Organic Chemistry Purification Techniques

MASTERING CHEMISTRY 1
STUDYROCKS
TARGET X+1-2021
CHEMISTRY
UNIT 12 : ORGANIC CHEMISTRY
SOME BASIC PRINCIPLES AND
TECHNIQUES
PURIFICATION OF ORGANIC COMPOUNDS: The methods which are generally employed for the
purification of organic compounds are
(i) Filtration (ii) Crystallisation (iii) Sublimation
(iv) Distillation (v) Fractional distillation (vi)Distillation under reduced pressure
(vii) Steam distillation (viii) Azeotropic distillation
(ix) Differential extraction (x) Chromatography
These are briefly discussed as follows:-
1. Filtration. This is the simplest technique for the separation of mixture and is
used when a mixture contains two components one of which is soluble in a
particular solvent and the other is not. The mixture is shaken with the solvent
and then filtered. The soluble component passes into the filtrate and the
insoluble component is left behind as a residue on the filter paper. The soluble
component is recovered from the filtrate by evaporating off or distilling off the
solvent.
Examples. The examples of a few mixtures which can be separated by this technique are given below :
(i) A mixture of salt and pepper, using water as a solvent in which salt dissolves but pepper does not.
(ii) A mixture of glass powder and sugar, using water as a solvent in which sugar dissolves but glass does not.
(iii) A mixture of sand and sulphur, using carbon disulphide as the solvent in which sulphur dissolves but sand
does not.
(iv) A mixture of sand and water by direct filtration.
2. Crystallisation: It is used to purify organic solids which dissolve in a particular
solvent either as such or on heating while the impurities do not dissolve in it.
A hot concentrated solution of the compound is prepared and this upon
filtration and cooling gives the crystals of the pure compound.
3. Sublimation: Sublimation is the process employed for those solids which
directly pass to the vapour state upon heating without passing through the
liquid state and the vapours upon cooling give back the solid state.
Heat
Solid Vapours
cool
Impure samples of naphthalene, anthracene, camphor, benzoic acid, NH4Cl, HgCl2 dry ice, salyciylic
acid, iodine etc. Can be purified by this method provided the impurities are non-volatile. The impure solid is
taken in the china dish and is covered with a perforated filter paper. An inverted gas funnel is placed over the
dish and its stem is plugged with cotton. The dish is heated gently when the substance volatalises and is collected
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on the inner cold surface of the funnel. This is known as sublimate. The perforated filter paper allows only the
vapours to go upwards but checks the sublimate from falling down back into the dish.
4. Simple Distillation. This method is used for the separation of a mixture of liquids ( usually a solution) in
which the components have a large difference in boiling point. The component with the lower boiling point
boils off first and its vapours are condensed by passing through a condenser (air condenser or water
condenser) and collected in a receiver. The higher boiling residue is left behind in the distillation flask .
Examples: (i) A mixture of benzene (b.pt. 353 K) and toluene (b.pt. 384K) can be separated by this method.
Benzene distils over at 353 leaving toluene behind in the distillation flask.
(ii) A solution of salt or sugar etc. in water can be separated by evaporating off water leaving behind the residue
of salt, sugar etc.
5. Fractional distillation: Sometimes we come across the mixture of two liquids which do not differ in their
boiling temperatures by about 10 K to 15 K e.g., a mixture of acetone (boiling point 329K ) and methyl
alcohol (boiling point 338K). The process of simple distillation can not be used to separate them, because
vapours of both the liquids will be formed simultaneously and the distillate will also contain both of them. In
such a case the process of fractional distillation is must which utilizes specially designed columns called
fractionating columns
Simple distillation Fractional distillation

6. Distillation under Reduced Pressure: Certain liquids have a tendency to decompose at temperature below
their boiling point. Such liquids cannot be purified by simple distillation and can be distilled at reduced pressure.
Distillation under Reduced Pressure: Steam distillation

As we know the boiling point of a liquid is the temperature at which the vapour pressure is equal to the
atmospheric pressure. Under reduced pressure the liquid will boil at low temperature and temperature of
decomposition will not be reached and thus escaped. e.g. the boiling point of glycerol is 563 K but it decomposes
much before this temperature. However if the pressure is reduced to 12 mm glycerol boils at 453K without
decomposition. Other examples are H2O2, concentration of sugarcane juice in sugar industry.
7. Steam distillation: This process is used to purify the substances which
(a) are volatile in steam but are not miscible with water
(b) possess sufficiently high vapour pressure at the boiling point of water (373K)

(c) contain non-volatile impurities.
Principle: In this process the pressure inside the distillation flask is reduced and the liquid gets distilled at a
temperature below its boiling point. This can be explained with the help of Dalton’s law of partial pressures as
follows:
The law states that the pressure exerted by the gaseous mixture in a container is the sum of partial pressures
of the constituent gases provided they do not react chemically.
i.e. P = P1 + P2 ,Where P is the total pressure while P1 and P2 are the partial pressures of the constituent
gases. The distillation flask contains the vapours of steam (vapour pressure = P1) and of the liquid to be purified
(vapour pressure = P2). Since the vapour pressure of each is less than the atmospheric pressure therefore the
liquid gets distilled under reduced pressure by applying this process.
The process of steam distillation can also be used to separate a mixture of two organic substances one of
which is steam volatile while the other is not . e.g. when steam is passed through a mixture of ortho - nitrophenol
and p-nitrophenol, the vapours of steam carry the vapours of o-nitrophenol along with them which gets
condensed in the receiver. P-nitrophenol is left behind in the distillation flask. e.g. Aniline, Nitrobenzene, Sandal,
Wood oil, Turpentine oil etc.
AZEOTROPIC DISTILATION Rectified spirit contains about 95% alcohol (b.p.351K) and 5% water
(b.p.373K) but alcohol and water cannot be separated from this mixture even though their boiling points differ
by 22K. This is due to the reason that at this composition, alcohol and water form an azeotrope (i.e. constant
boiling mixture) and thus both the components of the mixture distil together like a pure liquid. To remove water
from such a mixture, a special method called azeotropic distillation is used. Azeotropic distillation means
fractional distillation using a suitable volatile solvent. For example, in the present case, benzene is used.
Rectified spirit is mixed with a suitable amount of benzene and subjected to fractional distillation. The first
fraction obtained at 331.8K is a ternary azeotrope consisting of all the water, some alcohol and benzee (water
7.4% , benzene 74.1%, alcohol 18.5%). The second fraction is a binary azeotrope consisting of the remaining
benzene and some alcohol (benzene 67.7%, alcohol 32.3%) which distils over at 341.2 K. The third fraction which
distils at 351K absolute alcohol.
8. Differential extraction: This process is used to separate a given organic compound present in an aqueous
solution by shaking with a suitable organic solvent in which compound is more soluble as compared to water.
However the organic solvent and water must not be miscible with each other.
Process: The aqueous solution of the compound is mixed with a small quantity of the suitable organic solvent in
a separating funnel. The funnel is provided with a stop cock as well as a glass stopper.
The funnel is stoppered and the contents are shaken vigorously for some time. The funnel is now allowed to
remain undisturbed when organic liquid and water from separate layers as shown above. Most of the organic
compounds pass into the organic layer from the aqueous layer. The two layers funnel and is mixed with the
organic solvent. The process of extraction is repeated a number of times to extract the organic compound from
the are collected carefully by opening the stop cock. The aqueous layer is taken again in the separating aqueous
solution. But it may be noted that greater
the number of extractions employed, more will be the amount of the
organic substance extracted. The different fractions of the organic layer
obtained as above, are taken in a beaker or distillation flask and the liquid
is carefully evaporated to leave behind the pure substance. The process
of extraction can also be used to separate two immiscible organic liquids
such as aniline and water.
9. Chromatography: It is the modern technique used for the
separation and purification of organic compounds. The method was
discovered by Tswett, a Russian botanist in 1906 for the separation

of coloured pigments from a plant. But now this method is widely used for the separation and purification of
number of mixtures, weather coloured or colourless.
Chromatography
Chromatography is the most modern and versatile method used for the separation, purification and testing
the purity of organic compounds. This method was first discovered by Tswett, a Russian botanist, in 1906. The
name chromatography was originally derived from the Greek word chroma meaning colour and graphy for writing
because the method was first used for the separation of coloured substances (plant pigments) into individual
components. Now this method is widely used for separation, purification, identification and characterization of
the components of a mixture, whether coloured or colourless.
Chromatography is essentially a physical method of separation. It is defined as follows :
The technique of separating the components of a mixture in which separation is achieved by the
differential movement of individual components through a stationary phase under the influence of a
mobile phase.
Types of chromatography. The stationary phase can be either a solid or tightly bound liquid on a solid
support while the mobile phase can be either a liquid or a gas. Depending upon the nature of the stationary and
the mobile phases, the different types of chromatographic techniques commonly used are given in Table.
Depending upon the principle involved, chromatography can be divided into the following two categories.
(a) Adsorption chromatography
(b) Partition chromatography
(a) Adsorption chromatography
Principle of Chromatography : It is based upon the principle of distributing the components of a given organic
mixture between two phases; one of which is stationary and the other is mobile. The stationary phase can either
be solid or a liquid supported over a solid and the mobile phase may be liquid or gas. Over the years the number
of techniques such as column or adsorption chromatography, paper chromatography, thin layer chromatography,
thin layer chromatography and gas liquid chromatography have been developed. A brief discussion of the
adsorption or column chromatography is given below:-
Procedure: The process of chromatography is carried in a long glass column provided with a stop cock at its
bottom. The various steps involved are:-
(a) Preparation of column: A plug of cotton or glass-wool is placed at the bottom of the glass column provided
with stop cock as shown in the figure.
A number of adsorbents such as alumina (Al2O3), silica gel, magnesium oxide, starch, fuller’s earth etc. Can be
used in this process. The adsorbent is made into a slurry with a suitable solvent such as hexane or petroleum-
ether which is non polar in nature. This slurry is then packed in the column by gentle tapping so that there may
not be any air bubble in the column. The packing of the adsorbent constitutes the stationary phase

(b) Adsorption : The mixture under investigation containing the components A and B for e.g., is dissolved in the
minimum quantity of a suitable solvent and poured on the top of the column of the absorbent. As the solution
moves down the components A and B are adsorbed to different extents. The component which is adsorbed
strongly (say A) will be retained near the top while the other (say B) will be at lower level.
(c) Elution: It is the process of the extraction of the adsorbed components from the adsorbent with the help of
solvents of increasing polarities. The different solvents in order of increasing polarity are petroleum ether,
carbon tetrachloride, benzene, chloroform, diethyl ether, ethyl acetate, acetone, alcohol etc.
The solvent constitutes the mobile phase and is called eluent. The solvents of increasing polarities are run into
the column one by one. The less adsorbed component A will be eluted first by the solvent of low polarity. It is
collected in the conical flask placed below the column. Now the solvent of higher polarity is run into the column
and this elutes the component B which is more strongly adsorbed. If needed the elution by a particular solvent
can be repeated a number of times for complete separation. The different fractions which are collected are
subjected to evaporation or distillation of completely remove the solvent. Pure components are, thus, left in the
flask.
Thin layer chromatography (TLC). It is another type of adsorption chromatography in which
separation of the components of a mixture is achieved over a thin layer of an adsorbent. A thin layer (0.2 mm
thick) of an adsorbent such as silica gel or alumina) is spread over a plastic or glass plate of suitable size. A
suitable TLC plate is taken and two pencil lines are drawn across the width of the plate about 1 cm from each end.
The lower pencil line is called the starting line while the upper line is called the finish line or solvent front.
TLC chromatograph being developed

A solution of the mixture to be separated is applied as a small spot with the help of a capillary on the
starting line. The plate is then placed in a closed jar containing a suitable solvent (Fig.).
As the solvent moves up, the components of the mixture also move up along the plate to different
distances depending upon their degree or extent of adsorption. When the solvent front reaches the finish line,
the plate is removed and then dried in air.
The spots of coloured components are visible on TLC plate due to their original colour. The spots of the
colourless components which are invisible to the eye can be observed using the following visualization methods.
(i) Ultraviolet light. Organic compounds which fluoresce can be detected by placing the plate under UV
lamp having light of 254 nm. Since all organic compounds do not produce fluorescence under UV light, this
method is not of general applicability.
(ii) Iodine vapours. This is the most commonly used detection reagent. The developed TLC plate is
placed in a covered jar containing a few crystals of iodine. Spots of compounds which adsorb iodine will show
up as brown spots.
(iii) Chemical methods. Sometimes a suitable chemical reagent may be sprayed on the plate. For
example, amino acids can be detected by spraying the plate with ninhydrin solution. Similarly, aldehydes / ketones
can be detected by spraying the plate with the solution of 2, 4-dinitrophehylhydrazine
The various components on the developed TLC plate are identified through the retention factor, i.e., Rf
values (Fig.). It is defined as

Distance travelled by the compound (X)
Rf =
Dis tan cetravelled by the solvent front (Y)
Since the solvent front always moves faster on the TLC plate than the compounds, Rf values are usually
expressed as a decimal fraction.
(b) Partition chromatography. We have discussed above that column chromatography or TLC is a
liquid/solid chromatography i.e., the mobile phase is a liquid while the stationary phase is a solid. In contrast,
partition chromatography is a liquid/liquid chromatography in which both the mobile phase and the stationary
phase are liquids.
Paper chromatography is a type of partition chromatography. In paper
chromatography, a special quality paper called chromatographic paper is used.
Although paper consists mainly of cellulose, the stationary phase in paper
chromatography is not the cellulose but the water which is adsorbed or chemically
bound to it. The mobile phase is another liquid which is usually a mixture of two or
three solvent water as one of the components.
Principle. Paper chromatography works on the principle of partition i.e., it is based upon continuous
differential partitioning (or distribution) of the various components of the mixture between the stationary and the
mobile phases.
Process. A suitable chromatographic paper is selected and a starting line is drawn across the width of
the paper at about 1 or 2 cm from the bottom. A spot of the mixture of components to be separated is applied
on the starting line with the help of a fine capillary or syringe. The chromatographic paper is then suspended in a
suitable solvent mixture (Fig.)
(a) (b)
Apparatus for ascending chromatography
The solvent rises up the paper by capillary action and flows over the spot. The different components of
the mixture travel through different distances depending upon their solubility in or partitioning between the
stationary and the mobile phases. When the solvent reaches the top end of the paper, the paper is taken out and
allowed to dry. The paper strip so developed is called the chromatogram. The spots of the separated coloured
compounds are visible at different heights from the starting line and are identified by their Rf values as discussed
under TLC. The spots of the colourless compounds may, however, be observed either under ultraviolet light or
by the use of an appropriate spray reagent as discussed under TLC.
The type of chromatography discussed above is called ascending paper chromatography. Alternatively, the
paper can be folded into a cyclinder and the two ends dipped together as shown in Fig. 12.20b. This is also
sometimes called as circular chromatography.
There is yet another type of paper chromatography called discending paper chromatography. In this
type, the solvent is kept in a trough at the top of the chamber, spotted end of the paper is dipped in it, and the
solvent is allowed to flow down by capillary action and gravity. In this type, solvent flow is rapid and hence the
process is less time consuming than the ascending method.
Uses. Paper chromatography is especially used for separation of sugars and amino acids.

Type of chromatography Mobile/Stationary Phase Uses
1 Adsorption or column Liquid/solid Large scale separations
2 Thin layer chromatography Liquid/solid Qualitative analysis
3 High performance liquid Liquid/solid Qualitative and Quantitative
Chromatography (HPLC) Analysis
4 Gas liquid chromatography Gas/liquid Qualitative and Quantitative
(GLC) Analysis
5 Paper or Partition chroma- Liquid/liquid Qualitative and Quantitative
Tography Analysis
QUALITATIVE ANALYSIS. The qualitative analysis of an organic compound implies the detection of all the
major elements which can be present in it with the help of suitable chemical test.
Carbon and hydrogen are the essential constituents of all the organic compounds.
These are therefore, normally not detected. Apart from that the organic
compounds may contain nitrogen, sulphur, halogens, phosphorous and oxygen.
A brief procedure is given.
1. Detection of Carbon and Hydrogen:
These are detected with the copper oxide test
A small quantity of the organic compound is mixed with double the amount of pure and dry copper oxide. The
mixture is heated in ahard glass test tube which is fitted with a delivery tube having bulb in the centre as shown in
the figure the other end of the delivery tube is dipped in a tube containing lime water. The bulb in the delivery
tube is packed with anhydrous copper sulphate. On heating, The organic compound under goes combustion and
is oxidised to carbon-di-oxide and water vapours according to the following reaction:-

C + 2 CuO  CO2 + 2 Cu

2H + CuO  H2O + Cu
Now water vapour turns anhydrous copper sulphate, blue, and carbon di-oxide turns lime water
CuSO4 + 5H2O  CuSO4 . 5H2O

Anhd. copper Hydrated copper sulphate
sulphate (white) (blue)
Ca(OH)2 + CO2  CaCO3 + H2O
Lime water (milky)
2.Detection of Nitrogen
(i) Soda-lime test: A pinch of an organic compound is heated strongly with soda-lime (NaOH+CaO) in a test
tube. The evolution of ammonia gives the indication of nitrogen. For example:-
CH3CONH2 + [NaOH + CaO]  CH3COONa + NH3
Limitations: A large number of organic compounds such as nitro and diazo compounds do not liberate ammonia
under these conditions.
(ii) Lassaigne’s test: This is a confirmatory test for nitrogen in an organic compound. This test involves two
steps.
(a) Preparation of lassaigne’s extract: A small piece of dry sodium metal is heated gently in a fusion tube
till it melts to a shiny globule. At this stage a small amount of organic substance is added and the tube is
heated strongly. The red hot tube is plunged into distilled water contained in a china dish. The contents
of dish are boiled for couple of minutes, cooled and filtered. The filtered liquid is called as sodium extract
(S.E.) or

(b) Lassaigne’s extract.(L.E.)
(b) Test for nitrogen: The Lassaigne’s extract is usually alkaline. If not it may be made alkaline by the addition
of few drops of a dilute solution of sodium hydroxide. To a part of extract a small amount of freshly prepared
ferrous sulphate solution is added and the contents are warmed. A few drops of ferric chloride solution are then
added to the contents and the resulting solution is acidified with conc. Hydrochloric acid. The appearance of a
Bluish green or a Prussian blue colouration confirms the presence of nitrogen in the organic compound.
(c) Chemistry of the test of Nitrogen: During fusion, carbon and nitrogen present in the organic compound
combine with sodium to form sodium cyanide.
fusion
Na + C + N  NaCN.
(in compound)
Upon heating the extract with ferrous sulphate sodium ferro cyanide is formed as follows:
2NaCN + FeSO4  Na2 SO4 + Fe(CN)2
Fe(CN)2 + 4NaCN  Na4 [Fe(CN)6]
Sodium Ferrocyanide
The treatment with ferric chloride yield ferric ferro cyanide which has bluish green or Prussian blue colouration.
3Na4[Fe(CN)6] + 4 FeCl3  Fe4[Fe(CN)6]3 + 12 NaCl
Ferric ferrocyanide (prussian blue)
The function of adding concentrated hydrochloric acid is to destroy any Fe(OH)2 which might have been formed
by the action of FeSO4 with NaOH.
FeSO4 + 2NaOH  Fe(OH)2 + Na2SO4
(green)
Fe(OH)2 + 2HCl  FeCl2 + 2 H2O.
If this is not done the green colour of ferrous hydroxide will interfere with the detection of nitrogen.
(b) If the organic substance contains nitrogen and sulphur together, sodium sulphocyanide is formed in the
sodium extract which gives blood red colouration with FeCl3 due to the formation of ferric sulphocyanide.
Na + C + N + S  NaSCN
From organic Compound (Sodium sulphocyanide)
3 NaSCN + FeCl3  Fe (SCN)3 + 3 NaCl
Ferric sulphocyanide (blood red).
3. Detection of Sulphur: The presence of sulphur in an organic compound which does not contain nitrogen
is detected by the following tests:-
Lassaigne’s test: The procedure for the preparation of the extract is same as for nitrogen. In this the sulphur
present in the organic compound will combine with sodium on fusion to form sodium sulphide.
fusion
2Na + S  Na2 S Sod. Sulphide
The extract is divided into two parts as follows:
(i) Lead acetate test: One part of the extract is acidified with acetic acid and then lead acetate solution is added.
Formation of black precipitate confirms the presence of sulphur in the organic compound.
Na2S + Pb(CH3COO)2  PbS  + 2 CH3 COONa
Sodium extract Lead acetate (Black ppt.)
(ii) Sodium nitroprusside test. A few drops of sodium nitroprusside solution are added to the other part of the
Lassaigne’s extract. The appearance of purple colouration confirms the presence of sulphur.
Na2S + Na2 [Fe(CN)5NO]  Na4 [Fe(CN)5NO. S]
Sodium extract Sod. Nitroprusside sol. Purple colouration

Problem. Hydrazine does not give Lassaigne’s test for nitrogen. Comment.
Solution: H2N NH2 Hydrazine does not contain carbon and thus on fusion with sodium, it does not form
NaCN. (sod. Cyanide), which is a primary requirement to show Lassaigne’s test for nitrogen.
Problem. Diazonium salts do not give Lassaigne’s test for nitrogen. Comment.
Solution. Diazonium salts usually lose N2 on moderate heating before they have a chance to react with fused
sodium.
Problem. Lassaigne’s extract is made acidic before the addition of lead acetate in the test of sulphur.
Comment.
Solution:
H+
(CH3 COO)2 Pb + Na2S  2CH3 COONa + PbS 
Black ppt.
Lassaigne’s extract is made acidic because black precipitate of lead sulphide is insoluble in acidic medium.
4. Detection of Halogens: The presence of halogens in the organic compound is detected by the following test:-
(i) Beilstein’s test. A copper wire flattened at one end is heated in the oxidising flame of Bunsen burner. The
heating is continued till it does not impart blue colour to the flame. The hot end of copper wire is now touched
with the organic substance and is once again kept in the flame. The appearance of blue or green colour indicates
the presence of halogens in the organic compound.
Limitations. (a) Substances, such as urea, thiourea etc. Do not contain halogens (Cl,Br,I) but gives this test.
(b) It does not tell that which member of halogen family is present in the organic compound.
(ii) Lassaigne’s test. This is very reliable test for the detection of the halogens [Cl, Br, I] in an organic compound.
The procedure for the formation of extract is same as in nitrogen. During fusion, sodium will combine with the
halogen to form sodium halide.
Fusion
Na + X NaX (X = Cl, Br, I )
Sod. halide
The extract is boiled with conc. HNO3 to expel the gases. It is then cooled and treated with AgNO3 solution.
(a) A precipitate soluble in ammonium hydroxide solution indicates the presence of chlorine in the organic
compound.
NaCl + AgNO3  AgCl + NaNO3
White ppt.
(b) A dull yellow precipitate partially soluble in NH4OH solution indicates the presence of bromine in the organic
compound.
Na Br + AgNO3  Ag Br + NaNO3
(dull yellow ppt.)
(c) A yellow precipitate, partially soluble in NH4 OH indicates the presence of iodine .
AgNO3 + NaI  AgI  + NaNO3
(yellow ppt.)
Function of HNO3. In case, nitrogen and sulphur are present along with the halogens in the organic compound,
the Lassaigne’s test will also contain sodium sulphide (Na2S) and sodium cyanide (NaCN) along with the sodium
halide. Nitric acid decomposes sodium cyanide and sodium sulphide, which otherwise form black ppt. With
AgNO3.
NaCN + HNO3  NaNO3 + HCN
Na2S + 2HNO3  2NaNO3 + H2 S
(iii) Special test for bromine and iodine. The presence of bromine and iodine can also be detected by
performing carbon disulphide test with the Lassaigne’s extract. The extract is treated with a few drops of

carbon disulphide (or chloroform) and then with excess of freshly prepared chlorine water. The contents are
shaken and the tube is allowed to stand.
(i) An organe colour in carbon disulphide layer confirms Bromine.
(ii) A violet colour in carbon disulphide layer confirms iodine.
2NaBr + Cl2  2NaCl + Br2 (orange colour in CS2)
2NaI + Cl2  2NaCl + I2 ( violet colour in CS2)
5. Detection of Phosphorus:
In order to detect phosphorous, the organic compound is fused with sodium peroxide, when phosphorous is
converted into sodium phosphate.
fuse
5 Na2O2 + 2P  2Na3 PO4 + 2 Na2O
(compound) Sod.phosphate
The fused mass is extracted with water and the water extract is boiled with conc. HNO3. Upon cooling a few
drops of Ammonium molybdate solution are added. A yellow ppt. Confirms phosphorus.
Na3PO4 + 2 HNO3  H3 PO4 + 3 NaNO3
(Phosphoric acid)
H3PO4 + 12 (NH4) MoO4 + 21 HNO3  (NH4)3 PO4 .12 MoO3+21NH4NO3 + 12H2O.
6. Detection of Oxygen. There is no direct method to detect oxygen in an organic compound. It is present in
the form of functional groups such as  OH,  COOH, NO2 etc.
QUANTITATIVE ANALYSIS In the characterisation of the organic compound the next step after the
detection of the elements is their estimation i.e. we must know the percentages of the various elements present in
a given organic compound. Suitable methods have been employed for this purpose. These are discussed as
follows:
1.Estimation of Carbon and Hydrogen:
The presence of C and H in an organic compound can be estimated by Liebig method.
Apparatus for estimation of Carbon & Hydrogen

A known weight of the given dry organic compound, is taken in a small platinum cup and is heated strongly with
dry cupric oxide in an atmosphere of dry oxygen (or air) free from CO2. The carbon and hydrogen present in the
organic compound are oxidised to CO2 and water vapours respectively.
C + 2CuO  CO2 + 2Cu
(compound)
2H + CuO  H2 O + Cu
These vapours are passed through previously weighed potash-bulb and V-shaped calcium chloride tube.
The former absorbs CO2 while the latter will take up moisture or water vapours. The increase in weight of potash
bulb will correspond to the weight of CO2 while that of CaCl2 tube will yield the weight of water formed. From
the respective weights the percentage of carbon and hydrogen can be determined, by the formula.
12  Mass of CO 2  100
% age of carbon =
44  Mass of organic compound

2  Mass of H 2 O  100
% age of hydrogen =
Example. On complete combustion, 0.246 g of an organic compound gave 0.198g of carbon dioxide and
0.1014 g of water. Determine the percentage composition of carbon and hydrogen in the compound.
(NCERT)
Sol. Here, mass of the organic substance taken = 0.246 g
Mass of CO2 formed = 0.198 g Mass of H2O formed = 0.1014 g
(i) Percentage of Carbon
One mole of CO2 contains one gram atom of carbon.
i.e. 44 g of CO2 contain carbon = 12g
12
 0.4950 g CO2 will contain carbon = × 0.198 g
44
This is the mass of carbon present in 0.246 g of the compound.
12 100
 %age of carbon in the compound =  0.198  = 21.95
44 0.246
(ii) Percentage of Hydrogen
One mole of H2O contains two gram atoms of hydrogen.
i.e. 18 g of H2O contain hydrogen = 2 g
2
 0.1014g H2O will contain hydrogen = × 0.1014
18
This is the mass of hydrogen present in 0.2475g of the compound.
2 100
 %age of hydrogen in the compound = × 0.1014 × = 4.58
18 0.246
2. Estimation of nitrogen :
Estimation of N in an organic compound can be done by two ways:
(a) Duma’s method (b) Kjeldahl’s method.
(a) Duma’s method: A known mass of the given organic compound is heated with dry cupric oxide in a
combustion tube in an atmosphere of CO2. The gas is obtained by heating sodium-bi-carbonate and is bubbled
through conc. H2SO4 to remove moisture. A roll of oxidised copper gauze placed in the combustion tube which
prevents the backward diffusion of the gases evolved in the combustion. A layer of coarse copper oxide that fills
about 2/3 of the combustion tube helps in the oxidation of the organic compound. Upon heating carbon and
hydrogen present in the organic compound are oxidised to CO2 and water vapours respectively, while N2 is set
free.
Apparatus for the estimation of Nitrogen by Duma’s method

A small amount of nitrogen might be oxidised to its oxides but they are reduced back to nitrogen
with the help of reduced copper placed at the end of the combustion tube.
Oxides of N2 + Cu  CuO + N2

The gaseous vapours are then passed into Schiff’s nitrometer tube which contains in it about 40% KOH
solution. It is provided with mercury seal at the bottom to check the backward flow of the liquid. The reservoir
attached to the tube is used to record the volume of the nitrogen at the atmospheric pressure. Both CO2 and
water vapours are absorbed by KOH solution, and N2 gets collected over it. Its volume is recorded after careful
levelling i.e. by making the level of KOH solution in the nitrometer tube. The aqueous tension of the water
vapours corresponding to this temperature is recorded from the tables.
28 Volume of N 2 at NTP
Percentage of Nitrogen    100
22400 Mass of the substance taken
Mass of N 2 at NTP
  100
Mass of the substance taken
Ques. In a Dumas nitrogen estimation 0.3 g of an organic compound gave 50 cm3 of nitrogen collected
at 300K and 715 mm pressure. Calculate the percentage of nitrogen in the compound (vapour pressure
of water at 300 K is 15 mm).
Solution: Vapour pressure of gas = 715  15 = 700 mm
To calculate the volume of N2 at S.T.P.
V1 = 50 cm3 V2 = ?
P1 = 700 mm P2 = 760 mm
T1 = 300 K T2 = 273 K
PV PV PVT
Applying 1 1  2 2 or V2  1 1 2
T1 T2 P2 T1
700  50  273
 V2 = = 41.9 cm3
760  300
22400 cm3 of nitrogen at S.T.P. weight = 28g
28  41.9
41.9 cm3 of nitrogen at S.T.P. weight = = 0.0524g
22400
0.0524
Percentage of nitrogen =  100  17.46%
0.3
(b) Kjeldhal’s method: This method is convenient as compared to Duma’s method and is largely used to
estimate the value of nitrogen in food, fertilizers and drugs etc. However this method is not applicable to the
compounds having a nitro )-NO2) or a diazo group (-N  N-)
Principle: This method is based on the principle that when the nitrogenous compound is heated with conc.
H2SO4 in the presence of potassium sulphate, the nitrogen present in the compound is converted to ammonium
sulphate. The ammonium sulphate so formed is decomposed with excess of alkali and the ammonia evolved is
estimated volumetrically. The percentage of nitrogen is then calculated from the amount of ammonia.
Procedure: Step I.
A known weight of the given organic compound is heated with con. H2SO4 in Kjeldhal’s flask which is a round
bottomed flask having a long neck provided with loose stopper. A small amount of K2SO4 is added to raise the
boiling point of H2SO4. Traces of CuSO4 or Hg is generally added to catalyse the reaction. The heating is done
for two to three hours when carbon and hydrogen present in the compound are oxidised to CO2 and water vapour
respectively, while nitrogen is converted into ammonium sulphate.
H2SO4 H2SO4 H2SO4
C + 2O  CO2 2H + O  H2 O N  (NH4)2 SO4.
CO2 and H2O vapour escape through the loose stopper while (NH4)2 SO4 is left behind in the flask.

Apparatus for the estimation of Nitrogen by Kjeldahl’s method

Step II. The contents of the flask after cooling are transferred to a round bottomed flask. These are diluted with
water and a few drops of methyl orange indicator are added. The indicator will impart pink colour to the solution
which is acidic in nature. The flask is provided with a dropping funnel which contains about 40% NaOH solution.
It is also connected to a water condensor through a Kjeldhal’s trap. NaOH solution is dropped in the flask from
the dropping funnel till the colour of the solution in the flask changes to yellow which indicates an alkaline
medium. It is now heated and NaOH decomposes (NH4)2SO4 to evolve NH3.

(NH4)2 SO4 + 2NaOH  Na2SO4 + 2NH3 + 2H2O
Vapours of NH3 and H2O will evolve through the trap which retains water. The NH3 vapours are
condensed by a water condenser. The liquid NH3 formed is then absorbed in a known excess of standard acid
(dil. H2SO4 or HCl) taken in a conical flask. NH3 is neutralized by the acid.
2NH3 + H2 SO4  (NH4)2 SO4
NH3 + HCl  NH4 Cl.
The excess of the acid is diluted with water and its volume is determined by titrating it against standard
alkali solution. By subtracting it from the total volume, value of acid used against NH3 can be determined. With
the help of calculations the amount of NH3 absorbed by the acid and thus, the amount of N2 is determined.
1.4 NV
The % age of nitrogen in a compound is given by =
W
Where N = Normality of acid used V = volume of acid used
W = Weight of organic compound taken.
Problem.0.24g of an organic compound containing Nitrogen was Kjeldahalized and ammonia formed
was passed in 50 cm3 of N/4 H2 SO4 . The excess of acid required 77.0 cm3 of N/10 NaOH for complete
neutralisation. Calculate the percentage of nitrogen in the compound.
Solution: Volume of unused acid = volume of NaOH used
i.e. Volume of NaOH = 77.0 cm3
Normality of NaOH = 1/10N
Normality of acid = ¼ N
Volume of acid(V) = 50 cm3
Apply normality equation. N1V1 = N2V2
1 1 77
 V1   77orV1   4  30.8cm 3 .
4 10 10
Volume of acid used up = 30.8 cm3
Volume of acid used up = 50 – 30.8 = 19.2 cm3.

1.4  Volume of acid used  Normality of acid used
%age of N =
Mass of subs tan ce
1.4  19.2  1
=  28.00% Ans.
0.24  4
Ques. 0.35 g of an organic substance was Kjeldahlised and the ammonia obtained was passed into 100
cm3 of N/5 H2 SO4. The excess acid required 154 cm3 of N/10 NaOH for neutralisation. Calculate the
percentage of nitrogen in the compound.
Solution. Vol. of N/5 H2SO4 taken = 100 cm3
Let us first calculate the volume of excess N/5 H2SO4 which was neutralised by 154 cm3 of N/10
NaOH.
N1 V1 = N2 V2
Acid alkali
N N 154  5
 V1   154 or V1   77 cm 3
5 10 10
Vol. of acid used for neutralization of NH3 = 100 – 7 = 23cm3 of N/5
 Vol. of NH3 produced = 23 cm3 of N/5
Now 1000 cm3 of IN NH3 contain nitrogen = 14 g
14  23
23 cm3 of N/5 NH3 contain nitrogen =
5  1000
14  23  100
Percentage of nitrogen =  18.4%
5  100  0.35
Ques. 0.257 g of an organic substance was heated with conc. H2 SO4 and then distilled with excess of
strong alkali. The ammonia gas evolved was absorbed in 50 ml of N/10 HCl which required 23.2 ml of
N/10 NaOH for neutralisation at the end of the process. Determine the percentage of nitrogen in the
compound.
Solution:
N
Volume of HCl taken = 50
10
N
Volume of NaOH used for neutralization of unused acid = 23.2 ml
10
Now N1 V1 = N2 V2
NaOHHCl
N N
23.2 ml of NaOH ≡ 23.2 ml of HCl
10 10
N
 Volume of HCl unused = 23.2 ml
10
Vol of N/10 HCl required for neutralisation of NH3 = 50 – 23.2 = 26.8 ml
N N
26.8 ml of HCl ≡ 26.8 ml of
10 10
1000 ml of 1 N NH3 solution contains nitrogen = 14 g
14  26.8
26.8 ml of NH3 solution contains nitrogen =
10  1000
14  26.8  100
Percentage on nitrogen = = 14.6%
10  1000  0.257

Example. During nitrogen estimation present in an organic compound by Kjeldhal’s method, the
ammonia evolved from 0.5g of the compound in Kjeldahl’s estimation of nitrogen neutralized 10 ml of 1
M H2SO4. Find the percentage of nitrogen in the compound. (NCERT)
Sol. Volume of H2SO4 used = 10 ml of 1 M H2SO4
Now H2SO4 + 2NH3 ―→ (NH4)2SO4
Now 1 mole of H2SO4 reacts with 2 moles of NH3
 10 ml of 1 M H2SO4 ≡ 20 ml of 1 M NH3
Now 1000 ml of 1 M NH3 contains N = 14 g
14
 20 ml of 1 M NH3 will contain N = × 20
1000
But this amount of nitrogen is present in 0.5 g of the organic compound.
14  20 100
 Percentage of nitrogen =  = 56.0
1000 0. 5
Alternatively, %age of M
1.4  Vol. of acid used  Molarity of acid
=
Mass of the substance taken
1.4  10  2  1
= = 56.0
0. 5
3. Estimation of Halogens
Halogens are estimated by Carius method.
Principle: A known mass of the organic substance is heated with fuming HNO3 in a Carius tube. The silver
halide so obtained is separated, washed, dried and weighed. From the weight of silver halide formed, the
percentage of halogen can be calculated.
X + AgNO3  AgX
Halogen
Carbon, hydrogen or sulphur present in the compound will be oxidised to CO2, H2O and H2 SO4 respectively.
HNO3
C + 2O CO2
Procedure:The amount of halogen present in a given organic compound is estimated with the help of various
methods, as described below:
A small amount of AgNO3 and fuming HNO3 are taken in the carius tube made up of glass. A small amount of
weighed organic substance taken in a small tube is also introduced carefully into the
carius tube. The tube is placed in an outer iron packet and is then heated in a furnace at 553 – 563 K for about
5 hours when carbon, hydrogen, sulphur present in the
compound are oxidized respectively to CO2, H2O vapours and
H2SO4 . The halogen (X) present in the compound is
converted to silver halide which is precipitated.After heating
this for some time small hole is made in the capillary tube when
the gases escape slowly out of it . The tube is finally broken
and the contents of the tube are filtered. The precipitate AgX
obtained is washed, dried and finally weighed.
AgCl  Cl AgBr  Br AgI  I Carius method for estimation of halogens
143.5 35.5 188 80 235 127
35.5 Mass of AgCl  100

(a) %age of Cl = 
143.5 Mass of organic compound

80 Mass of AgBr  100
(b) %age of Br = 
188 Mass of organic compound
127 Mass of AgI  100
(c) %age of I = 
235 Mass of organic compound
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 converted into sulphuric acid. It is then precipitated with barium chloride as barium sulphate.
The precipitate is filtered, washed, dried and weighed. From the weight of BaSO4 formed, the percentage of
sulphur can be calculated. The main reactions are:
HNO3
S + H2O + 3O H2 SO4
H2 SO4 + BaCl2 BaSO4

ppt.
Procedure: Estimation of sulphur is also done in the carius tube About 0.2 g of the organic compound is heated
with about 5 cm3 of fuming HNO3 in a carius tube as described under the estimation of halogens. Upon heating
carbon and hydrogen are oxidised to CO2 and H2O vapour and sulphur changes to H2SO4, which is absorbed on
BaCl2 solution. Finally a precipitate of BaSO4 is obtained.
BaSO4  S
233 32
32  Mass of BaSO 4  100
%age of sulphur =
5. Estimation of Phosphorus :
For the estimation of phosphorus, the given organic compound is heated strongly with fuming nitric acid. The
phosphorus in the compound is oxidised to phosphoric acid. It is treated with magnesia mixture ( a solution
containing magnesium chloride, ammonium chloride and a little of ammonia). A precipitate of magnesium
ammonium phosphate MgNH4PO4 is formed. This is filtered, washed , dried and is then ignited to give
magnesium pyrophosphate (Mg2P2O7 ). From the weight of Mg2 P2 O7, phosphorus can be estimated.
P + HNO3  H3 PO4
in organic compound Phosphoric acid
H3 PO3 + Magnesia mixture  Mg NH4 PO4
(NH4 Cl + MgCl2) Magnesium ammonium phosphate
Heat
2MgNH4PO4 Mg2 P2 O7 + 2NH3 + H2 O
Magnesium pyrophosphate
This is filtered washed dried and is then ignited to give magnesium pyrophosphate Mg2P2O7 which is weighed.
Mg2P2O7  2P
222 62
62  Mass of Mg 2 P2 O 7  100
%age of Phosphorus =
Example. 0.12 g of an organic compound containing phosphorus gave 0.22g of Mg2P2O7 by the usual
analysis. Calculate the percentage of phosphorus in the compound.
Sol. Here, the mass of the compound taken = 0.12g
Mass of Mg2P2O7 formed = 0.22 g

Now 1 mole of Mg2P2O7 ≡ 2g atoms of P or (2 × 24 + 2 × 31 + 16 × 7)
= 222 g of Mg2P2O7 ≡ 62g of P
i.e., 222g of Mg2P2O7 contain phosphorus = 62 g
62
 0.22 g of Mg2P2O7 will contain phosphorus = × 0.22 g
222
But this is the amount of phosphorus present in 0.12 g of the organic compound.
62 0.22
 Percentage of phosphorus =  × 100 = 51.20
222 0.12
6. Estimation of Oxygen
There is no direct method for the estimation of oxygen in a given organic compound. It is estimated by
subtracting the sum of the percentages of all other elements in the compound from 100.
Percentage of oxygen = 100  (% of all other element.)
Ques. 0.15g of an organic compound gave 0.12 g of AgBr by Carius method. Fine the percentage of
bromine in the compound.
Solution: Mass of AgBr formed = 0.12 g
AgBr  Br
188 g of AgBr contain bromine = 80 g
80  0.12
0.12g of AgBr contain bromine = = 0.051g
188
0.051
Percentage of bromine =  100 = 34%
0.15
Ques. 0.395 g of an organic compound by Carius method for the estimation of sulphur gave
0.582 g of BaSO4. Calculate the percentage of sulphur in the compound.
Solution: Mass of BaSO4 = 0.582 g
We know BaSO4  S
233 32
233 g of BaSO4 contain sulphur = 32 g
32
0.582g of BaSO4 contains sulphur =  0.582
233
Wt. of sulphur 32  0.582
Percentage of sulphur =  100 =  100 =20.24%
Wt. of compound 233  0.395
DETERMINATION OF MOLECULAR MASS
Molecular mass of an organic compound can be determined by a number of methods. The principles
of important methods are discussed below :
1. Silver Salt Method : This method is used for determining the molecular masses of organic acids.
Principle : This method is based on the fact that most of the organic acids form insoluble silver salts
which upon ignition decompose to give silver residue.
Heat
RCOOAg  Ag
Silver salt Silver
(Residue)
From the known weights of silver salt and silver residue the equivalent mass of the acid can be calculated.
From this molecular mass can be calculated as :
Molecular mass of acid = Equivalent mass  Basicity .

Procedure : A small amount of unknown organic acid is dissolved in water and treated with slight excess
of ammonium hydroxide to neutralise the acid. The excess of ammonia is then boiled off. It is then treated with
sufficient amount of silver nitrate when a white precipitate of silver salt is obtained. The precipitate is separated
by filtration, washed and dried. A known weight (about 0.2g) of the dry silver salt is weighed in a crucible and
ignited until all decomposition is complete . Ignition is repeated till the crucible with the residue of silver has
attained a constant weight. From the weights of silver salt taken and the metallic silver residue obtained on
iginition, molecular mass of the acid is calculated.
Calculations :
Let the weight of silver salt taken = w g
Weight of silver residue = x g
Now one atom of hydrogen (H) is equivalent to one atom of silver (Ag). Therefore, one equivalent of
silver salt will contain one atom of silver in place of hydrogen. Thus, if E be the equivalent mass of acid then
equivalent mass of silver salt will be :
(E – H + Ag) or (E – 1 + 108) or (E + 107).
Now
Equivalent mass of silver salt Weight of silver salt

Equivalent mass of silver Weight of silver
E  107 w
 
108 x
w
or E + 107 =  108
x
 w 
 E =   108  - 107
 x 
Molecular mass of the acid = Equivalent mass  Basicity
If n be the basicity of acid, then
 w 
Molecular mass of the acid =   108  107  n
 x 
Ques. 0.456 of silver salt of dibasic acid gave a residue of 0.324 g of silver on iginition. Calculate the
molecular mass of the acid.
Solution.
Weight of silver salt taken = 0.456 g.
Equivalent of silver residue = 0.324 g
Now
Equivalent mass of silver salt Weight of silver salt

Equivalent mass of silver Weight of silver
E  107 0.456

108 0.324
0.456
E + 107 =  108
0.324
0.456  108
or E = - 107 = 152 – 107 = 45
0.324
Basicity of acid = 2 (dibasic acid)
Molecular mass = 45  2 = 90
2. Platinichloride Method for Bases

This method is used for determining the molecular masses of the bases.
Principle. This method is based on the fact that organic bases combine with chloroplatinic acid, H2PtCl6
to form insoluble double salts known as chloroplatinates or platinichlorides . These sasts when ignited leave
a residue of metallic platinum. From the known weights of chloroplatinate taken for ignition and the residual
platinum, the equivalent mass of the base can be calculated. Knowing the acidity of the base molecular mass of
the base :
Molecular mass = Equivalent mass  Acidity
Procedure. A small amount of unknown base is dissolved in hydrochloric acid to form soluble
hydrochloride. It is then treated with slight excess of platinum chloride when a precipitate of chloroplatinate is
obtained. The precipitate is separated by filtration, washed and dried. A known weight of chloroplatinate is
weighed in a crucible and ignited until constant weight is obtained. From the weight of chloroplatinate taken and
residual platinum obtained molecular mass of the base can be calculated.
Calculations
Weight of chloroplatinate taken = w g
Weight of platinum obtained = x g.
Let E be the equivalent mass of the base, then the molecular formula of the chloroplatinate will be
B2H2PtCl6.
 Molecular mass of chloroplatinate = 2E + 2 + 195 + (35.5  6)
= 2E + 410
One molecule of chloroplatinate on heating gives one atom platinum.
Heat
B2H2PtCl6  Pt
2E + 410 195
Molecular mass of the salt Weight of platinum salt

Atomic mass of platinum Weight of platinum
2 E  410 w

195 x
w
or 2E + 410 =  195
x
w 
2E =   195  - 410
x 
w 
 E =   195 - 410
x 
If n be the acidity of the base, then
n  w  
Molecular mass of base =    195  - 410  .
2  x  
Ques. 0.98 g of the platinichloride of a diacid base left on ignition 0.3585 g of platinum . Find the
molecular mass of the base.
Solution.
Now
Molecular mass of the salt Weight of salt

Atomic mass of platinum Weight of platinum
If E be the equivalent mass of the base, then
Molecular mass of chloroplatinate (B2H2PtCl6) = 2E + 410

Weight of salt taken = 0.98 g
Weight of platinum obtained = 0.3885 g
2 E  410 0.98 0.98
 , 2E + 410 =  195 , 2E + 410 = 533
195 0.3585 0.3585
533 - 410
2E = 533 – 410 E= = 61.5
2
Acidity of the base = 2 (diacid)
 Molecular mass = 61.5  2 = 123
3. Victor Meyer’s Method
This method is used for determining the molecular masses of volatile substances.
Principle. A known mass of the substance is heated in the Victor Meyer’s tube. The vapours produced
by the substance are made to displace an equal volume of air which can be collected over water. The volume of
the air displaced by vapours is measured at room temperature and atmospheric pressure. The volume is converted
to volume at S.T.P. From this the weight of substance which will displace 22.4 L of vapours at S.T.P. is calculated
and this gives the molecular mass.
Procedure. The apparatus consists of an outer jacket (J), Victor Meyer’s tube (A), graduated burette (O),
and Hofmann bottle (H). To start the experiment the liquid in the outer jacket is heated to boil. The outer jacket
is made of copper and contains a liquid whose boiling point is 20 – 30o higher than the boiling point of the volatile
substance. On heating, the air in the Victor Meyer’s tube will expand and will escape through the side tube S.
The heating is done for about half an hour so that the entire air present in the tube is expelled and then the side
tube S is connected to the graduated tube O
Then a small amount ( 0.2 – 0.5 g) is weighed carefully in the Hofmann’s bottle which is loosely stoppered. It is
immediately dropped in the Victor Meyer’s tube and the stopper is replaced. A small amount of ‘glass wool’ is
generally placed at the bottom of the tube to avoid any breaking of the tube when the Hofmann’s bottle is dropped.
The substance being volatile will immediately change into vapours which will displace an equivalent
volume of air. When the level of air becomes constant, the volume of the air displaced is noted by making the
two limbs to be same. The room temperature and the atomospheric pressure are noted.
Calculations : First of all volume is converted to volume at S.T.P. as :

Let the mass of the organic compound taken = w g.
Volume of air displaced = v cm3
Atmospheric pressure = P mm of Hg
Room temperature = to C or (t + 273) K.

Aqueous tension at toC = a mm of Hg
 Pressure of dry air = ( P – a) mm of Hg
Experimental conditions S.T.P. conditions
P1 = (P – a) mm P2 = 760 mm
T1 = (273 + t) K T2 = 273 K
V1 = v cm3 V2 = ?
PV P V PVT
Applying gas equation, 1 1  2 2 or V2  1 1 2
T1 T2 P2 T1
( P - a)  v  273
V2 = = x cm3 (say
(750  (273  t)
Now x cm3 of vapours at S.T.P. weight = w g
w
22400 cm3 of vaporus at S.T.P. should weigh =  22400
x
w
Molecular mass of substance =  22400
x
4. Volumetric Method
The volumetric method is used for determining the molecular mass of acids and bases. For
example, in case of an acid, a known mass of it is dissolved in water and titrated against standard alkali solution
using suitable indicator (phenolphthalein) . From the volume of alkali required for neutralisation of the acid,
molecular mass can be calculated.
Let the organic compound taken be w g and V1 cm3 of N1 alkali be used for its neutralisation.
Then,
V1 cm3 of N1 alkali = w g
w 1000
1000 cm3 of 1 N alkali = 
V1 N1
1000 cm3 of 1 N alkali corresponds to gram equivalent of the alkali, because acid and alkali always react in
equivalent proportions.
w 1000
Gram equivalent of the acid = 
V1 N1
 Molecular mass = Eq. wt.  Basicity
w 1000
=   Basicity
V1 N1
The molecular mass of the base can be determined in a similar manner.
Ques.In a Victor Meyer’s method, 0.170 g of a liquid displaced 59.2 cm3 of air at 300K and 746 mm
pressure. Calculate the molecular mass of the liquid (aq. Tension at 300 K = 26.5 mm).
Solution. Pressure of dry gas = 746 – 26.5 mm = 719.5 mm
Let us first calculate volume at S.T.P.
P1 = 719.5 mm P2 = 760 mm
T1 = 300 K T2 = 273 K
3
V1 = 59.2 cm V2 = ?
P1 V1 P2 V2 PVT 719.5  59.2  273
Now  or V2 = 1 1 2 or V2 = = 51.0 cm3
T1 T2 P2 T1 760  300
51.0 cm3 of the vapour weight = 0.170 g

0 .170
22400 cm3 of the vapours weight =  22400 = 74.67
51
Molecular mass = 74.67
Ques. 0.183 g of an aromatic monobasic acid required 15 ml of decinormal sodium hydroxide for
complete neutralisation. Calculate the molecular mass of the acid.
Solution.
Weight of acid = 0.183
Volume of NaOH used = 15 ml
N
Normality of NaOH =
10
15 ml of N/10 NaOH solution neutralised acid = 0.183 g
0.183
1000 ml of 1 N NaOH solution neutralise acid =  10  1000 = 122
15
But 1000 ml of 1N NaOH solution contain 1 gram equivalent of NaOH and therefore, it must neutralise
1 gram equivalent of the acid.
Equivalent mass of acid = 122
Molecular mass = 122  1 = 122 (Basicity = 1)
Ques. 7.5 g of monobasic acid are dissolved per litre of the solution. 20 ml of this acid solution required
25 ml of N/15 NaOH solution for complete neutralisation. Calculate the molecular mass of the acid.
Solution. Volume of acid taken = 20 ml
Volume of base required = 25 ml
N
Normality of base =
15
Applying normality equation,
N1V1 = N2 V2
Acid Base
N
or N1  20 =  25
15
25 N
 Normality of the acid = 
15  20 12
N
Now, 1000 ml of acid = 7.5 g
12
1000 ml of 1 N acid = 90
Equivalent mass of acid = 90
Molecular mass = 90  1 = 90 ( Basicity = 1)
MASS SPECTROMETER
The mass spectrometer is an instrument used to measure accurately molecular masses of substances. The
sample to be tested is introduced into the instrument (Fig.) and is then ionised by electrical discharge or
bombardment with high energy electrons. These electrons may knock an electron from a molecule of the
substance to give a positive ion called the parent ion.
M  M+ + e
Molecule Molecular ion
The parent molecular ion may also break up to give smaller positive ions called fragment ions. For
example, a molecule of 2, 3-dimethylpropane may break up as :
CH3


CH3  C  CH3  C5H+12 + e
| Parent tion
CH3 Mass = 72
2, 3 – Dimethylpropane
C4H9+ Mass = 57
+ +
C3H12 C3H5 Mass = 41
C2H5+ Mass = 29 Fig. Mass spectrometer
A beam of thee positive ions is passed through a magnetic field generated by an electromagnet. This exerts
a force on the positively charged ions at right angles to their direction of motion. If the beam contains ions of
different masses, they are deflected to different extents. The heavier ions are deflected less than the lighter ions
from their original path. As a result, the beam of positive ions gets split up into separate beams, one for each
mass. The ions are then detected on a recorder or a photographic plate. Therefore, the different ions give different
peaks. A plot of relative intensities of the peaks against the m/e is called mass spectrum of the substance.
The line of highest value of m/e is due to the molecular ion or the parent ion. Its mass gives the molecular mass
of the compound. The mass spectrum of 2,2,4-Trimethylpentane is shown in Fig. The peak for the molecular
ion, M+ is observed at 114 which gives the molecular mass. The other peaks correspond to fragment ions. The
masses of the fragment ions help the chemist to determine the structure of the substance and therefore, to identity
it . The relative heights of the peaks indicate the proportion of the ions of various masses and thus the relative
abundance of each isotope.
100
80
60
Relative intensity
40
20 M+ (114)
10 20 30 40 50 60 70 80 90 100 110 120

Fig. Mass spectrum of 2,2, 4-Trimethylpentane
Mass spectrum gives very accurate results. It can analyse a sample of very very small amount as small as 10-12
g.

NCERT Problems
1. What are hybridization states of each carbon atom in the following compounds ?
CH2 = C = O, CH3CH = CH2, (CH3)2CO, CH2 = CHCN, C6H6.
O
sp 2 sp sp3 sp 2 sp 2 sp 3 sp 3 sp 2 sp 2 sp
Ans. C H2 = C = O C H3 ― C H = C H2 C H3 ― C2 ― C H3 C H2 - C H ― C ≡ N
sp
H
sp2
Each C is sp2-hybridized
2. Indicate the - and -bonds in the following molecules :

C6H6, C6H12, CH2Cl2, CH2 = C = CH2, CH3NO2, HCONHH3
Ans.
3. Write bond-line formulas for : Isopropyl alcohol, 2, 3-dimethylbutanal, heptan-4-one.

Ans.
4. Give the IUPAC names of the following compounds :
Ans. (a) Propylbenzene (b) 3-Methylpentanenitrile (c) 2, 5-Dimethylheptane (d) 3-Bromo-3-chloroheptane

(e) 3-Chloropropanal (f) 2, 2-Dichloroethanol
5. Which of the following represents the correct IUPAC name for the compounds concerned :
a) 2,2-Dimethylpentane or 2-Dimethylpentane (b) 2, 4, 7-Trimethyloctane or 2, 5, 7-Trimethyloctane
c) 2-chloro-4-methylpentane or 4-chloro-2-methylpentane (d) But-3-yn-1-ol or But-4-ol-1-yne

Ans. (a) 2, 2-Dimethylpentane (b) 2, 4, 7-Trimethyloctane. For two alkyl groups on the same carbon its
locant is repeated twice, 2, 4, 7-locant set is lower than 2, 5, 7-. (c) 2-Chloro-4-methylpentane. Alphabetical
order of substituents. (d) But-3-yn-1-ol. Lower locant for the principal functional group, i.e., alcohol.
6. Draw formulas for the first five members of each homologous series beginning with the following
compounds.
(a) H-COOH (b) CH3COCH3 (c) H  CH = CH2.
Ans. See notes
7. Give condensed and bond line structural formulas and identify the functional group(s) present, if
any, for : (a) 2, 2-Trimethylpentane (b) 2-Hydroxy-1, 2, 3-propanetricarboxylic acid (c) Hexanedial
Ans. Condensed Bond line Functional group
8. Identify the functional groups in the following compounds :
9. Which is expected to be more stable, O2NCH2CH2O- or CH3CH2O- and why ?

Ans. O2N  CH2  CH2  O- is more stable than CH3  CH2  O- because NO2 group has
–I effect and hence it tends to disperse the –ve charge on the O-atom. In contrast, CH3CH2 has +I- effect.
It, therefore, tends to intensify the –ve charge and hence destabilizes it.
10. Explain why alkyl groups act as electron donors when attached to a -system.
Ans. Due to hyperconjugation, alkyl groups act as electron donors when attached to a -system as shown
below

11. Draw the resonance structures for the following compounds. Show the electron shift using curved-
arrow notation.
(a) C6H5OH (b) C6H5NO2 (c) CH3CH = CHCHO (d) C6H5  CHO
 
(e) C6H5  C H2 (f) CH3CH = CH C H2
Ans.
12. What are electrophiles and nucleophiles ? Explain with examples.

Ans. See notes.
13. Identify the reagents shown in bold in the following equations as nucleophiles or electrophiles
(a) CH3COOH + HO-  CH3COO- + H2O (b) CH3COCH3 + - CN  (CH3)2 C (CN) (OH)

(c) C6H6 + CH3 C O  C6H5COCH3
Ans. Nucleophiles : (a) and (b) and Electrophile : (c).
14. Classify the following reactions in one of the reaction type studied
a) CH3CH2Br + HS-  CH3CH2SH + Br- (b) (CH3)2C = CH2 + HCl  (CH3)2CCl  CH3
c) CH3CH2Br + HO-  CH2 = CH2 + H2O + Br-
d) (CH3)3C  CH2OH + HBr  (CH3)2CBrCH2CH3 + H2O
Ans. (a) Nucleophilic substitution (b) Electrophilic addition (c) Bimolecular elimination
d) Nucleophilic substitution with rearrangement.
15. What is the relationship between the members of following pairs of structures ? Are they structural
or geometrical isomers or resonance contributors ?

Ans. (a) Structural isomers (actually position isomers as well as metamers) (b) geometrical isomers
(c) resonance contributors because they differ in the position of electrons but not atoms.
16. For the following bond cleavages, use curved-arrows to show the electron flow and classify each as
homolysis or heterolysis. Identify reactive intermediate produced as free radical, carbocation and
carbanion.
 
(a) CH3O ― OCH3 ―――→ CH3 O + O CH3 (b) O + - OH ――――→ O + H2O
―
E
- +
(c) ―→ + + Br (d) + E ―→
+
Br
Ans.
Homolysis Heterolysis
 
a) CH3O ― OCH3 ――――→ CH3 O + O CH3 (b) O ――――――→ O+
H2O
Free radicals HO― + H ―
H H Carbanion
Heterolysis Heterolysis C
+ +
c) ―――――→ Br- (d) + E+ ―――――→
+
Br
Carbocation Carbocation
17. Explain the terms inductive and electromeric effects. Which electron displacement effect explains
the following correct orders of acidity of the carboylic acids ?
a) Cl3CCOOH > Cl2CHCOOH > ClCH2COOH (b) CH3CH2COOH > (CH3)2CHCOOH > (CH3)3C.COOH
Ans. See notes.
18. Give a brief description of the principles of the following techniques taking an example in each case
:
(a) Crystallisation (b) Distillation (c) Chromatography
Ans. See notes
19. Describe the method, which can be used to separate two compounds with different solubilities in a
solvent S.
Ans. Two compounds with different solubilities in a solvent S can be separated by fractional crystallization.
When a hot saturated solution of these two compounds is allowed to cool, the less soluble compound
crystallizes out first while the more soluble remains in the solution. The crystals are separated from the mother
liquor and the mother liquor is again concentrated and the hot solution again allowed to cool when the crystals
of the second (i.e., more soluble) compound are obtained. These are again filtered and dried.
20. What is the difference between distillation, distillation under reduced pressure and steam distillation
?
Ans. Distillation involves conversion of a liquid into vapours followed by condensation of the vapours thus
produced by cooling to get the pure liquid while the non-volatile impurities remain in the flask. This method
is commonly used for those liquids which are sufficiently stable at their boiling points and contain non-volatile
impurities.
Distillation under reduced pressure also involves conversion of a liquid into vapours by heating following
by condensation of the vapours thus produced by cooling but the pressure acting on the system is not
atmospheric but is reduced by using a vacuum pump. Since the boiling point of a liquid decreases as the
pressure acting on it is reduced, therefore, this method is used to purify such liquids which have high boiling
liquids or liquids which decompose at or below their boiling points.

Steam distillation is comparable to distillation under reduced pressure (vacuum distillation) even though
there is no reduction in the total pressure acting on the solution. Here, the mixture of organic liquid and water
boils at a temperature when the sum of the vapour pressures of the organic liquid (p1) and that of water (p2)
become equal to the atmospheric pressure (p), i.e., p = p1 + p2.
Since the vapour pressure of water around its boiling point is quite high and that of the liquid is quite low,
therefore, the organic liquid will boil at a temperature much lower than its normal boiling point and hence its
decomposition is avoided. Steam distillation is used to purify such liquids which are volatile in steam, insoluble
in water , possess a vpour pressure of about 10 – 5 mm of Hg and contain non-volatile impurities.
21. Discuss the chemistry of Lassaigne’s test.
Ans. See notes.
22. Differentiate between the principle of estimation of nitrogen in an organic compound by (i) Dumas
method (ii) Kjeldahl’s method.
Ans. see notes
23. Discuss the principle of estimation of halogens, sulphur and phosphorus present in an organic
compound.
Ans. See notes.
24. Explain the principle of paper chromatography.
Ans. See notes.
25. Why is nitric acid added to sodium extract before adding silver nitrate for testing halogens ?
Ans. Sodium extract is boiled with nitric acid to decompose NaCN and Na2S, if present, otherwise these
NaCN + HNO3  NaNO3 + HCN
Na2S + 2HNO3  2 NaNO3 + H2S 
Will react with AgNO3 and hence will interfere with the test as shown below :
NaCN + AgNO3  AgCN + NaNO3
Silver cyanide
(White ppt.)
Na2S + 2AgNO3  Ag2S + 2 NaNO3
Silver sulphide
(Black ppt.)
26. Explain the reason for the fusion of an organic compound with metallic sodium for testing nitrogen,
sulphur and halogens.
Ans. The organic compound is fused with sodium metal to convert these elements which are present in the
covalent form to ionic form.
27. Name a suitable technique of separation of the components from a mixture of calcium sulphate and
camphor.
Ans. A mixture of CaSO4 and camphor can be separated by the following two methods :
(i) Camphor is sublimable but CaSO4 is not, therefore, sublimation of the mixture gives camphor on the sides
of funnel while CaSO4 is left in the china dish.
(ii) Camphor is soluble in organic solvents like CHCl3, CCl4 etc. while CaSO4 is not. Therefore, when the
mixture is shaken with the solvent, camphor goes into solution while CaSO4 remains as residue. It is filtered
and evaporation of solvent gives camphor.
28. Explain, why an organic liquid vapourises at a temperature below its boiling point in its steam
distillation ?
Ans. In steam distillation, the mixture consisting of the organic liquid and water boils at a temperature when
the sum of the vapour pressure of the liquid (p1) and that of water (p2) becomes equal to the atmospheric
pressure (p), i.e., p = p1 + p2.

Since the vapour pressure of water around the boiling point of the mixture is quite high and that of liquid is
quite low (10 – 15 mm), therefore, the organic liquid distils at a pressure much lower than the atmospheric
pressure. In other words, the organic liquid vapourises at a temperature much lower than its normal boiling
point.
29. Will CCl4 gives white precipitate of AgCl on heating it with silver nitrate ? Give reason for your
answer.
Ans. When CCl4 is heated with AgNO3 solution, white ppt. of AgCl will not be formed. The reason being
that CCl4 is a covalent compound, therefore, it does not ionize to give Cl- ions needed for the formation of
ppt. of AgCl.
30. Why is a solution of potassium hydroxide used to absorb carbon dioxide evolved during the
estimation of carbon present in an organic compound ?
Ans. CO2 is acidic in nature, therefore, it reacts with the strong base KOH to form K2CO3.
2 KOH + CO2 ―→ K2CO3 + H2O
The increase in the mass of U-tube containing KOH then gives the mass of CO2 produced and form its mass
the percentage of carbon in the organic compound can be estimated by using the equation,
12 Mass of CO 2 formed
%C =   100
44 Mass of substance taken
31. Why is it necessary to use acetic acid and not sulphuric acid for acidification of sodium extract for
testing sulphur by lead acetate test ?
Ans. For testing sulphur, the sodium extract is acidified with acetic acid because lead acetate is soluble and
does not interfere with the test. If H2SO4 were used, lead acetate itself will react with H2SO4 to form white
ppt. of lead sulphate which will interfere with the test.
Pb (OCOCH3)2 + H2SO4  PbSO4  + 2 CH3 COOH
Lead acetate (White ppt.)
32. An organic compound contains 69% carbon and 4.8% hydrogen, the remainder being oxygen.
Calculate the masses of carbon dioxide and water produced when 0.20 g of this substance is subjected
to complete combustion.
Ans. We know that, %C =  × 100
Substituting the values of % of C and mass of the substance taken, we have,
69 =  × 100
44 0.2g
69  44  0.2
or Mass of CO2 formed =  0.506 g
12  100
2 Mass of H 2 O formed
similarly, %H=  × 100
Substituting the values of % of H and mass of the substance taken, we have,
2 Mass of H 2 O formed
4.8 =  × 100
18 0.2
4.8  18  0.2
or Mass of H2O formed =  0.506 = 0.0864 g.
2  100
33. A sample of 0.50 g of an organic compound was treated according to Kjeldahl’s method. The
ammonia evolved was absorbed in 50 ml of 0.5 M H2SO4. The residual acid required 60 mL of 0.5 M
solution of NaOH for neutralization. Find the percentage composition of nitrogen in the compound.
Ans. Step 1. To determine the volume of H2.SO4 used.

Volume of acid taken = 50 ml of 0.5 M H2SO4 = 25 ml of 1 M H2SO4
Volume of alkali used for neutralization of excess acid = 60 ml of 0.5 M NaOH
= 30 ml of 1 M NaOH
Now 1 mole of H2SO4 neutralizes 2 moles of NaOH (i.e. H2SO4 + 2NaOH  Na2SO4 + 2 H2O)
 30 ml of 1 M NaOH = 15 ml of 1 M H2SO4
 Volume of acid used by ammonia = 25 – 15 = 10 ml
Step 2. To determine percentage of nitrogen.
Again 1 mole of H2SO4 neutralizes 2 moles of NH3
 10 ml of 1 M H2SO4  20 ml of 1 M NH3
But 1000 ml of 1 M NH3 contain nitrogen = 14 g
14
 20 ml of 1 M NH3 will contain nitrogen = × 20 g
1000
But this much amount of nitrogen is present in 0.5 g of the organic compound
14 20
 Percentage of nitrogen = × × 100 = 56.0
1000 0.5
Alternatively, % of N can be determined by applying the following equation,
1.4  Molarity of the acid  Basicity of the acid  Vol. of the acid used
%N =
Mass of substance taken
Substituting the values of all the items in the above equation, we have,
1.4  1  2  10
%N = = 56.0
0. 5
34. 0.3780 g of an organic chloro compound gave 0.5740 g of silver chloride in Carius estimation.
Calculate the percentage of chlorine present in the compound.
Ans. Here, the mass of the substance taken 0 .3780 g
Mass of AgCl formed = 0.5740 g
Now 1 mole of AgCl  1 g atom of Cl
or (108 + 35.5) = 143.5g of AgCl  35.5 g of Cl
Applying the relation,
35.5 Mass of AgCl formed
Percentage of chlorine =  × 100
143.5 Mass of substance taken
35.5 0.5740
=  × 100 = 37.566 g.
143 0.3780
35. In the estimation of sulphur by Carius method, 0.468 g of an organic sulphur compound afforded
0.668g of barium sulphate. Find out the percentage of sulphur in the given compound.
Ans. Here, the mass of the substance taken = 0.468 g
Mass of BaSO4 formed = 0.668 g
Now 1 mole of BaSO4 = 1g atom of S
or (137 + 32 + 4 × 16) = 233g of BaSO4  32 g of S
32 Mass of BaSO 4 formed
Applying the relation, Percentage of sulphur =  × 100
32 0.668
=   100 = 19.60
233 0.468
36. In the organic compound CH2 = CH  CH2  CH2  C  CH, the pair of hydridised orbitals
involved in the formation of : C2 ― C3 bond is :
a) sp – sp2 (b) sp – sp3 (c) sp2 – sp3 (d) sp3 – sp3

Ans. When both double and triple bonds are present, double bond is given preference while numbering the
carbon
1 2 3 4 5 6
chain. Thus, CH2 = CH  CH2  CH2  C  CH

sp2 sp2 sp3 sp3 sp sp
 C2  C3 bond s formed by overlap of sp – sp orbitals.
2 3
Thus, option (c) is correct.

37. In the Lassaigne’s test for nitrogen in an organic compound, the Prussian blue colour is obtained
due to the formation of :
a) Na4 [Fe (CN)6] (b) Fe4 [Fe (CN)6]3 (c) Fe2 [Fe(CN)6] (d) Fe3 [Fe(CN)6]4
Ans. The Prussian blue colour is due to the formation Fe4 [Fe (CN)6]3. Thus, option (b) is correct.
38. Which of the following carbocation is most stable ?
   
a) (CH3)3 C C H2 (b) (CH3)3 C (c) CH3CH2 C H2 (d) CH3 C HCH2CH3
Ans. the order of stability of carbocation is : 3o > 2o > 1o
   
(a) (CH3)3C  C H2 (b) (CH3)3 C (c) CH3CH2 C H2 (d) CH3 C HCH2CH3
1  Carbocation
o o
3 Carbocation 1o Carbocation 2o Carbocation
Thus, option (b) is correct.
39. The best and latest technique for isolation, purification and separation of organic compounds is :
(a) Crystallisation (b) Distillation (c) sublimation (d) Chromatography
Ans. Chromatography. Thus, option (d) is correct.
40. The reaction : CH3CH2I KOH (aq)  CH3CH2OH + KI
(a) electrophilic substitution (b) nucleophilic substitution (c) elimination (d) addition.
Ans. This is an example of nucleophilic substitution reaction since the nucleophile I- is replaced by the
nucleophile OH- ion. Thus , option (b) is correct.
NOMENCLATURE
(A) Saturated Hydrocarbons:
1. Given the IUPAC names of the following
CH3
|
(i) CH3 ― CH ― CH2 ― CH ― CH3
|
CH2
|
CH3
CH3
|
(ii) CH3 ― CH ― CH2 ― C ― CH3
| |
CH3 CH3
(iii) CH3 ― CH ― CH ― CH3
| |
C2H5 C2H5

H3C C2H5 CH3
| | |
(iv) CH3CH2 ― C ― CH ― C2H5 (v) (CH3)3 CCH2CH2CHCH2CH3
|
CH2CH2CH3
(vi) CH3CH2CH2CHCH2CH2CH3
|
C(CH3)3
CH3
|
(vii) CH3CH2CHCH2CH2CH ― CH2 ― C ― CH3
| | |
CH3 CH ― CH3 CH3
|
CH2 ― CH3
C2H5 CH3
| |
(viii) CH3CH2CH ― CH ― CH2CH2CH ― CH3
|
CH3 ― C ― CH3
CH3
(ix) CH3CH2CH2CH2CHCH2CH2CH2CH3
|
CH2C(CH3)3
(x) CH3
|
CH3 – CH – CH – CH2 – CH2 – CH – CH2 – CH – CH3
| | |
CH3 CH3 CH2 – CH2 – CH2 – CH3
CH2 – CH3
|
(xii) CH3 – CH2 – CH2 – CH2 – CH2 – CH – CH2 – CH – CH2 – CH3
|
CH2
|
CH3 – C – CH3
|
CH2 – CH3
CH3 CH3
| |
CH3CH2 – CH – CH
|
(xiii) CH3CH2CH2CH2 – CH – CH – CH2CH2CH2CH3
|
CH2CH3

2. What is wrong with the following names ? Draw the structure they represent and give their correct
names
i) 1, 1-Dimethylpentane (ii) 2-Methyl-2-propylhexane (iii) 3-Dimethylpentane
iv) 4, 4-Dimethyl-3-ethylpentane (v) 4-(2-Methylethyl) heptane
(B) Unsaturated Hydrocarbons:
Give the IUPAC names of the following compounds :
CH3 CH3
| |
(i) CH3CH2CH2 ― C ― CH2 ― C = CH2
|
C2H5
CH3
|
(ii) CH3 ― CH ― C = CH
(iii) C6H5 ― CH = CH ― CH2Cl
(iv) CH3CH = CH – CH2Br
Cl
|
(v) CH2 = C – CH = CH2
CH2CH3
|
(vi) CH2 = CH ― CH ― C = CH2
|
Cl
(c ) Bond Line Notations:
(i) (ii)
(iii) Write bond-line formulas for : Isopropyl alcohol, 2, 3-dimethylbutanal, heptan-4-one.
(iv) Give the IUPAC names of the following compounds :
(D) Monofunctional Compounds

(i) C2H5 ― C ― CH2OH (ii) CH3 ― CH = CH ― CHO (iii) NH2 ― CH2 ― CH2 ― CH2 ― NH2
CH2
(iv) CH3 ― CH = CH ― COOH (v) (CH3)2C = CHCOCH3 (vi) CH2 = CH ― CN
(vii) OCH ― CHO (viii) HOOC ― C ≡ C ― COOH

CH3 CH3 OCH3
| | |
(ix) CH2 = C ― COOCH3 (x) CH3CH2 ― C(Cl) ― CH2 ― CONHCH2CH3 (xi) CH3 ― CH ― CHO
(xii) [(CH3)2 CH]3 COH (xiii) CH3CH2CHCH2CHO (xiv) CH3CHCH2CH3

| |
CH3 COOH
O
CN
(xv) CH3CH2CHOHCH2CH2CH(CH3)CH2CH3 (xvii) (xviii) Cl H
(E) Polyfunctional Compounds:
6. Give the IUPAC names for the following poly-functional compounds.
CH3
|
(i) CH3CH2O ― CH2 ― CHOH ― CH3 (ii) CH3 ― CH ― CH2 ― C ― CH3
| |
NO2 OH
CH3 OH
| |
(iii) CH2 = C ― CH ― CH2 ― CN (iv) CH3 CH ― COOH
|
CONH2
(v) HOOCCH2 ― CH ― C2COOH (vi) CH3 ― CH ― CH2 ― CH2
| | |
COOH COCH3 NH2
CH3 CH3
| |
(viii) CH3NH ― CH2CH2 ― C ― CH2CH3 (ix) HC ≡ C ― CH ― CHOH ― CH2COCl
|
CHO
CH3 CH3
| |
(x) CH3 ― CH ― C ― COOCH3 (xi) CH2 = C ― CHOH ― CH2 ― CHO
| |
Br OH
CH2CHO
(xii) CH3 ― COCH ― CH2 ― CH2Cl (xiii) Br
|
C2H5
(xiv) Cl Br (xv) Cl2CHCH2OH

O
(xvi) (xvii) O
(F) Additional Compounds:

(i) (ii) H3C CH2CHO (iii) CH = CH ― CH ― CH2CH3
O O
(iv) CH2CH2COCH3 (v) (vi) HOCH2 ― C ― CH = CHCH2COOH
COOCH3 |
CH3
C2H5 [CH2]9CH3 OH
(vii) (viii) (ix)
CH3 CH3[CH2]9 [CH2]9CH3
O
COOH
(x) = C=O (xi) (xii) ― CONHC6H5
OHC
(xiii)
8. Draw the structures of the following compounds :

(i) 2-Chlorohexane (ii) 6-Hydroxyheptanal (iii) Hex-3-en-1-oic acid
(iv) 2-Chloro-2-methylbutan-1-ol (v) 5, 5-Diethylnonan-3-ol
(vi) 1-Bromo-3-chlorocyclohex-1-ene (vii) 1, 3-Dimethylcyclohex-1-ene
(viii) Cyclohex-2-en-1-ol.
9. Write down the structural formulae of the following
(i) 4-Methylpent-4-en-2-one (ii) 3-Methylbut-1-yne (iii) 2-Ethyl-3-methylpent-1-ene
10. Write the condensed formulae for each of the following compounds :
(i) Isopropyl alcohol (ii) Methyl t-butyl ether (iii) 2-Chloro-1, 1, 1-trifluoroethane
(iv) 2-Methylbuta-1, 3-diene (v) But-2-en-1-ol

12. Write bond-line formulas for : Isopropyl alcohol, 2, 3-dimethylbutanal, heptan-4-one.

13. Give condensed and bond line structural formulas and identify the functional group(s) present, if
any, for : (a) 2, 2-Trimethylpentane (b) 2-Hydroxy-1, 2, 3-propanetricarboxylic acid (c) Hexanedial
14. Draw the structures of the following compounds :
(i) 2-Chlorohexane (ii) 6-Hydroxyheptanal (iii) Hex-3-en-1-oic acid
(iv) 2-Chloro-2-methylbutan-1-ol (v) 5, 5-Diethylnonan-3-ol
(vi) 1-Bromo-3-chlorocyclohex-1-ene (vii) 1, 3-Dimethylcyclohex-1-ene
(viii) Cyclohex-2-en-1-ol.
15. Write down the structural formulae of the following
(i) 4-Methylpent-4-en-2-one (ii) 3-Methylbut-1-yne (iii) 2-Ethyl-3-methylpent-1-ene
16. Write the condensed formulae for each of the following compounds :
(i) Isopropyl alcohol (ii) Methyl t-butyl ether (iii) 2-Chloro-1, 1, 1-trifluoroethane
(iv) 2-Methylbuta-1, 3-diene (v) But-2-en-1-ol
Competition Decoder
1. The IUPAC name of C6H5COCl is
a) chlorobenzyl ketone (b) benzene chloroketone
c) benzenecarbonyl chloride (d) chlorophenyl ketone IIT-2006
Sol. (c)
2. The number of structural isomers for C6H14 is IIT-2007
(A) 3 (B) 4 (C) 5 (D) 6
Sol. There are five structural isomers of C6H14 viz.
CH3  CH2  CH2  CH2  CH2  CH3 Hexane
CH3
CH3 – CH – CH2 – CH2 – CH3 2 - Methylpentane
CH3
CH3 – CH2 – CH – CH2 – CH3 3 – Methylpentane
CH3
CH3 – C – CH2 – CH3 2, 2- Dimethylbutane
CH3
CH3 CH3
CH3 – CH – CH – CH3 2, 3-Dimethylbutane

 (C)
3. Hyperconjugation involves overlap of the following orbitals
(a)  –  (b)  – p (c) p – p (d)  – IIT-2008

Sol. (b)
4. The correct statement(s) concerning the structures E, F and G is (are) IIT-2008
H3C O H3C OH HC CH3 3
H3C CH3 H3C CH3 H3 C OH
(a) E, F and G are resonance structures

(b) E, F and E, G are tautomers
(c) F and G are geometrical isomers
(d) F and G are diasteriomers
Sol. (b), (c), (d)
1. The correct stability order for the following species is IIT-2008
a) (II) > (IV) > (I) > (III) (b) (I) > (II) > (III) > (IV)
c) (II) > (I) > (IV) > (III) (d) (I) > (III) > (II) > (IV)
Sol. (D)
O O
I II
2o carbocation 2o carbocation
stabilized by stabilized by
resonance hyperconjugation
O O
III
IV
1o carbocation
stabilized by o
1 carbocation
resonance stabilized by
hyperconjugation
5. The correct statement(s) about the compound given below is (are) IIT-2008
Cl H
CH3
H3C
H
Cl
(a) The compound is optically active (b) The compound possesses centre of symmetry
(c) The compound possesses plane of symmetry(d) The compound possesses axis of symmetry
Sol. (a)
CH3
|
6. The IUPAC name of is
a) 3-methylcyclohexene (b) 1-methylcyclohex-2-ene

c) 6-methylcyclohexene (d) 1- methylcyclohex-5-ene AIIMS-2003
Sol. (a)
7. Which of the following compounds possesses the C – H bond with the lowest bond dissociation
energy ? AIIMS-2003

a) Toluene (b) Benzene (c) n-Pentane (d) 2, 2-Dimethylpropane
Sol. (a) More stable the free radical formed upon hemolytic fission of C – H bond, lesser is the bond
dissociation energy. Since the stability of the radicals formed from toluene, benzene, n-pentane, 2, 2-
dimethylpropane follows the order :
   
C6H5 C H 2  (CH3 )3 C  CH3 C HCH 2CH 2CH3  C6 H5 ,
Therefore, the C – H bond of toluene has the lowest bond dissociation energy.
8. Which of the following compound has wrong IUPAC name ?
a) CH3 – CH2 – CH2 – COO – CH2CH3 (b) CH3 – CH – CH2 – CHO
ethyl butanoate | 3-methylbutanal
CH3
c) CH3 – CH – CH – CH3 2-methyl-3-butanol (d) CH3 – CH – C – CH2 – CH3 AIEEE-2002
| | |
OH CH3 CH3 O
Sol. (c )
9. The arrangement of (CH3)3C –, (CH3)2CH–, CH3CH2 – when attached to benzene or unsaturated
group in increasing order of inductive effect is AIEEE-2002
a) (CH3)3C – < (CH3)2CH – < CH3CH2 – (b) CH3CH2 – < (CH3)2CH – < (CH3)3C –
c) (CH3)2CH – < (CH3)3C – < CH3CH2 – (d) (CH3)3C – < CH3CH2 – < (CH3)2CH –
Sol. (a)
10. The reaction,
H2 O
(CH3)3C – Br –→ (CH3)3C – OH is
a) elimination reaction (b) substitution reaction (c) free radical reaction (d) addition reaction
AIEEE-2002
Sol. (b)
11. The general formula CnH2nO2 could be for open chain
a) dialdehydes (b) diketones (c) carboxylic acids (d) diols AIEEE-2003
Sol. (c)
12. The IUPAC name of the compound
is
HO
a) 1, 1-dimethyl-3-cyclohexanol (b) 1, 1-dimethyl-3-hydroxycyclohexane
c) 3, 3-dimethyl-1-cyclohexanol (d) 3, 3-dimethyl-1-hydroxycyclohexane AIEEE-2004
Sol. (c)
13. The compound formed in the positive test for nitrogen with the Lassaigne solution of an organic
compound is
a) Fe4[Fe(CN)6]3 (b) Na3[Fe(CN)6] (c) Fe(CN)3 (d) Na4[Fe(CN)5COS] AIEEE-2004
Sol. (a)
14. The ammonia evolved from the treatment of 0.30 g of an organic compound for the estimation of
nitrogen was passed in 100 ml of 0.1 M sulphuric acid. The excess of acid required 20 ml of 0.5 M
sodium hydroxide solution for complete neutralization. The organic compound is
a) acetamide (b) benzamide (c) urea (d) thiourea AIEEE-2004
Sol. (c) Let the vol. of acid left unused =  ml of 0.1 M H2SO4
  × 0.1 × 2 = 20 × 0.5 × 1 or  = 50 ml
 Vol. of acid used = 100 – 50

= 50 ml of 0.1 M H2SO4
1.4  2  50  0.1
%N = = 46.6
0.3
%N in urea (NH2CONH2) = (28/60) × 100 = 46.6%, in acetamide (CH3CONH2) = ( 14/59) × 100
= 23.72%, in benzamide (C6H5CONH2) = (14/121) × (28/76) × 100 = 36.84%
Thus, option (c) is correct.
15. An organic compound having molecular mass 60 is found to contain C = 20%, H = 6.67% and N =
46.67% why rest is oxygen. On heating it gives NH3 alongwith a solid residue. The solid residue
gives violet colour with alkaline copper sulphate solution. The compound is
a) CH3NCO (b) CH3CONH2 (c) (NH2)2CO (d) CH3CH2CONH2 AIEEE-2005
Sol. (c) Out of the given compounds, only urea has N = 46.67%. Urea on heating gives a solid residue
called biuret which gives violet colour with alkaline CuSO4 solution
∆
H2NCO NH2 + H – NHCONH2 –→ H2NCONHCONH2 + NH3
Biuret
16. Due to the presence of an unpaired electron, free radicals are
a) Chemically reactive (b) Chemically inactive (c) Anions (d) Cations AIEEE-2005
Sol. (a)
17. The increasing order of stability of the following free radicals is
   
a) (CH3)2 C H < (CH3)3 C < (C6H5)2 C H < (C6H5)3 C
   
b) (C6H5)3 C < (C6H5)2 C H < (CH3)3 C < (CH3)2 C H
   
c) (C6H5)2 C H < (C6H5)3 C < (CH3)3 C < (CH3)2 C H
   
d) (CH3)2 C H < (CH3)3 C < (C6H5)3 C < (C6H5)2 C H AIEEE-2006

Sol. (a) More the number of phenyl groups, greater is the stabilization due to resonance, therefore, (C6H5)3 C

is more stable than (C6H5)2 C H. Further, more the number of methyl groups , larger is the number of
 
hyperconjugation structures and hence more stable is the radical, i.e., (CH3)3 C is more stable than (CH3)2 C
H. Thus, option (a) represents the correct increasing order of stability of the given free radicals.
18. The IUPAC name of the compound shown below is
Cl
Br
a) 2-bromo-6-chlorocyclohex-1-ene (b) 6-bromo-2-chlorocyclohexene
c) 3-bromo-1-chlorocyclohexene (d) 1-bromo-3-chlorocyclohexene AIEEE-2006
Sol. (c)
19. Which one of the following conformations of cyclohexane is chiral ?
a) Twist boat (b) Rigid (c) Chair (d) Boat AIEEE-2007
Sol. (a) Twisted boat is chiral as it does not have plane of symmetry.
Hence, (a) is correct.
20. The IUPAC name of is
a) 1, 1-diethyl-2, 2-dimethylpentane (b) 4, 4-dimethyl -5, 5-diethylpentane

c) 5, 5-diethyl-4, 4-dimethylpentane (d) 4-ethyl-4, 4-dimethylheptane AIEEE-2007
Sol. (d)
6 2
4 1
7 5 3
The correct answer is 3-Ethyl-4, 4-dimethylheptane.

Hence, (d) is correct
21. The correct decreasing order of priority for the functional groups of organic compounds in the
IUPAC system of nomenclature is AIEEE-2008
a) – CHO, – COOH, – SO3H, – CONH2 (b) – CONH2, – CHO, – SO3H, – COOH
c) – COOH, – SO3H, – CONH2, – CHO (d) – SO3H, – COOH, – CONH2, – CHO
Sol. (c)The correct decreasing order of priority for the functional groups of organic compounds in IUPAC
nomenclature is
– COOH, – SO3H, – CONH2, – CHO
22. In steam distillation of toluene, the pressure of toluene vapour is
a) equal to pressure of barometer (b) less than pressure of barometer
c) equal to vapour pressure of toluene in simple distillation
d) more than the vapour pressure of toluene in simple distillation AIPMT-2001
Sol. (b)
23. - : CH2 – C – CH3 and CH2 = C – CH3 are
|
O: :O:
.. ..
a) Resonating structures (b) Tautomers (c) Geometrical isomers (d) Optical isomersAIPMT-2002
Sol. (a)
24. Name of the compound given below is
a) 4-ethyl-3-methyloctane (b) 3-methyl-4-ethyloctane

c) 2, 3-diethylheptane (d) 5-ethyl-6-methyloctane AIPMT-2003
Sol. (a)
25. The best method for the separation of naphthalene and benzoic acid from their mixture is
a) Sublimation (b) Chromatography (c) Crystallisation (d) Distillation AIPMT-2005
Sol. (c) Both naphthalene and benzoic acid sublime on heating and hence cannot be separated by
sublimation. Benzoic acid is, however, soluble in hot water but not naphthalene and hence can be separated
by crystallization.
26. Which among the following is the most stable carbocation ?
   
a) CH3 C H 2 (b) C H 2 (c) (CH3)3 C (d) (CH3)2 C H 2 AIPMT-2005
Sol. (c)
27. The IUPAC name of
a) 2, 3-dimethylpentanoyl chloride (b) 3, 4-dimethylpentanoyl chloride

c) 1-chloro-1-oxo-2, 3-dimethylpentane (d) -2-ethyl-3-methylbutanoyl chloride AIPMT-2006

Sol. (a)
28. The stability of carbonions in the following :
a) RC = C
b) (c) R2C = CH (d) R3C - C H2 AIPMT-2008

Is in the order of :
1) (d) > (b) > (c) > (a) (2) (a) > (c) > (b) > (d) (3) (a) > (b) > (c) > (d) (4) (b) > (c) > (d) > (a)
Sol. The stability of the carbanion decreases as the electronegativity of the carbon carrying the –ve charge
decreases or the hybridization of carbon carrying the –ve charge changes from sp to sp2 to sp3. Thus, RC ≡ C- is
the most stable while R3C – CH2- is the least stable carbanion. Out of C6H5- and R2C = CH-, R2C = CH- is less
stable due to +1-effect of the two R groups. Thus, the overall stability decreases in the order :
RC ≡ C- > C6H5- > R2C = CH- > R3C – CH2- i.e., option (3) is correct.
29. The IUPAC name of the compound NEET-2017
(1) 5-formylhex-2-en-3-one (2) 5-methyl-4-oxohex-2-en-5-al

(3) 3-keto-2-methylhex-5-enal (4) 3-keto-2-methylhex-4-enal
Sol. (4)
30. The IUPAC name(s) of the following compound is(are) JEE ADVANCED-2017
Sol. (B, C)
1-Chloro-4-methylbenzene
31. Among the following, the number of aromatic compound (s) is- JEE ADVANCED-2017
Sol.(5)

32. Which of the following carbocations is expected to be most stable ? NEET-2018
Sol. (4) —NO2 group exhibit —l effect and it decreases with increase in distance. In option (4) positive
charge present on C-atom at maximum distance so —l effect reaching to it is minimum and stability is
maximum.
33. Which of the following is correct with respect to –I effect of the substituents? (R = alkyl)NEET-
2018
(1) —NH2<— OR< — F (2) — NR2 <— OR <— F
(3) — NR2 >— OR > — F (4) - NH2 > OR > F
Sol.(1) —I effect increases on increasing electronegativity of atom. So, correct order of —I effect is —
NH2<—OR<—F.
*Most appropriate Answer is option (1), however option (2) may also be correct answer.
34. Total number of isomers considering both structural and stereoisomers, of cyclic ethers with the
molecular formula C4H8O is____ JEE ADVANCED 2019
Sol. (10)
35. Which of the following compounds will show the maximum ‘enol’ content?
JEE MAINS 2019 APRIL 8 E
(a) CH3COCH2COCH3 (b) CH3COCHCONH2 (c) CH3COCH3 (d) CH3COCH2COOC2H5
Sol. (a) Possible enols of CH3COCH2COCH3 are as follows:
36. The IUPAC name of the following compound is JEE MAINS 2019 APRIL 8M
(a) 2-methyl-3-hydroxypentan-5-oic acid (b) 4,4-dimethyl-3-hydroxybutanoic acid

(c) 4-methyl-3-hydroxypentanoic acid (d) 3-hydroxy-4-methylpentanoic acid.
Sol. (d)

37. JEE ADVANCED 2020

Ans (c)

Ans. (A,B,C)

42. NEET 2020
43. JEE MAINS 2020 SEP 2,S1

45. JEE MAINS 2020 SEP 2S1

UNIT 13 : HYDROCARBONS
NCERT PROBLEMS
1. How do you account for formation of ethane during chlorination of methane ?
Ans. Chlorination of methane is a free radical reaction which occurs by the following mechanism :
Homolytic fission
.
Initiation : Cl  Cl  2 Cl
Chlorine radical
.
Propagation CH3  H + C l  CH3 + HCl
.
C H3 + Cl  Cl  CH3  Cl + .Cl ….. (i)
.
Termination C H3 + .CH3  CH3  CH3 …. (ii)
Ethane
. .
C H3 + C l  CH3  Cl …. (iii)
. .
C l + C l  Cl  Cl
.
From the above mechanism, it is evident that during propagation step, C H3 free radicals are produced which
.
may undergo three reactions, i.e. (i)  (iii). In the chain termination step, the two C H3 free radicals combine
together to form ethane (CH3  CH3) molecule.
2. Write IUPAC names of the following compounds :
(a) CH3CH = C (CH3)2 (b) CH2 = CH  C  C  CH3
(c) (d) CH2  CH2  CH = CH2
CH3
OH
(e) (f) CH3(CH2)4 CH (CH2)3 CH3

CH2  CH (CH3)2
(g) CH3  CH = CH  CH2  CH = CH  CH  CH2  CH = CH2

C2H5
CH3
4 3 2 1 1 2 3 4 5
Ans. (a) CH2CH = C  CH3 (b) CH2 = CH  C  C  CH3

2 – Methylbut-2-ene Pen-1-en-3-yne
4 3 2 1
(c) (d) CH2  CH2  CH = CH2
Buta-1, 3-diene 4 – Phenylbut-1-ene

CH3
OH 10 6–9 5 2-4 1
(e) (f) CH3(CH2)4 CH (CH2)3 CH3

 2
1CH2  CH (CH3)2

CH3
5 – ( 2- Methylpropyl) decane
10 9 8 7 6 5 4 3 2 1
(g) CH3  CH = CH  CH2  CH = CH  CH  CH2  CH = CH2


C2H5
4-Ethyldeca - 5, 8-triene
3. For the following compounds, write structural formula and IUPAC names for all possible isomers
having the number of double or triple bond as indicated :
(a) C4H8 (one double bond) (b) C5H8 (one triple bond)
Ans. Isomers of C4H8 having one double bond are :
CH3
CH3 CH3 CH3 H 
(i) CH3CH2  CH = CH2 (ii) C =C (iii) C =C (iv) CH3  C = CH2
H H H CH3
but-1-ene cis – but-2-ene trans – but -2- ene 2-methylprop-1-ene
CH3
2 1 2 1 
(b) (i) CH3CH2CH2C  CH (ii) CH3CH2  C  C  CH3 (iii) CH3  CH  C  CH
Pent-1-yne Pent-2-yne 3-Methylbut-1-yne
4. Write IUPAC names of the products obtained by the Ozonolysis of the following compounds :
(i) Pent-2-ene (ii) 3, 4-Dimethylhept-3-ene (iii) 2-Ethylbut-1-ene (iv) 1-Phenylbut-1-ene.
5 4 3 2 1 (i)O3/CH2Cl2, 195K
Ans. (i) CH3  CH2  CH = CH  CH3  CH3  CH2  CH = O + O= CH  CH3
(ii) Zn/H2O
pent-2-ene Propanal Ethanal
7 6 5 4 3 2 1 (i) O3,/ CH2Cl2, 195 K
(ii) CH3 CH2 CH2  C = C  CH2CH3  CH3CH2CH2  C = O + O = C  CH2CH3
  (ii) Zn/H2O  
CH3 CH3 CH3 CH3
3, 4-dimethylhept-3ene pentan-2-one butan-2-one
4 3 2 1 (i) O3, CH2Cl2, 196 K CH3CH2
(iii) CH3CH2  C = CH2  C = O + O = CH2
 (ii) Zn/H2O CH3CH2
CH2 - CH3
2- ethylbut-1-ene pentane-3-one methanal
4 3 2 1 (i) O3, CH2Cl2, 196K
(iv) CH3CH2  CH = CH  C6H5  CH3CH2CH = O + O = CH – C6H5
1-Phenylbut-1-ene (ii) Zn/H2O Propanal Benzaldehyde

5. An alkene ‘A’ on Ozonolysis gives a mixture of ethanal and pentan-3-one. Write the structure and
IUPAC name of ‘A’.
Ans. Step 1. Write the structure of the products side by side with their oxygen atoms pointing towards each
other
CH3CH2
C=O O = CHCH3
CH3CH2 Ethanal
Pentan-3-one
Step 2. Remove the oxygen atoms and join the two ends by a double bond, the structure of the alkene ‘A’ is
5 4
CH3CH2 3 2 1
C = CH  CH3
CH3CH2 3 – Ethylpent-2-ene
6. An alkene ‘A’ contains three C  C, eight C  H bonds, one C  C  -bond. ‘A’ on Ozonolysis gives
two moles of an aldehyde of molar mass 44 a.m.u. write the IUPAC name of ‘A’
Ans. (i) An aldehyde with molar mass of 44 a.m.u. is ethanal, CH3CH = O
(ii) Write two moles of ethanal side by side with their oxygen atoms pointing towards each other.
CH3CH = O O = CHCH3
Ethanal Ethanal
(iii) Remove the oxygen atoms and joi them by a double bond, the structure of alkene ‘A’ is
H H
 
CH3  CH = CH  CH3 or HCC = C  C H
But-2-ene    
H H H H
As required, but-2-ene has three C  C, eight C  H and one C  C -bond.
7. Propanal and pentan-3-one are the Ozonolysis products of an alkene ? What is the structural formula
of the alkene
Ans. (i) Write the structures of propanal and pentan-3-one with their oxygen atoms facing each other, we
have,
CH2CH3
CH3CH2CH = O O=C
Propanal CH2CH3
Pentan-3-one
(ii) Remove oxygen atoms and joins the two fragments by a double bond, the structure of the alkene is
2 1
6 5 4 3 CH2CH3
CH3CH2CH = C
CH2CH3
3 – Ethylhex-3-ene
8. Write chemical equations for the combustion reaction of the following hydrocarbons.
(i) Butane (ii) Pentene (iii) Hexyne (iv) Toluene

Ans. (i) C4H10 (g) + 13/2 O 2(g)  4 CO2 (g) + 5H2O (g)
Butane


(ii) C5H10 (g) + 15/2 O2 (g)  5 CO2 (g) + 5H2O(g)
Pentene

(iii) C6H10 (g) + 17/2 O2 (g)  6 CO2 (g) + 5H2O (g)
Hexyne

(iv) CH3 (g) or C2H8 (g) + 9 O2 (g)  7 CO2 (g) + 4H2O(g)
9. Draw the cis –and trans-structures for hex-2-ene. Which isomer will have higher b.p. and why ?
Ans. The structure of cis-and trans-isomer of hex-2-ene are :
CH3 CH2CH2CH3 CH3 H
C C C C
H H H CH2CH2CH3
cis-hex-2-ene trans-Hex-2-ene
(Higher dipole moment, higher b.p.) (Lower dipole moment, lower b.p.)
The dipole moment of molecule depends upon dipole-dipole interactions. Since cis-isomer has higher dipole
moment, therefore, it has higher boiling point.
10. Why is benzene extra-ordinary stable though it contains three double bonds ?
Ans. Resonance or delocalization of electrons usually leads to stability. Since in benzene all the six -electrons
of the three double bonds are completely delocalized to form one lowest energy molecular orbital which
surrounds all the carbon atoms of the ring, therefore, it is extra-ordinary stable.
Delocalization of 6 -electrons in benzene.

11. What are the necessary conditions for any system to be aromatic ?
Ans. The necessary conditions for a molecule to be aromatic are :
(i) It should have a single cyclic cloud of delocalized -electrons above and below the plane if the molecule.
(ii) It should be planar. This is because complete delocalization of -electrons is possible only if the ring is
planar to allow cyclic overlap of p-orbitals.
(iv) It should contain Huckel number of electrons, i.e. (4n + 2) -electrons where n = 0, 1, 2, 3…etc. A
molecule which does not satisfy any one or more of the above conditions is said to be non-aromatic.
12. Explain why the following systems are not aromatic ?
(i) CH2 (ii) (iii)
Ans. (i) sp3 CH2 . Due to the presence of a sp3 – hybridized carbon, the system is not planar. It
does
contain six -electronsbut the system is not fully conjugated since all the six -electrons do not form a single
cyclic electron cloud which surrounds all the atoms of the ring. Therefore, it is not an aromatic compound.
(ii) Due to the presence of a sp3 – carbon, the system is not planar. Further, it contains only
sp3

four electrons, therefore, the system is not aromatic because it does not contain planar cyclic cloud having (4n
+ 2) -electrons.
(iii)
Planar Tub shaped

Cyclooctatetraene is not planar but is tub shaped. It is, therefore, a non-planar system having 8 -electrons.
Therefore, the molecule is not aromatic since it does not contain a planar cyclic cloud having (4n + 2) -
electrons.
13. How will you convert benzene into
(i) p-nitrobromobenzene (ii) m-nitrochlorobenzene (ii) p-nitrotoluene (iv) acetophenone ?
Ans. (i) The two substituents in the benzene ring are present at p-positions. Therefore, the sequence of
reactions should be such that first an o, p-directing group, i.e., Br atom should be introduced in the benzene
ring and this should be followed by nitration. Thus,
(Br2, Anhyd. FeBr3 Conc. HNO3 + conc. H2, SO4, 
 Br 
(Bromination) (Nitration)
Benzene Bromobenzene
NO2
Separate by
O 2N Br + Br  O2N Br
Fractional distillation
p-Bromonitrobenzene o – Bromonitrobenzene p – Bromonitrobenzene
(major) (minor)
(ii) Here since the two substituents are at m-position w.r.t. each other , therefore, the first substitutent in the
abenzene ring should be a m-directing group (i.e., NO2) and then the other group (i.e. Cl) should be introduced.
Therefore, the sequence of reactions is :
conc. HNO3 Cl
+ conc. H2SO4,  Cl2 Anhyd. AlCl3
 NO2  NO2
(Nitration) (Chlorination)
Benzene Nitrobenzene m – Chloronitrobenzene
(iii) Here since the two substituents are at p-position w.r.t. each other, therefore, the first substituent in the
abenzene ring should ;be a o, p-directing group (i.e., CH3) and then the other group (i.e., NO2) should be
introduced.
CHCl, Anhyd. AlCl3 dil., HNO3 + dil. H2SO4, 
 CH3 
(F.C. alkylation) (Nitration)
Benzene Toluene
NO2
Separate by
O2N CH3 + CH3  O2N CH3
fractional
P – Nitrotoluene o-Nitrotoluene distillation p – Nitrotoluene

(major) (minor)
(iv) Acetophenone can be prepared by F.C. acylation using either acetyl chloride or acetic anhydride
O O
Anhyd. AlCl3
+ CH3  C  Cl  C  CH3 + HCl
Acetyl chloride (F.C. acylation)
Benzene Acetophenone
O O
CH3  C Anhyd. AlCl3
Or + O  C  CH3 + CH3COOH
CH3  C (F.C. acylation) Ethanoic acid
Benzene O Acetophenone
Acetic anhydride
14. In the alkane, CH3CH2  C(CH3)2  CH2  CH (CH3)2, identify 1o, 2o, 3o carbon atoms and give the
H-atoms bonded to each one of these.
Ans. The expanded formula of the given compound is
15 H attached to five 1o carbon

4 H attached to two 2o carbons
1 H attached to one 3o carbon
15. What effect does branching of an alkene chain on its boiling point ?
Ans. As the branching increases, the surface area of an alkane approaches that of a sphere. Since a sphere has
minimum surface area, therefore, van der Waal’s forces of attraction are minimum and hence the boiling point
of the alkane decreases with branching.
16. Addition of HBr to propene give 2-bromopropane, while in presence of benzoyl peroxide, the same
reactions gives 1-bromopropane. Explain an give mechanism.
Ans. Addition of HBr to propene is an ionic electrophilic addition reaction.in which the electrophile, i.e., H+
first adds to give a more stable 2o carbocation. In the 2nd second, the carbocation is rapidly attacked by the
nucleophile Br- ion to give 2- bromopropane
H  Br H+ + Br –
Slow

Step 1. CH3  CH = CH2 + H+  CH3  C H  CH3
Electrophile 2o Carbocation
(more stable)
Fast

Step 2. CH3  C H  CH2 + Br -  CH3  CH  CH3
Nucleophile 
Br
2- Bromopropane

.
In presence of benzoyl peroxide, the reaction is till electrophilic but the electrophile here is a B r free radical
which is obtained by the action of benzoyl peroxide on HBr

. .
C6H5CO  O  O  COC6H5  2 C6H5 CO O  2 C 6 H5 + 2 CO2
Benzoyl peroxide (Homolytic fission) Benzoyl radical Phenyl radical
(unstable)
.
C6H5 + H  Br  C6H6 + Br
Benzene
.
In the first step, B r radical adds to propene in such a way to so as to generate the more stable 2o free radical.
In the second step, the free radical thus obtained rapidly abstracts a hydrogen atom from HBr to give 1-
bromopropane.

. .
CH3  CH = CH2 + B r  CH3  C H  CH2 Br
2o Free radical
( more stable)
Fast
. .
CH3  C H  CHBr + H  Br  CH3  CH2  CH2Br + B r
1 – Bromopropane
From the above discussion, it is evident that although both reactions are electrophilic addition reactions
but it is due to different orientationof addition of H and Br atoms which gives different products.
17. Write down the products of Ozonolysis of 1, 2-dimethylbuenzene (o-xylene). How does the result
support Kekule structure of benzene ?
Ans. o – Xylene may be regarded as a resonance hybride of the following two Kekule structures.
Ozonolysis of each one these gives two products as shown below :
CH3 CH3
CH3 CH3

I II
(i) O3, CH2Cl2, 195K (i) O3, CH2Cl2, 195 K
(ii) Zn/H2O (ii) Zn/ H2O
CH3 CH3
 
2 C C CH3
O = CH O O C
Methylglyoxal O
Dimethylglyoxal
+
CH = O CH = O
 +2 
CH = O CH = O
Glyoxal Glyoxal

Thus, in all, three products are formed. Since all the three products cannot be obtained from any one of the
two Kekule structures, this shows that o –xylene is a resonance hybride of the two Kekule structures (1 and
II).
18. Arrange benzene, n-hexane and ethyne in decreasing order of acidic behaviour. Also give reason
for this behaviour.
Ans. The hybridization state of carbon in these three compounds is :
sp2 H
sp3 sp
CH3  (CH2)4  CH3 HCCH
Benzene Hexane Acetylene
2 3
Type of orbital : sp sp sp
s – Character : 33.3% 25% 50%
Since s-electrons are closer to the nucleus, therefore, as the s- character of the orbital making the C  H bond
increases, the electrons of C  H bond lie closer and closer to the carbon atom . In other words, the partial
+ve charge on the H-atom and hence the acidic character increases as the s- character of the orbital increases.
Thus, the acidic character decreases in the order : Ethyne > Benzene > Hexane.
19. Why does benzene undergo electrophilic substitution reactions easily and nucleophilic substitutions
with difficulty ?
Ans. Due to the presence of an electron cloud containing 6 -electrons above and below the plane of the ring,
benzene is a rich source of electrons. Consequently, it attracts the electrophiles (electron-deficient) reagents
towards it and repels nucleophiles (electron-rich) reagents. As a result, benzene undergoes electrophilic
substitution reactions easily and nucleophilic substitutions with difficulty.
20. How will you convert the following compounds into benzene ?
(i) Ethyne (ii) Ethene (iii) Hexane
Red hot Fe tube
Ans. (i) 3 HC  CH 
Ethyne 873 K
(ii) Ethene is first converted into ethyne and then to benzene as shown above.
Br2/CCl4 KOH (alc), 
CH2 = CH2  Br  CH2  CH2  Br 
Ethene 1, 2-Dibromoethane (Dehydrobromination)
Red hot Fe tube
HC  CH 
Ethyne 873 K
(ii) When vapours of hexane are passed over heated catalyst consisting of Cr2O3 , Mo2O3 and V2O5
at 773K under 10-20 atm pressure, cyclization and aromatization occurs simultaneously to afford
benzene.
CH3
CH2 CH3 Cr2O3/V2O5/Mo2O3 Aromatization
   
CH2 CH2 Cyclization ( - 3H2)
CH2 ( - H2) Cyclohexane Benzene
n-Hexane
21. Write structures of all the alkenes which on hydrogenation give 2- methylbutane ?
C
4 
Ans. The basic skeleton of 2-methylbutane is C  3C  2C  1C
Putting double bonds at various different positions and satisfying the tetracovalency of each carbon, the
structures of various alkenes which give 2-methylbutane on hydrogenation are :
CH3 CH3 CH3
4  2 1 1  4 1  3 4
CH3  CH  CH = CH2
3
CH3  C = CH  CH3
2 3
CH2 = C  CH2CH3
2
3-Methylbut-1-ene 2-Methylbut-2-ene 2-Methylbut-1-ene

22. Arrange the following set of compounds in order of their decreasing relative reactivity with an
electrophil, E+ .
a) Chlorobenzene, 2, 4-dinitrochlorobenzene, p- nitrochlorobenzene
b) Toluene p – H3C  C6H4  NO2 , p – O2N  C6H4  NO2.
Ans. The typical reactions of benzene are electrophilic substitution reaction. Higher the electron-density in
the benzene ring, more reactive is the compound towards these reactions. Since NO2 is a more powerful
electron-withdrawing group tan Cl, therefore, more the number of nitro groups, less reactive is the compound.
Thus, the overall reactivity decreases in the order :
Chlorobezene > p-nitrochlorobenzene > 2, 4-dinitrochlorobenzene
(b) Here, CH3 group is electron donating but NO2 group is electron-withdrawing. Therefore, the maximum
electron-density will be in toluene, followed by p-nitrotoluene followed by p-dinitrobenzene. Thus, the overall
reactivity decreases in the order :
Toluene > p – H3C  C6H4  NO2 > p – O2N  C6H4  NO2
23. Out of benzene, m-dinitrobenzene and toluene which will undergo nitration most easily and why ?
Ans. CH3 group is electron-donating while  NO2 group is electron-withdrawing . Therefore, maximum
electron density will be in toluene, followed by benzene and least in m-dinitrobenzene. Therefore, the ease of
nitration decreases in the order : toluene > benzene > m-dinitrobenzene.
24. Suggest name and another Lewis acid instead of anhydrous aluminium chloride which can be used
during ethylation of benzene.
Ans. Anhydrous FeCl3, SnCl4, BF3 etc.
25. Which is Wurtz reaction not preferred for preparation of alkanes containing odd number of carbon
atoms ? Illustrate your answer by taking one example.
Ans. For preparation of alkanes containing odd number of carbon atoms, a mixture of two alkyl halides has
to be used. Since two alkyl halides can react in three different ways, therefore, a mixture of three alkanes
instead of the desired alkae would be formed. For example, Wurtz reaction between 1-bromopropane and
1-bromobutane gives a mixture of three alkanes, i.e. hexane, heptane and octane as shown below :
Dry ether
CH3CH2CH2  Br + 2 Na + Br  CH2CH2CH3  CH3CH2CH2CH2CH2 CH3 + 2 NaBr
 Hexane
1-Bromopropane
Dry ether
CH3CH2CH2  Br + 2 Na + Br  CH2CH2CH2CH3  CH3CH2CH2CH2CH2CH3 + 2NaBr
1 –Bromopropane 1- Bromobutane  Heptane
Dry ether
CH3CH2CH2CH2 - Br + 2 Na + Br - CH2CH2CH2CH3  CH3CH2CH2CH2CH2CH2CH2CH3 + 2 NaBr
1 Bromobutane  octane

Competition Decoder
26. The number of isomers for the compound with molecular formula C2BrClFI is
a) 3 (b) 4 (c) 5 (d) 6 IIT-2001
F Br F I F Cl F I
Sol. (d) C=C , C=C , C=C C=C ;
Cl I Cl Br Br I Br Cl
F Cl F Br
C =C and C=C
I Br I Cl
27. Which of the following hydrocarbons has the lowest dipole moment ?
CH3 CH3
a) C=C (b) CH3C ≡ CCH3 (c) CH3CH2C ≡ CH (d) CH2 = CH – C ≡ CH IIT-2002
H H
Sol. (b) CH3C ≡ CCH3 being linear and symmetrical has lowest (or zero) dipole moment.
28. Consider the following reaction,

H3C – CH – CH – CH3 + B r → ‘X’ + HBr IIT-2002
| |
D CH3
  
a) CH3 – CH – CH – CH3 (b) CH3 – CH – C – CH3 (c) CH3 – C – CH – CH3 (d) CH3– C H – CH – CH3
| | | | | | |
D CH3 D CH3 D CH3 CH3
Sol. (b)
29. Identify the reagent from the following list which can easily distinguish between 1-butyne and 2-
butyne. IIT-2002
a) bromine, CCl4 (b) H2, Lindlar catalyst (c) dilute H2SO4, HgSO4 (d) ammoniacal Cu2Cl2 solution
Sol. (d)
5. 2-Hexyne gives trans-2-hexene on treatment with
a) Li/NH3 (b) Pd/BaSO4 (c) LiAlH4 (d) Pt/H2 IIT-2004
Sol. (a)
6. 2-Phenylpropene on acidic hydration gives
a) 2-Phenyl-2-propanol (b) 2-Phenyl-1-propanol (c) 3-Phenyl-1-propanol (d) 1-Phenyl-2-propanol
IIT-2004
OH
(i) H2SO4 |
Sol. (a) CH3 – C = CH2 CH3 – C – CH3
| (ii) boil with H2O |
C6H5 C6H5
2-Phenylpropene 2-Phenyl-2-propanol
7. CH3  CH = CH2  ? NOCl
The product of the following reaction is

(a) CH3  CH  CH2Cl (b)CH3  CH  CH2  NO
NO Cl

(c) CH3  CH2  CH  NO (d) ON CH2 CH2 CH2Cl IIT-2006
Cl
  
Sol. CH3  CH = CH2 NO
 CH3  CH  CH2 Cl
 CH3  CH  CH2  NO
NO Cl
 (b)
8. (CH3)2  CH  CH2  CH3 
Cl 2
(N) mixture of isomeric products C5H11Cl Fraction
  (F)
Distillati on
The number of compounds formed respectively for (N) and (F) are
(a) 6,6 (b) 6,4
(c) 4,4 (d) 3,3 IIT-2006
Sol.
*
Me2CHCH2CH3 
Cl 2
Cl  CH2  CH  CH2  CH3 & its enantiomer
Me
Cl
Me
C  CH2  CH3
Me
Cl
Me
CH  CH  CH3 & its enantiomer
Me *
Me
CH CH2  CH2 Cl
Me
Since, enantiomer have nearly same physical properties therefore on fractional distillation we will get just
four distinct compounds without resolution.
 (b)
9. Which is the decreasing order of strength of bases :
OH-, NH2-, HC ≡ C- and CH3CH2- ?
a) CH3CH2- > NH2- > HC ≡ C - > OH- (b) HC ≡ C- > CH3CH2- > NH2- > OH-
c) OH- > NO2- > HC ≡ C- > CH3CH2- (d) NH2- > HC ≡ C- > OH- > CH3CH2- IIT- 1993
Sol. (a)
10. When phenylmagnesium bromide reacts with tertbutanol, which of the following is formed ?
a) tert-Butyl ether (b) Benzene (c) tert-butylbenzene (d) conc. HBr IIT-2005
Sol. (b) C6H5MgBr + (CH3)3COH → C6H6 + (CH3)3COMgBr
11. Propyne and propene can be distinguished by
a) conc. H2SO4 (b) Br2 in CCl4 (c) alk. KMnO4 (d) AgNO3 in NH3 IIT-2000
Sol. (d) AgNO3 in NH3 reacts with propyne to give white ppt. of silver propynide while propene does not.
12. CH3 – CH = CH2 + NOCl → P. Identify the aduct P
NO
a) CH3 – CH – CH2 (b) CH3 – CH – CH2 (c) CH3 – CH2 – CH (d) CH2 – CH2 – CH2 IIT-2006
| | | | Cl | |
Cl NO NO Cl NO Cl
Sol. (a) NOCl ionizes as follows :
NOCl NO+ + Cl-

The addition occurs through the more stable carbocation intermediate to give 1-nitroso-2-chloroethane.
NO+ + Cl-
CH3 – CH = CH2 → CH3 – CH – CH2 → CH3 – CH – CH2
Propene | | |
NO Cl NO
13. The reagents for the following conversion
?
Br → H – ≡ – H is/are
Br
a) alcoholic KOH (b) alcoholic KOH followed by NaNH2
c) aqueous KOH followed by NaNH2
d) Zn/CH3OH IIT-2007
Sol. (b) Due to resonance, C – Br bond in vinyl bromide has some double bond character and hence is more
strongly held than in alkyl bromides
.. ..
CH2 = CH – Br : ←→ - : CH2 – CH = Br :
.. ..
Vinyl bromide
Therefore dehydrobromination of alkyl bromides occurs smoothly with alcoholic KOH but to removes HBr
from vinyl bromide, stronger base like NaNH2 in liq. NH3 is required.
Br KOH (alc.), ∆ Br NaNH2, liq NH3
Br H – ≡ – H
- HBr viny bromide - HBr
14. In the following reaction
the structure of the major product ‘X’ is IIT-2007
(A) O (B)
O2 N O
NO2
N
H N
H
(C) O (D)
O
N
H N
O2N
NO2 H
Sol. The benzene ring which is directly attached with Nitrogen atom of acidamide group is more activated than
the other, so nitration will take place at para position of this activated ring.
O2N
O O
conc. HNO3
N
N conc. H2SO4
H
H
 (B)
15. The ortho/para-directing group among the following is
a) COOH (b) CN (c) COCH3 (d) NHCOCH3 AIIMS-2003

Sol. (d)
16. The treatment of benzene with isobutene in the presence of sulphuric acid gives
a) Isobutylbenzene (b) tert-Butylbenzene (c) n-Butylbenzene (d) No reaction AIIMS-2003
+ C6H6
Sol. (b) (CH3)2 C = CH2 + H+ → (CH3)3 C CH3)3C – C6H5

+
Isobutene -H terr-Butylbenzene
17. Among the following the aromatic compound is AIIMS-2004
Sol. (a) Only (a) has 2 π-electrons and hence is aromatic. All others have 4 π electrons and hence are
antiaromatic.
18. 3-Phenylpropene on reaction with HBr gives (as a major product) AIIMS-2005
a) C6H5CH2CH(Br)CH3 (b) C6H5CH(Br)CH2CH3 (c) C6H5CH2CH2CH2Br (d) C6H5CH(Br)CH = CH2
3 2 1 H+ + 1, 2-Hydride + Br-
Sol. (b) C6H5 – CH2 – CH = CH2 → C6H5 – CH – CH – CH3 C6H5 – CH – CH2 – CH3 →
3-Phenylpropene | 2o Carbocation shift 2o Carbocation
H (less stable) (more stable)
C6H5 – CHBr – CH2CH3
19. The major product obtained on treatment of CH3CH2CH(F)CH3 with CH3O-/CH3OH is
a) CH3CH2CH(OCH3)CH3 (b) CH3CH = CHCH2 (c) CH3CH2CH = CH2 (d) CH3CH2CH2CH2OCH3
AIIMS-2005
Sol. (c) Saytzeff rule is not followed because
4 3 2 1 CH3O-
CH3 – CH2 – CH – CH3 CH3 – CH2 – CH = CH2
| CH3OH But-1-ene
F
Hydrogen on carbon-1 is much more acidic than that on carbon-3 and hence hydrogen is abstracted from
carbon-1 to give -1butene
20. The major product obtained on monobromination (Br2/FeBr3) of the following compound A is
AIIMS-2006
Sol. (b) Both OCH3 and CH3 are o, p-directing groups. The possible position of attack which are facilitated
by both OCH3 and CH3 are shown by arrows below :

Since OCH3 group is bulkier than CH3 group, therefore, due to steric hindrance the reaction does not occur
at positions 2 and 6 but instead occurs at position 4.
21. Which of the following species participate in sulphonation of benzene ring ?
a) H2SO4 (b) SO3 (c) HSO3 (d) SO2- AIIMS-2007
Sol. (b)
22. What of these will not react with acetylene ?
a) NaOH (b) ammoniacal AgNO3 (c) Na (d) HCl AIEEE-2002
Sol. (a)
23. What is the product formed when acetylene reacts with hypochlorous acid ?
a) CH3COCl (b) ClCH2CHO (c) Cl2CHCHO (d) ClCH2COOH AIEEE-2002
Sol. (c)
24. Butene-1 may be converted to butane by reaction with
a) Pd/H2 (b) Zn – HCl (c) Sn – HCl (d) Zn – Hg AIEEE-2003
Sol. (a)
25. On mixing certain alkane with chlorine and irradiating it with ultraviolet light, one forms only one
monochloroalkane. The alkane could be
a) neopentane (b) propane (c) pentane (d) isopentane AIEEE-2003
Sol. (a)
26. Which of the following has the minimum boiling point ?
a) n-Butane (b) 1-Butyne (c) 1-Butene (d) 1-Isobutene AIEEE-2004
Sol. (a) Because of greater polarizability, alkenes and alkynes have higher boiling points than their
corresponding alkanes.
27. Among the following compounds which can be dehydrated very easily is
a) CH3CH2CH2CH2CH2OH (b) CH3CH2CH2 – CHOH – CH3
CH3 CH3
| |
c) CH3CH2 – C – CH2 CH3 (d) CH3 – CH2 – CHCH2CH2OH AIEEE-2004
|
OH
Sol. (a)
28. 2-Methylbutane on reacting with bromine in the presence of sunlight gives mainly
a) 1-bromo-2-methylbutane (b) 2-bromo-2-methylbutane
c) 2-bromo-3-methylbutane (d) 1-bromo-3-methylbutane AIEEE-2005
Sol. (b) 3o H is abstracted most readily, i.e.,
Br
Br2/h  |
CH3 – CH – CH2CH3 CH3 – C – CH2CH3
| |
CH3 CH3
2-Methylbutane 2-Bromo-2-methylbutane
29. Of the five isomeric hexanes, the isomer which can give two monochlorinated compounds is
a) n-hexane (b) 2,3-dimethylbutane (c) 2, 2-dimethylbutane (d) 2-methylpentane AIEEE-2005
Sol. (b)
30. Alkyl halides react with dialkylcopper reagents to give
a) alkenes (b) alkylcopper halides (c) alkanes (d) alkenyl halides AIEEE-2005

–
R
Sol. (c) Cu Li+ + R’ – X → R – R’ + RCu + LiX
R Alkane
Lithium dialkylcuprate
31. Acid-catalysed hydration of alkenes except ethane leads to the formation of
a) primary alcohol (b) secondary or tertiary alcohols
c) mixture of primary and secondary alcohols (d) mixture of secondary and tertiary alcoholsAIEEE-2005
Sol. (b) Propene gives 2o alcohol while 2-methylpropene gives 3o alcohol.
(i) Conc. H2SO4
CH3 – CH = CH2 CH3 – CHOH – CH3
Propene (ii) H3O+ 2o Alcohol
O
| Conc. H2SO4
CH3 – C = CH2 (CH3)3COH
+
2-Methylpropene (ii) H3O 3o Alcohol
32. Elimination of bromine from 2-bromobutane results in the formation of
a) equimolar mixture of 1- and 2-butene (b) predominantly 2-butene
c) predominantly 1-butene (d) predominantly 2-butyne AIEEE-2005
Sol. (b)
33. HBr reacts with CH2 = CH – OCH3 under anhydrous conditions at room temperature to give
a) CH3CHO and CH3Br (b) BrCH2CHO and CH3OH (c) BrCH2 – CH2 – OCH3
d) H3C – CHBr – OCH3 AIEEE-2006
Sol. (d) Methyl vinyl ether is a very reactive gas. It readily undergoes hydrolysis with dilute acids to form
methanol and acetaldehyde. However, under anhydrous conditions at room temperature, it mainly
undergoes addition reaction as shown below :
H+
 .. 
(i) CH2 = CH – OCH3 → CH3 – C H – O CH3 ←→ CH3 – CH = O CH3
.. ..
Resonance stabilized
cartbocation
-
+Br

(ii) CH3 – C H – OCH3 –→ CH3 – CHBr – OCH3.
34. Phenylmagnesium bromide reacts with methanol to give
a) a mixture of anisole and Mg(OH)Br (b) a mixture of benzene and Mg(OMe)Br
c) a mixture of toluene and Mg(OH)Br (d) a mixture of phenol and Mg(OMe) Br AIEEE-2006
- +
Sol. (b) C6H5 – MgBr + H – OMe → C6H6 + Mg(OMe)Br.

35. Reaction of trans-2-phenyl-1-bromocyclopentane on reaction with alcoholic KOH produces
a) 4-phenylcyclopentane (b) 2-phenylcyclopentane (c) 1-phenylcyclopentane
d) 3-phenylcyclopentene AIEEE-2006
Sol. (d) E2 elimination occurs when the two atoms/groups to be eliminated are trans to each other and lie
in the same plane. Since in trans-2-phenol-1-bromocyclopentane.

the C2 – H is cis- w.r.t. C1 – Br, therefore, elimination does not occur according to Saytzeff rule. Instead C5
– H is trans to C1 – Br, therefore, elimination occurs on this side to give 3-phenyl-cyclopentene.
36. Presence of a nitro group in a benzene ring
a) deactivates the ring towards electrophilic substitution
b) activates the ring towards electrophilic substitution
c) renders the ring basic (d) deactivates the ring towards nucleophilic substitution AIEEE-2007
Sol. (a)
37. The treatment of CH3MgX with CH3C ≡ C – H produces AIEEE-2008
H H
| |
a) CH3 – C = C – CH3 (b) CH4 (c) CH3 – CH = CH2 (d) CH3C ≡ C – CH3
Sol. (b)Terminal alkynes being acidic react with Grignard reagents to give alkanes corresponding to the alkyl
group of the Grignard reagent, i.e.,
CH3 – C ≡ C – H + CH3 – MgX → CH3C ≡ CMgX + CH4
38. The hydrocarbon which can react with sodium in liquid ammonia is AIEEE-2008
a) CH3CH = CHCH3 (b) CH3CH2C ≡ CCH2CH3 (c) CH3CH2CH2C ≡ CCH2CH2CH3 (d) CH3CH2C ≡
CH
Sol. (d)Terminal alkynes being acidic react with Na/liq. NH3 to evolve H2.
Liq. NH3
2 CH3CH2C ≡ CH + 2Na –––––→ 2 CH3CH2C ≡ C- Na+ + H2
39. In the following sequence of reactions, the alkene affords the compound ‘B’
O3 H2O
CH3CH = CHCH3 A B.
The compound B is
a) CH3CH2COCH3 (b) CH3CHO (c) CH3CH2CHO (d) CH3COCH3
O3 O Zn/H2O
Sol. (b) CH3CH = CHCH3 → CH3CH CHCH3 2 CH3CHO
But-2-ene | | Ethanal
O O
40. The electrophile, E  attacks the benzene ring to generate the intermediate σ-complex. Of the
following, which σ-complex is of lowest energy ? AIEEE-2008
Sol. (d)Since – NO2 is a powerful electron withdrawing group, therefore, carbocations (a), (b), (c) are
destabilized. However, in option (d), there is no – NO2 group. Thus, σ-complex (d) is of lowest energy.
41. α-D-(+)-glucose and β-D-(+)-glucose are AIEEE-2008
a) anomers (b) enantiomers (c) conformers (d) epimers
Sol. (a)α-D-(+) glucose and β-D-(+)-glucose differ in configuration at the anomeric carbon, i.e., C1 and
hence are called anomers.

42. Which alkene on ozonolysis gives CH3CH2CHO and CH3COCH3 ?
a) CH3CH2CH = C(CH3)2 (b) CH3CH2CH = CHCH2CH3
c) CH3 CH2CH = CHCH3 (d) (CH3)2C = CHCH3 AIPMT-2001
Sol. (a)
43. When CH3CH2CHCl2 is treated with NaNH2, the product formed is
NH2 Cl
a) CH3 – CH = CH2 (b) CH3 – C ≡ CH (c) CH3CH2CH (d) CH3CH2CH AIPMT-2002
NH2 NH2
Sol. (b)
CH3
|
44. The compound, CH3 – C = CH – CH3 on reaction with NaIO4 in presence of KMnO4 gives
AIPMT-2003
a) CH3COCH3 (b) CH3COCH3 + CH3COOH (c) CH3COCH3 + CH3CHO (d) CH3CHO + CO2
CH3 CH3
| KMnO4 | NaIO4
KMnO4
Sol. (b) CH3 – C = CH – CH3 CH3 – C – CH – CH3 (CH3)2C = O + CH3COOH
| |
HO OH
(CH3)2 C = O +
CH3COOH
45. The correct order of reactivity towards the electrophilic substitution of the compounds aniline (I),
benzene (II) and nitrobenzene (III) is
a) III > II > I (b) II > III > I (c) I < II > III (d) I > II > III AIPMT-2003
Sol. (d)
46. Which one of the following order of acid strength is correct ?
a) RCOOH > ROH > HOH > HC ≡ CH (b) RCOOH > HOH > ROH > HC ≡ CH
c) RCOOH > HOH > HC ≡ CH > ROH (d) RCOOH > HC ≡ CH > HOH > ROHAIPMT-2003
Sol. (b)
47. The molecular formula of diphenylmethane, C13H12 is
CH2
How many structural isomers are possible when one of the hydrogens is replaced by a chlorine
atom ?
a) 4 (b) 8 (c) 7 (d) 18
48. Products of the following reaction :
(i) O3
CH3C ≡ CCH2CH3 –––––––→ … are
(ii) oxidation
a) CH3COOH + CH3COCH3 (b) CH3COOH + HOOCCH2CH3
c) CH3CHO + CH3CH2CHO (d) CH3COOH + CO2 AIPMT-2005
O3 O Oxidation
Sol. (b) CH3 – C ≡ C – CH2CH3 CH3 – C –– C – CH2CH3 CH3COOH + HOOCCH2CH3
| |
O O

Ozonide
49. Enthalpy of hydrogenation of cyclohexene is -119.5 kJ mol-1. If resonance energy of benzene is –
150.4 kJ mol-1, its enthalpy of hydrogenation would be
a) -358.5 kJ mol-1 (b) – 508.9 kJ mol-1 (c) – 208.1 kJ mol-1 (d) - 269.9 kJ mol-1 AIPMT-2006
Sol. (c) Enthalpy of hydrogenation of benzene = 3 × Enthalpy of hydrogen of cyclohexene –resonance
energy of benzene
= 3 ( -119.5) – ( - 150.4)
= - 298.1 kJ mol-1
50. Which of the compounds with molecular formula C5H10 yields acetone on ozonolysis ?
a) 2-Methyl-1-butene (b) 2-Methyl-2-butene (c) 3-Methyl-1-butene (d) Cyclopentane AIPMT-2007
Sol. (b)
51. Base strength of :
a) H3C CH2,
b) H2C = CH and
c) H – C ≡ C
is in the order : AIPMT-2008
1) (a) > (c) > (b) (2) (a) > (b) > (c) (3) (b) > (a) > (c) (4) (c) > (b) > (a)
Sol. The base strength decreases as the electronegativity of the carbon carrying the –ve charge increases or the
hybridization of the carbon carrying the –ve charge changes from sp3 to sp2 to sp. Thus, the basicity decreases
in the order :
H3CCH2- (1) > H2C = CH- (2) > (H – C ≡ C- (3). Thus , option (2) is correct.
52. H3C – CH -CH= CH2 + HBr → A
|
CH3
A (Predominatly ) is : AIPMT-2008
Br
|
a) CH3 – CH – CH – CH3 (b) CH3 – CH – CH – CH3 (c) CH3 – CH – CH2 – CH2Br (d) CH3-C –CH2CH3
| | | | | |
Br CH3 CH3 Br CH3 CH3
Sol. (a) Addition of a H+ at the terminal carbon first gives a 2o carbon (I) which undergoes 1, 2-hydride shift
to yield the more stable 3o carbocation (II). Nucleophilic attack by Br- ion on carbocation (II) finally gives 2-
bromo-2-methylbutane (A) as the final products.
H Br
+ -
H | + + Br |
H3C – CH – CH = CH2 → H3C – C – CH – CH3 → H3C – C – CH2CH3 → H3C – C – CH2CH3
| | | |
CH3 CH3 CH3 CH3
(I) 2-Bromo-2-
methylbutane(A)
53. The reaction of propene with HOCl (Cl2 + H2O) proceeds through the interrmediate :
(1) CH3 - CH+ - CH2 - OH (2) CH3 - CH+ - CH2 - Cl (3) CH3 - CH(OH) - CH2+ (4) CH3 - CHCl - CH2+
JEE-MAINS-2016
Sol. (2)

54. In the reaction AIPMT-2016
X and Y are
(1) X = 2-Butyne ; Y = 2-Hexyne (2) X = 1-Butyne; Y = 2-Hexyne
(3) X = 1-Butyne; Y = 3-Hexyne (4) X = 2-Butyne ; Y = 3-Hexyne
Sol.(3)
46. Which one is the correct order of acidity ? NEET-2017
Sol. (1) Correct order of acidic strength  CH  CH > CH3 - C  CH > CH2 = CH2 > CH3 - CH3
acc. to EN and Inductive effect.
47. Predict the correct intermediate and product in the following reaction : NEET-2017
Sol. (3)
48. 3-Methyl-pent-2-ene on reaction with HBr in presence of peroxide forms an addition product. The
number of possible stereoisomers for the product is : JEE MAINS 2017
(1) Zero (2) Two (3) Four (4) Six
Sol. (3)
Total stereo centers =2, Total stereo isomers = 4

49. Hydrocarbon (A) reacts with bromine by substitution to form an alkyl bromide which by Wurtz
reaction is converted to gaseous hydrocarbon containing less than four carbon atoms. (A) is
(1) CH = CH (2) CH2 = CH2 (3) CH4 (4) CH3 – CH3 NEET-2018
Sol. (3)
Hence the correct option is (3)

50. The trans-alkenes are formed by the reduction of alkynes with JEE MAINS-2018

(1) Na/liq. NH3 (2) Sn – HCl (3) H2 – Pd/C, BaSO4 (4) NaBH4
Sol. (1) Na in liquid ammonia carryout ant and partial hydrogenation of alkyne to trans alkene.
Na/liq.NH3 CH3 H
Sol. (1) CH3 – C≡C – CH3 ––—–––––→ C=C
H CH3
Trans alkene
51. Total number of hydroxyl groups present in a molecule of the major product P is _______
JEE ADVANCED 2019

Sol. (06)
52. An alkene A on reaction with O3 and Zn—H2O gives propanone and ethanal in equimolar ratio.
Addition of HCl to alkene A gives B as the major product. The structure of product B is
NEET-2019
Sol. (d)
Addition of HCl to an alkene (A) will take place according to Markownikoff’s rule.
53. The most suitable reagent for the following conversion, is NEET 2019
Sol. (c)
54. Among the following the reaction that proceeds through an electrophilic substitution is
NEET 2019

δ+
Sol. (c) : The attacking species in this reaction is an electrophile i.e., Cl. Therefore, it is an electrophilic
substitution reaction.
55. The major product of the following reaction is JEE MAINS 2019 APRIL 8 E
Sol. (a)
56. Which one of the following alkenes when treated with HC1 yields majorly an anti Markovnikov
product? JEE MAINS 2019 APRIL 8 E
(a) CH3O - CH = CH2 (b) Cl - CH = CH2 (c) H2N - CH= CH2 (d) F3C- CH= CH2
Sol. (d) 16. (d) As fluorine is most electronegative species therefore, among the given alkenes, maximum
probability to yield anti-Markovnikov product is from F3C — CH = CH2,

Consider the following transformations of a compound P

58. NEET 2020
59. NEET 2020
60. NEET 2020

62. JEE MAINS SEP 2 S2


Organic Chemistry Purification Techniques

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MASTERING CHEMISTRY 1

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Simple distillation Fractional distillation

Distillation under Reduced Pressure: Steam distillation

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TLC chromatograph being developed

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CuSO4 + 5H2O  CuSO4 . 5H2O

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Apparatus for estimation of Carbon & Hydrogen

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Apparatus for the estimation of Nitrogen by Duma’s method

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Apparatus for the estimation of Nitrogen by Kjeldahl’s method

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35.5 Mass of AgCl  100

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H2 SO4 + BaCl2 BaSO4

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Calculations : First of all volume is converted to volume at S.T.P. as :

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10 20 30 40 50 60 70 80 90 100 110 120

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2. Indicate the - and -bonds in the following molecules :

3. Write bond-line formulas for : Isopropyl alcohol, 2, 3-dimethylbutanal, heptan-4-one.

4. Give the IUPAC names of the following compounds :

Ans. (a) Propylbenzene (b) 3-Methylpentanenitrile (c) 2, 5-Dimethylheptane (d) 3-Bromo-3-chloroheptane

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8. Identify the functional groups in the following compounds :

9. Which is expected to be more stable, O2NCH2CH2O- or CH3CH2O- and why ?

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12. What are electrophiles and nucleophiles ? Explain with examples.

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chain. Thus, CH2 = CH  CH2  CH2  C  CH

Thus, option (c) is correct.

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(D) Monofunctional Compounds

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(xii) [(CH3)2 CH]3 COH (xiii) CH3CH2CHCH2CHO (xiv) CH3CHCH2CH3

(xiv) Cl Br (xv) Cl2CHCH2OH

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(F) Additional Compounds:

(i) (ii) H3C CH2CHO (iii) CH = CH ― CH ― CH2CH3

(vii) (viii) (ix)

CH3 CH3[CH2]9 [CH2]9CH3

8. Draw the structures of the following compounds :