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Organic Chemistry
Organic :
Chemistry:
σ bond

C
C C
H Some Basic
Some Basic
Principles And
Chapter - 12 Principles and
H
H

60
Techniques
Techniques
FAST TRACK : QUICK REVISION

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ORGANIC CHEMISTRY
It deals with the study of hydrocarbons (compounds of carbon and hydrogen
elements) and their derivatives.

phosphorus, halogens, etc. ID
Some organic compounds may also contain nitrogen, oxygen, sulphur,

Berzelius, proposed that a 'vital force' was responsible for the formation of
organic compounds.
U
This was rejected by F. Wohler who synthesised first organic compound urea
from an inorganic compound.
YG

NH4CNO NH2CONH2
Ammonium cyanate Urea

 Acetic acid was synthesised by Kolbe and methane by Berthelot.

 Types of hybridisation of C-atom :
D

Hybridisation Structure Bond angle Examples

sp3 Tetrahedral 109°28' Ethane, Methane
sp2 Trigonal 120° Ethene, Propene
U

sp Linear 180° Ethyne, Propyne

 Reasons for existence of large number of organic compounds:

ST

 Catenation : The property of atoms of an element to link with one another

forming chains of identical atoms is called catenation. Carbon exhibits
catenation to the maximum extent.
 Isomerism : It is the property by virtue of which two or more compounds
have the same molecular formula but different physical or chemical
properties.
  Formation of multiple bonds : Because of its small size carbon atom
is capable of forming multiple bonds with other atoms and this gives a
variety of compounds.
 CLASSIFICATION OF ORGANIC COMPOUNDS

60
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H
(Pysrole)

ID
U
YG

CLASSIFICATION OF CARBON ATOMS


On the basis of number of C attached
D

(i) Primary carbon atom : when carbon atom is attached with one other
carbon atom only, it is called primary or 1° carbon atom.
U

(ii) Secondary carbon atom : When carbon atom is attached with two
other carbon atoms, it is called secondary or 2° carbon atom.
(iii) Tertiary carbon atom : When carbon atom is attached with three
ST

other carbon atoms, it is called tertiary or 3° carbon atom.

(iv) Quaternary carbon atom : When carbon atom is attached with four
other carbon atoms, it is called quarterly or 4° carbon atom.
 Functional Group : The atom e.g., –Cl, –Br, etc., or group of atoms
e.g., –COOH, –CHO, which is responsible for the chemical properties of
the molecule, is called functional group.

Organic Chemistry: Some Basic Principles and Techniques 183

  Homologous Series : The series in which the molecular formula of
adjacent members differ by a – CH2 unit, is called homologous series and
the individual members are called homologous, e.g., The homologous
series of alkene group is

}
C2H4
C3H6
difference of —CH2 unit or 14 unit mass

60
C4H8
C5H10

The general characteristics of this series are :

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1. All the homologues contain same functional group. That's why their
chemical properties are almost similar.
2. All the members of a series have same general formula, e.g.,
Series General Formula
Alkanes
Alkenes
ID CnH2n+2
CnH2n
U
Alkynes CnH2n–2
Alcohol and ether CnH2n+2O
YG

Aldehyde and ketone CnH2nO

Acid and ester CnH2nO2

3. All the members can be prepared by almost similar methods.

4. With increase in the molecular weight of a series, the physical
D

properties vary gradually.

 Representation of Organic Compounds :
U

Organic compounds can be represented by the following ways:

(i) Complete Structural Formula : All the bonds present between any
two atoms are shown clearly. e.g.,
ST

H H H H

H C C C C H
H Cl H H

184 Chemistry Class XI

 Condensed Formula : All the bonds are not shown clearly. e.g.,
(ii)
CH3CHCH2CH3
Cl
CH3CH(CI)CH2CH3

Bond Line Formula : Every fold and free terminal represents a carbon
(iii)

60
and lines represent the bond. e.g.,
Cl CH3 C CH CH2CH3

CH3

E3

CH3 CH2 COOH OH

 IUPAC Nomenclature of Organic Compounds : Following rules are

used to write the IUPAC name of an organic compound.
Rule 1. : Longest chain rule : The chain containing the principal functional

is the longest possible chain.

ID
group, secondary functional group and multiple bonds as many as possible

In the absence of functional group, secondary group and multiple bonds,

U
the chain containing the maximum number of C-atoms will be the longest
possible chain e.g.,
YG
D
U

Word Root for Carbon Chain

Chain length Word root Chain length Word root
C1 Meth- C7 Hept
ST

C2 Eth- C8 Oct
C3 Prop- C9 Non
C4 But- C10 Dec
C5 Pent- C11 Undec
C6 Hex- C12 Dodec

Organic Chemistry: Some Basic Principles and Techniques 185

 Rule 2 : Lowest number rule : Numbering is done in such a way so that
(i) branching if present gets the lowest number.
(ii) the sum of numbers of side chain is lowest.
(iii) principal functional group gets the lowest number.
Select the principal functional group from the preference series :

60
COOH > SO3H > acid anhydride COOR > COX > CONH2
> CN > NC > CHO > C = O > OH > SH
> NH2 > = > ≡ > substituents

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Functional group other than the principal functional group are called
substituents.
Rule 3: Naming the prefix and suffixes : Prefix represents the substit-
uent and suffix is used for principal functional group.

respectively. ID
Primary suffix are ene, ane or yne used for double, single and triple bonds

Secondary suffixes are tabulated below :

No. Class Formula Prefix Suffix
U
1. Acid halides halocarbonyl —oyl halide
—carbonyl halide
YG

2. Alcohols —OH hydroxy —ol

3. Aldehydes —CHO formyl —al
—carbaldehyde
4. Ketones C=O oxo (keto) —one
D

5. Amides —CONH2 carbamoyl —amide

U

6. Amine —NH2 amino —amine

7. Carboxylic —COOH carboxy —carboxylic
acid acid
ST

8. Ester —COOR alkoxy —alkyl

carbonyl alkanoate
9. Nitriles —CN cyano —nitrile
10. Sulphonic acid —SO2—OH sulpho —sulphonic acid

186 Chemistry Class XI

  Nomenclature of substituted benzene compounds :

60
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ID
ISOMERISM
U
Structural isomerism Stereo isomerism
YG

Same molecular formula but Same molecular and structural

different structures formula but different configuration
Types e.g., Geometrical isomerism
1. Chain Isomerism (cis-trans isomerism)
e.g., Pentane and H3C CH3
D

2-Methylbutane C C
2. Position Isomerism H H
e.g., But-1-ene
U

Cis.But-2-ene
But-2-ene
3. Functional Isomerism H CH3
e.g., Propanal & Propanone C C
ST

Ethanol & Methoxymethane CH3 H

4. Metamerism Trans.But-2-ene
e.g., Pentan-2-one and
Pentan-3-one

Organic Chemistry: Some Basic Principles and Techniques 187

  Fission of a Covalent Bond :
(i) Homolytic Fission : In this one of the electrons of the shared pair
in a covalent bond goes with each of the bonded atoms. The neutral
chemical species thus formed, are called free radicals. Generally,
homolytic fission takes place in non-polar covalent molecules in the
presence of sunlight or high temperature.

60
Sunlight
A — B ––––––→ A* + B*

{
free radicals
Sunlight
Cl2 ––––––→ 2Cl*

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Free radicals are highly reactive, neutral and electron deficient species.
(ii) Heterolytic Fission : The covalent bond breaks in such a fashion that
the shared pair of electrons goes with one of the fragments.
more electronegative
–→

A — B ––––––→ A+
ID
electrophile
less electronegative
+ B–
nucleophile
–→

U
A — B ––––––→ A– + B+
nucleophile electrophile
YG

Heterolytic fission generally takes place in polar covalent molecules

but in non-polar molecules, it takes place in the presence of catalyst
like AiCl3 (anhy.), FeCl3 (anhy.) etc.
 Attacking Reagents :
These are of two types
(i) Electrophiles or Electrophilic Reagents
D

These are electron deficient species, i.e., behave as Lewis acids.

+
e.g., Cl+, NO2, CH3CO+ etc.
U

BF3, ZnCl2 (anhydrous), FeCl3 (anhydrous), AlCl3 (anhydrous)

(ii) Nucleophiles or Nucleophilic Reagents
These are negatively charged or neutral molecules with unshared
ST

electron pair.
— °° °°
e.g., OH, CN–, RNH 2, NH3
 Reaction Intermediates :
(i) Free radicals : These are the product of homolysis and contain
an odd electron. These are highly reactive planar species with sp2
hybridisation.
188 Chemistry Class XI
 Their order of stability is
° ° °
(C6H5)3C > (C6H5)2 CH > C6H5CH2
° °
> CH2 = CH –– CH 2 > 3° > 2° > 1° > CH2 = CH
Carbocations : These are the product of heterolysis and contain a
(ii)
carbon bearing positive charge. These are electron deficient species.
These are also polar chemical species i.e., sp2 hybridised with an

60
empty p-orbital.
empty p-orbital


 C

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Stability order of carbocation is
+ + +
(C6H5)3C > (C6H5)2 CH > C6H5CH2
+ +
> CH2 = CH –– CH2 > 3° > 2° > 1° > CH2 = CH
(iii) ID
Carbanions : These are the product of heterolysis and contain a carbon
bearing negative charge and 8 electrons in its valence shell.
These have pyramidal shape with sp3 hybridised carbon (having one
U
lone pair) order of stability of carbanions is
– – –
(C6H5)3C > (C6H5)2 CH > C6H5CH2
–
YG

> CH3 > 1° > 2° > 3° carbanions

 Electron Displacement in Covalent Bond
1. Inductive Effect : If shared pair is more shifted towards more
electronegative atom, the less electronegative atom acquires slight
positive charge and more electronegative atom acquires partial
D

negative charge,
+d –d
e.g., CH3 →— Cl
U

Permanent effect and propagates through carbon chain.

Atoms or groups having greater electron affinity than hydrogen are
said to have electron attracting or negative inductive effect (–l) while
ST

that having, smaller electron affinity than hydrogen are said to have
electron releasing or positive inductive effect (+l).
+ dd +d –d
e.g., CH3 →— CH2 →— Cl
+ ddd + dd +d –d
CH3 →— CH2 →— CH2 →— Cl
1° alkyl halide

Organic Chemistry: Some Basic Principles and Techniques 189

 Cl has –l effect and alkyl group has +I effect.
Order of groups producing –I effect is
R3N > – NO2 > – CN > – SO3H > – CHO > – CO > – COOH > – F
> – Cl > – Br > – I > – OH > – OR > – NH2 > – C6H5 > – H
Order of groups producing +l effect is
3° alkyl group > 2° alkyl group > 1° alkyl group > – CH3 > – H

60
 Applications of Inductive Effect
(i) Presence of groups showing +I effect increases the stability of
carbocation while presence of groups showing –I effect decreases
their stability.

E3
(ii) Strength of acid increases with the attachment of group showing –I
effect and decreases with the attachment of group showing +I effect.
(iii) Presence of +I showing groups increases the basic strength of amines.

ID
2. Electromeric Effect : Defined as the polarity produced in a multiple
bonded compound as a reagent approaches it. In the presence of
attacking reagent, the two p electrons are completely transferred to
any of the one atom. This effect is temporary.
U
It may be of +E type (when displacement of electron pair is away
from the atom of group) or of –E type (when displacement is towards
the atom or group).
YG

H H H + – H
C C Reagent C C
H H H H
e.g., +
E
D

–
C O Reagent C O
U

Nu–
3. Hyper-conjugation : It involves delocalisation of s electron of a
C – H bond of an alkyl group attached directly to an atom of
ST

unsaturated system or to an atom with an unshared p-orbital.

H
e.g., H+
–
CH2 CH2 CH2 CH CH2

This effect is also called no bond resonance or Baker Nathan effect.

190 Chemistry Class XI

 Applications of Hyper-conjugation
Stability of alkenes : More the number of a-hydrogen atoms, more
stable is the alkene.

CH3  
 CH3  CH3  
H3C C C C  > CH3CH C  > CH3 CH CH CH3
CH3 CH3
H2

60
Stability of Carbocation : Greater the number of alkyl groups
attached to positively charged carbon atom, the greater is the stability.
+ + +
e.g., (CH3)2CH > CH3 — CH > CH3

E3
4. Resonance Effect : When the properties of a molecule cannot be
shown by a single structure and two or more structures are required
to show all the properties of that molecule, then the structures are
called resonating structures or canonical forms and the molecule is

Conditions for resonance ID
referred as resonance hybrid. This phenomenon is called resonance.

(i) The arrangement of atoms must be identical in all the formula.

U
(ii) The energy content of all the canonical forms must be nearly
same.
(iii) Each canonical of p electrons. This effect may be of +R type or
YG

–R type.
Positive Resonance Effect (+R)
Electron donating groups with respect to conjugated system show
+R effect. Central atom of functional groups should be more
electronegative than the surrounding atoms or groups to show +R
D

effect. e.g., halogens, –OH, –OR, –NH2, NHCOR, etc.

°° + + +
NH2 NH2 NH2 NH2
U

-
-
ST

Negative Resonance Effect (–R)

Electron withdrawing groups with respect to conjugate system
show –R effect. Central atom of functional groups should be less
electronegative than surrounding atoms or groups to show –R effect.
e.g., halogens, –COOH, –COOR, CHO, –CN, –NO2, etc.

Organic Chemistry: Some Basic Principles and Techniques 191

 H C O H C O- H C O- H C O-

+ +

+
 Methods of Purification of Organic Compounds

60
Method Principle Applications
Crystallization Different solubilities of a given organic • Crystallization of sugar
compound and its impurities in the same (containing an impurity of
solvent. common salt) is achieved by

E3
shaking the impure solid with
hot ethanol at 348K (sugar
dissolves whereas common
salt remains insoluble).
Sublimation Some solid substances change from solid • Iodine from sodium chloride
to vapour state without passing through (as iodine sublimes readily

impurities.
ID
liquid state. Sublimable compounds
get separated from non-sublimable
leaving behind sodium
chloride).
• C a m p h o r, n a p h t a l e n e ,
anthracence, benzoic Acid,
U
etc. are purified.
Distillation It is used to separate • Hexane (b.p. 342K) and
• Volatile liquids from non-volatile toluene (b.p. 384K)
YG

impurities. • Chloroform (b.p. 334K) and

• Liquids having sufficient difference in aniline (b.p. 457K)
their boiling points.
– Fractional If the difference in boiling points of two • Crude oil in petroleum
Distillation liquids is not much, this method is used. industry is separated into
various useful fractions such
as gasoline, kerosene oil,
D

diesel oil, lubricating oil, etc.

– Steam This method is used to separate substances • Aniline is separated from
Distillation which are (i) steam volatile, (ii) immiscible aniline water mixture.
U

with water, (iii) posses a vapour pressure • Essential oils, turpentine oil,
of 10-15 mm Hg and (iv) contain non- o-nitrophenol, bromobenzene
volatile impurities. nitrobenenze, etc. can be
purified.
ST

Differential By shaking an aqueous solution of an • Benzoic acid can be extracted

Extraction organic compound with an organic from its water solution using
solvent in which the organic compound is benzene.
more soluble than in water. The organic
solvent and the aqueous solution should
be immiscible with each other so that they
can form two distinct layers which can
be separated by using separating funnel.
192 Chemistry Class XI
 Chromatography Differential movement of individual • Widely used for separation
components of a mixture through a purification, identification
stationary phase under the influence of a and characterization of the
mobile phase. components of a mixture,
whether coloured or
colourless.
– Adsorption Differential adsorption of the various
Chromatography components of a mixture on a suitable

60
adsorbent such as silica get or alumina.
– Column The mixture is passed through adsorbent • Mixture of naphthalene and
Chromatography packed in glass tube. benzophenone.
– Thin Layer The mixture is passed over adsorbent on • Amino acids can be detected
Chromatography a thin glass plate. by spraying the plate with

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ninhydrin solution.
– Partition Differential partitioning of components of
Chromatography a mixture between stationary and mobile
phases.
– Paper A special quality paper known as • For separation of sugars and
Chromatography
ID
chromatography paper is used. It contains
water trapped in it, which acts as the
stationary phase.
amino acids.
U
Types of Chromatography Mobile / Stationary Phase
Column Chromatography Liquid / Solid
Thin Layer Chromatography Liquid / Solid
YG

High Performance Liquid Chromatography (HPLC) Liquid / Solid

Gas Liquid Chromatography (GLC) Gas / Solid
Partition or Paper Chromatography Liquid / Solid

Element Detection Confirmatory Test Reactions

D

D
Carbon 2CuO + C ––→ 2Cu + CO2 CO 2 gas turns lime CO2 + Ca(OH)2 –→ CaCO3↓ + H2O
water milky. Lime water Milkiness
D
Hydrogen CuO + 2H ––→ Cu + H2O Water droplets appear CuSO4 + 5H2O –→ CuSO4.5H2O
on the cooler part of White Blue
U

the ignition tube and

also turns anhydrous
CuSO4 blue.
ST

Nitrogen Lassaigne's extract (L.E.) L.E. + FeSO4 + NaOH, FeSO4 + 2NaOH –→ Fe(OH)2 + Na2SO4
D
Na + C + N ––→ NaCN boil and cool + FeCl3 + Fe(OH) + 6NaCN –→
2
(L.E.) conc. HCl. Gives blue Na4[Fe(CN)6] + 2NaOH
or green colour.
3Na4[Fe(CN)6] + 4FeCl3 –→
Fe4[Fe(CN)6]3 + 12NaCl
Prussian blue

Organic Chemistry: Some Basic Principles and Techniques 193

 D
Sulphur 2Na + S ––→ Na2S – L.E. + sodium Na2S + Na2[Fe(CN)5NO] –→
(L.E.) nitroprusside Sodium nitroprusside
A deep violet colour. Na4[Fe(CN)5NOS]
– L.E. + CH3COOH + Deep violet
(CH3COO)2Pb CH3COOH
Na2S + (CH3COO)2Pb ––––––––→
Gives a black ppt.
Pbs↓ + 2CH3COONa
Black ppt.
D HNO3

60
Halogens Na + X ––→ NaX L.E. + HNO3 + AgNO3 NaX + AgNO3 ––––––→ AgX↓
(L.E.) – White ppt. soluble in ppt.
aq. NH3 (or NH4OH) AgCl + 2NH3(aq.) ––→ [Ag(NH3)2]Cl
confirms Cl. White Soluble
– Yellow ppt. partially ppt.
soluble in aq.

E3
NH 3 (or NH 4 OH)
confirms Br.
– Yellow ppt. insoluble
in aq. NH3 (or
NH4OH) confirms I.
D
Nitrogen Na + C + N + S ––→ As in test for nitrogen; NaSCN + FeCl3 ––→
and
sulphur
together
NaSCN

ID
instead of green or
Sodium thiocyanate blue colour, blood red

Na O , boil
(L.E.) colouration confirms
presence of N and S
both.
[Fe(SCN)Cl2 + NaCl
Blood red colour
U
Phospho- P ––––––––→
2 2
Na3PO4 Solution is boiled Na3PO4 + 3HNO ––→ H3PO4 + 3NaNo3
rus with nitric acid and
t h e n t r e a t e d w i t h H3PO4 + 12(NH4)2MoO4 + 21HNO3
ammonium molybdate ––→ (NH4)3PO4.12MoO3
YG

( N H 4) 2M o O 4.
Ammonium phosphomolybalate
Formation of yellow
(yellow ppt.)
ppt. indicates presence
of phosphate (hence, + 21NH4NO3 + 12H2O
phosphorus) in organic
compound.

 Quantitative analysis of organic compounds : The percentage composition

D

of elements presence an organic compound is determined by the methods

based on the following principles :
U
ST

194 Chemistry Class XI

 Elements Method
Carbon and Liebig's Combustion method :
Hydrogen A known mass of an organic compound is burnt in the presence of excess
of O2 and CuO.
y y
CxHy + (x + )O2 ––––→ D xCO2 + H2O
4 2
CO2 evolved is absorbed by conc. solution of KOH or ascarite (NaOH +

60
CaO).H2O produced is absorbed by anhydrous CaCl2 or Mg(ClO4)2.
Increase in masses of these absorbing compounds gives the masses of CO2
and H2O produced.
12 mass of CO2 formed
% of C = × 100;
44 mass of compound taken

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2 mass of H2O formed
% of H = × 100
18 mass of compound taken

Halogens Carius method :

X
AgNO3
AgX↓
At. mass of X
ID
Halogen in organic compound is precipitated as silver halide by boiling
with conc. NHO3 and then adding AgNO3.
HNO3, D

mass of AgX formed

U
% of X = × × 100
108 + At. mass of X mass of compound taken
Nitrogen Dumas method :
YG

Nitrogen containing organic compound is heated with CuO in an atmosphere

of CO2.
CxHyNz + 2x + ( y
2
)
CO2 –––→ xCO2 +
y
2
H2O + N2 + 2x +( y
2
)
Cu

N2 evolved gets collected over conc. KOH solution which absorbs all
other gases.
D

28 Vol. of N2 at STP
% of N = × × 100
22400 mass of compound taken
U

Kjeldahl's method :
Organic compound + H2SO4 (conc.) —→ (NH4)2SO4 2NaOH
——→ Na2SO4 +
2NH3 + 2H2O + 2NH3 + H2SO4 —→ (Na4)2SO4
ST

1.4 × molarity of acid × vol. of acid used × basicity of acid

% of N =
mass of compound taken

Organic Chemistry: Some Basic Principles and Techniques 195

 Sulphur Carius method :
Sulphur in organic compound is converted into H2SO4 by boiling with
Na2O2 or conc. HNO3 and is precipitated as BaSO4 by adding excess of
BaCl2 solution in water.
(i) HNO3, D
S → BaSO ↓
4
(ii) BaCl2
white ppt.
32 mass of BaSO4 formed

60
% of S = × × 100
233 mass of compound taken
Phosphorus Ignition method :
HNO3
P → H PO
heat 3 4

E3
D
H3PO4 + Mg2+ + NH4CL ——→ MgNH4PO4 + HCl
Magnesium ammonium
phosphate (white ppt.)
D
2MgNH4PO4 ——→ Mg2P2O7 + 2NH3 + H2O
Magnesium pyrophosphate

% of P =
62
222
× ID
mass of Mg P2O7 formed
mass of compound taken
× 100
U
YG
D
U
ST

196 Chemistry Class XI

 MIND MAP : ORGANIC CHEMISTRY

60
E3
ID
U
YG
D
U
ST

Organic Chemistry: Some Basic Principles and Techniques 197

 MULTIPLE CHOICE QUESTIONS (MCQ)

1. Homolytic fission of C-C bond in ethane gives an intermediate in which

carbon is:
a. sp3 hybridised b. sp2 hybridised
c. sp-hybridised d. sp3d- hybridized

60
2. The kind of delocalization involving sigma bond in conjugation with pi
electrons is called:
a. Inductive effect b. Hyperconjugation effect
c. Electromeric effect d. Mesomeric effect

E3
3. Which organic species has only one type of hybridized carbon?
⊕
a. CH2 = C = CH2 b. CH3 – CH – CH3
⊕
c. CH3 – C = CH

c. H2O

ID d. CH2 = CH – CH2
4. Which of the following can act as an electrophile?
a. CN– b. OH–
d. BF3
U
5. Which of the following is correct about the species: (CH3)3 – C+
a. It is planar b. Its C+ is sp2 hybridised
YG

c. A nucleophile can attack on its C+ d. All of these

6. Which of the following has all the effects namely Inductive, Mesomeric and
Hyperconjugative ?
a. CH3Cl b. CH3CH = CH2
c. CH3CH = CHCOCH2Cl d. CH2 = CH – CH = CH2
D

7. The most stable free radical among the following is:

• • • •
a. C6H5CH2CH2 b. C6H5CHCH3 c. CH3CH2 d. CH3CHCH3
U

8. Isomers of a compound must have :

a. Same physical properties b. Same chemical properties
ST

c. Same structural properties d. Same molecular weight

9. The type of isomerism not found in alkenes is :
a. Chain isomerism b. Geometrical isomerism
c. Metamerism d.Position isomerism

198 Chemistry Class XI

 10. Which of the following species have six p conjugated electrons?
+

a. b. CH2 = CH – CH = CH – CH2– c. d. All of these

N
11. The correct decreasing order of priority for the functional groups of organic
compounds in the IUPAC system of nomenclature is:

60
a. –COOH, –SO3H, –CONH2, –CHO
b. –SO3H, –COOH, –CONH2, –CHO
c. –CHO, –COOH, –SO3H, –CONH2
d. –CONH2, –CHO, –SO3H, –COOH

E3
12. The IUPAC name of CH3 – CH = CH – C ≡ CH is:
a. pent-3-en-1-yne b. pent-3-en-4-yne
c. pent-2-en-4-yne d. pent-2-en-3-yne
13. Different structures generated due to rotation about C-C axis of an organic
molecule are example of:
a. Geometrical isomerism
c. Optical isomerism
ID b. Conformational isomerism
d. Structural isomerism
U
14. Which of the following process is not used for the preparation of solid
impurities?
a. Distillation b. Sublimation
YG

c. Crystallisation d. Vapouristaion
15. Quantitative measurement of nitrogen in an organic compound is done by
the method:
a. Berthelot method b. Lassaigne method
c. Carius method d. Kjehldahl method
D

ANSWERS
1. a 2. b 3. d 4. d 5. d 6. c 7. b 8. d 9. c 10. d
U

11. a 12. a 13. b 14. d 15. a

FILL IN THE BLANKS

ST

1. The CH4 molecule has ____________ structure.

2. The property of carbon responsible for the large number of carbon compounds
is called ____________.
3. A triple bond between two carbon atoms is composed of one _________ and
_________ bonds.

Organic Chemistry: Some Basic Principles and Techniques 199

 4. An organic compound which decomposes below its boiling point can be
purified by ____________.
5. The central atom of CH2 = C = CH2 is __________ hybridized.
6. There is a difference of _________ mass units between two consecutive
members of a homologous series.
7. Geomerical isomerism happens due to _________ around p bond.

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8. Electrophiles are the species which attack the regions of _________ electron
density.
9. Hyperconjugation effect is also known as ___________ resonance.
10. In Duma’s method, the nitrogen present in an organic compound is set free

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as ____________.
ANSWERS
1. Tetrahedral 2. Catenation 3. s , two p 4. Vacuum distillation 5. sp
6. 14 7. Restricted rotation 8. high 9. No-bond 10. Nitrogen

1.
2.
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TRUE AND FALSE TYPE QUESTIONS

In homologous series all the members have the same physical properties.
IUPAC name of CH3CN is Methanenitrile.
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3. Cis-trans isomers have different dipole moments.
4. Ethanol and methoxymethane are position isomers.
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5. A free radical is a species with an unpaired valence electron.

6. Acetylene is a linear molecule.
7. Resonance brings down the stability of molecule.
8. Inductive effect is observed in p bond in presence of attacking reagent.
9. The percentage of carbon and hydrogen are estimated simultaneously in an
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organic compound by Liebig method.

10. Chromatography is the method used to separate and purify compounds when
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present in small amounts.

ANSWERS
1. F 2. F 3. T 4. F 5. T 6. T 7. F 8. F 9. T 10. T
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ASSERTION REASON TYPE QUESTIONS

The questions given below are Assertion (A) and Reason (R). Use the
following key to select the correct answer.
(a) If both assertion and reason are correct and reason is correct explanation for
assertion.
200 Chemistry Class XI
 (b) If both assertion and reason are correct but reason is not correct explanation
for assertion.
(c) If reason is correct but assertion is incorrect.
(d) If both assertion and reason are incorrect.
1. Assertion: But-1-ene and 2-Methylprop-1-ene are position isomers.
Reason: Position isomers have same molecular formula but different

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arrangement of carbon atoms.
2. Assertion: All the carbon atoms of But-2-ene lie in one plane.
Reason: All the carbon atoms in But-2-ene are sp2 hybridized.
3. Assertion: Alkanes having more than three carbon atoms exhibit chain

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isomerism.
Reason: All carbon atoms in alkanes are sp-hybridised.
4. Assertion: In CH2 = C = CH2, all the carbon atoms are sp2 hybridised.
Reason: All the hydrogen atoms lie in one plane.

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5. Assertion: Butane and 2-Methylbutane are homologues.
Reason: Butane is a straight chain alkane while 2-Methylbutane is branched
chain alkane.
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6. Assertion: Tertiary carbocations are generally formed more easily than
primary carbocations.
Reason: Hyperconjugation as well as inductive effect due to additional alkyl
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groups stabilize tertiary carbocations.

7. Assertion: Alkyl carbanions like ammonia have pyramidal shape.
Reason: The carbon atom carrying negative charge has an octet of electrons
8. Assertion: Carbocations are planar in nature.
Reason: Carbocations are sp2 Hybridised.
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9. Assertion: IUPAC name of compound CH3CH = CH – CHO is But-2-enal.

Reason: Functional group gets preference over multiple in IUPAC name of
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a compound.
10. Assertion: Compounds with difference in their boiling points by about 30°C
can be separated by simple distillation.
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Reason: All liquid mixture can be separated by distillation method.

ANSWERS
1. d 2. c 3. c 4. d 5. b 6. a 7.b 8. a 9. a 10. c

Organic Chemistry: Some Basic Principles and Techniques 201

 MATCH THE COLUMNS

Match the statements (a,b,c,d) in column I with the statements (I,ii,iii,iv) in

column II.
1. Column I Column II
a. Leibig method i. N2

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b. Dumas method ii. AgX
c. Kjehldahl method iii. CO2 and H2O
d. Carius method iv. NH3
2. Column I Column II

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a. Nonbenzenoid aromatic compound i. 50% s character
b. Catenation ii. Species containing single
unpaired nonbonding electrons
c. Free radical iii. Chain-forming property of

d. sp-hybridised carbon atom
ANSWERS
1. a. iiii b. iv c. i d. ii
ID an element
iv. Tropolone
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2. a. iv b. iii c. ii d. i
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ONE WORD ANSWER TYPE QUESTIONS

1 Write the formula of next higher homologue of C2H5OH.

2. Mention the hybridisation of underlined carbon in CH3C ≡ N.
3. What type of isomerism is shown by Pentane and 2-Methylbutane?
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4. Nucleophiles are Lewis acids or Lewis bases?

5. What type of bond fission results in the formation of free radicals?
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6 . What is the number of electrons present in the outermost shell of carbon in

the methyl radical?
7. What is the other name for no-bond resonance?
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8. What is the name of the Prussian blue coloured compound formed in

Lassaigne’s test for nitrogen in an organic compound?
9. SO3 is an electrophile or nucleophile in sulphonation reaction of benzene?
10. Name suitable technique of separation of the components from a mixture of
calcium sulphate and camphor.

202 Chemistry Class XI

 1-MARK QUESTIONS
1. Which unique property of carbon is responsible for the large number of
carbon compounds?
2. How many s and p bonds are there in propyne?
3. What is the hybridization of carbon in ethyne?
4. Which has the longest C – C bond length among ethane, ethene and ethyne.

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5. How many secondary carbon atoms are present in 2-Methylpentane?
6. Draw structure of 3-Isopropyl-2-methylhexane.
7. Draw bond line structure of CH3(CH2)6CH = CH(CH2)2 – COOH

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8. What are the bond angles in sp3, sp2 and sp hybrid orbitals?.
9. Write the formulae of first four members of homologous series of alkyne
family.
10. Write the correct of priority of the following functional groups:
–C ≡ N, >C = O, –OH, –COOH, –CONH2
11. Write IUPAC name of :
(i) CH3 – CH2 – CN
(ii) CH2 = CHCH2OH
ID
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(iii) CH3CH2CH(CH3) – CO – CH2CH3
(iv) CH3CH2 – O – CH2CH(CH3)CH3
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(v) Cl – CH2 – C ≡ CH
12. What type of isomerism is exhibited by Propanal and Propanone?
13. What is the essential condition for a compound to exhibit geometrical
isomerism?
14. Classify the following into electrophiles and nucleophiles:
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H+, NH3, AlCl3, NO2+, CN– , H2O, ROH, RNH2, Carbocation

15. What type of attacking reagents are produced by heterolytic cleavage of
covalent bond?
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16. Name each of the following species and indicate which member of each pair
is more stable:
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(i) CH3+, CH3CH2+

+ +
(ii) C6H5CHCH3, CH3CHCH3
• •
(iii) CH2 = CH – CH2 , CH = CH – CH3
– –
(iv) CH3 – CH2 , CH3 – CH – CH3

Organic Chemistry: Some Basic Principles and Techniques 203

 17. Identify electrophilic centre in CH3CHO.
18. What is state oh hybridization of positively charged carbon atom in
carbocation?
19. What is the effect of introducing an alkyl group on the stability of carbocation?
20. Out of Benzyl and ethyl carbocation which is more stable and why?
21. Arrange the following in increasing order of acidic strength:

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ClCH2COOH, CH3CH2COOH, ClCH2CH2COOH
22. Name two solvents which are commonly used to dissolve organic solids.
23. Name the technique that can be used for purification of iodine that contains
traces of NaCl.

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24. A liquid (10 mL) has three components A, B, C. which technique is suitable
to sparate A,B, C from such a small amount of mixture?
25. Name one commonly used adsorbent in column chromatography.
26. Under what condition do we use fractional distillation?
ID
27. A liquid compound starts decomposing well before its boiling point under
normal pressure. How will you purify it?
28. Which elements are normally not detected in an organic compound?
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29. For which type of compounds Kjehldahl’s method is not useful?
30. How do you precipitate sulphur in Carius method?
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31. Which method is used to estimate carbon and hydrogen?

32. What do we notice in Lassaigne’s test if the compound contains both nitrogen
and sulphur?

2-MARKS QUESTION
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1. How will you account for the presence of large number of organic
compounds?
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2. Draw the structural formulae of the following compounds:

(i) Ethoxypropane
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(ii) But-1-en-3-yne
(iii) 3,4,4,-Trimethylhex-1-yne
(iv) sec-butyl alcohol
(v) But-2-enoic acid
3. How is alkyl group represented? Give the structure and the names of the
alkyl groups which originate from (i) n-Butane (ii) isobutene

204 Chemistry Class XI

 4.
Give IUPAC name of the following compounds:
(i) C6H5 CH2 CH2OH
(ii) (CH3)2 CH2 CH2 CHO
(iii) CH2 = CH – C ≡ N
(iv) CH3 – CH – C – CH – CH3
| || |

60
Br O CH3
(v) CH3 – CH – CH = C – CH2 – COOH
| |
OH OH3

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5. What is functional isomerism? Give two examples.
6. Distinguish between position isomerism and functional isomerism.
7. What is metamerism? Give example.
8. How are free radicals formed?

radical?
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9. What is the effect of introducing an alkyl group on the stability of a free

10. Give two examples each of the groups exerting –I and + I effect when
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attached to a chain of carbon atoms.
11. A tertiary butyl carbocation is is more stable than isobutyl carbocation.
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Justify.
11. What do you understand by +R and –R effect?
12. Define hyperconjugation.
13. What is the difference between inductive and electromeric effect?
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14. All electrophiles are Lewis acids while nucleophile are Lewis bases. Explain.
15. What is the purpose of filtration through hot water funnel?
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16. What precautions are necessary while purifying an organic solid with the
help of crystallization process?
17. Discuss the principle of steam distillation.
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18. Discuss the role of fractionating column in fractional distillation.

19. How will you prepare Lassaigne’s extract? Name the elements which can be
detected from this extract?
20. Why do we boil Lassaigne’s extract with conc. HNO3 while detecting
halogens in an organic compound?

Organic Chemistry: Some Basic Principles and Techniques 205

 3-MARKS QUESTIONS

1. Discuss the orbital structure of ethene.

2. Define (i) Functional group (ii) Homologous series.
3. What do you understand by 1°, 2°, 3° and 4° carbon? Write one example
having atleast one carbon of each type.

60
4. Why stability of carbocations follows the order: tertiary>secondary>primary?
5. What are the various conditions essential for resonance?
6. Write resonance structures of CH2 = CH – CHO. Indicate relative stability of

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the contributing structures.
7. Inductive effect is of permanent nature while electromeric effect is only
temporary. Explain.
8. What is chromatography? Name different types of chromatographic
processes.
ID
9. You are given a mixture of methanol and acetone. Discuss the process which
you will employ to separate them.
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10. Explain the reason for the fusion of an organic compound with metallic
sodium for testing nitrogen, sulphur and halogens.
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5-MARK QUESTIONS

1. What are free radicals? Justify the stability of the aliphatic primary, secondary
and tertiary free radicals.
2. What is a carbanion? How is it formed? Discuss relative stability of primary,
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secondary and tertiary carbanion.

3. Arrange the following in the order of property indicated against each set:
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(i) – C6H5, – NO2, – COOH, – I, – F, – CH3, – C2H5 ( In the increasing

order of –I effect)
+
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+ +
(ii) CH3CH2CH2CH2 , (CH3)3C , CH3CH2CH2CHCH3 (In the order of
increasing stability)
– Cl, – CONH2, – CHO (In the increasing priority order if present in
(iii)
same molecule)

206 Chemistry Class XI

 4. Draw the resonance strutuctures for the following compounds. Show the
electron shift using curved arrow notation.
(i) C6H5NO2
(ii) CH3CH = CHCHO
(iii) C6H5OH
(iv) C6H5CH2+

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(v) CH3CH = CHCH2+
5. Suggest a method to separate the constituents from the following mixture:
(i) Mixture of two miscible liquids

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(ii) A mixture of oil and water
(iii) A mixture of plant pigments
(iv) A mixture of solid benzoic acid and sodium chloride

ID
(v) o-Nitrophenol and p-Nitrophenol present in the mixture.
6. 0.378g of an organic compound containing carbon and hydrogen was
subjected to combustion by Leibig’s method, the CO2 and H2O formed were
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passed through potash bulbs and anhydrous CaCl2 tube. At the end of the
experiment, the increase in the respective weights were 0.264g and 0.162g.
Calculate the percentage of carbon and hydrogen.
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(Ans: C = 19.05% , H = 4.76%)

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Organic Chemistry: Some Basic Principles and Techniques 207

 UNIT TEST
Time Allowed: 1 hr Maximum Marks : 20
General Instructions:
(i) All questions are compulsory.
(ii) Maximum marks carried by each question are indicated against it.

60
1. Write bond line formula for the following compound: [1]
HOCH2CH2CH2CH(CH3)CH(CH3)COOH

2. Write IUPAC name of the following compound: [1]

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CH3 – CH – C – CH – CH3
| || |
NO2 O CH3

3. The central atom of compound CH2 = C = CH2 is ______ hybridized. [1]

ID
4. There is a difference of _____________ mass units between two
consecutive members of a homologous series.
[1]
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5 Which of the following has all the effects namely : [1]
Inductive, Mesomeric and Hyperconjugative ?
(a). CH3Cl (b). CH3CH = CH2
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(c). CH3CH = CHCOCH2Cl (d). CH2 = CH – CH = CH2

6. (i) What type of isomerism is exhibited by the following pair of [1]

compounds?
CH3CH2CHO and CH3 – C – CH3
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||
O
(ii) Give one example each of nucleophile and electrophile.
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7. (i) Arrange the following in increasing order of stability:

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–
(CH3)3C– , CH3 – CH – CH3, CH3CH2–

(ii) Differentiate between inductive and electromeric effect.

208 Chemistry Class XI

 8. (i) When do we use hot water funnel for filtration?
(ii) How will you separate a mixture bof two organic compounds which
have different solubilities in the same solvent?
(iii) An organic liquid decomposes below its boiling point. How will you
purify it?

9. Draw the resonating structures of (a) Phenol (b) Benzaldehyde.

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10. Arrange the following in the order of property indicated against each set:
(i) –C6H5, –NO2, –COOH, –I, –F, –CH3, –C2H5
(In the increasing order of –I effect)

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+
+
(ii) CH3CH2CH2CH2 , (CH3)3 C+,
CH3CH2CH2CHCH3
(In the order of increasing stability)
(iii) –COOH , –CONH2, –CHO

(iv) HCOOH, CH3COOH, ClCH2COOH

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(In the increasing priority order if present in same molecule)

(Increasing order of acidic strength)

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(v) O2NCH2CH2O– , CH3CH2O–
(species having greater stability)
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*****
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Organic Chemistry: Some Basic Principles and Techniques 209