 
 A weighed amount of organic compound is heated
in a carius tube with sodium peroxide or fuming 2MgNH 4 PO4 

 Mg 2 P2O7  2 NH 3  H 2O
nitric acid. (Magnesium Pyrophosphate)
 Sulphur present in the compound is oxidised in to 62 wt. of Mg 2 P2O7 formed
sulphuric acid, which is treated with BaCl2 solution %P    100
222 wt. of organic compound
gives precipitate of BaSO4.
 It is filtered, the precipitate is washed, dried and  Phosphoric acid is precipitated as ammonium
weighed. phospho molybdate  NH 4 3 PO4 .12MoO3 by
adding ammonia and ammonium molybdate.
Atomic wt. of sulphur wt of BaSO4 formed (Molecular mass of (NH4)3PO4.12MoO3 = 1877)
%S    100
Mol. wt. of BaSO4 wt. of organic compound
31 wt of  NH 4 3 PO4 .12 MoO3 formed
%P   100
32 wt of BaSO4 formed 1877 wt. of organic compound
%S    100
233 wt. of organic compound
Estimation of Oxygen :
EX.13: In sulphur estimation, 0.157 g of an organic
 Usually percentage of oxygen in organic compound
compound gave 0.4813 g of barium sulphate. is determined by method of difference
What is the percentage of sulphur in the % of oxygen = 100 - (sum of the percentages of all
compound ? other elements)
Sol. 233g BaSO4 contain 32g sulphur  Oxygen present in the organic compound is
estimated by Aluise’s method.
32  0.4813
0.4813g BaSO4 contain g sulphur  A known amount of organic compound is
233 subjected to pyrolysis in a stream of nitrogen.
32  0.4813 100  The mixture of gaseous products containg oxygen
% of suphur =  42.10 is passed over red-hot coke, then all the oxygen is
233  0.157
EX.14: On heating 0.2g of an organic compound converted in to carbon monoxide.
with a mixture of barium chloirde and nitric compound 

 O2  other gaseous products
acid, 0.466g of barium sulphate was obtained. 1373 K
2C  O2   2CO
Calculate the percentage of sulphur.
Sol. Weight of substance = 0.2g  CO formed is quantitatively converted in to CO2
Weight of barium sulphate = 0.466g by passing over warm Iodine pentoxide  I 2O5 
Weight percentage of sulphur =
5CO  I 2O5  I 2  5CO2
0.466  32 100
 32
0.2  233 The resulting gaseous mixture  CO2 and I 2  is

Estimation of Phosphorus Carius passed through potassium iodide solution, which


absorbs iodine, and then passed over KOH to
Method : absorb CO2.
A weighed amount of organic compound is heated
16 wt . of CO2 formed
with fuming nitric acid, then phosphorus present in % of oxygen    100
44 wt . of organic compound
the compound is oxidised to phosphoric acid.
194 GENERAL ORGANIC CHEMISTRY
EX.15: 0.2g of an organic compound on analysis
Platinic Chloride Method for Bases :
gave 0.147g of carbondioxide, 0.12g of water
and 74.6 c.c of nitrogen at S.T.P. Calculate the  Organic bases combines with chloroplatinic acid
weight percentages of constituents.  H 2 PtCl6  to form insoluble platinichloride,
Sol. Weight of compound = W=0.2g which on ignition gives metallic platinum.
Weight of CO2  W1  0.147 g  If ‘B’ is mono acidic base then formula of saltwill
Weight of H 2O  W2  0.12 g be B2 H 2 Pt Cl6 .
Volume of N 2 at STP = 74.6 c.c. B2 H 2 Pt Cl6 

 Pt
% of carbon = Molecular mass of platinum salt Mass of platinum salt

Atomic mass of platinum Mass of platinum
W1  12  100 0.147  12  100
  20.04% If E in equivalent weight of base then
W  44 0.2  44
% of Hydrogen = 2 E  410 Mass of platinum salt

195 Mass of platinum
W 2  2  100 0.12  2  100
  6.66%
W  18 0.2  18 1  Mass of platinum salt 
% of Nitrogen = E  195  410 
2  Mass of platinum 
V2  28  100 7 4 .6
  4 6 .6 3 % Molecular mass of base = Equivalent mass of base
W  22400 8  0 .2 x acidity
Remaining is oxygen.
Emperical Formula :
% of Oxygen = 100   %C  % H  % N 
 The simplest whole number ratio between the atoms
= 100  73.33  26.67% of various elements present in one molecule of a
Note: Presently estimation of elements (C, H and substance is called emperical formula.
N) in organic compound is estimated by using Calculation of Emperical Formula :
CHN elemental analyser by taking very small The steps involved are
amount of substance (1-3 mg), results are displayed  Divide mass percentage of each element by its
on screen with in short time. atomic mass, gives relative number of atoms.
Chemical Methods Used to Find  Simplest ratio is obtained when the figures obtained
is divided by lowest number.
Molecular Mass Silver Salt Method  If the simplest ratio obtained is not a whole number
for Acids : ratio, then multiply all the figures with suitable integer
Organic acid form insoluble silver salts, which on to get simplest whole number ratio
heating undergoes decomposition to leave a residue  Write symbols of various elements side by side with
of metallic silver. above numbers at the lower right corner of each,
RCOO Ag   Ag which is emperical formula of compound.

Silver salt Silver  residue 
Molecular Formula :
Equivalent wt of silver salt mass of silver salt
 The actual number of atoms present in one molecule
Equivalent wt. of silver Mass of silver of a substance is called molecular formula.
E  108  1 Mass of silver salt Molecular formula = (Emperical formula)n
 where
108 Mass of silver
 Mass of silver salt  Molecular wt. of thecompound
E 108  107 n
Emperical formula weight of thecompound
 Mass of silver 
Molecular weight of acid = Equivalent weight of  If vapour density is given then molecular weight =
acid(E) x basicity. 2 x vapour density.

GENERAL ORGANIC CHEMISTRY 195


Determination of Molecular Formula of  The volume of air displaced is calculated at STP
Gaseous Hydrocarbons (Eudiometry) : PV
1 1 PV2 2
 Eudiometry is a direct method used to find condition by using T  T
1 2
molecular formula of gaseous hydrocarbon without
Mol. mass of volatile substance =
finding percentage composition of elements and its
molecular weight. Mass of substance taken
 22400
 A known volume of gaseous hydrocarbon is mixed Volume of air displaced in ml at STP
with excess of pure and dry oxygen in eudiometer
tube placed inverted in a trough of mercury.
 The mixture is exploded by passing an electric spark
between platinum electrodes. As a result carbon
Methods of PUrification of Organic
and hydrogen of hydrocarbon are oxidised to CO2
and H2O vapour respectively. Compounds
 The tube is allowed to cool to room temperature, then 1. A mixture of camphor and KCl can be
water vapour is condensed in to liquid water, whose separated by
volume occupied is almost negligible. Thus the gaseous 1) Evaporation 2) Sublimation
mixture left in eudiometer tube is CO2 and O2. 3) Filtration 4) Decantation
 Caustic potash solution is then introduced in to 2. Impure Naphthalene is purified by
eudiometer tube which absorbs CO2 completely. 1) Fractional crystallisation
The gas left is unused O2. 2) Fractional distillation
3) solvent extraction 4) Sublimation
2NaOH  CO2  Na2CO3  H 2O
3. Which of the following method is used for the
 Decrease in volume on introducing KOH solution purification of solids
gives volume of CO2 used. 1) Distillation under reduced pressure
 Some times volume of O2 left unused is found by 2) Distillation
introducing pyrogallol and noting the decreasein volume. 3) Steam distillation
 Let molecular formula of gaseous hydrocarbon is 4) Sublimation
C x H y . On combustion one volume of it forms 4. Simple distillation can be used to separate liquids
‘x’volumes of CO2 & ‘y/2 ’volumes of water vapour. which differ in their boiling points at least by
1) 50 C 2) 100 C
 y y
Cx H y   x   O2  xCO2  H 2O 3) 400 C-500 C 4) 1000C
 4  2
5. Simple distillation of liquids involves
 y simultaneously
1 vol  x   vol x vol y/2 vol
 4 1) Vapourisation and condensation
 For 1 volume of hydro carbon 2) Condensation and vapourisation
 y 3) Vapourisation and sublimation
Volume of O2 used =  x   vol 4) Sublimation and condensation
 4
Volume of CO2 produced = x vol. 6. A mixture of benzene and toluene can be
separated by
y 1) Crystallization 2) Solubility
Contraction on explosion and cooling = 1 
4 3) Separating funnel 4) Fractional distillation
(volume of liquid water is neglected) 7. The best and latest technique for isolation,
Determination of Molecular Mass by purification and separation of organic
compounds is
Victor Meyer’s Method : 1) Crystallization 2) distillation
 A known mass of the volatile substance is 3) sublimation 4) chromatography
vapourised in victor meyer’s method. 8. Chromatographic technique is used for the
 The vapours obtained displaces an equal volume separation is
of air in to graduated tube.
196 GENERAL ORGANIC CHEMISTRY
1) Camphor 2) Alcohol & Water 19. For which of the following compounds the
3) Acetone and Methanol 4) Plant pigments Lassaigne’s test for the detection of nitrogen
9. Chromatography is a technique based on will fail
1) Solubilities of solute 1) H 2 N  CO  NH 2
2) Adsorption of solute
3) Chemical adsorption followed by dispersion 2) C6 H 5  NH  NH 2 HCl
4) Differential adsorption of different constitents of 3) NH 2  NH 2 HCl
a mixture
10. A very common adsorbent used in column 4) H 2 N  CO  NH  NH 2 .HCl
chromatography is 20. Organic compound is fused with metallic
1) Powderd charcoal 2) Silica gel sodium for testing nitrogen, sulphur and
3) Chalk 4) Sodium carbonate halogens because
11. In column chromatography, the moving phase 1) To make the solution alkaline
consists 2) To convert into elemental state of nitrogen,
1) A substance which is to be separated sulphur and halogens
2) Mixture of eluent and substance to be separated 3) To convert covalent compound in to ionic
3) eluent compound
4) Absorbent 4) To decrease fusion temperature
12. The relative adsorption of each component of 21. In Lassaigne’s extract, nitrogen in organic
the mixture is expressed in terms of compound is converted to
1) Adsorption factor 2) Retardation factor 1) N2 2) NH3 3) NO 4) CN–
3) Co-factor 4) Sorption factor 22. The compound not formed in the positive test
13. Paper chromatography is for nitrogen with the Lassaigne’s solution of
1) Adsorption chromatography an organic compound is
2) Partition chromatography a) Fe4[Fe(CN)6]3 b) Na3[Fe(CN)6]
3) Ion exchange chromatography c) Fe(CN)3 d) Na3[Fe(CN)5NOS]
4) all of these 1) b, c, d 2) a, b 3) a, b, c 4) a only
14. In paper chromatogrpahy 23. The Lassaigne’s solution when heated with
1) Moving phase is liquid and stationary phase is solid ferrous sulphate and acidified with sulphuric
2) Moving phase is liquid and stationary phase is liquid acid gave intense blue colour indicating the
3) Moving phase is solid and stationary phase is solid presence of nitrogen. The blue colour is due
4) Moving phase is solid and stationary phase is liquid to the formation of
Qualitative analysis of Organic Compounds : 1) Na4  Fe  CN 6  2) Fe3  Fe  CN 6 
2
15. In detection of CO2, lime water turns milky 3) Fe2  Fe  CN 6  4) Fe4  Fe  CN 6  3
due to formation of 24. In the Lassaigne’s test the Sulphur present in
1) CaO 2) CaCl2 the organic compound first changes into
3) CaCO3 4) Ca(HCO3)2 1) Na2SO3 2) CS2 3) Na2SO4 4) Na2S
16. H2O vapours on passing through anhydrous 25. When lassaigne’s extract (Na2S) is acidified
CuSO4 turns it to with acetic acid and then lead acetate solution
1) Green 2) Blue 3) Violet 4) White is added to it, the colour of the precipitate is
17. Lassaigne’s test is used in qualitative analysis 1) Blue 2) Black 3) Red 4) White
to detect 26. Sodium extract gives blood red colour when
1) Nitrogen 2) Sulphur treated with FeCl3. FOrmation of blood red
3) Chlorine 4) All of these colour confirms the presence of
18. Which of the following elements in an organic 1) Only nitrogen 2) Only sulphur
compound cannot be detected by Lassaigne’s test? 3) Only halogens
1) N 2) S 3) Cl 4) H 4) Both Nitrogen and Sulphur

GENERAL ORGANIC CHEMISTRY 197


27. The presence of halogen in an organic 37. In organic compounds, Sulphur is estimated
compound is detected by as
1) Iodoform test 2) Molisch’s test 1) BaSO4 2) BaCl2
3) Layer test 4) Million’s test 3) Ba3(PO4)2 4) H2SO4
28. ClCH2COOH is heated with fuming HNO3 in 38. Organic compound  heat
  O2 + other gases
the presence of AgNO3 in carius tube. After 2C+O2  2CO
fibration and washing a white precipitate is 5CO+I2O5  I2+5CO2 the reactions given
obtained. The precipitate is of above form is basis of direct estimation of
1) Ag2SO4 2) ClCH2COOAg 1) Nitrogen in organic compound
3) AgCl 4) AgCN 2) Oxygen in organic compound
29. The Blistein’s test is a rapid test used for 3) Phosphorus in organic compound
organic compounds to detect 4) Iodine in organic compound
1) Phosphorous 2) Sulphur 39. 1.4 g of hydrocarbon on combustion gasve 1.8g
3) Halogens 4) Nitrogen water. The empirical formula of hydrocarbon is
Quantitative Analysis of Organic 1) CH 2) CH2 3) CH3 4) CH4
40. Molecular weight of an organic acid is given by
Compounds
30. Percentage of carbon in an organic compound Equivalent weight Basicity
1) 2) Equivalent weight
is determined by Basicity
1) Duma’s method 2) Kjeldahl’s method 3) (Equivalent weight) x (Basicity)
3) Carius method 4) Liebig’s method 4) (Equivalent weight) x (valency)
31. In the Liebig’s method for the estimation of C
and H, the organic compound is fused with
1) CuO pellets 2) Copper turnings
3) Iron fillings 4) Zinc-copper couple 01) 2 02) 4 03) 4 04) 3 05) 1 06) 4
32. In Duma’s method nitrogen in organic 07) 4 08) 4 09) 4 10) 2 11) 2 12) 2
compound is estimated in the form of 13) 2 14) 2 15) 3 16) 2 17) 4 18) 4
1) N2 2) NO 3) NH3 4) N2O5 19) 3 20) 3 21) 4 22) 1 23) 4 24) 4
33. In Kjeldhl’s method of estimation of nitrogen, 25) 2 26) 4 27) 3 28) 3 29) 3 30) 4
copper sulphate act as 31) 1 32) 1 33) 3 34) 4 35) 2 36) 2
1) Oxidizing agent 2) Reducing agent 37) 1 38) 2 39) 2 40) 3
3) Catalytic agent 4) Hydrolysing agent
34. Kjeldhal’s method cannot be used for the
estimation of nitrogen in

1) C6 H5  N  N  C6 H5 2) Methods of PUrification of Organic


N
Compounds :
NO2 1. Organic liquid vapourises at a temperature
below its boiling point in steam distillation
because
3) 4) All of these
1) Mixture boils when sum of vapour pressure of
COOH water and organic liquid becomes equal to
35. In Kjeldahl’s method, nitrogen present in the atmospheric pressure.
organic compound is first converted into 2) Steam distillation is actually distillation under
1) NH3 2) (NH4)2SO4 3) N2 4) NO increased pressure.
36. Halogen can be estimated by 3) Water vapour does not contribute to its boiling
1) Duma’s method 2) Carius method point
3) Leibig’s method 4) All of these 4) Atmospheric pressure is reduced

198 GENERAL ORGANIC CHEMISTRY


2. A liquid which decomposes at or below its halogens because
boiling point can be purified by 1) To neutralise alkaline solution of sodium fusion
1) steam distillation 2) simple distillation extract.
3) fractional distillation 2) To convert sodium cyanide and sodium sulphide
4) distillation under reduced pressure into HCN and H2S which are volatile.
3. Which of the following statement is incorrect? 3) To convert sodium cyanide and sodium sulphide
1) Fixed melting point can be used to test the purity in to sodium thiocyanate.
of the solid organic compound 4) To get white precipitate of AgCN and black
2) Hydrogen peroxide is purified by steam 10. Assertion (A) : Potassium can be used in lassigned
distillation. test.
3) Impurities cause a decrease in the melting point Reason (R) : Potassium reacts vigorously.
of the compound 11. Assertion (A) : During test for nitrogen with
4) Crystallisation is based on sparingly solubility of Lassaigne extract on adding FeCl3 solution
compound at low temperature sometimes a red precipitate is obtained.
Assertion & Reason Reason (R) : Sulphur is also present.
1) If both A and B are true and the R is the Comprehension
correct explanation of the A. An organic compound was fused with sodium
2) If both A and R are true but R is not the metal and extracted with distilled water. On
correct explanation of the A. adding fresh prepared FeSO4 solution followed
3) If A is true but R is false by the addition of FeCl2 and dil. HCl produced
4) If A is false but R is true greenish blue solution. 0.30 g fo the organic
4. Assertion (A) : A mixture of plant pigments can compound after kjeldahlisation evolved a gas
be separated by chromatogrphy. (X) which was passed on 100ml of 0.1 M
Reason (R) : Chromatography is used for the H2SO4. The excess of acid required 20 ml of
separation of coloured substances into individual 0.5 M NaOH for neutralisation.
components. 12. The blue colour of solution is due to
5. Assertion (A) : Moving phase is liquid and
1) K 4  Fe  CN 6  2) Na3  Fe  CN 6 
stationary phase is solid in paper chromatography.
Reason (R) : Papaer chromatography is used for 3) Na2  Fe  CN 5 NO  4) Fe4  Fe  CN 6  3
analysis of polar organic compounds.
6. Assertion (A) : Thiphene present in commercial 13. Dil. HCl is added to the solution in the above
benzene as an impurity can be removed by shaking test to
the mixture with cold concentrated H2SO4. 1) make the solution acidic
Reason (R) : Thipohene is a heterocyclic 2) to dissolve FeSO4 3) to dissolve Fe(OH)2
aromatinc compound. 4) to change FeSO4 to FeCl2
7. Assertion (A) : Refining of petroleum involves 14. The gas X obtained during kjeldahlisation is
fractional distillation 1) N2 2) N2O 3) NH3 5) N2H4
Reason (R) : Fractional distillation involves 15. The amount of acid left after neutralisation with
repeated distillation. base is
1) 10 ml 2) 90 ml 3) 50 ml 5) 80 ml
Qualitative Analysis of Organic 16. The organic compound which suitably fits into
Compounds the above data is
8. The covalent compound which does not give 1) CH3CONH2 2) C6H5CONH2
positive test in Lassaigne’s test is
S
1) 1, 3-Dinitrobenzene 2) Glycine
3) Urea 4) Hydrazine 3) 4) H2N-CO-NH2
H 2 N-C-NH 2
9. Nitric acid is added to sodium extract and
boiled before adding silver nitrate to test

GENERAL ORGANIC CHEMISTRY 199


26. 0.73g of organic compound on oxidation gave
Qualitative Analysis of Organic
1.32g of carbondioxide. The percentage of
Compounds carbon in the given compound will be
17. 0.246g of an organic compound on complete 1) 49.32 2) 59.32 2) 29.32 4) 98.64
combustion gave 0.198g oc carbondioxide and 27. An organic compound has C and H percentage
0.1014g of water, then the percentage in the ratio 6:1 by mass and C and O percentage
composition of carbon and hydrogen in the in the ratio 3:4 by mass the compound is
compound respectively. 1) HCHO 2) CH3OH
1) 4.58, 21.95 2) 21.95, 4.58 3) CH3CH2OH 4) (COOH)2
3) 45.8, 2.195 4) 2.195, 45.8 28. Assertion (A) : During digestion with concentrated
18. 0.2033g of an organic compound in Dumas H2SO4 nitrogen of organic compound is converted
method gave 31.7 mL of moist N2 at 140C and into (NH4)2SO4
758 mm pressure. Percentage of N2 in the Reason (R) : (NH4)2SO4 on heating with alkali
compound is (Aq. Tension at 140C = 14mm) liberates NH3.
1) 18.44% 2) 16.89% 3) 15.60% 4) 16.00% 29. Assertion (A) : Oils are purified by steam
19. 0.5g of an organic compound containing distillation.
nitrogen on kjeldahlising required 29 ml of N/5 Reason (R) : The compounds which decompose
H2SO4 for complete neutralisation of ammonia. at their boiling points can be purified by steam
The percentage of nitrogen in the compound is distillation
1) 33.34 2) 16.24 4) 21.64 4) 14.84 30. Assertion (A) : In Duma’s method when an
20. 29.5 mg of an organic compound containing
organic compound is heated with cupric oxide, ‘N’
nitrogen was digested according to Kjeldahl’s
is converted to N2 gas.
method and the evolved ammonia was absorbed
Reason (R) : Cupric oxide oxidizes carbon and
in 2omL of 0.1M HCl solution. The excess of
hydrogen to CO2 and water vapour
the acid required 15mL of 0.1M NaOH solution
for complete neutralization. The percentage of
nitrogen in the compound is
1) 23.7 2) 29.5 3) 59.0 4) 47.4
01) 1 02) 4 03) 2 04) 2 05) 4 06) 2
21. 0.197g of a substance when heated with strong
07) 2 08) 4 09) 2 10) 1 11) 1 12) 4
nitric acid and silver nitrate gave 0.3525g os
13) 1 14) 3 15) 3 16) 4 17) 2 18) 1
silver iodide. Percentage of iodine is 19) 2 20) 1 21) 2 22) 1 23) 4 24) 1
1) 95% 2) 96.70% 3) 95.50% 4) 98.05% 25) 1 26) 1 27) 1 28) 2 29) 3 30) 2
22. If 0.32g of an organic compound containing
sulphur produces 0.233 g of BaSO4. Then teh
percentage of sulphur in it is.
1) 10 2) 15 3) 20 4) 25
1. The ammonia evolved from the treatment of 0.3g
23. If 0.1g of an organic compound containing
of an organic compound for the estimation of
phosphorus gave 0.222g of Mg2P2O7, then the
nitrogen was passed in to 100 ml of 0.1M sulphuric
% of phosphorus in the compound is
aicd. The excess of acid requried 20 ml of 0.5M
1) 31 2) 0.2 3) 76 4) 62
sodium hydroxide solution for complete
24. 0.4g of an organic compound gave 0.188g of
neutralisation. The organic compound is
solver bromide by a halogen estimation
method. The percentage of bromine in the 1) Acetamide 2) benzamide
compound is (at. wt. of Ag=108, Br=80) 3) Urea 4) thiourea
1) 20 2) 40 3) 46 4) 60 2. 0.2g of an organic compound on analysis gave
25. The molecular formula of an organic compound 0.147g of carbondioxide, 0.12g of water and
is C4H9N. The volume of N2 that will be given 74.6 c.c of nitrogen at S.T.P. Calculate the
by 0.2g of the above compound at STP is .... (ml) weight percentage of oxygen?
1) 31.5 2) 50 3) 63 4) 93 1) 20.04 2) 6.66 3) 46.63 4) 26.67

200 GENERAL ORGANIC CHEMISTRY


3. If a compound on analysis was found to contain 12. 0.1092g of certain diabasic Organic acid
C=18.5%, H=1.55%, Cl=55.04% and neutralised 21ml of decinormal solution of
O=24.81%, then its empirical formula is NaOH. The molar mass of acid is
1) CHClO 2) CH2ClO 1) 75gmol-1 2) 52gmol-1
3) C2H2OCl 4) ClCH2O 3) 208gmol-1 4) 104gmol-1
4. An organic compound having molecular mass 13. Tyrosine, (an amino acid) is one of the
60 is found to contain C=20%, H=6.67%, and constitutent of certain protein and is present
N=46.67% while rest si oxygen on heating it to the extent of 0.22% by mass. If molar mass
gives NH3 along with a solid residue. The solid of tyrosine id 181gmol -1. The minimum
residue gives violet colour with alkaline molecular mass of protein is
copper sulphate solution. The compound is 1) 7 x 104 U 2) 82273U
(AIEEE-2005) 3) 92200U 4) Above 105U
1) CH3NCO 2) CH3CONH2 14. The Silver Salt of a Monobasic acid on ignition
3) (NH2)2CO 4) CH3CH2CONH2 gave 60% of Ag. The molecular mass of the
5. In a compound C, H and N atoms are present acid is
in 9:1:3:5 by weight. Molecular weight of 1) 37 2) 33 3) 73 4) 77
compound is 108. Molecular formula of 15. Each mole of Haemoglobin contains four moles
compound is(AIEEE-2002) of iron. If the percentage of iron in
1) C2H6N2 2) C3H4N Haemoglobin is 0.35% by mass. The molar
3) C6H8N2 4) C9H12N3 mass of Haemoglobin is
6. Certain organic compounds contains carbon 1) 6.4 x 104 gmol-1 2) 5.6 x 104 gmol-1
atoms twice the number of nitrogen atoms and 3) 6.4 x 105 gmol-1 4) 5.6 x105 gmol-1
hydrogen atoms are seven times the number 16. In Carius tube, the compound ClCH2COOAg
of nitrogen atoms. The compound is mono acidic was heated with fuming HNO3 & AgNO3. After
base and 0.45g of the compound neutralises filtration and washing, a white precipitate was
0.01 mole of HCl. The compound is formed. The precipitate is
1) (CH3)2NH 2) C2H5NH2 1) Ag2SO4 2) AgNO3
3) N2H4 4) Both 1 and 2 3) AgCl 4) ClCH2COOAg
7. 0.302g of organic compound gave 0.268g of 17. In Victor Meyer’s method 0.2g of an organic
silver bromide. The percentage of bromine in substance displaced 56ml of air at STP the
the sample is molecular weight of the compound is
1) 20 2) 50 3) 37.75 4) 75 1) 56 2) 112 2) 80 4) 28
8. In an estimation of S by Carius method 18. 116mg of a compound on vapourisation in a
0.2175g of the compound gave 0.5825g of Victor Meyer’s apparatus displaces 44.8mL
BaSO4 Percentage of S is of air measured at STP. The molecular mass
1) 36.78% 2) 45.50% of the compound is
3) 39.48% 4) 30.69% 1) 58g 2) 48g 3) 116g 4) 44.8g
9. If 0.75g of an organic compound in Kjeldahl’s 19. 10.0ml of a mixture of methane and ethylene
method neutralized 30ml of 0.25 NH2SO4, the was exploded with 30ml (excess) of oxygen.
percentage of nitrogen in the compound is After cooling, the volume was 21.0ml. Further
1) 20 2) 50 3) 80 4) 14 treatment with caustic potash reduced the
10. 0.28 g of an organic compound in Dumas volume to 7.0ml. The amounts of methane and
method liberated 24ml of nitrogen at STP. The ethylene in the mixture respectively are
percentage of nitrogen in the compound is 1) 5ml of CH4 + 5ml of C2H4
1) 20 2) 10.71 3) 80 4) 50 2) 6ml of CH4 + 4ml of C2H4
11. One gram of X-N2Cl on strong heating gave 3) 3ml of CH4 + 7ml of C2H4
160ml of N2 gas of STP what could be X 4) 4ml of CH4 + 6ml of C2H4
1) C6H5 2) CH3 3) C2H5 4) C6H13 20. 121g of an amide obtained from a carboxylic

GENERAL ORGANIC CHEMISTRY 201


ascid, RCOOH upon heating with alkali
liberated 17g of ammonia. The acid is C) HO NH 3Cl
1) Acetic acid 2) Propanoic acid
3) Benzoic acid 4) Butanoic acid O2 N NH NH 3 Br
21. An organic liquid has atomic ratio C:H:N:S as D)
NO2
2:3:1:1. Each mole of this basic liquid can be
neutralised by 2 mole of HCl. Also 1.02g of Column-II
chloroplatinate of this base, on ignition gave 0.4g I) Sodium fusion extract of the compound gives
of platinum. The ratio of molecular mass to prussian blue colour with FeSO4
emperical mass of liquid is (at. wt of Pt is 195) II) Gives yellow precipitate with AgNO3 solution
1) 1 2) 2 3) 3 4) 4 which is sparingly soluble in NH4OH
22. Silver salt of certain Organic acid with atomic III) Gives white precipitate with AgNO3 solution
ratio C:H:O as 2:3:2 contains 65.06% of IV) Gives yellow precipitate with AgNO3 solution
silver. If each molecule of acid has two whcih is insoluble in NH4OH
ionisable H atoms, the formula of the acid 1) A-III; B-I,IV; C-I, III; D-I, II
1) C3H6O3 2) C4H6O4 2) A-I; B-IV; C-II, III; D-I, II
3) C2H3O2 4) C3H6O2 3) A-III; B-I, IV; C-I, II; D-II, III
23. 9.9g of an amide with molecular formula 4) A-III; B-IV; C-I, II; D-III, IV
C4H5NxOy on heating with alkali liberated 1.7g 27. List-I (Chromatographyprocess)
of ammonia. If the percentage of oxygen is A) Ion exchange chromatography
32.33%, then the ratio of N & O atoms in the B) GSC
compound is C) GLC
1) 2:1 2) 1:2 3) 2:5 4) 2:3 D) Paper chromatography
24. A complex compound of cobalt with the List-II (Stationary phase-Mobile phase)
composition Co=22.58%, H=5.79%, 1) Liquid - liquid
N=32.2%, O=12.20% and Cl=27.17% on 2) solid - liquid
heating, loses ammonia to the extent of 3) solid - gas
32.63% of its mass. The number of molecules 4) liquid - gas
of ammonia present in one molecule of the 4) solid - solid
cobalt complex is (At. mass of Co=58.9) The correct match is
1) 7 2) 5 3) 8 4) 12 1) A-2, B-3, C-4, D-1 2) A-3, B-2, C-4, D-1
25. 5.0g of certain metal, X (atomic mass = 27) is 3) A-4, B-3, C-2, D-1 4) A-1, B-3, C-4, D-2
converted into 61.7% crystalline sulphate 28. List-I (Process of purification)
containing 48.6% by mass of water of A) Crystallization
crystallization. The simplest formula of the B) Sublimation
compound is C) Fractional distillation
D) Steamdistillation
1) X 2  SO4 3 18 H 2O 2) X 2  SO4 3 14 H 2O
List-II (Principle involved the process)
3) X 2  SO4 3 16 H 2O 4) X 2  SO4 3 12 H 2O 1) Liquids which are immiscible in water possessing
high boiling point, steam volatile.
26. Match column-I with their characteristic
2) The compound should be soluble in the solvent
reaction in column-II
at its boiling temperature
Column-I
3) The compound should have high vapour
A) NH 2  NH 3Cl pressure below its melting point
4) Liquids which has B.Pt difference less than 400C
The correct match is
NH 3 I
B) HO 1) A-2, B-3, C-4, D-1 2) A-2, B-3, C-1, D-4
COOH 3) A-4, B-2, C-1, D-3 4) A-3, B-2, C-4, D-1

202 GENERAL ORGANIC CHEMISTRY


29. List-I (Colour) List-II (Element) 0.147  12  100
A) blood red 1) Cl   20.04%
0.2  44
B) Prussian blue 2) S
C) Violet 3) N and S W2  2  100
% of Hydrogen =
D) White 4) P W  18
5) N
0.12  2  100
The correct match is   6.66%
1) A-1, B-4, C-2, D-3 2) A-2, B-4, C-3, D-1 0.2  18
3) A-3, B-5, C-2, D-1 4) A-4, B-3, C-2, D-1 W2  28  100
30. List-I (Colour) List-II (Element) % of Nitrogen =
W  22400
A) Prussian blue 1) [Fe(CN)5NOS]4–
B) Violet 2) Fe4[Fe(CN)6]3 74.6
  46.63%
C) Blood red 3) [Fe(SCN)]2+ 8  0.2
D) Colourless 4) AgCl Remaining is oxygen
5) Na4[Fe(CN)6] % of Oxygen = 100 - (%C + %H + %N)
The correct match is = 100 - 73.33 = 23.67 %
1) A-4, B-1, C-3, D-2 2) A-3, B-1, C-2, D-4 4. Element % Relative no. Simplest
3) A-1, B-2, C-3, D-4 4) A-2, B-1, C-3, D-4 composition of atoms ratio
C 20 1.67
I
H 6.67 6.67
01) 3 02) 4 03) 1 04) 3 05) 3 06) 1 4
07) 3 08) 1 09) 4 10) 2 11) 1 12) 4 N 46.67 3.33
13) 2 14) 3 15) 1 16) 3 17) 3 18) 1 2
19) 2 20) 3 21) 1 22) 2 23) 2 24) 2 O 26.66 1.67
25) 1 26) 1 27) 1 28) 1 29) 3 30) 4 1
Emperical formula (CH4N2O)
molecular weight of organic compound = 60
n x 60 = 60, n=1
1. Number of milli equivalents of  Molecular formula = CH4N2O
H2SO4 = N x V(ml) = 20 O
number of milli equivalents of NaOH used to
i.e., NH  C  NH
neutralise excess of H2SO4 = 10 2 2 urea 
milli equivalents of acid used to neutralise ammonia
= 20 - 10 = 10 O O
% of nitrogen = NH 2  C  NH 2  NH 2  C  NH 2  

1.4  N  V  ml  1.4  10
  46.66 O O
0.3 0.3
% of nitrogen in urea NH 2  C  NH  C  NH 2  NH 3
 28  When gently heated, urea loss ammonia to form
 NH 2CONH 2   100  46.6 
 60  biuret. When an aqueous biuret solution is treated
2. Weight of compound = W = 0.2g with NaOH solution and a drop of CuSO4
weight of CO2 = W1 = 0.147g solution, a violet colour is produced. This is known
Weight of H2O = W2 = 0.12g as biuret test, which is characteristic of all
Volume of N2 at STP = 74.6 c.c compounds containing.
% of Carbon = 7  C  NH
||
O

GENERAL ORGANIC CHEMISTRY 203


5. Element weight Relative no. Simplest 0.1092
ratio of atoms ratio M  3
 104 gmol 1
1.05  10
9 3 13. 0.22 of tyrosin is present in protein = 100g; 181g
C 9  3
12 4 of tyrosin is present in protein
1 100  181
H 1 1 4   82272.7 g
1 0.22
3.5 1  108W 
N 3.5  1 14. Molar mass of an acid = n   107 
14 4  x 
Emperical formula = C3H4N  108  100 
molecular weight of the compound = 108  1  107   180  107  73u
 60 
54n = 108
n=2 15. No.of iron atoms per molecule = 4
molecular formula = (Emperical formula)n Mass of iron per molecule = 4 x 56 = 224u
= (C3H4N)2 0.35 parts by mass of iron is present in
= C6H8N2 haemoglobin = 100parts
6. 0.45g of base = 0.01 mole of HCl 224 parts mass of iron is present in haemoglobin
0.45 100  224
 0.01 mole   64000 (or) 6.4  104 gmol 1
or Molar mass of 0.35
GMWt
16. In Carius method, Cl is converted into AgCl.
0.45 18. 44.8mL of air displaced by
compound =  45 gmol 1
0.01 116
Now as per given condition, atomic ratio C:H:N  116mg  g , So, 22400mL of air
1000
is 2:7:1 Emperical formula is
116 22400
Mol. mass 45 displaced by,   58 g
   1 . Thus, both the 1000 44.8
Emperical mass 45
19. Let the vol.of CH 4 = xml
formulae are correct.
vol.of C2H4 = (10-x)ml
11. N2 produced by 1g of XN2Cl = 160ml
Equations for combuston of CH4 and C2H4
160 respectively are :
 mole
22400 i) CH 4  2O2  CO2  2 H 2O
1mole of N2 will be produced from salt xml 2xml xml
22400 ii) C2 H 4  3O2  2CO2  2 H 2O
  140 g
160 (10-x) 3(10-x) 2(10-x)ml
Molar mas of XN2Cl=140gmol-1 Vol. after contraction and cooling i.e., Vol. of CO2
Molar mass of X = 140-28-35.5=76.5gmol-1 produces +O2 left unused = 21ml;
This pertains to C6H5 group. Vol.of CO2 produced = 21-7 = 14ml...(iii)
12. H 2 X  2 NaOH  Na2 X  2 H 2O But from eq.(i) and (ii), total vol.of CO2 produced
milli moles of NaOH consumed = 21 x 0.1 = 2.1 = xml + 2(10-x)ml....(iv)
1 Equating (iii) & (iv), x+2(10-x)=14 (or) x=6
milli moles of acid = (milli moles of base) Vol. of CH4 = 6ml and C2H4 = 10-6=4ml
2
1 20. RCONH 2  NaOH  RCOONa  NH 3
  2.1  1.05 i.e. one mole of amide on reaction with NaOH
2
moles of acid = 1.05 x 10–3; 1.05 x 10-3 = give one mole of ammonia (NH3)
0.1092 Molecular mass of RCONH2 is
A + 12 + 16 + 14 +2 = 121
mwt.
204 GENERAL ORGANIC CHEMISTRY
A + 44 = 121  A = 77 = 0.383 : 5.74 : 2.3 : 0.766 : 0.766 : 1.94
Hence, R group with mol. Wt.(A) is C6H5 = 1 : 15 : 6 : 2 : 2 : 5
Thus aicd is C6H5COOH Thus, the complex contains six N-atoms out of
21. Emp. formula is C2H3NS, acidity of base = 2, which 5 are present in form of NH3.
2  1.02  195  5  100
Molecular mass = 2   410   87 gmol 1 25. % of M in crystalline sulphate =  82%
 0.4  61.7
Molar mass 87 % of water = 48.6% (given)
 1
Emp mass 87 %of SO 24 = 100 - (48.6 + 8.2) = 43.2%
22. Emperical formula is C2H3O2
8.2 43.2 48.6
X : SO42  : H 2O : :
 108W  27 96 18
Mol. mass = Basicity   107 
 x  = 0.3 : 0.45 : 2.7 = 1 : 1.5 : 9 = 2 : 3 : 18.
 108 100 
 2  107   118.0
 65.06 
Mol mass 118
 2 Method of Purification of Organic
Emperical mass 59
Mol. formula = (C2H3O2)2 = C4H6O4
Compounds :
23. 1 mole of NH3 (17g) will be obtained from 1mole 1. A mixture contains four solid organic
compounds A, B, C and D. On heating only C
9.9 changes from solid state to vapour state
of amide   17  99 g
1.7 directly. C can be separated from the rest in
Mol.wt of amide = 99 the mixture by
12  4 1) Distillation 2) Sublimation
%of C = 100  48.48
99 3) Fractional distillation 4) Crystallisation
5 1 2. Anthracene is purified by
%of H =  100  5.05 1) Filtration 2) Crystallisation
99
3) Distillation 4) Sublimation
14 x 1400 x 3. Separation of two substances by fractional
% of N =  100 
99 99 crystallisation depends upon their difference in
16 y 1600 y 1) Densities 2) Solubilities
% of C = 100 
99 99 3) melting point 4) Boiling points
But % of O = 32.33 (given) 4. Simple distillation can be used to separate
1600 y 32.33  99 1) A mixture of benzene (b.p. 800C) and thiophene
 32.33 or y  2 (b.p. 840C)
99 1600
Further % of N = 100-(48.48+5.05+32.33) 2) A mixture of ethanol (b.p. 78.16C) and water
(b.p. 1000C)
1400 x 3) A mixture of ether (b.p. 350C) adn toluene (b.p.
But % N = (as calculated above)
99 1100C)
1400 x 4) None of the above
 14.14  x  1 thus
99 5. Ortho and para nitrophenols can be separated
x : y that is N : O = 1 : 2 by
24. Ratio of CO : H : N : O : Cl : NH3 1) crystallization 2) Steam distillation
22.58 5.79 32.2 12.26 27.17 32.63 3) sublimation 4) solvent extraction
 : : : : :
58.9 1 14 16 35.5 17 6. Two volatile liquids A and B differ in their

GENERAL ORGANIC CHEMISTRY 205


boiling points by 150C. The process which can 3) Only gas 4) All of these
be used to separated them is 15. Components present in the mixture separated
1) Fractional distillation over the adsorbent column, is called
2) Steam distillation 1) Chromatography 2) Band specturm
3) Distillation under reduced pressure 3) Line spectrum 4) Distribution
4) Simple distillation 16. Two substances when separated on the basis
7. In steam distillation, the sum of the vapour of partion coefficient between two liquid phase,
pressure of the volatile compound and that of then the technique is known as
water is 1) column chromatography
1) Equal to atmospheric pressure 2) paper chromatography
2) Less than atmospheric pressure 3) GLC 4) TLC
3) More than atmospheric pressure 17. Fixed melting point of an organic compound
4) Exactly half of the atmospheric pressure informs
8. Turpentine oil can be purified by 1) Purity of an organic compund
1) Steam distillation 2) Vacuum distillation 2) Conductivity of compound
3) Fractional distillation 4) Sublimation 3) Chemical nature of compound
9. Elution is the process used for 4) Whether the compound is liquid or gas.
1) Crystallization of a compound Qualitative Analysis of Organic
2) Sublimation of a compound
Compounds :
3) Extraction of a compound
18. The presence of carbon in an organic
4) Distillation of a compound compound is detected by heating it with
10. Chromatographic techniques of purification 1) Sodium metal to convet it into NaCN
can be used for
2) CaO to convert it into CO which burns with
1) Coloured compounds 2) Liquids blue flame
3) Solids 4) All of these 3) CuO to convert it into CO2 which turns lime
11. Chromatography is a valuable method for the water milky
separation, isolation, purification and 4) Cu wire to give a bluish - green flame
identification of the constituents of a mixture
19. In Lassaigne’s method organic compound
and it is based on general principle of
fused with
1) Rates at which components moves under the 1) Sodium metal 2) Zinc dust
influence of mobile phase
3) Sodium carbonate and Zinc dust
2) Phase distribution
4) Calcium metal
3) Interphase separation 4) Phase operation
20. Which of the following statements is not
12. In adsorption chromatography mobile phase applicable to Lassaigne’s test?
will be
1) The extra elements (N, S and halogens) are
1) Only solid 2) Only liquid tested as their inorganic salts.
3) Only gas 4) Liquid as well as gas 2) During fusion of organic compound with sodium,
13. Which of the following can be used as Na2S, NaCN and NaX are formed.
adsorbent in adsorption chromo\atography 3) It can even be used for the detection of hydrogen
1) Silica gel 2) Alumina in the organic compound.
3) Cellulose powder 4) All of these 4) It is possible to differentiate between the different
14. In column chromatography stationary phase is halogens.
1) Only solid 2) Only liquid 21. A compoudn which does not give a positive

206 GENERAL ORGANIC CHEMISTRY


result in the Lassaigne’s test for nitrogen is 3) Pure and dry O2 4) Pure and dry He
1) Urea 2) Hydroxyl amine 31. In the Liebig’s method, if ‘w’ is the mass of
3) Glycine 4) Phenylhydrazine compound taken and ‘x’ is amount of CO2
22. Medium of sodium extract is formed then
1) Neutral 2) Basic 12  x 12 w
1) %C = 2) %C =  100
3) Acidic 4) Depends on organic compound 16  w 44 x
23. Organic compound containing nitrogen and
12 x 12 x
sulphur are preent in Lassaigne’s extract as 3) %C =   100 4) %C = 
44 w 44 w
1) NaCNS 2) NaSCN 3) Na2S 4) NaCN
24. The compound that doe not give a blue colour 32. In kjeldahl’s method to estimate nitrogen,
in Lassaigne’s test compound is heated with conc. H2SO4 in
presence of
1) Aniline 2) Glycine 3) Pyridine 4) Urea
1) CaSO4 2) (NH4)2SO4
25. In lassaigne’s test for nitrogen, the blue colour
is due to the formation of 3) CuSO4 4) P2O5
1) Sodium cyanide 33. In Kjeldahl’s method, potassium sulphate acts
as
2) Sodium ferrocyanide
1) Catalytic agent 2) Dehydrating agent
3) Ferric Ferrocyanide
3) Boiling Point elevator 4) Reducing agent
4) Potassium ferrocyanide
34. In Carius method halogens are estimated as
26. Lassaigne’s test gives a violet colouration with
sodium nitroprusside, it indicates presence of 1) X2 2) BaX2 3) PbX2 4) AgX
1) N 2) S 3) O 4) Cl 35. In organic compounds, phosphorus is finally
estimated as
27. For detection of sulphur in an organic
compound, sodium nitroprusside is added to 1) Mg2P2O7 2) H3OP4
the sodium extract. A violet colour is obtained 3) Mg3(PO4)2 4) P2O5
which is due to the formation of 36. An alkane has Carbon and Hydrogen ratio (by
mass) is 5.1428 : 1. Its molecular formula is
1) Fe4  Fe  CN 6  3
1) C7H19 2) C5H12 3) C6H14 4) C8H18
2) Fe  SCN 3 37. If two compounds have the same emperical
formula but different molecular formulae they
3) Na4  Fe  CN 5 NOS  must have
4) Na2  Fe  CN 5 NOS  1) Different percentage composition
2) Different molecular weight
28. The function of boiling the sodium extract with 3) same viscosity 4) same vapourdensity
conc. H NO 3 before testing the halogens is
1) To convert Fe++ into Fe+++
2) To make solution clear
3) To make solution acidic 01) 2 02) 4 03) 2 04) 3 05) 2 06) 1
4) To destroy cyanide and sulphide ions 07) 1 08) 1 09) 3 10) 4 11) 1 12) 4
29. Liebig’s method is used for the estimation of 13) 4 14) 1 15) 1 16) 2 17) 1 18) 3
1) Nitrogen 2) Sulphur 19) 1 20) 3 21) 2 22) 2 23) 2 24) 3
3) Carbon and hydrogen 4) Halogens 25) 3 26) 2 27) 3 28) 4 29) 3 30) 3
30. Which gas is introduced into the combustion 31) 3 32) 3 33) 3 34) 4 35) 1 36) 3
tube in Liebig’s method? 37) 2
1) Pure and dry CO2 2) Pure and dry N2

GENERAL ORGANIC CHEMISTRY 207


7. 0.303 g of an organic compound was analysed
for nitrogen by Kjeldhahl’s method. The
ammonia gas evolved was absorbed in 50ml of
0.05M H2SO4. The excess acid required 25ml
Method of Purification of Organic of 0.1M NaOH for neutralization. The
Compounds : percentage of nitrogen in the given compound is
1. Which of the following statements is not 1) 11.5 2) 23 30 12.5 4) 14.5
correct regarding purification of liquids by 8. 0.50g of an organic compound was
steam distillation? Kjeldahlised and the NH 3 evolved was
1) Impurities must be non-volatile absorbed in 50ml of 0.5M H2SO4. The residual
2) The liquid must be completely immiscible with acid required 60cm3 of 0.5M NaOH. The
water percentage of nitrogen in the organic
compound is
3) The liquid must possess high boiling point
1) 14 2) 28 3) 56 4) 42
4) The liquid must be miscible in water
9. 0.99g of organic compound containing halogen
2. Distillation under reduced pressure method is
when heated with furning HNO3 is presence
used to purity the liquids in which the liquids
of AgNO3 in a carius tube gave 0.287g of white
1) have high boiling points precipitate. The percentage of halogen is
2) have low boiling points 1) 29.6 2) 71.7 3) 35.4 4) 64.2
3) do not decompose at their boiling points 10. Insulin contains 3.4% sulphur, the minimum
4) highly volatile molecular weight of insulin is
3. Components of rectified spirit cannot be 1) 350 2) 470 3) 560 4) 940
separated by distillation because 11. 0.12g of an organci compound gave 0.22g
1) it forms an Azetropic mixture Mg 2 P 2 O 7 by the usual analysis. The
2) it has components with same boiling points percentage of phosphorus in the compound is
3) it contains immiscible liquids 1) 15.23 2) 38.75 3) 51.20 4) 60.92
4) it has high vapour pressure 12. In Dumas method 0.5 g of an organic
compound containing nitrogen gave 112 ml of
Qualitative Analysis nitrogen at S.T.P. The percentage of nitrogen
4. Which of the following compounds will give in the given compound is
blood red colour while doing the Lassaigne’s 1) 28 2) 38 3) 18 4) 48
test for N? 13. Compound A contains 20% C, 46.66% n and
1)  NH 2  2 CO 2) C6 H 5 SO3 H 6.66% H. It gave NH3 on heating with NaOH.
A can be
3)  NH 2  2 CS 4) CHCl3 1) CH3CONH2 2) NH2CONH2
5. CCl4 contains four chlorine atoms whne it is 3) C6H5CONH2 4) CH3NHCONH2
heated with silver nitrate solution then the
number of moles of AgCl formed is
1) 4 2) 2 3) 0 4) 3
01) 4 02) 1 03) 1 04) 3 05) 3 06) 2
6. 0.2 g of an organic compound on complete
combustion produces 0.18 g of water, then the 07) 1 08) 3 09) 2 10) 4 11) 3 12) 3
percentage of hydrogen in its (Aq. tension at 13) 2
288K = 12.7mm)
1) 5 2) 10 3) 20 4) 15

208 GENERAL ORGANIC CHEMISTRY