Chemistry: Cbse (Part-Ii)

CHEMISTRY
CBSE (PART-II)
S.No. Content Page
01. HALOALKANES & HALOARENES (UNIT-10) 01 – 70
02. ALCOHOLS, PHENOLS & ETHERS (UNIT-11) 71 – 142
03. ALDEHYDES, KETONES & CARBOXYLIC ACIDS

143 – 216
(UNIT-12)
04. AMINES (UNIT-13) 217 – 279
05. BIOMOLECULES (UNIT-14) 280 - 345
06. NAME REACTION 346 - 353
07. CHEMICAL TEST 354 – 357
08. CBSE SAMPLE PAPER WITH SOLUTIONS 358 – 374
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CBSE
ALLEN
UNIT-10 : HALOALKANES & HALOARENES
UNIT INDEX
• Theory 01-21
• Exercise-1_Intext Questions 22-25
• Exercise-2_NCERT Exercise Questions 26-37
• Exercise-3_Exemplar 38-47
• Exercise-4_MCQ, A/R, Case Based Questions 48-56
• Previous Years Questions 57-66
• Practice Test 67-70
THEORY
TOPIC : NAMING
Halo alkane - Halogen derivatives of alkane are known as Halo alkane.
Structure : R - X Common name : Alkyl halide
IUPAC name : Halo Alkane
Halo arene - Halogen derivatives of arene are known as halo arene
Structure : Ar - X Common Name : Aryl halide
IUPAC name : Halo arene
Important Alkyl halide
S. Structure Common Name IUPAC Name
No. R–X Alkyl halide Halo Alkane
1. CH3Cl Methyl chloride Chloromethane
2. CH3CH2–Cl Ethyl chloride Chloroethane
3. CH3CH2CH2Cl n-Propyl chloride Chloropropane
4. CH 3 CH CH 2 iso-Propyl chloride 2-Chloropropane
Cl
5. CH3 CH2 CH2 CH2 n-Butyl chloride 1-Chlorobutane
Cl
6. CH3 CH CH2 CH3 sec-Butyl chloride 2-Chlorobutane
Cl
7. CH3 CH CH2 Cl iso-Butyl chloride 1-Chloro-2-methylpropane
CH3
8. CH3 ter-Butyl chloride 2-Chloro-2-methylpropane
CH3 C Cl
CH3
9. CH3–CH2–CH2–CH2–CH2–Cl n-Pentyl chloride 1-Chloropentane
10. CH3 CH CH2 CH2 Cl iso-Pentyl chloride 1-Chloro-3-methylbutane
CH3
node06\B0BC-BD\Kota\Board Material\Chemistry\Booklets\CBSE\Part-2
11. CH3 neo-Pentyl chloride 1-Chloro-2,2-Dimethylpropane

H3 C C CH2 Cl
CH3
12. CH2Cl2 Methylene chloride Dichloromethane
13. CHCl3 Chloroform Trichloromethane
14. CH2 = CH – Cl Vinyl chloride Chloroethene
15. CH2 = CH – CH2 – Cl Allyl chloride 3-Chloropropene
E 1
Chemistry
ALLEN
Classification of Halogen derivatives
Halogen Derivatives
Alkyl halides Alkenyl halides Alkynyl halides Aryl halides
Mono halides Di halides Trihalides Tetra halides

C2H5 -X CH2 -X CH2 -X CX4
CH2 -X CH -X
CH2 -X
(i) Primary alkyl halide (ii) Sec. alkyl halides (iii) ter. alkyl halides
1° 2° R
R CH2 X R CH R 3°
R C R
X
X
Halogen Derivatives
I. Compounds containing II. Compounds containing

sp3C – X bond sp 2C – X bond
(X = F, CI, Br, I) (X = F, CI, Br, I)
(a) Alkyl halide/Halo alkanes (a) Viniylic halides

(R-X) sp2
sp3 CH2 CH (Vinyl group)
R CH2 (Alkyl group) X
(b) Allylic halides CH2 CH X
sp3 (b) Aryl halides
CH2 CH CH2 (Allyl group)
X sp2
X
Allylic carbon
sp3
CH2 CH CH2 X
Allylic carbon
X
(c) Benzylic halides

CH2— (Benzyl group) CH3
CH2 X Benzyl halide
2 E
CBSE
ALLEN
DIHALIDES
Dihalogen derivatives of alkane are known as dihalides.
Dihalides are of 3 types:
(i) Gem dihalide: If both halogen atoms are attached to the same carbon atom it is known as gem
dihalide.
X
General structure: R–CH
X
Common name: Alkylidene halide
Cl
Example: CH3–CH Ethylidene chloride
Cl
Cl
CH3–CH2 –CH Propylidene chloride
Cl
(ii) Vic-dihalide : If both halogen atoms are attached to the adjacent carbon atom it is known as vic
or vicinal dihalide.
General structure: R–CH–CH 2
X X
Common name: Alkylene halide / Alkylene dihalide
Example: CH2–CH2 Ethylene chloride
Cl Cl
CH3–CH–CH 2 Propylene chloride
Cl Cl
(iii) , -dihalide:
If both halogen atoms are attached to the terminals of carbon chain it is known as -dihalide.
(at least three carbon atoms should be present in carbon chain)
  
General Structure: CH2–CH2--------CH2
X X
Common name: Polymethylene halide
(Poly means: Number of –CH2–, methylene)
Example: CH2–CH2–CH2 Tri methylene bromide
Br Br
CH2–CH2 –CH2–CH2 Tetramethylene bromide
Br Br
GENERAL METHODS OF PREPARATIONS OF HALO ALKANE
(I) By photochemical Halogenation of alkane
(II) By hydrohalogenation of alkene
(III) By alcohols
(IV) By halogens exchange
E 3
Chemistry
ALLEN
I By photochemical Halogenation of alkane (Free Radical substituting reaction)
(i) The substitution reaction in which 2-3free radical part of substrate is replaced by attacking free
radical, known as free radical substitution reaction.
(ii) It is characteristics reaction of Alkane.
(iii) This reaction occurs in presence of UV light or at high temp.
(iv) It is a chain reaction which proceed in three steps.
(a) Chain initiation step
(b) Chain propagation step
(c) Chain termination step
(v) eg. of FSR : Photo chemical halogenation of Alkane
UV light
R H + X2 R X + HX
Homolytic fission (X2 = Cl2 , Br2 ) Alkyl halide
(Non polar substrate) Halo alkane
Note (1) : Reactivity order of halogen towards alkane
F2 > Cl2 > Br2 > I2
Note (2) : Displacement/Substitution order of hydrogen free radical towards FSR
3°H > 2°H > 1°H
Note (3) : Fluorination and Iodination of alkane does not occurs by photochemical halogenation
because fluorination of alkane is very fast and exothermic reaction which cannot be easily
control while iodination is very slow.
General reaction of photo chemical halogenation of alkane
UV light
R H + X2 R X+ H X
Alkane (Cl2 , Br2)
Example of FSR : Photochemical chlorination of alkane
 Cl
Eg.1 CH4 
UV light  CH3Cl
2
 Cl
Eg.2 C2H6 
UV light  C2H5Cl (one monochloro alkane is formed)
2
 Cl
CH3–CH3 
UV light  CH3–CH2–Cl
2
Eg.3 C3H8
+Cl2
C3H7Cl
UV light
Two monochloro alkane are formed
(i) CH3 CH2 CH2 Cl
+Cl2 n-propyl chloride

CH3 CH2 CH3 UV light
Propane
(ii) CH3 CH CH3
Cl
iso-propyl chloride
 Cl
Eg.4 C4 H10 
UV light  C 4 H 9 Cl (Four mono chloro alkane are formed)
2
Butane
4 E
CBSE
ALLEN
Having two chaing isomers
(i) CH3 CH2 CH2 CH2 Cl
(a) +Cl2 n-butyl chloride
CH3–CH 2–CH2–CH3
UV light
n-butane
(ii) CH3 CH CH2 CH3
Cl
Sec. butyl chloride
(i) CH3 CH CH2 Cl
+Cl2
(b) CH3 CH CH3 UV light
CH3
iso butyl chloride
CH3 CH3
iso butane
(ii) CH3 C Cl
CH3
ter. butyl chloride
II. By hydrohalogenation of alkene (By the addition of H-X on alkenes)
eg: CH2= CH2 + HX  CH3 – CH2X
eg: CH3– CH = CH2 + HX  CH3–CH–CH 3
X
EAR
Isopropyl halide
CH3 CH3
eg. CH3–C=CH2 HCl
CH3–C–CH2
Cl H 
eg. R–CH=CH2 + HBr Peroxide
R–CH–CH2
FAR
H Br
III. By Alcohols :
(a) By the action of hydrogen halides :
H X
R – CH2 – OH   RCH2 – X
(b) By the action of phosphorous halides :
R – OH + PCl5  R–Cl + POCl3 + HCl
3R – OH + PCl3  3RCl + H3PO3
Red P+X
R – OH 
X  Br ,I  R – X
2
2 2 2
PBr3 and PI3 are less stable, thus for bromides (P + Br2) and for iodides (P + I2)
mixture is used.
By reaction with Thionyl chloride (Darzen's procedure) :
(c)
R – OH + SOCl2 
Pyridine
 R – Cl + SO2 + HCl
(4) By Halogen exchange :
R – Cl or R – Br + KI 
dry acetone
 R – I + KCl or KBr (Finkelstein reaction)
2CH3Cl + Hg2F2  Water
CH3 – F + Hg2Cl2 (Swart reaction)
Note : Finkelstein reaction can only be used to prepare R – I and Swart's reaction can only be
used to prepare R – F.
E 5
Chemistry
ALLEN
CHEMICAL REACTIONS OF ALKYL HALIDE
I Nucleophilic substitution reactions (NSR)
II. Elimination reactions
III. Reaction with metals
I. Nucleophilic substitution reaction or SN reaction or NSR
The substitution reaction in which nucleophile part of substrate is replaced by attacking
nuclophile, known as nucleophilic substitution reaction.
* It is characteristics reaction of Alkyl halide, Ether.
* SN reaction are of two types (i) SN1 reaction (ii) SN2 reaction
 1
Alkyl halide shows nucleophilic substitution reaction d ue to polar nature of C—X bond,
R–X shows, SN reaction.
 1 1 1
C—X + Nu C—Nu + X
Alkyl halide attacking Nucleophilic Halide
(Substrate) nucleophile substituting ion
Polar substrate * which attacks product
*which is being to the
attacked substrate
Explanation of SN1 reaction :
Unimolecular nucleophilic substitution reaction (SN1)
In case of SN1 reaction, rate of reaction depends upon the concentration of only one reactant
(substrate) i.e. alkyl halide
Rate of reaction  [R – X]
(experimental)
 Order of reaction = 1
* It follows the first order kinetics. Hence it is first order nucleophilic substution reaction,
which is represent by SN1.
SN1 reaction proceed in two steps
Step-I : In this step alkyl halide undergoes hetrolytic fission and form an intermediate
carbocation. This step is slow hence it is RDS.
 1 Slow
R—X R + 1X
RDS
Alkyl halide Carbocation Halide
(Substrate) ion
Hetrolytic
fission
Step-II : The carbocation being a reacting chemical species it immediately react with
nucleophilic part of attacking reagent to gives nucleophilic substituting product. It is fast step,
hence does not effect the rate of reaction.
1 Fast
RNu R-Nu
Alkyl halide Nucleophilic
(Substrate) substituting
Hetrolytic product
fission
6 E
CBSE
ALLEN
Note : (1) Reactivity order of alkyl halide towards SN1 reaction is depends on the stability order
of carbocation.
The reactivity order for SN1 reaction  stability of carbocations formed by halides.
 Reactivity order of halides towards (SN1) reaction as follows :
Benzyl halide > Allylhalide > 3° halide > 2° halide > 1° halide > methyl halide.
 
C6 H 5 C H 2  CH 2  CH  C H 2  R  (3  2  1)
Benzyl Allyl Alkyl
carbocation carbocation carbocation
(3  2  1)
Note : (2) Allylic and benzylic halides show high reactivity towards the SN1 reaction. The
carbocation thus formed gets stabilised through resonance as shown below:
 
H2C = C – CH2 H2C – C = CH2
H H
Resonating structures of Allylic carbocation
 CH2  CH2 CH2 CH2
 
(Resonating structures of benzylic carbocation)

Note : (3) Those alkyl halide which having same halogen atoms their reactivity order towards
SN1 reaction as follows.
R3CX > R2CHX > R – CH2 – X > CH3 – X
Note: (4) Those alkyl halide which having different halogen, their reactivity towards SN1 and
SN2 raction as follows
R–I > R – Br > R – Cl > R–F
In above case alkyl iodide gives SN1 and SN2 reaction fast as it is a better living group or bulky
size of iodide ion.
Mechanism of following reaction:
(CH3)3CBr + KOH  (CH3)3COH + KBr
ter. butyl bromide ter. butyl alcohol
2-Bromo-2-Methyl propane 2-Methyl Propan-2-ol
Type of reaction: SN1
Mechanism : above reaction proceed in two steps:

Step-I : Alkyl halide (terbutyl bromide) undergoes hetrolytic fission.
KOH  K+ + OH
CH3 CH3
H3 C–C–Br Slow H3 C–C + Br
RDS
CH3 CH3
E 7
Chemistry
ALLEN
Step-II : An intermediate carbocation form substituting product with attacking nucleophile
K+ + Br–  KBr
CH3 CH3
H3 C–C + H3 C–C – OH
CH3 CH3
Explanation of SN2 Reaction Mechanism

Biomolecular nucleophilic substitution reaction (SN2) :
In case of SN2 reaction, rate of reaction depends upon the concentration of reactant (substrate)
and attacking reagent (nucleophile)
1
Rate of reaction (experimental)  [R – X] [N u]
 order of reaction = 2.
* It follows the second order kinetics. Hence it is second order nucleophilic substitution
reaction, which is represent by SN2.
* SN2 reaction proceed in single step:
1  1 Slow   1 Fast 1
Nu + C—X Nu---------C----------X Nu–C + X
RDS  
Attacking Alkyl halide Nucleophilic Halide
nucleophile substrate Transition state
substituting ion
product
In case of SN2 reaction attacking nucleophile attacks from the back side to the electron deficient
carbon of alkyl halide. There are two reactions take place simultaneously (i) weakening of bond
between carbon and halogen, (ii) bond formation between carbon and attacking nucleophile.
Due to this an unstable state is formed, that is known as transition state in which carbon atom
gets pentavalency. This step is very slow, hence it is RDS. After forming the transition state
halide ion removed fastly and gives nucleophilic substituting product. The configuration of
carbon atom is inverted which is known as inversion of configuration. Commonly it is known
as Walden inversion.
1
Note : (1) Reactivity of alkyl halide towards SN 2 
steric hindrance
Note : (2) Those alkyl halide which have same halogen, their reactivity towards SN2 reaction as
follows :
CH3X > R–CH2X > R2CHX > R3CX
CH3X > CH3CH2–X > (CH3)2CHX > (CH3)3CX
8 E
CBSE
ALLEN
Mechanism of following reaction.
CH3Br+  CH3OH + KBr
Methyl bromide Methyl alcohol
Bromo methane Methanol
Types of reaction SN2 :

Mechanism :
KOH  K+ + OH
H
1
H  1
Slow 1  1 Fast H 1
OH + H C—Br HO---------C----------Br HO–C H + Br
RDS   H
H H H
Attacking Methyl Methyl Bromide
Transition state alcohol ion
nucleophile bromide
Difference between SN1 and SN2 reaction
SN1 reaction SN2 reaction
Unimolecular nucleophilic substitution Bimolecular nucleophilic substitution

reaction reaction
1. In this type of reaction, rate of reaction 1. In this type of reaction, rate of reaction
depends only on the concentration of depends on the concentration of
substrate i.e. alkyl halide substrate and attacking reagent
Rate  [R – X] 
Rate  [R – X] [N u]
2. It is first order reaction 2. It is second order reaction
3. This reaction proceed in two steps 3. This reaction proceed in single step
4. In case of SN1 reaction, carbocation form as a 4. In case of SN2 reaction transition state is
intermediate. formed
5. Ter. alkyl halide most reactive towards SN1 5. Methyl halide rapidly react towards SN2
reaction reaction
6. Eg. (CH3)3CBr + KOH  (CH3)3COH + KBr 6. Eg. CH3Br + KOH  CH3OH + KBr
E 9
Chemistry
ALLEN
IMPORTANT NUCLEOPHILIC SUBSTITUTION REACTIONS OF ALKYL HALIDE
+ –
NaOH
R–OH + NaX
+–
KOH
R–OH + KX
AgOH
R–OH + AgX
Ag2O
R–OH + AgX
Moist
H2O
R–OH + HX

– +
R–ONa
R–OR + NaX (Williamson ether synthesis reaction)
ether
O
– + O
R–C–OAg
R–C–OR + AgX
ester
+ –
 1 NaI
R–X R–I + Nax (Finkelstein reaction)
Acetone
CH3X, R-CH2X, R2CHX, R3CX AgF
R–F + AgX (Swarts reaction)
 1
H–NH2 + –
SN 1 R–NH2 + HX  RNH3X KOH R–NH2 + KX + H2O
1°amine
H
1
SN2 R–N H + – KOH
R2NH + HX  R2NH2X R2NH + KX + H 2O
2°amine
1
R2NH + – KOH
R3N + HX  R3NHX R3N + KX + H2O
3°amine
R3 N +–
R4NX
Tetra Alkyl Ammonium Halide
2H
R–H + HX
LiAlH4 Alkane
KCN
R–CN
Alkyl cyanide
AgCN
R–N=C
Alkyl isocyanide
+–
KO–N=O R–O–N=O
Alkyl nitrite
O
AgNO2
R–N
O
Nitroalkane
Note (1): Substitution by Cyanide group (–CN)
—C  N 
 R—C  N
(Alkyl nitrile or Alkyl cyanide)
R—X + KCN 
 R—CN + K—X
10 E
CBSE
ALLEN
Note (2): Substitution by cyanides (—NC) group

—N  C 
 R — NC
(Alkyl isonitrile or Alkyl is cyanide)

R — X  Ag — C  N 
H 2 O/C2 H5 OH
 R — N  C  AgX
Note (3): Substitution by Nitrite group (—ON=O)

—O—N=O 
 R—O—N=O
R—X + K—O—N=O 
 R—O—N=O + K—X
Alkyl nitrile
O
Note (4): Substitution by Nitro group N
O
O O
N R N
O O
O
R—X+Ag—O—N=O R N + AgX
O
Nitroalkane
STEREO CHEMICAL ASPECTS OF NSR:

Monochromatic light Monochromatic light Monochromatic light
not linear polarized linear polarized linear polarized
rotated
high intensity Polarizer Polarimetry cell with Analyzer Detector

light bulb chiral analyte
(1) Ordinary light: These waves vibrates equally in all directions.

(2) Nicol prism: It is made by crystalline CaCO3 and paste with Canada balsom layer.
(3) Plane Polerised Light(PPL): Such a beam of light which has vibrations only in one plane is
called PPL.
(4) Optically active compound: Certain compound rotate the plane polarized light when it is
passed through their solution by Nicol prism, such compounds are called optically active
compounds.
(5) Optical isomers and optical isomerism:
Optically active compounds rotate PPL clockwise and anticlockwise, on this basis such types of
compounds are two types:
E 11
Chemistry
ALLEN
(a) dextro rotatory or d or + compounds:
Compounds which rotates PPL towards clockwise called as dextro rotatory or 'd' or '+'
isomer.
(b) Laevo rotatory or  or - compounds:
Compounds which rotates PPL towards anticlockwise called as laevo rotatory or 'l' or '-'
Such d and  isomers of a compounds are called optical isomers and phenomenon is
termed as optical isomerism.
(6) Chiral or chirality:
The object which are non-superimposed on their mirror image, are called to be chiral and the
property is known as chirality.
CHIRALITY
An object that cannot be superimposed
on its mirror image is called chiral
Mirror Mirror
Chiral objects NonChiral objects

Nounsperimposable Sperimposable
mirror images mirror images
A chiral molecule and its mirror image

(7) Achiral: The objects which are superimposed on their mirror images are called achiral.
H3 C CH3 H3C
H3 C OH HO CH3 H3C OH
H H H
A B C
180º
C Obtained by rotating B by 180º C is superimposable on its mirror image A

F obtained by rotating E by 180º F is non-superimposable on its mirror image D
Therefore, D and F are Enantiomers.
(8) Enantiomers: Stereo isomers are mirror image of each other and cannot be superimposed on
each other, these isomers are enantiomers among them one is dextrorotatory and other of laevo
rotatory.
12 E
CBSE
ALLEN
(9) Racemic mixture and racemisation:
A mixture containing two enantiomrers in equal proportions will have zero optical rotation as
the rotation due to one isomer with be cancelled by other iosomers. Such a mixture is known as
racemic mixture or racemic modification.
The process of conversion of enantiomers into a racemic mixture is known as racemisation.
# A racemic mixture is represented by prefixing d before the name.
Explain inversion, retention, and racemisation with suitable example.

C2H5 C2H5 C2H5
H H H
Y Y
Y X Y
CH3 CH3 CH3
Product-B Reactant Product-A
Inversion Retention
(Optically active) (Optically active)
Y
Racemisation
Product is mixture of
A+B
(Optically inactive)
There are three outcomes for a reaction as an asymmetric carbon atom.
Consider the replacement of a group X by Y in the following reaction:-
(1) If A is the only compound obtained, the process is called retention of configuration.
(2) If B is the only compound obtained, then the process is called 'inversion of configuration'
(3) If a 50 : 50 mixture of above to is obtained then the process is called racemisation (optically
inactive)
A SN1reaction proceed with racemisation while SN2 reaction proceed with complete
stereochemical inversion. Explain by taking example of optically active alkyl halide
CASE1-1 : SN1 reaction proceed with racemisation
*
CH 3–CH–CH2 –CH3 + KOH CH 3–CH–CH2 –CH3 + KBr
Br OH
2-Bromobutane butan-2-ol
(Optically active) (Optically inactive)
Mechanism:
+ –
KO H K + OH
H3C CH3
Step-I : Br
Slow
 + Br Θ
H
CH2CH3 H CH2CH3
E 13
Chemistry
ALLEN
CH3 CH3
CH3
Step-II : HO HO– + –
OH OH
H H SP
2
CH2 CH3
CH2CH3 H CH2–CH3
Trigonal Planar
(+) Butane -2-ol (–) Butane -2-ol
Therefore SN1 reaction of optically active halide are accompanied by racemisation.
CASE-2 SN2 reaction proceed with stereo chemical inversion.
When (-)-2-bromooctane is allowed to react with NaOH, (+)-octan-2-ol is formed with the –OH
group occupying the position opposite to what bromide had occupied.
This SN2 reaction of optically active halides are accompanied by inversion of
configuration.
CH3–CH–C6H13 + KOH CH3–CH–C6H13
Br OH
(–) 2-bromooctane (+) octan-2-ol
Mechanism
H3C CH3 CH3

– slow
– – fast
OH +
H Br HO ------ ------- Br HO
H + Br–
H C6H13
C6H13 C6H13
Attacking (–)2-Bromooctane Transition state (+) octan-2-ol
nucleophile d-isomer
-isomer
(optical active)
(optical active)
Change the configuration
of carbon
II. Elimination reaction (Dehydrohalogenation of Alkyl halide)
Alcoholic KOH/NaOH is dehydrohologenating agent
When a haloalkane with -hydrogen atom is heated with alcoholic solution of potassium
hydroxide, there is elimination of hydrogen atom from -carbon and a halogen atom from the
-carbon atom. As a result, an alkene is formed as a product. Since -hydrogen atom is
involved in elimination, it is often called -elimination.
B: H
C=C +B–H+X –
C C
B = Base ; X = Leaving group
Alcoholic KOH
Ex. (i) CH3 – CH2 – Br   CH2 = CH2 + HBr
CH2–CH2
H Br
14 E
CBSE
ALLEN
Note: If there is possibility of formation of more than one alkene due to the availability of more than
one -hydrogen atoms, usually one alkene is formed as the major product. These form part of a
pattern first observed by Russian chemist, Alexander Zaitsev (also pronounced as Saytzeff)
who in 1875 formulated a rule which can be summarised as “in dehydrohalogenation
reactions, the preferred product is that alkene which has the greater number of alkyl
groups attached to the doubly bonded carbon atoms.”
Ex. (i) CH3–CH–CH2–CH3 Alcoholic KOH CH2=CH–CH 2–CH 3 + CH 3–CH=CH–CH3
Br 19% 81%
But-1-ene But-2-ene
OR
(Minor) (Major)
CH2–CH–CH–CH3
H Br H
2-Bromobutane
Ex. (ii) 2-bromopentane gives pent-2-ene as the major product.
Br
 | 
H 3C  CH 2  CH  CH  CH 3 
OH
 H 3C  CH 2  C H  C H C H 2 
OH
 H3 C  CH 2  CH 2  CH  CH 2
| |
H H
Pent-2 ene (81%) 2-Bromopentane Pent-1-ene (19%)
III. Reaction with metals

(i) Reaction with Mg
R–X + Mg 
Dry ether
R–MgX
Alkyl halide Magnesium Alkyl magnesium halide
Grignard reagent
(organo-metallic compound)
(ii) Reaction with sodium
Wurtz Reaction
Alkyl halides react with sodium in dry ether to give hydrocarbons containing double the
number of carbon atoms present in the Alkyl halide. This reaction is known as Wurtz reaction.
Example: (1) R – X + 2Na + X – R 
Dry ether
R – R + 2NaX
Example: (2) CH 3 Br  2Na  BrCH 3  CH 3  CH 3  2NaBr

dry ether
Bromomethane Ethane
C2 H 5 Br  2Na  BrC2 H 5 

dry ether
 CH 3CH 2 CH 2 CH 3
Example: (3)
Bromoethane n  Butane
Example: (4) CH3–CH–Br Na

Dry ether CH3–CH–CH–CH3
CH3 CH3 CH3
CH3 CH3 CH3
Example: (5) H3C–C–Br Na
H3C—C—C—CH3
Dry ether
CH3 CH3 CH3
E 15
Chemistry
ALLEN
General ESR of Benzene:
H E
 
+ E + H
Benzene Attacking Elecrophilic

electrophile substituting
product
Important ESR Attacking electrophile (E)
Halogenation:
Chlorination Cl+ (Chloronium)
Bromination Br+ (Bromonium)
Nitration:
(a) By Dil HNO3
(b) By concentrate HNO3 +
NO2 (Nitronium)
OR
By nitrating mixture
(Conc. HNO3 + Conc. H2SO4)
Friedel Craft reaction: 
(a) Alkylation CH3 (Methylium)
O
(b) Acetylation C–CH3 (Acetylium)
Formylation: O
(a) Gattermann Koch aldehyde C–H (Formylium)
synthesis reaction
Sulphonation SO3 (Sulphur tri oxide)
GENERAL METHODS OF PREPARATION OF HALOARENE

Cl
Cl2

Anhydrous AlCl3
Benzene Chloro
Benzene
Cu2Cl2/HCl

 Ar–Cl + N2
Ar N2 X Sandmeyar Reaction
Cu2Br2/HBr Ar–Br + N2
Cu / HCl
Ar–Cl + N2 + CuX


Ar N2 X Gattermann Reaction
ArBr + N2 + CuX
Cu/HBr
 
Ar N 2 Cl + KI  ArI + KCl + N2
16 E
CBSE
ALLEN
 
C6 H 5 N 2 Cl + KI C6H5I + KCl + N2
     

Ar N 2 Cl + H B F4 
 HCl
 Ar N 2 BF4   Ar–F + BF3 + N2
O
+ –
NO NH2 N2Cl
6H NaNO2 + HCl
Sn + HCl 273-278K
Nitro benzene Aniline Benzenediazonium

chloride
Diazotisation reaction
ESR OF CHLOROBENZENE
Cl Cl
(1) Chlorination
Cl
Cl2
+
anhyd AlCl 3
1,2-Dichloro benzene Cl
(Minor) 1,4-Dichloro benzene
(Major)
Cl
(2) Nitration Cl
conc. HNO3 NO2
+
conc. H 2SO4
1-Chloro-2-nitrobenzene NO2
(Minor) 1-Chloro-4-nitrobenzene
Cl
(Major)
(3) Sulphonation Cl Cl
conc. H 2SO4 SO3H
Chloro +
Benzene 
o/p directing 2-Chlorobenzene sulphonic acid SO3H
(Minor) 4-Chlorobenzene sulphonic acid
(Major)
(4) Friedel Craft reaction
(Alkylation)
Cl Cl
CH3Cl CH3
anhyd-AlCl3 +
1-Chloro-2-methylbenzene
CH3
(Minor)
(5) Friedel Craft reaction (Major)
(Acetylation) Cl Cl
COCH3
CH3COCl
+
anhyd AlCl 3
2-Chloroacetophenone
(Minor) COCH3
(Major)
E 17
Chemistry
ALLEN
Note : Replacement by hydroxyl group
Chlorobenzene can be converted into phenol by heating in aqueous sodium hydroxide solution
at a temperature of 623K and a pressure of 300 atmospheres.
Cl OH

(i) NaOH, 623 K , 300 atm
(ii)H

The presence of an electron withdrawing group (-NO2) at ortho- and para-positions increases
the reactivity of haloarenes.
Cl OH

(i) NaOH, 443 K
(ii)H

NO2 NO2
Cl
OH
NO2
NO2

(i) NaOH, 368 K
(ii)H

NO2 NO2
Cl
OH
O2N NO2
O2N NO2

H O
warm
2
NO2 NO2
The effect is pronounced when (-NO2) group is introduced at orthoand para- positions.
However, no effect on reactivity of haloarenes is observed by the presence of electron
withdrawing group at meta-position.
Aryl halides are extremely less reactive towards nucleophilic substitution reactions due to the
following reasons:
(i) Resonance effect : In haloarenes, the electron pairs on halogen atom are in conjugation with -
electrons of the ring and the following resonating structures are possible.
:
:Cl : Cl Cl Cl
C—Cl bond acquires a partial double bond character due to resonance. As a result, the bond
cleavage in haloarene is difficult than haloalkane and therefore, they are less reactive towards
nucleophilic substitution reaction.
18 E
CBSE
ALLEN
(ii) Difference in hybridisation of carbon atom in C—X bond: In haloalkane, the carbon atom
attached to halogen is sp3 hybridised while in case of haloarene, the carbon atom attached to
halogen is sp2-hybridised.
X
2
sp -hybrid carbon
H
C sp3-hybrid carbon
R X
H
The sp2 hybridised carbon with a greater s-character is more electronegative and can hold the
electron pair of C—X bond more tightly than sp3-hybridised carbon in haloalkane with less
s-chararcter. Thus, C—Cl bond length in haloalkane is 177pm while in haloarene is 169 pm.
Since it is difficult to break a shorter bond than a longer bond, therefore, haloarenes are less
reactive than haloalkanes towards nucleophilic substitution reaction.
Physical Properties of Haloalkanes-
1. Physical State
  They are colourless liquids at room temperature but alkyl bromides and iodides develop
colour when exposed to light.
  CH3Cl, CH3Br, C2H5Cl and some CFCs are gases at room temperature.
2. Solubility
  Although alkyl halides are polar in nature, then also they are insoluble in water. This is so
because the energy required to break the bonds between haloalkanes is larger than the energy
released during formation of hydrogen bonds between alkyl halides and water (Hydration
energy).
They are soluble in organic solvents like alochol, benzene, ether etc.
3. Boiling point
  Boiling point of alkyl halides is higher than their parent hydrocarbons because they are polar
in nature and thus they show dipole-dipole interaction.
 Boiling point  molar mass
 CH3Cl < CH3CH2Cl < CH3(CH2)2Cl < CH3(CH2)3Cl

 Boiling point  length of carbon chain.
1
 BP 
Branching
 BP  surface area
 Boiling point  number of halogen atom.
4. Density
Alkyl fluorides and chlorides are lighter than water whereas alkyl Bromides and iodides are
heavier than water.
Density  size of alkyl group
Density  number of halogen atoms
Density  molar mass
E 19
Chemistry
ALLEN
Physical Properties of Haloarenes :
1. State– They are volatile liquids or solids at room temperature.
2. Boiling Point
Their boiling point is nearly same to haloalkanes containing same number of carbon atoms.
Order of boiling point :
I Br Cr F
3. Density : All arylhalides are heavier than water

4. Solubility : They are insoluble in water but are soluble in organic solvents.
POLYHALOGEN COMPOUNDS:
Carbon compounds containing more than one halogen atom are usually referred to as
polyhalogen compounds.
(1) Dicloromethane (CH2Cl2):
(a) Dicloromethane is widely used as a solvent as a paint remover.
(b) It is also used as a metal cleaning and finishing solvent.
(c) In humans, direct skin contact with methylene chloride causes intense burning and mild
redness of skin.
(2) Trichloromethane(chloroform) (CHCl3):
(a) Chloroform is used as general anesthetic in surgery.
(b) Chloroform is slowly oxidized by air in the presence of sunlight to an extremely
poisonous gas, carbonyl chloride, also known as phosgene.
It is therefore stored in closed dark colored bottles completely filled so that air is kept out.
light
2CHCl3 + O2  2COCl2 + 2HCl
Phosgene
(3) Triiodomethane (Iodoforms)
Iodoforms used as antiseptic due to the liberation of free iodine and not due to iodoform itself.
(4) Tetrachloromethane(CCl4) / Carbontetrachloride / Pyrin
Used as cleaning fluid, fire extinguisher.
(5) Freons: ChloroFlouroCarbon/CFCs

The chloro fluoro derivatives of methane and ethane are called freon.
CHF2Cl (monochloro difluoro methane)
CF2Cl2 (di-chloro difluoro methane)
Most useful is CF2Cl2 (Freon– 12)
20 E
CBSE
ALLEN
Nomenclature of freons :
Freon – cba
c = nc—1
b= nH+1
a = nF
c  n C1  1  1  0 
CF2Cl2  b  n H 1  0  1  1 Freon–012
a=n F =2 
c=n C–1 =2–1=1 

C2F4Cl2  b=n H–1– =0+1=1 Freon–114
a=n F =4 
Properties :
(i) Freon is a gas (B.P. –29.8°C)
(ii) It is chemically inert.
Uses :
(i) As a refrigerant in freeze and A. C.
(ii) In fire extinguisher, X-ray equipments.
DDT: Dichlorodiphenyltrichloroethane
Cl
CCl3CH O + 2H Cl CCl3CH
Cl
Dichloro diphenyl trichloro ethane
(DDT)
Cl
Cl
Cl Cl
Cl
H
DDT
It is used as pesticides.
E 21
Chemistry
ALLEN
EXERCISE-1 INTEXT QUESTIONS
1. Write the structure of the following compounds :
(i) 2-Chloro-3-methylpentane (ii) 1-Chloro-4-ethylcyclohexane
(iii) 4-tert. Butyl-3-iodoheptane (iv) 1, 4-Dibromobut-2- ene
(v) 1-Bromo-4-sec. butyl-2-methylbenzene
Cl
Cl CH3
1 2 3 4 5
Ans. (i) CH3–CH–CH–CH–CH3 (ii)
2-Chloro-3-methyl pentane
C2H5
1-Chloro-4-ethylcyclohexane
I
1 2 3 4 5 6 7 1 2 3 4
(iii) CH3–CH2–CH–CH–CH2–CH2–CH3 (iv) Br–CH2–CH=CH–CH2–Br
CH3–C–CH3 1,4-Dibromobut-2-ene
CH3
4-tert-Butyl-3-iodoheptane
Br
1 2 CH3
6
(v)
3
5
4
CH3–CH–CH2–CH3
1-Bromo-4-sec-butyl-2-methylbenzene
2. Draw the structure of major monohalo products in each of the following reactions :
CH2CH3 Br2, heat or
OH
(i) + SOCl2 (ii) O2N UV light
CH2OH CH3
heat
(iii) + HCl (iv) + HI
HO
heat
(v) CH3CH2Br + NaI (vi) + Br2
UV light
CH–CH3
Cl
Ans. (i) (ii) O2N
4-(1-Bromoethyl)
Chlorocyclohexane
Nitrobenzenen
CH2C
CH3
(iii) (iv) I
HO
4-Chloro methylphenol 1-Iodo-1methylcyclohexane
Br
(v) CH 3CH 2 I (vi)

Iodoethane
3-Bromocyclohexane
22 E
CBSE
ALLEN
3. Arrange each set of compounds in order of increasing boiling points.
(i) Bromomethane, Bromoform, Chloromethane, Dibromomethane.
(ii) 1-Chloropropane, Isopropyl chloride, 1-Chlorobutane.
Br Br
Ans. (i) CH3–Cl < CH3–Br < CH2–Br < Br–CH–Br (increases M.W.)
Chloromethane Bromomethane Dibromomethane Bromoform
Cl
(ii) CH3–CH–CH3 < Cl–CH2–CH2–CH3 < Cl–CH2–CH2–CH2–CH3
Isopropyl chloride 1-Chloropropane 1-Chlorobutane
4. Which alkyl halide from the following pairs would you expect to react more rapidly by an SN2
mechanism? Explain your answer.
(i) CH3CH2CH2CH2Br or CH3CH2CHCH3
Br
CH3
(ii) CH3CH2CHCH3 or H3C–C–Br
Br CH3
(iii) CH3CHCH2CH2Br or CH3CH2CHCH2Br

CH3 CH3
1
Ans. (i) S N2 
Hindrance on carbon
CH3CH2CH2CH2Br > CH3CH2CH–CH3
Br
1-Bromobutane (1°) 2-Bromobutane (2°)
(more hindrance)
CH3
(ii) CH3–CH2–CH–CH3 > CH3–C–Br
Br CH3
2-Bromobutane (2°) 2-Bromo-2-methylpropane (3°)
1° 1°
(iii) CH3–CH–CH2–CH2–Br > CH3–CH2–CH–CH2–Br
CH3 CH3
1-Bromo-3-methylbutane (1°) 1-Bromo-2-methylbutane (1°)
(More hindrance)
5. In the following pairs of halogen compounds, which compound undergoes faster SN1 reaction ?
Cl
Cl Cl
(i) and (ii) and Cl
Cl

Ans. (i) 2-Chloro-2-methylpropane (3°) 3° more stable

(I)
Cl

(ii)
2-Chloroheptane (2°) 2° more stable
(I)
E 23
Chemistry
ALLEN
6. Identify A, B, C, D, E, R and R1 in the following :
dry ether H 2O
Br + Mg A B
R – Br + Mg dry ether C D2O CH3CHCH3

D
CH3 CH3
Na ether Mg H2O
CH3––––––––––CH3
1
R –X D E
CH3 CH3
Ans. (A) MgBr (B)
CH3
(C) CH3–CH–MgBr (D) H3C–C–MgBr
CH3 CH3
(E) CH3–CH–CH3
CH3
7. Write IUPAC names of the following:

H3C H
H CH3
(i) H
(ii) H
H Br
H Br
H3C
H3C
H3C CH3
H3C CH3
(iii) (iv) H
H
H Br
H Br
H
H3C
H3C H
H CH3
(v) H (vi)
H
H Br
H Br
H
H
Ans. (i) 4-Bromopent-2-ene (ii) 3-Bromo-2-methylbut-1-ene

(iii) 4-Bromo-3-methylpent-2-ene (iv) 1-Bromo-2-methylbut-2-ene
(v) 1-Bromobut-2-ene (vi) 3-Bromo-2-methylpropene
8. Write the products of the following reactions:
(i) H
H H
(ii) CH3–CH2–CH = CH2 + HCl  

Peroxide
CH2– C = CH 2 + HBr
(iii) H
CH2– CH2– CH2– Br
Ans. (i) (ii) CH3  CH 2 – CH  CH3 (iii)

H |
Cl
H Br H H
24 E
CBSE
ALLEN
9. Haloalkanes react with KCN to form alkyl cyanides as main product while AgCN forms
isocyanides as the chief product. Explain.
Ans. KCN is predominantly ionic and provides cyanide ions in solution. Although both carbon and
nitrogen atoms are in a position to donate electron pairs, the attack takes place mainly through
carbon atom and not through nitrogen atom since C—C bond is more stable than C—N bond.
However, AgCN is mainly covalent in nature and nitrogen is free to donate electron pair forming
isocyanide as the main product.
10. In the following pairs of hydrogen compounds, which would undergo SN2 reaction faster ?
CH2Cl and Cl ; and ----------------------------

I
Cl
Ans. CH2Cl It is primary halide and therefore undergoes SN2 reaction faster.
I As iodine is a better leaving group because of its large size, it will be

released at a faster rate in the presence of incoming nucleophile.
11. Predict the order of reactivity of the following compounds in SN1 and SN2 reactions :
(i) The four isomeric bromobutanes
(ii) C6H5CH2Br, C6H5CH(C6H5)Br, C6H5CH(CH3)Br, C6H5C(CH3)(C6H5)Br
Ans. (i) CH3CH2CH2CH2Br < (CH3)2CHCH2Br < CH3CH2CH(Br)CH3 < (CH3)3CBr (SN1)
CH3CH2CH2CH2Br > (CH3)2CHCH2Br > CH3CH2CH(Br)CH3 > (CH3)3CBr (SN2)
12. Although chlorine is an electron withdrawing group, yet it is ortho-, para- directing in
electrophilic aromatic substitution reactions. Why ?
Ans. Reactivity is thus controlled by the stronger inductive effect and orientation is controlled by
resonance effect.
E 25
Chemistry
ALLEN
EXERCISE-2 NCERT EXERCISE
1. Name of the following halides according to IUPAC system and classify them as alkyl, allyl,
benzyl (primary, secondary, tertiary), vinyl or aryl halides :
(i) (CH3)2CHCH(Cl)CH3 (ii) CH3CH2CH(CH3)CH(C2H5)Cl
(iii) CH3CH2C(CH3)2CH2I (iv) (CH3)3CCH2CH(Br)C6H5
(v) CH3CH(CH3)CH(Br)CH3 (vi) CH3C(C2H5)2CH2Br
(vii) CH3C(Cl)(C2H5)CH2CH3 (viii) CH3CH=C(Cl)CH2CH(CH3)2
(ix) CH3CH=CHC(Br)(CH3)2 (x) p-ClC6H4CH2CH(CH3)2
(xi) m-ClCH2C6H4CH2C(CH3)3 (xii) o-Br–C6H4CH(CH3)CH2CH3
CH3 Cl CH3 Cl
4 3 2 1 6 5 4 3 2 1
Ans. (i) CH3––CH–––CH––CH3 (ii) CH3––CH2––CH––CH––CH2––CH3
2-Chloro-3-methylbutane 3-Chloro–4–methylhexane
(Secondary alkyl halide) (Secondary alkyl halide)
CH3 CH3 Br
4 3 2 1 4 3 2 1
CH3––CH2––C––CH2––I CH3––C––CH2––CH
(iii) (iv)
CH3 CH3
1-Iodo-2, 2-dimethylbutane 1-Bromo-3,3-dimethyl-1-phenylbutane
(Primary alkyl halide) (Secondary benzyl halide)
CH3
CH3 Br CH2
4 3 2 1
CH3––CH–––CH––CH3 CH3––C–––CH2––Br
(v) (vi)
2-Bromo-3-methylbutane CH2
(Secondary alkyl halide) CH3
3-Bromomethyl-3-methylpentane
Cl
3 4 5 Cl CH3
CH3––C–––CH2––CH3 1 2 3 4 5 6
(vii) 2 (viii) CH3––CH = C––CH2––CH––CH3
CH2 3-Chloro-5-methylhex-2-ene
1
CH3 (Vinyl halide)
3-Chloro-3-methylpentane
(Tertiary alkyl halide)
CH3
1 2 3
CH2––CH––CH3
Br
Ph  Cl
4 3
1 2 3 4 5 5
(ix) CH3––CH = CH––C––CH3 (x) 6

2 Aryllic
1
CH3 Cl
4-Bromo-4-methylpent-2-ene 1-Chloro-4-(2-methylpropyl) benzene
(Allyl halide) (Aryl halide)
CH3
1' 2' 3' 1' 2' 3'
CH2––C––CH3 CH3––CH––CH2––CH3
3 2
2
CH3   1 Br
 Ph  CH2  Cl
4 3
1 Benzylic
(xi) 5
6 CH2Cl (xii) 4 6
5
1-Bromo-2-(1-methylpropyl) benzene
1-Chloromethyl-3-(2,2-dimethylpropyl) benzene
(Aryl halide)
(Primary benzyl halide)
26 E
CBSE
ALLEN
2. Give the IUPAC names of the following compounds
(i) CH3CH(Cl)CH(Br)CH3 (ii) CHF2CBrCIF
(iii) ClCH2C  CCH2Br (iv) (CCl3)3CCl
(v) CH3C(p-ClC6H4)2CH(Br)CH3 (vi) (CH3)3CCH = CClC6H4I-p
Cl Br F Cl
4 23 1 2 1
Ans. (i) CH3––CH––CH––CH3 (ii) F––CH––C––F
2-Bromo-3-chlorobutane Br
1-Bromo-1-chloro-1,2,2-trifluoroethane
Cl
Cl–C–Cl
4 3 2 1
Cl Cl
1 2 3
(iii) Cl–CH2–C C–CH2–Br (iv) Cl––C––C––C––Cl
1-Bromo-4-chlorobut-2-yne Cl Cl Cl
2-(Trichloromethyl)–1,1,1,2,3,3,3-heptachloropropane
1
CH3 CH3
3' 2' 14 2 3
4' 1'
2 Cl–C=CH–C–CH3
Cl C Cl 1' 6'
5' 6' 3 2' CH3
(v) CH–Br (vi) 5'
4 3'
4'
CH3 I
3-Bromo-2,2-bis(4'-chlorophenyl) butane 1-Chloro-1-(4-iodophenyl)-3,3-dimethylbut-1-ene
3. Write the structures of the following organic halogen compounds.
(i) 2-Chloro-3-methyl pentane (ii) p-Bromochlorobenzene
(iii) 1-Chloro-4-ethylcyclohexane (iv) 2-(2-Chlorophenyl)-1-iodooctane
(v) 2-Bromobutane (vi) 4-tert-butyl-3-iodoheptane
(vii) 1-Bromo-4-sec-butyl-2-methyl benzene (viii) 1,4-Dibromobut-2-ene
Ans. (i) 2-Chloro-3-methyl pentane CH –CH–CH–CH –CH 3 2 3
Cl CH3
Cl
(ii) p-Bromochlorobenzene
Br
Cl
(iii) 1-Chloro-4-ethylcyclohexane
CH2CH3
(iv) 2-(2-Chlorophenyl)-1-idodooctane CH2–CH–CH2–CH2–CH2–CH2–CH2–CH3
Cl
I
(v) 2-Bromobutane CH2–CH–CH2–CH3

Br
I
(vi) 4-Tert-butyl-3-iodoheptane CH3–CH2–CH–CH–CH2–CH2–CH3

CH3–C–CH3
CH3
Br
CH3
(vii) 1-Bromo-4-sec-butyl-2-methyl benzene
CH3–CH–CH2–CH3
(viii) 1,4-Dibromobut-2-ene CH2–CH=CH–CH2
Br Br
E 27
Chemistry
ALLEN
4. Which of the following has the highest dipole moment?
(i) CH2Cl2 (ii) CHCl3 (iii) CCl4
H H H Cl Cl Cl
C C C
Ans. (i) (ii) (iii)
Cl Cl Cl Cl Cl Cl
Dichloromethane (CH 2Cl2) Trichloromethane (CHCl)3 Carbon tetrachloride (CCl4)
 = 1.60D  = 1.08D  = 0D
CCl4 < CHCl3 < CH2Cl2

5. A hydrocarbon C5H10 does not react with chlorine in dark but gives a single monochloro
compound C5H9Cl in bright sunlight. Identify the hydrocarbon.
Ans.
Cyclopentane (C5H 10)
The reactions involved in the question are :

Cl2 No reaction
dark
Cl
sun Cl2
ligh
t
Cyclopentane
Mono chlorocyclopentane (C5H 10)
6. Write the isomers of the compound having formula C4H9Br.

Ans. There are four isomers of the compound having the formula C4H9Br. These isomers are given
below.
4 3
Br
2 1 4 3 2 1
(a) CH3–CH2–CH2–CH2–Br (b) CH3–CH–CH–CH3
1-Bromobutane 2-Bromobutane
CH3 Br
3 1 3 2 1
2
(c) CH3–CH–CH2–Br (d) CH3–C–CH3
1-Bromo-2-methylpropane CH3
2-Bromo-2-methylpropane
7. Write the equations for the preparation of 1-iodobutane from

(i) 1-butanol (ii) 1-chlorobutane (iii) but-1-ene
Al2O 3 H–Br
Ans. (i) CH3–CH2–CH2–CH2–OH 
CH3–CH2–CH=CH2
R2O2/
NaI
CH3–CH2–CH2–CH2–Br CH3–CH2–CH2–CH2–I
Acetone
dry acetone
(ii) CH3–CH2–CH2–CH2–Cl + NaI (Finkelstein reaction) NaCl + CH3–CH2–CH2–CH2–I
1-Chlorobutane 1-Iodobutane
Peroxide
(iii) CH3–CH2–CH=CH2 + HBr (Anti-Markovnikov's addition)
NaI/dry acetone
NaBr + CH3–CH2–CH2–CH2 – I CH3–CH2–CH2–CH2 – Br
1-Iodobutane 1-Bromobutane
28 E
CBSE
ALLEN
8. What are ambident nucleophiles ? Explain with an example.
Ans. Ambident nucleophiles are nucleophiles having two nucleophilic sites.
For example, nitrite ion is an ambident nucleophile.
 

O — N  O 
 
9. Which compound in each of the following pairs will react faster in SN2 reaction with OH—?
(i) CH3Br or CH3I (ii) (CH3)3CCl or CH3Cl
Ans. (i) CH3 – I is more reactive because Iis better leaving group than Br
CH3
(ii) H3C–C–Cl < CH3– Cl
CH3
In case of (CH3)3CCl, the attack of the nucleophile at the carbon atom is hindered of the presence
of bulky substituents on that carbon atom bearing the leaving group.
10. Predict all the alkenes that would be formed by dehydrohalogenation of the following halides
with sodium ethoxide in ethanol and identify the major alkene.
(i) 1-Bromo-1-methylcyclohexane
(ii) 2-Chloro-2-methylbutane
(iii) 2,2, 3-Trimethyl-3-bromopentane
CH3 CH3
Br
Ans. (i) C2H 5ONa/C2H 5OH
+ HBr
(Only one alkene)
CH3 CH3
C2H 5ONa/C2H 5OH
CH3–––CH2–––C–––CH3 –HBr
CH3–––CH=C–––CH3
(ii) Br 2-Methyl-2-butene major
+
CH3
CH3–––CH2–––C=CH2
2-Methyl-1-butene minor
CH3 Br CH3

C2H 5ONa/C2H 5OH
(iii) CH3–––C–––C–––CH2–––CH3 –HBr
CH3–––C–––C=CH–––CH3
CH3 CH3 CH3 CH3

3,4,4-Trimethypent -2-ene (I) (major)
+
CH3 CH2
CH3–––C–––C–––CH2–––CH3
CH3
2-Ethyl-3, 3-dimethybut-1-ene (II)
11. How will you bring about the following conversion ?

(i) Ethanol to but-1-yne (ii) Ethane to bromoethene
(iii) Propene to 1-nitropropane (iv) Toluene to benzyl alcohol
(v) Propene to propyne (vi) Ethanol to ethyl fluoride
(vii) Bromomethane to propanone (viii) But-1-ene to but-2-ene
(ix) 1-Chlorobutane to n-octane (x) Benzene to biphenyl
E 29
Chemistry
ALLEN
Ans. (i) CH3 CH2 OH 
SOCl2 .Pyridine
 CH3 CH2 Cl  SO2  HCl
Ethanol Chloroethane
HC  CH  NaNH2 
(a) Ethyne  HC  CNa Liq.NH3
Sodium acetylide
CH  CNa  CH3  CH2  Cl  CH3 CH2  C  CH  NaCl

But 1  yne
(b) CH  CMgBr  CH3 CH2 Cl  CH3 CH2  C  CH  MgClBr

But 1  yne
Br2/UV light KOH(alc.), 

(ii) CH3–CH3 or heat CH3–CH2Br + HBr CH2 = CH2
Ethane Bromoethane –HBr
Ethene
KOH(alc.) Br2/CCl4
CH2 = CHBr BrCH2–CH2Br

vic-Dibromide
Bromoethene
OR
H  Br
CH 3  CH3  2Cl 2 
 CH 3  CHCl2 
hv Alc.KOH

 CH  CH 
1mole
CH2  CH  Br
(iii) CH3  CH  CH2  HBr  CH3  CH2  CH2Br   AgBr  CH 3  CH2  CH2 NO2
Peroxide AgNO 2
Pr opene 1 Bromopropane 1 Nitropropane
CH3 CH2Cl CH2OH

Cl2/UV light NaOH(alc.)
(iv) or heat NaCl
Toluene Benzyl chloride Benzyl alcohol
Br2./CCl4 NaNH2
(v) CH3–CH=CH2 CH3–––CH–––CH2 LiqNH 3
CH3–C CH
Propene Br Propyne
Br
1,2-Dibromopropane
PCl5
(vi) CH3–CH2–OH –POCl3, –HCl
CH3–CH2– Cl
Ethanol Chloroethane
AgF
CH3–CH2– F
Ethyl fluoride
KCN (alc) CH3–MgBr
(vii) CH3 – Br CH3 – CN CH3–C=NMgBr
Bromomethane Acetonitrile
CH3
Hydrolysis H 3O +
CH3–C=O
CH3
Propanone
Br
HBr
(viii) CH3CH2CH=CH2 (Markovnikov CH3CH2CHCH3
But-1-ene addition) 2-Bromobutane
KOH (alc)/ –HBr
CH3CH2=CHCH3
2-Butene
dry ether
(ix) 2CH3CH2CH2CH2–Cl + 2Na –2NaCl CH3CH2CH2CH2CH2CH2CH2CH3
1-Chlorobutane n-Octane
Br
Br2/Fe Na
(x) dark Dry ether + 2NaBr
Benzene Bromobenzene Diphenyl
30 E
CBSE
ALLEN
12. Explain why
(i) the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride ?
(ii) alkyl halides, though polar, are immiscible with water ?
(iii) Grignard reagent should be prepared under anhydrous conditions ?
– –
Cl Cl
 +  +
Ans. (i) sp
2
sp
3
Chlorobenzene Cyclohexylchloride
+M of –Cl and – I of–Cl are in opposite direction so dipole moment is decreased in

chlorobenzene.
(ii) No H-bonding of halide with water.
(iii) Grignard reagents in the presence of moisture, they react with H2O to give alkanes.
  
R Mg X  H2 O  R  H  Mg(OH)X
Grigrard Alkane
reagent
13. Give the uses of freon 12, DDT, carbon trtrachloride and iodoform.
Ans. Uses of Freon - 12 Freon-12 (dichlorodifluoromethane, CF2Cl2) is commonly known as CFC. It
is used as a refrigerant in refrigerators and air conditioners.
Uses of DDT (p-p–dichlorodiphenyltrichloroethane) is one of the best known insecticides.
Uses of carbontetrachloride (CCl4)
(i) It is used for manufacturing refrigerants and propellants for aerosol cans.
(ii) It is used as a solvent in the manufacture of pharmaceutical products.
(iii) It is used as a fire extinguisher.
Uses of iodoform (CHI3) Iodoform was used earlier as an antiseptic. The antiseptic property of
iodoform is only due to the liberation of free iodine when it comes in contact with the skin.
14. Write the structure of the major organic product in each of the following reactions.
(ii)  CH3 3 CBr  KOH 
heat 
ethanol
(i) CH 3 CH2 CH2 Cl  Nal 
ace t o n e
heat
(iii) CH3 CH(Br)CH2 CH3  NaOH 

water

 (iv) CH3 CH2 Br  KCN 
aq.acetone

(v) C6H5ONa + C2H5Cl  (vi) CH3CH2CH2OH + SOCl2 

(vii) CH3CH2CH  CH2  HBr 
Peroxide
 (viii) CH3CH = C(CH3)2 + HBr 
acetone
Ans. (i) CH3CH2CH2Cl + Nal heat CH3CH2CH2l + NaCl
1-Chloropropane (Finkelstein reaction) I – Iodopropane

ethanol
(CH3)3CBr + KOH heat CH3– C =CH2 + KBr + H2O
(ii) 2-Bromo-2-methylpropane (Dehydrohalogenation) CH 3
2-Methylpropane
(iii) CH3 CH(Br)CH2 CH3  NaOH  CH3 CH(OH)CH2 CH3  NaBr
water
2-Bromobutane Butan-2-ol
E 31
Chemistry
ALLEN
CH 3 CH2 Br  KCN 
aq.ethanol
 CH 3 CH2 CN  KBr
(iv) Nucleophilic
 substitution  Cyanoethane
(v) C H ONa  C2H5 Cl  

 C6 H5  O  C2 H5  NaCl
6 5
Sodium phenoxide
William son ' s
Chloroethane  synthesis  Phenetole
(vi) CH3 CH2 CH2 OH  SOCl2  CH3 CH2 CH2 Cl  SO2  HCl
1-Propanol 1 Chloropropane
(vii) CH3 CH2 CH  CH2  HBr   CH 3 CH2 CH2 CH2  Br

Peroxide
Anti  Markovnikov ' s
But 1  ene  addition  1-Bromobutane
Br
(viii) CH3CH=C(CH3)2 + HBr (Markovnikov

CH3– CH2 – C – CH3
2-Methylbut-2-ene addition) CH3
2-Bromo-2-methylbutane
15. Write the mechanism of the following reaction :

EtOH  H2O
nBuBr  KCN   nBuCN
Ans. The given reaction is :
EtOH  H2O
nBuBr  KCN   nBuCN
The given reaction is an SN2 reaction. In this reaction, CN– acts as the nucleophile and attacks
the carbon atom to which Br in attached. CN– ion is an ambident nucleophile and can attack
through both C and N. In this case, it attacks through the C- atom.
C3H5 C3H5
C–Br NC C Br
H H H
H
C3H5 –
NC—C + Br
H
H
16. Arrange the compounds of each set in order of reactivity towards SN2 displacement :
(i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
(ii) 1-Bromo-3-methylbutane,2-Bromo-2-methylbutane,3-Bromo-2-methylbutane
(iii) 1-Bromobutane, 1-Bromo-2, 2-dimethylpropane, 1-Bromo-2-methylbutane,1-Bromo
3-methylbutane.
1
Ans. (i) SN 2 
Hindrance on carbon
Br Br
CH3CH2CH2CH2CH2 – Br > CH3CH2CH2CHCH3 > CH3CH2CCH3

CH 3
1-Bromopentane (1°) 2-Bromopentane (2°) 2-Bromo-2-methylbutane (3°)
CH 3 Br Br
(ii) CH3CHCH2CH2Br > CH3CHCHCH3 > CH3CCH2CH3

CH 3 CH 3
1-Bromo-3-methylbutane 2-Bromo-3-methylbutane 2-Bromo-2-methylbutane
(1°) (2°) (3°)
32 E
CBSE
ALLEN
CH3
CH3–CH2–CH2–CH2–Br CH3–CH–CH2–CH2–Br
(iii)
1-Bromobutane (1°) 1-Bromo-3-methylbutane (1°)
CH 3
CH 3
CH3–C–CH2–Br
CH3–CH2–CH–CH2–Br
CH 3
1-Bromo-2-methylbutane (1°) 1-Bromo-2, 2-dimethylpropane
(more branching at nearer distance)

Hence, the increasing order of reactivity of the given compounds towards SN2 is :
1-Bromo-2, 2-dimethylpropane < 1-Bromo-2-methylbutane < 1-Bromo-3-methylbutane < 1-Bromobutane.
17. Out of C6H5CH2Cl and C6H5CHClC6H5, which is more easily hydrolysed by aqueous KOH ?
Ans. C6H5 CHCl C6H5 (more reactive)
+
C6H5–CH2–Cl –
–Cl
C6H5–CH2
Benzyl chloride (1°) 1° carbocation
Cl
+
C6H5–CH–C6H5 –
–Cl C6H5–CH–C6H5
Chlorodiphenylmethane 2° carbocation
(more stable intermediate)

18. p-Dichlorobenzene has higher m.p. and lower solubility than those of o-and m-isomers. Discuss.
Cl Cl Cl
Cl
Ans. Cl
Cl
p-Dichlorobenzene o-Dichlorobenzene m-Dichlorobenzene
p-Dichlorobenzene is more symmetrical than o-and m-isomers. For this reason, molecules of
p - dichlorobenzene are more closely than o-and m-isomers in the crystal lattice. Therefore, more
energy is required to break the crystal lattice of p-dichlorobenzene.
19. How the following conversions can be carried out ?
(i) Propene to propan-1-ol (ii) Ethanol to but-1-yne
(iii) 1-Bromopropane to 2-bromopropane (iv) Toluene to benzyl alcohol
(v) Benzene to 4-bromonitrobenzene (vi) Benzyl alcohol to 2-phenylethanoic acid
(vii) Ethanol to propanenitrile (viii) Aniline to chloro benzene
(ix) 2- Chlorobutane to 3, 4-dimethylhexane
(x) 2-Methyl-1-propene to 2-chloro-2-methyl propane

(xi) Ethyl chloride to propanoic acid (xii) But-1-ene to n-butyliodide
(xiii) 2-Chloropropane to 1- propanol (xiv) Isopropyl alcohol to iodoform
(xv) Chlorobenzene to p-nitrophenol (xvi) 2-Bromopropane to 1-bromopropane
(xvii) Chloroethane to butane (xviii) Benzene to diphene
(xix) tert-Butyl bromide to isobutyl bromide (xx) Aniline to phenylisocyanide
E 33
Chemistry
ALLEN
HBr/Peroxide (i) BH3/THF
CH3–CH=CH2 CH3–CH2–CH2–Br or CH3–CH=CH2 CH3CH2CH2–OH
Ans. (i) (Ani-Markovnikov
addition) 1-Bromopropane (ii) H2O2/OH
Propene
(Nucleophilic
Aq KOH/
substitution)
CH3–CH2–CH2–OH
Propan-1-ol
KOH(alc)/
CH3–CH2–CH2–Br (Dehydrohalogenation)
CH3–CH=CH2
(iii) 1-Bromopropane Propene
HBr Markovnikov
addition
Br
CH3–CH–CH3
2-bromopropane
Br Br
Br2/FeBr3 HNO 3/H 2SO 4
(v) Dark (Nitration)
Benzene Bromobenzene NO2
4-Bromonitrobenzene
CH2OH CH2Cl CH2CN

(vi) PCl5 KCN, Aq. ethanol
–POCl3,–HCl –KCl
Benzyl alcohol Benzyl cyanide
(Hydrolysis) +
H /H 2O
2 1
CH2COOH
2-Phenylethanoic acid
(vii) CH3  Ethanol

CH2  OH  
 CH3  CH2  Br   CH3  CH2  CN
red P / Br KCN,Aq.ethanol
2
Bromoethane Propanenitrile
+ –
NH2 N2Cl Cl
NaNO2+2HCl,
273-278 K Cu2Cl2
(viii) –NaCl, –2H 2O + N2
Aniline Benzenediazonium Chlorobenzene
chloride
Cl CH 3 CH 3
2Na/dry ether
(ix) 2CH3–CH–CH2–CH3 (Wurtz reaction) CH3–CH2–CH–CH–CH2–CH3 + 2NaCl
2-Chlorobutane 3, 4-Dimethylhexane
CH3 CH2
(x) CH3–C=CH2 HCl
(Markovnikov
CH3–C–CH3
addition)
2-Methyl-1-propene Cl
2-Chloro-2-methylpropane
KCN/aq. ethanol
(xi) CH3–CH2–Cl (nucleophilic
CH3–CH2–CN + KCl
substitution) Propanenitrile
Ethylchloride
(Hydrolysis) H+/H2O
CH3–CH2–COOH
Propanoic acid
34 E
CBSE
ALLEN
HBr/Peroxide
(xii) CH3–CH2–CH=CH2 (Anti-Markovnikov
CH3–CH2–CH2–CH2–Br
addition) Bromobutane
But-1-ene
Finkelstein Nal/dry acetone
reaction
CH3–CH2–CH2–CH2—1
n- Butyl iodide
Cl
KOH(alc)/ (i) BH3/THF
(xiii) CH3–CH–CH3 (Dethydrohalogenation)
CH3–CH=CH2 CH3CH2CH2OH
Propene (ii) H2O2/OH
2-Chloropropane
HBr/Peroxide (Anti-Markovnikov
addition)
Aq. KOH/
CH3–CH2–CH2–OH (Nucleophilic
CH3–CH2–CH2–Br
1-Propanol substitution) 1-Bromopropane
OH O
CrO 3
(xiv) CH3–CH–CH3 (Oxidation)
CH3–C–CH3
Propanone
Isopropyl alcohol
NaOI (Iodoform reaction)

O
CH3–C–ONa + CHI3
Iodoform
Cl Cl Cl OH
HNO 3/H 2SO 4 (i) NaOH, 433 K
(xv) (Nitration) (ii) dil HCl
Chlorobenzene NO2 NO2 NO2
p-Chloronitrobenzene p-Chloronitrobenzene p--Nitrophenol
(Major product)
Br
KOH(alc)/
CH3–CH–CH3 CH3–CH=CH2+HBr
(xvi) Dehydrohalogenation
Propene
2-Bromopropane
(Anit-Markovnikov HBr/peroxide
addition)
CH3–CH2–CH2–Br
1- Bromopropane
(xvii) CH3 CH2  Cl 

 CH3  CH2  CH2  CH3  2NaCl
2Na / dryether
 Wurtz reaction 
Chloroethane Butane
Br
KOH(alc)/ HBr/Peroxide
CH3–C–CH3 CH3–C=CH2 CH3–CH–CH2–Br
(xix) Dehydrohalogenation (Anit-Markovnikov
CH3 CH3 addition) CH3
Tert-Butylbromide 2-Methylpropene Isobutyl bromide
NH2 NC
CHCl3, 3KOH,
(xx) (Carbylamine reaction)

+ 3KCl + 3H2O
Aniline Phenyl isocyanide
20. The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols but in the
presence of alcoholic KOH, alkenes are major products. Explain.
Ans. OH– ion is highly solvated in an aqueous solution and as a result, the basic character of OH– ion
decreases. Therefore, it cannot abstract a hydrogen from the -carbon. So
R–Cl + Aq. KOH  R–OH + KCl
E 35
Chemistry
ALLEN
On the other hand, an alcoholic solution of KOH contains alkoxide (RO–) ion, which is a strong
base. Thus, it can abstract hydrogen from the -carbon of the alkyl chloride and form an alkene
by eliminating a molecule of HCl.
R  CH2  CH2  Cl  KOH(alc)  R  CH  CH2  KCl  H2 O
Alkyl chloride Alkene
21. Primary alkyl halide C4H9Br(a) reacted with alcoholic KOH to given compound (b). Compound
(b) is reacted with HBr to give (c) which is an isomer of (a). When (a) is reacted with sodium
metal it gives compound (d), C8H18 which is different from the compound formed when n-butyl
bromide is reacted with sodium. Give the structural formula of (a) and write the equations for all
the reactions.
Ans. There are two primary alkyl halides having the formula, C4H9Br. They are n-butyl bromide and
isobutyl bromide.
CH3–CH2–CH2–CH2–Br CH3–CH–CH2–Br
n-Butyl bromide CH3
Isobutyl bromide
Therefore, compound (a) is either n-butyl bromide or isobutyl bromide.

Now, compound (a) reacts with Na metal to give compound (b) of molecular formula, C8H18.
Which is different from the compound formed when n-butyl bromide reacts with Na metal.
Hence, compound (a) must be isobutyl bromide.
2CH3 CH2 CH2 CH2 Br 

2Na / dry ether
( Wurtz reaction )
 CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH3  2NaBr
n  Butyl bromide n-Octane
2Na/dry ether
CH3CHCH2Br (Wurtz reaction)
CH3CHCH2CH2CHCH3 +2NaBr
CH3 CH3 CH3
Isobutyl bromide (a) 2, 5-Dimethylhexane (d)
Thus, compound (d) is 2, 5–Dimethylhexane,

It is given that compound (a) reacts with alcoholic KOH to give compound (b). Hence,
compound (b) is 2–Methylpropene.
KOH (alc)/
CH3–CH–CH2–Br (Dehydrohalogenation)
CH3–C=CH2+HBr
CH3 CH3
Isobutyl bromide (a) 2-Methylpropene (b)
Also, compound (b) reacts with HBr to given compound (c) which is an isomer of (a). Hence
compound (c) is -2-Bromo-2-methylpropane.
Br
HBr
CH3–C=CH2 (Markovnikov addition)
CH3–C–CH3
CH3 CH3
2-Methylpropene (b) 2-Bromo-2-methylpropane (c)
(an isomer of (a))
36 E
CBSE
ALLEN
22. What happens when
(i) n-butyl chloride is treated with alcoholic KOH,
(ii) bromobenzene is treated with Mg in the presence of dry ether,
(iii) chlorobenzene is subjected to hydrolysis,
(iv) ethyl chloride is treated with aqueous KOH,
(v) methyl bromide is treated with sodium in the presence of dry ether,
(vi) methyl chloride is treated with KCN.
KOH(alc.) / 
Ans. (i) CH3  CH2  CH2  CH2  Cl 
(Dehydrohalogenation)
 CH3  CH2  CH  CH2  KCl  H2 O
n  Butyl chloride But  l  ene
(ii) Phenylmagnesium bromide is formed.

Br MgBr
dry ether
+Mg
Bromobenzene Phenylmagenesium bromide
(iii) Chlorobenzene does not undergo hydrolysis under normal conditions. However, it
undergoes hydrolysis when heated in an aqueous sodium hydroxide solution at a
temperature of 623 K and a pressure of 300 atm to form phenol.
Cl OH
(i) NaOH, 623 K, 300 atm
(ii) H +
Chlorobenzene Phenol
CH 3  CH2  Cl   CH 3  CH2  OH  KCl

( aq.) KOH
(iv) (Hydrolysis )
Ethyl chloride Ethanol
(v) 2CH3  Br  2Na 

Dry ether
( Wurtz reaction)
 CH3  CH3  2NaBr
Methyl bromide Ethane
(vi) CH3  Cl  KCN 

Nucleophilic substitution
 CH3  CN  KCl
Methyl chloride Methyl cyanide
E 37
Chemistry
ALLEN
EXERCISE-3 EXEMPLAR
1. Which of the following alcohols will yield the corresponding alkyl chloride on reaction with
concentrated HCl at room temperature ?
(a) CH3CH2—CH2—OH (b) CH3CH2—CH—OH
CH3
CH3
(c) CH3CH2—CH—CH2OH (d) CH3CH2—C—OH
CH3 CH3
Ans. (a)
2. Identify the compound Y in the following reaction :
+ –
NH3 N2Cl
NaNO2+HCl Cu2Cl2
Y+N2
273-278K
Cl
Cl Cl
(a) (b) (c) (d)

Cl Cl
Ans. (a)
3. Toluene reacts with a halogen in the presence of iron (III) chloride giving ortho and para halo
compounds. The reaction is:
(a) Electrophilic elimination reaction (b) Electrophilic substitution reaction
(c) Free radical addition reaction (d) Nucleophilic substitution reaction
Ans. (b)
4. Arrange the following compounds in increasing order of their boiling points :
CH3
CH3
(i) CH—CH2Br (ii) CH3CH2CH2CH2Br (iii) H3C—C—CH3
CH3 Br
(a) ii < i < iii (b) i < ii < iii (c) iii < i < ii (d) iii < ii < i
Ans. (c)
5. In which of the following molecules carbon atom marked with asterisk (*) is asymmetric ?
H D H H
C* C* C* C*
(i) I Cl (ii) I Cl (iii) OH CH3 (iv) H CH3
Br Br C2H5 C2H5
(a) i, ii, iii and iv (b) i, ii and iii (c) ii, iii and iv (d) i, iii and iv
Ans. (b)
38 E
CBSE
ALLEN
6. Which of the following structures is enantiomeric with the molecule (A) given below ?
H
CH3
C
H5C2 Br
(A)
H CH3
C2H5 H
(a) C (b) C
H3C Br Br C2H5
H Br
Br H
(c) C (d) C
H3C C2H5 H5C2 CH3
Ans. (a)
7. Chlorobenzene is formed by reaction of chlorine with benzene in the presence of AlCl3. Which of
the following species attacks the benzene ring in this reaction ?
(a) Cl– (b) Cl+ (c) AlCl3 (d) [AlCl4]–
Ans. (b)
8. What is ‘A’ in the following reaction ?
CH2–CH=CH2
+ HCl A
CH2–CH=CH2 CH2–CH2–CH2–Cl
Cl
(a) (b)
Cl
CH2–CH–CH3 CH–CH2–CH3
Cl
(c) (d)
Ans. (c)
9. Which of the following alkyl halides will undergo SN1 reaction most readily ?
(a) (CH3)3C–F (b) (CH3)3C–Cl (c) (CH3)3C–Br (d) (CH3)3C–I
Ans. (d)
10. Reaction of C6H5CH2Br with aqueous sodium hydroxide follows ……….
(a) SN1 mechanism
(b) SN2 mechanism
(c) Any of the above two depending upon the temperature of reaction
(d) Saytzeff rule
Ans. (a)
E 39
Chemistry
ALLEN
11. Which of the following compounds will give racemic mixture on nucleophilic substitution by
OH– ion ?
Br
CH3—CH—Br CH3—C—CH3 CH3—CH—CH2Br
(i) (ii) (iii)
C2H5 C2H5 C2H5
(a) I (b) i, ii and iii (c) ii and iii (d) i and iii
Ans. (c)
Directions (Q.No.12-14) In the questions 12 to 14 arrange the compounds in increasing order of rate
of reaction towards nucleophilic substitution.
Cl
Cl Cl
NO2
12. (i) (ii) (iii)
NO2
(a) i < ii < iii (b) iii < ii < i (c) i < iii < ii (d) iii < i < ii
Ans. (c)
Cl
Cl Cl
CH3
13. (i) (ii) (iii)
CH3
(a) i < ii < iii (b) i < iii < ii (c) iii < ii < i (d) ii < iii < i
Ans. (d)
Cl Cl
O2N NO2
Cl
14. (i) (ii) (iii)
NO2 NO2

(a) iii < ii < i (b) ii < iii < i (c) i < iii < ii (d) i < ii < iii
Ans. (d)
15. Which is the correct increasing order of boiling points of the following compounds ?
1-iodobutane,1-bromobutane, 1-chlorobutane, Butane
(a) Butane < 1-chlorobutane < 1-bromobutane < 1-iodobutane
(b) 1-iodobutane < 1- bromobutane < 1- chlorobutane < Butane
(c) Butane < 1-iodobutane < 1-bromobutane < 1-chlorobutane
(d) Butane < 1-chlorobutane < 1-iodobutane < 1-bromobutane
Ans. (a)
16. Which is the correct increasing order of boiling points of the following compounds ?
1-bromoethane, 1-bromopropane, 1-bromobutane, Bromobenzene
(a) Bromobenzene < 1-bromobutane < 1-bromopropane < 1-bromoethane
(b) Bromobenzene < 1-bromoethane < 1-bromopropane < 1-bromobutane
(c) 1-bromopropane < 1-bromobutane < 1-bromoethane < Bromobenzene
(d) 1-bromoethane < 1-bromopropane < 1-bromobutane < Bromobenzene
Ans. (d)
40 E
CBSE
ALLEN
(SHORT ANSWER TYPE)
17. Which of the following compounds (i) and (ii) will not react with a mixture of NaBr and H2SO4.
Explain why ?
OH
(i) CH3CH2CH2OH (ii)
Ans. Partial double bond character of a bond increases the strength of the bond and hence, decreases
the stability. Phenol will not react with a mixture of NaBr and H2SO4 because it is resonance
stabilised. Due to resonance, partial double bond character arises in C—O bond of phenol and it
becomes more stable than alcohol. (CH3CH2CH2OH).
Reaction 2NaBr + 3H2SO4  2NaHSO4 + SO2 + Br2 + 2H2O
OH OH
Br Br
Br2/H2O
Phenol
Br
CH3CH2CH2OH 
Br2
 No reaction
18. Why is the solubility of haloalkanes in water very low ?
Ans. Haloalkanes are slightly soluble in water. For the solubility to haloalkane in water, energy is
required to overcome the attractions between its own molecules and to break the bonds between
water molecules.
Less energy is released when new attractions are set up between the haloalkanes and the water
molecules as these are not as strong as the original hydrogen bonds in water.
19. Classify the following compounds as primary, secondary and tertiary halides :
(a) 1-bromobut-2-ene (b) 4-bromopent-2-ene (c) 2-bromo-2-methylpropane
Ans. The structural formula of the given compounds are :
CH3
(a) H 3C–H 2 C=HC – H 2 C–Br (b) CH3–CH–CH=CH–CH3 (c) H3C—C—CH3
1 Bromo but  2  ene
(Primary halide)
Br Br
4-Bromo but-2-ene 2-bromo-2-methylpropane
(Secondary halide) (Tertiary halides)
20. Compound ‘A’ with molecular formula C4H9 Br is treated with aq. KOH solution. The rate of
this reaction depends upon the concentration of the compound ‘A’ only. When another optically
active isomer ‘B’ of this compound was treated with aq. KOH solution, the rate of reaction was
found to be dependent on concentration of compound and KOH both.
(i) Write down the structural formula of both compounds ‘A’ and ‘B’.
(ii) Out of these two compounds, which one will be converted to the product with inverted
configuration.
E 41
Chemistry
ALLEN
Ans. (i) As the rate of reaction depends upon the concentration of compound ‘A’ (C4H9Br) only
therefore, the reaction is proceeded by SN1 mechanism and the given compound will be
tertiary alkyl halide i.e., 2-bromo-2-methylpropane and the structure is as follow
CH3
H3C—C—Br (A)
CH3
Optically active isomer of (A) is 2-bromobutane (B) and its structural formula
•
is CH3–CH2–CH CH3
(B)
Br

(ii) As compound (B) is optically active therefore, compound (B) must be 2-bromobutane.
Since, the rate of reaction of compound (B) depends both upon the concentration of
compound (B) and KOH, hence, the reaction follow SN2 mechanism. In SN2 reaction,
nucleophile attack from, the back side, therefore, the product of hydrolysis will have
opposite configuration.
CH2CH3 CH2CH3
CH2CH3 ….. …..
C—Br HO C Br C—CH3
H H HO
CH3 CH3 CH 3
21. Write the structures and names of the compounds formed when compound ‘A’ with molecular
formula C7H8 is treated with Cl2 in the presence of FeCl3.
Ans. When compound ‘A’ with molecular formula C7H8 is treated with Cl2 in the presence of FeCl3
o-chlorotoluene or p-chlorotoulene will be formed as the compound A with molecular formula
C7H8 is toluene.
CH3 CH3 CH3
Cl
Cl2/FeCl3
+
FeCl3
Toluene o-chlorotoluene
(M.F C7H8) Cl
(minor)
p-chlorotoluene
(major)
22. Which of the following haloalkanes reacts with aqueous KOH most easily ? Explain giving
reason.
(i) 1-bromobutane (ii) 2-bromobutane
(iii) 2-bromo-2-methylpropane (iv) 2-chlorobutane
Ans. 2-bromo-2-methylpropane (iii), is a tertiary alkyl halide and it will form a stable carbocation on
ionisation.
Br CH3
Ionisation + OH –
H3C—C—CH3 –Br–
H3C—C—CH3 CH3–C–OH
CH3 CH3 CH3
2-bromo-2-methylpropane 3° carbocation (stable) 2-methyl-2-propanal
42 E
CBSE
ALLEN
23. Allyl chloride is hydrolysed more readily than n-propyl chloride. Why ?
Ans. As we know that SN1 mechanism depends upon the stability of carbocation. Allyl chloride on
hydrolysis gives resonance stabilised carbocation while no resonance is observed in the
carbocation formed by n-propyl chloride.
  –
 Cl
CH 2  CH  CH 2 Cl   CH 2  CH  CH 2  Cl
Allyl chloride
 
CH 2  CH  CH 2  CH 2  CH  CH 2
(Resonance stabilised
carbocation)
 
 Cl
CH 3  CH 2  CH 2  Cl   CH 3  CH 2  CH 2  Cl
n  butyl ( Not stabilised by resonance)
chloride
Hence, allyl chloride undergoes hydrolysis much faster than n-propyl chloride.
24. tert-Butylbromide reacts with aq. NaOH by SN1 mechanism while n-butylbromide reacts by SN1
mechanism. Why ?
Ans Tert. butyl bromide reacts with aq. NaOH as follows :
CH3 CH3
SN1
H3C—C—Br H3C—C+ + Br–
CH3 CH3
tert Butylbromide 3° carbocation
(3° alkyl halide) (more stable)
CH3 CH3
H3C—C+ + OH– H3C—C—OH
CH3 CH3
tert. butyl bromide when treated with aq. NaOH, it forms tert. carbocation which is more stable
intermediate. This intermediate is further attacked by –OH ion.
As tert, carbocation is highly stable so tert butylbromide follow SN1 mechanism.
In case of n-nutylbromide, primary carbocation is formed when is least stable so, it does not
follow SN1 mechanism. Here, steric hindrance is very less so, it follow SN2 mechanism. In SN2
mechanism, –OH will attack from backside and a transition state is formed.
The leaving group is then pushed off the opposite side and the product is formed.
CH2–CH2–CH3 CH2–CH2–CH3 CH2–CH2–CH3
C HO…..C…..Br C
H Br –
OH H H + Br—
H H H
H
n-butyl bromide transition state n-butyl alcohol
E 43
Chemistry
ALLEN
25. Predict the major product formed when HCl is added to isobutylene, Explain the mechanism
involved.
Ans. Reaction between the isobutylene added to HCl.
Cl
Markownikoff’s
H3C—C = CH2 + HCl rule
H3C—C—CH3
CH3 CH3
Isobutylene 2-chloro-2-methylpropane
Electrophilic addition reaction takes place in accordance with Markownikoff’s rule.

26. How can you obtain iodoethane from ethanol when no other iodine containing reagent except NaI
is available in the laboratory ?
Ans. CH 3CH 2OH 
Red P/Br2
 CH 3CH 2 Br 
NaI
CH3CH 2 I  NaBr
27. Cyanide ion acts as an ambident nucleophile. From which end it acts as a stronger nucleophile in
aqueous medium ? Give reason for your answer.
–
Ans. Cyanide ion (:C  N) is an ambident nucleophile because it can react either through carbon or
through nitrogen. Since, C—C bond is stronger than C—N bond so, cyanide ion will mainly
attack through carbon to form alkyl cyanide.
–
R—X + :C  N  R—C  N + X–
Alkyl cyanide Alkyl cyanide
(Matching the Columns)

28. Match the compounds given in Column-I with the effect given in Column-II.
Column-I Column-II
(A) Chloramphenicol (1) Malaria
(B) Thyroxine (2) Anaesthetic
(C) Chloroquine (3) Typhoid fever
(D) Chloroform (4) Goiter
(5) Blood substituent
Ans. A-3, B-4, C-1, D-2
29. Match the items of Column-I and Column-II.
Column-I Column-II
(A) SN1 reaction (1) vic-dibromides

(B) Chemicals in fire extinguisher (2) gem-dihalides
(C) Bromination of alkenes (3) Racemisation
(D) Alkylidene halides (4) Saytzeff rule
(E) Elimination of HX from alkyl halide (5) Chlorobromocarbons
Ans. A-3, B-5, C-1, D-2, E-4
44 E
CBSE
ALLEN
30. Match the structures of compounds given in Column-I with the classes of compounds given in
Column-II.
Column-I Column-II
(A) CH3—CH—CH3 (1) Aryl halide

X
(B) CH2 = CH — CH2 — X (2) Alkyl halide
(C) X (3) Vinyl halide
(D) CH2 = CH—X (4) Allyl halide
Ans. A-2, B-4, C-1, D-3

31. Match the reaction given in Column I with the types of reaction given in Column II.
Column-I Column-II
(A) Cl Cl Cl (1) Nucleophilic aromatic

Cl Cl substitution
Fe/Cl2 +
(B) CH3—CH=CH2 + HBr CH3—CH—CH3 (2) Electrophilic aromatic

Br substitution
(C) CH3–CH–I CH3–CH–OH (3) Saytzeff elimination
OH
(D) Cl OH (4) Electrophilic addition
+ NaOH
NO2 NO2
(E) CH3CH2CHCH3 alc. (5) Nucleophilic substitution

KOH CH3CH=CHCH3
Br (SN1)
Ans. A-2, B-4, C-5, D-1, E-3
E 45
Chemistry
ALLEN
32. Match the structures given in Column I with the names in Column II.
Column-I Column-II
(A) Br (1) 4-bromopent-2-ene
(B) (2) 4-bromo-3-methylpent-2-ene

Br
(C) (3) 1-bromo-2-methylbut-2-ene

Br
(D) (4) 1-bromo-2-methypent-2-ene

Br
Ans. A-1, B-2, C-3, D-4

33. Match the reactions given in Column I with the names given in Column II.
Column-I Column-II
(A) Na (1) Fittig reaction
X + RX R
(B) X (2) Wurtz-Fittig reaction
Ether + 2NaX
+ 2Na
(C) +– (3) Finkelstein reaction

N2 X X
Cu2X2
+ N2
(D) C2H5Cl + NaI 

Dry acetone
 C2H5I + NaCl (4) Sandmeyer reaction
Ans. A-2, B-1, C-4, D-3
(ASSERTION AND REASON)
In the following questions a statement of Assertion (A) followed by a statement of Reason (R)
is given. Choose the correct answer out of the following choices.
(a) Both (A) and (R) correct and (R) is correct explanation of (A).
(b) Both (A) and (R) correct and (R) is not correct explanation of (A).
(c) (A) is correct but (R) is wrong.
(d) (A) Assertion is wrong but (R) reason is correct.
34. Assertion (A) : Phosphorus chlorides (tri and penta) are preferred over thionyl chloride for the
preparation of alkyl chlorides from alcohols.
Reason (R) : SOCl2 give pure alkyl halides.
Ans. (b)
46 E
CBSE
ALLEN
35. Assertion (A) : The boiling points of alkyl halides decrease in the order RI > RBr > RCl >RF
Reason (R) : The boiling points of alkyl chlorides, bromides and iodides are considerably higher
than that of the hydrocarbon of comparable molecular mass.
Ans. (b)
36. Assertion (A) : KCN reacts with methyl chloride to give methyl isocyanide.
Reason (R) : CN– is an ambident nucleophile.
Ans. (d)
37. Assertion (A) : tert-butyl bromide undergoes Wurtz reaction to give 2,2,3,3-tetramethylbutane.
Reason (R) : In Wurtz reaction, alkyl halides react with sodium in dry ether to give hydrocarbon
containing double the number of carbon atoms presents in the halide.
Ans. (b)
38. Assertion (A) : Presence of a nitro group of ortho or para position increases the reactivity of
haloarenes towards nucleophilic substitution.
Reason (R) : Nitro group, being an electron withdrawing group decreases the electron density
over the benzene ring.
Ans. (a)
39. Assertion (A) : In monohaloarenes, electrophilic substitution occurs at ortho and para positions.
Reason (R) : Halogen atom is a ring deactivator.
Ans. (b)
40. Assertion (A) : Aryl iodides can be prepared by reaction of arenes with iodine in the presence of
an oxidising agent.
Reason (R) : Oxidising agent oxidises I2 into HI.
Ans. (d)
41. Assertion (A) : It is difficult to replace chlorine by –OH in chlorobenzene in comparison to that
in chloroethane.
Reason (R) : Chlorine carbon (C–Cl) bond in chlorobenzenes has a partial double bond character
due to resonance.
Ans. (a)
42. Assertion (A) : Hydrolysis of (–)-2-bromobutane proceeds with inversion of configuration.
Reason (R) : This reaction proceeds through the formation of a carbocation.

Ans. (c)
43. Assertion (A) : Nitration of chlorobenzene leads to the formation of m-nitrochlorobenzene.
Reason (R) : –NO2 group is a m-directing group.
Ans. (d)
E 47
Chemistry
C
N
ALLEN
EXERCIS
E SE-4 MCQ,
M A/R
R, CASE B
BASE QU
UESTIONS
S
(IIntroductio
on)
1.
1 Gem- dibromide is:
i
(a) CH
H 3CH(Br)C
CH(Br)CH 3 (b) CH 3CBr2 CH
H3
(c) CH C 2  Br 
H 2 (Br)CH 2 CH (d) CH 2 BrCH 2Br
2.
2 Whichh of the folloowing halidde is 2o ?
(a) Isoopropyl chlooride (b) Issobutyl chlooride (c) n-propyl
n chloride (d)) n-butyl chloride
3.
3 The geeneral formuula for alky
yl halides is::
(a) Cn H 2n 1X (b) Cn H 2n  2 X (c) Cn H n 1X (d)) Cn H 2n X
4.
4 Whichh of the folloowing strucctures is enaantiomeric with
w the molecule givenn below :
(a) (b) (c) (d))
5.
5 Moleccules whose mirror imaage is non-ssuperimposaable over th hem are knoown as chirral. Which of
o
the folllowing mollecules is ch
hiral in natuure?
(a) 2-B
Bromobutanne (b) 1--Bromobutaane (c) 2-Bromopro
2 opane (d)) 2-Bromopropan-2-ol
(Nucleeophilic Su ubstitution Reactions
R (NSR))
(
6.
6 Ethyl bbromide cann be converrted into ethhyl alcohol by
b –
(a) Heating with dilute
d hydroochloric acidd and zinc
(b) Booiling with an
a alcoholicc solution off KOH
(c) Thee action of moist
m silverr oxide
(d) Refluxing metthanol
7.
7 Cl  KCN 
C2 H5C   X , 'X' is –
(a) C2 H 6 (b) CH 3CH 2 CH
H 2 OH,
H 3  C(CH 3 )(OH)  CH
(c) CH H3 (d) C2 H 5CN
8.
8 The reeactivities off methyl chloride, proppyl chloridee and chlorobenzene aree in the ordeer –
(a) Meethyl chloridde > propyl chloride > chlorobenzzene
(b) Proopyl chloridde > methyl chloride > chlorobenzzene
(c) Meethyl chloridde > chlorobbenzene > ppropyl chlorride
(d) Chhlorobenzenne > propyl chloride

c >m methyl chlooride
9.
9 R  X  NaOH   ROH  NaX N
The abbove reactioon is classifiied as:
(a) Nuucleophilic substitution
s (b) Electrophili
E ic substitutioon
(c) Redduction (d) Oxidation
O
10.
1 In nuclleophilic alipphatic substtitution, the nnucleophiless are generally:
(a) Acids (b) Bases (c) Salts
S (d)) Neutral mo
olecules
48
4 E
 CBSSE
ALLEN
A
(EAR
R & Elimin
nation)
11.
1 CH3–C CH2–Cl  
aalc.KOH
 A, the productt is :
(a) CHH3CH2OK (b) CH
C 3CHO
(c) CHH3CH2OCH2CH3 (d) CH
C 2 = CH2
12.
1 Dehyddrohalogenaation of an alkyl
a halide is:
(a) Ann addition reeaction (b) A substitution reactionn
(c) Ann eliminationn reaction (d) An
A oxidatio on reaction
13.
1 What pproduct is formed
f when n 1-chlorobbutane react with alcoho olic KOH –
(a) 1-bbutene (b) 2--butene (c) 1-butanol
1 (d)) 2-butanol
14.
1 In whiich of the following,
f addition
a of HBr does notn take plaace against Markownik koff's rule or
o
Anti-MMarkownikooff addition of HBr is nnot observed d for –
(a) Proopene (b) But-1-ene (c) But-2-ene
B (d)) Pent-2-enee
15.
1 The prropene reactts with HBrr to form –
(a) Ethhane (b) Hexane
H (c) 1-bromo-pro
1 opane (d)) 2-bromo propane
p
(ESR,, Name Rea action)
16.
1 The fuunction of annhydrous AlCl
A 3 in the F Friedel-Craaft's reaction
n is to –
(a) Abbsorb water (b) Absorb
A HCll
(c) To produce eleectrophile (d) To
T produce nucleophilee
17.
1 On treeating a mixxture of two o alkyl haliddes with sod dium metal in dry etherr, 2-methyl propane waas
obtained. The alkyyl halides are
a :
(a) 2-cchloropropaane and chlo oromethane
(b) 2-cchloropropaane and chlo oroethane
(c) Chloromethanne and chlorroethane
(d) Chhloromethanne and 1-chlloropropanee
18.
1 Toluenne reacts with
w a halogen in the ppresence of iron (III) chloride givving ortho and a para halo
compoounds. The reaction
r is :
(a) Eleectrophilic elimination
e reaction
(b) Eleectrophilic substitution
s reaction
(c) Freee radical adddition reacction
(d) Nuucleophilic substitution
s reaction
19.
1 Whichh of the folloowing is halogen exchaange reactio on?
(a) R X + NaI  RI + NaX
(b)
(c)
(d)
20.
2 Benzenne on treatm
ment with a mixture off conc. HNO
O3 and conc.. H2SO4 at ggives –
(a) Nittrobenzene (b) m-dinitroben
m nzene (c) p-dinitroben
p nzene (d)) o-dinitrobeenzene
E 49
9
Chemistry
ALLEN
(Physical Properties, Chemical Test)
21. Arrange the following compounds in increasing order of their boiling points.
CH3
H3C
(A) CH—CH2Br (B) CH3CH2CH2CH2Br (C) H3C C CH3
H3C
Br
(a) (B) < (A) < (C) (b) (A) < (B) < (C) (c) (C) < (A) < (B) (d) (C) < (B) < (A)
22. Arrange the following compounds in increasing order of their density.
(i) CH2Cl2 (ii) CHCl3 (iii) CCl4
(a) (iii) < (ii) < (iii) (b) (iii) < (i) < (ii) (c) (iii) < (i) = (ii) (d) (i) < (ii) < (iii)
23. Which is the correct increasing order of boiling point of the following compounds?
I-bromoethane, 1-bromopropane, 1-bromobutane, bromobenzene
(a) Bromobenzene < 1-bromobutane < 1-bromopropane < 1-bromoethane
(b) Bromobenzene < 1-bromoethane < 1-bromopropane < 1-bromobutane
(c) bromopropane < 1-bromobutane < 1-bromoethane < 1-bromobenzene
(d) bromoethane < 1- bromopropane < 1-bromobutane < 1-bromobenzene
24. Write the name of chemical test which is used to distinguish between ethyl Bromide and
Bromobenzene?
(a) Lucas test (b) Silver nitrate test (c) Neutral FeCl3 test (d) None of these
25. C2H5Cl + AgNO3  X + C2H5–NO2
What is X?
(a) White ppt of AgCl (b) Yellow ppt of AgCl
(c) Black ppt of AgCl (d) None of these
26. Allylic halide is –
(a) Compound in which halogen atom is bonded to sp3 hybridised carbon atom next to aromatic ring
(b) Compound in which halogen atom is bonded to sp3 hybridised carbon atom next to carbon-
carbon double bond
(c) Compound in which halogen atom is bonded to an alkyl group
(d) None of these above
27. Which of the following is primary bromide?
(a) 3-bromopentane (b) 2-bromopentane (c) 1-bromopentane (d) All of these
28. Common name given to 2-chloropropane.
(a) n-propyl chloride (b) isopropyl chloride (c) isobutyl chloride (d) None of these
29. What should be the correct IUPAC name for diethylbromomethane?
(a) 1-bromo-1, 1-diethylmethane (b) 3-bromopentane
(c) 1-bromo-1-ethylpropane (d) 1-bromopentane

H3C H
30. The IUPAC name of is –

H Br
CH3
(a) 2-bromopent-4-ene (b) 2-bromopent-3-ene
(c) 4-bromopent-2-ene (d) 4-bromopent-1-ene
50 E
CBSE
ALLEN
31. Compound containing Csp — X bond is –
(a) chloroethyne (b) chloropropane (c) chloropropene (d) All of these
(Method of Preparation)
32. Alkyl halides can be synthesised from –
(a) alcohol (b) hydrocarbon (c) halogen exchange (d) All of these
33. Select the byproduct formed in the reaction.
ROH + PCl5  RCl + ..... +.....
(a) POCl3 + HCl (b) H3PO3 + No other byproduct
(c) H3PO3 + HCl (d) POCl3 + No other byproduct
CH3
Fe/dark
34. + X2
CH3 CH3
+
X X
This reaction is:
(a) Nucleophilic substitution (b) electrophilic substitution
(c) Nucleophilic elimination (d) electrophilic elimination
35. R — X + NaI R — I + NaX
The solvent which is used in this reaction is ?
(a) acetone (b) dry acetone (c) water (d) ethyl acetate
36. Alkyl halides can be obtained by all methods excepts –
(a) CH3—CH2—OH + HCl 
ZnCl2
 (b) CH2=CH—CH3 + HBr 
(c) C2H5OH + NaCl  (d) CH3COOAg + Br2 / CCl4  h

(Physical & Chemical Properties)
37. KCN is ...A... compound and AgCN is ...B... compound. Here, A and B refer to–
(a) ionic, covalent (b) ionic, ionic (c) covalent, ionic (d) covalent, covalent
38. In which case the approach of nucleophile is easy as shown in figure?
H
H
H C
Nu: X Nu: H
H X
H H
H
H H
H H
C C
Nu: H Nu: H
X X
H H C
H C H C
H
H H HH H
(a) methyl (b) Ethyl (c) Isopropyl (d) Tert-butyl

E 51
Chemistry
ALLEN
39. The allylic and benzylic halides undergo –
(a) SN1 mechanism (b) SN2 mechanism
(c) Both SN1 and SN2 mechanism (d) None of the above
40. SN2 reaction proceeds with ..... while SN1 proceeds with .....
(a) racemisation, complete inversion (b) complete racemisation, inversion
(c) complete inversion, racemisation (d) inversion, racemisation
41. Which of the following molecule is chiral?
(a) Butane-1-ol (b) Butan-2-ol (c) Butan-4-ol (d) All of these
42. CH3CH2MgBr is referred as –
(a) ethyl magnesium bromide (b) methyl magnesium bromide
(c) Grignard reagent (d) Both (a) and (c)
43. Aryl halide are extremely less reactive towards nucleophilic substitution reaction due to –
(a) resonance effect (b) instability of phenyl cation
(c) repulsion (d) All of these
ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. b a a a a b d a a b
Q. No. 11 12 13 14 15 16 17 18 19 20
Ans. d c a c d c a b a a
Q. No. 21 22 23 24 25 26 27 28 29 30
Ans. c d d b a b c b b c
Q. No. 31 32 33 34 35 36 37 38 39 40
Ans. a d a b b c a a a c
Q. No. 41 42 43
Ans. b d d
52 E
CBSE
ALLEN
ASSERTION AND REASON
Directions : In the following questions an Assertion (A) is followed by a corresponding

Reason (R) Use the following keys to choose the appropriate answer.
1. Assertion (A) : Aryl halides are not prepared by reaction of phenol with thionyl chloride.
Reason (R) : Carbon oxygen bond in phenol is difficult to break due to partial double bond
character.
2. Assertion (A) : Finkelstein reaction is carried out in presence of acetone.
Reason (R) : It facilitates the forwards reaction according to Le Chatelier's Principle by

precipitating by products.
3. Assertion (A) : The boiling points of chlorides, bromides and iodides are considerable higher
than those of the hydrocarbons of comparable molecular mass.
Reason (R) : C–X bond is polar.
4. Assertion (A) : For the same alkyl group, the boiling points of alkyl halides decrease in the
order: RI > RBr > RCl > RF
Reason (R) : With the increase in size and mass of halogen atom, the magnitude of van der Waal
forces increases.
5. Assertion (A) : The para-isomers are high melting as compared to their orthoand meta-isomers.
Reason (R) : Charge separation is higher in para isomer.
6. Assertion (A) : Solubility of haloalkanes in water is low.
Reason (R) : Less energy is released when new attractions are set up between the haloalkane and
the water molecules.
7. Assertion (A) : Haloalkanes are readily soluble in organic solvents.
Reason (R) : The C–X bond is highly polar.
8. Assertion (A) : CN is an ambidentnucelophile.
Reason (R) : It process two nucleophilic centres.
E 53
Chemistry
ALLEN
9. Assertion (A) : Tertiary alkyl halides follow SN2 mechanism.
Reason (R) : Tertiary carbocation is more stable.
10. Assertion (A) : Haloarenes are less reactive towards substitution reactions.
Reason (R) : The electron pairs on the halogen atom are in conjugation with -electrons of the ring.
ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. a a b a c a c a d a
54 E
CBSE
ALLEN
CASE BASED
Case Base-I
Due to greater polarity as well as higher molecular mass as compared to the parent hydrocarbon,
the intermolecular forces of attraction (dipole-dipole and van der Waals) are stronger in the
halogen derivatives. That is why the boiling points of chlorides, bromides and iodides are
considerably higher than those of the hydrocarbons of comparable molecular mass. The attraction
get stronger as the molecules get bigger in size and have more electrons.
(a) Explain why 1-iodobutane has higher boiling point than 1-chlorobutane ?
Ans. In case of halogens, due to greater molarity and higher molecular mass and also
intermolecular forces of attraction.
OR
1-Bromopropane is more stronger halogen derivative than Bromobenzene. Why ?
Ans. Due to intermolecular attraction forces.
(b) How are the intermolecular forces of attraction in hydrocarbons affect their derivatives.
Ans. As the number of carbon atoms increase, the boiling point increases because the
intermolecular forces increase stronger the intermolecular forces of attraction the more
energy is required to break those forces.
(c) Arrange following alkyl group in order of increasing of boiling points :
RCl, RI, RBr
Ans. RCl < RBr < RI
Case Base-II
Nucleophilic substitution reactions in aryl halides occur only under drastic conditions, whereas
electrophilic substitution reactions such as halogenation, nitration, sulphonation and Friedel-
raft's reaction occur easily. In these reaction stronger electrophile replaces weaker electrophile.
The electrophilic substitution reactions in haloarenes occur slowly and requires more drastic
conditions. This is due to the ortho- and para-directing influence of halogeri atom attached to a
benzene ring which can be undcrston by following resonating structures.
  
X X X X X
1 1
1

(a) Out of Chlorobenzene and p-nitrochlorobenzene, which one is more reactive towards
nucleophilic substitution reaction and why ?
Ans. p-nitrochlorobenzene undergoes nucleophilic substitution reaction faster than
chlorobenzene due to resonance effect.
E 55
Chemistry
ALLEN
(b) Which would undergo SN2 reaction faster in the following pair :
C6H5 – CH2 – CH2 – Br and C6 H 5  CH  CH 3
|
Br
Ans. C6H5–CH2CH2–Br
(c) Out of chlorobenzene and benzyl chloride, which one gets easily hydrolysed by aqueous
NaOH and why ?
Cl CH2Cl
Ans.
The benzyl chloride is more hydrolysed in aquation NaOH as in chloro benzene the lone
pair of chlorine are in conjugation with -Bond of benzene due to which partial double
bond character develop & it reduce its reactivity.
OR
Which compound in each of the following pairs will react faster in SN2 reaction with
–OH why?
(i) CH3Br or CH3I (ii) (CH3)3CCl or CH3Cl
Ans. (i) CH3I will react faster as compared to CH3Br because CH3I has lower bond
dissociation energy & iodide is better leaving group. In the presence of nucleophile it
will be released at a faster rate.
(ii) CH3Cl will react faster as compared to (CH3)3CCl because 1º halide undergo SN2
mechanism faster than 3º halides to minimize steric hindrance
56 E
CBSE
ALLEN
PREVIOUS YEARS QUESTIONS
SECTION-A (ONE MARK QUESTIONS)
1. The conversion of an alkyl halide into an alkene by alcoholic KOH is classified as
[1] [CBSE 2023]
(a) a substitution reaction (b) an addition reaction
(c) a dehydrohalogenation reaction (d) a dehydration reaction
Ans. (c)
2. Racemisation occurs in [1] [CBSE 2023]
(a) SN1 reaction (b) SN2 reaction
(c) Neither SN1 nor SN2 reaction (d) SN2 reaction as well as SN1 reaction
Ans. (a)
3. Which of the following belongs to the class of Vinyl halides? [1] [CBSE 2023]
(a) CH2 = CHCH2CH2Cl (b) CH 2  C  CH 3
|
Br
(c) CH2 = CH – CH2 – Br (d) CH  C – Br
Ans. (b)
4. Retention of configuration is observed in [1] [CBSE 2023]
(a) SN1 reaction (b) SN2 reaction
(c) Neither SN1 nor SN2 reaction (d) SN2 reaction as well as SN1 reaction
Ans. (a)
5. Auto oxidation of chloroform in air and sunlight produces a poisonous gas known as
[1] [CBSE 2023]
(a) Tear gas (b) Mustard gas (c) Phosgene gas (d) Chlorine gas
Ans. (c)
6. Inversion of configuration occurs in [1] [CBSE 2023]
2 1
(a) SN reaction (b) SN reaction
2 1
(c) Neither SN nor SN reaction (d) SN1 as well as SN2 reaction
Ans. (a)
7. Assertion (A): Chlorobenzene is resistant to electrophilic substitution reaction.
Reason (R): C–Cl bond in chlorobenzene acquires double bond characters due to resonance.
[1] [CBSE 2023]
Ans. (d)
8. Assertion (A) : Chlorobenzene is resistant to nucleophilic substitution reaction at room

temperature.
Reason (R) : C-Cl bond gets weaker due to resonance. [1] [CBSE 2023]
Ans. (c)
9. Assertion (A) : Nucleophilic substitution of iodoethane is easier that chloroethane.
Reason (R) : Bond enthalpy of C-I bond is less than that of C-Cl bond. [1] [CBSE 2023]
Ans. (a)
E 57
Chemistry
ALLEN
10. In the following reaction : [1] [CBSE Term-I, 2022]
CH3 CH3
Na/dry ether
R –X CH3 CH3
CH3 CH3
R in the above reaction is
CH3 CH3 CH3 CH3 CH3

CH3
(a)CH3 CH2 (b) CH3 CH2 (c) CH3–C– (d) CH3 H
CH3 CH3 CH3 CH3 CH3 CH3
Ans. (c)
11. 2-Bromo-2-methylpropane is allowed to react with alcoholic KOH solution. The major product
formed is : [1] [CBSE Term-I, 2021-22]
CH3 CH3 CH3 CH3
– +
(a) CH3–C–OH (b) CH3–C–O–C2H5 (c) CH3–C–O K (d) CH3 –C = CH2
CH3 CH3 CH3
Ans. (d)
CH3 CH
CH3 C CH2 
 H3C–C=CH2 + HBr
Alcoholic KOH
Br H
Alcoholic KOH is dehydrohalogenating agent.
12. Which of the following molecules is chiral in nature ? [1] [CBSE Term-I, 2021-22]
Br Br Br CH3
(a) CH3–C–CH3 (b) CH3–C–H (c) CH3–C–H (d) CH3–C–CH2–Br
C2H5 C2H5 CH3 C2H5
Br
Ans. (b) H3C C* H
C2H5
The carbon which have four different atom/group of atoms, known as chiral carbon.
13. An SN1 reaction of an enantiomerically pure chiral alkyl halide gives a product :
[1] [CBSE Term-I, 2021-22]

(a) with retention of configuration (b) with inversion of configuration
(c) with recemisation (d) with partial racemisation
Ans. (c) Racemisation
In case of optically active alkyl halides, SN1 reactions are accompanied by racemisation.
58 E
 CBSSE
ALLEN
A
14.
1 Whichh of the follo
owing is mo
ost reactive towards nu
ucleophilic substitution
s n reaction ?
[1] [CB
BSE Term-I, 2021-222]
C
Cl Cl Cl Cl
CH3 CH3
(a) (b) (c) (d))
N
NO2 CH3 CH3
Ans.
A (a) Duue to –NO2 is
i electron withdrawing
w g group. inccreases the Reactivity
R oof Haloaren
nes.
15.
1 Whichh of the follo
owing belon
ngs to the cllass of allyllic halides ? [1] [CB
BSE Term-I, 2021-22]
X
X
(a) (b) (c) (d))
X
Ans.
A (d)
3
sp
3
ssp
CH2–X
Allylic h
halide s 3
sp
These are the com mpounds in which halo gen atom iss borded to an sp3 hybrridised carbon atom nexxt
to C = C i.e. to an
n allylic carb
bon.
16.
1 Out off the follow
wing, the on
ne which is most reacttive towardss nucleophiilic substitu
ution reactioon
is [1] [CBSEE Comparttment, 20211]
H2 = CH – Cl
(A) CH C (B) C6H5 – Cl
H3CH = CH
(C) CH H – Cl (D) CH3 – CH2 – CH2 – Cll
Ans.
A (D)
17.
1 Identiffy the chirall molecule in
i the follow
wing pair : [1] (C
CBSE 20199)
(i) (ii)
Cl
Cl
Ans.
A (i)
18.
1 What hhappens wh
hen brominee attacks (1) (C
CBSE 20199)
CH2 = CH – CH2 – C CH
Ans.
A CH 2  CH  CH 2  C  C  Br
B
|
Br
19.
1 Write tthe IUPAC name of fo
ollowing com
mpound. [1] (C
CBSE 20199)
H CH3
H
H
H Br
Ans.
A 3-brom
mo-2-methyyl prop-1-en
ne
E 59
9
Chemistry
ALLEN
20. Out of Chlorobenzene and Cyclohexyl chloride, which one is more reactive towards nucleophilic
substitution reaction and why ? [1] (CBSE 2019)
Ans. Cyclohexyl chloride; Because of partial double bond character of C–Cl bond in Chlorobenzene/
Resonance effect/sp3 hybridised carbon in cyclohexyl chloride whereas sp2 carbon in
chlorobenzene.
X
X
21. Out of and , which is an example of vinylic halide? [1] (CBSE 2018)
X
Ans.
22. Which of the following two reactions is SN2 and why ? [1] (CBSE 2018)
(i) (ii)
Ans. (i) Inversion of configuration

SECTION-B (TWO MARKS QUESTIONS)
23. How would you differentiate between SN1 & SN2 reaction mechanism of substitution reaction ?
Give one ex. of each. [2] (CBSE 2020)
Ans. In SN1 mechanism of substitution reaction the rate of reaction depends upon the concentration of
only one reactant which is tert. butyl bromide.
It involves the formation of carbocation intermdediate.
In SN2 mechanism of substitution reaction, the rate of reaction depends upon the conc. of both
reactants
It involves the formation of transition slate and inversion of configuration.
24. Complete reaction : [2] (CBSE 2019)
CH3
(i) + HI ? (ii) CH3CH2CH =CH2 + HBr  ?
CH3
Ans. (i) I (ii) CH 3  CH 2  CH  CH 3
|
Br
25. Which one in the following pairs undergoes SN1 substitution reaction faster and why?
Cl
(i) Cl or
Cl
(ii) or Cl [2] (CBSE 2019)
Ans. (i) tertiary halide reacts faster than sec. halide tertiary carbocation intermediate.
(ii) reacts faster because of greater stability of secondary carbocation than primary
60 E
CBSE
ALLEN
SECTION-C (THREE MARKS QUESTIONS)
26. Answer any 3 of the following " [3] [CBSE 2023]

(a) Which isomer of C5H10 gives a single monochloro compound C5H9Cl is bright sunlight ?
(b) Arrange the following compounds in increasing order of reactivity towards SN2 reaction :
2-Bromopentane, 1- Bromopontane, 2-Bromo-2-methylbutane
(c) Why p-dichlorobenzene has higher melting point than those of ortho-and meta-isomers ?
(d) Identify A and B in the following :
Br
Mg H 2O
Dry ether A B
Ans. (a) Cyclo pentane

CH3
Cl2
sunlight

(b) 2-Bromo-2-methylbutane < 2-Bromopentane < 1-Bromopentane
(c) It is due to symmetry of P-dichlcro benzene that fits in crystal lattice better as compare to
ortho and meta Isomers.
Br MgBr
(d) Mg H2O
Dry ether
A B
27. Give reasons : [1 × 3 = 3 ][CBSE Compartment, 2021]

(a) Grignard reagent should be prepared under anhydrous conditions,
(b) Alkyl halides are immiscible with water although they are polar, and
(c) Chloroform is stored in dark coloured bottles filled up to the brim.
Ans. (a) Grignard reagents in the presence of moisture, they react with H2O to give alkanes.
  
R Mg X  H2 O  R  H  Mg(OH)X
Grigrard Alkane
reagent
(b) The molecules of water are held together by hydrogen bonds, As the new force of attraction
between water and alkyl halide molecules are weaker than the forces of attraction already
existing between alkyl halide- alkyl halide molecules and water-water molecules, they
cannot form H-bond with water.

(c) Chloroform is slowly oxidised by air in the presence of light to an extremely poisonous gas
phosgene (carbonyl chloride). It is therefore stored in closed dark coloured bottles
completely filled so that air is kept out.
2CHCl3 + O2 
Light
 2COCl2 + 2HCl
Phosgene
E 61
Chemistry
ALLEN
28. Give reasons for the following [3] (CBSE 2020)
2
(i) Ethyl iodide undergoes SN reaction faster than ethyl bromide
(ii) (±) 2-Butanol is optically inactive.
(iii) C–X bond length in halobenzene is smaller than C–X bond length in CH3–X.
Ans. (i) Iodide is better leaving group because of its larger size than bromide therefore ethyl idoide
under goes SN2 reaction faster than ethyl bromide.
(ii) +2 butanol is a racemic mixture it is a mixture which contains two enatiomers in equal
proportion and thus have zero optical rotation so it is optically inactive.
(iii) Due to delocalisation of lone pairs of electron of X atom over the benzene ring. C–X bond
in halogenzen acquire some = bond character while in CH3–X, C–X bond is a single bond.
29. Write IUPAC name of the following compounds - [3] (CBSE 2020)
Cl
CH3
(a) CH3–C–—CH–CH3 (b) (c) CH3–CH–CH2—CH–CH3
CH3 Br Cl
CH3 Cl
Cl
Ans. (a) 2-Chloro-3,3-dimethylbutane
(b) 1,4-dichloro-2-methylbenzene
(c) 2-bromo-4-chloropentane
30. Rearrange the compounds of each of the following sets in order of reactivity towards SN2
displacement
(I) 2-bromo-2-methyl butane, 1-bromopentane, 2-bromopentane
(II) 1-bromo-3-methylbutane, 2-bromo-2-methyl butane, 3-bromo-2-methyl butane
(III) 1-bromobutane, 1-bromo-2, 2-dimethyl propane
1-bromo-2-methyl butane, 1-bromo methyl butane. [3] (CBSE 2019)
2
Ans. (I) SN reaction depends upon steric hinderance. More is steric hinderance slower the reaction,
so order of reactivity is 1º > 2º > 3º
1-bromopentane > 2-bromopentane > 2-bromo-2-methyl butane
(II) 1-bromo-3-methyl butane > 3-bromo-2-methyl butane > 2-bromo-2-methyl butane.
(III) 1-bromo butane > 1-bromo-3-methyl butane > 1-bromo-2-methyl butane >
1-bromo-2-dimethyl propane
31. (i) What is meant by chirality of a compound give an example?

(ii) Which one of the following compound is more easily hydrolysed by KOH & Why?
CH3CHClCH2CH3 or CH3CH2Cl
(iii) Which one under goes SN2 substitution reaction & Why? [3] (CBSE 2019)
I Cl
or
62 E
CBSE
ALLEN
Ans. (i) Chirality An object or molecule which is non-superimposable on its mirror image is called
chiral and the property of being chiral is known as chirality eg. lactic acid.
CH3CH(OH)COOH.
H 3C CH3
H—C—OH OH—C—H
COOH COOH
Mirror
(ii) CH3CHClCH2CH3 is more reactive than CH3CH2CH2CH2Cl as the former one gives more
stable carbocation intermediate.
H H H
H3 C H3 C + – H3 C
CCl C OH C— OH
H3CCH2 H3CCH2 H3CH2C
(iii) Iodide is a better leaving group because of its larger size thesefore it undergoes SN2
reaction faster.
32. (I) Write a chemical test to distinguish between
(a) Chlorobenzene & benzyl chloride
(b) Chloroform & CCl4
(II) Why is methyl chloride hydrolysed more easily than chlorobenzene [3] (CBSE 2019)
Ans. (I) (a) Benzyl chloride when treated with AgNO3 solution will give a white ppt. while
chlorobenzene will not.
(b) CHCl3 when treateed with 1º amine & KOH gives offensive smelling isocyanides while
CCl4 does not show this test.
(II) Chlorobenzene is stabilised by resonance so has a = bond character between C & Cl, C is
sp2 hybridised so more electronegative thus Cl– is not replaced easily
:
–Cl :
:
:
:
+Cl :
:
Cl : + Cl : : Cl :
:
33. Among all the isomers of molecular formula C4H9Br, identify : [3] (CBSE 2019)
(a) The one isomer which is optically active.
(b) The one isomer which is highly reactive towards .

(c) The two isomers which give same product on dehydrohalogenation with alcoholic KOH.
Ans. (a) CH3CH2CH(Br)CH3
(b) CH3CH2CH2CH2Br
(c) (CH3)3Br and (CH3)2CHCH2Br
E 63
Chemistry
ALLEN
34. (a) Identify the chiral molecule in the following pair : [3] (CBSE 2018)
&
OH OH
(i) (ii)
(b) Write the structure of the product when chlorobenzene is treated with methyl chloride in
the presence of sodium metal and dry ether.
(c) Write the structure of the alkene formed by dehydrohalogenation of
1-bromo-1-methylcyclohexane with alcoholic KOH.
Ans. (a) The chiral molecule.

OH
(b)
Br CH3 CH3 CH2
Alc. KOH/
(c) +
(major) (minor)
35. The following compounds are given to you : [3] (CBSE 2018)
2-Bromopentane, 2-Bromo-2-methylbutane, 1-Bromopentane
(a) Write the compound which is most reactive towards SN2 reaction.
(b) Write the compound which is optically active.
(c) Write the compound which is most reactive towards -elimination reaction.
Ans. (a) 1–Bromopentane
(b) 2–Bromopentane
(c) 2–Bromo–2–methylbutane
SECTION-D (FOUR MARKS QUESTIONS)

36. Plane of plane polarised light produced by passing ordinary light through Nicol prism is rotated
when it is passed through the solutions of certain compounds. Such compounds are called
optically active compounds.
In case of optically active alkyl halides, the product formed as a result of SN2 mechanism has the
inverted configuration as compared to the reactant.
64 E
CBSE
ALLEN
In case of optically active alkyl halides, SN1 reactions are accompanied by racemisation.
When a haloalkane with -hydrogen atom is heated with alcoholic solution of potassium
hydroxide, there is elimination of hydrogen atom from -carbon and a halogen atom from the -
carbon atom.
(a) Which would undergo SN2 reaction faster in the following pair :
C6H5 – CH2 – CH2 – Br and C 6H 5 – CH – CH 3
Br
Ans. C6H5 – CH2CH2 – Br
(b) Which one of the following compound is more easily hydrolysed by KOH & Why.
CH3CHClCH2CH3 or CH3CH2Cl
Ans. CH3CHClCH2CH3 is more reactive than CH3CH2CH2CH2Cl as the former one gives more
stable carbocation intermediate.
H3C H H3C H – HC
H
3
C OH
+
CCl C— OH
H3CCH2 H3CCH2 H3CH2C
(c) Out of Chlorobenzene and p-nitrochlorobenzene, which one is more reactive towards
nucleophilic substitution reaction and why ?
Ans. p-nitrochlorobenzene undergoes nucleophilic substitution reaction faster than
chlorobenzene due to resonance effect.
OR
Write the structure of the alkene formed by dehydrohalogenation of 1-bromo-1-methylcyclohexane
with alcoholic KOH.
Br CH3 CH3 CH2
Alc. KOH/
Ans. +
(major) (minor)
SECTION-E (FIVE MARKS QUESTIONS)
37. Read the given passage and answer the questions number 1 to 5 that follow :
The substitution reaction of alkyl halide mainly occurs by SN1 or SN2 mechanism. Whatever
mechanism alkyl halides follow for the substitution reaction to occur, the polarity of the carbon
halogen bond is responsible for these substitution reactions. The rate of SN1 reactions are
governed by the stability of carbocation whereas for SN2 reactions steric factor is the deciding
factor. If the starting material is a chiral compound, we may end up with an inverted product or
racemic mixture depending upon the type of mechanism followed by alkyl halide. Cleavage
of ethers with HI is also governed by steric factor and stability of carbocation, which
indicates that in organic chemistry, these two major factors help us in deciding the kind of
product formed. [1× 5 = 5] (CBSE 2020)
E 65
Chemistry
ALLEN
(i) Predict the stereochemistry of the product formed if an optically active alkyl halide
undergoes substitution reaction by SN1 mechanism. [1]
(ii) Name the instrument used for measuring the angle by which the plane polarised light is
rotated. [1]
(iii) Predict the major product when 2-Bromopentane reacts with alcoholic KOH. [1]
(iv) Give one use of CHI3. [1]
(v) Write the structures of the products formed when anisole is treated with HI. [1]
Ans. (i) Racemic Mixture
(ii) Polarimeter
(iii) Pent-2-ene/CH3CH=CHCH2CH2
(iv) Antiseptic
(v) CH3I + C6H5OH
66 E
CBSE
ALLEN
PRACTICE TEST
SECTION-A
1. Which of the following will NOT undergo SN1 reaction with OH ? [1]
(a) CH2=CH–CH2Cl (b) (CH3)3CCl
CH2CH2Cl CH2Cl
(c) (d)
2. Which of the following is a free radical substitution reaction ? [1]

(a) Benzene with Br2/AlCl3 (b) Acetylene with HBr
(c) Methane with Br2/hv (d) Propene with HBr/(C6H5COO)2
3. Elimination reaction of 2-Bromo-pentane to form pent-2-ene is: [1]
(i) -Elimination reaction (ii) Follow Zaitsev rule
(iii) Dehydrohalogenation reaction (iv) Dehydration reaction
(a) (i), (ii), (iv) (b) (i), (ii), (iii)
(c) (i), (iii), (iv) (d) (ii), (iii), (iv)
4. The alkane that gives only one mono-chloro product on chlorination with Cl2 in presence of
diffused sunlight is :- [1]
(a) 2,2-dimethylbutane (b) neopentane (c) n-pentane (d) Isopentane
5. In the reaction with HCl, an alkene reacts in accordance with the Markovnikov's rule, to give a
product 1–chloro–1–methylcyclohexane. The possible alkene is :- [1]
CH2 CH3 CH3
(a) (A) (b) (B) (c) (A) and (B) (d)
6. Assertion (A): tert-Butyl bromide undergoes Wurtz reaction to give 2,2,3,3-tetramethylbutane.

Reason (R): In Wurtz reaction, alkyl halides react with sodium in dry ether to given hydrocarbon
containing double the number of carbon atoms present in the halide. [1]
7. Assertion (A) : Presence of a nitro group at ortho or para position increases the reactivity of
haloarenes towards nucleophilic substitution.
Reason (R) : Nitro group, being an electron withdrawing group decreases the electron density
over the benzene ring. [1]

SECTION-B
8. Suggest a possible mechanism for the reaction n BuBr + KCN  n-BuCN [2]
9. Which halogen compound in each of the following pairs will react faster in SN2 reaction : [2]
(i) CH3Br or CH3I
(ii) (CH3)3 C – Cl or CH3 –Cl
E 67
Chemistry
ALLEN
10. Complete reaction : [2]
CH3
(i) + HI ? (ii) CH3CH2CH=CH2 + HBr  ?
11. Write a chemical test to distinguish between [2]

(a) Chlorobenzene & benzyl chloride (b) Chloroform & CCl4
SECTION-C
12. What happens when [3]
(i) ethyl chloride is treated with NaI in the presence of acetone,
(ii) chlorobenzene is treated with Na metal in the presence of dry ether,
(iii) methyl chloride is treated with KNO2?
Write chemical equations in support of your answer.
13. How do you convert the following : [3]
(i) Prop-1-ene of Propan-2-ol
(ii) Bromobenzene to 2-bromoacetophenone
(iii) 2-bromobutane to But-2-ene
SECTION-D
14. Haloalkenes with P-hydrogen atom can undergo elimination in presence of alcoholic KOH. If
there is possibility of formation of more than one alkene due to the availability of more than one
P-hydrogen atoms, usually one alkene is formed as the major product. These form part of a
pattern first observed by Russian chemist, Alexander Zaitsev (also pronounced as Saytzeff) who
in 1875 formulated a rule which can be summarised as ''in dehydrohalogenation reactions, the
preferred product is that alkene which has the greater number of alkyl groups attached to the
doubly bounded carbon atoms.'' [4]
(a) What is the increasing order of nucleophilicity for I–, Cl– and Br–.
(b) Which one is nucleophilic substitution reaction among the following ?
(c) What happens in an SN1 reaction on chiral centres ?
OR
Write two example of nucleophilic substitution reaction ?
SECTION-E
15. Write the major monohalo product(s) in each of the following reactions: [5]
CH2–CH=CH2
UV light Peroxide
(i) +Br2 ? (ii) +HBr ?
CH2OH
Heat
(iii) +HCl ? (iv) PCl5
CH2OH
OH
(v) CH2–CH = CH 2 + HBr
68 E
CBSE
ALLEN
PRACTICE TEST SOLUTIONS
SECTION-A
1. (c)
2. (c)
3. (b)
4. (b)
5. (c)
6. (a)
7. (a)
SECTION-B
C3H5 C3H5
C3H5
8. C–Br NC C Br NC—C
–
+ Br
H H H H
H H
9. (i) CH3Br (ii) CH3–Cl
CH3
CH3–CH2–CH–CH3
10. (i) I (ii)
Br
11. (a) Benzyl chloride when treated with AgNO3 solution will give a white ppt. while
chlorobenzene will not.
(b) CHCl3 when treateed with 1º amine & KOH gives offensive smelling isocyanides while
CCl4 does not show this test.
SECTION-C
12. (i) C2H5Cl + NaI Acetone C2H 5I + NaCl
Dry ether
(ii) Cl + 2Na + Cl  +2NaCl

(iii) CH3Cl + KNO2   CH3–ONO + KCl
+
13. (i) H2O/H
CH3–CH=CH 2 CH3–CH(OH)–CH3
Br Br O
CH3COCl/Anhy AlCl3 C–CH3
(ii)

Br
(iii) KOH(Alc)
CH3–CH2–CH–CH 3 CH3–CH=CH–CH3
E 69
Chemistry
ALLEN
SECTION-D
– – –
14. (a) Cl < Br < I
(b) R  CH 2  CH  CH 2 Br  NH 3 
 CH 3  CH 2  CH  CH 2 NH 2
| |
CH3 CH 3
(c) There is inversion more than retention leading to partial racemization.

OR
(i) C2H5 – Br + NH3  C2H5 – NH2 + NH2Br
Cl 
OH
+ NaOH  
H3O
(ii)  + NaCl

SECTION-E
Br
CH2–CH2–CH2Br
15. (i) (ii)
CH2Cl
(iii) (iv) CH2Cl
HO
CH2–CH – CH3
(v)
Br
70 E
 CBSSE
ALLEN
A
U
UNIT-1
11 : AL
LCOHO
OLS, PH
HENOL
LS & ET
THERS
S
UNIT
U INDEEX
• Theorry 71-97
• Exerciise-1_Intexxt Question
ns 98-1003
• Exerciise-2_NCEERT Exercise Question ns 104-111
• Exerciise-3_Exemmplar 112-117
• Exerciise-4_MCQ Q, A/R, Casse Based Q
Questions 118-1226
• Previoous Years Questions
Q 127-138
• Practiice Test 139-142
T
THEORY
Y
AL
LCOHOL
LS
Alcohol
A : Hyydroxy deriivatives of hydrocarbon
h n (alkane alkene
a ..... ) are known as alcohol.
NAMING
N A
AND CLAS
SSIFICATIION OF AL
LCOHOLS
S
I. Based
d on no. of – OH group
ps
(i) Moonohydric alcohol

a C2H5 OH Ethyl alccohol
CH 2  OH
(ii) Dih
hydric alcoohol | Ethylenee glycol
CH 2  OH
CH 2  OH
|
(iii) Trrihydric alccohol CH  OH Glyceroll
|
CH 2  OH
II. pound contaaining Csp3  OH :

Comp
In thiss class of alcohol

a p3 hybridiseed carbon atom
the – OH grouup is attached to an sp a of alkyyl
group. They are further
fu classified as folllows
E 71
1
Chemistry
ALLEN
Classification of Monohydric alcohols on the basis of position of –OH group :
(A) Primary, Secondary, Tertiary alcohols :
(i) Primary alcohol (ii) Secondary alcohol (iii) Tertiary alcohol
1º R 2º R
R – CH2 – OH CH – OH 3°
sp3 sp3 R – 3C – OH
R sp
Functional : – CH 2 – OH R
group Functional : CH – OH
group Functional : – C – OH
group
H 3C CH3
e.g. CH3–OH e.g. CH–OH e.g. H3C–C–OH
Methyl alcohol H 3C
CH3
Isopropyl alcohol
ter.butyl alcohol
CH –CH –OH
3 2 CH3–CH–CH2–CH3
Ethyl alcohol
OH
sec. butyl alcohol
(B) Allylic alcohols
sp3
CH2 = CH – CH2 –
allyl group
sp3
(i) primary allylic alcohol CH2 = CH – CH2 – OH
H
(ii) secondary allylic alcohol CH2 = CH – C – OH
–C–
–C–
(iii) tertiary allylic alcohol CH2 = CH – C – OH
–C–
(C) Benzylic alcohol :

3 sp3
sp
CH2 –
C6H 5 – CH2 – Benzyl group
sp3 –C–
–C–
CH2 – OH
H – C – OH
–C – C – OH
Benzyl alcohol
(primery) Secondary Tertiary
72 E
CBSE
ALLEN
NOMENCLATURE OF ALCOHOLS
Structure Common Name IUPAC Name

R – OH Alkyl alcohol Alkanol
1. CH3OH Methyl alcohol Methanol
2. CH3 – CH2 – OH Ethyl alcohol Ethanol
3. CH3 – CH2 – CH2– OH n-Propyl alcohol Propan-1-ol
4. CH3 – CH – OH Iso propyl alcohol Propan-2-ol
|
CH3
5. CH3 – CH2 – CH2– CH2 – OH n-Butyl alcohol Butan-1-ol
6. CH3 – CH – CH2 – CH3 Sec-Butyl alcohol Butan-2-ol
|
OH
7. CH3 – CH – CH2 – OH Iso butyl alcohol 2-Methyl propan-1-ol
|
CH3
CH3
|
8. H3C – C – OH ter-Butyl alcohol 2-Methyl propan-2-ol
|
CH3
9. CH3 – CH2 – CH2– CH2– CH2 – OH n-Pentyl alcohol Propan-1-ol
10. CH3 – CH – CH2– CH2– OH Iso pentyl alcohol 3-Methyl-butan-1-ol

|
CH3
CH3
|
11. CH3 – C – CH2 – OH Neopentyl alcohol 2,2-Dimethyl propan-1-ol
|
CH3
12. CH2 – CH2 Ethylene glycol Ethane-1, 2-diol

| |
OH OH
13. CH2 – OH Glycerol Propane-1, 2, 3-triol

|
CH – OH
|
CH2 – OH
OH – Cyclohexanol
14.
OH
– 2-Methylcyclopentanol
15. CH3
E 73
Chemistry
ALLEN
GENERAL METHOD OF PREPARATIONS OF ALCOHOLS
1. From alkene
(i) By acid catalysed hydration of alkene
dil. H2SO4
C=C + H 2O C–C
or H+
Alkene H OH
Alcohol
CH 2  CH 2
H
CH 2  CH 2  H 2 O 
 | |
e.g. (1)
Ethene H OH
Ethanol
CH 3  CH  CH 2
H
CH 3  CH  CH 2  H 2 O 
 | |
e.g. (2)
Pr opene OH H
Pr opan  2  ol
The mechanism of the reaction involves the following three steps:
Step 1: Protonation of alkene to form carbocation by electrophilic attack of H3O+.
H2SO4  H+ + H2SO4¯
H2O + H+  H3O+
H H
— :
— —

: :
+
C=C + H— O — H —C—C + H2O
Step 2: Nucleophilic attack of water on carbocation.

H H H
— —
— —
— —
—
 
: :
—C—C + H2O —C—C—O —H
Step 3: Deprotonation to form an alcohol.

::
HH H OH
— —

— —
— —
 — C — C — + H3O
—C—C—O—H + H2O
—
(ii) By hydroboration oxidation of alkene

R  CH  CH 2 R – CH – CH2
H |
R  CH  CH 2 + H–B  H
H R – CH – CH2 B
|
R  CH  CH 2 or H
Alkene 1 R – CH – CH2
BH
2 2 6 |
Boron hydride H
ENH > ENB OR
(R – CH2 – CH 2 – )3B
Trialkyl borane
1B H 3R  CH 2  CH 2
(3NaOH  3H 2O2 )
R – CH = CH2 
2 2 6 (R – CH2 – CH2 –)3B  | + Na3BO3 + 3H2O
OH
74 E
CBSE
ALLEN
2. From carbonyl compound : By reduction of aldehyde and ketone
LiAlH4 (LAH) : Lithium aluminium hydride

NaBH4 (SBH) : Sodium boron hydride
 LiAlH4 is stronger reducing agent than NaBH4.
 LiAlH4 reduces all polar -bond compounds.
 NaBH4 reduces generally following 4 compounds :
R R R H
C=O ; C=O ; C=O ; C=N–R
X H R H
Acid halide Aldehyde Ketone
• LiAlH4 and NaBH4 not reduces non-polar -bond compounds. (Alkene and Alkyne)
Reducing agent
C = O + H2 / 2H C–O
| |
H H
R Pd R
(i) C = O + H2 CH – OH / R – CH 2 – OH
H H
Aldehyde Primary alcohol
R NaBH4 R
(ii) C = O + 2H CH – OH
R R
Ketone Sec. alcohol
3. By reduction of carboxylic acid and acid derivatives
O
|| LiAlH4
R  C  OH + 4H   R – CH2 – OH + H2O
By reduction of acid derivatives
O
|| LiAlH4
R  C  Cl + 4H   R – CH2 – OH + HCl
Acid chloride
O
|| LiAlH

4
 R – CH2 – OH + R – OH
R  C  OR  4H
Ester
O O
|| || LiAlH

8H  R  CH 2  OH  H 2 O
4
R CO  CR
Acid anhydride
Note : Acid amide do not reduces to alcohol.
E 75
Chemistry
C
N
ALLEN
4.
4 Formaation of Alccohol by Haloalkaness :
5.
5 Formaation of alccohol by Aliphatic am
mine :
CH2–NH2 + NaNO2 
CH3–C Conc.HCl  CH3 – CH2 – OH + N2 + NaCl + H 2O
 HNO2 + NaCl)
O2 + HCl 
(NaNO
CH3–C
CH2–N H2
+ CH3–CH2–OH+
+N2+H2O
H
HO–N=O
6.
6 From Grignard reagent
r
Carbonnyl compouund i.e. aldeehyde and kketone show
ws nucleophiilic additionn reaction.
Generral reaction
n
 -

-  
  - – + + H – OH
R – MggX + C=O C–O 
 C – O MgX C – OH + MgM X 
OH
| |
Carrbonyl comppound R
R
Pr./Sec./Ter alcohol
Preparration of prrimary, secoondary andd tertiary allcohol from Grignard rreagent. (R
R – MgX).
OR
Formaation of following alco ohols from CH3 – MgBr.
(i) CCH3CH2OH H Ethyll alcohol (prri. alcohol)
H 3C
(ii) CH – OHO Isoprropyl alcohool (sec. alco
ohol)
H 3C
CH 3
|
(iii) H 3C  C  O
OH Tertiaary butyl al cohol (ter. alcohol)
a
|
CH 3
H
(i) C=O
H
1. R – CH2 – OH
(ii) H2O Pri. alcohool
Hint : R – MgX H
(i) C=O
R R
2. CH – OH
O
R
(ii) H2O
Sec. alcohool
R
(i) C=O R
R
3. R – C – OH H
(ii) H2O R
Ter. alcohool
76 E
CBSE
ALLEN
1. Formation of primary alcohol
+ - 
H – OH
-   H H  - H – + + H2O
R – MgX + C=O C–O 
H C – O MgX
H H |
formaldehyde R
R – CH2 – OH OR H C – OH + Mg X
H OH
propyl alcohol R
Formation of ethyl alcohol
 - 
-   H H  - H – +
CH3 – MgBr + C=O C – O 
H C – O MgBr + H – OH
H H |
CH3
formaldehyde
methanal
H Br
CH3CH2OH OR H C – OH + Mg OH
|
CH3
Common name : Ethyl alcohol (1° alcohol)
IUPAC name : Ethanol
2. Formation of secondary alcohol
-   H H  - H – +
 R C – O MgX
R R |
Aldehyde R
+ - 
+ H – OH
R X
CH – OH + Mg
R OH
Sec. alcohol
Formation of iso propyl alcohol

 - 
-   H H  - H + –
C – O 
 + H – OH
CH3 – MgBr + C=O C – O MgBr
H3C H3 C H 3C |
Acetaldehyde CH 3
Ethanal
H  Br
C – OH + Mg
H3C | OH
CH3
Common name : Iso propyl alcohol
IUPAC name : Propan-2-ol (sec. alcohol)
E 77
Chemistry
ALLEN
3. Formation of tertiary alcohol
-   R R  - R – +
 R C – O MgX
R R |
R
+ - 
+ H – OH
R
R C – OH + Mg X
R OH
Ter. alcohol
Formation of tertiary butyl alcohol

-   H3C H3C + – + – +
CH3 – MgBr + C=O C–O  H 3C C
 – O MgBr
H3C H3C H 3C
|
Common name : Acetone CH3
IUPAC : Propanone + - 
+ H – OH
CH 3
|
H 3C Br
H 3C  C  OH OR C – OH + Mg
H 3C | OH
|
CH3
CH 3
Common Name : Tertiary butyl alcohol
IUPAC Name : 2-methyl propan-2-ol
CHEMICAL REACTION OF ALCOHOL (R – OH)
Chemical Reaction of Alcohol (R – OH)
I. Reactions involving II. Reactions involving

cleavage of R–O–H bond cleavage of carbon-oxygen (C-O)
R – OH
bond in alcohols
I. Reactions involving cleavage of R – O – H
–O–H bond cleavaging order in these type of reactions :
Primary alcohol > Secondary alcohol > Tertiary alcohol

1. Reaction with metal : Alcohol react with active metals such as Na, K, Al to gives corresponding
alkoxides and hydrogen.
2R–OH + 2Na  2R–ONa + H2
2C2H5OH + 2Na  2C2H5ONa + H2
Ethylalcohol Sodium ethoxide
78 E
CBSE
ALLEN
CH 3  CH 3 
|  
 | 
6H 3C  C  OH  2Al 2  CH  C  O  Al  3H 2
  3

|
 | 
CH 3  CH 3 3

tertiary butyl alcohol
Aluminium
tertiary butyl oxide
Decreasing order of reactivity of alcohols towards sodium metal is :
Primary alcohol > Secondary alcohol > Tertiary alcohol
(Reactions as above)
Note : The above reactions shows that alcohols and phenols are acidic in nature. In fact alcohols
-
and phenols are bronsted acids i.e. they can donate a proton to a stronger base (B:) .
- .. .. -
B: + H – O
.. – R B – H + R – O:
..
Proton Alcohol Conjugate Conjugate
accepter Proton acid base
donner
(Base) (Acid)
Acidity of alcohols :
The acidic character of alcohols is due to the polar nature of O–H bond. An electron-releasing
group (–CH3, –C2H5) increases electron density on oxygen tending to decrease the polarity of
O–H bond. This decreases the acid strength. For this reason, the acid strength of alcohols
decreases in the following order :
R R
R CH2OH > CHOH >> R C—OH
R R
Primary Secondary Tertiary
Alcohols are, however, weaker acids than water. This can be illustrated by the reaction of water
with an alkoxide.
: :
: :
: :
R—O: + H—O— H R —O— H + OH :

Base Acid Conjugate Conjugate
acid base
This reaction shows that water is a better proton donor (i.e., stronger acid) than alcohol. Also, in
the above reaction, we note that an alkoxide ion is a better proton acceptor than hydroxide ion,
which suggests that alkoxides are stronger bases (sodium ethoxide is a stronger base than sodium
hydroxide).
Alcohols act as Bronsted bases as well. It is due to the presence of unshared electron pairs on
oxygen, which makes them proton acceptors.
E 79
Chemistry
ALLEN
2. Esterification
(i) Alcohols and phenols react with carboxylic acid, acid chloride and acid anhydride to form
esters.
Esterification :
R  C  OH  R  OH R  C  OR  H 2 O
conc. H2SO4
||  
 ||
O O
Conc. H2SO4 is used as catalyst and dehydrating agent.
CH 3  C  OC2 H 5  H 2 O
conc. H SO
Ex. CH3 – C – OH + H – OC2H5 

2 4
 ||
|| O
O
Ph  C  O C2 H 5  H 2 O
conc. H2SO4
Ex. Ph – C – OH + H – OC2H5  ||
|| O
O
Dry HCl can also be used as dehydrating agent.
CH 3  C  OC2 H 5  H 2 O
Dry.HCl
Ex. CH – C – OH + H – OC H   ||
3 2 5
|| O
O
II. Reaction involving cleavage of carbon-oxygen (C – OH) bond in alcohol (R – OH)
Reactivity order of alcohols towards C—OH bond cleavage reaction

R
R
R—C—OH > CH—OH > R—CH2—OH
R
R
Tertiary Secondary Primary
alcohol alcohol alcohol
1. Reaction with halogen acids
Anhydride ZnCl2
R – OH + H – X R–X + H2O
Alkylhalide
Anhydride ZnCl2 R – Cl + H2O
R – OH + HCl
conc. Turbidity
Note: Mixture of conc. HCl + anhydrous ZnCl2 is known as Lucas Reagent. It is used for
distinguish between primary, secondary and tertiary alcohols.

* Note : Reactivity of alcohol towards halogen acids / Lucas Reagent
R
R
R – C – OH > CH – OH > R – CH2 – OH
R
R
* Reactivity of halogen acids towards alcohol
H – I > H – Br > H – Cl
80 E
CBSE
ALLEN
2. Reaction with PCl3 / PCl5 / SOCl2
(a) 3R – OH + PCl3  3R – Cl + H3PO3
R–OH Cl
R – O H + Cl P
R–OH Cl

(b) R – OH + PCl5  R – Cl + POCl3 + HCl
(c) R  OH  SOCl2 

C H N  R – Cl + SO2 + HCl (Darzen reaction)
Pyridine
Thionylchloride 5 5
3. Dehydration of alcohols (Elimination reaction)

* Conc. H2SO4, H3PO4, anhydrous ZnCl2, anhydrous Al2O3, are dehydrating agent.
| |
General reaction : – C – C – 
agent 
Dehydrating
C = C + H 2O
| |
H OH Alkene
Alcohol
Dehydrating order of alcohols
R R
R C OH > CH OH > R CH2 – OH
R R
ter. alcohol sec. alcohol pri. alcohol
e.g. (i) C2H 5OH H2SO4
CH2 – CH 2 CH2 = CH 2 + H2O
443 K
| |
H OH Ethene
Ethyl alcohol
(pri. alcohol)
e.g. (ii) CH3 – CH – CH3 85% H 3PO4

CH3 – CH = CH2 + H 2O
440 K
OH Propene
CH2 – CH – CH2
OH H
Isopropyl alcohol
(sec. alcohol)
E 81
Chemistry
ALLEN
CH3 CH3 CH 3
20% H3PO4 |
e.g.(iii) CH3 – C – OH H3C – C – OH CH3 – C = CH2 + H 2O
358 K
CH3 CH2–H 2-methyl propene
ter. butyl alcohol
(ter. alcohol)
2-methyl propan-2-ol
Note : above reaction involving complete molecule of alcohol
OXIDATION OF ALCOHOLS :
Strong oxidizing agents
(i) H+/KMnO4
(ii) H+/K2Cr2O7
(iii) CrO3 + aq. H2SO4 + Acetone (jones reagent)
Function :
1° alcohol acid
2° alcohol ketone
3° alcohol no reaction
Mild oxidising agent :

(i) Cu / 300°C
(ii) CrO3 / Pyridine / HCl + CH2Cl2
(iii) CrO3 / Pyridine Collin's reagent
(iv) PDC – Pyridinium dichromate
(v) CrO3 / acetone or anhydrous CrO3
(vi) PCC / Pyridinium chloro cromate / Mixture of Pyridine + CrO3 + conc.
HCl
Function :
1° alcohol aldehyde
2° alcohol ketone
3° alcohol no reaction except Cu / 300°C
(i) Oxidation of Primary alcohols

H KMnO or
R — CH2 — OH  4
H /K Cr O
 RCHO 
Room temp.  RCOOH
[O]
2 2 7
(primary alcohol) (Aldehyde) (same carbon acid)

CrO
R – CH2 – OH 
3
 R – CHO
Pri. alcohol
CH3 – CH = CH – CH2OH  PCC
 CH3 – CH = CH – CHO
Note : Pyridinium chloro-chromate (PCC), a complex of CrO3, a complex of CrO3 with
pyridine and HCl
82 E
CBSE
ALLEN
(ii) Oxidation of Secondary alcohols
R  CH  R ' R CR'
| CrO3 ||
 
OH O
sec. alcohol ketone
  [O]
H /KMnO4 or H /KMnO4 No reaction
R – CH – R' R–C–R Room temp.
| H/K 2CrO7 ||
High temp.
OH O Acids (less carbon)
(s-alcohol) (same carbon)
Ketone
CH 3CH 2  CH  CH 3 
[O]
 CH 3CH 2  C  CH 3 
[O]
 CH3COOH + CH3COOH
high temp.
| ||
OH O
R
(iii) [O]
R–C–R No reaction
Room temp.
OH
(t-alcohol)
2. Catalytic Dehydrogenation (Elimination reaction) :

(i) CH3CH2OH 
Cu
300°C CH3CHO + H2
(primary- alcohol ) (Acetaldehyde)
(ii) CH 3  CH  CH 3 
Cu
300°C
CH 3  C  CH 3  H 2
| ||
OH O
(secondary- alcohol) (Acetone)
CH 3 CH 3
| |

Cu
CH 3  C  CH 2  H 2 O [dehydration]
(iii) CH 3  C  OH 300°C
| (2  methyl propene)
CH 3
(ter.alcohol)
When the vapours of a primary or a secondary alcohol are passed over heated copper at 573 K,
dehydrogenation takes place and an aldehyde or a ketone is formed while tertiary alcohols
undergo dehydration.
SOME COMMERICALLY IMPORTANT ALCOHOLS
Methanol and ethanol are among the two commercially important alcohols.
1. Methanol
Methanol, CH3OH, also known as ‘wood spirit’, was produced by destructive distillation of
wood.
E 83
Chemistry
C
N
ALLEN
Prepaaration : Methanol
M is produced bby catalyticc hydrogenation of caarbon mono
oxide at higgh
d in the pressence of ZnO – Cr2O3 catalyst.
pressuure and tempperature and c
CO  2H 2 
C 
ZnO–Cr2 O3
200–300atm
 CH 3OH
573–673K
Propeerties :
Methaanol is a collourless liqu
uid and boills at 337 K.
K It is highly poisonouus in nature.. Ingestion of
o
even small quantiities of meth
hanol can caause blindness and larg
ge quantitiess causes eveen death.
Uses :
Methaanol is used as a solventt in paints, vvarnishes an
nd chiefly for
f making fformaldehy
yde.
2.
2 Ethan
nol
Prepaaration :
Ethanool, C2H5OH
H, is obtaineed commerccially by feermentation,, the oldest method is from sugarrs.
The suugar in mollasses, sugaarcane or fruuits such ass grapes is converted tto glucose and fructosse,
(both oof which haave the form
mula C6H12O 6), in the presence
p of an enzymee, invertase. Glucose annd
fructosse undergo fermentatio
on in the ppresence off another en
nzyme, zym h is found in
mase, which
yeast.
C12H222O11 + H2O   C6 H12 O6  C6 H12 O6

Invertase
Glu cos e Fructose
C6H12O6  
Zymase
 2C2H5OH+
O 2CO2
Propeerties : Ethaanol is a colourless liquuid with boiling point 351
3 K.
Uses :
It is ussed as a solvvent in pain
nt industry aand in the prreparation of
o a numberr of carbon compounds
c .
Note-11 Denaturaated Alcoho
ol : The com
mmercial allcohol is made unfit foor drinking by mixing in
it some copper suulphate (to give
g it a collour) and py oul smellingg liquid). Itt is known as
yridine (a fo a
denatu
uration of alcohol
a .
Note-22 Absolute Alcohol : 100%
1 pure eethyl alcoho
ol is known as absolutee alcohol.
Note-33 Rectified Spirit : Th
he rectifiedd spirit conttains it totall of 95.5% of ethanol and 4.5% of
o
water. It is also reeferred to ass the industrrial alcohol..
Note-44 Power Allcohol : Power alcohool is a liquid
d mixture co
ontaining 880% petrol, 20% ethanol
and a ssmall amouunt of Benzeene + Ether.. It is usefull in the field
d of automoobiles to gen
nerate energgy
for its operations.
84 E
CBSE
ALLEN
ETHERS
Ether: Di alkyl derivatives of water (H–O–H) is known as ether.
General Structure : R–O–R
* Ether is also known as dehydrate of alcohols.
Functional group: –O–
Ethers are of two types–
(i) Simple ether or symmetrical ether: The ethers in which similar alkyl groups are attached
to the divalent oxygen (i.e. functional group of –O– ether) known as simple ether.
Structure Common name IUPAC
R–O–R Dialkyl ether Alkoxy alkane
1. CH3–O–CH3 Dimethyl ether Methoxy methane
2. CH3–CH2–O–CH2–CH3 Diethyl ether Ethoxy ethane
(ii) Mixed ether or unsymmetrical ether: The ethers in which different alkyl groups are
attached to the divalent oxygen (–O–) is known as mixed or unsymmetrical ether.
Structure Common name IUPAC
R–O–R' Alkyl Alkyl' ether Alkoxy alkane
1. CH3–O–CH2–CH3 Ethyl methyl ether Methoxy ethane
CH3
2. H3C–C–O–CH3 ter Butyl methyl ether 2-Methoxy-2-methyl propane
CH3
Aromatic ether:
OR
(Ar–O–R)
Alkyl aryl ether
OCH3
Common name : Anisole

IUPAC : Methoxy benzene
OC2H 5
Common name : Phenetole

IUPAC : Ethoxy benzene
E 85
Chemistry
ALLEN
COMMON AND IUPAC NAMES OF SOME ETHERS
Compound Common name IUPAC name
CH3OCH3 Dimethyl ether Methoxymethane
C2H5OC2H5 Diethyl ether Ethoxyethane
CH3OCH2CH2CH3 Methyl n-propyl ether 1- Methoxypropane
C6H5OCH3 Methyl phenyl ether Methoxybenzene
(Anisole) (Anisole)
C6H5OCH2CH3 Ethyl phenyl ether Ethoxybenzene
(Phenetole)
C6H5O(CH2)6– CH3 Heptylphenyl ether 1-Phenoxyheptane
CH3O – CH – CH3 Isopropyl methyl ether 2-Methoxypropane
|
CH3
C6H5– O – CH2 – CH2– CH – CH3 Phenyl isopentyl ether 3- Methylbutoxybenzene
|
CH3
CH2—CH2
1,2- Dimethoxyethane
OCH3 OCH3
H3C CH3
OC2H5 2- Ethoxy-
-1,1-dimethylcyclohexane
GENERAL METHOD OF PREPARATION OF ETHER

1. By dehydration of alcohols
H2SO4
CH3CH2OH CH 3CH 2OCH 2CH3
413 K
(excess) Diethylether
Ethyl alcohol
H2SO4
CH 2 = CH2
413K
C2H5OH
H2SO4
C2H5OC2H5
413K
MECHANISM (Application of SN2)

Mechanism
The formation of ether is a nucleophilic bimolecular reaction (SN2) involving the attack of
alcohol, as indicated below
Step (1) : H2SO4  H+ + HSO4¯
..  
H
CH3 – CH2 – O.. – H + H CH3 – CH2 – O
.. H
Ethyl alcohol protonated alcohol
(first molecule)
86 E
CBSE
ALLEN
 CH2CH3
  H slow
Step (2) : ..
CH3 – CH2 – O: + CH3 – CH2 – O
   CH3 – CH2 – O
.. + H2O
.. H
H
H protonated alcohol
Ethyl alcohol
(second molecule)
(nuclophile attack)

Step (3): CH3 – CH2 – O – CH 2 – CH 3 
 CH3 – CH – O – CH2 – CH3 + H+
H
H+ + HSO4¯  H2SO4
Note : This method is sutable for the preparation of ethers having primary alkyl groups only. The
alkyl group should be unhindered and the temperature be kept low. Otherwise the reaction
favours the formation of alkene.
Note : The reaction follows SN1 path way when the alcohol is secondary or tertiary (out of
syllabus)
2. Williamson synthesis reaction / Williamson ether synthesis reaction
(A) Formation of simple ether (symmetrical ether)
  – ..
R – X + R – ONa R–O
.. – R + NaX
Alkyl halide Sodium Symm.
alkoxide Ether
Laboratory method:
– +
C2H5Br + C2H5ONa C2H5OC2H5 + NaBr
ethyl Sodium Diethyl
bromide ethoxide ether
(B) Formation of unsymmetrical ether
 ..
R – X + R' – ONa  R – O
.. – R + NaX
Case-I : Ethers containing substituted alkyl groups (secondary or tertiary) may also be
prepared by this method. The reaction involves SN2 attack of an alkoxide ion on primary
alkyl halide. Better results are obtained if the alkyl halide is primary.
CH3 CH3
.. 
Example CH3 – C – ONa
.. + CH3 – Br CH3 – O – C – CH3 + NaBr
CH3 CH3
Methylbromide
Sodium ter butyloxide 2-Methoxy-2-Methyl propane
Bromo methane
E 87
Chemistry
ALLEN
Mechanism (Application of SN2)
CH3 CH3
– + – +
CH3–C–ONa H3C–C–O + Na
CH3 CH3
tert butyloxide
CH3 H CH3 H
–  Slow 1 1
H3C–C–O + C—Br H3C–C–O--------C---------Br
H H H H
CH3 CH 3
transition state
CH3
H3C–C–O–CH3 + Br¯
CH3
Na   Br – 
 NaBr
Case-II :
In case of secondary and tertiary alkyl halids, elimination reaction competes over
substitution reaction. If a tertiary alkylhalide is used, an alkene is the only reaction product
and no ether is formed. It is because alkoxide ion not only nucleophiles but strong bases as
well. They react with alkyl halides leading to elimination reaction.
Eg.
CH3
CH3 CH3
2-Bromo-2-methylpropane 2-methylpropene
CHEMICAL REACTIONS OF ETHERS
1. Reaction with halogen acids : Cleavage of C–O bond in ethers.
The reaction of dialkyl ether gives two alkyl halide molecules with halogen acids.
* Note: Reacitivity order of H–X towards ethers
HI  H  Br  H  Cl
   HF
Bond length  Reaction occurs at

 B.E. high temp
(i) Reaction of simple ether with HX:

 1  1
R–O–R + H–X R–X + R–OH
excess +H–X
C–O
R–X + H 2O
88 E
CBSE
ALLEN
OR
R–O–R + 2HX  2R–X + H2O
Example: C2H5–O–C2H5 + H–I  C2H5I + C2H5–OH
excess HI
C2H 5I + H2O
(ii) Reaction of mixed ether with HX:
Ethers with two different groups are also cleaved in the same manner.
 1  1
R–O–R' + H–X R–X + R'–OH
Case-I: If one of the alkyl group is tertiary alkyl group in mixed ether then the halide form
is a tertiary alkyl halide. It is because the departure of leaving group (HOCH3) creates a
more stable carbocation i.e. (CH3)3C tertiary carbocation and reaction follows SN1
mechanism (according to following mechanism).
CH3 1 CH3
  1
Example: CH3—C—O—CH3 + HI H3C—C—I + CH3OH
CH3 CH3
-------------- ---------
Common name : ter butyl methyl ether ter butyl iodide Methyl alcohol
IUPAC : 2-Methoxy-2-Methyl propane 2-Iodo-2-methyl-Propane Methanol
Mechanism: (Application of SN1)

CH3 CH3
 1  H –
Step-1: H3C C O – CH3 + H–I H3C—C — O + I
CH3
CH3 CH3
Protonated
ether
CH3 CH3
 H
H3 C C O Slow H3C—C + CH3OH
CH3 RDS ---------
CH3 CH3
tert. butyl carbocation
CH3 CH3
1 Fast
Step-2: H3C C + I H3C—C – I
CH3 CH3
--------------
tert. butyl iodide
E 89
Chemistry
ALLEN
Case-II: If primary or secondary alkyl groups present in mixed ether, it is the lower alkyl
groups formed alkyl halide with H–X through SN2 mechanism.
 1
Example: CH3–O–CH2–CH3 + H–I CH3I + CH3CH2OH
Ethyle methyle ether Concentrated Methyl Ethyl
iodide alcohol
Note: The reaction takes place with HBr or HI because these reagent are sufficiently acidic.
Mechanism: (Application of SN2)
Mechanism of an ehter with concentrated HI starts with protonation of ether molecules.
 1  H 1
Step-1: CH3–O–CH2–CH3 + H–I CH3 – O + I
CH2–CH3
Protonated ether
H H
Step-2: I
1
+ C O–CH2–CH3 Slow 1 1
I-----C-----O–CH2CH3 CH3I + CH3CH2O
1
RDS
H
H H H H
Iodide ion
(attacking CH3CH2OH
nucleophile)
OCH3
Case-III: Reaction of aromatic ether with HI i.e. Anisole Or C6H5 O CH3
In case of anisole, methylphenyl oxonium ion is formed by protomation of ether. The bond
between-O–CH3 is weaker than the bond between –O–C6H5 because the carbon of phenyl group
is sp2 hybridised and there is a partial double bond charcter.
Therefore the attack by I– ion breaks –O–CH3 bond to form CH3I. Phenols do not react further to
give halides because the sp2 hybridised carbon of phenol cannot undergo nucleophilic
substitution reaction needed for conversion to the halide.
OCH3 O
+ CH3I
ANISOLE
Resonating structures of Anisole : It is clear by resonating structures of anisole that due to
.. ..
+M effect of – OCH
.. 3 / – .. group electron density increases at ortho and para postion both
OR
(L.P. es –  es conjugation). Therefore attacking electrophile attacks at ortho and para position
and ortho and para substituting products are formed in their ESR. Hence anisole is ortho and para
directing.
OCH3 +OCH3 +OCH3 +OCH3 OCH3
I II III IV V
90 E
 CBSSE
ALLEN
A
Prepaaration of anisole
–+
OH ONaa OCH3
+NaO
OH CH 3Cl
P
Phenol Sodiumm A
Anisole
phenoxiide
Electrophili
E ic substituttion reactio ons of Anisoole :
(ii) Haloggenation: Phhenylalkyl ethers undeergo usual halogenatio
h n in the bennzene ring, e.g., anisoole
underggoes brominnation with bromine inn ethanoic acid a even in
n the absennce of iron (III)
( bromidde
catalysst. It is due to the activ
vation of bennzene ring by
b the meth
hoxy group. Para isomeer is obtaineed
in 90%
% yield.
OCH3 OCH3 OCH3
Br
B 2 in
Br
Ethhanoic acid
Anisole
Br Br
p-Broomoanisole o-Bromoanisole
(
(Major) (Minor)
(iii) Friedeel-Crafts reaction:
r Anisole
A unddergoes Frieedel-Crafts reaction, ii.e., the alk
kyl and acyyl
groupss are introduuced at orth
ho and para positions by
b reaction with
w alkyl hhalide and acyla halide in
the preesence of annhydrous aluuminium chhloride (a Lewis
L acid) as
a catalyst.
(A) A Alkylation
OCH3 OCH3 O 3
OCH
CH3
Anhydd.AlCl3
+CHH3Cl CS
S2 +
Meethyl
chlo
oride
A
Anisole C 3
CH
2-Meth
hoxytoluene 4-Methox
xytoluene
(M
Minor) (Maajor)
(B) A
Acetylation
n
OCH3 OCH3 OCH3
C
COCH3
Anhyd.AlCl3
+ CH3COCl +
Ethanoyl
Anisole chloride
COCH3
2-Methoxy- 4-MMethoxy
acetophenonee acettophenone
(Minor) (
(Major)
(iiii) Nitrattion: Anisoole reacts with
w a mixtuure of conccentrated su
ulphuric andd nitric acid
ds to yield a
mixturre of ortho and

a para nittroanisole.
OCH
H3 OCH3 OCH3
N 2
NO
H2SO4
HNO3 +
Anisolle NO2
2-Nitroanisolee 4-N
Nitroanisole
(Minor) (Major)
E 91
1
Chemistry
C
N
ALLEN
P
PHENOL
LS
Phenool : The simmplest hydro
oxy derivatiive of benzene is know
wn as phenool in which
h – OH grouup
2
attacheed with sp hybridised carbon of bbenzene.
Functiional group
p of phenoll : C 2– OH
H
sp
Nomen
nclature off Phenol & examples oof phenolicc compound
ds :
OH
H CH3 CH
H3 CH3
OH
H
OH
OH
Comm
mon Name Pheno
ol o-C
Cresol m-Cressol pp-Cresol
IUPAC
C Name Pheno
ol 2-Metthylphenol 3-Methylp
phenol 4--Methylphen
nol
OH
H O
OH OH
OH
OH
OH
Comm
mon name Catecchol Ressorcinol Hyydroquinonee or quinol
Benzene-1,2-diool Ben
nzene-1,3- diol
d B
Benzene-1,4
4- diol
GENERAL
G L METHOD
D OF PREP
PARATION
N OF PHE
ENOL
1.
1 From haloareness : Chlorob benzene is ffused with NaOH
N at 62
23K and 3220 atmospheeric pressurre.
Phenoll is obtainedd by acidificcation of soodium pheno
oxide so pro
oduced.
Cl ONa+ OH
623 K H
HCl
+ NaOH
N m
300 atm
Chloro Sodium Phenol

Benzene
B Phenoxide
2.
2 From benzenesu ulphonic acid : Benzenne is sulpho
onated with oleum andd benzene su
ulphonic acid
so forrmed is coonverted to sodium pphenoxide on heating with mollten sodium m hydroxidde.
Acidiffication of thhe sodium salt
s gives phhenol.
SO3H OH
Oleum (i) NaOH

+
H2S2O7 (ii) H
Ben
nzene Benzene Ph
henol
sulphonic
acid
92 E
CBSE
ALLEN
3. From diazonium salts : A diazonium salt is formed by treating an aromatic primary amine with
nitrous acid (NaNO2 + HCl) at 273-278 K. Diazonium salts are hydrolysed to phenols by
warming with water or by treating with dilute acids.
 s
NH2 N2Cl OH
NaNO2 H2O
+HCl Warm + N2 + HCl
Aniline Benzene diazonium Phenol

chloride
4. From cumene
Phenol is manufactured from the hydrocarbon, cumene. Cumene (isopropylbenzene) is oxidised
in the presence of air to cumene hydroperoxide. It is converted to phenol and acetone by treating
it with dilute acid. Acetone, a by-product of this reaction, is also obtained in large quantities by
this method.
CH3 CH3
—
CH3—CH CH3—C—O—O—H OH
O2 H+
H2O + CH3COCH3
cumene Cumene Phenol Acetone

hydroperoxide
ELECTROPHILIC SUBSTITUTION REACTION OF PHENOL
Resonating structures of Phenol :
It is clear by resonating structures of phenol that due to +M effect of group electron density
increases at ortho and para postion both (L.P. es –  es conjugation). Therefore attacking
electrophile attacks at ortho and para position and ortho and para substituting products are
formed in their ESR. Hence phenol is ortho and para directing.
O—H +O—H +O—H +O—H O—H
1. Nitration of Phenol
(a) With dilute HNO3 : With dilute nitric acid at low temperature (298 K), phenol yields a
mixture of ortho and para nitrophenols.
OH OH OH
NO2
Dilute HNO3
+
Phenol o-Nitrophenol
NO2
p-Nitrophenol
E 93
Chemistry
ALLEN
(b) With conc. HNO3 :
With concentrated nitric acid, phenol is converted to 2,4,6-trinitrophenol. The product is
commonly known as picric acid.
OH OH
O2N NO2
Conc.HNO3
Phenol
NO2
2,4,6-Trinitrophenol
(picric acid)
2. Halogenation :
On treating phenol with bromine, different reaction products are formed under different
experimental conditions.
(a) With liquid bromine
OH OH OH
Br
Br 2 in CS2
273 K
+
Phenol
Br
2-Bromo Phenol 4-Bromo Phenol
(b) With bromine water

OH OH
Br Br
+ 3 Br2 H2O + 3HBr
Phenol Br
2,4,6-Tribromophenol
(white ppt)
3. Kolbe’s reaction
Phenoxide ion generated by treating phenol with sodium hydroxide is even more reactive than
phenol towards electrophilic aromatic substitution. Hence, it undergoes electrophilic substitution
with carbon dioxide, a weak electrophile. Ortho hydroxybenzoic acid is formed as the main
reaction product.
OH ONa OH
COOH
NaOH (i) CO2
+
(ii) H
Phenol Sodium 2-Hydroxybenzonic acid

Phenoxide (Salicylic acid)
94 E
CBSE
ALLEN
4. Reimer-Tiemann reaction
On treating phenol with chloroform in the presence of sodium hydroxide, a –CHO group is
introduced at ortho position of benzene ring. This reaction is known as Reimer - Tiemann
reaction.
The intermediate substituted benzal chloride is hydrolysed in the presence of alkali to produce
salicylaldehyde.
+ +
OH O Na O Na OH
CHCl2 CHO CHO
+
CHCl3+ aq NaOH NaOH H
Intermediate Salicylaldehyde
5. Reaction of phenol with zinc dust

OH
+ Zn + ZnO
6. Oxidation
OH O
Na2Cr2O7 + H2SO4

Phenol
O
benzoquinone
7. Conversion of Phenol to Aspirin

OH ONa OH OCOCH3
COOH COOH
+ CH3COOH
Salicylic acid Aspirin
8. Acetylation of Salicylic acid

OH OCOCH3
COOH COOH
+ CH3COOH
Salicylic acid Aspirin

Physical Properties of Alchohols
1. Physical State
 Lower alcohols are colourless liquids with a characterstic smell.
 Higher members are colourless, odourless, waxy solids.
E 95
Chemistry
ALLEN
2. Boiling Point
 Alochols have higher boiling point then corresponding hydrocarbons because of the
presence of H–bonding (intermolecular) in then
CH4 < CH3Cl < CH3OH
Non–polar Dipole–dipole H–bond
 B.P.  No. of carbon atoms.

 CH3OH < C2H5OH < C3H7OH < C4H9OH
1
 B.P.  suface area 
Branching
3. Solubility
 Due to the formation of intermolecular H–bonding, alcohols are soluble in water
R—O—H
H—O—H
intermolecular H–bonding
 Lower alcohols are highly soluble in water, solubility decreases with increase in number of
carbon atoms due to decrease in extent of Hydrogen bonding. Since larger the alkyl
group/hydrocarbon parts more will be the resistance to hydrogen bonding with water.
CH3OH > C2H5OH > C3H7OH > C4H9OH.
1
Solubility  Branching 
surface area
CH3
CH3CH2CH2OH < CH3—CH—CH2—OH < CH3—C—OH
CH3 CH3
4. Pscyological Action
 Alcohols have pscyological action on human beings since they affect CNS.
 Methanol is poisnous in nature and on consumption it causes blindness, unconsciousness or
even death.
Physical properties of Phenols :
1. Colurless liquid or solids, but they turn reddish brown due to oxidation with atmospheric oxygen.
2. They are, soluble in water  they can form hydrogen bond with water.
They are less soluble in water than alcohols because the benzene ring decreases the tendency of
formation of H–bond.
All phenols are soluble in organic solvents.
3. Phenols has higher boiling point than benzne due to the presence of intermolecular hydrogen
bonding.
96 E
CBSE
ALLEN
Physical Properties of Ethers
1. Physical state: Diethyl ether (CH3—O—CH3) and ethyl methyl ether are gases at room
temperature while others are colourless liquids having ether like smell.
2. Boiling point: Ethers have lower boiling point than corresponding isomeric alcohols
because of the absence of intermolecular H-bonding in ethers. They have slightly higher
boiling point than corresponding hydrocarbons due to presence of weaker dipole-dipole
interactions. Boiling point of ethers increases with increase in molar mass due to increase
in vander-waal forces of attraction.
3. Solubility : Ethers having upto 3 carbon atoms are soluble in waer due to formation of
hydrogen bonds with water.
R H H
O O
R H H
O
H-bond
Solubility decreases with increases in number of carbon atoms. All ethers are soluble in
organic solvents like benzene, alcohols, etc.
4. Polar Nature: Since, the oxygen atom bonded to alkyl group in ethers is more
electronegetive than the carbon atoms of the alkyl group, so the C–O bonds are polar in
nature.
Since the dipole moment due to the polar C–O bonds are not opposite to each other,
therefore all ethers have a dipole moment and are polar.
+
R
–
O Net dipole
R
+
E 97
Chemistry
ALLEN
1. Classify the following as primary, secondary and tertiary alcohols :
CH3
(i) CH3–C–CH2–OH (ii) H2C = CH – CH2OH

CH3
OH
CH–CH3
(iii) CH3–CH2–CH2–OH (iv)

CH3
CH2–CH–CH3 CH2=CH–C–OH
(v) OH (vi) CH3
Ans. Primary alcohol  (i), (ii), (iii)

Secondary alcohol  (iv), (v)
Tertiary alcohol  (vi)
2. Identify allylic alcohols in the above examples.
Ans. Allylic that means C = C – C – OH
The alcohols given in (ii) and (vi) are allylic alcohols.
3. Name the following compounds according to IUPAC system.
CH 2OH CH2OH
(i) CH3–CH2–CH–CH–CH–CH3 (ii) CH3–CH–CH2–CH–CH–CH3

CH 2Cl CH3 CH 3 OH
OH
(iii)
Br
(iv) H2C=CH–CH–CH2–CH2–CH3 (v) CH3 – C = C – CH2OH
OH CH3 Br
Ans. (i) 3-Chloromethyl - 2- isopropylpentan-l-ol

(ii) 2, 5 - Dimethylhexane - 1, 3 - diol
(iii) 3-Bromocyclohexanol
(iv) Hex-1-en-3-ol
(v) 2-Bromo-3-methylbut-2-en-1-ol
4. Show how are the following alcohols prepared by the reaction of a suitable Grignard reagent on
methanal ?
CH2OH
(i) CH3–CH–CH2OH (ii)
CH3
 H 2O
Ans. (i) H–C–H + CH3–CH–MgBr H–CH CH3 CH2–CH–CH3
O CH3 OMgBr CH3 OH CH3
98 E
CBSE
ALLEN
MgBr CH2OMgBr CH2OH
H 2O
(ii) H–C–H + + Mg(OH)Br
O
Methanal Cyclohexylmagnesium Cyclohexylmethanol
bromide
5. Write structures of the products of the following reactions :

(i) CH3  CH  CH2 
H O/H
 2
O O
NaBH4
(ii) CH2 – C–O–CH3
H
NaBH4
(iii) CH3–CH2–CH–CHO
CH3
+
Ans. (i) CH3–CH=CH2

H 2O/H
CH3–CH–CH3
Propene OH
Propan-2-ol
O OH
CH2–C–OCH3 NaBH 4
CH2–C–OCH3
(ii) O H O
Methyl (2-oxocyclohexyl) Methyl (2-hydroxycyclohexyl)

ethanoate ethanoate
NaBH 4
(iii) CH3–CH2–CH–CHO H
 CH3–CH2–CH–CH2OH
CH3 CH3
2-Methylbutanal 2-Methylbutan-l-ol
6. Give structures of the products you would expect when each of the following alcohol reacts with
(a) HCl-ZnCl2 (b) HBr and (c) SOCl2.
(i) Butan-1-ol (ii) 2-Methylbutan-2-ol
Cl
HCl+ZnCl2
Ans. (a) (i) CH3–CH2–CH2–CH2–OH CH3–CH2–CH–CH3
Butan - 1- ol
OH Cl
HCl+ZnCl2
(ii) CH3–CH2–C–CH3 CH3–CH2–C–CH3 + H2O
CH3 CH3
2-Methylbutan - 2 - ol (3°) 2-Chloro - 2- Methylbutane
(White turbidity)
Tertiary alcohols react immediately with Lucas' reagent.

(B) (i) CH CH CH CH OH + HBr –H O
3 2 2 CH –CH –CH–CH
2
2
3 2 3
Butan -1-ol Br
OH Br
(ii) CH3–CH2–C–CH3+HBr CH3–CH2–C–CH3 + H2O
CH3 CH3
2-Methylbutan - 2 - ol (3°) 2-Bromo-2-Methylbutane
(C) (i) CH3CH2CH2CH2OH  SOCl2  CH3CH2 CH2CH2Cl  SO2  HCl

Butan-1-ol 1-chlorobutane
OH Cl
(ii) CH3–CH2–C–CH3+SOCl2 CH3–CH2–C–CH3 + SO2 + HCl
CH3 CH3
2-Methylbutan - 2 - ol 2-Chloro-2-Methylbutane
E 99
Chemistry
ALLEN
7. Predict the major product of acid catalysed dehydration of
(i) l-methylcyclohexanol and
(ii) butan-1-ol
OH CH3 CH3
Dehydration
Ans. (i) H
+ + H2O
1-Methylcyclohexanol 1-Methylcyclohexene
(Major product)
(ii) CH3 CH2 CH2 CH2 OH 

Dehydration
H
 CH3 CH  CHCH3  H2 O
Butan-1-ol But 2  ene
(Major product )
8. Ortho and para nitrophenols are more acidic than phenol. Draw the resonance structures of the
corresponding phenoxide ions.
– –
O O O O O
Ans. – –
–
(Resonance structure of the phenoxide ion)

O O O O O O
+ + + +
N N N N N+ N+
— — — — — —
O O O O O O O O— O O O O
(Resonance structures of p-nitrophenoxide ion)
– –
O O O— O O O
O O O O
+
N +
N
+
N N N
O —
O— O — – + O—
O—
–
(Resonance structures of o-nitrophenoxide ion)

It can be observed that the presence of nitro groups increases the stability of phenoxide ion.
9. Write the equations involved in the following reactions :
(i) Reimer - Tiemann reaction
(ii) Kolbe - Schmidt reaction
OH OH OH OH
CHCl3+Alc. NaOH
CHO COOH
Ans. (i) (ii) (i) NaOH + CO2
(ii) H +
Phenol (Salicylaldehyde)
10. Write the reactions of Williamson synthesis of 2-ethoxy-3-methylpentane starting from ethanol
and 3-methylpentan-2-ol.
Ans. C2 H5 OH 
HBr
 C2H5 Br
Ethanol Bromoethane
Na
CH3–CH2–CH–CH–CH3 CH3–CH2–CH–CH–ONa
CH3 OH CH3 CH3
3-Methylpentan-2-ol Sodium 3-Methylpentan-2-oxide
CH3–CH2–CH–CH–ONa+C2H5Br CH3–CH2–CH–CH–OC2H5 + NaBr

CH3 CH3 CH3 CH3
2-Ethoxy-3-methylpentane
100 E
CBSE
ALLEN
11. Which of the following is an appropriate set of reactants for the preparation of 1-methoxy-4-
nitrobenzene and why ?
Br ONa
(i) + CH3ONa (ii) + CH3Br
NO2 NO2
Ans. Set (ii) is an appropriate set of reactants for the preparation of 1-methoxy-4-nitrobenzene.
ONa OCH3
1
6 2
+ CH3Br + NaBr
5 3
4
NO2 NO2
1-Methoxy-4-nitrobenzene
In set (i), Bromine atom is stable by resonance.
12. Predict the products of the following reactions :
OC2H5
(i) CH3–CH2–CH2–O–CH3 + HBr  (ii) + HBr
OC2H5 Conc.H SO
(iii) 2 4
Conc.HNO 3 (iv) (CH3 )3 C  OC2H5 

HI


Ans. (i) CH 3  CH 2  CH2  O  CH3  HBr  CH3  CH2  CH2  OH  CH 3  Br (S N 2)

n  propylmethyl ehter Pr opanol Bromomethane
OC2H5 OH
(ii) + HBr + C2H5Br (SN2)
Ethoxybenzene Phenol Bromoethane

OC2H5 Conc.H2SO 4 OC2H5 OC2H5
(iii) Conc.HNO 3 + (Nitration)
NO2 NO2
Ethoxybenzene 1-Ethoxy-4-nitrobenzene 2-Ethoxynitrobenzene
(Major) (Minor)
(iv) (CH 3 )3 C  OC2 H5 
HI

 (CH3 )3 C  I  C 2 H5 OH (S N 1)
tert  Butyl ethyl ether tert  Butyliodide Ethanol
13. Give IUPAC names of the following compounds :

CH3—CH—O—CH2CH3
(i) CH —CH—CH—CH—CH OH
3 (ii) 2
—
—
Cl CH3 CH3 CH3
OH NO2
H3C CH3 OC2H5
(iii) (iv)
Ans. (i) 4-Chloro-2,3-dimethylpentan-1-ol (ii) 2-Ethoxypropane

(iii) 2,6-Dimethylphenol (iv) 1-Ethoxy-2-nitrocyclohexane
14. You will notice that the reaction produces a primary alcohol with methanal, a secondary alcohol
with other aldehydes and tertiary alcohol with ketones. Give the structures and IUPAC names of
the products expected from the following reactions :
(a) Catalytic reduction of butanal.
(b) Hydration of propene in the presence of dilute sulphuric acid.
(c) Reaction of propanone with methylmagnesium bromide followed by hydrolysis.
E 10
1
Chemistry
ALLEN
Ans. (a) CH3 – CH 2 – CH 2 – CH 2 – OH
Bu tan 1 ol
(b) CH3—CH—CH3
—
OH
Propan-2-ol
CH3
—
(c) CH3—C—OH
—
CH3
2– Methylpropan–2–ol
15. Arrange the following sets of compounds in order of their increasing boiling points:
(a) Pentan-1-ol, butan-1-ol, butan-2-ol, ethanol, propan-1-ol, methanol.
(b) Pentan-1-ol, n-butane, pentanal, ethoxyethane.
Ans. (a) Methanol, ethanol, propan-1-ol, butan-2-ol, butan-1-ol, pentan-1-ol.
(b) n-Butane, ethoxyethane, pentanal and pentan-1-ol.
16. Arrange the following compounds in increasing order of their acid strength: Propan-1-ol, 2, 4,
6-trinitrophenol, 3-nitrophenol, 3,5-dinitrophenol, phenol, 4-methylphenol.
Ans. Propan-1-ol, 4-methylphenol, phenol, 3-nitrophenol, 3, 5-dinitrophenol, 2, 4, 6-trinitrophenol.
17. Write the structures of the major products expected from the following reactions:
(a) Mononitration of 3-methylphenol
(b) Dinitration of 3-methylphenol
(c) Mononitration of phenyl methanoate.
Ans. The combined influence of –OH and –CH3 groups determine the position of the incoming group.
OH OH OH OCOCH3
O2N O2N
(a) and (b) (c)

CH3 CH3 CH3
NO2 NO2 NO2
18. The following is not an appropriate reaction for the preparation of t-butyl ethyl ether.
CH3 CH3
C2H5ONa + CH3 —C—Cl CH3 —C—OC2H5
CH3 CH3
(i) What would be the major product of this reaction ?

(ii) Write a suitable reaction for the preparation of t-butylethyl ether.
Ans. (i) The major product of the given reaction is 2-methylprop-1-ene.
It is because sodium ethoxide is a strong nucleophile as well as a strong base. Thus
elimination reaction predominates over substitution.
102 E
CBSE
ALLEN
CH3 CH3
+
: :
(ii) CH3—C—CONa+CH3 CH2Cl CH3 —C—OC2H5
CH3 CH3
Phenols are also converted to ethers by this method. In this, phenol is used as the
phenoxide moiety.
–
: :
:
:OH :O + O–H
Na
+ NaOH R–X
CH3
CH3
— —
19. (i) CH3— CH2—CH—CH2—O—CH2 —CH3 (ii) CH3—CH2—CH2—O—C—CH2 —CH3
CH3
(iii) CH2—O—
CH3
— —
Ans. (i) CH3—CH2—CH—CH2OH + CH3 CH2I (ii) CH3CH2CH2OH + CH3CH2—C—I
CH3 CH3
(iii) CH2I + —OH

E 10
3
Chemistry
ALLEN
1. Write IUPAC names of the following compounds :
CH3
(i) CH3–CH–CH–C–CH3 (ii) H3C–CH–CH2–CH–CH–CH2–CH3
CH3 OH CH3 OH OH C2H5
(iii) CH3–CH–CH–CH3 (iv) HO–CH2–CH–CH2–OH

OH OH OH
CH3 CH3
OH
(v) (vi)
OH
CH3 CH3
OH
(vii) (viii)
OH CH3
CH3
(ix) CH3–O–CH2–CH–CH3 (x) C6H5–O–C2H5
CH3
(xi) C6H5–O–C7H15(n–) (xii) CH3–CH2–O–CH–CH 2–CH3
CH3
Ans, (i) 2, 2, 4-Trimethylpentan-3-ol (ii) 5-Ethylheptane-2, 4-diol
(iii) Butane-2, 3-diol (iv) Propane-1, 2, 3-triol
(v) 2-Methylphenol (vi) 4-Methylphenol
(vii) 2, 5-Dimethylphenol (viii) 2, 6-Dimethylphenol
(ix) 1-Methoxy-2-methylpropane (x) Ethoxybenzene
(xi) 1-Phenoxyheptane (xii) 2-Ethoxybutane
2. Write structures of the compounds whose IUPAC names are as follows :
(i) 2-Methylbutan-2-ol (ii) 1-Phenylpropan-2-ol
(iii) 3,5-Dimethylhexane-1, 3, 5-triol (iv) 2, 3-Diethylphenol
(v) 1-Ethoxypropane (vi) 2-Ethoxy-3-methylpentane
(vii) Cyclohexylmethanol (viii) 3-Cyclohexylpentan-3-ol
(ix) Cyclopent-3-en-1-ol (x) 3-Chloromethylpentan-1-ol

OH OH
Ans. (i) CH3—C—CH2—CH3 (ii) CH2–CH–CH3
CH3
OH OH OH
(iii) HO—CH2—CH2—C—CH2—C—CH3 (iv) C2H5
CH3 CH3 C2H5
104 E
CBSE
ALLEN
CH3
(v) CH3–CH2–O–CH2–CH2–CH3 (vi) CH3–CH2–O–CH–CH–CH2–CH3
CH3
CH2OH OH
(vii) (viii) CH3–CH2–C–CH2–CH3
OH
CH2Cl
(ix) (x) CH3–CH2–CH–CH2–CH2–OH
3. Draw the structures of all iosmeric alcohols of molecular formula C5H12O and give their IUPAC
names. Classify them as primary, secondary and tertiary alcohols.
Ans. (a) CH3CH2CH2CH2CH2OH (b) CH3 CH2 CH CH2 OH
CH3
Pentan–1–ol 2–Methylbutan–1–ol
CH3
(c) CH3 CH CH2 CH2 OH (d) CH3 C CH2 OH
CH3 CH3
3-Methylbutan-1-ol 2, 2-Dimethylpropan-1-ol
(e) CH3 CH2 CH2 CH CH3 (f) CH3 CH2 CH CH2 CH3
OH OH
Pentan-2-ol Pentan-3-ol
CH3
(g) CH3 CH CH CH3 (h) CH3 CH2 C OH
CH3 OH CH3
3–Methylbutan–2–ol 2–Methylbutan–2–ol
Primary alcohols – (a), (b) (c) and (d)
Secondary alcohols – (e), (f) and (g)
Tertiary alcohols – (h)
4. Explain why propanol has higher boiling point than that of the hydrocarbon, butane ?
Ans. Propanol undergoes intermolecular H-bonding because of the presence of –OH group. On the
other hand, butane does not
+ – + – + –
H–O H–O H–O
C3H7 C3H7 C3H7
5. Explain why are alcohols comparatively more soluble in water than the corresponding
hydrocarbons.
Ans. Hydrogen bonding exist between alcohol and water molecules while hydrocarbons are nonpolar,
they can not form H-bond with water molecule.
E 10
5
Chemistry
ALLEN
6. What is meant by hydroboration oxidation reaction? Illustrate it with an example.
Ans. CH3–CH=CH2+(H–BH2)2 CH3–CH–CH2
Propene Diborane H BH2
CH3–CH=CH2
CH 3–CH=CH 2
(CH3–CH2–CH2)3B (CH3–CH2–CH2)2BH
3H2O2,OH—
3CH3–CH2–CH2–OH+B(OH)3
Propan-1-ol
7. Give the structures and IUPAC names of monohydric phenols of molecular formula C7H8O.
OH
OH
OH
Ans. C7H8O  CH3 
 CH3  CH3
2–Methylphenol 3–Methylphenol 4–Methylphenol
8. While separating a mixture of ortho and para nitrophenols by steam distillation, name the isomer
which is steam volatile. Give reason.
Ans. o-Nitrophenol is steam volatile due to intramolecular hydrogen bonding.
9. Give the equation of reaction of preparation of phenol from cumene.
O O H
OH
Ans. 
O2
 
dil.H 2SO4
 + CH3COCH3
10. Write chemical reaction for the preparation of phenol from chlorobenzene.
Ans. Chlorobenzene is fused with NaOH (at 623 K and 320 atm pressure) to produce sodium
phenoxide, which give phenol on acidification.
Cl ONa OH
623 K HCl
+ 2NaOH
320 atm
Chlorobenzene Sodium phenoxide Phenol
11. You are given benzene, conc. H2SO4 and NaOH. Write the equations for the preparation of
phenol using these reagents.
SO3H SO3Na – OH
Ans. 
H 2SO4
 
NaOH
 
(i)OH
(ii) H 
12. Show how will you synthesize :

(i) l-phenylethanol from a suitable alkene.
(ii) cyclohexylmethanol using an alkyl halide by an SN2 reaction
(iii) pentan-1-ol using a suitable alkyl halide ?
CH=CH2 CH–CH3
+
H
Ans. (i) +H2O OH
Phenylethene 1-phenylethanol
CH2Cl CH2OH
(ii) + aq. NaOH + NaCl
Chloromethylcyclohexane Cyclohexylmethanol
(iii) CH3CH2CH2CH2CH2Cl + aq. NaOH CH3CH2CH2CH2CH2OH + NaCl

1-Chloropentane Pantan-1-ol
106 E
CBSE
ALLEN
13. Give two reactions that show the acidic nature of phenol. Compare acidity of phenol with that of
ethanol.
Ans. The acidic nature of phenol can be represented by the following two reactions.
(i) Phenol reacts with sodium to give sodium phenoxide, liberating H2.
OH ONa
+ Na + 1 H2
2
Phenol Sodium phenoxide
(ii) Phenol reacts with sodium hydroxide to give sodium phenoxide and water as by-products.
OH ONa
+ NaOH + H2O
Sodium phenoxide
The acidity of phenol is more than that of ethanol. This is because after losing a proton, the
phenoxide ion undergoes resonance and gets stabilized whereas ethoxide ion does not.
O O O O O
14. Explain why is ortho-nitro phenol more acidic than ortho-methoxy phenol?
Ans. Electron withdrawing effect of nitro group and electron releasing effect of methoxy group.
15. Explain how does the –OH group attached to a carbon of benzene ring activates it towards
electrophilic substitution?
Ans. Electron density at o- and p-position increases and thus the electrophile attacks easily.
 
.. :O H :O H 
:
:O H :O H :OH
1
   1
16. Give equations of the following reactions :

(i) Oxidation of propan-1-ol with KMnO4 solution.
(ii) Bromine is CS2 with phenol.
(iii) Dilute HNO3 with phenol.
(iv) Treating phenol with chloroform in presence of aqueous NaOH.
Ans. (i) CH3 CH2 CH2 OH 
KMnO4
 CH 3 CH2 COOH
Propan-1-ol Propanoic acid
OH OH OH
Br2 in CS2 Br
(ii) 273 K
+
Phenol
Br
p-Bromophenol o-Bromophenol
(Major) (Minor)
OH OH OH
(iii) dilute HNO 3 NO2
+
NO2
o-Nitrophenol p-Nitrophenol
E 10
7
Chemistry
ALLEN
–+ –+
OH ONa ONa
CHCl3 + aq.NaOH CHCl2 NaOH
CHO
(iv)
Intermediate H+
OH
CHO
Salicylaldehyde
17. Explain the following with an example.

(i) Williamson ether synthesis.
(ii) Unsymmetrical ether.
Ans. (i) Williamson's ether synthesis :
Williamson ether synthesis is a laboratory method to prepare symmetrical and
unsymmetrical ethers by allowing alkyl halides to react with sodium alkoxides.
R – X + R' – O Na R – O – R' + NaX
Alkyl halide Sodium alkoxide Ether
This reaction involves SN2 attack of the alkoxide ion on the alkyl halide. Better results are
obtained in case of primary alkyl halides.
CH3 CH3
– +
CH3–CH–O Na + CH3–Br CH3–O–CH–CH3+NaBr
If the alkyl halide is secondary or tertiary, then elimination competes over substitution.
(ii) Unsymmetrical ether :
An unsymmetrical ether is an ether where two alkyl groups on the two sides of an oxygen
atom differ. For example : ethyl methyl ether (CH3–O–CH2CH3).
18. How are the following conversions carried out ?
(i) Propene  Propan-2-ol
(ii) Benzyl chloride  Benzyl alcohol
(iii) Ethyl magnesium chloride  Propan-1-ol.
(iv) Methyl magnesium bromide  2-Methylpropan-2-ol.
+
Ans. (i) CH –CH=CH +H O

3 2
H
CH –CH–CH
2 3 3
OH
Propene Propan–2–ol
CH2Cl CH2ONa CH2OH
H+
(ii) + NaOH
NaCl
Benzyl chloride Benzyl alcohol
Et
– + H
+
(iii) H–C–H + Et Mg Cl H–C–H Et–CH2–OH + Mg(OH)Cl

O OMgCl
CH3
H3C – +
C=O+CH3–MgBr CH3–C–OMgBr
(iv) H3C
CH3
Adduct
H2O
OH
Mg(OH)Br+CH3–C–CH3
CH3
2-Methylpropan-2-ol
108 E
CBSE
ALLEN
19. Give reason for the higher boiling point of ethanol in comparison to methoxymethane.
Ans. Ethanol undergoes intermolecular H-bonding due to the presence of –OH group, resulting in the
association of molecules. On the other hand, methoxymethane does not undergoes H-bonding.
Hence, the boiling point of ethanol is higher than that of methoxymethane.
20. Illustrate with examples the limitations of Williamson synthesis for the preparation of certain
types of ethers.
Ans. The reaction of Williamson synthesis involves SN2 attack of an alkoxide ion on a primary alkyl
halide.
CH3 CH3
+
CH3–C–O Na + CH3 – Cl CH3–O–C–CH3 + NaCl
CH3 CH3
But if secondary or tertiary alkyl halides are taken in place of primary alkyl halides, then
elimination would compete over substitution. As a result, alkenes would be produced. This is
because alkoxides are nucleophiles as well as strong bases. Hence, they react with alkyl halides,
which results in an elimination reaction.
CH3
CH3–C–Cl +NaO–CH3 CH3–C=CH2 + CH3OH + NaCl
CH3 CH3
Tertiary alkyl halide Alkene
21. How is l-propoxypropane synthesised from propan-1-ol ? Write mechanism of this reaction.
+
H
Ans. 2CH3CH2CH2–OH CH3CH2CH2–O–CH2CH2CH3
Propane-1-ol 1-Propoxypropane
The mechanism of this reaction involves the following three steps :
Step 1 : Protonation
+
H
H +
CH3CH2CH2–O–H CH3CH2CH2–O –H
Propane-1-ol
Step 2 : Nucleophilic attack
+ H +
CH3CH2CH2–O + CH3–CH2–CH2–O CH3CH2CH2–O–CH2–CH2–CH3
H
H H
+
H2 O
Step 3 : Deprotonation
+ +
CH3CH2CH2–O–CH3CH2CH2 CH3CH2CH2 – O – CH2CH2CH3 + H
H 1-Propoxypropane
22. Preparation of ethers by acid dehydration of secondary or tertiary alcohols is not a suitable
method. Give reason.
Ans. The formation of ethers by dehydration of alcohol is a bimolecular reaction (SN2) involving the
attack of an alcohol molecule on a protonated alcohol molecule. In this method, the alkyl group
should be unhindered. In case of secondary or tertiary alcohols, the alkyl group is hindered. As a
result, elimination dominates substitution. Hence, in place of ethers, alkenes are formed.
23. Write the equation of the reaction of hydrogen iodide with :
(i) 1-propoxypropane
(ii) Methoxybenezene and
(iii) Benzyl ethyl ether
E 10
9
Chemistry
ALLEN
373 K
Ans. (i) C2H5CH2–O–CH2C2H5 + HI CH3CH2CH2–OH+CH3CH2CH2 – I
l-Propoxypropane Propan-1-ol 1-Iodopropane
OCH3 OH
(ii) + HI + CH3–I (SN2)

Methoxy benzene Phenol
CH2–O–C2H5 CH2l
(iii) + HI + C2H5–OH (SN1)

Benzyl ethyl ether Benzyl iodide Ethanol
24. Explain the fact that in aryl alkyl ethers

(i) The alkoxy group activates the benzene ring towards electrophilic substitution and
(ii) It directs the incoming substituents to ortho and para positions in benzene ring.
O–R
+ HI
Ans.
Aryl alkyl ether
In arly alkyl ethers, due to the + R effect of the alkoxy group, the electron density in the benzene
ring increases as shown in the following resonance structure.
O–R + O–R + O–R + O–R O–R
Thus, benzene is activated towards electrophilic substitution by the alkoxy group.

(ii) It can also be observed from the resonance structures that the electron density increases
more at the ortho and para positions than at the meta position. As a result, the incoming
substituents are directed to the ortho and para positions in the benzene ring.
25. Write the mechanism of the reaction of HI with methoxymethane.
Ans. The mechanism of the reaction of HI with methoxymethane involves the following steps :
Step1 : Protonation of methoxymethane :
H
+ –
CH3–O–CH3 + H—I CH3–O–CH3 + I
Step2 : Nucleophilic attack of I–

H
+
–
I + CH3–O–CH3 CH3I + CH3OH
26. Write equations of the following reactions :

(i) Friedel-Crafts reaction-alkylation of anisole.
(ii) Nitration of anisole.
(iii) Bromination of anisole in ethanoic acid medium.
(iv) Friedel-Craft's acetylation of anisole.
110 E
CBSE
ALLEN
OCH3 OCH3 OCH3
Anhyd AlCl3 CH3
Ans. (i) + CH 3Cl
CS2 +
CH3
Anisole 4-Methoxytoluene 2-Methoxytoluene
(Major) (Minor)
OCH3 OCH3 OCH3
H 2SO 4 NO2
(ii) HNO 3
+
NO2
Anisole 2-Nitroanisole 4-Nitroanisole
(Minor) (Major)
OCH3 OCH3 OCH3
Br2 in Br
(iii) Ethanoic acid
+
Br
Anisole p-Bromoanisole o-Nitroanisole
(Major) (Minor)
OCH3 OCH3 OCH3
Anhyd AlCl 3 COCH3
(iv) + CH 3COCl +
COCH3
Anisole Ethanoyl chloride 2-Methoxy- 4-Methoxy-
acetophenone acetophenone
(Minor) (Major)
27. When 3-methylbutan-2-ol is treated with HBr, the following reaction takes place :
Br
HBr
CH3–CH–CH–CH3 CH3–C–CH2–CH3
CH3 OH CH3
Give a mechanism for this reaction.
Ans. The mechanism of the given reaction involves the following steps :
Step 1 : Protonation
+
H
CH3–CH–CH–CH3 CH3–CH–CH–CH3
CH3 OH CH3 OH2
+
3-Methylbutan-2-ol
Step 2 : Formation of 2° carbocation by the eleimination of a water molecule

+
CH3–CH–CH–CH3 –H2O
CH3–CH–CH–CH3
CH3 O+H2 CH3
2°Carbocation
Step 3 : Re-arrangement by the hydride-ion shift
H
+ 1-2-hydride shilt +
CH3–C–CH–CH3 CH3–C–CH2–CH3
CH3 CH3
3°Carbocation
(more stable)
Step 4 : Nucleophilic attack

Br
+ —
CH3–C–CH2–CH3 Br CH3–C–CH2–CH3
CH3 CH3
2-Bromo-2-methylbutane
E 11
1
Chemistry
ALLEN
EXERCISE-3 EXEMPLAR
1. What is the correct order of reactivity of alcohols in the following reaction ?
R—OH + HCl 
ZnCl2
 R—Cl + H2O
(a) 1° > 2° > 3° (b) 1° < 2° > 3° (c) 3° > 2° > 1° (d) 3° > 1° > 2°
Ans. (c)
2. CH3CH2OH can be converted into CH3CHO by ………
(a) catalytic hydrogenation
(b) treatment with LiAlH4
(c) treatment with pyridinium chlorochromate (pcc)
(d) treatment with KMnO4
Ans. (c)
3. Which of the following compounds is aromatic alcohol ?
OH CH2 OH CH2OH OH
CH3 CH3
(A) (B) (C) (D)
(a) A, B, C, D (b) A, D (c) B, C (d) A
Ans. (b)
4. Which of the following compounds will react with sodium hydroxide solution in water ?
(a) C6H5OH (b) C6H5CH2OH (c) (CH3)3COH (d) C2H5OH
Ans. (a)
5. Phenol is less acidic than ………
(a) ethanol (b) o-nitrophenol
(c) o-methylphenol (d) o-methoxyphenol
Ans. (b)
6. Which of the following is most acidic ?
(a) Benzyl alcohol (b) Cyclohexanol (c) Phenol (d) m-chlorophenol
Ans. (d)
7. Mark the correct order of decreasing acid strength of the following compounds :
OH OH CH2OH OH OH
OCH3 NO2
NO2 OCH3
(i) (ii) (iii) (iv) (v)

(a) V > IV > II > I > III (b) II > IV > I > III > V
(c) IV > V > III > II > I (d) V > IV > III > II > I
Ans. (b)
112 E
CBSE
ALLEN
8. Arrange the following compounds in increasing order of boiling point. Propan-1-ol, butan-1-ol,
butan-2-ol, pentan-1-ol
(a) Propan-1-ol, butan-2-ol, butan-1-ol, pentan-1-ol
(b) Propan-1-ol, butan-1-ol, butan-2-ol, pentan-1-ol
(c) Propan-1-ol, butan-2-ol, butan-1-ol, pentan-1-ol
(d) Propan-1-ol, butan-1-ol, butan-2-ol, pentan-1-ol
Ans. (a)
(SHORT ANSWER TYPE)
9. Name the factors responsible for the solubility of alcohols in water.
Ans. Solubility of alcohols in water depends upon the two factors.
(i) Hydrogen bonding Higher the extent of hydrogen bonding, higher is the solubility. The
hydrogen group of alcohol from hydrogen bonding. Solubility increases with increase in
the number of –OH groups in alcohols of comparable molecular masses.
H3 C—CH2 —CH2 —OH < CH3 —CH—CH2 —OH
(i) (ii)
OH
(i) Compound (ii) will form stronger H-bond due to two –OH group and hence has higher
boiling point.
(ii) Size of alkyl/aryl group Higher the size of alkyl/aryl group (hydrocarbon part), lower is the
extent of hydrogen bonding and lower is the solubility. Hence,
H3C—CH2—OH > CH3CH2—CH2OH > CH3CH2CH2—CH2OH
10. What is denatured alcohol ?
Ans. Alcohol is used in large quantities in the manufacture of alcoholic liquors. It continuous use
damages the various vital organs. Therefore, to refrain the people from drinking alcohol, heavy
excise duty is levied on the sale of alcoholic beverages. But, it is used in various industries as it is
a very good solvent.
Therefore, industrial alcohol must be cheap. Thus, to provide cheaper alcohol to industries and
to refrain people from drinking alcohol, it is mixed with some copper sulphate, pyridine methyl
alcohol or acetone.
Alcohol is made unfit for drinking by mixing some quantity of any of these substances in it. This
is called denatured alcohol.
11. Out of 2-chloroethanol and ethanol which is more acidic and why ?
Ans. 2-chloroethanol is more acidic than ethanol. Due to —I effect (electron withdrawing group) of
the Cl-atom electron density in O—H bond decreases. So, O—H bond of 2-chloroethanol
becomes weaker than O—H bond of ethanol. Thus, 2-chloroethanol is more acidic than ethanol.
Cl CH2 CH2 O H > CH3 CH2  O H
Stronger acid due to –I effect of Cl.
E 11
3
Chemistry
ALLEN
12. Out of o-nitrophenol and p-nitrophenol, which is more volatile ? Explain.
Ans. o-nitrophenol is more volatile than p-nitrophenol due to presence of intramolecular hydrogen
bonding. In para nitrophenol intermolecular hydrogen bonding is present. This intermolecular
hydrogen bonding causes the association of molecules.
O O O
N H
----HO N O
O O---HO N
O---
o-nitrophenol p-nitrophenol
(Intramolecular H-bonding) (Intermolecular H-bonding)
13. Out of o-nitrophenol and o-cresol which is more acidic ?
Ans. The acidic character of alcohols is due to the polar nature of O—H bond. Higher the polarity of
O—H bond, more will be the acidic strength. Due to —I and –R effect of nitro group, electron
density decreases in the O—H bond of o-nitrophenol and thus polarity increases.
+
O—H O OH O O—H O1 O—H
N N N CH3
+ – + 1
O O O
(–I effect) (–R effect) (+I effect)

Whereas due to +I effect of –CH3 group, electron density increases in the O–H bond of o-cresol.
Thus, O–H bond of o-nitrophenol is weaker than O–H bond of o-cresol and o-nitrophenol is more
acidic than o-cresol.
14. Arrange the following compounds in increasing order of acidity and give a suitable explanation.
Phenol, o-nitrophenol, o-cresol
Ans. Nitro group shows –I and –R effect as follows :
+
O—H O OH O O—H O1
N N N
+ +
O O – O1 etc.
(–I effect) (–R effect)

Due to this –I and –R effect of o-nitrophenol, it is a stronger acid than phenol. On the other hand,
–CH3 group produces +I effect –I and –R effect increases the acidic strength by increasing the
polarity of –OH bond while +I effect decreases the polarity due to increase in electron density on
–OH bond. So, o-cresol is a weaker acid than phenol. Thus, the correct order of o-cresol < phenol
< o-nitrophenol.
15. What happens when benzene diazonium chloride is heated with water ?
Ans. When benzene diazonium chloride is heated with water then phenol is formed.
1
N2 Cl OH
H2 O
+ N2 + HCl
warm
Benzene diazonium Phenol

chloride
114 E
CBSE
ALLEN
16. Name the enzymes and write the reactions involved in the preparation of ethanol from sucrose by
fermentation.
Ans. Sucrose is converted to glucose and fructose in the presence of an enzyme, invertase or sucrose.
Glucose and fructose undergo fermentation in the presence of another enzyme, zymase. Both
these enzymes are present in yeast.
C12H22O11 + H2O 
Invertase/sucrose
C6H12O6 + C6H12O6
Sucrose Glucose Fructose
C6H12O6  2CH3CH2OH + 2CO2
Zymase
Glucose/Fructose Ethanol
17. Explain why is O=C=O non-polar while R—O—R is polar ?
Ans. CO2 is a linear molecule. The dipole moment of two C=O bonds are equal and opposite and they
cancel each other and hence the dipole moment of CO2 is zero and it is a non-polar molecule.
O=C=O
=0
While for ethers, two dipoles are pointing in the same direction. These two dipoles do not cancel
the effect of each other. Therefore, there is a finite resultant dipoles and hence R—O—R is a
polar molecule.
O
R 110° R
0
18. Write steps to carry out the conversion of phenol to aspirin.
Ans.
OH ONa OH OH
COONa COOH
NaOH CO2/400K dil HCl
–H2O 4-7 atm –NaCl
(Kolbe’s
Phenol Sodium Salicylic
reaction)
phenoxide acid
COOH COOH
OH OCOCH3
H+
+ (CH3CO)2O + CH3COOH
Acetic
2-hydroxybenzoic anhydride
Acetylsalicylic acid
acid
2-acetoxy benzoic acid
or
or aspirin
Salicylic acid
19. In Kolbe’s reaction, instead of phenol, phenoxide ion is treated with carbon dioxide. Why ?
Ans. In phenoxide ion, the ability to give lone pair of electrons to the benzene ring is more in
comparison to phenols. Therefore, the reactivity of phenoxide ion towards electrophilic
substitution reaction is more in comparison to phenols.
E 11
5
Chemistry
ALLEN
Thus, phenoxide ion being a stronger nucleophile reacts easily with CO2 (weak electrophile) than
phenols in Kolbe’s reaction.
OH ONa OH
COOH
NaOH (i) CO2
(ii) H+
(Kolbe’s reaction) 2-hydroxybenzoic acid
Note : Kolbe’s process is also known as Kolbe-Schmitt reaction. This reaction is precursor to
aspirin.
20. Dipole moment of phenol is smaller than that of methanol. Why ?
Ans. Dipole moment depends upon the polarity of bonds. Higher the polarity of bonds in molecule,
higher will be its dipole moment. In phenol carbon is sp2 hybridised and due to this reason
benzene ring is producing electron withdrawing effect.
On the other hand, carbon of methanol is sp3 hybridised and produces electron releasing effect
(+I effect). Thus, C—O bond in phenol is less polar than C—O bond in methanol and therefore,
the dipole moment of phenol is smaller than that of methanol.
OH
and CH3OH
=1.71D
=1.54D
21. Ethers can be prepared by Williamson synthesis in which an alkyl halide is reacted with sodium
alkoxide. Di-tert-butyl ether can’t be prepared by this method. Explain.
Ans. In order to prepared di-tert-butyl ether, sodium tert-butoxide must be reacted with tert-butyl
bromide. Alkoxides are not only nucleophiles but they are strong base as well. They reacts with
3° alkyl halides leading to the elimination reaction.
When tert-butyl-bromide reacts with sodium tert-butoxide instead of substitution, elimination
takes place. As a result of this elimination reaction, iso butylene is formed instead of di-tert butyl
ether.
CH2—H CH3 CH2 CH3
Elimination
H3C—C—Br + Na—O—C—CH3 H3C—C—CH3+H3C—C—OH+NaBr
Iso-butylene
CH3 CH3 CH3
Sodium, tert butoxide 2-methylpropan-2-ol
Tert-butyl bromide
CH2—H CH3
Substitution
H3C—C—Br + Na—O—C—CH3 No reaction
CH3 CH3
Tert-butyl bromide Sodium, tert butoxide
116 E
CBSE
ALLEN
22. Why is the C—O—H bond angle in alcohols slightly less than the tetrahedral angle whereas the
C—O—C bond angle in ether is slightly greater?
••
Ans. The bond angle in C— O —H in alcohols is slightly less than tetrahedral angle (109°28’). It is
••
due to the repulsion between the unshared electrons pairs of oxygen. In alcohols, two lone pair of
electrons are present. Therefore, there is comparatively more repulsion and less bond angle.
The C—O—C bond angle in ether is slightly greater than the tetrahedral angle due to the
repulsive interaction between the two bulky (—R) groups.
H O H O H
H — C 108.9° H H — C 111.7° C — H
H Methanol H H
Methoxymethane
23. The carbon-oxygen bond in phenol is slightly stronger than that in methanol. Why ?
Ans. Positive resonance effect is observed in phenols. Due to this +R effect, lone pair of electrons of
–OH group are in conjugation with electrons of the ring and the following resonance hybrid are
obtained.
OH OH
From the above resonating structure, it is very clear that C—O bond of phenol acquires some
partial double bond character while the C—O bond of methanol is purely single bond. Therefore,
the carbon-oxygen bond in phenol is slightly stronger than that in methanol.
E 11
7
Chemistry
ALLEN
EXERCISE-4 MCQ, A/R, CASE BASED QUESTIONS
(CLASSIFICATION, PREPARATION OF ALCOHOL, REDUCTION)
1. Butane-2-ol is:
(a) Primary alcohol (b) Secondary alcohol
(c) Tertiary alcohol (d) Aldehyde
2. In the following reaction 'A' is:
C2 H 5 MgBr  H 2 C  CH 2 
H 2O
A
\ /
O
(a) C2 H 5CH 2 CHO (b) C2 H 5CH 2 CH 2 OH (c) C2 H 5CH 2 OH (d) C2 H 5CHO
3. C2 H 5 MgI reacts with HCHO to form last product–
(a) CH 3CHO (b) C3 H 7 OH (c) CH3COCH 3 (d) CH 3COOCH 3
4. The reagent(s) used for the reduction of aldehydes and ketone is/are:
(a) finely divided metals such as Pt/Pd/Ni (b) sodium borohydride
(c) lithium aluminium hydride (d) All of the above
5. Which of the following are not used to convert RCHO into RCH2OH?
(a) H2/Pd (b) LiAlH4
(c) NaBH4 (d) Reaction with RMgX followed by hydrolysis
6. Which of the following alcohol contains Csp3 – OH bond?
(a) Allylic alcohol (b) Vinylic alcohol (c) Phenols (d) None of these
7. Give IUPAC name of the compound given below:
H 3C  CH  CH 2  CH 2  CH  CH 3
| |
Cl OH
(a) 5-chlorohexan-2-ol (b) 2-chlorohexan-5-ol
(c) 2-hydroxy-5-chlorohexane (d) 2-chloro-5-hydroxyhexane
8. Alkenes react with water in the presence of acid as catalyst to form alcohols.
The reaction takes place in accordance with –
(a) Hofmann elimination rule (b) Saytzeff rule
(c) Markownikoff's rule (d) Anti-Markownikoff's addition
9. Arrange the following compounds in the increasing order of boiling point.

Propan-1-ol, butane-1-ol, butan-2-ol, pentan-1-ol.
(a) Propan-1-ol, butan-2-ol, butan-1-ol, pentan-1-ol
(b) Propan-1-ol, butan-1-ol, butan-2-ol, pentan-1-ol
(c) Pentan-1-ol, butan-2-ol, butan-1-ol, propan-1-ol
(d) Pentan-1-ol, butan-1-ol, butan-2-ol, propan-1-ol
118 E
CBSE
ALLEN
(CHEMICAL REACTION OF ALCOHOL, OXIDATION)
10. Propene, CH 3  CH  CH 2 can be converted to 1-propanol by oxidation. Which set of reagents
among the following is ideal to effect the conversion?
(a) Alkaline KMnO 4 (b) B2 H 6 and alkaline H 2 O 2
(c) O3 / Zn dust (d) OsO 4 / CH 4 , Cl2
11. Conc. H 2SO 4 reacts with C2 H 5OH at 170o C to form –

(a) CH 3COCH 3 (b) CH 3COOH (c) CH 3CHO (d) C2 H 4
12. Isopropyl alcohol heated at 300o C with copper catalyst to form –

(a) Acetone (b) Dimethyl ether (c) Acetaldehyde (d) Ethane
13. The final product of the oxidation of ethyl alcohol is :
(a) Ethane (b) Acetone (c) Acetaldehyde (d) Acetic acid
14. Lucas test is used to distinguish between –
(a) 1o , 2o and 3o alcohols (b) 1o , 2o and 3o amines
(c) Aldehydes and ketones (d) Alkenes and alkynes
15. The acidic character of alcohols is due to the –
(a) non-polar nature of O-H bond (b) polar nature O-H bond
(c) non-polar nature of C-O bond (d) polar nature of C-O bond
(PREPARATION & PROPERTIES OF PHENOL)
16. Sodium benzene sulphonate reacts with NaOH and then on acidic hydrolysis, it gives:
(a) Phenol (b) Benzoic acid
(c) Benzene (d) Disodium benzaldehyde
17. Phenol is obtained by heating aqueous solution of –
(a) Aniline (b) Benzene diazonium chloride
(c) Benzoic acid (d) None of these
18. The reaction of conc. HNO3 and phenol forms –
(a) Benzoic acid (b) Salicylic acid
(c) o-and p-nitrophenol (d) Picric acid
19. At low temperature phenol reacts with Br2 in CS2 to form–
(a) m-bromophenol (b) o-and p-bromophenol

(c) p-bromophenol (d) 2, 4, 6-tribromophenol
20. In presence of NaOH, phenol react with CHCl3 to form o-hydroxy benzaldehyde. This reaction
is called–
(a) Riemer-Tiemann's reaction (b) Sandmeyer's reaction
(c) Hoffmann's degradation reaction (d) Gattermann's aldehyde synthesis
E 11
9
Chemistry
ALLEN
21. Which of the following compound(s) is/are aromatic alcohols?
OH CH2OH CH2OH OH
OH
HO CH3 CH3
I II III IV
(a) I, II, III and IV (b) I and IV (c) II and III (d) I
22. The reaction of alcohol/phenol with acid chloride is carried out in the presence of a pyridine in
order to –
(a) neutralise HCl which is formed during the reaction
(b) shift the equilibrium to right hand side
(c) Both (a) and (b)
(d) None of these
23. In the given reaction,
OH
Br2 in CS2
273 K
'X'
is:
Br2 water
'Y'
OH OH OH OH
Br Br
(a) X Y (b) X Y
Br Br
OH OH OH OH
Br Br Br Br
(c) X Y (d) X Y
Br Br Br Br
24. Mark the correct order of decreasing acid strength of the following compounds.
OH OH OH OH OH
OCH3 NO2
I III IV
NO2 OCH3
II V
(a) V > IV > II > I > III (b) II > IV > III > I > V
(c) IV > III > II > I > V (d) I > II > III > IV > V
120 E
CBSE
ALLEN
25. Phenol is less acidic than –
(a) ethanol (b) o-nitrophenol
(c) o-methylphenol (d) o-methoxyphenol
(PREPARATION & PROPERTIES OF ETHER)
26. Dimethyl ether and ethyl alcohol are:
(a) Branched isomer (b) Position isomer (c) Functional isomer (d) Tautomer
27. Diethyl ether can be decomposed by heating with:
(a) HI (b) NaOH (c) Water (d) KMnO 4
28. Methyl-terbutyl ether on heating with HI of one molar concentration gives:
(a) CH 3 I  (CH 3 )3 COH (b) CH 3OH  (CH 3 )3 Cl
(c) CH 3 I  (CH 3 )3 Cl (d) None of the above
29. Dimethyl ether when heated with excess HI gives:
(a) CH 3I and CH 3OH (b) CH 3I and H 2 O
(c) C2 H 6  CH 3 I and CH 3OH (d) CH 3 I and HCHO
30. IUPAC name of m-cresol is ___________.
(a) 3-methylphenol (b) 3-chlorophenol (c) 3-methoxyphenol (d) benzene-1, 3-diol
31. C6H5OCH2CH3 is named as:
(a) phenetole (b) ethylphenyl ether
(c) ethoxy benzene (d) All of these
32. IUPAC name of the compound CH3–CH–OCH3 is:
CH3
(a) 1-methoxy-1-methylethane (b) 2-methoxy-2-methylethane
(c) 2-methyoxpropane (d) isopropylmethyl ether
33. In the given reaction,
OCH3
Br2 in
ethanoic
Product formed is:

OCH3 OCH3
Br
(a) (90% yield) (b) (90% yield)
Br
OCH3 OCH3
(c) (90% yield) (d) (10% yield)

Br Br
E 12
1
Chemistry
ALLEN
34. The large difference in the boiling points of alcohols and ethers is due to the presence of –
(a) van der Waals' forces in alcohols (b) dipole-dipole interaction in alcohols
(c) hydrogen bonding in alcohols (d) ion-ion interaction in alcohols
35. Williamson's synthesis involves the ..... attack of an alkoxide ion on primary alkyl halide.
(a) SN1 (b) SN2 (c) E1 (d) E2
ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. b b b d d a a c a b
Q. No. 11 12 13 14 15 16 17 18 19 20
Ans. d a d a b a b d b a
Q. No. 21 22 23 24 25 26 27 28 29 30
Ans. a c d b b c a a b a
Q. No. 31 32 33 34 35
Ans. d c a c b
122 E
CBSE
ALLEN
Following questions have assertion followed by reason. Answer them according to following
options:
1. Assertion (A) : Bond angle in alcohol is slightly less than tetrahedral angle.
Reason (R) : Unshared pair of oxygen repel each other.
2. Assertion (A) : Carbon oxygen bond in phenol is shorter in phenol.
Reason (R) : Due to conjugation of lone pair with benzene ring.
3. Assertion (A) : The bond angle is slightly greater than the tetrahedral angle due to the repulsive
interaction between the two bulky (–R) groups.
Reason (R) : Lone pairs on oxygen repel each other.
4. Assertion (A) : The boiling points of alcohols and phenols increase with increase in the number
of carbon atoms.
Reason (R) : van der Waals forces increases with increase in size of carbon chain.
5. Assertion (A) : Some of the alcohols are volatile in nature.
Reason (R) : Alcohols have hydrogen bonding.
6. Assertion (A) : Alcohols and phenols are acidic in nature.
Reason (R) : They can donate a proton to a stronger base(B:).
7. Assertion (A) : Secondary alcohols are less acidic than primary alcohols.
Reason (R) : Electronegativity of the carbon atom is higher in secondary alcohol.
8. Assertion (A) : Phenol is more acidic than a primary alcohol.
Reason (R) : Phenoxide ion is more stable than alkoxide ion.
9. Assertion (A) : m-nitrophenol is less acidic than p-nitrophenol.
Reason (R) : An electron withdrawing group increases acidity of phenol.
10. Assertion (A) : Tertiary alcohols do not undergo oxidation reaction.

Reason (R) : They need drastic condition to get oxidise.
11. Assertion : p-nitrophenol is more acidic than phenol.
Reason (R) : Nitro group helps in the stabilisation of the phenoxide ion by dispersal of negative
charge due to resonance
E 12
3
Chemistry
ALLEN
12. Assertion (A) : Boiling points of alcohols and ethers are high.
Reason (R) : It can form intermolecular hydrogen-bonding.
13. Assertion (A) : Ethanol is a weaker acid than phenol.
Reason (R) : Sodium ethoxide may be prepared by the reaction of ethanol with aqueous NaOH.
ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. a a b a b a c b b c
Q. No. 11 12 13
Ans. a a a
124 E
CBSE
ALLEN
CASE BASED
Case I
Phenols undergo electrophilic aromatic substitution reaction readily because –OH group attached to
the benzene ring activates the benzene ring towards electrophilic substitution reaction.
Further, it directs the incoming group to ortho and para positions in the ring as these positions
become electron rich due to the resonance effect.
The delocalisation of electrons (or resonance) can be represented as
+ + +
OH OH OH OH OH
1

Common electrophilic aromatic substitution reactions taking place in phenol are nitration,
sulphonation and halogenation.
(a) What happended when phenol treated with dfilute nitric acid at low temperature ?
Ans. Phenol treatment with dilute nitric acid undergo nitration at low temperature to give a
mixture of ortho and para nitrophenol.
OH OH OH
NO2
dil. HNO3 +
–H2O
NO2
OR
Complete the following reaction :
OH
'X' and 'Y'
OH OH
Br
Ans. 'X'  'Y' 
Br
(b) Write the IUPAC name and structure of picric acid ?
OH
Ans.
O2N NO2
NO2
2,4,6-trinitrophenol or
picric acid
(c) Why the incoming group direct attached to ortho and para positions in the rings ?
Ans. Because of these positions become electron rich due to the resonance effect.
E 12
5
Chemistry
ALLEN
Case II
In phenol, OH-group directly attached to sp2-hybridised carbon of benzene ring acts as an
electron withdrawing group and is responsible for the acidic nature of phenol. Due to this, the
lone pair of electrons of O—H are involved in resonance with C-atoms of benzene ring. As a
result of resonance, the oxygen atom acquires a partial positive charge. This weakens the O—H
bond and, thus facilitates the release of a proton.
As a result, phenols behave as Bronsted acids. The reaction of phenol with aqueous NaOH
indicates that phenols are stronger acids than alcohols.
The reactions of phenol with metals such as Na, Al and NaOH indicate its acidic nature.
(a) Which reaction indicates that phenols are stronger acids than alcohols ?
Ans. The reaction of phenol with aqueous NaOH indicates that phenols are stronger acids than
alcohols.
(b) What is the decreasing order of acidic nature of phenols ?
Phenols, m-cresol, o-cresol, p-cresol
Ans. Phenol > m-cresol > o-cresol > p-cresol
(c) Which will increase the acidity of phenol ?
Ans. –NO2, –CN, –halogen groups wil increase the acidity of phenol. these are electron
withdrawing groups and stabilize the negative charge of phenoxide ion.
OR
p-nitrophenol is more acidic than phenol, why ?
Ans. Nitro group helps in the stabilisation of phenoxide ion by dispersal of negative.
126 E
CBSE
ALLEN
PREVIOUS YEAR QUESTIONS
1. Which of the following reactions are feasible ? [1] (CBSE-2023)

(a) CH3CH2Br + Na+O–C(CH3)3  CH3CH2–O–C(CH3)3
(b) (CH3)3C –Cl + Na+O–CH2CH3  CH3CH2–O–C(CH3)3
(c) Both (a) and (b)
(d) Neither (a) nor (b)
Ans. (a)
2. The C–O–C bond angle in the ether molecule is : [1] (Term-I _2021-2022)
(a) 101° (b) 90° (c) 120° (d) 180º
Ans. (a)
3. Which of the following reagents will not convert ethyl alcohol into ethyl chloride ?
[1] (Term-I_2021-2022)
(a) PCl5 (b) NaCl (c) SOCl2 (d) HCl/ZnCl2
Ans. (b)
4. Phenol on being heated with concentrated H2SO4 and then with concentrated HNO3
gives : [1] (Term-I _2021-2022)
(a) o-nitrophenol (b) 2,4,6-trinitrophenol (c) p-nitrophenol (d) m-nitrophenol
Ans. (b)
5. Lucas reagent produces cloudiness immediately with : [1] (Term-I _2021-2022)
CH3
(a) CH3–C–CH3 (b) CH3–CH–CH2–CH3
OH OH
(c) CH3–CH2–CH2–OH (d) CH3–CH–CH2–OH
CH3
Ans. (a)
6. Major products formed by heating (CH3)3C–O–CH2–CH3 with HI are: [1] (Term-I _2021-2022)
(a) (CH3)3C–I and CH3CH2OH (b) (CH3)3C–OH and CH3CH2I
(c) (CH3)3C–I and CH3CH2I (d) (CH3)3C–OH and CH3CH2OH
Ans. (a)
7. A compound (X) with the molecular formula C3H8O can be oxidised is another compound (Y)
whose molecular formula is C3H6O2. The compound (X) may be: [1] (Term-I_2021-2022)
(a) CH3–CH2–OCH3 (b) CH3–CH–CH3
OH
(c) CH3–CH2–CH2–OH (d) CH3–CH2–CHO
Ans. (c)
E 12
7
Chemistry
ALLEN
H O
8. In the following reaction: CH 3  Br 
dry ether  X 
Mg 2
 Y . 'Y' will be :
[1] (Term-I _2021-2022)
(a) CH4 (b) CH3MgBr (c) CH3–OH (d) CH3–CH3
Ans. (a)
9. Arrange the following compounds in decreasing order of their acidic character :
OH OH OH
CH3 NO2 [1] (Term-I_2021-2022)

(I) (II) (III)
(a) II > I > III (b) II > III > I (c) III > I > II (d) I > II > III
Ans. (b)
10. Match the following :
I II
(i) Salicyl aldehyde (A) Kolbe's reaction
(ii) o-nitrophenol (B) Williamson's synthesis
(iii) Salicylic acid (C) Intramolecular Hydrogen bonding
(iv) p-nitrophenol (D) Reimer-Tiemann reaction
(v) Unsymmetrical ether
Which of the following is the best matched option ? [1] (Term-I _2021-2022)
(a) i-A, ii-C, iii-D, iv-B (b) i-D, v-B, iii-C, iv-A
(c) i-D, v-B, ii-C, iii-A (d) i-B, ii-C, iii-A, iv-D
Ans. (c)
11. Which of the following intermediates is formed in the reaction shown below ?
CH3 – CH2 – OH + HI CH3 – CH2 – I + H2O [1] (Term-I _2021-2022)
 
(a) CH 3CH 2 O H 2 (b) CH 3  CH 2
 
(c) Both CH 3CH 2 O H 2 and CH 3  CH 2 (d) CH 3CH 2  O CH 2  CH 3
Ans. (c)
+ – + H
CH3– CH2– O – H + H– I CH3– CH2– O +I
H
+
CH3– CH2 + H2O

CH 3  C H 3  I  CH 3  CH 2  I
128 E
CBSE
ALLEN
12. The reaction :
OH OH
1. CHCl3 + NaOH(aq) CHO
+
2. H3O
is an example of [1] (Term-I _2021-2022)

(a) Reimer-Tiemann reaction
(b) Kolbe's reaction
(c) Williamson's synthesis
(d) Wurtz reaction
Ans. (a) Reimer Tiemann (formylation) Rxn
OH OH OH O
H OH
CH –H2O C–H
+ Cl–CH Cl + KOH OH
Cl KOH –HCl
–2KCl
Salicyl aldehyde
B2H6
13. In the following reaction : PhCH = CH2 – (?) (Where Ph is Phenyl)
H2O2/OH
The product formed is : [1] (Term-I _2021-2022)

(a) PhCH–CH3
OH
(b) PhCH2 – CH2 – OH

(c) PhCH2CHO
(d) Ph–C–CH3
O
H O /NaOH
Ans. (b) Ph CH = CH2 + B2H6 (Ph–CH2–CH2–)3B 
2 2

 3Ph–CH2–CH2–OH
14. Phenol is more acidic than ethanol because : [1] (Term-I _2021-2022)
(a) Ethoxide ion is more stable than Phenoxide ion
(b) Phenoxide ion is more stable than Ethoxide ion
(c) Phenol undergoes electrophilic substitution reaction.
(d) Phenol undergoes protonation easily.

Ans. (b)
O
Due to resonance phenoxide ion is more stable and availability of H+ ion increases. While
RO– do not shows resonance and it is re-combine with H+ ion and availability of H+ decreases.
E 12
9
Chemistry
ALLEN
15. The structure(s) of the major product (s) expected from the mononitration of 3-methylphenol will
be : [1] (Term-I _2021-2022)
OH OH OH OH
O2N NO2
(a) and (b) and
CH3 CH3 CH3 CH3
NO2 NO2
OH OH
OH OH NO2
(c) O2N NO2 (d) and
and O2N CH3 CH3
CH3 CH3
OH OH OH
dil. HNO3 NO2
Ans. (a) +
CH3 CH3 CH3
NO2
16. 1-Phenylethanol may be prepared by the reaction of C6H5MgBr with : [1] (Term-I_2021-2022)
(a) CH3–C– CH3 (b) CH3–CHO (c) HCHO (d) CH3–CH2–CHO
O
Ans. (b)
H3C H3C + – H3C
C6H5 MgBr + C=O C–O C – OMgBr
H H H
C6H5
+ H2O
CH3–CH–OH H3C Br
C6H5 C–OH + Mg OH
1-Phenyl Ethanol H
C6H5
17. Which reagent will be required for one step conversion of benzenediazonium chloride to
phenol ? [1] (Term-I_2021-2022)
(a) Cu2Cl2 (b) NaOH(aq) (c) H2O (d) Alcoholic KOH
Ans. (c)
N2+Cl– OH
H2O
warm + N2 + HCl
N2+Cl– OH

+H2O + N2 + HCl
130 E
CBSE
ALLEN
18. Write the IUPAC name of the following compound : [1] (CBSE 2020)
CH = CH – CH 2 – OH
Ans. 3-phenyl-prop-2-en-1-ol
19. Write the IUPAC name of the given compound : [1] (CBSE 2019)
CH3
CH3 C CH2 OH
CH3
Ans. 2, 2–Dimethylpropan–1–ol
20. Rearrange the following compounds in the increasing order of their boiling points:
CH3 – CHO, CH3 – CH2 – OH, CH3 – CH2 – CH3 [1] (CBSE 2019)
Ans. CH3 – CH2 – OH > CH3 – CHO > CH3 – CH2 – CH3
21. Write the IUPAC name of the following : [1] (CBSE 2018)
CH3
CH3 – C – CH – CH3
C2H5 OH
Ans.
22. Write the chemical equation involved in the following reactions : [2] (CBSE 2023)
(a) Reimer-Tiemann reaction
(b) Acetylation of Salicylic acid
– + – +
OH O Na O Na OH
CHCl2 CHO CHO
Ans. (a) CHCl3 + aq NaOH NaOH H+
COOH COOH
OH OCOCH3
(b)
Acetyl salicylic
acid
(Aspirin)
E 13
1
Chemistry
ALLEN
23. (a) Arrange the following compounds in the increasing order of their acid strength :
p-cresol, p-nitrophenol, phenol
(b) Write the mechanism (using curved arrow notation) of the following reaction :
H O
CH2 = CH2  3
CH3 – CH2+ + H2O [2] (CBSE 2020)
OR
Write the structures of the products when Butan-2-ol reacts with the following :
(i) CrO3 (ii) SOCl2
Ans. (a) p-cresol < Phenol < p-nitrophenol
H H
+
(b) C=C + H – O+ – H  – C – C + H 2O
OR
O Cl
(i) H 3C CH3 (ii) H 3C CH3

24. How would you convert ethanol to ethene? [2] (CBSE 2019)
Ans. Mechanism : The dehydration of ethanol involves the following steps :
(i) Formation of protonated alcohol :
H H H H H
H – C – C – O – H + H+ 
 H – C – C – O+ –– H
Fast
H H H H
Ethanol Protonated alcohol
(ii) Formation of carbocation :
H H H H H
H – C – C – O+ – H 
Slow
 H – C – C+ + H2O
H H H H
(iii) Formation of ethene :
H H
H H
H – C – C+   C=C + H+
H H
H H
25. Write the mechanism of the following reaction: [2] (CBSE 2019)
HBr
CH3CH2OH CH3CH2Br + H2 O
Ans. (i) Formation of protonated alcohol :
H H H H H
H – C – C – O – H + H+ 
 H – C – C – O+ –– H
Fast
H H H H
Ethanol Protonated alcohol
132 E
CBSE
ALLEN
(ii) Formation of carbocation :
H H H H H
H – C – C – O+ – H 
Slow
 H – C – C+ + H2O
H H H H
H H H H
+ –
(iii) H – C – C + Br 
 H – C – C–Br
H H H H
26. Write the equations involved in the following reactions: [2] (CBSE 2018)
(i) Reimer – Tiemann reaction
(ii) Williamson’s ether synthesis.
–+ –+
OH ONa ONa
CHCl2 CHO
Ans. (i) CHCl3 + aq.NaOH NaOH
+
Intermediate H
OH
CHO
Salicylaldehyde
(ii) Williamson ether synthesis is a laboratory method to prepare symmetrical and

unsymmetrical ethers by allowing alkyl halides to react with sodium alkoxides.
R – X + R' – O Na R – O – R' + NaX
Alkyl halide Sodium alkoxide Ether
This reaction involves SN2 attack of the alkoxide ion are obtained in case of primary alkyl
halides.
CH3 CH3
– +
CH3–CH–O Na + CH3–Br CH3–O–CH–CH3+NaBr
If the alkyl halide is secondary or tertiary, then elimination competes over substitution.
27. (i) Write the mechanism of the following reaction : [3] (CBSE 2023)
H+
2CH 3CH 2 OH  CH 3 – CH 2 – O – CH 2 – CH 3 + H 2 O
413 K
(ii) Why ortho-nitrophenol is steam volatile while para-nitrophenol is not?

OR
(b) What happens when
(i) Anisole is treated with CH3Cl/anhydrous AlCl3?
(ii) Phenol is oxidised with Na2Cr2O7/H+ ?
(iii) (CH3)3C–OH is heated with Cu/573 K ?
Write chemical equation in support of your answer.
E 13
3
Chemistry
ALLEN
Ans. (a)
(i) The mechanism of the reaction involves the following three steps:
H
H+
: :
: :
Step (i) : CH3—CH2—O—H CH3—CH2—O+—H
H +
+ CH3—CH2—O—CH2CH3 + H2O
Step (ii) : CH3CH2 —O: + CH3—CH2—O
:
H H
H
+
Step (iii) : CH3CH2— O —CH2CH3 CH3CH2—O—CH2CH3+H+
H
(ii) O-nitrophenol is steam volatile due to intra molecular hydrogen bonding while
P-nitrophenol is less volatile due to inter molecular H-bonding which causes the
association of molecules.
OCH3 OCH3 OCH3
CH3
(b) (i) +
CH3
Acetyl salicylic 2-methoxy
acid Toluene
(Aspirin)
OH O
(ii) Benzoquinone
O
CH3 CH3
(iii) CH3 – C –OH CH3 – C = CH2
CH3
28. Give reasons for the following:

(a) Protonation of Phenols is difficult whereas ethanol easily undergoes protonation.
(b) Boiling point of ethanol is higher than that of dimethyl ether.
(c) Anisole on reaction with HI gives phenol and CH3–I as main products and not iodobenzene
and CH3OH. [3] (CBSE 2020)
Ans. (a) In phenols lone pair of electron on oxygen are delocalized over benzene ring due to
resonance but in alcohol lone pair of electron on oxygen are localized & hence available for
protonation / + R- effect in phenol but not in ethanol.
(b) Due to intermolecular Hydrogen bonding
(c) Weaker (O-CH3) bond and stronger(O-C6H5) bond ,due to resonance / carbon in benzene is
sp2 hybridized due to which partial double bond character.
134 E
CBSE
ALLEN
29. Give reasons for the following :
(i) p-nitrophenol is more acidic than p-methylphenol.
(ii) Bond length of C – O bond in phenol is shorter than that in methanol.
(iii) (CH3)3C – Br on reaction with sodium methoxide (Na+ –OCH3). Gives alkene as the main
product and not an ether. [3] (CBSE 2019)
Ans. (i) Due to withdrawing effect of –NO2 group & donating effect of –CH3 group or
4-nitrophenoxide ion is more stable than 4-methylphenoxide ion
(ii) Due to +R effect of – OH group in phenol / due to sp2 hybridization of C–atom in
C–OH group in phenol whereas sp3 hybridization of C–atom in C–OH group in methanol.
(ii) Williamon’s synthesis is not applicable for tertiary alkyl halides as they yield alkenes
instead of ethers. The reaction of CH3ONa with (CH3)3C–Br gives exclusively 2–methyl
propene.
CH3
: :
CH3 – C – Br + Na – O – CH3 CH3 – C = CH 2 + NaBr

CH3 CH3
30. How would you obtain the following:
(i) Benzoquinone from phenol
(ii) 2-Methylpropane-2-ol from methylmagnesium bromide
(iii) Propane-2-ol from propene [3] (CBSE 2018)
Ans. (i) Benzoquinone from phenol
OH O
Na2Cr 2O7
H2SO4
O
Phenol benzoquinone
(ii) 2-Methylpropane-2-ol from methylmagnesium bromide

CH3 CH3 Br
H2O/H+
CH3 MgBr + CH3 C CH3  CH3 C CH3 CH3 C CH 3 + Mg
Methyl
Magnessium O O MgBr OH OH
bromide Propanone 2-Methypropane-2-ol
(iii) Propane-2-ol from propene

Br OH
HBr Aq. KOH
CH3 CH = CH2 CH3 – CH – CH3 -KBr CH3 CH CH3
Propane 2-Bromopropane Propane-2-ol

or 2-Propanol
31. How would you convert following: [3] (CBSE 2018)

(i) Phenol to benzoquinone
(ii) Propanone to 2-methylpropan-2 ol
(iii) Propene to propan-2-ol
E 13
5
Chemistry
ALLEN
OH O
Ans. (i) K2Cr2O7

H2SO4
O
Phenol benzoquinone
CH3 CH3
CH3
(ii) C = O + CH3MgBr  [CH3– C– OMgBr] H2O
CH3 C OH + Mg (OH) Br
CH3
Propanone CH3 CH3
2-methyl propan-2-ol
+
(iii) H
CH3 CH = CH2 + H2O CH3– CH – CH3
propene
OH
propan-2-ol
32. Alcohols and phenols react with active metals such as sodium, potassium and aluminium to yield
corresponding alkoxides/phenoxides and hydrogen. The acidic character of alcohols is due to the
polar nature of O–H bond. An electron-releasing group (–CH3, –C2H5) increases electron density
on oxygen tending to decrease the polarity of O–H bond. The hydroxyl group, in phenol is
2
directly attached to the sp hybridised carbon of benzene ring which acts as an electron
withdrawing group.
(a) Arrange the following alocohols in increasing order of their reactivity towards
esterification reaction.
CH3–CH2–OH, (CH3)2CH–OH, (CH3)3C–OH
Ans. CH3–CH2–OH < (CH3)2CH–OH < (CH3)3C –OH
(b) Arrange the following alcohols in increasing order of their reactivity towards dehydration
reaction.
CH3–CH2–OH, (CH3)2CH–OH, (CH3)3C–OH
Ans. (CH3)3C –OH < (CH3)2CH–OH < CH3–CH2–OH
(c) Why phenol are more acidic than alcohol? Explain.
Ans. Because phenolate conjugate base is resonance stabilised. The methoxide conjugate base
has no such stabilisation and therefore is formed much more reluctantly.
OR
Why boiling points of alcohols are higher than hydrocarbons and ethers of comparable
molecular mass? Explain.
Ans. Alcohols can form H-bonds with water and break the H-bonds already existing between
water molecules. Therefore, they are water soluble.
On contrary, hydrocarbons and ethers cannot form H-bonds with water and thus are
insoluble in water.
136 E
CBSE
ALLEN
33. Write the structure of the main products formed in the following reactions:
O
CH2–C–O–CH3 NaBH4
(a)
O
+
H2O, H
(b) HCHO + CH3MgBr
CH3 +
H2O, H
(c) [3] (CBSE Compartment_2021)
OR
(a) Carry out the following conversions : [1 × 2 = 2]
(i) Propene to propan-2-ol
(ii) Benzyl chloride to benzyl alcohol
(b) Arrange the following compounds in increasing order of their acidic strength : [1]
4-Methylphenol, Phenol, 4-Nitrophenol
OH
CH2–C–OCH3
Ans. (a)
O
(b) CH3CH2–OH
CH3
(c) OH
OR
 H Br
(a) (i) CH2=CH–CH3   CH3-CH-CH3 
aq KOH
CH3-CH-CH3
Br OH
Propan-2-ol
O
C–Cl CHO CH2–OH
H2 LiAlH4
(ii)
BaSO4,Pd 2H
OH OH OH
(b) < <
CH3 NO2
E 13
7
Chemistry
ALLEN
34. (a) Out of t-butyl alcohol and n-butanol, which one will undergo acid catalyzed dehydration
faster and why ?
(b) Carry out the following conversions :
(i) Phenol to salicylaldehyde
(ii) t-butylchloride to t-butyl ethyl ether
(iii) Propene to Propanol [2 + 3 = 5] (CBSE 2020)
Ans. (a) Tert-butyl alcohol, because it forms more stable 3º carbocation than 1º carbocation.
OH
OH OH OH CHO
H Cl NaOH CH –H2O
(b) (i) + Cl – CH +
– HCl
OH
Cl NaOH
– 2NaCl Salicyaldehyde
C2H 5Cl
(ii) (CH3)3CCl + NaOH (aq)  (CH3)3COH  (CH3)3CONa (CH3)3COC2H5
B2 H 6 (3NaOH + 3H 2O 2)
(iii) CH3CH=CH2 (CH3 – CH2 – CH2 –)3B CH3 – CH 2 – CH 3
|
OH
35. (a) How can you obtain Phenol from :
(i) Cumene, (ii) Benzene sulphonic acid, (iii) Benzene diazonium-chloride ?
(b) Write the structure of the major product obtained from dinitration of 3-methylphenol.
(c) Write the reaction involved in Kolbe's reaction. [5] (CBSE 2019)
CH3 CH3
CH2–CH CH3–C–O–O–H OH
+
Sol. (a) (i) O2 H
+ CH3COCH3
H2O
SO 3H OH
(ii) (i) NaOH
+
(ii) H
+ –
N2Cl OH
(iii) H2 O
+N2+HCl
OH
O 2N
(b)
CH3
NO2
OH ONa OH
COOH
(i) CO2
(c) NaOH
(ii) H+
2-Hydroxybenzoic acid
(Salicylic acid)
138 E
CBSE
ALLEN
PRACTICE TEST
SECTION-A
1. Which of the following substituted phenols is the strongest acid? [1]
OH OH OH OH
(1) (2) (3) (4)

NO2 O CH3 C2H5 CH3

2. CH3CH2CH = CH2 

B2 H 6
H O,H O ,OH –
Z [1]
2 2 2
What is Z ?
(1) CH3CH2CH2CH2OH (2) CH3CH2CHCH3
OH
(3) CH3CH2CH2CHO (4) CH3CH2CH2CH3

3. Reaction between acetone and methylmagnesium chloride followed by hydrolysis will give: [1]
(1) Isobutyl alcohol (2) Isopropyl alcohol
(3) Sec. butyl alcohol (4) Tert. butyl alcohol
4. Anisole on cleavage with HI gives: [1]

I OH I OH
(1) + C2H5OH (2) + CH3I (3) + CH3OH (4) + C2H5I

5. When vapours of a secondary alcohol is passed over heated copper at 573 K, the product formed
is :- [1]
(1) a carboxylic acid (2) an aldehyde (3) a ketone (4) an alkene
6. Assertion : Phenol forms 2, 4, 6 – tribromophenol on treatment with Br2 in H2O at 273K.
Reason : Bromine polarises in H2O. [1]
7. Assertion : Phenols give o- and p-nitrophenol on nitration with conc. HNO3 and H2SO4 mixture.
Reason : –OH group in phenol is o–, p– directing. [1]
SECTION-B
8. How do you convert:
(i) Phenol to toluene
(ii) Formaldehyde to Ethanol [2]
9. Explain the mechanism of acid catalysed hydration of an alkene to form corresponding
alcohol. [2]
10. Write the chemical equations involved in the following reactions:
(i) Kolbe's reaction
(ii) Friedal- Crafts acetylation of anisole. [2]
11. Explain the following behaviours : [2]
(i) Alcohols are more soluble in water than the hydrocarbons of comparable molecular masses.
(ii) Ortho-nitrophenol is more acidic than ortho-methoxyphenol.
E 13
9
Chemistry
ALLEN
SECTION-C
12. Write the structures of the main products in the following reactions: [3]
O
NaBH4
CH2–C–OCH 3
(i) ?
O
CH = CH2
H+
(ii) + H2O ?
OC2H 5
(iii) + HI ?
13. Predict the reagent for carrying out the following coversions : [1 × 3 = 3]
(i) Phenol to benzoquinone
(ii) Anisole to p-bromoanisole
(iii) Phenol to 2,4,6-tribromophenol
SECTION-D
14. The acidic character of alcohols is due to the polar nature of O–H bond. An electron releasing
group (–CH3, –C2H5) increases electron density on oxygen tending to decrease the polarity of O–
H bond. This decreases the acid strength. In substituted phenols, the presence of electron
withdrawing groups such as nitro group, enhances the acidic strength of phenol. This effect is
more pronounced when such a group is present at ortho and para positions. It is due to the
effective delocalisation of negative charge in phenoxide ion when substituent is at ortho or para
position. On the other hand, electron releasing groups, such as alkyl groups, in general, do not
favour the formation of phenoxide ion resulting in decrease in acid strength. Cresols, for
example, are less acidic than phenol. [1+1+2 = 4]
(a) Arrange the following compounds in increasing order of their acid strength :
Propan-1-ol, 2,4,6-trinitrophenol, 3-nitrophenol, 3,5-dinitrophenol, Phenol, 4-methyl phenol
(b) Why cresols are less acidic than phenol ?
(c) Who is resposible for acidic nature of phenols ?
OR
Why do electron withdrawing groups increase acidity of phenols ?
SECTION-E
15. [5]
(a) Give equations of the following reactions :

(i) Phenol is treated with conc. HNO3.
(ii) Propene is treated with B2H6 followed by H2O2/OH–.
(iii) Sodium t-butoxide is treated with CH3Cl.
(b) How will you distinguish between butan-1-ol and butan-2-ol ?
(c) Arrange the following in increasing order of acidity :
Phenol, ethanol, water
140 E
CBSE
ALLEN
SECTION-A
1. (a)
2. (a)
3. (d)
4. (b)
5. (c)
6. (a)
7. (d)
SECTION-B
OH CH3
Anhyd. AlCl3
8. (i) +Zn
CH3Cl
H2O/H+
(ii) HCHO+CH3MgX CH3CH2OMgX CH3CH2OH
9. Step I : Protonation of alkene to form carbocation by electrophilic attack of H3O+.

H2O + H+  H3O+
H H
+ +
C=C + H–O–H –C–C + H2O
Step II : Nucleophilic attack of water on carbacation.

H H H
+ +
–C–C + H2O –C–C–O–H
Step III : Deprotonation to form an alcohol.

H H H OH
+
–C–C–O—H + H2O –C—C– + H 3O+
OH ONa OH
COOH
(i) CO2
10. (i) NaOH
(ii) H+
(Salicylic acid)
OCH3 OCH3 OH
COCH 3
(ii) Anhyd. AlCl3
+CH 3COCl +
COCH3
11. (i) Due to formation of intermolecular H-bonding with water.
(ii) Nitro is withdrawing group which decrease the e– density and stabilised the intermediate
phenoxide ion which makes the equilibrium shifts in forward direction.
E 14
1
Chemistry
ALLEN
SECTION-C
O OH
NaBH4
CH—C—OCH CH—C—OCH
12. (i) 2 3 2 3
O O
CH – CH2 CH – CH3
H+
(ii) + H2O OH
OC2H5 OH
(iii) + HI + C2H5 – I
13. (i) (K2Cr2O7 + H2SO4) (Na2Cr2O7 + H2SO4)

(ii) Br2 in CH3COOH
(iii) Br2 aq./Bromine water
SECTION-D
14. (a) Propan-1-ol < 4-methyl phenol < Phenol < 3-nitrophenol < 3,5-dinitrophenol, Phenol <
2,4,6-trinitrophenol
(b) Cresols are less acidic than phenols because of presence of electron releasing groups which
is not favour the formation of phenoxide ion.
(c) The acidity of phenols is due to their ability to lose hydrogen ions to form phenoxide ions.
OR
Electron-withdrawing substitutes make a phenol more acidic by stabilizing the phenoxide
ion through delocalization of the negative charge and through inductive effect.
SECTION-E
OH OH
O2 N NO2
conc. HNO 3
15. (a) (i)
NO2
(ii) CH3–CH=CH2+(H–BH2)2 (CH3–CH2–CH3)3B

H2O 3H2O2,OH¯
3CH3–CH2–CH2–OH
CH3 CH3
(iii) CH–C–ONa
3 + CH3Cl CH–C–O–CH
3 3
CH3 CH3
(b) On heating with NaOH/I2, Butan-2-ol forms yellow ppt of iodoform (CH4) whereas butan-
1-ol does not (or any other correct chemical test)
(c) Ethanol < Water < Phenol
142 E
CBSE
ALLEN
UNIT-12 : ALDEHYDES, KETONES AND CARBOXYLIC ACIDS

UNIT INDEX
• Theory 143-161
THEORY
NAMING
S.No. Structure Common Name IUPAC Name
O
|| Formaldehyde Methanal
HCH
1.
O
|| Acetaldehyde Ethanal
CH 3  C  H
2.
O
|| Propionaldehyde Propanal
CH 3  CH 2  C  H
3.
O
|| n-Butyraldehyde Butanal
CH 3  CH 2  CH 2  C  H
4.
O
||
CH 3  CH  C  H Iso butyraldehyde 2-methyl propanal
|
5. CH 3
6. CCl3CHO Chloral 2, 2, 2-trichloroethanal

O
|| Acryl aldehyde Prop-2-ene-1-al
CH 2  CH  C  H
7.
O
|| Crotonaldehyde But-2-ene-1-al
CH3  CH  CH  C  H
8.
E 143
Chemistry
ALLEN
O
|| Acetone Propanone
CH 3  C  CH 3
9.
O
|| Ethyl Methyl Ketone Butanone
CH 3  C  CH 2 CH 3
10.
O
|| Formic acid Methanoic acid
11. H  C  OH
O
|| Acetic acid Ethanoic acid
CH 3  C  OH
12.
O
|| Propionic acid Propanoic acid
CH 3  CH 2  C  OH
13.
O
|| n-butyric acid Butanoic acid
CH 3  CH 2  CH 2  C  OH
14.
O
||
CH 3  CH  C  OH Iso butyric acid 2-Methyl propanoic acid
|
15. CH 3
O
|| Acrylic acid Prop-2-ene-1-oic acid
CH 2  CH  C  OH
16.
O
|| Crotonic acid But-2-ene-1-oic acid
CH3  CH  CH  C  OH
17.
CARBONYL COMPOUNDS : ALDEHYDE, KETONE
PREPARATION OF ALHDEHYDE AND KETONE
1. By oxidation of alcohols (Detail in Unit-11)
2. By dehydrogenation of alcohols (Detail in Unit-11)
3. By ozonolysis of alkene
O
H2O/Zn
C=C + O3 C C C=O
–H2O2
(Alkene)
O O
Alkylene ozonide Carbonyl compound
H2O2 + Zn  ZnO + H2O
144 E
CBSE
ALLEN
H H H O H H
H2O/Zn
(i) C=C + O3 C C 2 C=O
H H H H –H2O2 H
O O Formaldehyde
Zn + H2O2  ZnO + H2O

H H H O CH3 H2O/Zn H
(ii) C=C + O3 C C 2 C=O
H3C CH3 H3C CH3 –H2O2 H3C
O O Acetaldehyde

H3C CH3 H3C O CH3 +H O/Zn H3C
(iii) C=C + O3 C C 2
2 C=O
H3C CH3 H3C CH3 +H2O2/Zn H3C
O O Acetone

4. By hydration of alkyne
H
dilH2SO4
|
Tautomerism
e.g. (1) H  C  C  H  H 2 O 
HgSO4  H  C  C  H  H  C CH
Acetylene | | | ||
H OH H O
(Enol form) Acetaldehyde
(Keto form)
H
dilH SO
|
e.g. (2) CH 3  C  C  H  H 2 O 
HgSO4 
2 4
CH 3  C  C  H  CH3  C  C  H
Pr opyne | | || |
OH H O H
(Enol form) Acetone
(Keto form)
PREPARATION OF ALDEHYDES
1. From acyl chloride (acid chloride): (Rosenmund Reduction)
Acyl chloride (acid chloride) is hydrogenated over catalyst, palladium on barium sulphate. This
reaction is called Rosenmund reduction.
O O
Ar/R–C–Cl + H Pd–BaSO4 Ar/R–C–H
2
O O
CH3–C–Cl + H2 Pd–BaSO4 CH3–C–H + HCl
O O
C–Cl C–H
+ H2 Pd-BaSO4
E 145
Chemistry
ALLEN
2. From nitriles and esters: (Stephen Reaction)
Nitriles are reduced to corresponding imine with stannous chloride in the presence of
hydrochloric acid, which on hydrolysis give corresponding aldehyde.

H3 O
RC  N 
(SnCl2  HCl)  RCH
2H
 NH  RCHO
Note :
(1) This reaction is called Stephen reaction.
Alternatively, nitriles are selectively reduced by diisobutylaluminium hydride,
(DIBAL-H) to imines followed by hydrolysis to aldehydes:
1.AlH(i  Bu)
RCN 
2.H O
2
 R  CHO
2
1. AlH(i-Bu)
CH3  CH CH  CH2CH2  CN 2. H 2O CH3  CH CH  CH2CH2  CHO
Note :
(2) Similarly, esters are also reduced to aldehydes with DIBAL-H.
O O
1. DIBAL-H
CH3(CH2)9  C  OC2H5 2. H2O CH3(CH2)9  C  H
3. From Aromatic hydrocarbons :
Aromatic aldehydes (benzaldehyde and its derivatives) are prepared from aromatic
hydrocarbons by the following methods:
(i) Use of chromyl chloride (CrO2Cl2): Chromyl chloride oxidises methyl group to a
chromium complex, which on hydrolysis gives corresponding benzaldehyde.
CH3 (i) CrO2Cl2/CS2 CHO
+
(ii) H 3O
Toluene Benzaldehyde
This reaction is called Etard reaction.
(ii) By side chain chlorination followed by hydrolysis –
Side chain chlorination of toluene gives benzal chloride, which on hydrolysis gives
benzaldehyde. This is a commercial method of manufacture of benzaldehyde.
CH3 CHCl2 CHO
2Cl / hv light
2 H O+ 3
373 K
Toluene Benzal chloride Benzaldehyde

(iii) By Gatterman - Koch aldehyde synthesis reaction –
When benzene or its derivative is treated with carbon monoxide and hydrogen chloride
in the presence of anhydrous aluminium chloride or cuprous chloride, it gives

benzaldehyde or substituted benzaldehyde.
CHO
+ (CO + HCl) Anhydrous AlCl3
Benzaldehyde
146 E
CBSE
ALLEN
O
CO + HCl H–C–Cl
O O
H – C – Cl + AlCl3 H–C + AlCl4
This reaction is known as Gatterman-Koch reaction.

PREPARATION OF KETONE
1. From acyl chlorides
Treatment of acyl chlorides with dialkylcadmium, prepared by the reaction of cadmium
chloride with Grignard reagent, gives ketones.
2R  Mg  X + CdCl2 R2Cd + 2Mg(X)Cl
2R'  C  Cl + R2Cd 2R'  C  R + CdCl2
O O
2. From Acid Nitrile

R–MgX + [R–CN  R–C=NR–C=NMgX
R
X R + H2O
Mg + C=O
NH2 R
3. From benzene or substituted benzenes
When benzene or substituted benzene is treated with acid chloride in the presence of anhydrous
aluminium chloride, it affords the corresponding ketone. This reaction is known as Friedel-
Crafts acylation reaction.
O
O
C
+ Ar / R  C  Cl
Anhyd. AlCl 3 Ar / R
Orbital diagram of carbonyl group

-bond
sp2
 sp2
sp 2 .. sp2
2
C
sp Carbon Oxygen
sp2
Polar nature of carbonyl group

 .. 
 ..  
C = O: C O: C O
 
e– Cloud Polar Carbonyl group
E 147
Chemistry
ALLEN
CHEMICAL REACTIONS OF CARBONYL COMPOUNDS
(I) (II) (III) (IV) (V) (VI)

Nucleophilic Nucleophilic Reduction Oxidation Reaction of Other
Addition Addition Reaction Reaction -Hydrogen Reaction
Reactions Elimination Containing
Reactions Compound
(Reactions with
Ammonia
Derivative )
I. NUCLEOPHILIC ADDTION REACTIONS (NAR)
Nucleophilic addition reactions is characteristics reaction of carbonyl compound (Aldehyde /
Ketone) and cyano compound (H–C , R–C  N).
General NAR :
 Nu
C=O + ENu C
E
Mechanism : NAR proceed in two steps
Step-1 : Nucleophilic addition :
+–  sp3 O
ENu + C=O C O C
sp2 Nu
e–deficient e– rich deficient
 More reactive  Less reactive
Less stable  More stable
Step-2 : Electrophilic addition :
  OE
E + C––O E C
Nu
Nu
Nucleophilic addition reactions
1
Reactivity of carbonyl compound towards NAR  –I effect 
 I effect
1. Reaction with HCN : ...... cyanohydrene is formed.

Gen. reaction :
OH
C = O + HCN C
CN
.... cyanohydrene
148 E
CBSE
ALLEN
Mechanism (Board mechanism)
Step (1): Nuclophilic addition
   
H CN + C=O C–O C–O + H
CN
Step (2) : Electrophilic addition
 OH
C–O + H C
CN
CN
.... cyanohydrene
H H OH
e.g. (1) C = O + HCN C
H3C H3C CN
Acetaldehyde Acetaldehyde cyanohydrene
H3C H 3C OH
(2) C = O + HCN C
H3C H 3C CN
Acetone Acetone cyanohydrene
2. Reaction with NaHSO3 : ..... Sodium hydrogen sulphite adduct is formed.
OH
C = O + NaHSO3 C
OSO2Na
Bisulphite addition
compund (crystalline)
Mechanism :
NaHSO3  Na+ + HSO3¯
O
||
HSO3¯  H+ + SO32– / O – S – O
O
||  O
Step (1) O – S – O + C=O C–O C
O–S–O
||
O
 OH
O Na+, H+ O Na Proton transfer 
Step(2) C C   C 
O – S – ONa
O–S–O O–S–OH
|| || ||
O O O
3. Reaction with alcohol
R Dry HCl gas R OH R OR'
(i) C = O + R' – OH 
 C + R' – OH
C
H H OR' Dry HCl gas H OR'
Aldehyde Hemiacetal Acetal
E 149
Chemistry
ALLEN
R Dry HCl gas R OH  R'OH R OR'
(ii) C = O + R' – OH 
 C 
Dry HCl gas C
R R OR' R OR'
Ketone Hemiketal Ketal
R CH2 – OH
C=O + | R O – CH2
R  C + H2O 
CH2 – OH R O – CH2
Ketone Ethylene
Ethylene glycol ketal
glycol
II. NUCLEOPHILIC ADDITION - ELIMINATION REACTION
Reaction with ammonia derivatives
Gen. Reaction
C = O + H2 N – Z C = N – Z + H 2O
NO2 O
||
Z = – OH, – NH2, – NH , – NH NO2 ,  NH  C  NH 2 , –R
Mechanism
H OH –H2O
N–Z + C=O  C+–O– C H C=N–Z
H N 
Z
Nucleophilic Addition Elimination
Important ammonia derivatives
1. NH2OH Hydroxyl amine
2. NH2 – NH2 Hydrazine
3. NH2 – NH Phenyl hydrazine
NO2
4. NH2 – NH NO2 2,4-Dinitrophenyl hydrazine
O
||
5. NH 2  NH  C  NH2 Semicarbazide
6. R – NH2 Alkyl amine
Important Reaction with Ammonia Derivatives :
1. Reaction with Hydroxyl amine : ………. oxime is formal
C = O + H2N – OH C = N – OH + H2O
…….Oxime
2. Reaction with Hydrozine : ………. Hydrozone is formed
C = O + H2N NH2 C = N NH2 + H2O

…….Hydrozone
150 E
CBSE
ALLEN
3. Reaction with Phenyl hydrazine : ……….Phenyl hydrozone is formed
C=O + H2N NH C=N NH + H2 O

…….Phenyl hydrozone
4. Reaction with 2,4-Dinitro phenylhydrozine : ………. 2,4-Dinitro phenyl hydrozone is formed
NO2 NO2
C=O + H2N NH NO2 C=N NH NO2

…….2,4-Dinitrophenyl hydrozone
5. Reaction with Semi carbazide : ………. semi carbazone is formed
O O
C = O + H2N NH – C – NH2 C = N NH – C – NH2 + H2O
…….Semi carbazone
6. Reaction with alkyl amine : ………. Imine is formed
C = O + H2 N – R C = N – R + H2O
…….N-Alkyl amine
III. REDUCTION REACTION
1. Clemmensen Reduction:
The carbonyl group of aldehydes and ketones is reduced to CH2 group on treatment with
zincamalgam and concentrated hydrochloric acid [Clemmensen Reduction] or with hydrazine
followed by heating with sodium or potassium hydroxide in high boiling solvent such as
ethylene glycol (Wolff-Kishner Reduction).
Zn-Hg/HCl
C=O + 4H CH2 + H2O (Clemmensen Reduction)
Alkane
2. Wolff-Kishner Reduction:
CH2–OH
NH2NH2
C=O C=NNH2 KOH/CH2–OH CH2 + N2 (Wolf Kishner reduction)
–H2O , 180°C Alkane
IV. OXIDATION REACTIONS

Iodoform Test/Haloform Reaction:

O
||
The alcohols which oxidised to CH3  C  group (eg. CH3–CH2–OH, CH3–CH–CH3 ,
OH
CH3–CH–CH 2–CH3, CH3–CH–R ) and the carbonyl compound which contains group
OH OH
E 151
Chemistry
ALLEN
O
O O O C
 || || || CH3 
 eg. CH3  C  H , CH3  C  CH3 , CH3  C  R ,  gives iodoform test
 
/ haloform reaction.
Reagents of iodoform test : NaOH + I2

Iodoform test : Organic compound + (NaOH + I2)  Yellow ppt of iodoform CHI3 is
formed.
O
||
(The alcohols which oxidised in to CH3  C  group and the carbonyl compound which contain
O
||
CH3  C  group)
Important iodoform reactions
O
||  
1. CH3 – CH2 – OH + 4I2 + 6NaOH  CHI 3 + H – C – ONa + 5NaI + 5H 2O
yellowppt
O
||  
2. CH 3  CH  CH 3  4I 2  6NaOH  CHI3 + CH3 – C – ONa + 5NaI + 5H2 O
|
OH
O O
|| ||  
3. CH3  C  H  3I 2  4NaOH  CHI3 + CH3 – C – ONa + 3NaI + 3H2 O
O O
|| ||  
4. CH3  C  CH3  3I 2  4NaOH  CHI3 + CH3 – C – ONa + 3NaI + 3H2 O
O O
|| ||  
5. R  C  CH3 NaOX
 CHX3 + R – C – ONa
H CH3 H CH3
6. C=C 
NaOCl
 CHCl3 + C=C 
H 3C C – CH3 H 3C C – ONa
O O
2. Reaction with Tollen's reagent (Tollen's Test)
Freshly prepared ammonical AgNO3 solution is known a Tollen's reagents.

When an aldehyde heated with freshly prepared ammonical AgNO3 solution i.e. Tollen's
reagent, a bright silver mirror is produced due to formation of silver metal, which shows
O
||
presence of C  H group. In this reaction, the aldehydes are oxidised to corresponding
carboxylic acid.
152 E
CBSE
ALLEN
O O
|| ||
RCH + 2[Ag(NH )
3 2 ]+ + 3OH  RCH + 2Ag  4NH 3  H 2 O
silver mirror
OR
NH4OH + AgNO3  AgOH + NH4OH
2AgOH  Ag2O + H2O
O O
|| ||
R  C  H + Ag2O  R  C  OH + 2Ag
silver mirror
3. Fehling's test :
Fehling solutions are of following two types :
(i) Fehling A-solution :
Aqueous solution of CuSO4 is known as fehling A-solution
(ii) Fehling B-solution :
Alkaline solution of sodium potassium tartarate
(Rochelle salt)
O
|| 
HO – CH – C – ONa
| 
HO – CH – C – OK
||
O
Fehling A and fehling B solution are mixed in equal amount. On heating an aldehyde with
fehling A and Fehling B solution, a reddish brown ppt is obtained which shows that aldehyde
 O 
 || 
 C  H  group present in given organic compound.
 
CuSO4 + 2NaOH  Cu(OH)2 + Na2SO4
from from
fehling-A fehling-B
solution solution
Cu(OH)2 CuO + H2O

cupric
oxide
O O
|| ||

R  C  H  2CuO   R  C  OH + Cu2O
Cuprous oxide
(Reddish brown ppt)
OR
O O
||  ||
R  C  H + 2Cu2+ + 5OH  R  C  OH + Cu2O
Reddish brown ppt
Note : Aromatic aldehyde such as Benzaldehyde does not shows fehling test.
E 153
Chemistry
ALLEN
V. REACTION DUE TO -HYDROGEN:
1. Aldol reaction and Aldol condensation reaction :-
Acidity of -hydrogens of aldehydes and ketones:
The aldehydes and ketones undergo a number of reactions due to the acidic nature of -
hydrogen.
The acidity of -hydrogen atoms of carbonyl compounds is due to the strong electron
withdrawing effect of the carbonyl group and resonance stabilisation of the conjugate base.
O O O
 OH
CCC CC C C
– (H2O)
H :B Enolate ion
O
Aldol : The organic compound which contains aldehyde C H and alcohol (–OH) groups
known as Aldol.
Aldehyde + Alcohol = Aldol
O
Ketol : The organic compound which contains ketone C and alcohol (–OH) groups
known as ketol.
Ketone + Alcohol = Ketol
Aldehyde or ketone having atleast one -hydrogen undergoes a reaction in the presence of
dilute base as a catalyst to form aldol/ketol respectively. This is known as aldol reaction. On
dehydration aldol or ketol gives , -unsaturated carbonyl compound, now the overall reaction
is known as aldol condensation reaction.
Aldol reaction are of following two types :-
1. Simple aldol condensation reaction :
When aldol condensation reaction is carried out between -H containing aldehyde, known as
simple aldol condensation reaction. In this reaction, two molecules of carbonyl compounds will
participate.
eg.(i) H O H O O
CH3–C + CH2–C–H Dil.NaOH CH3–C–CH2–C–H  CH3–CH=CH–C–H
H+ Crotonaldehyde
O H OH
Acetaldehyde Aldol (,-unsaturated
aldehyde)
eg.(ii) H CH3 O H CH3 O CH3 O
CH3–CH2–C + CH–C–H Dil.NaOH CH3–CH2–C–CH–C–H  CH3–CH2–CH=C–––C–H
H+
O H OH ,-unsaturated
Aldol aldehyde
Propionaldehyde
Ketol condensation :
CH3 O CH3 O CH3 O
CH3–C + CH2–C–CH3 Dil.NaOH CH3–C–CH2–C–CH3  CH3–C=CH–C–CH3
H+
O H OH ,-unsaturated
Acetone Ketol ketone
154 E
CBSE
ALLEN
2. Cross Aldol condensation reaction :
When aldol condensation reaction is carried out between two different -H containing
aldehyde/ketone then it is known as cross aldol/ketol condensation reaction.
CH3CHO
+ 1. NaOH
2. 
CH3  CH CH  CHO + CH3CH2  CH C  CHO
CH3CH2CHO
But-2-enal CH3
form by two molecules of ethanal 2-Methylpent-2-enal
form by two molecules
of propanal
Simple or self aldol condensation products
+
CH3  CH C  CHO + CH3CH2  CH CHCHO
CH3
2-Methylbut-2-enal Pent-2-enal
form by one molecule of ethanal and one molecule of propanal
cross aldol condensation products

Note: Ketones can also be used as one component in the cross aldol reactions.
O
OH–
CHO + C – CH3 + 293K CH CH C
O
1,3-Diphenylprop-2-en-1-one
(Benzalacetophenone)
VI. OTHER REACTIONS
Cannizzaro reaction:
Aldehydes which do not have an -hydrogen atom, undergo self oxidation and reduction
(disproportionation) reaction on heating with concentrated alkali. In this reaction, one
molecule of the aldehyde is reduced to alcohol while another is oxidised to carboxylic acid
salt.
H O
H H 
C O + C O + Conc. KOH H  C  OH + H  C
H H OK
H
Formaldehyde
Methanol Potassium formate

2 CHO + Conc. NaOH CH2OH + COONa
Benzaldehyde Benzyl alcohol Sodium benzoate

Aldol Reaction Cannizzaro Reaction
The carbonyl compound which have The aldehyde which do not have -H gives
-hydrogen gives aldol reaction with dilute Cannizzaro reaction with conc. base.
base. O O
e.g. CH3CHO, CH3CH2CHO, CH3COCH3 || ||
e.g. H – C – H , C 6 H 5 – C – H
E 155
Chemistry
ALLEN
CARBOXYLIC ACID
Method of preparation of Carboxylic Acid (Aliphatic and Aromatic)
From primary alcohols and aldehydes :
1. Primary alcohols are readily oxidised to carboxylic acids with common oxidising agents such as
potassium permanganate (KMnO4) in neutral, acidic or alkaline medium or by potassium
dichromate (K2Cr2O7) and chromium trioxide (CrO3) in acidic medium.
1.alkalineKMnO
RCH 2 OH 

4
 RCOOH
2.H2 O
CrO  H SO
CH 3 (CH 2 )8 CH 2 OH 
3 2

4
 CH 3 (CH 2 )8 COOH
2.H2 O
Carboxylic acids are also prepared from aldehydes by the use of mild oxidising agents.
2. From alkylbenzenes :
Aromatic carboxylic acids can be prepared by vigorous oxidation of alkyl benzenes with
chromic acid or acidic or alkaline potassium permanganate. The entire side chain is oxidised to
the carboxyl group irrespective of length of the side chain. Primary and secondary alkyl groups
are oxidised in this manner while tertiary group is not affected. Suitably substituted alkenes are
also oxidised to carboxylic acids with these oxidising reagents.
CH3 COOK +
COOH
KMnO4–KOH H3O
Heat
Benzoic acid
CH2CH2CH3 COOK +
COOH
KMnO 4–KOH H3O

Benzoic acid
3. From nitriles and amides :
Nitriles are hydrolysed to amides and then to acids in the presence of H+ or OH as catalyst.
Mild reaction conditions are used to stop the reaction at the amide stage.
O
+ – + –
H or OH H or OH
R  CN H2O
R  C  NH2 
RCOOH
+
H3O
CH3CONH2  CH3COOH + NH3
Ethanamide Ethanoic acid
CONH2 + COOH
H3O
+ NH 3

Benzamide Benzoic acid

4. From Grignard reagents :

Grignard reagents react with carbon dioxide (dry ice) to form salts of carboxylic acids which in
turn give corresponding carboxylic acids after acidification with mineral acid.
    X
R–MgX + O=C=O O=C–O O=C–OMgX + H–OH O=C–OH + Mg
OH
R R
156 E
CBSE
ALLEN
5. From hydrolysis acid derivatives
O O
+
R–C–NH2 H or OH R–C–OH
H2O
O O
R–C–Cl H2O R–C–OH + HCl
O O
R–C–OR +H2O R–C–OH + ROH
O O O
R–C–O–C–R +H2O 2R–C–OH
COOC2H 5 +
COOH
H3O
+ C2H 5OH
Ethyl benzoate Benzoic acid

NaOH
CH3CH2CH2COOC2H5 CH3CH2CH2COONa + C2H 5OH
+
Ethyl butanoate H3O
CH3CH2CH2COOH
Butanoic acid
CHEMICAL REACTIONS OF CARBOXYLIC ACID

I. Reaction involving cleavage of – O – H Bond :
1. Acidity
Reactions with metals and alkalies
The carboxylic acids like alcohols evolve hydrogen with electropositive metals and form salts
with alkalies similar to phenols. However, unlike phenols they react with weaker bases such as
carbonates and hydrogencarbonates to evolve carbon dioxide. This reaction is used to detect the
presence of carboxyl group in an organic compound.
O O
–+
2 R–C–OH + 2Na 2R–C–ONa + H2
O O
2 CH3–C–OH + Na2CO3 2CH3–C–ONa + CO2 + H2O
O O
2 CH3–C–OH + NaHCO3 CH3–C–ONa + CO2 + H2O
O O
–+
R–C–OH + NaOH R–C–ONa + H2O
E 157
Chemistry
ALLEN
II. Reaction involving cleavage of – C – OH bond:
1. Formation of anhydride :
Carboxylic acids on heating with mineral acids such as H2SO4 or with P2O5 give corresponding
anhydride.
O O O O
H+,  CH –C–O–C–CH
CH3–C–OH + CH3–C–OH 3 3
or
Ethanoic anhydride
P2O5,
2. Esterification :
Carboxylic acids are esterified with alcohols or phenols in the presence of a mineral acid such
as concentrated H2SO4 or HCl gas as a catalyst.
O O
+
R–C–OH + R'–OH H R–C–OR' + H2O
3. Reactions with PCl3, PCl5 and SOCl2

The hydroxyl group of carboxylic acids, behaves like that of alcohols and is easily replaced by
chlorine atom on treating with PCl5, PCl3 or SOCl2. Thionyl chloride (SOCl2) is preferred
because the other two products are gaseous and escape the reaction mixture making the
purification of the products easier.
O O
(i) 3R–C–OH + PCl3 R–C–Cl + H3PO3
O O
(ii) R–C–OH + PCl5 R–C–Cl + POCl3 + HCl
O O
(iii) R–C–OH + SOCl2 R–C–Cl + SO2 + HCl
4. Reaction with ammonia

Carboxylic acids react with ammonia to give ammonium salt which on further heating at high
temperature give amides. For example:
O O O
–+
CH3–C–OH + NH3 CH3–C–ONH4  CH3–C–NH2
Acetic acid Ammonium –H2O Acetamide
acetate
O O O
–+
C–OH C–ONH4 C–NH2
+ NH3 
H2O
Benzoic acid Ammonium Benzamide
benzoate
158 E
CBSE
ALLEN
O O O
–+
C–OH C–ONH4 CONH2 C
NH3  –NH3
NH
–+ –2H2O
C–OH C–ONH4 CONH2 Strong C
heating
O O Phthalamide O
Phthalic acid Ammonium Phthalimide
phthalate
O
||
III. Reaction involving C  OH group:
1. Reduction
Carboxylic acids are reduced to primary alcohols by lithium aluminium hydride or better with
diborane. Diborane does not easily reduce functional groups such as ester, nitro, halo, etc.
Sodium borohydride does not reduce the carboxyl group.
R  COOH 
(i)LiAH 4 /either or B2 H5
(ii) H O
R  CH 2 OH
3
2. Decarboxylation of sodium salt of mono carboxylic acid :

Carboxylic acids lose carbon dioxide to form hydrocarbons when their sodium salts are heated
with sodalime (NaOH and CaO in the ratio of 3 : 1). The reaction is known as decarboxylation.
R  COONa 
NaOH & CaO
Heat
 R  H  Na 2 CO3
3. Kolbe electrolysis :
Alkali metal salts of carboxylic acids also undergo decarboxylation on electrolysis of their
aqueous solutions and form hydrocarbons having twice the number of carbon atoms present in
the alkyl group of the acid. The reaction is known as Kolbe electrolysis.
O O
Electrolysis – +
2R–C–ONa 2R – C – O + 2Na
(aq)
Reaction at Anode:
O O

2R – C – O 2R – C – O + 2e–
O
2R – C – O R – R + 2O = C = O
Alkane
Reaction at Cathode:
2Na+ + 2e–
E 159
Chemistry
ALLEN
IV. Reaction involving hydrocarbon (– R) part :
1. Halogenation
Carboxylic acids having an -hydrogen are halogenated at the -position on treatment with
chlorine or bromine in the presence of small amount of red phosphorus to give -
halocarboxylic acids. The reaction is known as Hell-Volhard-Zelinsky reaction.
(i) X2/Red phosphorus
R  CH2  COOH (ii) H2O
R  CH  COOH
X
X Cl, Br
-Halocarboxylic acid
ESR of Benzoic acid
(i) Nitration of benzoic acid
COOH COOH
+
Conc. HNO3
Conc. H2SO4
NO2
Benzoic acid m-Nitrobenzoic acid
(ii) Halogenation of benzoic acid
COOH COOH
Br2 / FeBr3
Br
Benzoic acid m-Bromobenzoic acid
Note : Aromatic carboxylic acids undergo electrophilic substitution reactions in which the carboxyl
group acts as a deactivating and meta-directing group. They however, do not undergo Friedel-
Crafts reaction (because the carboxyl group is deactivating and the catalyst aluminium
chloride (Lewis acid) gets bonded to the carboxyl group).
ESR of Benzaldehyde acid

(i) Nitration of Benzaldehyde
CHO CHO
Conc. HNO3
Conc. H2SO4
NO2
Benzaldehyde m-Nitro Benzaldehyde
(ii) Halogenation of Benzaldehyde

CHO CHO
Br2/FeBr3
Br
Benzaldehyde m-Bromo Benzaldehyde
160 E
CBSE
ALLEN
Physical properties of aldehyde and ketones
(i) Methanal is gas at room temperature.
(ii) Ethanal is a volatile liquid.
(iii) Boiling point of aldehyde and ketones are higher than hydrocarbons and ethers of
comparable molecular masses. Because weak intermolecular association arises in aldehyde
and ketones due to dipole-dipole interactions.
(iv) Lower members are miscible with water in all proportions because they form hydrogen
bond with water
'
(v) Solubility of aldehydes and ketones decreases when the length of alkyl chain increases.
(vi) All aldehyde and ketones are fairly soluble in organic solvents like benzene, ether,
methanol, chloroform etc.
(vii) The lower aldehydes have sharp pungent odour, as size of molecule increases, the odour
becomes less pungent more fragrant
Physical Properties of carboxylic acid

(i) Aliphatic carboxylic acids upto nine carbon atoms are colourless liquids at room
temperature with unpleasant odour, while higher carboxylic acids are wax like solids and
odourless due to their low volatility.
(ii) Solubility- Aliphatic carboxylic acids upto 4 carbon atoms are completely soluble in H2O
due to formation of H bonds with water. Solubility decreases with increases in number of C
atoms, larger the hydrocarbon, more it will retard the formation of hydrogen bond. Benzoic
acid is almost insoluble in cold water but soluble in hot water. All carboxylic acids are
soluble in organic solvents like alcohols, ethers and benzene.
(iii) Boiling points-Carboxylic acids have higher boiling points because they have high extent
of hydrogen bonding with water.
(iv) Melting points-The melting points of aliphatic carboxylic acids do not show a regular
pattern.
E 161
Chemistry
ALLEN
1. Write the structures of products of the following reactions :
O
C
(i) C2H5 Cl
Anhyd. AlCl3 (ii) (C6H5CH2)2Cd + 2CH3COCl 
CH3
2 1 CrO2Cl2
(iii) H3C – C C –H 
Hg , H2SO4
 (iv) 2H 3O
+
NO2
O O
C C
Ans. (i) + H5C2 Cl
Anhyd. AlCl3
C2H5 + HCl
Benzene ethyl phenylketone
O
CH2 – C – CH3
(ii) (C6H5CH2)2Cd + 2CH3COCl 2 + CdCl2
1-Phenylpropanone
OH O
Hg2+, dil. H2SO 4 Tautomerises
(iii) H C – C  C – H + H – OH
3 H3C – C = CH2 H3C – C – CH3
Propyne Propanone
CH3
1 CrO 2Cl2 OCrCl2OH H 3O
+
(iv) 2CS2
O2N CH O2N CHO
OCrCl2OH
NO2 p - Nitrobenzaldehyde
p - Nitrotoluene
2. Arrange the following compounds in increasing order of their boiling points.

CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3
Ans. CH3 CH2 CH3  CH3 OCH3  CH3 CHO  CH3 CH2 OH
non polar more polar H  bond i ng
3. Arrange the following compounds in increasing order of their reactivity in nucleophilic addition
reactions.
(i) Enthanal, Propanal, Propanone, Butanone.
(ii) Benzaldehyde, p-Tolualdehyde, p-Nitrobenzaldehyde, Acetophenone.
Hint : Consider steric effect and electronic effect.
1
Ans. Reactivity of carbonyl compound (+)ve charge on sp2 C  steric hindrence

O O O O
(i) C C C C
CH3 H CH3CH2 H CH3 CH3 CH3 CH2CH3

Ethanal Propanal Propanone Butanone
The +I effect of the alkyl group increases in the order :

Ethanal < Propanal < Propanone < Butanone
If +I effect increases then (+)ve charge on sp2 C decreases.
So reactivity order is :
Butanone < Propanone < Propanal < Ethanal
162 E
CBSE
ALLEN
O
CHO CH3 CHO
C
CH3
(ii)
NO2 CHO
p-Nitrobenzaldehyde p-Tolualdehyde Benzaldehyde Acetophenone
more – I less – I +I of –CH3
–I group on >C = O inreases (+)ve charge so reactivity order is

Acetophenone < p-tolualdehyde < Benzaldehyde < p-Nitrobenzaldehyde
4. Predict the product of the following reactions :
O
(i) + HO – NH2
H
+
O O2N
(ii) + NH2 – NH NO2
O
H+
(iii) R – CH = CH – CHO + NH 2 – C – NH – NH2
O
C
+
(iv) CH3
+ CH3CH2NH2
H
O N–OH
Ans. (i) + HO – NH2
H
+
O2N
O O2N NNH NO2
(ii) + NH2 – NH NO2
O O
+
H
(iii) R – CH = CH – CHO + NH 2 – C – NH – NH2 R – CH = CH – CH = N – NH – C – NH2
O H3C
C C = N – CH2CH3
+
(iv) CH3
+ CH3CH2NH2
H
5. Show how each of the following compounds can be converted to benzoic acid.
(i) Ethylbenzene (ii) Acetophenone (iii) Bromobenzene
(iv) Phenylethene (Styrene)
CH2CH3 COOK COOH
Ans. (i)
+
KMnO 4 – KOH H 3O

Ethylbenzene Benzoic acid
COCH3 COOK COOH

+
KMnO 4 – KOH H 3O
(ii)

Acetophenone Benzoic acid
O
Br MgBr C COOH
Mg H 3O +
(iii) O=C=O
OMgBr
Ether dry ice
Bromobenzene Benzoic acid
CH=CH2 COOK
+ COOH
KMnO 4 – KOH H 3O
(iv) + HCOOK

Phenylethene
E 163
Chemistry
ALLEN
6. Which acid of each pair shown here would you expect to be stronger?
(i) CH3CO2H or CH2FCO2H (ii) CH2FCO2H or CH2ClCO2H
(iii) CH2FCH2CH2CO2H or CH3CHFCH2CO2H
(iv) F C
3 COOH or H3C COOH
Ans. Acidic strength

(i) CH3CO2H < CH2FCO2H (ii) CH2F CO2H > CH2ClCO2H
(iii) CH2FCH2CH2COH < CH3CHFCH2CO2H (iv) F3C COOH > H3C COOH
7. Give names of the reagents to bring about the following transformations:

(i) Hexan-1-ol to hexanal (ii) Cyclohexanol to cyclohexanone
(iii) p-Fluorotoluene to p-fluorobenzaldehyde (iv) Ethanenitrile to ethanal
(v) Allyl alcohol to propenal (vi) But-2-ene to ethanal
Ans. (i) C5H5NH+ CrO3Cl–(PCC)
(ii) K2Cr2O7 in acidic medium
(iii) CrO3 in the presence of acetic anhydride/1. CrO2Cl2 2. HOH
(iv) (Diisobutyl) aluminium hydride (DIBAL-H)
(v) PCC
(vi) O3/H2O-Zn dust
8. Arrange the following compounds in the increasing order of their boiling points:
CH3CH2CH2CHO, CH3CH2CH2CH2OH, H5C2 –O– C2H5, CH3CH2CH2CH2CH3
Ans. The molecular masses of these compounds are in the range of 72 to 74. Since only butan-1-ol
molecules are associated due to extensive intermolecular hydrogen bonding, therefore, the
boiling point of butan-1-ol would be the highest. Butanal is more polar than ethoxyethane.
Therefore, the intermolecular dipole-dipole attraction is stronger in the former. n-Pentane
molecules have only weak van der Waals forces. Hence increasing order of boiling points of the
given compounds is as follows :
CH3CH2CH2CH2CH3 < H5C2 – O – C2H5 < CH3CH2CH2CHO < CH3CH2CH2CH2OH
9. Would you expect benzaldehyde to be more reactive or less reactive in nucleophilic addition
reactions than propanal ? Explain your answer.
Ans. The carbon atom of the carbonyl group of benzaldehyde is less electrophilic than carbon atom of
the carbonyl group present in propanal. The polarity of the carbonyl group is reduced in
benzaldehyde due to resonance as shown below and hence it is less reactive than propanal.
10. An organic compound (A) with molecular formula C8H8O forms an orange-red precipitate with
2,4-DNP reagent and gives yellow precipitate on heating with iodine in the presence of sodium
hydroxide. It neither reduces Tollens' or Fehlings' reagent, nor does it decolourise bromine water
or Baeyer's reagent. On drastic oxidation with chromic acid, it gives a carboxylic acid (B) having
molecular formula C7H6O2. Identify the compounds (A) and (B) and explain the reactions
involved.
164 E
CBSE
ALLEN
Ans. (A) forms 2,4-DNP derivative. Therefore, it is an aldehyde or a ketone. Since it does not reduce
Tollens' or Fehling reagent, (A) must be a ketone. (A) responds to iodoform test. Therefore, it
should be a methyl ketone. The molecular formula of (A) indicates high degree of unsaturation,
yet it does not decolourise bromine water or Baeyer's reagent. This indicates the presence of
unsaturation due to an aromatic ring. Compound (B), being an oxidation product of a ketone
should be a carboxylic acid. The molecular formula of (B) indicates that it should be benzoic acid
and compound (A) should, therefore, be a monosubstituted aromatic methyl ketone. The
molecular formula of (A) indicates that it should be phenyl methyl ketone (acetophenone).
Reactions are as follows :
O
O 2N O2N
C H3C
CH3 + H 2NHN NO 2 –H2O
C N  NH NO2
(A)
C8 H 8 O 2,4-Dinitrophenylhydrazine 2,4-DNP derivative
11. Write chemical reactions to affect the following transformations:

(i) Butan-1-ol to butanoic acid
(ii) Benzyl alcohol to phenylethanoic acid
(iii) 3-Nitrobromobenzene to 3-nitrobenzoic acid
(iv) 4-Methylacetophenone to benzene-1,4-dicarboxylic acid
(v) Cyclohexene to hexane-1,6-dioic acid
(vi) Butanal to butanoic acid.
CrO  H SO
Ans. (i) CH3CH2CH2CH2OH 
Jones reagent
 CH3CH2CH2COOH
3 2 4
Butan-1-ol Butanoic acid


(ii) C6H5CH2OH 
HBr
 C6H5CH2Br 
KCN
 C6H5CH2CN 
H O

 C6H5CH2COOH 2
O O
+
Mg CO2 H3O
(iii) Br ether
MgBr (dry ice)
C C
OMgBr OH
O2 N O2N O2N O2 N
3-Nitrobromobenzene 3-Nitrobenzoic acid
COCH COOK COOH
KMnO4/KOH dil. H2SO4
(iv) H3C KOOC HOOC

4-Methylacetophenone Dipotassium benzene- Benzene-1, 4-dicarboxylic
1, 4-dicarboxylate acid (Terephthalic acid)
KMnO 4–H2SO4 COOH

(v) COOH
Cyclohexene Hexane-1, 6-dioic acid (Adipic acid)
(vi) CH3CH2CH2CHO 

Ammoniacal AgNO
(Tollens' reagent)
 CH3CH2CH2COOH 3
Butanal Butanoic acid
E 165
Chemistry
ALLEN
1. What is meant by the following terms? Give an example of the reaction in each case.
(i) Cyanohydrin (ii) Acetal
(iii) Semicarbazone (iv) Aldol
(v) Hemiacetal (vi) Oxime
(vii) Ketal (viii) Imine
(ix) 2, 4-DNP-derivative (x) Schiff's base
Ans. (i) Cyanohydrin :
Organic compound which have –CN and –OH group in structure.
OH
R NaCN
R
C=O + HCN C–CN
R' R'
Cyanohydrin
(ii) Acetal :
Acetals are gem-dialkoxy alkanes in which two alkoxy groups are present on the terminal
carbon atom.
OR' OR'
R'OH, dry HClgas R" – OH
RCHO R–CH +
R–CH +H2O
H
Aldehyde OH OR"
Hemiacetal Acetal
(iii) Semicarbazone :
Semicarbazones are derivatives of aldehydes and ketones produced by the condensation
reaction between a ketone or aldehyde and semicarbazide.
O O
C=O + H2–N–NH–C–NH2 H2O + C=N–NH–C–NH2
Semicarbazide Semicarbazone
(iv) Aldol :
A -hydroxy aldehyde or ketone is known as an aldol. It is produced by the condensation
reaction of two molecules of the same or one molecule each of two different aldehydes or
ketones with H in the presence of a base.
dil
CH3–C–H + H–CH2–C–H NaOH CH3–CH–CH2–CHO
O O OH
Aldol
(v) Hemiacetal :
Hemiacetal are -alkoxyalcohols
Aldehyde reacts with one molecule of a monohydric alcohol in the presence of dry HCl
gas.
OR
R'OH, dry HClgas
RCHO R–CH
OH
Hemiacetal
166 E
CBSE
ALLEN
(vi) Oxime :
Oximes are a class of organic compounds having the general formula .
.. OH .. OH
N N
R H R R'
Aldoxime Ketoxime
On treatment with hydroxylamine in a weakly acidic medium, aldehydes or ketones form
oximes.
(vii) Ketal :
Ketals are gem-dialkoxyalkanes in which two alkoxy groups are present on the same
carbon atom within the chain.
R' OR
R 2R–OH
R—C—OR" C=O H
 R—C—R
OR'" R
OR
General structure of a ketal Ketone Ketal
(viii) Imine :
Imines are C=N–R or C=NH . Imines are produced when aldehydes and ketones react with
R–NH2
C=O + H2–N–R C=N–R + H2O
(ix) 2, 4-DNP–derivative :
2, 4-dinitrophenylhydrazones are 2, 4-DNP-derivatives, which are produced when
aldehydes or ketones react with 2, 4-dinitrophenylhydrazine in a weakly acidic medium.
NO2 NO2
C=O + H2–NNH NO2 H2O + C=NNH NO2
2,4-Dinitrophenydrazine 2,4-Dinitrophenylhydrazone
To identify and characterize aldehydes and ketones, 2, 4-DNP derivatives are used.
(x) Schiff's base : is C = NR (R is not Hydrogen) (R may be –Ph)
Aldehydes and ketones on treatment with primary aliphatic or aromatic amines in the
presence of trace of an acid yields a Schiff's base.
Trace of H +
R–CH=O + H2—N—R R–CH=N—R' + H2O
Aldehyde 1° amine Schiff's base
2. Draw structures of the following derivatives.

(i) The 2, 4-dinitrophenylhydrazone of benzaldehyde

(ii) Cyclopropanone oxime
(iii) Acetaldehydedimethylacetal
(iv) The semicarbazone of cyclobutanone
(v) The ethylene ketal of hexan-3-one
(vi) The methyl hemiacetal of formaldehyde
E 167
Chemistry
ALLEN
NO2 N–OH
Ans. (i) CH=NNH NO2 (ii)
O
OCH3
(iii) CH3–CH (iv) NNH–C–NH2
OCH3
H2C CH2
O H H H OH
O
C=O + H–O–CH3 C=O
(v) H3C – CH2 – C – CH2 – CH2 – CH3 (vi) H OCH3
H
3. Predict the products formed when cyclohexanecarbaldehyde reacts with following reagents.
(i) PhMgBr and then H3O+
(ii) Tollen's reagent
(iii) Semicarbazide and weak acid
(iv) Excess ethanol and acid
(v) Zinc amalgam and dilute hydrochloric acid
OMgBr OH
CH=O Ph–MgBr C H H 3O
+ C H
Ans. (i) Ph Hydrolysis Ph
Cyclohexane- Cyclohexylphenylcarbinol
carbaldehyde
O
CH=O C–O–
+ 2[Ag(NH3)2] + 3OH
+ –
+ 2Ag + 4NH3 + 2H2O
(ii)
Silver mirror
Cyclohexane- Cyclohexane-
Tollen's reagent carboxylate ion
carbaldehyde
O
CHO O
CH=NNH–C–NH2 + H2O
(iii) + H2NNH–C–NH2
Semicarbazide
Cyclohexane- Cyclohexanecarbaldehyde
carbaldehyde semicarbazone
OC2H5
CHO H OC2H5 Dry HCl gas
+ C OC H + H O
2 5 2
(iv) H
Cyclohexane- H OC2H5
carbaldehyde Ethanol (Excess) Cyclohexanecarbaldehyde
diethyl acetal
CH3
CHO Zn/Hg–HCl
(v) (clemmensen
reduction)
Cyclohexane- Methylcyclohexane
carbaldehyde
4. Which of the following compounds would undergo aldol condensation, which the Cannizzaro
reaction and which neither ? Write the structures of the expected products of aldol condensation
and Cannizzaro reaction.
(i) Methanal (ii) 2-Methylpentanal

(iii) Benzaldehyde (iv) Benzophenone
(v) Cyclohexanone (vi) 1-Phenylpropanone
(vii) Phenylacetaldehyde (viii) Butan-1-ol
(ix) 2, 2-Dimethylbutanal
168 E
CBSE
ALLEN
Ans. Aldehydes and ketones having at least one -hydrogen undergo aldol condensation (ii), (v), (vi),
(vii) gives aldol condensation.
Aldehydes (only) having no -hydrogen undergo Cannizzaro reactions. (i), (iii), (ix) gives
cannizzaro reaction.
Compound (iv) is a ketone having no -hydrogen atom and compound (viii) Butan-1-ol is an
alcohol. Hence, these compounds do not undergo either aldol condensation or cannizzaro
reactions.
Aldol condensation
CH3
2CH3CH2CH2—CH—CHO dil. NaOH CH3CH2CH2—CH—CH—C—CH2CH2CH3
CH3 CH3 OH CHO
(ii) 2-Methylpentanal
O
dil NaOH
2 O
(v) Cyclohexanone
O CH3
dil NaOH
(vi) 2 C—CH2CH3 C=C—C
CH2 O
1-Phenylpropanone
CH3
CHO
dil NaOH
2 CH2CHO CH2—CH=C
(vii) Phenylacetaldehyde
Cannizzaro reaction :
H
H H
(i) 2 C=O + conc. KOH H—C—OH + C—OK
H O
H
Methanal Methanol Potassium methanoate
O
(iii) 2 CHO+conc.KOH CH2—OH + C—OK
Benzaldehyde Benzyl alcohol Potassium benzoate
CH3 CH3 CH3

conc.NaOH
(ix) CH3CH2—C—CHO CH3CH2—C—CH2—OH + CH3CH2—C—C—ONa
CH3 CH3 CH3O
2, 2-Dimethylbutanal 2, 2-Dimethylbutan-1-ol Sodium 2, 2-dimethylbutanoate
5. How will you convert ethanal into the following compounds ?

(i) Butane-1, 3-diol (ii) But-2-enal (iii) But-2-enoic acid
OH OH
dil NaOH NaBH4
CH3CHO CH3—CH—CH2—CHO (Redcution) CH3—CH—CH2—CH2—OH
Ans. (i) Ethanal 3-Hydroxybutanal Butane-1, 3 - diol
OH
dil NaOH 
CH3CHO CH3—CH—CH2—CHO –H2O
CH3–CH=CH–CHO
(ii) Ethanal 3-Hydroxybutanal But - 2 - enal
(iii) When treated with Tollen's reagent, But-2-enal produced in the above reaction produces
but -2-enoic acid.
+ –
[Ag(NH3)2] OH
CH3–CH=CH–CHO Tollen's reagent
CH3CH=CHCOOH
But-2-enal But-2-enoic acid
E 169
Chemistry
ALLEN
6. Write structural formulas and names of four possible aldol from propanal and butanal. In each
case, indicate which aldehyde acts as nucleophile and which as electrophile.
Ans. (i) Taking two molecules of propanal, one which acts as a nucleophile and the other as an
electrophile.
OH CH3
dil NaOH
2CH3CH2CHO CH3CH2—CH—CH—CHO
Propanal 3-hydroxy - 2 - methylpentanal
(ii) Taking two molecules of butanal, one which acts as a nucleophile and the other as an
electrophile.
OH CH2CH3
dil NaOH
2CH3CH2CH2CHO CH3CH2CH2—CH—CH—CHO
Butanal 2-Ethyl - 3 - hydroxyhexanal
(iii) Taking one molecule each of propanal and butanal in which propanal acts as a nucleophile
and butanal acts as an electrophile.
OH CH3
CH3CH2CH2CHO + CH3CH2CHO CH3CH2CH2—CH—CH—CHO
Butanal Propanal 3-Hydroxy - 2 -methylhexanal
(Electrophile) (Nucleophile)
(iv) Taking one molecule each of propanal and butanal in which propanal acts as an
electrophile and butanal acts as a nucleophile.
OH CH2CH3
CH3CH2CHO + CH3CH2CH2CHO CH3CH2—CH—CHCHO
Propanal Butanal 2-Ethyl - 3 - hydroxypentanal
(Electrophile) (Nucleophile)
7. An organic compound (A) (molecular formula C8H16O2) was hydrolysed with dilute sulphuric
acid to give a carboxylic acid (B) and an alcohol (C). Oxidation of (C) with chromic acid
produced (B). (C) on dehydration gives but-1-ene. Write equations for the reactions involved.
Ans. Hydrolysis of ester gives acid and alcohol
O O
dil H2SO4
CH3CH2CH2–C–OCH2CH2CH2CH3 CH3CH2CH2–C–OH + CH3CH2CH2CH2OH
Butylbutanoate Butanoic acid Butan-1-ol
(A) (B) (C)
O
CH3CH2CH2–C–OH
CrO3/CH3COOH Butanoic acid
Oxidation (B)
CH3CH2CH2CH2 -OH
Dehydration
–H2O
CH3CH2CH=CH2
But-1-ene
(Only 1-Alkanol gives acid on oxidation)

8. Arrange the following compounds in increasing order of their property as indicated :
(a) Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tert-butyl ketone

[Reactivity towards HCN]
(b) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH, CH3CH2CH2COOH
[Acid strength]
(c) Benzoic acid, 4-Nitrobenzoic acid, 3,4–Dinitrobenzoic acid, 4–Methoxybenzoic acid
[Acid strength]
(d) CH3COCl, CH3CONH2, CH3COOCH3, (CH3CO)2O [Reactivity in hydrolysis]
170 E
CBSE
ALLEN
Ans. (a) Di-tert-butyl ketone < Methyl tert-butyl ketone < Acetone < Acetaldehyde
(b) (CH3)2CHCOOH,< CH3CH2CH2COOH < CH3CH(Br)CH2COOH,<CH3CH2CH(Br)COOH
(c) 4-Methoxybenzoic acid < Benzoic acid < 4-Nitrobenzoic acid < 3, 4-Dinitrobenzoic acid
(d) CH3CONH2 < CH3COOCH3 < (CH3CO)2O < CH3COCl
9. Give simple chemical tests to distinguish between the following pairs of compounds.
(i) Propanal and Propanone (ii) Acetophenone and Benzophenone
(iii) Phenol and Benzoic acid (iv) Benzoic acid and Ethyl benzoate
(v) Pentan-2-one and Pentan-3-one (vi) Benzaldehyde and Acetophenone
(vii) Ethanal and Propanal
Ans. (i) By Tollen's test
(a) Propanal reduces Tollen's reagent, fehling solution, Benedict solution but propanone
(ketone) does not reduces.
(b) Iodoform test :
CH3–C–CH3
Propanone gives iodoform test but propanal (CH3–CH2–CHO) does not.
O
(ii) Acetophenone and Benzophenone can be distinguished using the iodoform test.
Acetophenone gives iodoform test but benzophenone does not.
(iii) Phenol and benzoic acid can be distinguished by ferric chloride test and NaHCO3 test.
(a) Phenol gives voilet colour with FeCl3.
(b) Benzoic acid gives CO2 with NaHCO3 while phenol does not.
(iv) Benzoic acid and Ethyl benzoate can be distinguished by sodium bicarbonate test.
Sodium bicarbonate test :
Benzoic acid react with NaHCO3 to produce brisk effervescence due to the evolution of
CO2 gas but ethylbenzoate does not.
(v) Pentan-2-one and pentan-3- one can be distinguished by iodoform test. Pentan-2-one gives
iodoform test but pentan-3-one does not.
(vi) Benzaldehyde and acetophenone can be distinguished by the (a) Tollen's test (b) Iodoform
test. Benzaldehyde gives Tollen's test where as acetophenone gives iodoform test.
(vii) Ethanal and propanal can be distinguished by iodoform test. Ethanal gives iodoform test but
propanal does not.
10. How will you prepare the following compounds from benzene ? You may use any inorganic
reagent and any organic reagent having not more than one carbon atom
(i) Methylbenzoate (ii) m - Nitrobenzoic acid
(iii) p - Nitrobenzoic acid (iv) Phenylacetic acid
(v) p - Nitrobenzaldehyde
CH3 COOH COOCH3


Ans. (i) + CH3–Cl
AlCl3 KMnO4 H
CH3OH
(ii) In above reaction if

COOH COOH
HNO 3
+ H 2SO 4
(Nitration) NO2
E 171
Chemistry
ALLEN
CH3 CH3 COOH
CH3Cl/
Anhyd. AlCl 3 HNO 3/H2SO 4 KMnO 4–KOH 
+
(iii) (Friedel-Craft (Nitration) H 3O
alkylation)
Benzene NO2 NO2
(Major) p-Nitrobenzoic acid
CH3 CH2Br CH2CN CH2COOH

CH3Cl/
+
Anhyd.AlCl3 Br2 and hv Alc. KCN, H /H 2O
(iv)
Benzene Toluene Benzylbromide Benzylcyanide Phenylacetic aicd
CH3 CH3 CHO
CH 3Cl/
Anhyd.AlCl3 HNO3/H 2SO4 CrO3
(v)
Benzene NO2 NO2
p-Nitrobenzaldehyde
11. How will you bring about the following conversions in not more than two steps ?
(i) Proapnone to Propene (ii) Benzoic acid to Benzaldehyde
(iii) Ethanol to 3-Hydroxybutanal (iv) Benzene to m-Nitroacetophenone
(v) Benzaldehyde to Benzophenone (vi) Bromobenzene to 1-Phenylethanol
(vii) Benzaldehyde to 3-Phenylpropan-1-ol
(viii) Benazaldehyde to -Hydroxyphenylacetic acid
O OH
Ans. (i) CH3–C–CH3
NaBH4
CH3–CH–CH3
conc.H 2SO 4

CH3–CH=CH2
Propene
COOH COCl CHO
SOCl2 H2
(ii) Pd–BaSO 4
Benzoic acid Benzaldehyde

OH
CrO 3 dil.NaOH
(iii) CH3–CH2–OH CH3CHO (Aldol CH3CHCH2CHO
Ethanol condensation) 3-hydroxybutanal
COCH3 COCH3
CH 3COCl,
Anhyd AlCl3 HNO 3/H 2SO 4
(iv) (Friedel-Craft
alkylation) NO2
Benzene
O
CHO COOH COCl + Anhyd.AlCl3 C
[O] SOCl2
(v) (Oxidation) (Friedel-Craft acylation)
Benzaldehyde Benzophenone
OH
Br MgBr H3C–CH
Mg/dry ether (i) CH3CHO
(vi) (ii) H 2O
Bromobenzene 1-Phenylethanol
CHO CH=CHCHO CH2CH2CH2OH

(i) NaOH Ni/H2
(vii) + CH3CHO (ii)  (Catalytic
hydrogenation)
Benzaldehyde (Aldol condensation) 3-Phenylpropan-1-ol
CHO OH OH
+
HCN H /H 2O
(viii) C6H5–CH–CN C6H5–CH–COOH
-Hydroxyphenylacetic acid
Benzaldehyde
172 E
CBSE
ALLEN
12. Describe the following :
(i) Acetylation (ii) Cannizzaro reaction
(iii) Cross aldol condensation (iv) Decarboxylation
Ans. (i) Acetylation :
To introduce acetyl group CH3–C– in an organic compound.
O
Pyridine
CH3CH2OH + CH3COCl CH3COOC2H5 + HCl
Ethanol Acetyl Ethylacetate
Chloride
(ii) Cannizzaro reaction :

The self oxidation-reduction (disproportionation) reaction of aldehydes having no -
hydrogens on treatment with concentrated alkalis is known as the Cannizzaro reaction. In
this reaction, two molecules of aldehydes participate where one is reduced to alcohol and
the other is oxidized to carboxylic acid.
O
2 C + conc. KOH H–CH2–OH + HCOOK
H H methanol Potassium
a methanal methanoate
(iii) Cross-aldol condensation :

Reaction between two different aldehydes, or two different ketones, or an aldehyde and a
ketone (having -H) in presence of base is called a cross-aldol condensation.
CH3
dil 
CH3–C–H + CH3–C–CH3 KOH CH3–C–CH2–C–H –H2O CH3–C=CH–C–H
O O OH O CH3 O
(iv) Decarboxylation :
Decarboxylation refers to the reaction in which carboxylic acids lose carbon dioxide to
form hydrocarbons when their sodium salts are heated with soda-lime.
Soda-lime (mixture of NaOH and CaO in 3:1 ratio)
CH3–COONa
Sodium ethanoate

CH4 + Na2CO3
Methane
13. Complete each synthesis by giving missing starting material, reagent or products.
CH2CH3 COOH
KMnO4 SOCl2
(i) KOH, heat (ii) heat
COOH
O
H2NCONHNH2
C
(iii) C6H5CHO (iv)
O [Ag(NH 3)2]+
CHO
NaCN/HCl
(v) (vi)
CHO COOH
C6H5CHO (i) NaBH4
CH3COCH2COOC2H5 (ii) H+
(vii) +
dil.NaOH

(viii)
CH3CH2CHO
CrO3
(ix) OH (x) CH2 CHO
(i) O3
O
(xi) (ii) Zn-H 2O
E 173
Chemistry
ALLEN
CH2CH3 COOK
KMnO4
Ans. (i) KOH, heat
Ethylbenzene Pot benzoate

COOH COCl
SOCl2
(ii)
COOH COCl
Phthalic acid Phthaloyl chloride

O
(iii) C6H5CHO + H2NCONHNH2 C6H5–CH = N–NH–C–NH2
Benzaldehyde Semicarbazide Benzaldehyde semicarbazone
O
COCl C
+ Anhyd AlCl3
+ HCl
(iv) F.C. acylation
Benzene Benzoyl chloride Benzophenone

O [Ag(NH3)2] + O
(v) CHO COOH

4-Oxocyclohexanecarbaldehyde 4-Oxocyclohexanecarboxylate
anion
OH
CHO CH
(vi) NaCN/HCl CN
COOH COOH
2-Formylbenzoic acid 2-[1-Hydroxycyanomethly]

benzoic acid
(vii) C6H5CHO
Benzaldehyde
dil.NaOH 3 2 1
+  C6H5CH=C–CHO
CH3CH2CHO CH3
Propanal 2-Methyl - 3 - phenyl
prop - 2 - enal
(i) NaBH 4
(viii) CH3COCH2COOC2H5 (ii)H+ CH3CH(OH)CH2COOC2H5
Ethyl 3-oxobutanoate Ethyl-3-hydroxybutanoate
CrO 3–H 2SO 4
(ix) OH O
Chclohexanol Cyclohexanone
CHO
(x) CH2
BH3
CH2 B H 2O 2/OH
—
CH2OH PCC
3
Methylenecyclohexane Cyclohexanecarbaldehyde
(xi) (i) O 3
2 O
(ii) Zn-H 2O
Cyclohexylidene cyclohexane Cyclohexanone
14. Give plausible explanation for each of the following :

(i) Cyclohexanone forms cyanohydrin in good yield but 2, 2, 6-trimethylcyclohexanone does
not.
(ii) There are two-NH2 group in semicarbazide. However, only one is involved in the formation
of semicarbazones.
(iii) During the preparation of esters a carboxylic acid and an alcohol in the pressence of an acid
catalyst, the water or the ester should be removed as soon as it is formed.
Ans. (i) Cyclohexanones form cyanohydrins according to the following equation.
O OH CN
Cyclohexanone Cyanohydrin
174 E
CBSE
ALLEN
In 2, 2, 6 - trimethyl cyclohexanone, methyl groups at -positions offer steric hindrance
and as a result, CN– cannot attack effectively.
O
H3C CH3
CH3
2, 2, 6 - Trimethyl cyclohexanone
For the reason, it does not form a cyanohydrin.
O O+ O—
(ii) C NH2 C NH2 C NH2
+ +
H2N N H2N NH H2N NH
H
The electron density on –NH2 group involved in the resonance also decreases. As a result,
it cannot act as a nucleophile. Since the other – NH2 group is not involved in resonance; it
can act as a nucleophile and can attack carbonyl - carbon atoms of aldehydes and ketones
to produce semicarbazones.
+
H
(iii) RCOOH + R'OH RCOOR' + H2O
carboxylic acid Alcohol Ester water
If either water or ester is not removed as soon as it is formed, then it reacts to give back the
reactants as the reaction is reversible.
15. An organic compound contains 69.77% carbon, 11.63% hydrogen and rest oxygen. The
molecular mass of the compound is 86. It does not reduce Tollen's reagent but forms an addition
compound with sodium hydrogensulphite and give positive idoform test. On vigorous oxidation
it gives ethanoic and propanoic acid. Write the possible structure of the compound.
Ans. % of carbon = 69.77%
% of hydrogen = 11.63%
% of oxygen = {100–(69.77 + 11.63)}% = 18.6%
Thus, the ratio of the number of carbon, hydrogen and oxygen atoms in the organic compound
can be given as:
69.77 11.63 18.6
C:H:O  : : = 5.81:11.63:1.16 = 5:10:1
12 1 16
Therefore, the empirical formula of the compound is C5H10O. Now, the empirical formula mass
of the compound can be given as :
5 × 12 + 10 × 1 + 1 × 16 = 86
Molecular mass of the compound = 86 (given)
Therefore, the molecular formula of the compound is given by C5H10O.
Since the given compound does not reduce Tollen's reagent, it is not an aldehyde. Again the
compound forms sodium hydrogen sulphate addition products and gives a positive iodoform test.
Since the compound is not an aldehyde, it must be a methyl ketone.
The given compound also gives a mixture of ethanoic acid and propanoic acid.
Hence, the given compound is pentan-2-one.
O
CH3–C–CH2–CH2–CH3
Pentan-2-one
E 175
Chemistry
ALLEN
The given reactions can be explained by the following equations :
OH
CH3–C–CH2CH2CH3
–
SO3Na+
NaHSO3 (Addition Product)
O
NaOH/I2
CH3–C–CH2CH2CH3 CH3CH2CH2COONa + CHI3
Pentan-2-one Sodium butanoate Iodoform
[O] (Yellow ppt)
CH3COOH + CH3CH2COOH
Ethanoic acid Propanoic acid
16. Although phenoxide ion has more number or resonating structures than carboxylate ion,
carboxylic acid is a stronger acid than phenol. Why ?
Ans. Resonance structures of phenoxide ion are :
O O O O O
I II III IV V
Un equivalent resonating structures
–
O O
R—C – R—C
O O
I' II'
Equivalent resonating structures, more stable
176 E
CBSE
ALLEN
EXERCISE-3 EXEMPLAR
1. Addition of water to alkynes occurs in acidic medium and in the presence of Hg2+ ions as a
catalyst. Which of the following products will be formed on addition of water to but-1-yne under
these conditions ?
O O
 
(a) CH 3 – CH 2 – CH 2 – C– H (b) CH 3 – CH 2 – C– CH 3
O O O
  
(c) CH 3 – CH 2 – C– OH  CO 2 (d) CH 3 – C– OH – H – C– H
Ans. (b)
2. Which of the following compounds is most reactive towards nucleophilic addition reactions ?
O O
 
(a) CH 3 – C– H (b) CH 3 – C– CH 3
(c) (d)

Ans. (a)
3. The correct order of increasing acidic strength is ………. .
(a) phenol < ethanol < chloroacetic acid < acetic acid
(b) ethanol < phenol < chloroacetic acid < acetic acid
(c) ethanol < phenol < acetic acid < chloroacetic acid
(d) chloroacetic acid < acetic acid < phenol < ethanol
Ans. (a)
O

4. Compound Ph – O – C– Ph can be prepared by the reaction of ………. .
(a) phenol and benzoic acid in the presence of NaOH
(b) phenol and benzoyl chloride in the presence of pyridine
(c) phenol and benzoyl chloride in the presence of ZnCl2
(d) phenol and benzaldehyde in the presence of palladium
Ans. (b)
5. The reagent which does not react with both, acetone and benzaldehyde ?
(a) Sodium hydrogen sulphite (b) Phenyl hydrazine
(c) Fehling’s solution (d) Grignard reagent

Ans. (c)
6. Cannizzaro’s reaction is not given by …………. .
CHO
(a) (b) CHO (c) HCHO (d) CH3CHO
CH3
Ans. (d)
E 177
Chemistry
ALLEN
7. Which products is formed when the compound CHO is treated with concentrated

aqueous KOH solution ?
(a) CHO
(b) CH2OH

(c)
(d)
Ans. (b)
8. CH 3 – C  CH 
40%H 2SO 4
 A 
Isomerisation
 CH 3 – C– CH 3
1%HgSO 4

O
Structure of ‘A’ and type of isomerism in the above reaction are respectively
(a) Prop-1-en-2-ol, metamerism (b) Prop-1-en-1-ol, tautomerism
(c) Prop-2-en-2-ol, geometrical isomerism (d) Prop-1-en-2-ol, tautomerism
Ans. (d)
9. Compounds A and C in the following reaction are ……… .
H 2SO 4 ,
CH 3CHO 
(i) CH 3MgBr
(ii) H 2O
(A)  (B) 
Hydroboration oxidation
(C)
(a) identical (b) positional isomers

(c) functional isomers (d) optical isomers
Ans. (b)
10. Which is the most suitable reagent for the following conversion ?
O O
 
CH 3 – CH  CH – CH 2 – C– CH 3 
 CH 3 – CH  CH – CH 2 – C– OH
(a) Tollen’s reagent (b) Benzoyl peroxide
(c) I2 and NaOH solution (d) Sn and NaOH solution

Ans. (c)
11. Which of the following compounds will give butanone on oxidation with alkaline KMnO4
solution ?
(a) Butan-1-ol (b) Butan-2-ol (c) Both (a) and (b) (d) None of these
Ans. (b)
178 E
CBSE
ALLEN
12. In Clemmensen reduction, carbonyl compound is treated with ……… .
(a) zinc amalgam + HCl (b) sodium amalgam + HCl
(c) zinc amalgam + nitric acid (d) sodium amalgam + HNO3
Ans. (a)
(SHORT ANSWER TYPE QUESTIONS)
13. Why is there a large difference in the boiling points of butanal and butan-1-ol ?
Ans. Butan-1-ol has intermolecular H-bonding as shown below
2 4
1 O–H---O
3
H
Butanol has polar polar O–H bond due to which it shows intermolecular H-bonding which is not
possible in case of butanal due to absence of polar bond. Instead of it has only weak dipole-
dipole interactions. Hence, butanal has higher boiling point than butan-1-ol.
14. Write a test to differentiate between pentan-2-one and pentan-3-one.
Ans. Iodofrom test (yellow ppt. formed when heated with sodium hypohalite) pentan-2-one gives
positive test as it contains COCH3 group whereas pentan-3-oen does not.
O

CH 3CH 2 CH 2 – C– CH 3  I2 / NaOH
(Iodoform test )
 CHl3  CH 3CH 2 COONa
Yellow
ppt
O

CH 3CH 2 – C– CH 2 CH 3 
I2 / NaOH
 No yellow ppt. of CHI3
Pentan-3-one
15. Give the IUPAC names of the following compounds.

CH = CH – CHO
CHO
(a) (b)

(c) CH 3 – CH 2 – C– CH 2 – CHO (d) CH2 – CH = CH – CHO

O
Ans. Following are the IUPAC names of the compounds :

CH = CH – CHO
CHO
(a) (b)
3-phenylprop-2-en-1-al Cyclohexanecarbaldehyde

(c) CH 3 – CH 2 – C– CH 2 – CHO (d) CH 2 – CH  CH – CHO
 But 2en 1al
O
3oxopen tan 1al
E 179
Chemistry
ALLEN
16. Give the structure of the following compounds.
(a) 4-nitropropiophenone
(b) 2-hydroxycyclopentanecarbaldehyde
(c) Phenyl acetaldehyde
Ans. (a) 4-nitropropiophenone
O2N 4 1

(b) 2-hydroxycyclopentanecarbaldehyde
2 OH
1 CHO
(c) Phenyl acetaldehyde

17. Write IUPAC names of the following structures
CHO Br
C HO
(a) | (b) (c)
CHO
CHO
CHO
Ans. The IUPAC names of the following structures are
CHO
Br
C HO
(a) | (b) (c)
CHO CHO
Ethan 1,2dial CHO 3-bromobenzaldehyde
Benzene-1,4-y dicarbaldehyde

18. Name the electrophile produced in the reaction of benzene with benzoyl chloride in the presence
of anhydrous AlCl3. Name the reaction also.
Ans. Benzene, on reaction with benzoyl chloride undergo formation of benzophenone through
intermediate benzoylinium cation.
Benzoylinium Benzophenone
cation

This is an example of Friedel-Craft acylation reaction.
180 E
CBSE
ALLEN
19. Oxidation of ketones involves carbon-carbon bond cleavage. Name the products formed on
oxidation of 2, 5-dimethylhexan-3-one.
Ans. According to Popoff’s rule, the unsymmetrical ketone on oxidation, CC bond cleavage and
CH3
|
keto group with CH 3 – CH – group
CH3 O CH3 CH3
|  | |
CH 3 – CH – C– CH 2 – CH – CH3 
[O]
 CH 3 – CH – COOH
(2,5 dimethylhexan-3-one) (2  methylpropanoic acid)
CH3
|
 CH 3 – CH – CH 2 – COOH  CH 3 – C– CH 3
(3 methylpropanoic acid) 
O
(Pr opan  2  one)
CH3
CH3
Propan-2-one
20. Arrange the following in decreasing order of their acidic strength and give reason for your
answer.
CH 3CH 2 OH, CH 3COOH, ClCH 2 COOH, FCH 2COOH, C6 H 5CH 2 COOH
Ans. FCH 2 COOH  CICH 2 COOH  C6 H5CH 2 COOH  CH 3COOH  CH 3CH 2OH
Reasons
(i) More the electron withdrawing nature of substituent, more is the acidic strength. sp2
hybridisation.
(ii) Alcohols are weakly acidic than carboxylic acids.
21. Compound ‘A’ was prepared by oxidation of compound ‘B’ with alkaline KMnO4. Compound
‘A’ on reduction with lithium aluminium hydride gets converted back to compound ‘B’. When
compound ‘A’ is heated with compound B in the presence of H2SO4 it produces fruity smell of
compound C to which family the compounds ‘A’, ‘B’ and ‘C’ belong to ?
Ans. Since, B and A on heating together in the presence of acid produces ester (a fruity smell).
[B] 
Alk.KMnO4
[O]
[A]
Alcohol Carboxylic acid

[A]  [B] 
H 2SO4
 [C]  H 2 O
Acid Alcohol Ester

(fruity smell)
22. Arrange the following in decreasing order of their acidic strength. Give explanation for the
arrangement.
C6 H 5COOH, FCH 2 COOH, NO 2 CH 2 COOH
Ans. The decreasing order of their acidic strength
NO 2CH 2 COOH  FCH 2 COOH  C6 H 5COOH
E 181
Chemistry
ALLEN
Acidic strength decreases as the number of electron withdrawing substituents(s) linked to
-carbon atom or carboxylic group of carboxylic acid decreases. Electron withdrawing ability of
NO2, F and C6H5 are as follows :
–NO 2  –F  C6 H 5 –
23. Carboxylic acids contain carbonyl group but do not show the nucleophilic addition reaction like
aldehydes or ketones. Why ?
Ans. Carboxylic acid contain carbonyl group but do not show nucleophilic addition reaction like
aldehyde and ketone. Due to resonance as shown below the partial positive charge on carbonyl
carbon atom is reduced.
O O–
 | 
– C– O – H 
 –C  O– H
24. Why are carboxylic acid more acidic than alcohols or phenols although all of them have
hydrogen atom attached to a oxygen atom (–O–H) ?
Ans. Carboxylic acids are more acidic than or phenol, although all of them have O–H bond. this can
be explained on the basis of stability of conjugate base obtained after removal of H+ from acid or
phenol.

O:
: :

O:
: :
R O
(Carboxylic acid) [More stable carboxylate anion]


O:
: :
[Less stable phenoxide ion]
Hence, dissociation of O–H bond in case of carboxylic acid become easier than that of phenol.
Hence, carboxylic acid are stronger acid than phenol.
(MATCHING THE COLUMNS)
25. Match the common names given in Column I with the IUPAC names given in Column-II.
Column-I Column-II
(Common names) (IUPAC names)
A. Cinnamaldehyde 1. Pentanal
B. Acetophenone 2. Prop-2-en-al
C. Valeraldehyde 3. 4-methylpent-3-en-2-one
D. Acrolein 4. 3-phenylprop-2-en-al
E. Mesityl oxide 5. 1-phenylethanone
Ans. A  (4) ; B  (5) ; C  (1) ; D  (2) ; D  (3)

182 E
CBSE
ALLEN
26. Match the acids given in Column-I with their correct IUPAC names given in Column-II.
Column-I Column-II
(Acids) (IUPAC names)
A. Phthalic acid 1. Hexane-1, 6-dioic acid
B. Oxalic acid 2. Benzene-1, 2-dicaboxylic acid
C. Succinic acid 3. Pentane-1, 5-dioic acid
D. Adipic acid 4. Butane-1, 4-dioic acid
E. Glutaric acid 5. Ethane-1, 2-dioic acid
Ans. A  (2) ; B  (5) ; C  (4) ; D  (1) ; D  (3)
27. Match the reactions given in Column I with the suitable reagents given in Column II.
Column-I Column-II
(Reactions) (Reagents)
A. Benzophenone  Diphenylmethane 1. LiAlH4
B. Benzaldehyde  1-phenylethanol 2. DIBAL-H
C. Benzaldehyde  1-phenylethanol 3. Zn(Hg)/Conc. HCl
D. Phenyl benzoate  Benzaldehyde 4. CH3MgBr
Ans. A  (3) ; B  (4) ; C  (1) ; D  (2)
28. Match the example given in Column I with the name of the reaction in Column II.
Column-I Column-II
(Example) (Reaction)
A. O O 1. Friedel-Crafts acylation
Pd–C/BaSO4
CH3—C—Cl + H2 CH3—C—H
B. CHO CH3OH COO–Na+ 2. HVZ reaction
NaOH
+
C. O 3. Aldol condensation
C—CH3
O
AlCl3
+ CH3—C—Cl
D. Br2/Red P 4. Cannizzaro’s reaction

R—CH2—COOH R—CH—COOH
Br
E. CH3 — CN 
(i)SnCl2 /HCl
(ii) H O/H 
 CH3CHO 5. Rosenmund’s reduction
2
F. 2CH3CHO 
NaOH
 CH3–CH = CHCHO 6. Stephen’s reaction
Ans. A  (5) ; B  (4) ; C  (1) ; D  (2) ; E  (6) ; F  (3)
E 183
Chemistry
ALLEN
options:
29. Assertion (A) : Formaldehyde is a planar molecule.
Reason (R) : It contains sp2-hybridised carbon atom.
Ans. (a)
30. Assertion (A) : Compound containing – CHO group are easily oxidised to corresponding
carboxylic acids.
Reason (R) : Carboxylic acids can be reduced to alcohols by treatment with LiAlH4.
Ans. (b)
31. Assertion (A) : The -hydrogen atom in carbonyl compound is less acidic.
Reason (R) : The anion formed after the loss of -hydrogen atom is resonance stabilised.
Ans. (d)
32. Assertion (A) : Aromatic aldehydes and formaldehyde undergo Cannizaro reaction.
Reason (R) : Aromatic aldehydes are almost as reactive as formaldehyde.
Ans. (c)
33. Assertion (A) : Aldehydes and ketones, both react with Tollen’s reagent to form silver mirror.
Reason (R) : Both, aldehydes and ketones contain a carbonyl group.
Ans. (d)
184 E
CBSE
ALLEN
(INTRODUCTION)
1. In aldehydes and ketones, carbon of carbonyl group is
(a) sp3 hybridised (b) sp2 hybridised (c) sp hybridised (d) Unhybridised
2. Glyoxal is [BVP 2003]
(a) CH2O–CH2O (b) CH 2 OH (c) CHO (d) CH 2 OH
| | |
CH2OH CHO CHO
3. Aldehydes are isomeric with
(a) Ketones (b) Ethers (c) Alcohols (d) Fatty acids
4. IUPAC name of CH3COCH3 is
(a) Acetone (b) 2-propanone
(c) Dimethyl ketone (d) Propanal
5. Which of the aldehyde is most reactive ?
(a) C6H5–CHO (b) CH3CHO
(c) HCHO (d) All the equally reactive
(PREPARATION)
6. The end product in the following sequence of reaction is
HC  CH 
1%HgSO 4
 A 
CH3 MgX
 B 
[O]

20%H 2SO 4
(a) Acetic acid (b) Isopropyl alcohol (c) Acetone (d) Ethanol
O
||
7. In the following reaction, product P is R  C  Cl 
H2
P
Pd  BaSO 4
(a) RCH2OH (b) RCOOH (c) RCHO (d) RCH3

8. Acetophenone is prepared from
(a) Rosenmund reaction (b) Sandmayer reaction
(c) Wurtz reaction (d) Friedel craft reaction
9. Compound which gives acetone on ozonolysis
(a) CH 3  CH  CH  CH 3 (b) (CH 3 ) 2 C  C(CH 3 ) 2
(c) C6 H 5CH  CH 2 (d) CH 3CH  CH 2
10. Catalyst used in Rosenmund reduction is

(a) Pd / BaSO4 (b) Zn-Hg couple
(c) LiAlH4 (d) Ni/H2
11. Acetophenone is prepared by the reaction of which of the following in the presence of catalyst
(a) Phenol and acetic acid (b) Benzene and acetone
(c) Benzene and acetyl chloride (d) Phenol and acetone
E 185
Chemistry
ALLEN
12. Isopropyl alcohol on oxidation gives
(a) Acetone (b) Acetaldehyde (c) Ether (d) Ethylene
13. Which of the following compound gives a ketone with Grignard reagent
(a) Formaldehyde (b) Ethyl alcohol (c) Methyl cyanide (d) Methyl iodide
14. In the Rosenmund's reduction, taken with catalyst Pd acts as
(a) Promotor (b) Catalytic poison (c) Cooperator (d) Absorber
15. The Clemmenson reduction of acetone yields
(a) Ethanol (b) Ethanal (c) Propane (d) Propanol
16. Benzaldehyde can be prepared by oxidation of toluene by
(a) Acidic KMnO4 (b) K2Cr2O7 (c) CrO2Cl2 (d) All of these
17. C6 H 6  CO  HCl 
Anhy AlCl3
 X  HCl
Compound X is
(a) C6H5CH3 (b) C6H5CH2Cl (c) C6H5CHO (d) C6H5COOH
18. The reagent used in Gatterman Koch aldehyde synthesis is
(a) Pb/BaSO4 (b) alkaline KMnO4
(c) acidic KMnO4 (d) CO + HCl
(PROPERTIES)
19. Identify the reactant X and the product Y
CH 3  CO  CH 3  X  (CH 3 )3 C  OMg  Cl
Hydrolysis
Y  Mg (OH) Cl
(a) X  MgCl2 ; Y  CH 3CH  CH 2 (b) X  CH 3 MgCl; Y  C2 H 5COCH 3
(c) X  CH 3 MgCl; Y  (CH 3 )3 C  OH (d) X  C2 H 5 MgCl; Y  (CH 3 )3 C  OH
20. Reduction of Aldehydes and Ketones to hydrocarbon take place in the presence of
(a) Zn amalgam and HCl acid (b) Pd/BaSO4
(c) Anhydrous AlCl3 (d) Ni/Pt
21. Reduction of > C = O to CH2 can be carried out with
(a) Catalytic reduction (b) Na/C2H5OH
(c) Wolf-Kischner reduction (d) LiAlH4
22. Which of the following gives aldol condensation reaction

O
||
(a) C6H5OH (b) C6 H 5  C  C6 H 5
O O
|| ||
(c) CH 3CH 2  C  CH 3 (d) (CH 3 )3 C  C  CH 3
186 E
CBSE
ALLEN
23. Which of the following products is formed when benzaldehyde is treated with and the addition
product so obtained is subjected to acid hydrolysis
(a) Secondary alcohol (b) A primary alcohol
(c) Phenol (d) Tert-Butyl alcohol
24. Which of the following organic compounds exhibits positive Fehling test as well as iodoform test
(a) Methanal (b) Ethanol (c) Propanone (d) Ethanal
25. Which of the following compound will undergo self aldol condensation in the presence of cold
dilute alkali
(a) C6H5CHO (b) CH3CH2CHO (c) CH  C–CHO (d) CH2=CH–CHO
26. Acetaldehyde when treated with dilute NaOH gives
(a) CH3CH2OH (b) CH3COOH
(c) CH 3  CH  CH 2  CHO (d) CH3–CH3
|
OH
27. C2H5CHO and (CH3)2CO can be distinguished by testing with
(a) Phenyl hydrazine (b) Hydroxylamine (c) Fehling solution (d) Sodium bisulphite
28. Which of the following does not give iodoform test
(a) CH3CH2OH (b) CH3OH (c) CH3CHO (d) PhCOCH3
29. Which of the following will not give the iodoform test
(a) Acetophenone (b) Ethanal (c) Benzophenone (d) Ethanol
30. The light yellow compound produced when acetone reacts with iodine and alkali, is
(a) CH3.CO.CH2I (b) CH3I (c) CHI3 (d) None of these
ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. b c a b c c c d b a
Q. No. 11 12 13 14 15 16 17 18 19 20
Ans. c a c b c c c d c a
Q. No. 21 22 23 24 25 26 27 28 29 30
Ans. c c a d b c c b c c
E 187
Chemistry
ALLEN
options:
1. Assertion (A) : Solubility of n-alcohol in water decreases with increase in molecular weight.
Reason (R) : The reactive proportion of the hydrocarbon part in alcohols increases with
increasing molecular weight which permits enhanced hydrogen bonding with water.
2. Assertion (A) : p-nitrophenol is a stronger acid than o-nitrophenol.
Reason (R) : Intramolecular hydrogen bonding makes the o-isomer weaker than the p-isomer.
3. Assertion (A) : Acetic acid does not undergo haloform reaction.
Reason (R) : Acetic acid has no alpha hydrogen.
4. Assertion (A) : When pure d-(+)-2methytbutanal is treated with dilute H2SO4, it is racemised
completely.
Reason (R) : It's -carbon is chiral which undergo keto-enol tautomerism in the presence of
acid catalyst.
5. Assertion (A) : When benzaldehyde (C6H5CHO) is treated with concentrated NaOH solution in
D2O, Cannizzaro reaction occur but no C–D (bonds with deuterium) is formed.
Reason (R) : Cannizzaro reaction involves hydride transfer mechanism.
6. Assertion (A) : Benzoic acid, 3,4-dinitrobenzoic acid, 4-methoxybenzoic acid are in increasing
order of acidic strength.
Reason (R) : The have—COOH group.
7. Assertion (A) : Cl — CH2COOH is a stronger acid than CH3COOH.
Reason (R) : —CI group exhibits +I effect.

8. Assertion (A) : 2R—COOH + 2Na  2R— COONa  H 2 
Reason (R) : Reaction shows the acidic nature of carboxylic acid.
9. Assertion (A) : Acid chloride is formed when carboxylic acids are treated with thionyl chloride.
Reason (R) : When carboxylic acid are treated with thionyl chloride, acid chloride is formed.
The reaction is as follows:
CH 3COOH  SOCl2 
 CH3 COCl  SO2   HCl 
Acetic acid Acetyl chloride
ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9
Ans. d a d a a d c a a
188 E
CBSE
ALLEN
CASE BASED
Case I
An efficient, aerobic catalytic system for the transformation of alcohols into carbonyl
compounds under mild conditions, copper-based catalyst has been discovered. This copper-
based catalytic system utilises oxygen or air as the ultimate, stoichiometric oxidants, producing
water as the only by-product.
R1 5% CuCl; 5% Phen; R1
2 2 equiv. K2CO3
R OH O
H 5% DBADH2; O2; 2
1 Toluene, 70° to R 2
A wide range of primary, secondary, allylic and benzylic alcohols can be smoothly oxidised to
the corresponding aldehydes or ketones in good to excellent yields. Air can be conveniently
used instead of oxygen without affecting the efficiency of the process. However, the use of air
requires slightly longer reaction times.
This process is not only economically viable and applicable to large-scale reactions but it is also
environmentally friendly.
(a) The transformation of alcohols into carbonyl compounds under mild conditions which
type has been discovered in this system, what is the by product ?
Ans. Catalytic system for transformation of alcohols into carbonyl compounds under mild
conditions, copper based catalyst has been discovered. In this system utilises oxygen or
air and producing water as only by product.
OR
Write the decreasing order of reaction ?
CH3–C–H , C2H5–C–H , C2H5–C–CH3
O O O
Ans. CH3–C–H > C2H5–C–H > C2H5–C–CH3
O O O
(b) Benzyl alcohol on treatment with this copper-based catalyst gives a compound 'A' which
on reaction with KOH gives compounds 'B' and 'C'. Compound 'B' on oxidation with
KMnO4-KOH gives compound 'C'. Compounds 'A', 'B' and 'C' are :
(a) banzaldehyde, benzyl alcohol, potassium salt of benzoic acid
(b) banzaldehyde, potassium salt of benzoic acid, benzyl alcohol
(c) banzaldehyde, benzoic acid, benzyl alcohol
(d) benzoic acid, benzyl alcohol, benzaldehyde
Ans. k
(c) An organic compound 'X' with molecular formula C3H8O on reaction with this copper
based catalyst gives compound 'Y' which reduces Tollen's reagent. 'X' on reaction with
sodium metal gives 'Z'. What is the product of reaction of 'Z' with 2-chloro-2-
methylpropane?
(a) CH3CH2CH2OC(CH3)3 (b) CH3CH2OC(CH3)3
(c) CH2 = C(CH3)2 (d) CH3CH2CH = C(CH3)2
Ans. k
E 189
Chemistry
ALLEN
Case II
Carboxylic acids evolve hydrogen with metals and form salts with alkalies similar to phenols.
However, unlike phenols, they react with weaker bases likesodium carbonate and hydrogen
carbonate to evolve carbon dioxide.
In aqueous solution, carboxylic acids ionise and exist in dynamic equilibrium between the
resonance stabilised carboxylate ions and the hydronium ions.
O O O– O
R—C + H2O H3O+ + R — C —
R—C — R—C –
—
OH O O O
–
Resonance stabilisation of carboxylate anion is more than that of undissociated carboxylic acid.
Therefore, greater stability of carboxylate ion is responsible for the acidic character of
carboxylic acids. Carboxylic acids are more acidic than alcohols because carboxylate anions are
more stable than alkoxide ions, so carboxylic acids have strong tendency to release a proton.
(a) CH3COOH is more acidic than CH3CH2OH. Why ?
Ans. CH3COOH is more acidic than CH3CH2OH because carboxylate aninos are more stable
than alkoxide ions. So CH3COOH have strong tendency to release a proton.
(b) Complete the following reactions :
CH3COOH + SOCl2 
Ans. CH3COOH + SOCl2 CH3COCl + SO2 + HCl
(c) Which factor is responsible for the acidic character of carboxylic acid ?
Ans. Resonance stabilisation of carboxylate anion is more than that of dissociated carboxylic
acid therefore, greater stability of carboxylate ion is responsible for the acidic character
of carboxylic acids.
OR
Complete the following reactions :
CH3COOH + NaOH 
COOH
CH3
+ NaOH 

CH3COOH + C2H5OH 
H 2SO 4

Ans. CH3COOH + NaOH CH3–COONH

COOH CH3
CH3
+ NaOH 
CaO


CH3COOH + C2H5OH  C–COOC2H5
H 2SO 4
190 E
CBSE
ALLEN
1. Which of the following is most reactive in nucleophilic addition reactions? [1] (CBSE 2023)
(a) HCHO (b) CH3CHO (c) CH3COCH3 (d) CH3COC2H5
Ans. (a)
2. Which of the following does not give aldol condensation reaction? [1] (CBSE 2023)
(a) CH3–CHO (b)
CHO
(c) (d) CH3COCH3

CHO

Ans. (c)
3. Iodoform test in not given by [1] (CBSE 2020)
(a) Ethanol (b) Ethanal (c) Pentan-2-one (d) Pentan-3-one
Ans. (d) Pentan-3-one
4. What is the correct IUPAC name of the given compound ? [1] (CBSE 2020)
(a) 2,2-Dimethylbutanoic acid (b) 2-Carboxyl-2-methylbutane
(c) 2-Ethyl-2-methylpropanoic acid (d) 3-Methylbutane carboxylic acid
Ans. (a) 2,2-Dimethylbutanoic acid
5. Write the structure of 2-hydroxybenzoic acid. [1] [CBSE 2019]
COOH
Ans. OH
6. Write the IUPAC name of the following : [1] [CBSE 2018]

O
CH3–CH2–CH=CH–C–H
Ans. Pent-2-ene-1-al
7. De the following conversions in not more than two steps : [2] [CBSE 2023]
(a) CH3CN to
CH3–C–CH3
O
(b)
COOH to
O
NMgBr
Ans. (a) CH3N CH3 C
CH3
(b) COO
E 191
Chemistry
ALLEN
8. Arrange the following compounds in increasing order of their property as indicated in bracket :
(Any two) [2] [CBSE Term – II_2022]
CH3
(i) CH3–CHO, CH3–C–CH3, CH3–C–C–CH3,
O O CH3
(reactivity towards HCN)
(ii) CCl3–COOH, CF3–COOH, (CH3)3C–COOH

(acid strength)
COOH COOH COOH COOH

NO2
(iii) ; ; ;
NO2 NO2 OCH3

(acid strength)
CH3 H3C H3C

Ans. (i) CH3–C–C–CH3 < C=0 < C=0 3<2<1
H3C H
O CH3
(ii) (CH3)3CCOOH < CCl3COOH < CCl3COOH < CF3COOH 3<1<2

COOH COOH COOH COOH
NO2
(iii) < < < 3<4<2<1
OCH3 NO2 NO2
9. What happens when [2] [CBSE-2020]

(a) Propanone is treated with methylmagnesium bromide and then hydrolysed, and
(b) Benzene is treated with CH3COCl in the presence of anhydrous AlCl3
Ans. (a) (CH3)3C-OH/tertiary butyl alcohol is formed.
(b) C6H5COCH3/acetophenone is formed
10. Write structures of main compounds A and B in each of the following reactions :
[2] [CBSE 2019]
PCl H /Pd BaSO

(a) C6 H5COOH 
5  A 
2 4 B
(i)CH MgBr
(b) CH 3 CN 
3

 A  
Zn(Hg)/conc.HCl
B
(ii) H 3 O
Ans. (a) A = C6H5COCl B = C6H5CHO

(b) A = CH3COCH3 B = CH3CH2CH3
192 E
CBSE
ALLEN
11. Write structures of main compounds A and B in each of the following reactions :
[2] [CBSE 2019]
CH OH /dry HCl(g)
(a) CH 3 CH 2 OH 
PCC
 A 
3 B
(b) C 6 H 5 COCH 3 

NaOI
A  B
Ans. (a) A CH3CHO ; B CH3–CH–OH  

OCH3
 (b) C6 H 5 COCH 3  CHI 3  C6 H 5 – COONa
NaOI
12. How do you convert the following ? [2] [CBSE 2018]

(a) Ethanal to Propanone
(b) Toluene to Benzoic acid
OR
Account for the following :
(a) Aromatic carboxylic acids do not undergo Friedel–Crafts reaction.
(b) pKa value of 4-nitrobenzoic acid is lower than that of benzoic acid.
Ans. (a) Ethanol to propanone :-

O O MgX
(Grignard reagent)
CH3 – C – H + CH3 – Mg X  CH 3 – CH H O/H+ CH3 – CH – OH
2
CH3 CH3
(Ethanol) (Adduct)
CrO3
O
CH3 – C – CH 3
Propanone
(b) Toluene to Benzoic Acid 
CH3 COOK COOH
KMnO4
+
–KOH/ H3O
Benzoic acid
OR
(a) In case of aromatic carboxylic acid –COOH attach to the benzene ring having electron
withdrawing effect and deactivated the benzene ring, hence do not exhibit Friede-Craft
reaction.
(b) pKa value of 4-nitrobenzoic acid is lower than benzoic acid is due to e– withdrawing nature
of —NO2 attach at para position of benzene due to which tendency to loose H+ ion
increases and acidic character increases.

13. Write the reagents used in the following reactions : [2] (CBSE 2018)
?
(i) C 6 H 5  CO  CH 3   C 6 H 5  CH 2  CH 3
?
(ii) CH 3  COOH   CH 3  COCl
Ans. (i) Zn-Hg, HCl or H2N–NH2 & KOH/Glycol , 
(ii) PCl5 / PCl3 / SOCl2 (Any one)
E 193
Chemistry
ALLEN
14. (a) What happens when [3] (CBSE Term – II_2022)

(i) Propanone is treated with CH3MgBr and then hydrolysed ?
(ii) Ethanal is treated with excess ethanol and acid ?
(iii) Methanal undergoes Cannizzaro reaction ?
OR
(b) Write the main product in the following reactions :
(i) 2CH3COCl + (CH3)2Cd 
(ii) CH3CH2CHO 
Zn (Hg)/Conc.HCl

(iii) COONa + NaOH CaO


[1 × 3 = 3]
p
CH3 CH3
Ans. (a) (i) C = O + CH3MgBr C — OMgBr
CH3 CH3
CH3
H+ H2O
CH3
Br
CH3 – C – OH + Mg
CH3 OH
2-Methyl propan-2-ol
CH3 OC2H5
HCl
(ii) CH3–C–H + C2H5OH C
Excess H OC2H5
O
(iii) 2HCHO 

conc. NaOH
CH3OH + HCOONa
OR
(b) (i) CH3COCH3
Acetone
(ii) CH3CH2CH3
Propane
(iii)
Cyclohexane
15. (a) (i) Which acid of the following pair would your expect to be stronger ?
F–CH2–COOH or CH3–COOH
(ii) Arrange the following compounds in increasing order of their boiling points :
CH3CH2OH, CH3–CHO, CH3–COOH
(iii) Given simple chemical test to distinguish between Benzaldehyde and
Acetophenone. [1 × 3 = 3] (CBSE Term – 2_2022)
194 E
CBSE
ALLEN
OR
(b) (i) Which will undergo faster nucleophilic addition reaction ?
Acetaladehyde or Propanone
(ii) What is the composition of Fehling's reagent ?
(iii) Draw structure of the semicarbazone of Ethanal. [1×3=3]
Ans. (a) (i) F–CH2–COOH due to electron withdrawing effect of F.
(ii) CH3CHO < CH3CH2OH< CH3–COOH
(iii) Iodoform test :
COCH3 COONa 
4NaOH + 3I2 + CHI3 + + 3NaI + 3H2O
Acetophenone will give iodoform test with yellow ppt.

CHO
+ 4NaOH + 3I2  No reaction
Benzaldehyde give tollen's test but acetophenone will not give tollen's test.
OR
(b) (i) Acetaldehyde, due to less steric hindrance.
(ii) Fehling solution A – aqueous solution of CuSO4.
Fehling solution B – Roschelle salt (sodium potassium tartarate + NaOH)
O
H3C H3C O
+ H2N – HN – C – NH2
C=O C = N – NH – C – NH2 + H2O
(iii) (Semicarbazide)
H H Acetaldehyde
Acetaldehyde Semicarbazone
16. (a) Give reasons :

(i) Benzoic acid is a stronger acid than acetic acid. [3] (CBSE 2019)
(ii) Methanal is more reactive towards nucleophilic addition reaction than ethanal.
(b) Give a simple chemical test to distinguish between propanal and propanone.
Ans. (a) (i) Due to the electron donating inducting effect (+I) by the alkyl group on acetic acid
destabilise the conjugate base of acetic acid.
(ii) Aldehyde which is a functional group (CHO) is more reactive due to less steric
effect.
(b) Propanal being an aldehyde reduces Fehling's solutions to a red-brown ppt of Cu2O, but
propanone being a ketone does not. Propanone being a ketone does not.
Propanal being an aldehyde reduces Tollen's reagent to a silver mirror but propanone being
a ketone does not.
E 195
Chemistry
ALLEN
17. (a) Write the structures of A, B, C and D in the following reactions: [3] (CBSE 2018)
(i) SnCl2–HCl dil..NaOH heat
CH3CN A B C
(i) H2O
HCN
(b) Distinguish between:

(i) C6H5–CH=CH–COCH3 and C6H5–CH=CH–CO CH2CH3
(ii) CH3CH2COOH and HCOOH
(c) Arrange the following in the increasing order of their boiling points :
CH3CH2OH, CH3COCH3, CH3COOH
OH
Ans. (a) A : CH3CHO B : CH3–CH–CH2CHO
OH
C : CH3—CH=CH—CHO D : CH3–CH CN
(b) (i) Heat both the compounds with NaOH and I2, C6H5–CH=CH–COCH3 gives yellow
ppt of iodoform while C6H5–CH=CH–CO CH2CH3 does not.
(ii) Add ammonical silver nitrate solution (Tollens’ reagent), HCOOH gives silver mirror
while CH3CH2COOH does not.
(c) CH3COCH3 <CH3CH2OH <CH3COOH]
18. Predict the products of the following reactions : [3] (CBSE 2018)
H N NHCONH
(i) CH3 — C  O 
2 2
?
|
CH3
(a)KMnO /KOH
(ii) C 6 H 5  CH 2  CH 3 4
(b)H 
?
COOH
conc.HNO /H SO
(iii) 
3 2 4
Ans. (i) CH3–C=N–NH–CO–NH2

CH3
(ii) C6H5– COOH
COOH
(iii)
NO 2
196 E
CBSE
ALLEN
19. The carbon - oxygen double bond is polarised in aldehydes and ketones due to higher
electronegativity of oxygen relative to carbon. Therefore they undergo nucleophilic addition
reactions with a number of nucleophiles such HCN, NaHSO3, alcohols, ammonia derivatives and
Grignard reagents. Aldehydes are easily oxidised by mid oxidising agents as compared to
ketones. The carbonyl group of carboxylic acid does not give reactions of aldehydes and ketones.
Carboxylic acids are considerable more acidic than alcohols and most of simple phenols.
Answer the following : [4] (CBSE 2023)
(a) Write the name of the product when an aldehyde reacts with excess alcohol in presence of
dry HCl.
(b) Why carboxylic acid is a stronger acid than phenol ?
(c) (i) Arrange the following compounds in increasing order of their reactivity towards
CH3MgBr:
CH3CHO, (CH3)3C–C–CH3, CH3–C–CH3
O O
(ii) Write a chemical test of distinguish between propanal and propanone.

OR
(c) Write the main product in the following :
O
[Ag(NH3)2]+
(i)
CHO
CHO
H2NCONHNH2
(ii)
OR1 OR1
Ans. (a) Acetal ; R–CHO R–CH R–OH
OH OR1
Hemiacetal acetal
(b) Because carboxylate ion in much more resonance stabilised than phenoxide ion as negative
charge is delocalised over two electronegative O-atom in carboxylate anion while in phenol
negative charge is delocalised over only one O-atom and electro positive carbon atom.
(c) (i)
O O
(ii) Propanal being an aldehyde reduces Fehling's solutions to a red-brown ppt of Cu2O,
but propanone being a keton does not. Propanone being a ketone does not.
Propanal being an aldehye reduces Tollen's reagent to a silver mirror but propanone
being a ketone does not.
Propanone responds to Iodoform test whereas propanol does not.
E 197
Chemistry
ALLEN
OR
O O
(c) (i)
CHO COOH
CHO CH=N–NH–CONH2
(ii)
20. Aldehydes differ from ketones in their oxidation reactions. Aldehydes are easily oxidised to
carboxylic acids on treatment with common oxidising agents like nitric acid, KMnO4, K2Cr2O7
etc. Even mild oxidising agents mainly Tollens' reagent and Fehling solution also oxidise
aldehydes. Ketones are generally oxidised under vigorous conditions.
Aldehydes and ketones undergo nucleophilc addition reactions onto the carbonyl group with a
number of nucleophiles such as HCN, NaHSO3, alcohols, ammonia derivatives and Grignard
reagents. The -hydrogens of aldehydes and ketones are acidic due to which they undergo Aldol
condensation. [1+1+2=4] (CBSE 2022)
(a) Why is the oxidation of Aldehydes easier than Ketones ?
Ans. Because oxidation of aldehydes involves cleavage of C—H bond which is easier and in
ketones involve C—C bond which is difficult.
(b) Write a simple chemical test to distinguish between Acetone and Ethanal.
Ans. On heating with Tollens’ reagent, ethanal gives silver mirror while acetone does not.
(or any other suitable chemical test)
(c) Arrange the following compounds in the increasing order of their reactivity towards
nucleophilic addition reaction :
Ethanal, Acetone, Propanal, Acetophenone
Ans. Acetophenone < Acetone < Propanal < Ethanal
OR
Arrange the following compounds in increasing order of their boiling points.
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3
Ans. CH3CH2 CH3  CH3OCH3  CH3CHO  CH3CH2 OH
non polar morepolar H  bond ing

21. (a) Draw the structures of the following derivatives : [1 × 2 = 2]
(i) 2, 4-DNP of benzaldehyde (CBSE Compartment_2021)
(ii) Propanone oxime
(b) Complete the following synthesis : [2]
CH2CH
KMnO4
(i) KOH, heat
?
CH3COCl
(ii) ?
anhyd. AlCl3
(c) Carboxylic acid is a stronger acid than phenol. Justify. [1]

198 E
CBSE
ALLEN
OR
(a) An organic compound ‘A’ with molecular formula C4H8O2 was hydrolysed with dil. H2SO4
to give a carboxylic acid ‘B’ and an alcohol ‘C’. ‘C’ on dehydration gives ethene and ‘C’
also on oxidation gives back ‘B’. Identify ‘A’, ‘B’ and ‘C’ and write the chemical
equations for the reactions involved. [3]
(b) How will you convert ethanal into the following compounds ? [1 × 2 = 2]
(i) Ethanol (ii) Ethane
NO2
Ans. (a) (i)
C = N NH NO2
H
H3C
(ii) C = N – OH
H3C
O
COOH C–CH3
(b) (i) (ii)
O O O O O
(c)
I II III IV V
Un equivalent resonating structures
–
O O
R—C – R—C
O O
I' II'
Equivalent resonating structures, more stable
The carboxylate ion is more stabilised than phenoxide ion, so carboxylic acids are more acidic
than phenols.
OR
O
A  CH3–C–OC2H5
O
B  CH3–C–OH
(a)
C  C2H5OH
O O
H2O
CH3–C–OC2H5 CH3–C–OH + C2H5OH
C4H8O2 dil. H2SO4 (B) (C)
(A)
C 2 H 5 OH 
H 2 SO 4
443K
 CH 2  CH 2
(C) Ethene
E 199
Chemistry
ALLEN
O O
[O] [O]
C2H5–OH (H2SO4 + K2Cr2O7)
CH3–C–H CH3–C–OH
(C) (B)
O
(b) (i) LiAlH4
CH3 – C– H + 2H CH3 – CH2 – OH
Ethanal Ethanol
H
(ii) 4H
C=O CH3–CH3 + H2O
H3C Ethanal Zn– Hg, HCl Ethane
22. (a) How will you convert the following : [5] [CBSE 2020]
(i) Propanone to Propan-2-ol
(ii) Ethanal to 2-hydroxy propanoic acid
(iii) Toluene to benzoic acid
(b) Give simple chemical test to distinguish between :
(i) Pentan-2-one and Pentan-3-one
(ii) Ethanal and Propanal
OR
(a) Write the products of the following reactions :
Zn – Hg
(i) CH3 – C – CH3 ?
conc. HCl
O
Pd – BaSO4
(ii) CH3 – C – Cl + H2 ?
O
COOH
Br2 / FeBr3
(iii) ?
(b) Which acid of each pair shown here would you expect to be stronger ?
(i) F – CH2 – COOH or Cl – CH2 – COOH
OH
(ii) or CH3COOH
Ans. (a) (i) Ni/H2

(ii) HCN, H3O+

(iii) Alkaline KMnO4
(b) (i) Pentan-2-one and pentan-3- one can be distinguished by iodoform test. Pentan-2-one
gives iodoform test but pentan-3-one does not.
(ii) Ethanal and propanal can be distinguished by iodoform test. Ethanal gives iodoform
test but propanal does not.
200 E
CBSE
ALLEN
OR
(a) (i) CH3–CH2–CH3
(ii) CH3–CHO
COOH
(iii)
Br
(b) (i) F–CH2–COOH
(ii) CH3COOH
23. (a) Write a suitable chemical equation to complete each of the following transformations :
(i) Butan-1-ol to butanoic acid
(ii) 4-Methylacetophenone to benzene-1,4-dicarboxylic acid [5] [CBSE 2019]
(b) An organic compound with molecular formula C9H10O forms 2,4-DNP derivative, reduces
Tollen's reagent and undergoes Cannozzaro's reaction. On vigorous oxidation it gives
1,2-benzenedicarboxylic acid. Identify the compound.
OR
(a) Give chemical tests to distinguish between
(i) Propanol and propanone
(ii) Benzaldehyde and acetophenone
(b) Arrange the following compounds in an increasing order of their property as indicated :
(i) Acetaldehyde, Acetone, Methyl tert-butyl ketone (reactivity towards HCN)
(ii) Benzoic acid, 3,4-Dinitrobenzoic acid, 4-methoxybenzoic acid (acid strength)
(iii) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH (acid strength)
(i)KMnO /KOH 
Ans (a) (i) CH 3 CH 2 CH 2 CH 2 OH  4
(ii)dilute H SO
2
CH 3 CH 2 CH 2 COOH
2 4
O
(i)KMnO4 /KOH,
(ii) Me C–Me 
(ii) diluteH2SO4
HOOC COOH
Benzene-1,4-dicarboxylic acid
4-Methylacetophenone
[Terephthalic acid]
OR
(i) Iodoform test given by propanone. It gives yellow ppt of CHI3.
C– C–CH3 I + NaOH C– C–ONa + CHI3 (yellow ppt)
2
O O
(ii) Tollen's test given by benzaldehyde. It gives silver mirror ppt.
CHO COOAg
+
Ag(NH3)2
(b) (i) methyl tert-butyl ketone < acetone < acetaldehyde

(ii) (CH3)2CHCOOH < CH3CH(Br)CH2COOH < CH3CH2CH(Br)COOH
(iii) 4-methoxybenzoic acid < Benzoic acid < 3,4-dinitrobenzoic acid
E 201
Chemistry
ALLEN
24. (a) Write the chemical reaction involved in Etard reaction. [5] (CBSE 2020)
(b) Arrange the following in the increasing order of their reactivity towards nucleophilic
addition reaction:
CH3–CHO, C6H5COCH3, HCHO
(c) Why pKa of Cl–CH2–COOH is lower than the pKa of CH3COOH ?
(d) Write the product in the following reaction.
1.(i  Bu)2 AlH
CH3CH2CH=CH–CH2CN 2.H O 
2
(e) A and B are two functional isomers of compound C3H6O. On heating with NaOH and I2,
isomer A forms yellow precipitate of iodoform whereas isomer B does not form any
precipitate. Write the formulae of A and B.
CH3 CH(OCrOHCl2)2 CHO
CS H3O+
Ans. (a) +CrO2Cl2 2
Toluene Chromium complex Benzaldehyde

(b) C6H5COCH3 < CH3CHO < HCHO
(c) stronger -I effect of Cl , stronger acid less pka/strong electron withdrawing power of Cl.
(d) CH3CH2CH=CH–CH2CHO
(e) A : CH3COCH3
B : CH3CH2CHO
25. (a) Write the products formed when CH3CHO reacts with the following reagents:
[5] [CBSE 2020]
(i) HCN
(ii) H2N–OH
(iii) CH3CHO in the presence of dilute NaOH
(b) Give simple chemical tests to distinguish between the following pairs of compounds
(i) Benzoic acid and Phenol
(ii) Propanal and Propanone
OR
(a) Account for the following
(i) Cl–CH2COOH is a stronger acid than CH3COOH
(ii) Carboxylic acid do not give reactions of carbonyl group.
(b) Write the chemical equations to illustrate the following name reactions:
(i) Rosenmund reduction
(ii) Cannizzaro's reaction

(c) Out of CH3CH2–CO–CH2–CH3 and CH3CH2–CH2–CO–CH3, which gives iodoform test?
Ans. (a) (i) CH3 – CH(OH)CN
(ii) CH3 – CH = NOH
OH
(iii) CH3CHO dil NaOH
CH3—CH—CH2—CHO
Ethanal 3-Hydroxybutanal
202 E
CBSE
ALLEN
(b) (i) NaHCO3 test: Benzoic acid being an acid produces brisk effervescence with
NaHCO3 solution while ethylbenzoate does not.
C6H5COOH + NaHCO3  C6H5 COONa + CO2  + H2O
Benzoic acid Sod. Benzoate
(ii) By Tollen's test
(a) Propanal reduces Tollen's reagent, Fehling solution, Benedict solution but
propanone (ketone) does not reduces.
(b) Iodoform test : Propanone CH3–C–CH3 gives iodoform test but propanal (CH3–
O
CH2–CHO) does not.
OR
(a) (i) Cl is widrawing in nature hence a stablize more carboxylate anion which favours the
forward equllibrium.
(ii) Becuase of resonance charge sepration with between one carbon and two oxygen
atom hence bond polarity reduces so it do not nucleophilic addition reaction.
COCl CHO
H2
(b) (i) Pd–BaSO 4
Benzaldehyde
(ii) HCHO + HCHO 

NaOH
 CH3OH + H COONa
Methanal Methanol
(c) CH3CH2–CH2–CO–CH3
26. (a) Give chemical tests to distinguish between the following : [5] [CBSE 2019]
(i) Benzoic acid and ethyl benzoate.
(ii) Benzaldehyde and acetophenone.
(b) Complete each synthesis by giving missing reagents or products in the following:
COOH
SOCl
(i) 
Heat 
2
COOH
H2NCONHNH2
(ii) C6 H5CHO 
(iii) CH2 CHO
Ans. (a) (i) Benzoic acid and ethyl benzoate

These two compounds can be distinguished by the following tests:

 NaHCO3 test: Benzoic acid being an acid produces brisk effervescence with
NaHCO3 solution while ethylbenzoate does not.
C6H5COOH + NaHCO3  C6H5 COONa + CO2  + H2O
Benzoic acid Sod. Benzoate
NaHCO3 Sol.
C 6 H 5 COOC 2 H 5 
 No effervescence due to evolution of CO2 gas.
E 203
Chemistry
ALLEN
 Iodoform test: Ethylbenzoate on boiling with excess of Na OH solution gives ethyl
alchohol which on heating with iodine gives yellow ppt. iodoform.
Boil
C 6 H 5COOCH 2 CH 3  NaOH   C 6 H 5 COONa  CH 3 CH 2 OH
Ethyl benzoate Sod. benzoate Ethyl alcohol
CH 3CH 2 OH  4I 2  6NaOH 
heat
H COONa  CHI 3  5NaI  5H 2 O
Ethanol Sodium Idoform
formate (Yellow ppt)
(ii) Benzaldehyde and acetophenone
These can be distinguished by the iodoform test.
Iodoform test: Acetophenone being a methyl ketone when treated with NaOI gives
yellow ppt of iodoform but benzophenone does not.
C 6 H 5COOCH 3  3 NaOI  C 6 H 5 COONa  CHI 3   2NaOH
Acetophenone Sodium Iodoform
benzoate (Yellow ppt)
C 6 H 5 COC 6 H 5 
NaOI
No yellow ppt. of CHI3
COOH COCl
SOCl2
(b) (i)
heat
COOH COCl
Phthalic acid Phthyaloyl Chloride
O
(ii) C6H 5–CH = N – NH – C –NH 2

(1) HBO
(iii) CH2 (2) CuO,  CHO
27. (a) Illustrate the following name reactions: [5] [CBSE 2019]
(i) Hell - Volhard - Zelinsky reaction
(ii) Wolff - Kishner reduction reaction
(b) How are the following conversions carried out :
(i) Ethylcyanide to ethanoic acid
(ii) Butan-1-ol to butanoic acid
(iii) Methylbenzene to benzoic acid
Write chemical equation for the involved reactions.
Ans. (a) (i) Hell - Volhard - Zelinsky reaction : Aliphatic carboxylic acids react with bromine
or chlorine (but not iodine and fluorine) in the presence of small amount of red
phosphorus to give exclusively mono -halogenated acids. This is known as Hell-
Volhard-Zelinsky (HVZ) reacation. The reaction is given by aliphatic acids having -
hydrogen./ Bromine reacts smoothyl.
CH3CH2COOH + Br2 

Re d P
CH3CHBrCOOH + HBr
(ii) Wolff - Kishner reduction reaction : The Carbonyl group of aldehydes and
Ketones is reduced to CH2 group on treatment with hydrazine followed by heating
with potassium hydroxide in high boiling solvent wush as ethylene glycol.
CH3 NH NH CH3 KOH/ethylene glycol CH3
C = O –H O 2 2
C = NNH2 heat
CH2 + N2
CH3 2CH3 CH3
Acetone Propane
204 E
CBSE
ALLEN
O
Conc. HCl Br 2-NaOH
(b) (i) CH3 CH2 CN CH3 CH2 C NH2 CH3 CH 2 NH 2
Partial hydrolysis
Ethyl cyanide Propionamide Ethylamine
HONO K2Cr2O7/H2SO4
CH3 CH2 OH CH3 COOH
–N2, –H 2O Oxidation
Ethanol Ethanoic acid
K2Cr2O7/H2SO4
(ii) CH3 CH2 CH2 CH2 OH CH3 CH2 CH2 COOH
Oxidation
Butan-1-ol Butanoic acid
CH3 COOH
K2Cr2O7+H2SO4
(iii)
Oxidation
Mythylbenzene Benzoic acid
28. (a) Illustrate the following name reactions giving a chemical equation in each case:
(i) Clemmensen reaction
(ii) Cannizzaro’s reaction
(b) Describe how the following conversions can be brought about:
(i) Cyclohexanol to cyclohexan 1-one
(ii) Ethylbenzene to benzoic acid
(iii) Bromobensen to benzoic acid [5] [CBSE 2019]
Ans. (a) (i) Clemmensen reaction: The carbonyl group of aldehyde & ketone is reduced to
–CH2– group on treatment with Zinc amalgam & concentrated hydrochlric acid.
O
Zn–Hg
CH3– C – H CH3– CH2–H
Ethanal HCl
Ethane
O
Zn–Hg
CH3– C – CH3 CH3– CH2–CH3
Propanone HCl Propane
(ii) Cannizzaro’s reaction: Aldehydes which do not contain any - hydrogen atom such
as formaldehyde, benzaldehyde undergo self oxidations and reduction on treatment
with concentrated alkali. A mixture of alcohol & a salt of carboxylic acid are formed.
O O H O
NaOH – +
(1) H – C – H + H – C – H H – C – OH + H – C – O Na
50%
H
O O O
(2) NaOH – +
–C–H+ –C–H – CH2 + – C – O Na
50%
OH
E 205
Chemistry
ALLEN
OH O
CrO3, H2SO4
(b) (i)
Cyclohexanol Cyclohexan-1-one
CH2CH3 COOH
–
(ii) KMnO4/OH
Vigorous Oxidation
Ethylbenzene Benzoic acid

Br Mg Br COOH
+
(iii) Mg/dry ether (i) Dry ice, (ii) H3 O
Grignard reaction
Bromobenzene Phenylmagnesium Benzoic acid

bromide
29. (a) How will you bring about the following conversions : [5] [CBSE 2018]
(i) Ethanol to 3-hydroxybutanal
(ii) Benzaldehyde to Benzophenone
(b) An organic compound A has the molecular formula C8H16O2. It gets hydrolysed with dilute
sulphuric acid and gives a carboxylic acid B and an alcohol C. Oxidation of C with chromic
acid also produced B. C on dehydration reaction gives but-1-ene. Write equations for the
reactions involved.
Ans. (a) (i) Ethanol to 3-hydroxybutanal
K2Cr2O7/H2SO4
CH3CH2OH Oxidation
CH3CHO
Ethanol Ethanol
OH
Dil NaOH
CH3CHO+H–CH2–CHO (Aldol condensation)
CH3–CH–CH2–CHO
Ethanal (2 molecules) 3-hydroxybutanal
(ii) Benzaldehyde to Benzophenone

O=C–H O=C–
O
CaCO3 Distill
(C6H5 – C – O)2Ca –CaCO3
(Benzophenone)
(b) The relevant equations for all the reactions involved may be explained as follows :
O Butyl butanoate
dil. H SO
2 4
CH3CH2CH2 . COCH2CH2CH3 CH3CH2CH2OH + CH3CH2CH2CH2OH
Hydrolysis
A(m. f. C8H16O2) B(Butanoic acid) C(Butane-1-ol)
CrO3
CH3CH2CH2OH Oxidation CH3CH2CH2CH2COOH
C(Butane-1-ol) B(Butanoic acid)
Dehydration
CH3CH2CH2OH (–H2O) CH3CH2CH=CH2
C(Butane-1-ol) D(But-1-ene)
Therefore, (A) Butyl butanoate, (B) Butanoic acid, (C) Butan-1-ol, (D) But-1-enel
206 E
CBSE
ALLEN
30. (a) Write chemical equations to illustrate the following name bearing reactins :
(i) Cannizzaro's reaction
(ii) Hell-Volhard-Zelinsky reaction [5] [CBSE 2018]
(b) Give chemical tests to distinguish between the following pairs of compounds :
(i) Propanal and Propanone
(ii) Acetophenone and Benzophenone
(iii) Phenol and Benzoic acid
Ans. (a) (i) NaOH  CH OH + H COONa
HCHO + HCHO  3
Methanal Methanol
(ii) CH3 COOH + Cl2 

Re d P
Cl CH2 COOH + HCl
acetic acid Chloro acetic acid
Acetophenone Benzophenone
(i) +ve iodoform test (ii) –ve Iodoform Test
O O
CH3– C – C
I2/NaOH I2/NaOH
O
– +
No Reaction
CHI3+ – C – O Na
Iodoform
(iii) Distinction between Phenol and Benzoic acid : Phenol gives a violet colouration
with neutral FeCl3 solution while benzoic acid gives buff coloured ppt. of ferric
benzoate.
3C6H5OH + FeCl3 (C6H5O)3 Fe + 3HCl
Phenol Violet colouration
3C6H5COOH + FeCl3  (C6H5COO)3Fe + 3HCl

Benzoic acid Buff coloured ppt.
31. (a) An organic compound A contains 69.77% carbon, 11.63% drogen and the rest is oxygen.
The molecular mass of the compound is. It does no reduce Tollen's reagent but forms an
addition product with dium hydrogen sulphite and gives positive iodoform test. On
vigoroud dation it gives ethanoic and propanoic acids. Write the possible structure the
compound A.
(b) Write the chemical tests to distinguish between the following pairs of compounds :
(i) Acetophenone and Benzophenone
(ii) Ethanal and Propanal [5] [CBSE 2018]
E 207
Chemistry
ALLEN
Ans. (i) Acetophenone and Benzophenone : These can be distinguish the iodoform test.
Acetophenone when treated with NaOI (I2/NaOH) gives low ppt. of iodoform but
benzophenone does not.
C6H5COCH3 + 3NaOI C6H5COONa + CHI3 + 2NaOH
Acetophenone Sod. benzoate Iodoform

(yellow ppt)
C6H5COC6H5 
NaOI
 No yellow ppt of CHI3
Benzophenone.
(ii) Ethanal and Propanal : These can be distinguish by the iodo form test. Ethanal when treated
with NaOI (I2/NaOH) gives yellow ppt of iodoform but propanal does not give yellow ppt.
CH3CHO + 3I2 + 4NaOH HCOONa + CHI3 + 3NaOI
Ethanal Sod. formate Iodoform + 3H2O

(yellow ppt.)
CH3CH2CHO 
NaOI
 No yellow ppt of CHI3
Propanal
32. (a) Giving a chemical equation for each, illustrate the following processes :
(i) Cannizzaro reaction
(ii) Acetylation
(iii) Decarboxylation
(b) State chemical tests to distinguish between the following pairs of compounds :
(i) Propanal and Propanone
(ii) Phenol and Benzoic acid [5] [CBSE 2018]
conc. NaOH
Ans. (a) (i) HCHO + HCHO    CH3OH + H COONa
Methanal Methanol
(ii) Acetylation : The replacement of an active hydrogen of alcohol phenols or amines with
an acyl group to form the corresponding esters amides is called acylation.
Pyridine
CH3COCl + CH3CH2OH  CH3COOC2H5 + HCl
Acetyl chloride Ethyl alcohol Ethyl acetate
(iii) Decarboxylation :
NaOH+CaO
CH3 – COO– Na+ Soda line
CH4 + Na2CO3

208 E
CBSE
ALLEN
(b) (i) Propanal Propanone
(1) Give +ve Test with Tollents (1) Give –ve Test with Tollen's Reagent
Reagent, Fehling solution Fehling solution. Benedict solution.
(2) With Cu/300°C give (2) With Cu/300°C give
propanol (1° alcohol) propan–2–ol (2° alchol)
(ii) Phenol & Benzoic acid
Benzoic acid given alteruences with NaHCO3 whereas phenol does not give any
alteruencese (envolved CO2)
O = C – OH O = C – O –Na+
+ NaHCO 3 + H2O + CO2
OH
+ NaHCO 3 No Reaction
33. (A), (B) and (C) are three non-cyclic functional isomers of a carbonyl compound with molecular
formula C4H8O. Isomers (A) and (C) give positive Tollens' test whereas isomer (B) does not give
Tollens' test but gives positive Iodoform test. Isomers (A) and (B) on reduction with
Zn(Hg)/conc. HCl give the same product (D). [5] [CBSE 2018]
(a) Write the structures of (A), (B), (C) and (D).
(b) Out of (A), (B) and (C) isomers, which one is least reactive towards addition of HCN
Ans. (a) (A)  CH3 – CH2 – CH2 – CHO (B)
O
 CH3 – C – CH2 – CH3
CH3 O
(C) CH3 – CH – C – H
(D) CH3 – CH2 – CH2 – CH3
(b) B is ketone, so it will be less reactive towards nucleophilic addition reaction, with HCN
due to + I effect & steric hinderance
(Inductive)
34. (a) Write the product(s) in the following reactions : [5] [CBSE 2018]
O
(i) + HCN ?
COONa
(ii) + NaOH 
  ?
CaO
(a) DIBAL H
(iii) CH3 – CH = CH – CN 
(b) H O ?
2
E 209
Chemistry
C
N
ALLEN
(b) G
Give simplee chemical tests
t to distiinguish betw
ween the following paiirs of compo
ounds :
((i) Butannal and Butaan-2-one
((ii) Benzooic acid and
d Phenol
OR
(a) W
Write the reeactions involved in thee following :
((i) Etard reaction
((ii) Stephen reduction
(b) H
How will yoou convert the
t followinng in not mo
ore than two
o steps :
((i) Benzooic acid to Benzaldehyd
B de
((ii) Acetoophenone to Benzoic accid
((iii) Ethannoic acid to 2-Hydroxyeethanoic aciid
Ans.
A (a) ((i)
((ii)
C = CH – CHO
((iii) CH3 – CH
(b) ((i) Tollenn's reagent test
t : Add aammoniacall solution off silver nitraate (Tollen'ss Reagent) in
both the
t solutions. Butanal ggives silver mirror wheereas Butan––2–one does not.
((ii) Add neutral
n FeCl3 in both thhe solutionss, phenol fo
orms violet colour but benzoic acid
does not.
n
OR
(a) ((i) Etard reaction
CH 3 CH(OCrOHCl2)2 CHO
CS2 H3O+
O2Cl2
+CrO
Tolueooe Chhromium com

mplex Benzaaldehyde
Or
CH 3 CHO
(i) CrO2Cl2, CS2
+
(ii) H3O
Tolueooe Benzalldehyde
((ii) Stephen reaction


H O
H 
RCN + SnCl2 + HCl H 
 RCH = NH 3
 RCHO
OR
(i) CrO Cl ,CS
RCN  
2 2
(ii) H O
2
RCH
HO
3
210 E
CBSE
ALLEN
COOH COCl CHO
SOCl2 Resonmund's
(b) (i) reduction
Pd/BaSO 4
Benzoic Benzoyl Benzaldehyde
acid chloride
COCH3 COONa COOH
+
I 2/NaOH H3O
(ii)
Acetophenone Sodium benzoate Benzoic

acid
Cl2/P KOH(Aq)
(c) CH3COOH CH2COOH CH2COOH
Cl OH
E 211
Chemistry
ALLEN
PRACTICE TEST
SECTION-A
1. Identify compound (A) in the following reaction : [1]
CHO
H2|Pd|BaSO4
A
(a) Benzoyl chloride (b) Toluene

(c) Acetophenone (d) Benzoic acid
2. Reaction between benzaldehyde and acetophenone in presence of dilute NaOH is known as : [1]
(a) Cross Aldol condensation (b) Aldol condensation
(c) Cannizzaro's reaction (d) Cross Cannizzaro's reaction
3. An organic compound 'X' having molecular formula C5H10O yields phenyl hydrazone and gives
negative response to the Iodoform test and Tollen's test. It produces n-pentane on reduction. 'X'
could be :- [1]
(a) 2-pentanone (b) 3-pentanone
(c) n-amyl alcohol (d) pentanal
4. Reaction by which Benzaldehyde cannot be prepared :- [1]
(a) +Zn/Hg and conc. HCl
(b) +CrO2Cl2 in CS2 followed by H3O
(c) + H2 in presence of Pd+BaSO4
(d) + CO + HCl in presence of anhydrous AlCl3
5. The correct order of decreasing acid strength of trichloroacetic acid (A), trifluoroacetic acid (B),
acetic acid (C) and formic acid (D) is: [1]
(a) A > B > C > D (b) A > C > B > D (c) B > A > D > C (d) B > D > C > A
6. Assertion (A) : Pentan-2-one be distinguished from pentan-3-one by iodoform test.
Reason (R) : Pentan-2-one is a methyl ketone whereas pentan-3-one is not. [1]
7. Assertion (A) : The pKa value of acetic acid is lower than that of phenol.
Reason (R) : Phenoxide ion is more resonance stabilised. [1]
SECTION-B
8. A and B are two functional isomers of compound C3H6O. On heating with NaOH and I2, isomer
A forms yellow precipitate of iodoform whereas isomer B does not form any precipitate. Write
the formulae of A and B. [2]
212 E
CBSE
ALLEN
9. Account for the following : [2]
(a) Aromatic carboxylic acids do not undergo Friedel–Crafts reaction.
(b) pKa value of 4-nitrobenzoic acid is lower than that of benzoic acid.
10. Write the chemical equations to illustrate the following name reactions: [2]
(i) Rosenmund reduction (ii) Cannizzaro's reaction
11. (A), (B) and (C) are three non-cyclic functional isomers of a carbonyl compound with molecular
formula C4H8O. Isomers (A) and (C) give positive Tollens' test whereas isomer (B) does not give
Tollens' test but gives positive Iodoform test. Isomers (A) and (B) on reduction with
Zn(Hg)/conc. HCl give the same product (D).
(a) Write the structures of (A), (B), (C) and (D).
(b) Out of (A), (B) and (C) isomers, which one is least reactive towards addition of HCN ? [2]
SECTION-C
12. How will you convert the following in not more than two steps : [3]
(i) Benzoic acid to Benzaldehyde (ii) Acetophenone to
Benzoic acid
(iii) Ethanoic acid to 2-Hydroxyethanoic acid
13. Write the structures of A, B, C and D in the following reactions: [3]
(i) SnCl2–HCl dil..NaOH heat
CH3CN A B C
(i) H2O
HCN
SECTION-D
14. Type 1 : Passage question 1 :- [1+1+2=4]
Read the given passage and answer the following questions.
Aldehydes and ketones containing atleast one -H atom undergo a reaction in the presence of
dilute alkali as catalyst to form -hydroxy ketols. When two different aldehydes or ketones
combine them mixture of four products are formed, then reaction is called cross-aldol
condensation.
(a) Complete the following reaction :


dil.NaOH
2CH3CHO  
 ..…..(A)…….. 
H2O
 …….(B)…….
(b) What happened when propanone goes aldol condensation with dil. NaOH. Write the
reaction ?
(c) When aldols readily lose water the product formed ?
OR
What is the product of benzaldehyde reacts with CH3CHO in presence of dil. NaOH.
E 213
Chemistry
ALLEN
SECTION-E
15. Write the product(s) in the following reactions : [5]
O
(i) + HCN ?
COONa
(ii) + NaOH 
CaO

 ?
(a) DIBAL  H
(iii) CH3 – CH = CH – CN 
(b) H O 2
 ?
H 2 N  NHCONH 2
(iv) CH 3  C  O  ?
|
CH
3
(a)KMnO 4 /KOH
(v) C 6 H 5  CH 2  CH 3 
(b)H 
?
214 E
CBSE
ALLEN
SECTION-A
1. (a)
2. (a)
3. (b)
4. (a)
5. (c)
6. (a)
7. (d)
SECTION-B
8. A : CH3COCH3
B : CH3CH2CHO
9. (a) In case of aromatic carboxylic acid – COOH attach to the benzene ring having electron
withdrawing effect and deactivated the benzene ring, hence do not exhibit Friede-Craft
reaction.
(b) pKa value of 4-nitrobenzoic acid is lower than benzoic acid is due to e¯ withdrawing nature
of – NO2 attach at para position of benzene due to which tendency to loose H+ ion increases
and acidic character increases.
10.
COCl CHO
H 2
11. (i) Pd–BaSO4
Benzaldehyde
NaOH
(ii) HCHO + HCHO CH3OH + HCOONa
Methanal Methanol
SECTION-C
O
||
12. (a) (A)  CH3 – CH2 – CH2 – CHO (B)  CH 3  C  CH 2  CH 3
CH 3 O
| ||
(C) CH 3  CH  C H (D) CH3 – CH2 – CH2 – CH3
(b) B is ketone, so it will be less reactive towards nucleophilic addition reaction, with HCN
due to + I effect & steric hinderance
(Inductive)
E 215
Chemistry
ALLEN
COOH COCl CHO
SOCl 2 Resonmund's
13. (i) reduction
Pd/BaSO 4
Benzoic Benzoyl Benzaldehyde
acid chloride
COCH3 COONa COOH
I 2 /NaOH H 3O +
(ii)
Acetophenone Sodium benzoate Benzoic
acid
CH3 KMnO COOK COOH
(iii) 4
+
–KOH/ H3O
Benzoic acid
SECTION-D
14. (a) (A) CH3–CH–CH2–CHO
OH
3-Hydroxybutanal
(B) CH3–CH=CH–CHO
But-2-enol
OH O
dil. NaOH
(b) 2CH3—C—CH3 CH3—C—CH2—C
O CH3 CH3
4-hydroxy-4-methyl pentan-2-one
(c) , -unsaturated carbonyl compound
OR
Cinnanaldehyde is formed.
O
dil.
CHO + CH3—CH CH = CH—CH
NaOH
O Cinnanaldehyde
SECTION-E
OH
15. (i) CN
(ii)
(iii) CH3 – CH = CH – CHO

(iv) CH 3  C  N  NH  CO  NH 2
|
CH 3
(v) C6H5–COOH
216 E
CBSE
ALLEN
UNIT-13 : AMINES
UNIT INDEX
• Theory 217-229
THEORY
PART-I : ALIPHATIC AND AROMATIC AMINE
AMINE : Alkyl Derivatives of Ammonia is Known as Amine.
H
|
–H –H –H
H–N R – NH2 R2 – NH R3 – N
| +(–R) +(–R) +(–R)
H
Ammonia Primary amine Sec. amine Ter. amine
functional group functional group functional group
– NH2 NH
N
Aliphatic amine : Primary amine (R – NH2), Secondary amine (R2NH), Ter. Amine (R3N)
Aromatic amine :
NH2 CH2–NH2
(1) Aryl amine (2) Aryl Alkyl amine
Structure of Amines
sp3 Hybradised
N Pyramidal shape
 3
3 sp 108º
–
R sp R
R
1º, 2º  107º
3º  108º 
 Steric Hinderance
  In amines, the Nitrogen atom is sp3 Hybradised.
  Out of the 4 sp3 hybriadised orbitals, three form (sp3 – sp3) bonds with alkyl groups or
(sp3 – s) bonds with Hydrogen atom, and the 4th contains lone pair electrons.
  Due to lone pair – bond pair repulsion, the tetrahedral shape of amines changes to pyramidal,
the bond angle also decreases from 107º to 108º in tertiary amines.
E 217
Chemistry
ALLEN
Nomenclature of Some Alkylamines and Arylamines:
Structure Common name IUPAC name
CH3–CH2–NH2 Ethylamine Ethanamine
CH3–CH2–CH2–NH2 n-Propylamine Propan-1-amine
CH 3  CH  CH 3
| Isopropylamine Propan-2-amine
NH 2
CH 3  N  CH 2  CH 3
| Ethylmethylamine N-Methylethanamine
H
CH 3  N  CH 3
| Trimethylamine N, N-Dimethylmethanamine
CH 3
1 2 3 4
C2 H 5  N  CH 2 CH 2 CH 2 CH 3
|
n-butyl diethyl amine N, N–Diethylbutan-1-amine
C2H5
1 2 3
NH 2  CH 2 CH  CH 2
Allylamine Prop-2-ene-1-amine
NH2–(CH2)6–NH2 Hexamethylenediamine Hexane-1, 6-diamine
NH2
Aniline Aniline or Benzenamine
NH2
CH3
o-Toluidine 2-Methylaniline
NH2
4-Bromobenzenamine
p-Bromoaniline
Br or 4-Bromaniline
N(CH3)2
N, N-Dimethylaniline N, N-Dimethylbenzenamine
218 E
CBSE
ALLEN
GENERAL METHOD OF PREPARATION OF ALIPHATIC AND AROMATIC AMINE
1. Reduction of nitro compounds
Nitro compounds are reduced to amines by passing hydrogen gas in the presence of finely
divided nickel, palladium or platinum and also by reduction with metals in acidic medium.
Nitroalkanes can also be similarly reduced to the corresponding alkanamines.
NO2 NH2
H2/Pd
(i)
Ethanol
NO2 NH2
Sn + HCl
(ii)
or Fe + HCl
Note: Reduction with iron scrap and hydrochloric acid is preferred because FeCl2 formed gets
hydrolysed to release hydrochloric acid during the reaction. Thus, only a small amount of
hydrochloric acid is required to initiate the reaction.
2. Ammonolysis of alkyl halides
+ –
+ – + NaOH
:
NH3 + R—X R–NH3X R–NH3 + NaX + H2O

Alkyl ammonium Primary amine
halide
The free amine can be obtained from the ammonium salt by treatment with a strong base:
Note (i) : Ammonolysis has the disadvantage of yielding a mixture of primary, secondary and
tertiary amines and also a quaternary ammonium salt. However, primary amine is obtained as a
major product by taking large excess of ammonia.
Note (ii) : The order of reactivity of halides with amines is RI > RBr >RCl.
3. Reduction of nitriles
Nitriles on reduction with lithium aluminium hydride (LiAlH4) or catalytic hydrogenation
produce primary amines. This reaction is used for ascent of amine series, i.e., for preparation
of amines containing one carbon atom more than the starting amine.
R – C N 
Na (Hg)/C H5OH 
H 2 /Ni
R – CH2 – NH2
2
4. Reduction of amides
The amides on reduction with lithium aluminium hydride yield amines.
O
(i) LiAlH
R–C–NH 2 (ii) H O R–CH2–NH2
4
5. Gabriel phthalimide synthesis

Gabriel synthesis is used for the preparation of primary amines. Phthalimide on treatment with
ethanolic potassium hydroxide forms potassium salt of phthalimide which on heating with alkyl
halide followed by alkaline hydrolysis produces the corresponding primary amine.
E 219
Chemistry
ALLEN
O O O
C C   C
+ KOH   +R–X
N–H N K N–R
C C C
O O O
Phthalimide Potassium Phthalimide N-Alkylphthalimide
O
C – OH + H2O
R – NH2
+
1° amine
C – OH
O
Note: Aromatic primary amines cannot be prepared by this method because aryl halides do not
undergo nucleophilic substitution with the anion formed by phthalimide.
6. Hoffmann bromamide degradation reaction
Hoffmann developed a method for preparation of primary amines by treating an amide with
bromine in an aqueous or ethanolic solution of sodium hydroxide. In this degradation reaction,
migration of an alkyl or aryl group takes place from carbonyl carbon of the amide to the
nitrogen atom. The amine so formed contains one carbon less than that present in the amide.
O
R – C – NH2 + Br2+ 4NaOH  R – NH2 + Na2CO3 + 2NaBr + 2H2O
O
CH3—C—NH2 + Br2 + 4NaOH  CH3NH2 + Na2CO3 + 2NaBr + 2H2O
O
CH3—CH2—C—NH2 + Br2 + 4NaOH  CH3NH2 + Na2CO3 + 2NaBr + 2H2O
O

Ar – C– NH 2  Br2  4NaOH 
 Ar – NH 2  Na 2CO3  2NaBr  2H 2O
O
C–NH2 NH2
+ Br2 + 4NaOH + Na2CO3 + 2NaBr + 2H2O
220 E
CBSE
ALLEN
CHEMICAL REACTION OF AMINE
1. Basic character of amines
Amines, being basic in nature, react with acids to form salts.
+ –
R – NH 2 + H X R – NH3 X (Salt)
+ –
NH2 NH3Cl
+ HCl
Aniline Anilinium chloride

Amine salts on treatment with a base like NaOH, regenerate the parent amine.

  H O  X
R N H 3X  OH  RNH 2 2
Note :
(i) Basic character of amines can be better understood in terms of their Kb and pKb values
as explained below:


 R  N H 3  OH
R – NH2 + H2O 

 

 R  N H 3   OH 
K=
[R  NH 2 ][H 2O]
 

 R  N H 3   OH 
K[H2O] =
[R  NH 2 ]
 

 H 3   OH 
Kb = 
R N
or
[R  NH 2 ]
(ii) pKb = – log Kb

Larger the value of Kb or smaller the value of pKb, stronger is the base.
(iii) Alkylamines are stronger bases than ammonia. Thus, the basic nature of aliphatic
amines should increase with increase in the number of alkyl groups. This trend is
followed in the gaseous phase. The order of basicity of amines in the gaseous phase
follows the expected order: tertiary amine > secondary amine > primary amine > NH3.
(iv) The order of basic strength in case of methyl substituted amines and ethyl substituted
amines in aqueous solution is as follows:
(CH3)2NH > CH3NH2 > (CH3)3N > NH3
(C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3
E 221
Chemistry
ALLEN
NH2
(v) The pKb value of aniline is quite high, it is because in aniline or other
arylamines, the –NH2 group is attached directly to the benzene ring. It results in the
unshared electron pair on nitrogen atom to be in conjugation with the benzene ring and
thus making it less available for protonation.
(vi) Proton acceptability or the basic nature of aniline or other aromatic amines would be
less than that of ammonia. In case of substituted aniline, it is observed that electron
releasing groups like –OCH3, –CH3 increase basic strength whereas electron
withdrawing groups like –NO2, –SO3H, –COOH, –X decrease it.
2. Alkylation
Amines undergo alkylation on reaction with alkyl halides.

H    
R—X  
R—N R2NH +R–X R3 N
+R–X
R4NX
H —HX
3. Acylation
Aliphatic and aromatic primary and secondary amines react with acid chlorides, anhydrides and
esters by nucleophilic substitution reaction. This reaction is known as acylation. The products
obtained by acylation reaction are known as amides. The reaction is carried out in the presence
of a base stronger than the amine, like pyridine, which removes HCl so formed and shifts the
equilibrium to the right hand side.
(i) CH3 H CH3
Base 
:
C2H5–N–H + C—Cl C2H5—N—C—Cl C2H5–N–C–CH3+ HCl

H O H O– H O
Ethanamine Acetyl N-Ethylethanamide
(Primary amine) Chlorid
(ii) H
Base
C2H 5–N + CH3–C–Cl C2H5–N –– C–CH3+H–Cl
C2H 5 O C2H 5 O
N-Ethylethanamine N, N-Diethylethanamide
(iii) C6H 5—N —H + CH 3—C—O—C—CH 3 C6H 5—N—C—CH 3 + CH3COOH

H O O H O
Benzenamine Ethanoic N-Phenylethanamide
anhydride or Acetanilide
Note : Amines also react with benzoyl chloride (C6H5COCl). This reaction is known as
benzoylation.
CH3 NH2  C6 H5COCl  CH3 NHCOC6 H5  HCl
Methana min e Benzyl chloride N  Methylbenzamide
222 E
CBSE
ALLEN
4. Carbylamine reaction
Aliphatic and aromatic primary amines on heating with chloroform and ethanolic potassium
hydroxide form isocyanides or carbylamines which are foul smelling substances. Secondary
and tertiary amines do not show this reaction. This reaction is known as carbylamine reaction or
isocyanide test and is used as a test for primary amines.

Ar/R – NH2 + CHCl3 + 3KOH  Heat
 Ar/R – N  C + 3KCl + 3H2O
5. Reaction with Hinsberg reagent
(Distinguish between pre./sec./ter. amine)
It can be distinguish by Hinsberg reagent. Benzenesulphonyl chloride (C6H5SO2Cl), which is
also known as Hinsberg’s reagent, reacts with primary and secondary amines to form
sulphonamides.
(i) The reaction of benzenesulphonyl chloride with primary amine yields N-
ethylbenzenesulphonyl amide. The hydrogen attached to nitrogen in sulphonamide is
strongly acidic due to the presence of strong electron withdrawing sulphonyl group.
Hence, it is soluble in alkali.
O O
S–Cl + H–N–C2H5 S–N–C2H5 + HCl
O H O H
N-Ethylbenzenesulphonamide
(soluble in alkali)
(ii) In the reaction with secondary amine, N,N-diethyl-benzenesulphonamide is formed.
Since N, N-diethylbenzene sulphonamide does not contain any hydrogen atom attached
to nitrogen atom, it is not acidic and hence insoluble in alkali.
O O
S–Cl + H–N–C2H5 H3C S–N–C2H5 + HCl
O C2H 5 O C2H 5
N,N-Diethylbenzenesulphonamide
(insoluble in alkali)
(iii) Tertiary amines do not react with benzenesulphonyl chloride.
Note: This test is used for the distinction of primary, secondary and tertiary amines and
also for the separation of a mixture of amines. However, these days benzenesulphonyl
chloride is replaced by p-toluenesulphonyl chloride.
6. Reaction with Nitrous acid
(Distinguish between aliphatic and aromatic amine)
(a) Primary aliphatic amines react with nitrous acid to form aliphatic diazonium salts which
being unstable, liberate nitrogen gas quantitatively and alcohols. Quantitative evolution
of nitrogen is used in estimation of amino acids and proteins.


NaNO HCl H O
R–NH2 + HNO2 
2
[R  N 2 Cl] 
2
 ROH + N2 + HCl
NaNO2 + HCl  HNO2 + NaCl
R–NH2
+ — R–OH + N2 + H2O
HO–N=O
E 223
Chemistry
ALLEN
(b) Aromatic amines react with nitrous acid at low temperatures (273-278 K) to form
diazonium salts

NaNO  2HCl
C6 H 5  NH 2 
2  C6 H 5  N 2 Cl  NaCl  2H 2 O
273278K
Aniline Benzenediazonium
chloride
   nephthol  NaOH
Orange dye is formed
ELECTROPHILIC SUBSTITUTION REACTION OF ANILINE

1. Halogenation (Bromination)
(a) Bromination: Aniline reacts with bromine water at room temperature to give a white
precipitate of 2,4,6-tribromoaniline.
NH2 NH 2
Br Br
+ 3Br2Br2 / H2O + 3HBr
Br
2, 4, 6- Tribromoaniline
(White PPT)
(b) Bromination of aniline by protection of –NH2 group.
The main problem encountered during electrophilic substitution reactions of aromatic
amines is that of their very high reactivity. Substitution tends to occur at ortho- and
para-positions. If we have to prepare monosubstituted aniline derivative, how can the
activating effect of –NH2 group be controlled ? This can be done by protecting the -NH2
group by acetylation with acetic anhydride, then carrying out the desired substitution
followed by hydrolysis of the substituted amide to the substituted amine.
H H H
H N N N
:N C–CH3 C–CH3 C–CH3
H O O Br
O O

 Py
+ CH3—C—Cl +


Acetyl Acetanilide o-Bromo
chloride acetanilide Br
O O
p-Bromoacetanilide
CH3–C–O–C–CH
  3
  H2O
Acetic anhydride
H H
N N
H H Br
+
Br o-Bromoaniline
p-Bromoaniline
(Major)
224 E
CBSE
ALLEN
The lone pair of electrons on nitrogen of acetanilide interacts with oxygen atom due to resonance
as-
O
O
: 
—N—C—CH3 —N = C—CH3
H
2. Nitration
(a) Nitration of aniline by protection of –NH2 group : By protecting the –NH2 group by
acetylation reaction with acetic anhydride, the nitration reaction can be controlled and
the p-nitro derivative can be obtained as the major product.
H H H
H N N N
:N C–CH3 C–CH3 C–CH3
H O O NO2
O O
Py HNO3
+ CH3—C—Cl +
or 288 K
Aniline O O Acetanilide o- Nitroacetanilide NO2
CH3–C–O–C–CH3 p- Nitroacetanilide
H2O
H H
N N
H NO H
2
+
o-Nitroaniline
NO2
p-Nitroaniline
(Major)
(b) Direct nitration : Direct nitration of aniline yields tarry oxidation products in addition
to the nitro derivatives. Moreover, in the strongly acidic medium, aniline is protonated
to form the anilinium ion which is meta directing. That is why besides the ortho and
para derivatives, significant amount of meta derivative is also formed.
NH2 NH2 NH2 NH2

NO2
(HNO3 + H2SO4)
+ +
288 K
NO2
Aniline
NO2
51% (47%) (2%)
p-nirtoaniline p-nirtoaniline m-nirtoaniline o-nirtoaniline
E 225
Chemistry
C
N
ALLEN

 C6H 5NH2 + H 2SO4  C6H 5NH3HS
( SO 4)

NH3
Anilinium
m ion
(m-directting)
3.
3 Sulp
phonation
Aniliine reacts with
w concen ntrated sulphhuric acid to
t form anilinium hydrrogensulphate which on
o
heatiing with sullphuric acid
d at 453-47 3K producees p-aminob d, commonly
benzene sullphonic acid
know
wn as sulphaanilic acid, as the majoor product.
Note
N : Aniliine does notn undergoo Friedel-CCrafts reactiion (alkylaation and aacetylation) due to saalt
form
mation with aluminium chloride, tthe Lewis acid,
a which is used as a catalyst. Due to thiis,
nitrogen of aniline acquires positive ccharge and hence acts as a strongg deactivatiing group for
fo
furthher reaction..
Physical
P Prooperties off Amines
1.
1 Physiccal State
 Am mines upto 3 member caarbon atomss are colourrless liquids, having a ccharactersticc smell.
 Metthyl amine is gas at roo om temperaature, rest hiigher are solids.
 Mo ost of the am
mines have a charactersstic fishy sm
mall/odours.
 Aro omatic aminnes have an unpleasant odour and are liquids at a room tem
mperature.
2.
2 Solubiility
All thrree classes of
o amines arre soluble inn water. They form Hy ydrogen bonnd with wateer.
Solubiility decreasses with increase in nnumber of carbon
c atomm and size oof alkyl gro
oups thus, 1º
aminess are most soluble.
s
1º aamines > 2º amines > 3º aminnes
H
|
R H
H O—H R
| | |
|
R—N H—O—H
H R—N H—O
| | R—N H—O
| |
H O—H H O—H
O
R H
| |
H H
 Aro
omatic aminnes are insoluble in waater. The larrge hydrocarrbon part (bbenzene ring
g) retards thhe
form
mation of H–bond.
H
 Aniiline is almoost insoluble in water.
 All amines are soluble in non-polar
n soolvents likee Ether, Alcohol, Benzeene etc.
226 E
CBSE
ALLEN
3. Boiling Point
 The Boiling Point of amines are higher than their corresponding Hydrocarbons. They are polar
in nature and thus they form intermolecular Hydrogen bonds.

H
– + –
R N H N R
+ H H +
 Order of Boiling Point :
1º > 2º > 3º
Because of more extensive H-bonding in 1º Amines.
 But since the electronegativity of Nitrogen (3) is less than oxygen (3.5). The intermolecular
Hydrogen bonds in amines are weaker than alcohols and carboxylic acids. Hence, amines have
lower boiling point than corresponding alcohols and carboxylic Acids.
E 227
Chemistry
ALLEN
PART-II_DIAZONIUM SALTS
 
The organic compound which have general formula is Ar N 2 X , known as Diazonium salt.
Ar  Aryl group

X  Cl¯, Br¯, HSO4¯, BF4¯
 
N2Cl
Benzene diazoniumn chloride
 
N2Br
Benzene diazonium bromide
 
N2HSO4
Benzene diazonium hydrogen sulphate
 
N2BF4
Benzene diazonium tetrafluoroborate
Resonating structure of arene diazonium ion.

    
NN N=N N=N N=N NN
 

GENERAL METHOD OF PREPARATION OF DIAZONIUM SALT
Benzenediazonium chloride is prepared by the reaction of aniline with nitrous acid at 273-
278K. Nitrous acid is produced in the reaction mixture by the reaction of sodium nitrite with
hydrochloric acid. The conversion of primary aromatic amines into diazonium salts is known as
diazotisation. Due to its instability, the diazonium salt is not generally stored and is used
immediately after its preparation.
 
273278K
C6H5NH2 + NaNO2 + 2HCl   C6 H 5 N 2 Cl + NaCl + 2H2O
Benzenediazonium
chloride
PHYSICAL PROPERTIES
(1) Benzenediazonium chloride is a colourless crystalline solid.
(2) It is readily soluble in water and is stable in cold but reacts with water when warmed.
(3) It decomposes easily in the dry state.
(4) Benzenediazonium fluoroborate is water insoluble and stable at room temperature.
228 E
CBSE
ALLEN
CHEMICAL REACTION OF DIAZONIUM SALTS
Cl
Cu2Cl2/HCl
+ N2
Br
Cu2Br2/HBr Sandmeyer
+ N2 Reaction
CN
CuCN / KCN
+ N2
Cl
Cu / HCl
+ N 2 + CuX

NH2 N2Cl Br Gatterman
Reaction
(NaNO2 + HCl) Cu / HBr
273 – 278K + N 2 + CuX
Aniline Benzene
diazonium I
6H Sn/HCl
chloride
O Diazotisation KI
+ N 2 + KCl
(aq)
N

N2BF4 F
HBF4 
Nitrobenzene + BF3 + N2
Fluoro boric
acid
Benzenediazonium NO 2
tetrafluoro borate
NaNO2 + NaBF4 + N2
Cu, 
H3PO2 + H2O
+ N 2 + H3PO3 + HCl
CH3CH2OH
+ N 2 + CH 3CHO + HCl
H OH
N=N OH
– HCl
p-Hydroxy azobenzene (orange dye) Coupling

reaction
H NH2
N=N NH 2
p-Amino Azobenzene (yellow dye)
E 229
Chemistry
ALLEN
1. Classify the following amines as primary, secondary or tertiary :
NH2 N(CH3)2
(i) (ii) (iii) (C2H5)2CHNH2 (iv) (C2H5)2NH
Ans. Primary : (i) and (iii)

Secondary : (iv)
Tertiary : (ii)
2. (i) Write structures of different isomeric amines corresponding to the molecular formula, C4H11N
(ii) Write IUPAC names of all the isomers.
(iii) What type of isomerism is exhibited by different pairs of amines ?
Ans. (i), (ii) The structures and their IUPAC names of different isomeric amines corresponding to the
molecular formula, C4H11N are given below :
(a) CH3–CH2–CH2–CH2–NH2 Butanamine (1°)
NH2
(b) CH3–CH2–CH–CH3 Butan - 2- amine (1°)
CH3
(c) CH3–CH–CH2–NH2 2-Methylpropanamine (1°)
CH3
(d) CH3–C–NH2 2-Methylpropan -2-amine (1°)
CH3
(e) CH3- CH2 - CH2 – NH – CH3 N-Methylpropanamine (2 °)

(f) CH3–CH2–NH – CH2–CH3 N-Ethylethanamine (2°)
CH3
(g) CH3–CH–NH–CH3 N-Methylpropan-2-amine (2°)
CH3
(h) CH3–CH2–N–CH3 N, N-Dimethylethanamine (3°)
(iii) The pairs (a) and (b), (e) and (g) exhibit position isomerism.
The pairs (a) and (c); (b) and (d) exhibit chain isomerism
The pairs (e) and (f) and (g) exhibit metamerism.
All primary amines exhibit functional isomersim with secondary and tertiary amines and
vice- versa.
3. How will you convert
(i) Benzene into aniline
(ii) Benzene into N, N–dimethylaniline
(iii) Cl–(CH2)4–Cl into hexan-1, 6-diamine ?
230 E
CBSE
ALLEN
NO2 NH2
HNO 3/ H 2SO 4 H 2/Pd
Ans. (i) (Nitration) Ethanol
Benzene Nitrobenzene Aniline
H CH3
NO2 NH2 N N
CH3 CH3
HNO 3/ H 2SO 4 H 2/Pd CH3Cl CH 3Cl
(ii) (Nitration) Ethanol
Benzene Aniline N, N–Dimethylaniline
Ethanolic NaCN H 2/Ni

(iii) Cl–(CH2)4–Cl N  C–(CH2)4–C  N H2N–CH2–(CH2)4–CH2–NH2
1,4-Dichlorobutane Hexane-1, 6-diamine
4. Arrange the following in increasing order of their basic strength :

(i) C2H5NH2, C6H5NH2, C6H5CH2NH2 and (C2H5)2NH
(ii) C2H5NH2, (C2H5)2NH, (C2H5)3N, C6H5NH2
(iii) CH3NH2, (CH3)2NH, (CH3)3N, C6H5NH2, C6H5CH2NH2
Ans. (i) C6H5NH2 < C6H5CH2NH2 < C2H5NH2 < (C2H5)2NH
(ii) C6H5NH2 < C2H5NH2 < (C2H5)3 N < (C2H5)2 NH
(iii) C6H5NH2 < C6H5CH2NH2 < (CH3)3 N < CH3NH2 < (CH3)2NH
5. Complete the following acid-base reactions and name the products :
(i) CH3CH2CH2NH2 + HCl 
(ii) (C2H5)3N + HCl 
+ –
CH3CH2CH2NH2 + HCl CH3CH2CH2NH3Cl
Ans. (i) n-Propylamine n-Propylammoniumchloride
+ –
(ii) (C2H5)3N + HCl (C2H5)3 NHCl
Triethylamine Triethylammoniumchloride
6. Write reactions of the final alkylation product of aniline with excess of methyl iodide in the
presence of sodium carbonate solution.
Ans. Aniline reacts with methyl iodide to produce N, N-dimethylaniline.
H CH3
NH2 N N
CH3 CH3
CH 3l CH 3l
Aniline N, N–Dimethylaniline
With excess methyl iodide, in the presence of Na2CO3 solution, N, N-dimethylaniline produces
N, N, N-trimethylanilinium carbonate.
CH3 + +
N N(CH3)3I— N(CH3)3
CH3
Na2CO3 CO32— + 2NaI
+ CH3I
2
N, N–Dimethylaniline N, N, N–Trimethylanilinium Iodide N, N, N–Trimethylanilinium Carbonate
E 231
Chemistry
ALLEN
7. Write chemical reaction of aniline with benozyl chloride and write the name of the product
obtained.
H
.. Base
Ans. N–H + C–Cl +
N – C – Cl HCl + N—C
H O H O H O
N-Phenylbenzamide
Aniline Benzoyl chloride
8. Write structures of different isomers corresponding to the molecular formula, C3H9N. Write
IUPAC names of the isomers which will liberate nitrogen gas on treatment with nitrous acid ?
Ans. The structures of different isomers corresponding to the molecular formula, C3H9N are given
below :
(a) CH3–CH2–CH2–NH2
Propan-1-amine (1°)
NH2
(b) CH3–CH–CH3
Propan-2-amine (1°)
(c) CH3–NH–C2H5
N-Methylethanamine (2°)
CH3
(d) CH3–N–CH3
N, N-Dimethylmethanamine (3°)
1° amines, i.e. (a) propan -1-amine, and (b) Propan - 2-amine will liberate nitrogen gas on
treatment with nitrous acid.'
CH3CH2CH2NH2 + HNO2 CH3CH2CH2OH + N2 + HCl
Propan -1-amine Propan -1-ol
CH3–CH–CH3 + HNO2 CH3–CH2–CH2 +N2 + HCl
NH2 OH
Propan-2-amine Propan-2-ol
9. Convert
(i) 3-Methylaniline into 3-nitrotoluene.
(ii) Aniline into 1, 3, 5- tribromobenzene
+ –
NH2 N2Cl
Ans. (i) 273-278 K
+ NaNO2 + 2HCl + NaCl + 2H2O
CH3 CH3
3-Methylaniline HBF 4
+ –
NO2 N2BF4
NaNO 2
NaBF4 + N2 + Cu,
CH3 CH3
3-Nitrotoluene
+ –
NH2 NH2 N2Cl
Br Br Br Br Br Br
Br2/H2O NaNO 2/HCl H 2O
(ii) H 3PO 2
Aniline Br Br Br
1,3,5 - Tribromobenzene
232 E
CBSE
ALLEN
10. Write chemical equations for the following reactions:
(i) Reaction of ethanolic NH3 with C2H5Cl.
(ii) Ammonolysis of benzyl chloride and reaction of amine so formed with two moles
of CH3Cl.
H
Ans. (i) C2H 5–Cl NH 3
C2H5–NH2 C2H5–Cl
C2H5–N–C2H5 C H –Cl C2H 5–N–C2H5
2 5 C2H5–Cl
(C2H 5)3NCl
quaternary
C2 H 5 ammonium salt
Chlorethane Ethanamine N-Ethylethanamine N,N-Diethylethanamine

NH3 2CH3Cl
(ii) C6H 5–CH 2–Cl C6H 5–CH 2NH2 C6H5–CH2–N–CH3
CH3
Benzylchloride Benzylamine N,N-Dimethylphenylmethanamine
11. Write chemical equations for the following conversions:
(i) CH3.CH2.Cl into CH3.CH2.CH2.NH2
(ii) C6H5.CH2.Cl into C6H5.CH2.CH2.NH2
Ans. (i) CH3  CH 2  Cl 
Ethanolic NaCN
 CH3  CH 2  C  N 
Re duction
 CH3  CH 2  CH 2  NH 2
Chlorethane Phenylethanenitrile Pr opan 1a min e
(ii) C6 H 5  CH 2  Cl 
 C6 H 5  CH 2  C  N  C6 H 5  CH 2  CH 2  NH 2
Ethanolic NaCN H2 / Ni
Chlorophenylmethane Phenylethanenitrile 2 P henylethana min e

(Benzyl chloride) (Benzyl cyanide)
12. Write structures and IUPAC names of

(i) the amide which gives propanamine by Hoffmann bromamide reaction.
(ii) the amine produced by the Hoffmann degradation of benzamide.
Ans. (i) Propanamine contains three carbons. Hence, the amide molecule must contain four carbon
atoms. Structure and IUPAC name of the starting amide with four carbon atoms are given
below :
CH3–CH2–CH 2–C–NH 2 Butanamide
O
(ii) Benzamide is an aromatic amide containing seven carbon atoms. Hence, the amine formed
from benzamide is aromatic primary amine containing six carbon atoms.
NH2
Aniline or benzenamine
13. Arrange the following in decreasing order of their basic strength:

C6H5NH2, C2H5NH2, (C2H5)2NH, NH3
Ans. The decreasing order of basic strength of the above amines and ammonia follows the following
order :
(C2H5)2NH > C2H5NH2 > NH3 > C6H5NH2
14. How will you convert 4-nitrotoluene to 2-bromobenzoic acid ?
CH3 CH3 CH3 CH3
Br Br Br
Ans. Br2 Sn / HCl NaNO2 / HCl
273-278 K
NO2 NO2 NH2 N2Cl

H2O H3PO2
COOH CH3
Br Br
KMnO4
–
OH
E 233
Chemistry
ALLEN
1. Write IUPAC names of the following compounds and classify them into primary, secondary and
tertiary amines.
(i) (CH3)2CH NH2 (ii) CH3 (CH2)2NH2 (iii) CH3 NH CH (CH3)2
(iv) (CH3)3C NH2 (v) C6H5NHCH3 (vi) (CH3CH2)2NCH3
(vii) m-Br C6H4NH2
Ans. (i) Propan - 2 - amine (p)
(ii) Propan - 1 - amine (p)
(iii) N - methyl - 2 - propanamine (s)
(iv) 2 - methyl propan - 2 - amine (p)
(v) N - methyl aniline (s)
(vi) N - ethyl - N - methyl ethanamine (t)
(vii) 3 - Bromo benzenamine or 3 - Bromoaniline (p)
2. Give one chemical test to distinguish between the following pairs of compounds.
(i) Methylamine and dimethylamine (ii) Secondary and tertiary amines
(iii) Ethylamine and aniline (iv) Aniline and benzylamine
(v) Aniline and N - methylaniline
Ans. (i) Methylamine gives carbylamine reaction on heating with CHCl3 and alcoholic KOH. Gives
foul smelling (Carbyl amine)
CH3 NH2 + CHCl3 + 3KOH 
Heat
 CH 3 NC + 3KCl + 3H2O
Carbylamine
where as Dimethylamine does not give this reaction.

(ii) Secondary amines given Hinsberg's test. Its gives insoluble substance with Hinsberg's
reagent (C6H5SO2Cl) which is not affected by base.
R 2 NH  C6 H 5SO 2Cl  R 2 NSO 2C6 H 5 (N, N-Dialkyl benzene sulphonamide)
Sec. amine Benzene sulphonyl Insoluble in alkali
chloride
Where as tertiary amine does not react with Hinsberg's reagent.

(iii) Aniline gives azo dye test : Dissolve Aniline in conc. HCl and add ice - cold solution of
HNO2 (NaNO2 + dil HCl) at 273 K and then treat it with an alkaline solution of 2-napthol.
Appearance of brilliant orange or red dye indicates aromatic amine (ie Aniline).
Where as aliphatic amine (ie ethylamine) does not form dye. It will give brisk
effervescence due to the evolution of N2 but solution remain clear.
273 K
N  NCl + 2H2O
+ —
NH2 + con. HCl + HNO2
Benzene diazonium
Chloride
OH OH
Dil NaOH
N  NCl +
+ —
PH 9-10
N=N + HCl
2-Naphthol 1-Phenylazo-2-naphthol
(Orange dye)
234 E
CBSE
ALLEN
(iv) Nitrous acid test : Benzylamine reacts with nitrous acid (HNO2) to form a diazonium salt
which being unstable even at low temperature, decomposes with evolution of N2 gas.
 
 H 2O
C6 H 5CH 2 NH 2 
HNO2
 C6H 5CH  N  NCl –    C6H 5CH 2OH  N 2  HCl
 
HCl
Aniline reacts with HNO2 to form benzene diazonium chloride which is stable at 273-278
K and hence does not decompose to evolve N2 gas.
+
NaNO 2HCl +
NNCl
–
NH2 273 - 278 K
Aniline Benzenediazonium chloride
(v) Carbylamine test : Aniline being a primary amine gives carbylamine test, i.e, when heated
with an alcoholic solution of KOH and CHCl3, it gives an offensive smell of phenyl
isocyanide. In contrast, N-methylaniline, being secondary amine does not give this test.

C6 H5 NH2  CHCl 3  3KOH   C6 H5 NC
Aniline 1 a min e  alc. Phenyl isocyanide
offensive smell
 
C6 H5  NH  CH3  
 No reaction
3 CHCl / KOH alc
N  methylaniline 2 a min e
3. Account for the following :

(i) pKb of aniline is more than that of methylamine.
(ii) Ethylamine is soluble in water whereas aniline is not.
(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide.
(iv) Although amino group is o- and p-directing in aromatic electrophilic substitution reactions,
aniline on nitration gives a substantial amount of m-nitroaniline.
(v) Aniline does not undergo Friedel-Crafts reaction.
(vi) Diazonium salts of aromatic amines are more stable than those of aliphatic amines.
(vii) Gabrial phthalimide synthesis is preferred for synthesising primary amines.
Ans. (i) In aniline, the lonepair of electrons on the N-atom are delocalized over the benzene ring.
Resulting, electron density on the nitrogen decreases. On the other hand, in CH3NH2, +I
effect of CH3 increases the electron density on the N-atom. Thus, aniline is a weaker base
than methylamine and hence its pKb value is higher than that of methylamine.
(ii) Ethylamine dissolves in water because it forms hydrogen bonds with water molecules. In
aniline due to large, hydro carbon part, the extent of H - bonding decreases considerably
and hence aniline is insoluble in water.
(iii) Methylamine being more basic than water, accepts a proton from water liberating OH
ions.
.. +
CH3 NH2 + H – OH CH3 NH3 + OH—
These OHQ ions combine with Fe+3 ions present in H2O to form brown precipitate of
hydrated ferric oxide.
FeCl3  Fe+3 + 3Cl—
2Fe 3  6OH —  2Fe  OH 3 or Fe2 O3 .3H2 O
Hydrated ferric oxide  Brown ppt.
E 235
Chemistry
ALLEN
(iv) Nitration is usually carried out with a mixture of conc. HNO3 and conc. H2SO4. In presence
of these acids, most of aniline gets protonated to form anilinium ion. Thus in presence of
acids, the reaction mixture consists of aniline and anilinium ion. Now –NH2 groups in
aniline is o, p-directing and activating while the NH 3 group in anilinium ion in m-
directing and deactivating.
NH2 NH2 NH2
+ NO+2 NO2
+
NO2 o-Nitroaniline 2%
–H+ +H+
p-Nitroaniline (51%)
+ +
NH3 NH3 NH2
+ NO+2 NH4OH
+
–H
NO2 NO2
Anilinium ion
m-Nitroaniline (47%)
(v) Aniline being a Lewis base, reacts with lewis acid AlCl3 to from a salt.
.. +
C 6 H 5 NH 2 + AlCl3 C 6 H 5 N H 2 AlCl3-
As a result, N of aniline acquires positive charge and hence it acts as a strong deactivating
group for electrophilic substitution reaction, consequently, aniline does not undergo Friedel
– Crafts reaction
(vi) The diazonium salts of aromatic amines are more stable than those of aliphatic amines due
to dispersal of the positive charge on the benzene ring as shown below.
+ + + + +
N  N.. N = N.. N = N.. N = N.. N  N..
..
..
..
+ +
(vii) Gabriel phthalimide reaction gives pure primary amines without any contamination of
secondary and tertiary amines. Therefore, It is preferred for synthesising (aliphatic) primary
amines.
4. Arrange the following :
(i) In decreasing order of the pKb values :
C2H5NH2, C6H5NHCH3, (C2H5)2NH and C6H5NH2
(ii) In increasing order of basic strength:

C6H5NH2, C6H5N(CH3)2, (C2H5)2 NH and CH3NH2
(iii) In increasing order of basic strength :
(a) Aniline, p-nitroaniline and p-toluidine
(b) C6H5NH2, C6H5NHCH3, C6H5CH2NH2
(iv) In decreasing order of basic strength in gas phase :
C2H5NH2, (C2H5)2NH, (C2H5)3N and NH3
236 E
CBSE
ALLEN
(v) In increasing order of boiling point :
C2H5OH, (CH3)2NH, C2H5NH2
(vi) In increasing order of solubility in water :
C6H5NH2, (C2H5)2NH, C2H5NH2
Ans. (i) C6H5NH2 > C6H5NH–CH3 > C2H5NH2 > (C2H5)2NH
(ii) C6H5NH2 < C6H5N(CH3)2 <CH3NH2 <(C2H5)2 NH
(iii) (a) p – nitroaniline < aniline < p - toluidine
(b) C6H5 NH2 <C6H5NHCH3 <C6H5CH2NH2
(iv) (C2H5)3 N > (C2H5)2NH > C2H5NH2 > NH3
(v) (CH3)2 NH < C2H5NH2 < C2H5OH
(vi) C6H5NH2 < (C2H5)2 NH < C2H5NH2
5. How will you convert :
(i) Ethanoic acid into methanamine (ii) Hexanentirile into 1-aminopentane
(iii) Methanol to ethanoic acid (iv) Ethanamine into methanamine
(v) Ethanoic acid into propanoic acid (vi) Methanamine into ethanamine
(vii) Nitromethane into dimethylamine (viii) Propanoic acid into ethanoic acid
3 
CH 3 COOH  
 CH 3 COCl   CH3 CONH2 
Hoffmann bromo amide reaction  CH 3 NH 2
SOCl2 NH excess Br2 / KOH
Ans. (i) Ethanoic acid ethanoyl chloride ethanamide
 CH3  CH2 4 COOH   CH3  CH2  4 COCl


(ii) CH3 (CH)4 CN 

H3 O
Hydrolysis
PCl5
Hexanenitrile Hexanoic acid
3

 CH3  CH2  4 CONH2   CH3  CH2  4 NH2

NH excess Br2 / KOH
1-pentanamine
  
CH3 OH   CH3 Cl   CH3 CN 
PCl5 KCN alc
H3 O
(iii) CH3 COOH
Methanol Ethanenitrile Ethanoic acid
O
 CH C–NH   CH3  NH2
Br2
(iv) CH3  CH2  NH2 
HNO2

 CH3 CH2  OH 
[O]
 CH3 COOH 
NH3
 3 2
KOH

P  I2
(v) CH3 COOH 
LiAlH4
Re duction
CH3 CH2 OH   CH3 CH2 I 
KCN
 KI
 CH3 CH2 CN 
H2 O / H
 CH 3 CH2 COOH
Ethyliodide Ethylcyanide Pr opionic acid
P  I2
(vi) CH3 NH2 
HNO2
 N2 ,  H2 O
 CH3 OH   CH3 I 
KCN
 KI
 CH3 CN 
Na / C2 H5 OH
Reduction
 CH3 CH2 NH2
Methyliodide Ethanamine
CHCl3  KOH Na  C2 H5 OH
(vii) CH 3 NO2 
Sn / HCl
 CH3 NH2   CH3 NC 
Reduction
 CH3 NHCH3
Dimethylamine
(viii) CH 3CH2COOH 

NH3

 CH3 CH2 CONH2 
Br2 / KOH

 CH2 CH2 NH2
Propanoic acid Propanamide
6. Describe a method for the identification of primary, secondary and tertiary amines. Also write
chemical euqations of the reactions involved.
Ans. Benzene sulphonyl chloride (C6H5SO2Cl), Which is also known as Hinsberg's reagent, reacts
with primary and secondary amine to form sulphonamides.

O O
(i) S–Cl + H–N–C2H5 S–N–C2H5 + HCl
O H OH
N-Ethylbenzene sulphonamide
(soluble in alkali)
The hydrogen attached to nitrogen in sulphon amide is strongly acidic due to the presence
of strong electron with drawing sulphonyl group. Hence it is soluble in alkali.
E 237
Chemistry
ALLEN
O O
(ii) S–Cl + H–N–C2H5 S–N– C2H5 + HCl
O C2H5 O C2H5
N,N-Diethylbenzene sulphonamide
(insoluble in alkali because there is no
hydrogen atom attached to Nitrogen)
(iii) Tertiary amines do not react with benzene sulphonyl chloride.

This property of amines reacting with benzene sulphonylchloride in a different manner is
used for the distinction of primary, secondary and tertiary amines.
7. Write short notes on the following :
(i) Carbylamine reaction (ii) Diazotisation
(iii) Hafmann's bromamide reaction (iv) Coupling reaction
(v) Ammonolysis (vi) Acetylation
(vii) Gabriel phthalimide synthesis
Ans. (i) Carbylamine reaction : Aliphatic and aromatic primary amines on heating with
chloroform and ethanolic potassium hydroxide form isocyanide or carbylamines which are
foul smelling substances. Secondary and tertiary amines do not show this reaction. This
reaction is known as carbylamine reaction or isocyanide test and is used as a test for
primary amine.
R  NH 2  CHCl3  3KOH 
Heat
 R  NC  3KCl  3H 2O
(ii) Diazotisation reaction : When a cold solution of a primary aromatic amine in a dilute
mineral acid (HCl or H2SO4) is treated with a cold solution of nitrous acid at 273 – 278 K.
arenediazonium salt is formed. This reaction is called diazotisation reaction.
e.g. : NaNO2 + HCl  HNO2 + NaCl
NH2 N NCl
273 - 278 K
+ HNO2 + HCl + 2H2O
Aniline Benzene diazonium

(1° Aromatic amine) chloride
(iii) Hoffmann's Bromamide Reactions : The conversions of a primary amide to a primary

amine containing one carbon atom less than the original amide on heating with a mixture of
Br2 in presence of NaOH or KOH is called Haffmann's bromamide reaction. For example,

CH 3 CH2 CONH2  Br2  4KOH   CH3 CH2 NH2  2KBr  K 2 CO3  2H2 O
Ethylamine

C6 H 5 CONH2  Br2  4KOH   C6 H5 NH2  2KBr  K 2 CO3  2H2 O
Benzamide Aniline
This reaction is extremely useful for converting a higher homologue to the next lower
homologue.
238 E
CBSE
ALLEN
(iv) Coupling Reaction : The reaction of diazenium salts with phenols and aromatic amines to
form azo compounds of the general formula Ar – N = N – Ar is called coupling reaction. In
this reaction, the nitrogen atoms of the diazo group are retained in the product. The
coupling with phenols takes place in mildly alkaline medium while with amines it occurs
under faintly acidic conditions.
For example
273 - 278 K
N NCl +
+ –
OH (pH 9 - 10)
N=N OH+HCl
Benzene diazonium Phenol P-Hydroxy azobenzene

Chloride (orange dye)
273 - 278 K
N NCl +
+ –
NH2 (pH 4–5)
N=N NH2
Benzene diazonium Aniline P-Amino azobenzene

Chloride (yellow dye)
CH3
273 - 278 K, OH—
NaO3S N+NCl– + N(CH3)2 NaO3S N=N N + HCl
CH3
Methyl orange
(v) Ammonolysis : The process of cleavage of the C–X bond by ammonia molecule is known
as ammonolysis.
R–NH2 +R–X R2–NH + RX R3N + RX R4N+ X—
(1°) (2°) (3°) Quarternary
ammonium salt
O
(vi) Acetylation : The process of introducing an acetyl group (CH3–C– ) into a molecule is called
acetylation. Common acetylating agents used are acetyl chloride and acetic anhydride.
O O
CH3–CH2–NH2+CH3–C–Cl CH3–C–NH–CH2CH3+HCl
N-Ethyl acetamide
O
O
CH3–CH2–NH2 + CH3–C
Ethanamine
O CH3– C – NH – CH2– CH3 + CH3COOH
CH3–C N - Ethyl acetamide
O
Acetic anhydride
(vii) Gabriel Phthalimide Synthesis : In this reaction phthalimide is converted into its
potassium salt by treating it with alcoholic potassium hydroxide. Then potoassium
phthalimide is heated with an alkylhalide to yield an N–alkylphthalimide which is
hydrolysed to phthalic acid and primary amine by heating with HCl or KOH solution.
CO CO CO
KOH (alc) C2H 5I
NH –H 2O NK NC2H5
–KI
CO CO CO
N – Ethylpthalimide
COOH
H 2O, H +
(Hydrolysis) + C2H5NH2
COOH Ethylamine
Phthalic acid
Aromatic primary amines cannot be prepared by this method.
E 239
Chemistry
ALLEN
8. Accomplish the following conversions :
(i) Nirobenzene to benzoic acid
(ii) Benzene to m-bromophenol
(iii) Benzoic acid to aniline
(iv) Aniline to 2,4,6-tribromofluorobenzene
(v) Benzyl chloride to 2-phenylethanamine
(vi) Chlorobenzene to p-chloroaniline
(vii) Aniline to p-bromoaniline
(viii) Benzamide to toluene
(ix) Aniline to benzyl alcohol
+
NO2 NH2 N  NCl— CN COOH
(i) Fe/HCl NaNO 2/HCl CuCN/KCN H 3O

Ans. (i) (ii) NaOH 273-278 K Hydrolysis
Nitrobenzene Aniline Benzene diazonium Benzonitrile Benzoic acid

Chloride
NO2 NO2 NH2

Conc.HNO3
+Conc.H2SO4 Br2/Fe Sn + HCl
(ii) 333 K
Br Br
Benzene Nitrobenzene m-Bromoaniline
m-Bromonitrobenzene
N2Cl OH
NaNO2/HCl Boiling
273-278 K dil H2SO 4
Br Br
m-Bromophenol
COOH COCl CONH2 NH2
PCl5 2NH 3 Br2 + KOH

(iii) -NH 4Cl
Benzoic acid Benzoyl Chloride Benzamide Aniline

+ –
NH2 NH2 N=NBF4 F
Br Br Br Br Br Br
Br2/H 2O NaNO2/HBF 4 Heat
(iv) 273-278 K
Aniline
Br Br Br
2,4,6-Tribromonoaniline 2,4,6-Tribromo fluoro benzene
CH2Cl CH2CN CH2CH2NH2
(v) KCN (alc). Heat LiAlH 4

–KCl
Benzyl Chloride Phenyl ethanenitrile 2-Phenyl ethanamine
Cl Cl Cl
Conc. HNO3
+ Conc. H 2SO 4 Sn/HCl
(vi) Nitration (Reduction)
Chlorobenzene
NO2 NH2
P-Nitro chlorobenzene p-Chloro aniline
(Major product)
240 E
CBSE
ALLEN
NH2 NHCOCH3 NHCOCH3 NH2
(CH 3CO) 2O/CH 3COOH Br2/CH 3COOH H 2O/OH —

(vii)
Aniline Acetanilide
Br Br
p-Bromo acetanilide p-Bromo aniline
(Major product)
+
CONH2 NH2 N2Cl—
Br2/NaOH NaNO 2/HCl

(viii) Heat 273-278 K
Diazotisation
Benzamide Aniline Benzene diazonium
Chloride
CH3
H 3PO 2–H 2O/Cu, Heat CH3Cl/Anhyd.AlCl3
Benzene Toluene
+ —
NH2 N2Cl
NaNO 2/HCl H3PO2–H2O/Cu, Heat CH 3Cl/Anhyd. AlCl3

(ix) 273-278 K
Aniline Benzene diazonium Benzene

Chloride
CH3 CH2Cl CH2OH
Cl2(1 mole),hv KOH (aq.)

383 K (Hydrolysis)
Toluene Benzyl Chloride Benzylalcohol
9. Give the structures of A, B and C in the following reactions :

NaOH  Br2
(i) CH3CH2I   A  B  C
–
NaCN OH
Partial hydrolysis

(ii) C6H5N2Cl 
CuCN
 A 
H 2O/H
B 
NH3

C
(iii) CH3CH2Br   A   B  C
KCN LiAlH4 HNO 2
0 C

NaNO2  HCl
(iv) C6H5NO2 
Fe/HCl
 A 
273K
  B 
H 2O/H

C
(v) CH3COOH   B 
 A 
NH3 NaNO2 /HCl NaOBr

C
(vi) C6H5NO2 
Fe/HCl
 A 
HNO2
273K
 B 
C6H5OH
C
O
NaCN OH
—
NaOH + Br2
Ans. (i) CH3CH2I CH3CH2CN
Partial hydrolysis
CH3—C—NH2 CH3–NH2
Iodoethane Propanenitrile (A) Ethanamide (B) Methanamine (C)
CuCN H 2O/H NH3 Heat

(ii) C6H5N2Cl C6H5CN
hydrolysis
C6H5COOH C6H5COONH4 C6H5CONH2
Benzenediazonium Cyanobenzene Benzoicacid (B) Benzamide (C)
Chloride (A)
KCN LiAlH 4
(iii) CH3CH2Br CH3CH2CN CH3CH2CH2NH2
Bromoethane Propanenitrile (A) Propan-1-amine (B)
HNO 2,0C° +
[CH3CH2CH2N NCl—]
E 241
Chemistry
ALLEN
Fe/HCl NaNO 2/HCl + H 2O/H+
(iv) C6H5NO2 C6H5NH2 C6H5N  NCl— Heat
C6H5OH
Nitrobenzene Aniline (A) Benzenedizonium Phenol (C)
Chloride (B)
(v) CH3COOH
NH3
CH3CONH2
NaOBr
CH3NH2
NaNO2/HCl
CH3O–CH3
Heat
Ethanamide (A) Methanamine (B) Dimethyl ether
Fe/HCl HNO 2 + C6H 5OH

(vi) C6H5NO2 C6H5NH2
273 K
C6H5N NCl— N=N OH
Nitrobenzene Aniline (A) Benzenediazonium
Chloride (B) p-Hydroxyazo benzene (C)
10. An aromatic compound 'A' on treatment with aqueous ammonia and heating forms compound 'B'
which on heating with Br2 and KOH forms a compound 'C' of molecular formula C6H7N. Write
the structures and IUPAC names of compounds A, B and C.
Br2 + KOH
Ans. C6H5COOH
(i) (aq.) NH3
Heat
C6H5CONH2 C6H5NH2
Benzoic aicd (A) Benzamide (B) Aniline (C)
m.f. = C7H 7NO mf = C6H 7N
11. Complete the following reactions :

(i) C6H5NH2 + CHCl3 + alc. KOH 
(ii) C6H5N2Cl + H3PO2 + H2O 
(iii) C6H5NH2 + H2SO4 (conc.) 
(iv) C6H5N2Cl + C2H5OH 
(v) C6H5NH2 + Br2 (aq.) 
(vi) C6H5NH2 + (CH3CO)2O 
(vii) C6H5N2Cl (i) HBF4
(ii) NaNO2 /Cu,
Ans. (i) C6H5NH2 + CHCl3 + 3KOH (alc.) Heat

(Carbylamine reaction)
C6H5N =C
Aniline Phenyl isocyanide
(offensive smell)
(ii) C6H5N2Cl + H3PO2 + H2O C6H6 + N2 + H3PO3+HCl

Benzenediazonium Benzene
Chloride
+ —
(iii) C6H5NH2 + H2SO4 (Conc.) C6H5NH3HSO4
Anilinium hydrogen
Aniline sulphate
(iv) Reduction
C6H5N2Cl + C2H5OH C6H6 + CH3CHO + N2 + HCl
Benzene diazonium Benzene Ethanal

Chloride
NH2 NH2
Br Br
(v) + 3Br2(aq.) + 3 HBr
Br
Aniline 2,4,6-Tribromoaniline
242 E
CBSE
ALLEN
O
O
H3C—C CH3COOH
(vi) C6H5NH2 + O C6H5–NH–C–CH3 + CH3COOH
or Pyridine
H3C—C
(Acetylation)
O
Aniline Acetic anhydride Acetanilide
+ HBF4 +– NaNO 2/Cu
(vii) C6H5N2Cl
—
C6H5 N2BF4 Heat
C6H5 NO2 + BF3 + NaF
Benzene diazonium
Benzenediazonium Nitrobenzene
Chloride
tetra fluoroborate
12. Why aromatic primary amines can not be prepared by Gabriel phthalimide synthesis ?
Ans. The success of Gabriel phthalimide reaction depends upon the nucleophilic attack by the
phthalimide anion on the organic halogen compound.
O O
C 
C

N + R—X N—R
C C
O O
Phthalimide anion N-Alkylphthalimide
O
C
N + Ar—X × No reaction
Arylhalide
C
[Stable by resonance]
O
Phthalimide anion
As arylhalides do not undergo nucleophilic substitution reaction easily, aromatic primary amines
cannot be prepared by Gabriel phthalimide reaction.
13. Write the reactions of (i) aromatic and (ii) aliphatic primary amines with nitrous acid.
+
NH2 N  NCl—
Ans. (i) + HNO2 + HCl 273-278 K

+ 2 H2O
Aniline Benzene diazonium

Chloride
273-278 K + H 2O
(ii) [CH3CH2–N  N] Cl
—
CH3CH2NH2 +HNO2+ HCl CH3CH2OH+N2+HCl
Ethylamine Ethanediazonium Chloride Ethanol
(Unstable)
14. Give plausible explanation for each of the following :

(i) Why are amines less acidic than alcohols of comparable molecular masses ?
(ii) Why do primary amines have higher boiling point than tertiary amines ?
(iii) Why aliphatic amines are stronger bases than aromatic amines ?

Ans. (i) Loss of a proton from an amine gives amide ion (NH) while loss of a proton from alcohol

gives an alkoxide ion (OR) as shown below.

R-NH2 R-NH + H+
Amine Amide ion

R-O-H R-O+H+
Alcohol Alkoxide ion
As O is more electronegative than N, So negative charge on more electronegative atom is

 
more stable, As R  O is more stable than RN H . Therefore amines are less acidic than
alcohols.
E 243
Chemistry
ALLEN
(ii) Due to the presence of two H-atoms on N-atoms of 1° amines, they undergo extensive
intermolecular H-bonding while 3° amines due to the absence of H-atoms on N-atom there
is no hydrogen bonding takes place. So primary amines have higher b.p. than tertiary
amines of comparable molecular mass.
R R R
N—H N—H N—H
-----H -----H H
Inter molecular Hydrogen bonding in 1° amines.
R
|
R —N
|
R
No hydrogen bonding
(iii) Aliphatic amines are stronger bases than aromatic amines because :
(a) Due to resonance in aromatic amines, the lone pair of electrons on the nitrogen atom
gets delocalised over the benzene ring thus is less available for protonation.
(b) The aryl amine ions, have lower stability than the corresponding aliphatic amines i.e.,
protonation of aromatic amines is not favoured.
244 E
CBSE
ALLEN
EXERCISE-3 EXEMPLAR
1. Which of the following is a 3° amine ?
(a) 1-methylcyclohexylamine (b) Triethylamine
(c) tert-butylamine (d) N-methylaniline
Ans. (b)
2. Amongst the following, the strongest base in aqueous medium is…………
(a) CH3NH2 (b) NCCH2NH2 (c) (CH3)2NH (d) C6H5NHCH3
Ans. (c)
3. Which of the following is the weakest Bronsted base ?
NH2
NH2
(a) (b) N–H (c) (d) CH3NH2

Ans. (a)
4. Benzylamine may be alkylated as shown in the following equation ?
C6H5CH2NH2 + R –– X  C6H5CH2NHR
Which of the following alkyl halides is best suited for this reaction through SN1 mechanism ?
(a) CH3Br (b) C6H5Br (c) C6H5CH2Br (d) C2H5Br
Ans. (c)
5. Which of the following reagents would not be a good choice for reducing an aryl nitro compound
to an amine ?
(a) H2(excess)/Pt (b) LiAlH4 is ether (c) Fe and HCl (d) Sn and HCl
Ans. (b)
6. In order to prepare at 1° amine from an alkyl halide with simultaneous addition of one CH2 group
in the carbon chain, the reagent used as source of nitrogen is ……
(a) Sodium amide, NaNH2 (b) Sodium azide, NaN3
(c) Potassium cyanide, KCN (b) Potassium phthalimide C6H4 (CO)2N–K+
Ans. (c)
7. Amongst the given set of reactants, the most appropriate for preparing 2° amine is ….
(a) 2° R –Br + NH3
(b) 2° R –Br + NaCN followed by H2/Pt
(c) 1° R –NH2 + RCHO followed by H2/Pt

(d) 1° R –Br (2 mol) + potassium phthalimide followed by H3O+/heat.
Ans. (c)
8. Hofmann bromamide degradation reaction is shown by ……
(a) ArNH2 (b) ArCONH2 (c) ArNO2 (d) ArCH2NH2
Ans. (b)
E 245
Chemistry
ALLEN
9. Methylamine reacts with HNO2 to form …..
(a) CH3 –O– N = 0 (b) CH3 –O– CH3 (c) CH3 OH (d) CH3 CHO
Ans. (c)
10. In the nitration of benzene using a mixture of conc. H2SO4 and conc. HNO3, the species which
initiates the reaction is ……..
(a) NO2 (b) NO+ (c) NO 2 (d) NO 2
Ans. (c)
11. The most reactive amine towards dilute hydrochloric acid is …….
NH2
CH3 CH3
NH–CH3 NH–CH3
(a) CH3 – NH2 (b) CH (c) CH (d)
3
3

Ans. (b)

12. The reaction Ar N 2 Cl 
Cu/HCl
 ArCl  N 2  CuCl is named as ……..
(a) Sandmeyer reaction (b) Gattermann reaction
(c) Claisen reaction (d) Carbylamine reaction
Ans. (b)
13. Best method for preparing primary amines from alkyl halides without changing the number of
carbon atoms in the chain is :
(a) Hofmann bromamide reaction (b) Gabriel phathalimide synthesis
(c) Sandmeyer reaction (d) reaction with NH3
Ans. (b)
14. Which of the following compound will not undergo azo coupling reaction with benzene
diazonium chloride ?
(a) Aniline (b) Phenol (c) Anisole (d) Nitrobenzene
Ans. (d)
15. Which of the following compounds is the weakest Bronsted base ?
NH2 NH2 OH OH
(a) (b) (c) (d)

Ans. (c)
16. Which of the following should be most volatile ?

I. CH3CH2CH2NH2 II. (CH3)3N
CH3CH2
III. NH IV. CH3CH2CH3
CH3
(a) II (b) IV (c) I (d) III
Ans. (b)
246 E
CBSE
ALLEN
17. What is the role of HNO3 in the nitrating mixture used for nitration of benzene ?
Ans. HNO3 acts as a base in the nitrating mixture and provide the electrophile, NO2+ on reaction with
H2SO4 as follows
NO
2
NO2

18. Why is NH2 group of aniline acetylated before carrying out nitration ?
Ans. In order to check the activation of benzene ring by amino group, first it is acetylated with acetic
anhydride or acetyl chloride in presence of pyridine to form acetanilide which can be further
nitrated easily by nitrating mixture.
NH2 NHCOCH3 NHCOCH3 NHCOCH3
(CH3CHO)2O Conc. HNO3 NO2
Pyridine Conc. H2SO4 228 k +
o-nitroacetanilide
NO2 (major product)
p-nitroacetanilide
(major product)

19. What is the product when C6H5CH2NH2 reacts with HNO2 ?
Ans. C6H5CH2NH2 on reaction with HNO2 produces C6H5CH2N2+ Cl– as follows :

CH2–NH2 CH2–N NCl CH2–OH
HNO2
H2O,
Diazonium Benzyl alochol
salt

20. Give the structure of ‘A’ in the following reaction.
CH3
(i) NaNO2 + HCl, 273-278 K
(ii) H3PO2,H2O
A
NO2
NH2
Ans. Complete conversion can be shown as :
CH3 CH3
(i) NaNO2 + HCl
273-278 K
NO2 NO2
NH2 N2Cl
2-nitro-4-methyl
aniline
CH
Cu+
(ii) H3PO2, H2O
+ H3PO3 + HCl + N2
3-methyl
NO2
nitrobenzene

E 247
Chemistry
ALLEN
21. Why does acylation of –NH2 group of aniline reduces its activating effect ?
Ans. Acylation of –NH2 group of aniline reduces its activity due to resonance of lone pair of nitrogen
towards the carbonyl group hence o-,p– directive influence of amino group get disturbed.
NH2 NHCOR
RCOCl
N
The resonating structure are
O O
H C H C
N R N R
22. Under what reaction condition (acidic, basic) the coupling reaction of aryl diazonium chloride
with aniline is carried out ?
Ans. In strongly basic conditions, benzenediazonium chloride is converted into diazohydroxide and
diazoate as both of which are not electrophilic and do not couple with aniline.


C6 H 5 N  NC l  OH  SO 2 CH 5  N  N  OH 
NaOH

 C6H 5  N  N  ONa

Diazohydroxide Sodium diazoate
Similarly, in highly acidic condition, aniline gets converted into anilinium ion. from this, result
aniline is no longer nucleophilic acid and hence will not couple with diazonium chloride.Hence,
the reaction is carried out under mild conditions i.e., pH–4–5.

C6 H 5 NH 2  H  
 C6 H 5  N H 3
Aniline Aniliniumion
(coupling do not occur)
23. Predict the product of reaction of aniline with bromine in non-polar solvent such as CS2.
Ans. Aniline on reaction with Br2 in non-polar solvent CS2 produes 2,4,6 tribomo aniline.
NH2 NH2
Br Br
Br2
CS2 < 5oC
Aniline
Br
2,4,6 tribromo
aniline
Aniline has high reactivity towards bromine as it gives the triply substituted product.
25. Arrange the following compounds in increasing order of dipole moment.
CH3CH2CH3,CH3CH2NH2, CH3CH2OH
Ans. Dipole moment of amine, alcohol and hydrocarbon can be explained on the basis of bond polarity
of C–H, N–H and O–H bond. As the bond polarity increase, dipole moment increases
CH3CH2CH3 < CH3 CH3NH2 < CH3CH2OH
248 E
CBSE
ALLEN
26. A primary amine, RNH2 can be reacted with CH3–X to get secondary amine, R–NHCH3 but the
only disadvantage is that 3° amine and quaternary ammonium salts are also obtained as side
products. Can you suggest a method where RNH2 forms only 2° amine ?
KOH/CHCl3 H2/Pd
RNH2 RNC RNHCH3
Ans. Primary amine
Carbylamine reaction alkyl iso cyanide Secondary amine
Primary amines show carbylamines reaction in which two H-atoms attached to N-atoms of NH2
are replaced by one C-atom. On catalytic reduction, isocyanide (formed) produces secondary
amine and not tertiary or quaternary salts.
27. Complete the following reaction.
OH
+
ArN2Cl–
OH–
Ans. The reaction exhibits azo-coupling reaction of phenols. Benzene diazonium chloride reacts with
phenol in such a manner that the para position of phenol is coupled with diazoniu salt to form p-
hydroxy azobenzene.
–
+H OH OH N=N OH + H2O + Cl–
Benzene diazonium Phenol p-hydroxyazobenzene
chloride (Orange dye)
28. Suggest a route by which the following conversion can be accomplished.

O
NH–CH3
NH2

Ans. Complete conversion can be performed as

O
NH2
NH2
Cyclohexyl Cyclohexyl
amide amide
NH–CH3
Cyclohexyl Cyclohexyl
isocyanide methyl amine
29. Identify A and B in the following reaction.

O
Cl

E 249
Chemistry
ALLEN
Ans. Complete conversion can be performed as
O O
Cl CN
(A)
H2/Pd
(Catalytic hydrogenation)
O
CH2–NH2
(B)
Hence,
O O
CN NH2
A= B=
3-(2-oxocyclohexyl 2-(3-aminopropyl
propanenitrile) -cyclohex-1-one
30. How will you carry out the following conversions ?

(i) Toluene 
 p-toluidine
(ii) p-toluidine diazonium chloride 
 p-toluic acid
Ans.
(i) Conversion of toluene to p-toluidine can be done as
CH3 CH3 CH3
HNO3/H2SO4 Fe/HCl
[H]
Toluene
NO2 NO2
4-methyl p-toluidine
nitrobenzene
(ii) Conversion of p-toluidine chloride to p-toluic acid can be done as
CN COOH
CuCN H2O/H+
CH3 CH3 CH3

p-toluidien diazonium p-tolulic acid
chloride
31. How will you carry out the following conversion ?

NH2 NO2
Br
250 E
CBSE
ALLEN
Ans. Conversion of aniline to m-bromo nitrobenzene can be completed as
NH2 NO2 NO2

HNO2 HBF4 NaNO2 Br2/CH3COOH
273-278 K Cu, D
Br
Benzene Benzene diazonium chloride Nitrobenzene m-bromonitrobenzene
32. How will you carry out the following conversion ?

NH2 NO2 NH2 NO2
(i) (ii)
Br Br Br Br
I
Ans. (i) Conversion of aniline to 3, 5-dibromoitrobenzene can be completed as
NH2 NHCOCH3 NHCOCH3 NH2
Aniline Acetanilide
NO2 NO2
p-nitroacetanilide p-nitroaniline
Br2/CH3COOH
NH2
Br Br Br Br Br Br
NO2 NO2 NO2

3.5-dibromonitrobenzene
(ii) Conversion (A) given below is same as in part (i) given above after that reaction (B) can be
carried out.
NH2 I
Br Br Br Br Br Br
(A) (B)
Aniline
NO2 NO2 NO2
(Matching the columns)
33. Match the reactions given in Column-I with the statements given in Column-II.
Column-I Column-II
A. Ammonolysis 1. Amine with lesser number of carbon atoms.
B. Gabriel phthalimide synthesis 2. Detection test for primary amines.
C. Hofmann bromamide reaction 3. Reaction of phthalimide with KOH and R–X
D. Carbylamine reaction 4. Reaction of alkylhalides with NH3
Ans. A  (4) ; B  (3) ; C  (1) ; D  (2)
E 251
Chemistry
ALLEN
34. Match the compounds given in Column-I with the items given in Column-II.
Column-I Column-II
A. Benzene sulphonyl chloride 1. Zwitter ion
B. Sulphanilic acid 2. Hinsberg reagent
C. Alkyl diazonium salts 3. Dyes
D. Aryl diazonium salts 4. Conversion to alcohols
Ans. A  (2) ; B  (1) ; C  (4) ; D  (3)
(Assertion and Reason)
In the following questions a statement of Assertion (A) followed by a statement of Reason (R)
is given. Choose the correct answer out of the following choices.
35. Assertion (A) : Acylation of amines gives a monosubstituted product whereas alkylation of
amines gives polysubstituted product.
Reason (R) : Acyl group sterically hinders the approach of further acyl groups.
Ans. (c)
36. Assertion (A) : Hofmann’s bromamide reaction is given by amide.
Reason (R) : Primary amines less basic than secondary amines.
Ans. (b)
37. Assertion (A) : N-ethylbenzene sulphonamide is soluble in alkali.
Reason (R) : Hydrogen attached to nitrogen in sulphonamide is strongly acidic.
Ans. (d)
38. Assertion (A) : N, N-diethylbenzene sulphonamide is insoluble in alkali.
Reason (R) : Sulphonyl group attached to nitrogen atom is strong electron withdrawing group.
Ans. (d)
39. Assertion (A) : Only a small amount of HCl is required in the reduction of nitro compounds with
iron scrap and HCl in the presence of steam.
Reason (R) : FeCl2 formed gets hydrolysed to release HCl during the reaction.
Ans. (d)
40. Assertion (A) : Aliphatic 1° amines can be prepared by Gabriel phthalimide synthesis.
Reason (R) : Aryl halides undergo nucleophilic substitution with anion formed by phthalimide.
Ans. (c)
41. Assertion (A) : Acetanilide is less basic aniline.
Reason (R) : Acetylation of aniline results in decrease of electron density on nitrogen.
Ans. (a)
252 E
CBSE
ALLEN
(INTRODUCTION OF N-CONTAINING COMPOUND)
1. Which of the following is 1° amine
(a) Ethyl diamine (b) Dimethyl amine
(c) Trimethyl amine (d) N-methyl aniline
(PREPARATION OF N)
2. Reaction CH 3CONH 2 
NaOBr
 gives
(a) CH3Br (b) CH4 (c) CH3COBr (d) CH3NH2
3. Acetamide changes into methylamine by
(a) Hofmann bromamide reaction (b) Hofmann reaction
(c) Friedel-Craft's reaction (d) Hinsberg reaction
4. When methyl iodide is heated with ammonia, the product obtained is
(a) Methylamine (b) Dimethylamine
(c) Trimethylamine (d) A mixture of the above three amines
5. The Hinsberg's method is used for
(a) Preparation of primary amines (b) Preparation of secondary amines
(c) Preparation of tertiary amines (d) Separation of amine mixtures
6. In the following reaction, X is
NaNO 2  HCl
X 
Bromination
 Y    Z 
Boiling
 Tribromobenzene
C2H5OH
(a) Benzoic acid (b) Salicylic acid (c) Phenol (d) Aniline
7. Carbylamine reaction is given by
(a) 1° amine (b) 3° amine (c) 2° amine (d) Quarternary salts
8. The reaction
C6 H 5 NH 2  CHCl3  3KOH  C6 H 5 NC  3KCl  2H 2O
is known as
(a) Carbylamine reaction (b) Reimer-Tiemann reaction
(c) Kolbe reaction (d) Hofmann's degradation
9. Aromatic primary amine when treated with cold HNO2 gives
(a) Benzyl alcohol (b) Nitro benzene (c) Benzene (d) Diazonium salt
10. Which of the following compound is the strongest base

(a) Ammonia (b) Aniline (c) Methylamine (d) N-methyl aniline
11. The diazonium salts are the reaction products in presence of excess of mineral acid with nitrous
acid and
(a) Primary aliphatic amine (b) Secondary aromatic amine
(c) Primary aromatic amine (d) Tertiary aliphatic amine
E 253
Chemistry
ALLEN
12. In acid medium nitrobenzene is reduced to aniline as shown in the reaction
C6 H 5  NO 2  6[H]  C6 H 5  NH 2  2H 2O
The reducing agent used in this reaction is …….
(a) LiAlH4 (b) Sn/HCl (c) Na/alcohol (d) H2/Ni
13. Gabriel's phthalimide synthesis is used for the preparation of
(a) Primary aromatic amine (b) Secondary amine
(c) Primary aliphatic amine (d) Tertiary amine
(PROPERTIES)
14. Which of the following compound is expected to be most basic
(a) Aniline (b) Methylamine (c) Hydroxylamine (d) Ethylamine
15. Aniline when treated with HNO2 and HCl at 0°C gives
(a) Phenol (b) Nitrobenzene
(c) A diazo compound (d) None of these
16. Which one is weakest base
(a) Ammonia (b) Methylamine (c) Dimethylamine (d) Trimethylamine
17. Primary amines can be distinguished from secondary and tertiary amines by reacting with
(a) Chloroform and alcoholic KOH (b) Methyl iodide
(c) Chloroform alone (d) Zinc dust
18. Which of the following is azo- group
(a) –N= (b) –N=N– (c) –NH– (d) –CO–NH–
19. The decreasing order of the basic character of the three amines and ammonia is
(a) NH 3  CH 3 NH 2  C 2 H 5 NH 2  C6 H 5 NH 2 (b) C2 H 5 NH 2  CH 3 NH 2  NH 3  C6 H 5 NH 2
(c) C6 H 5 NH 2  C2 H 5 NH 2  CH 3 NH 2  NH 3 (d) CH 3 NH 2  C2 H 5 NH 2  C6 H5 NH 2  NH 3
20. Correct order of increasing basicity is
(a) NH 3  C6 H 5 NH 2  (C 2 H 5 ) 2 NH  C 2H 5 NH 2  (C2H 5 )3 N
(b) C6 H 5 NH 2  NH 3  (C2 H 5 )3 N  (C2 H 5 ) 2 NH  C2H 5 NH 2
(c) C6 H 5 NH 2  NH 3  C2 H 5 NH 2  (C2 H 5 )3 N  (C2H 5 ) 2 NH
(d) C6 H 5 NH 2  (C2 H 5 )3 N  NH 3  C2 H 5 NH 2  (C2H 5 ) 2 NH

21. Aniline on treatment with excess of bromine water gives

(a) Aniline bromide (b) o-bromoaniline
(c) p-bromoaniline (d) 2, 4, 6-tribromoaniline
22. Unpleasant smelling carbylamines are formed by heating alkali and chloroform with
(a) Any amine (b) Any aliphatic amine
(c) Any aromatic amine (d) Any primary amine
254 E
CBSE
ALLEN
23. When an organic compound was treated with sodium nitrite and hydrochloric acid in the ice cold,
nitrogen gas was evolved copiously. The compound is
(a) A nitro compound (b) A primary amine
(c) An aliphatic primary amine (d) An aromatic primary amine
24. Aniline on treatment with conc. HNO3 + conc. H2SO4 mixture yields
(a) o- and p-nitroanilines (b) m-nitroanilines
(c) A black tarry matter (d) No reaction
25. Which of the following is most basic
(a) C6H5NH2 (b) (CH3)2NH (c) (CH3)3N (d) NH3
26. If methyl is alkyl group, then which order of basicity is correct
(a) R 2 NH  RNH 2  R 3 N  NH 3 (b) R 2 NH  R 3 N  RNH 2  NH 3
(c) RNH 2  NH 3  R 2 NH  R 3 N (d) NH 3  RNH 2  R 2 NH  R 3 N
27. Arrange the following in increasing order of basicity CH 3 NH 2 , (CH 3 ) 2 NH,C6 H 5 NH 2 ,(CH 3 )3 N
(a) (CH 3 )3 N  (CH 3 ) 2 NH  CH 3 NH 2  C6H 5 NH 2
(b) (CH 3 )3 N  (CH 3 ) 2 NH  CH 3 NH 2  C6 H 5 NH 2
(c) C6 H 5 NH 2  (CH 3 )3 N  CH 3 NH 2  (CH 3 ) 2 NH
(d) C6 H 5 NH 2  (CH 3 )3 N  CH 3 NH 2  (CH 3 ) 2 NH
28. Aniline and methyl amine can be differentiated by
(a) Reaction with chloroform and aqueous solution of KOH
(b) Diazotisation followed by coupling with phenol
(c) Reaction with HNO2
(d) None of these
29. Electrophilic substitution of with bromine gives
(a) 1, 4, 6-tribromo aniline (b) 2, 4, 6-tribromo aniline

(c) 4-bromo aniline (d) 3-bromo aniline
30. During acetylation of amines what is replaced by acetyl groups
(a) Hydrogen atom attached to nitrogen atom
(b) One or more hydrogen atoms attached to carbon atom

(c) One or more hydrogen atoms attached to nitrogen atom
(d) Hydrogen atoms attached to either carbon atom or nitrogen atom
31. Ethyl amine on acetylation gives
(a) N-ethyl acetamide (b) Acetamide
(c) Methyl acetamide (d) None
E 255
Chemistry
ALLEN
32. Identify the product Z in the following reaction
C6H 5 NH 2 
(AC)2 O
X 
Br2 /CCl4
 Y 
HOH
Z
(a) p-Bromoaniline (b) p -Bromoacetophenone
(c) o-Bromoacetophenone (d) o-Bromoacetonilide
33. Complete the following reaction :
RNH2 + H2SO4 
(a) [R NH 3 ] HSO 4 (b) [R NH 3 ]2 SO 24
(c) R NH 2 .H 2SO 4 (d) No reaction

34. The reduction of which of the following compound would yield secondary amine ?
(a) Alkyl nitrite (b) Carbylamine
(c) Primary amine (d) Secondary nitro compound
ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. a d a d d d a a d c
Q. No. 11 12 13 14 15 16 17 18 19 20
Ans. c b c d c a a b b c
Q. No. 21 22 23 24 25 26 27 28 29 30
Ans. d d c c b a c b b c
Q. No. 31 32 33 34
Ans. a a b b
256 E
CBSE
ALLEN
Following questions have assertion followed by reason. Answer them according to
following options:
1. Assertion (A) : A primary amine when treated with NaNO2/ HCl gives a primary alcohol.
Reason (R) : Reaction proceeds by the formation of carbocation intermediate.
2. Assertion (A) : CH3CH3(CH3)NCH2CH3 on treatment with aqueous HCl produces two
stereoisomeric forms of quaternary ammonium salts.
Reason (R) : Salts will have chiral centre.
3. Assertion (A) : Aniline when treated with NaNO2 /HCl gives at 0°C flowed by coupling with
-naphthol gives a dark blue colour precipitate.
Reason (R) : The compound is coloured due to extended conjugation.
4. Assertion (A) : Hoffmann's bromamide reaction is given by primary amides.
Reason (R) : Primary amines during the reaction follow acidic hydrolysis.
5. Assertion (A) : Amines are pyramidal in shape.
Reason (R) : Nitrogen atom in amines is sp3-hybridised.
6. Assertion (A) : In strongly acidic solution, aniline becomes less reactive towards electrophilic
reagents.
Reason (R) : Due to protonation of amino group the lone pair of electrons on nitrogen is not
available for donation to benzene ring by resonance.
7. Assertion (A) : Salts of Benzene Diazonium are water soluble.
Reason (R) : Because of the covalent nature of such salts these are water soluble.
8. Assertion (A) : p-fluoroanilinium ion is more acidic than anilinium ion.
Reason (R) : Electron density in the N—H bond of p-fluoroanilinium ion decreases and release
of a proton from p-fluoroanilinium ion is much easier than from anilinium ion.
9. Assertion (A) : Anilinium hydrogen sulphate, on heating forms a mixture of ortho- and para-
amino benzene sulphonic acids.
Reason (R) : p-Amino benzene sulphonic acid exists as zwitter ion.
ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9
Ans. a a a c b a c a b
E 257
Chemistry
ALLEN
CASE BASED
Case-I
(Read the passage given below and answer the following questions)
Amines are alkyl or aryl derivatives of ammonia formed by replaced of one or more hydrogen
atoms. Alkyl derivatives are called aliphatic amines and aryl derivatives are know as aromatic
amines. The presence of aromatic amines can be identified by performing dye test. Aniline is
the simplest example of aromatic amine. It undergoes electrophilic substitution reactions in
which –NH2 group strongly activates the aromatic ring through delocalisation of lone pair of
electrons of N-atom. Aniline undergoes electrophilic substitution reactions. Ortho and para
positions to the –NH2 group become centres of high electrons density. Thus, –NH2 group is
ortho and para directing and powerful activating group.
(a) Name the species formed when secondary amines react with nitrous acid to form a
yellow green oily layer.
Ans. N-nitroso amine
OR
Which reaction is used to convert primary aromatic amines into their diazonium salts ?
Ans. Diazotisation
(b) Arrange the following compounds in the increasing order of their reactivity in
nucleophilic addition reaction. Ethanal, propanal, propanone, butanone
Ans. Butanone < propanone < propanal < ethanal
As we move from ethanal to butanone, +I-effect of alkyl group increases. The electron
density on the carbon atom progressively increases and , hence attack by nucleophile
becomes slower. Further, due to increase in the size of bulkier alkyl groups from ethanal
to butanone, the attack of nucleophile is also hindered.
(c) Complete the following reactions :
+ –
(i) C6 H 5 N 2 Cl + H3PO2 + H2O 
NH2
(ii) 
Br2 /H 2 O


+ –
Ans. (i) C6 H 5 N 2 Cl + H3PO2 + H2O  C6 H 6  N 2   H 3 PO3  HCl

Benzene
NH2
NH2 Br 6 1
Br
2
 

Br2 /H 2 O
(ii) 5 3

4
Br
2,4,6-tribromo aniline
258 E
CBSE
ALLEN
Case II
Amines are derivatives of ammonia, wherein one or more hydrogen atoms have been replaced
by a substituent such as an alkyl or aryl group. Although capillary columns are generally
preferred, there are many examples where separation is better by using packed columns,
especially for low-boiling amines. This study concerns derivatization of amines and diamines
and shows that MTBSTFA is the recommended reagent for silylation of the amine functionality
because this reagent forms a more stable derivative than MSTFA, BSTFA or BSA. The solvent
used is important because amines can be difficult to silylate. A detailed description of mass
spectral interpretation of amines is provided. Organic compounds with an odd number of
nitrogen atoms will have an odd nominal mass ; therefore, the M++ peak in the mass spectrum
of compounds having on odd number of nitrogen atoms will be at on odd m/z value. Although
EI mass spectrometry is considered to be the most.
(a) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide.
Ans. Methylamine being more basic than water, accepts a proton from water and OH– ions
are produced. These OH– ions reacts with Fe3+ (from FeCl3) to form hydrated ferric
oxide.
CH3NH2 + H—OH  CH 3 NH 3  OH 
FeCl3  Fe3+ + 3Cl–
2Fe3+ + 6OH–  2Fe(OH)3 or Fe2O3 . 3H2O
Hydrated ferric oxide
(Brown ppt)
(b) A compound Z with molecular formula C3H9N reacts with C6H5SO2Cl to give a solid,
insoluble in alkali. Identify the Z.
Ans. Secondary amine when reacts with benzene sulphonyl chloride, it yields N, N-
dimethylbenzene sulphonamide.
O
S—Cl + CH3—NH—C2H5
N-methyl ethanamine
O (2°-amine)
(Z)
O
S—N—C2H5 + HCl
O CH3
N-ethyl, N-methylbenzene
sulphonamide
(Insoluble in alkali)
(c) (i) What happens, when aniline reacts with aqueous solution of bromine in the
absence of catalyst ?
(ii) Aniline is treated with acetic anhydride ?
E 259
Chemistry
ALLEN
Ans. (i) Halogenation reaction takes place when aniline reacts with aqueous solution of
bromine water in the absence of catalyst.
The reaction is as follows :
NH2 NH2
Br Br
Br2H2O
+ 3Br2(aq) + 3HBr

Bromine
Aniline water Br
2,4,6-tribromoaniline
(Light yellow ppt.)
(ii) Acetylation reaction occurs forming acetanilide.

The reaction is as follows :
NH2 NHCOCH3

Acetic Ethanoic
Aniline anhydride Acetanilide acid

OR
An aromatic compound A on treatment with aqueous ammonia on heating forms a
compound B, which on heating with Br2 and KOH forms a compound C of molecular
formula C6H7N. Write the structures and IUPAC names of compounds A, B and C.
A 
aq.NH3

 B 
Br2 /KOH

 C6 H 7 N
(C)
OR
(i) Illustrate the Gattermann reaction with an example.
(ii) Give chemical tests to distinguish between a primary and a secondary amine.
Ans. To determine the structures of B and C
Compound B on heating with Br2 and KOH forms compound C. So, B is an amide and
C is amine.
The molecular formula of C is C6H7N which tells us that it is aniline (C6H5NH2) and
thus B should be benamide that undergoes Hoffmann bromamide degradation reaction
to give aniline.
C6 H 5CONH 2 
Br2 /KOH
 C6 H 5 NH 2

Benzamide Aniline
(B) (C)
To determine the structure of A

Compound A on treatment with aqueous ammonia forms B (C6H5CONH2), so A must
be benzoic acid (C6H5COOH).
C6 H 5COOH 
aq. NH3
C6 H 5CONH 2
Benzoic acid Benzamide
(A) (B)
260 E
CBSE
ALLEN
OR
(i) Gattermann reaction : In this reaction, chlorine or bromine group is introduced at the
benzene ring by treating the diazonium salt solution with corresponding halogen acid in
the presence of copper powder. For example.
+ Cu
N2 Cl– HCl
Cl + N2+ HCl
Benzene Chlorobenzene
diazonium
chloride
(ii) The chemical tests to distinguish between a primary and a secondary amine are given
below :
Tests 1° amine 2° amine
Carbylamine 1° amine on heating with 2° amine does not give this
reaction KOH and CHCl3 gives test.
unpleasant smell of
carbylamine (RNC).
RNH2 + CHCl3 + 3KOH
(Alc.)

  RNC + 3KCl + 3H2O
With HNO2 1° amine gives N2 along with 2° amine gies oily liquid of
alcohol. nitrosoamine.
RNH2 + HNO2  R2NH2 + HNO2 
ROH + N2 - + H2O R 2 N.NO  H 2 O
 
Oily
E 261
Chemistry
ALLEN
1. Among the following, which is the strongest base ? [1] (CBSE 2023)
(a) (b)
NH2 H3C NH2

(c) CH2 – NH2 (d)

O2N NH2

Ans. (c)
2. When Benzene diazonium chloride reacts with phenol, it forms a dye. This reaction is
called [1] (CBSE 2023)
(a) Diazotisation reaction (b) Condensation reaction
(c) Coupling reaction (d) Acetylation reaction
Ans. (c)
3. Among the following, which has the highest value of pKb? [1] (CBSE 2023)
(a) NH2 (b) NH2–NH2
(c) H3C NH2 (d) O2N NH2
Ans. (d)
4. In cold conditions, aniline is diazotized and then treated with N, N-dimethylaniline to give a
coloured product. The structure of the coloured product is : [1] (CBSE Compartment_2021)
(a) (CH3)2–N NH (b) CH3 N=N NH2
(c) OH N=N (d) (CH3)2–N N=N
Ans. (d)
5. Out of the following, the strongest base in aqueous solution is [1] (CBSE 2020)
(a) methylamine (b) Dimethylamine
(c) Trimethylamine (d) Aniline
Ans. (b)
6. Arrange the following in decreasing order of basic character : [1] (CBSE 2019)
C6H5NH2, (CH3)3N, C2H5NH2
Ans. (CH3)3N > C2H5NH2 > C6H5NH2
7. Arrange the following in increasing order of pKb values : [1] (CBSE 2019)
C6H5CH2NH2, C6H5NHCH3, C6H5NH2
Ans. C6H5CH2NH2 < C6H5NHCH3 < C6H5NH2
262 E
CBSE
ALLEN
8. Arrange the following in decreasing order of solubility in water : [1] (CBSE 2019)
(C2H5)2NH, C2H5NH2, C6H5NH2
Ans. (C2H5)2NH > C2H5NH2 > C6H5NH2
9. Write the IUPAC name of the given compound: [1] (CBSE 2018)
CH 3  NH  CH 2  CH  CH 3
|
CH 3
Ans. N-methyl-2-methylpropanamine / 2-methyl-N-methylpropanamine
10. The conversion of primary aromatic amines into diazonium salts is known as ........
[1] (CBSE 2018)
Ans. Diazotization
11. Rearrange the following in an increasing order of their basic strengths:
C6H5NH2, C6H5N(CH3)2, (C6H5)2NH and CH3NH2. [1] (CBSE 2018)
Ans. (C6H5)2NH < C6H5NH2 < C6H5N(CH3)2 < CH3NH2
12. Arrange the following compounds in an increasing order of basic strengths in their aqueous
solutions :
NH3, CH3NH2, (CH3)2NH, (CH3)3N [1] (CBSE 2018)
Ans. The order of basic strength of methyl substituted amines in aqueous solution is.
(CH3)2NH > CH3NH2 > (CH3)3N > NH3

13. An Organic compound (A) with molecular formula C3H7NO on heating with Br2 and KOH forms
a compound (B). Compound (B) on heating with CHCl3 and alcoholic KOH produces a foul
smelling compound (C) and on reacting with C6H5SO2Cl forms a compound (D) which is soluble
in alkali. Write the structures of (A), (B), (C) and (D). [2] (CBSE Term-II 2022)
Ans. CH3 – CH2 – CONH2+ Br2 + KOH CH3 – CH2 – NH2
(A) (B)
CHCl3+KOH
O CH3 – CH2 – N C
S–NH–CH2–CH3 (C)
O
(D)
14. Describe a method for the identification of CH3NH2, (CH3)2NH and (CH3)3N. Also write the
chemical equations for the reactions involved. [2] (CBSE Compartment_2021)
Ans. Hinsberg's Reagent (Benzene sulphonyl chloride) used for distinguish between primary amine,
sec. amine and ter. amine.
(i) Pri. amine react with benzene sulphonyl chloride to form N-alkyl benzene sulphonamide
which is soluble in base due to presence of active hydrogen.
O O
H H
S-Cl + N–CH3 –HCl
S-N
H CH3
O O
Methyl amine N–Methyl Benzene Sulphon amide
(Soluble in base)
E 263
Chemistry
ALLEN
(ii) Sec. amine react with Hinsberg reagent to form N, N–dialkyl benzene sulphonamide, which
insoluble in base.
O O
CH3 CH3
S–Cl + H–N S––N
CH3 –HCl CH3
O O
N,N-Dimethyl Benzene Sulphon amide)
(Insoluble in base)
(iii) Ter. amine do not react with Hinsberg reagent.

15. Write the structures of A, B and C in the following reactions: [2] (CBSE 2020)
 Br /KOH CH COCl/pyridine
(a) C6H5— COO–NH4+   A 
2
B 
3
C
NaNO /Cu CHCl alc.KOH
(b) C6 H 5 N 2 BF4 

2
 A 
Sn/HCl
 B 
3
C
Ans. (a) A : C6 H5 CONH2

B : C6 H5 NH2
C : C6 H5 NHCOCH3
(b) A : C6 H5 NO2
B : C6 H5 NH2
C : C6H5 NC
16. An aromatic compound ‘A’ of molecular formula C7H7ON undergoes a series of reactions as
shown below. Write the structures of A,B, C, D and E in the following reactions :
[2] (CBSE 2020)
Br2+KOH NaNO2+HCl CuCN
(C7H7ON) A C6H5NH2 B C
273 K
CHCl3+NaOH H2O
D E
+
NNCl
–
CONH2 CN N C OH
Ans.
A= B= C= D= E=
17. Describe the following giving the relevant chemical equation in each case : [2] [CBSE 2019]
(i) Carbylamine reaction

(ii) Hofmann's bromamide reaction
Ans. (i) R–NH2 + CHCl3 + 3KOH 
Heat
 R–NC + 3HCl + 3H2O
O
(ii) R–C–NH2 + Br2 + 4NaOH  RNH2 + Na2CO3 + 2NaBr + 2H2O
264 E
CBSE
ALLEN
18. Identify A and B in each of the following processes: [2] [CBSE 2018]
(i) CH 3CH 2Cl 
 A 
B
NaCN reduction
Ni/H 2
(ii) C6 H 5 NH 2 
NaNO 2 /HCl
A 
C6 H5 NH 2
OH 
B
Ans (i) CH3CH2Cl
NaCN
CH3CH2C N
reduction
CH3CH2CH2NH2
Chloroethane propanenitrile propan-1-amine
(A) (B)
NaNO2/HCl C6H5NH2
(ii) C6H5NH2 C6H5 – N2+Cl- OH
- N=N NH2
Benzene diazonium
Chloride (A) p-Aminoazobenzene
(B)
19. Give the chemical tests of distinguish between the following pairs of compounds :
(i) Ethylamine and Aniline
(ii) Aniline and Benzylamine [2] [CBSE 2018]
Ans. (i) Ehylamine and Aniline: Ethylamine with HNO2 (NaNO2 + dil HCl) at 273 - 278 K give a
brisk evolution of N2 gas with the formation of primary alcohols.
273 278K
C2 H 5 NH 2  HONO   C2 H 5 OH  N 2  H 2O
Ethylamine Ethylalcohol
Aniline with HNO2 at 273-278 K followed by treatment with an alkaline solution of

naphthol when a brilliant yellow, orange or red coloured dye is obtained.
NH 2
273-278K + - 2
+ HONO + HCl N NCl + 2H O
Aniline Benzene-diazoniun chloride
(ii) Aniline and Benzylamine: Benzylamine reacts with nitrous acid to form a diazonium salt
which is unstable at low temperature, decomposes with evolution of N2 gas.
C6 H 5 CH 2 NH 2 
HONO
HCl
 [C6 H 5 CH 2  N   NCl ] 
H 2O
 C6 H 5 CH 2 OH  N 2   HCl
Benzylamine unstable Benzyl alcohol
Aniline reacts with HNO2 to form benzene diazonium Chloride which is stable at
273-278K and hence does not decompose to evolve N2 gas.
NaONO, HCl
NH2 273-278K
N+ NCl-
Aniline Benzenediazonium
chloride
20. Give reasons : (CBSE Term-II 2022)

(i) Ammonolysis of alkyl halides is not a good methods to prepare pure primary amines.
(ii) Aniline does not give Friedel-Crafts reaction.
(iii) Although –NH2 group is o/p directing in electrophilic substitution reactions, yet aniline on
nitration gives good yield of m-nitroaniline. [1 × 3 = 3]
E 265
Chemistry
ALLEN
Ans. (i) Ammonolysis of alkyl halides gives primary amine which behaves as a nucleophile and an
subsequent reaction with alkyl halide found 2°, 3° amines and finally forms quaternary
ammonium salt which is difficult to separate.
(ii) Aniline does not undergo Friedel-Craft reaction due salt formation with aluminium
chloride, the Lewis acid, which is used as catalyst. Due to this, N-atom of aniline acquires
positive charge and hence, it acts as strong deactivating group for further reaction.
NH2 NH2 NH2 NH2
Conc.HNO3
NO2
+ +
Conc. H2SO4
(iii) NO 2
Aniline NO2
(51%) (47%) (2%)


+
NH3

In strongly acidic medium aniline is protonated to form anilinium


ion in which
– NH 3 group, + acts as meta directing.

+ +
:
C6H5NH2 + H HSO4– C6H 5NH3 HSO4–

 
NH2 NH3HSO4
+ H2SO4 
Lewis acid
Lewis base Anilinium hydrogen
Anilinium sulphate
(m-directing) (m–directing)
21. Give the structures of A and B in the following sequence of reactions : [3] (CBSE 2020)
(a) CH 3COOH 
 A 
NH3
NaOBr

B
NaNO 2  HCl
(b) C6 H 5 NO 2 
Fe/HCl
 A 
05 C
 B

(c) C6 H 5 N 2 Cl 
CuCN

 A 
H 2O/H
B
OR
(a) How will you distinguish between the following pairs of compounds : [1 × 2 = 2]
(i) Aniline and Ethanmine
(ii) Aniline and N-methylaniline
(b) Arrange the following compounds in decreasing order of their boiling points : [1]
Butanol, Butanamine, Butane
Ans. (a)  (A) CH3CONH2 (B)  CH3NH2
(b)  (A) C6H5NH2 (B)  C6H5N2Cl
(c)  (A) C6H5CN (B)  C6H5COOH
OR
266 E
CBSE
ALLEN
(a) (i) Add ice cold (NaNO2 + HCl) followed by phenol or  -Naphthol to both the
compounds.
Aniline forms orange red dye while ethylamine doen't
(ii) Add CHCl3 and KOH (alc.) to both the compounds.
Aniline gives four smelling isocyanides while N-Methylaniline doesn't
(b) Butanol > Butanmine > Butane
22. Give reasons for the followings : [3] (CBSE 2020)
(a) Acetylation of aniline reduces its activation effect.
(b) CH3NH2 is more basic than C6H5NH2
(c) Although –NH2 is o/p directing group, yet aniline on nitration gives a significant amount of
m-nitroaniline.
Ans. (a) Due to the resonance, the electron pair of nitrogen atom gets delocalised towards carbonyl
group/ resonating structures.
(b) Because of +l effect in methylamine electron density at nitrogen increases whereas in
aniline resonance takes place and electron density on nitrogen decreases / resonating
structures.
(c) Due to protonation of aniline/formation of anilinium ion
23. Complete the following reactions : [3] (CBSE 2019)
CN
(a) H2 / Ni
CH3
Br H3PO2+H2O
(b)
+
N2Cl–
CH2–NH2
(c) Ethanolic KOH
+ CHCl3
OR
How do you convert the following :
(a) N-phenylethanamide to p-bromoaniline
(b) Benzene diazonium chloride to nitrobenzene
(c) Benzoic acid to aniline
CH2NH 2 CH3
Br CH2NC
Ans. (a) (b) (c)
OR
O O
H–N–C–CH3 H–N–C–CH 3 NH2
– +
Br2 OH or H
(a) CH3COOH
Br Br
E 267
Chemistry
ALLEN
– + –
N+
2 Cl N 2BF 4 NO2
NaNO2
(b) +HBF4
Fluoroboric Cu,
acid
COOH CONH2 NH2
NH3 Br2/KOH
(c) Heat
Benzoic acid Benzamide Aniline
24. Give the structures of A,B and C in the following reactions: [3] (CBSE 2019)
Sn + HCl NaNO2 + HCl HO
(i) C6H 5NO2 A B 2 C
273 K
H2O/H+ NH3 Br2 + KOH
(ii) CH3CN A B C

+
Ans. (i) (A) C6H5NH2 (B) C6H5N  NCl— (C) C6H5OH
Aniline Benzenedizonium Phenol
Chloride
O
(ii) (A) CH3COOH (B) CH3—C—NH2 (C) CH3–NH2
Propanoic acid Ethanamide Methanamine
25. Write the main products of the following reactions : [3] (CBSE 2019)
HNO
(i) CH3CH2NH2 
0ºC  ?
2
(ii) S – Cl + H – N – C2H 5 ?
O H
O
N–H CH3– C – Cl
(iii) H Base ?
O
O
N – C – CH3
Ans. (i) CH3CH2OH (ii) S – N – C2H 5 (iii) H
O H
26. Account for any two of the following: [3] (CBSE 2018)
(a)
Amines are basic substances while amides are neutral.

(b) Nitro compounds have higher boiling points than the hydrocarbons having almost the same
molecular mass.
(c) Aromatic amines are weaker bases than aliphatic amines.
Ans. (a) Amines are strong bases and react with minerals acids to form ammonium salt which are
natural from which amines are liberated by treatment with strong base.
+ – –
RNH2 + HCl  RNH3Cl OH

RNH2 + H2 O
268 E
CBSE
ALLEN
(b) The nitro compounds are highly polar molecules because nitro compounds is a strong
electron withdrawing group
O
C N
+
O-
Due to this polarity they have strong intermolecular dipole-dipole interactions which causes
them to have high boiling points in comparison to the hydrocarbons non-polar having the
most same molecular mass.
(c) In aromatic amines the lone pair of electron on nitrogen is involved in resonance with the
benzene ring shown below for aniline.
..
NH2
+
NH 2
+
NH2
+
NH2
..NH
2
It shows this pair of electron is less available in comparison to that in case of aliphatic
amine where alkyl groups are also electron releasing.

27. Read the given passage and answer the following questions.
Basic character of amines of depend upon the ease for the formation of cation by accepting a
proton form the acid. The more stable the cation is relative to the amine, more basic is the amine.
Basicity of an amine in aqueous solution depends upon the stability of ammonium cation formed
by accepting proton from water.
The stability of ammonium cation depends upon the following three factors :
(i) +I – effect (alkyl group) (ii) Steric effects (alkyl group) (iii) Solvation effect
(a) Which of the following compound cannot be prepared from Sandmeyer reaction.
Chlorobenzene, Fluorobenzene, Bromobenzene
Ans. Fluorobenzene
OR
Write the structures and name of X, Y and Z in the following reaction :

C6H5N2Cl 
CuCN
 X 
H 2 O/H
 Y 
NH3

 Z
+ – 
Ans. C6 H 5 N 2 Cl 
CuCN
 C6 H 5CN 
H 2 O/H
 C6 H 5COOH 
NH3

 C6 H 5CONH 2
Benzene (X) (Y) ( Z)
diazonium chloride
X is cyanobenzene
Y is benzoic acid
Z is benzamide
(b) Which of the following is formed when primary amines are heated with chloroform and
ethanolic potassium hydroxide.
Isocyanides, cyanides, cyanohydrins
Ans. Isocyanides
E 269
Chemistry
ALLEN
(c) Write the structure of products formed :
(i) CH3CH2NH2 + CHCl3 + alc. KOH 
NH2
NaNO2/HCl
(ii) Boiling HO2/H+
Ans. (i) CH 3CH 2 NH 2  CHCl3 + 3KOH (alc.)

Ethyl amine Chloroform Ethyl isocyanide

NH2 +
NNCl– OH
(ii) NaNO2/HCl Boiling H2O/H+
273-278 K
Aniline Benzene Phenol
diazonium
chloride
28. (a)(I) Give reasons: [5] (CBSE 2023)

(i) Aniline on nitration gives good amount of m-nitroaniline, though-NH2 group is o/p
directing in electrophilic substitution reactions.
(ii) (CH3)2 NH is more basic than (CH3)3N in an aqueous solution.
(iii) Ammonolysis of alkyl halides is not a good method to prepare pure primary amines.
(II) Write the reaction involved in the following :
(i) Carbyl amine test
(ii) Gabriel phthalimide synthesis
OR
(b)(I) Write the structures of A, B and C in the following reactions :
CuCN H2/O/H+ NH3
A B C
(i) 
NO2
Fe/HCl NaNO2+HCl C H OH
(ii) A B 2 5 C
273
(II) Why aniline does not undergo Friedal-Crafts reaction ?

(III) Arrange the following in increasing order of their boiling point:
C2H5OH, C2H5NH2, (C2H5)3N
270 E
CBSE
ALLEN
NH2 NH2 NH2 NH2
Conc.HNO3
NO2
Ans. (a)(I) (i) Conc. H2SO4
+ +
NO 2
Aniline NO2
(51%) (47%) (2%)


+
NH3

In strongly acidic medium aniline is protonated to form anilinium
 ion in

which – NH 3 group, + acts as meta directing.
+ +
:
C6H5NH2 + H HSO4– C6H 5NH3 HSO4–

 
NH2 NH3HSO4
+ H2SO4 
Lewis acid
Lewis base Anilinium hydrogen
Anilinium sulphate
(m-directing) (m–directing)
(ii) It is the combination of electron releasing nature of alkyl group, H-bonding and steric factors
determine the stability of ammonium cations formed in solution therefore
Et 2 NH  Et 3 N  EtNH 2 is order of Kb.
(iii) Alkyl halide on reaction with NH3 under goes nucleophlic substitution reaction and
forms 1º, 2º, 3º amines and finally form quaternary ammonium salt. Which is difficult
to separate.
(II) (i) R  NH 2  CHCl3  3KOH 
Heat
 R  NC  3KCl  3H 2O
O O O
C KOH C – + R–X C
N–H NK N–R
(ii) C C C
O O O
Phthalimide N-Alkylphthalimide
O
O
C –
NaOH(aq) C ONa+
N–R – + R – NH2
C ONa+ (1° amine)
C
O
O
OR
O
(b)(I) (i) A CN B COOH C C–NH2
NH2
(ii) A B C
E 271
Chemistry
ALLEN
(II) Aniline being a Lewis base, reacts with lewis acid AlCl3 to from a salt.

C6 H 5 NH 2  AlCl3 
 C6 H 5 N H 2 AlCl3 ¯
As a result, N of aniline acquires positive charge and hence it acts as a strong deactivating
group for electrophilic substitution reaction, consequently, aniline does not undergo Friedel
– Crafts reaction.
(III)  C2H3 3 N  C2H5 NH 2  C2H5OH

29. (a) Write the structures of the main products when aniline reacts with the following reagents :
(i) Br2 water (ii) HCl (iii) (CH3CO)2O/pyridine
(b) Arrange the following in the increase order of their boiling point :
C2H5NH2, C2H5OH, (CH3)3N
(c) Give a simple chemical test distinguish between the following pair of compounds
(CH3)2 – NH and (CH3)3N [5] (CBSE 2019)
NH2 NH2
Br Br
+
NH3 Cl– O
Ans. (a) (i) (ii) (iii) NH–C–CH3
Br
(b) (CH3)3N < C2H5NH2 < C2H5OH
(c) By Hinsberg test-Add Hinsberg reagent (Benzene sulphonyl chloride) in both compounds
(CH3)2–NH forms ppt insoluble in KOH while (CH3)3–N does not react (or any other
correct test)
30. (a) Write the reactions involved in the following : [5] (CBSE 2018)
(i) Hoffmann bromamide degradation reaction
(ii) Diazotisation
(iii) Gabriel phthalimide synthesis
(b) Give reasons :
(i) (CH3)2NH is more basic than (CH3)3N in an aqueous solution.
(ii) Aromatic diazonium salts are more stable than aliphatic diazonium salts.
Ans. (a) (i) Hoffmann Bromamide degradation reaction :
O

R – C – NH2 + Br2 + 4NaOH R – NH2 + Na2CO3 + 2NaBr + 2H2O
(ii) Diazotisation
273–278 K + –
C6H5NH2 + NaNO2 + 2 HCl CC66H
H55N2Cl
NH 2 Cl

Aniline Aromatic diazonium
272 E
CBSE
ALLEN
(iii) Gabriel phthalimide synthesis
O O
C C CO
Alc. KOH –+ –KBr
NH NK
N N–C2H 5
C2H5Br/
C C CO
n-ethyl phthalimide
O O
(Potassium pthalimide)
H2O OH–/
COOH
C2H5 – NH2 +
COOH
ethanamine
(b) (i) Because of the combined factors of inductive effect and solvation or hydration effect.
(ii) The aromatic diazonium salt more stable than Aliphatic diazonium salt due to
resonance.
   
NN N=N N=N N=N
 

E 273
Chemistry
ALLEN
PRATICE TEST
SECTION-A
1. Which of the following amine will give the carbylamine test?
NHC2H5 NH2 NHCH3 N(CH3)2
(a) (b) (c) (d)

2. The correct order of the basic strength of methyl substituted amines in aqueous solution is :-
(a) (CH3)2NH > CH3NH2 > (CH3)3N (b) (CH3)3N > CH3NH2 > (CH3)2NH
(c) (CH3)3N > (CH3)2NH > CH3NH2 (d) CH3NH2 > (CH3)2NH > (CH3)3N
3. The correct increasing order of basic strength for the following compounds is :
NH2 NH2 NH2
(I) (II) (III)

NO2 CH3
(a) III < I < II (b) III < II < I (c) II < I < III (d) II < III < I
4. Which of the following reactions is appropriate for converting acetamide to methanamine ?
(a) Hoffmarnn hypobromamide reaction (b) Stephens reaction
(c) Gabriels phthalimide synthesis (d) Carbylamine reaction
5. Propanamide on reaction with bromine in aqueous NaOH gives:
(a) Propanamine (b) Ethanamine
(c) N-Methyl ethanamine (d) Propanenitrile
6. Assertion (A) : Basicity of aromatic amines generally lower than alkyl amines.
Reason (R) : Presence of -electrons in the ring decreases the basic character.
7. Assertion (A) : Reactivity of aniline towards electrophilic reagents increases in strongly acidic
solution.
Reason (R) : The amine group being completely protonated in strongly acidic medium, the lone
pair of electrons of nitrogen atom are no longer available for resonance.
SECTION-B
8. Write the reactions involved in the following : [2]
(i) Hofmann bromamide degradation reaction
9. (a) Arrange the following in increasing order of pKb values : [2]
C6H5CH2NH2, C6H5NHCH3, C6H5NH2

(b) Arrange the following in decreasing order of solubility in water :
(C2H5)2NH, C2H5NH2, C6H5NH2
+
H2O/H NH3 Br + KOH
10. CH3CN A B 2 C [2]

11. Write the structures of the main products when aniline reacts with the following reagents : [2]
(i) Br2 water (ii) HCl (iii) (CH3CO)2O/pyridine
274 E
CBSE
ALLEN
SECTION-C
12. Account for the following: [3]
(i) Primary amines (R-NH2) have higher boiling point than tertiary amines (R3N).
(ii) Aniline does not undergo Friedel – Crafts reaction.
(iii) (CH3)2NH is more basic than (CH3)3N in an aqueous solution.
13. Complete the following reaction equations :
O
LiAlH 4
(i) R–C–NH2  H O 
2
(ii) C6H5N2Cl + H3PO2 + H2O 

(iii) C6H5NH2 + Br2(aq) 
SECTION-D
14. Amines are very reactive due to the difference in electronegativity between nitrogen and
hydrogen atoms and due to the presence of unshared pair of electrons over N-atom. The number
of hydrogen atoms attached to the N-atom decides the course of reactions of amine, that is why
amines differ in many reactions. In aromatic amines like aniline, electron density at ortho and
para-positions with respect to –NH2 group is high. Therefore, this group is ortho or para directing
and a powerful activating group.
(a) Which one of the following will give carbylamine test ?
(b) What pKb of aniline is more than that of methyl amine ?
(c) Write equations for :
(i) carbylamine reaction
(ii) Hoffmann bromamide reaction
OR
Answer the following questions :
(i) What is ammonolysis ? Write the reaction involved.
(ii) Give a good method for the synthesis of primary amine as a product ? Also, give the
reaction.
SECTION-E
15. (a) Write the structures of the main products of the following reactions :
NH2
(CH3CO)2O
(i)
Pyridine
(ii) (CH3)2NH
SO2Cl
(iii)
(b) Give a simple chemical test to distinguish between Aniline and N, N-dimethylaniline.
(c) Arrange the following in the increasing order of their pKb values :
C6H5NH2, C2H5NH2, C6H5NHCH3
E 275
Chemistry
ALLEN
SECTION-A
1. (b)
2. (a)
3. (c)
4. (a)
5. (b)
6. (c)
7. (d)
SECTION-B
8. (i) Hoffmann Bromamide degradation reaction :
O

R – C – NH2 + Br2 + 4NaOH R – NH2 + Na2CO3 + 2NaBr + 2H2O

O O
C C CO
Alc. KOH – KBr
NH N C2H5
C2H5Br/
C C CO
e-ethyl pthalimide
O O
(Potassium pthalimide)
H2O OH¯ / 
COOH
C2H5 – NH2 +
ethanamide COOH
9. (a) C6H5CH2NH2 < C6H5NHCH3 < C6H5NH2

(b) (C2H5)2NH > C2H5NH2 > C6H5NH2
O
CH 3COOH || CH 3  NH 2
10. (A) (B) (C)
Pr opanoic acid CH 3  C  NH 2 Methana mine
Ethanamide
NH2
Br Br
11. (i)
Br
+
NH Cl¯
3
(ii)
O
(iii) NH – C – CH3
276 E
CBSE
ALLEN
SECTION-C
12. (i) Due to the presence of two H-atoms on N-atoms of 1° amines, they undergo extensive
intermolecular H-bonding while 3° amines due to the absence of H-atoms on N-atom there
is no hydrogen bonding takes place. So primary amines have higher b.p. than tertiary
amines of comparble molecular mass.
R R R
N—H N—H N—H
-----H -----H H
Inter molecular Hydrogen bonding in 1° amines.
R
|
R —N
|
R
No hydrogen bonding
(ii) Aniline being a Lewis base, reacts with lewis acid AlCl3 to from a salt.

C6H 5 NH 2  AlCl3 
 C6 H5 N H 2 AlCl3 ¯
As a result, N of aniline acquires positive charge and hence it acts as a strong
deactivating group for electrophilic substitution reaction, consequently, aniline does not
undergo Friedel - Crafts reaction.
(iii) It is the combination of electron releasing nature of alkyl group, H-bonding and steric
factors determine the stability of ammonium cations formed in solution therefore is order
of Kb.
O
LiAlH 4
13. (i) R–C–NH2  H O  R–CH2–NH2
2
(ii) C6H5N2Cl + H3PO2 + H2O  C6H6 + N2 + H3PO3 + HCl

NH2
Br Br
(iii) C6H5NH2 + Br2(aq)  + 3HBr
Br
SECTION-D
14. (a) 1° amine
(b) Resonance
(c) (i) Carbylamine reaction : Aliphatic and aromatic primary amines on heating with
chloroform and ethanoilic potassium hydroxide form isocyanides or carbylamine
which are foul smelling substances. This reaction is known as carbylamine reaction.
This reaction is used as a test for primary amine.

CH 3CH 2 NH 2  CHCl3  3KOH   CH 3CH 2 NC  3KCl  3H 2 O
Ethanamine
E 277
Chemistry
ALLEN
(ii) Hoffmann bromamide reaction : It is a method used for the preparation of primary
amines by treating an amide with bromine in an aqueous or ethanolic solution of
sodium hydroxide. The amines so formed contains one carbon less than that present
in the parent amides.
O

R—C—NH2 + Br2 + 4NaOH   R—NH2 + Na2CO3 + 2NaBr + 2H2O
OR
(i) The process of cleavage of the C—X bond by ammonia molecule is known as
ammonolysis.
R—X + NH3 RNH2 
R —X
 R2NH 
RX
 R3N 
R —X
 R4N+X–
Possible products are :
RNH2, R2NH, R3N, R4N+X–
(ii) Gabriel phthalimide reaction is a process that is used to synthesis primary amine.
Phthalimide on treatment with ethanoic KOH gives potassium phthalimide which on
heating with a suitable alkyl halide gives N-substituted phthalimides, which upon
subsequent hydrolysis with dil. HCl under pressure or with alkali gives primary
amines.
CO CO
NH + KOH (alc.)
–H2O N–K+
CO CO
Phthalimide Potassium phthalimide
C2H5/ –KI
COOH CO
H+/H2O
C2H5NH2 + N—C2H5

Ethylamine COOH CO
Phthalic acid N-ethylphthalimide
This reaction is called Gabriel phthalimide reaction.
SECTION-E
O
NH2 NH–C–CH3
O
15. (a) (i)  (CH 3CO) 2 O
Pyridine
+ CH3–C–CH3
SO2Cl O
S N CH3
(ii) 
(CH3 ) 2 NH

O CH3
N, N–dimethyl benzenesulphonamide

N2 Cl
(iii) 
CH3CH 2OH
 + N2 + HCl + CH3CHO
278 E
CBSE
ALLEN
(b) Test to distinguish aniline & N, N-dimethyl aniline
(c) Increasing order

C2 H 5  NH 2  C6 H 5 NH  CH 3  C6 H 5  NH 2
E 279
Chemistry
ALLEN
UNIT-14: BIOMOLECULES
UNIT INDEX
• Theory 280-304
THEORY
INTRODUCTION
The organic compounds which are essential for growth and maintenance of life are called
biomolecules.
Examples: carbohydrates, proteins, vitamins, lipids, enzymes, hormones etc.
CARBOHYDRATES
Cx(H2O)y is its general formula
 According to the old concept the hydrate of carbon is known as carbohydrate.
Definition of carbohydrates according to the new concept:
The optically active compounds which are either itself be or gives poly-hydroxy carbonyl
compound on hydrolysis are called carbohydrates.
Examples:
1. Glucose – It is poly-hydroxy aldehyde.
2. Fructose – It is poly –hydroxy ketone.
3. Sucrose – On hydrolysis it gives glucose+fructose.
4. Maltose – On hydrolysis it gives two units of glucose.
5. Lactose – On hydrolysis it gives glucose and galactose.
6. Starch – On complete hydrolysis it gives ‘n’ no. of glucose.
Source of carbohydrates.
Green plants are the main source of carbohydrates in which carbohydrates are formed by the
process of photosynthesis.
Main functions of carbohydrates in plants.
1. Support the plant structure in the form of cellulose.

2. It stores chemical energy due to sugar and starch.
Biological functions of crabohydrates.
1. It provides heat and energy to the body.
2. It forms cell membrane.
3. It forms skeleton of plants
280 E
CBSE
ALLEN
CLASSIFICATION OF CARBOHYDRATES
1. Classification of carbohydrates on the basis of hydrolysis.
On the basis of their behavior to hydrolysis carbohydrates are broadly classified into three
groups:
(i) Monosaccharides : A carbohydrate that cannot be hydrolyzed further to give simpler unit
of polyhydroxy aldehyde or ketone is called a monosaccharide. Some common examples
are glucose, fructose, ribose, etc.
 Monosaccharides are further classified on the basis of number of carbon atoms and the
functional group present in them. If a monosaccharide contains an aldehyde group, it is
known as an aldose and if it contains a keto group, it is known as a ketose.
 Number of carbon atoms constituting the monosaccharide is also introduced in the name as
is evident from the examples given in Table.
Carbon Atoms General Terms Aldehyde Ketone
3 Triose Aldotriose Ketotriose
4 Tetrose Aldotetrose Ketotetrose
5 Pentose Aldopentose Ketopentose
6 Hexose Aldohexose Ketohexose
(ii) Oligosaccharides : The carbohydrates which gives 2-10 monosaccharide units on their
hydrolysis are known as oligosaccharides.
(a) Disaccharides : Which gives 2 similar or different monosaccharides units on their
hydrolysis.
Examples: 1. Sucrose – On hydrolysis it gives glucose + fructose.
2. Maltose – On hydrolysis it gives two units of glucose.
3. Lactose – On hydrolysis it gives glucose and galactose.
(b) Trisaccharides : Which gives 3 similar or different monosaccharides units on their
hydrolysis.
(iii) Polysaccharides : The carbohydrates which gives more than 10 Monosaccharides units on
their hydrolysis are known as polysaccharides.
Examples : starch, cellulose, glycogen
2. Classification of carbohydrates on the basis of physical properties:

On the basis of physical properties carbohydrates are classified into two types:
(i) Sugar : It is white crystalline solid, sweet in taste, soluble in water .
Examples – glucose, fructose, sucrose etc.
(ii) Non-sugar: It is amorphous, tasteless, partially or insoluble in water.
Examples – starch, cellulose, glycogen etc.
E 281
Chemistry
ALLEN
3. Classification of carbohydrates on the basis of reduction:
(i) Reducing sugar – The carbohydrates which have following properties are known as
reducing sugar.
(a) All those carbohydrates which reduce Tollen’s reagent and Fehling solution.
(b) In which carbonyl group such as aldehyde or ketone group is present in free state
(c) They form oxime with hydroxyl amine.
Example : Glucose, Fructose, Maltose, Lactose.
(ii) Non-Reducing sugar – The carbohydrates which have following properties are known as
non-reducing sugars.
(a) All those carbohydrates which do not reduce Tollen’s reagent and Fehling solution.
(b) In which carbonyl group such as aldehyde or ketone group is not present in free state.
(c) They do not form oxime with hydroxyl amine.
Example : Sucrose.
The monosaccharides such as glucose, fructose are reducing sugars. Some disaccharides such as
maltose and fructose
GLUCOSE
Preparation
(a) From sugar : If sucrose is boiled with dilute hydrochloric acid or sulphuric acid in alcoholic
solution, glucose and fructose are obtained in equal amounts.
H 
C12 H22 O11  H2 O  C6 H12 O6  C6 H12 O6
Cane Sugar Glucose Fructose
(b) From starch : Commercially glucose is obtained by hydrolysis of starch by boiling it with dilute
sulphuric acid at 393K under pressure.
H
(C6 H10 O5 ) n  nH 2 O  nC 6 H12 O6
Starch Glucose
or
Cellulose
Chemical Reactions of Glucose

A glucose molecule contains following functional groups :
H 1 O
(i) One carbonyl group C=O
C
2
O H C OH
|| 3
(ii) One aldehyde group —C — H HO C H
4
H C OH
5
(iii) Four secondary alcohol group CH — OH H C OH
6
CH2OH

(iv) One primary alcohol group — CH2 — OH
282 E
CBSE
ALLEN
1. Reaction with HI :
CHO CH 3
| |
(CHOH) 4 
HI
 (CH 2 )4
| |
CH 2 OH CH 3
Glucose n  hexane
2. Reaction with hydroxyl amine NH2OH
CHO CH  N  OH
| |
H2 N OH
(CH – OH) 4  (CH  OH) 4
| |
CH 2 OH CH 2 OH
Glucose Glucose Oxime
Reaction with hydrogen cyanide HCN
CN
|
CHO CH  OH
| |
(CH – OH) 4 
HCN
 (CH  OH) 4
| |
CH 2 OH CH 2 OH
Glucose Glucose Cyanohydrin
3. Reaction with acetic anhydride or acetyl chloride :
CHO CHO O
| | ||
(CH – OH) 4 
5CH3COCl
OR  (CH  O – C – CH 3 ) 4
| O O | ||
|| ||
CH 2 OH CH3 —C—O—C—CH3 CH 2 – O – C – CH 3
Glucose Glucose Pentacetate
4. Reaction with bromine water :
CHO COOH
| |
(CH – OH) 4  (CH – OH) 4
Br2 water
| |
CH 2 OH CH 2 OH
Glucose Gluconic acid
5. Reaction with nitric acid :

CHO COOH
| |
(CH – OH) 4 
Oxidation
HNO3  (CH – OH) 4
| |
CH 2 OH COOH
Glucose Saccharic acid
E 283
Chemistry
ALLEN
Configuration of Monosaccharides
For assigning the configuration of monosaccharides, it is the lowest asymmetric carbon atom
(as shown below) which is compared. As in (+) glucose, -OH on the lowest asymmetric carbon is
on the right side which is comparable to (+) glyceraldehyde, so it is assigned D-configuration
CHO
H C OH
HO C H
CHO H C OH
H OH H C OH
CH2OH CH2OH
D–(+)–Glyceraldehyde D–(+)–Glucose
STRUCTURE OF MONOSACCHARIDES
1. Structure of Glucose :
(A) Fischer's formula of Glucose
It was found that glucose forms a six-membered ring in which -OH at C-5 is involved in ring
formation. This explains the absence of -CHO group and also existence of glucose in two
forms as shown below. These two cyclic forms exist in equilibrium with open chain structure.
O
1 1 1
H C OH H C HO C H
2 2 2
H OH H OH H OH
3 O 3 3 O
HO H HO H HO H
4 4 4
H OH H OH H OH
5 5 5
H H OH H
6 6 6
CH2OH CH2OH CH2OH
-D-(+)–Glucose D-(+)–Glucose -D-(+)–Glucose
Fischer's formula of glucose
(B) Haworth's structure of glucose or Pyranose's structure of glucose.
The two cyclic hemiacetal forms of glucose differ only in the configuration of the hydroxyl
group at C1, called anomeric carbon (the aldehyde carbon before cyclisation). Such
isomers, i.e., -form and -form, are called anomers. The six membered cyclic structure of
glucose is called pyranose structure ( or ), in analogy with pyran. Pyran is a cyclic organic
compound with one oxygen atom and five carbon atoms in the ring. The cyclic structure of
glucose is more correctly represented by Haworth structure as given below.
6 6
CH2OH CH2OH
O 5 O 5 O
H H H OH
H H
4 1 4 1
OH H OH H
HO 3 2 OH HO 3 2 H
Pyran H OH H OH
-D-(+)-Glucopyranose -D-(+)-Glucopyranose
(-Pyranose ring) (-Pyranose ring)
Hawaorth Structure of glucose

284 E
CBSE
ALLEN
Note :
(i) Due to formation of intermolecular hemi acetal bond, the carbonyl carbon atom becomes
asymmetric. Hence, two isomers are formed which are known as  and -isomers.
(ii) Glucose is mainly found in the form of 6-membered ring structure which shows similarities
in pyrine. Hence, they are known as pyranose structure.
(iii) C-1 Bonded with two oxygen atoms. Hence, it is known as anomeric carbon.
2. Structure of Fructose
CH2OH HOCH2 O
C O C
HO C H HO C H
H C OH H C OH
H C OH H C OH
CH2OH CH2OH
D(–)Fructose D(–)Fructose
(A) Fischer's projection formula of fructose.
1 2 1
2
HOH2C C OH HO C CH2OH
3 3
HO H O HO H O
4 4
H OH H OH
5 5
H H
6 6
CH2OH CH2OH
-D-(–)–Fructofuranose -D-(–)– Fructofuranose
(B) Haworth structure of fructose.

The cyclic structures of two anomers of fructose are represented by Haworth structures as given.
6 O 1 6
OH– CH2 O
CH2OH OH– CH2 OH
O 5 2 5 2
H H
H HO OH H HO CH2OH
1
Furan 4 3 4 3
OH H OH H
-D-(–) Fructosefuranose -D-(–) Fructosefuranose
Haworth Structures of fructose
Note :(i) Fructose is found mainly in five membered ring structures which is similar to the structure
Furan. Hence, Haworth structures are also known as Furanose structure.
(ii) Due to the intermolecular bonding i.e. hemi acetal and hemi ketal bond in monosaccharide.
(such as glucose and fructose) cyclic structures are formed so that carbonyl carbon becomes
asymmetric.
E 285
Chemistry
ALLEN
Structures of Disaccharides
Disaccharides : A disaccharide is the sugar formed when two monosaccharide are joined by
glycosidic linkage.
 The two monosaccharides are joined together by an oxide linkage formed by the loss of a water
molecule. Such a linkage between two monosaccharide units through oxygen atom is called
Glycosidic linkage.
(i) Structure of sucrose
One of the common disaccharides is sucrose which on hydrolysis gives equimolar mixture of D-
(+)-glucose and D-(–)-fructose.

C12H22O11 + H2O H
 C6H12O6 + C6H12O6
Sucrose -D-(+) Glucose -D-(–) Fructose
(a) Fischer's Projection formula
Glycosidic Bond
1 1
H O
H OH HO CH2–OH CH2–OH
1
C 2C
C
1
2C
| | |
2| 3 2
H–C–OH HO–C–H H–C–OH HO–C–H Hemiketal
3
3| | O 3 | | O Bond
 H2 O
 
4
HO–C–H O H–C–OH HO–C–H O H–C–OH
4
| | 4| |
4 5
H–C–OH H–C H–C–OH H–C
5
6 | 5| |
5|
H–C CH2–OH H–C 6 CH –OH
2
6|
6| -D(–) Fructose Hemiacetal
CH2–OH CH2–OH Bond
-D(+) Glucose
Fischer's Projection formula of sucrose
(b) Haworth structure of sucrose
6
CH2–OH
5 1
O O
H H HO– CH2
H H
4 1
2 5
OH H O
OH
3 2 Glycosidic H HO CH
6
2OH
H linkage 4
OH 3
OH H
-D-(+) Glucose -D-(–) Fructose
Haworth structure of sucrose

 These two monosaccharides are held together by a glycosidic linkage between C1 of -glycose
and C2 of -fructose.
 Hydrolysis of sucrose brings about a change in the sign of rotation, from dextro (+) to laevo (–)
and the product is named as invert sugar.
 The reducing groups of glucose and fructose are involved in glycosidic bond formation, sucrose
is a non-reducing sugar.
286 E
CBSE
ALLEN
(ii) Maltose (C12H22O11) : Maltose is composed of two -D-glucose units in which C1 of one
glucose (I) is linked to C4 of another glucose unit (II). The free aldehydes group can be
produced at C1 of second glucose in solution and it shows reducing properties so it is a
reducing sugar.
2(C6 H10 O5 ) n  nH2 O 
Diastase
nC12 H22 O11
Starch Maltose
C12 H22 O11  H2 O 

 2C6 H12 O6Dilute HCl
Maltose
Maltose Glu cose
6 6
CH2–OH CH2–OH
5 5
O O
H H H H
H H
4 1 4 1
OH H O OH H
OH OH
3 2 Glycosidic 3 2
H OH linkage H OH
-D Glucose -D Glucose
(I) (II)
Haworth structure of maltose
(iii) Lactose (C12H22O11) : It is more commonly known as milk sugar since this disaccharide is
found in milk. It is composed of -D-galactose and -D-glucose. The linkage is between
C1 of galactose and C4 of glucose. Hence it is also a reducing sugar.
C12 H 22 O11  H 2 O  C 6 H12 O 6  C 6 H12 O 6
Lactose D (  ) Glucose D (  ) Galactose
6 6
CH2OH CH2OH
O O
HO H5 H H
5
OH
4 1 O 4 1
H OH H H OH H H
3 2 3 2
H OH H OH
 - D - Galactose  - D - Glucose
Lactose
STRUCTURES OF POLYISACCHARIDES
1. Starch : Starch is the main storage polysaccharide of plants. It is the most important dietary source
for human beings. High content of starch is found in cereals, roots, tubers and some vegetables. It is
a polymer of -glucose and consists of two components Amylose and Amylopectin.
Amylose : Amylose is water soluble component which constitutes about 15-20% of starch.
Chemically amylose is a long unbranched chain with 200-1000 -D-(+)-glucose units held by
C1- C4 glycosidic linkage.
6
CH2OH CH2OH CH2OH
H H H 5 H H H
H H H
4 1 4 1 4 1
O OH H OH H OH H O
3 2
H OH H OH H OH
–Link –Link
Amylose
E 287
Chemistry
ALLEN
Amylopectin : Amylopectin is insoluble in water and constitutes about 80-85% of starch. It is a
branched chain polymer of -D-glucose units in which chain is formed by C1-C4 glycosidic
linkage whereas branching occurs by C1-C6 glycosidic linkage.
CH2OH CH2OH
H H H H
H H
4 1 4 1
O OH H OH H
–Link
H OH H OH
O Branch at C8
6
CH2OH CH2 CH2OH
H H H 5 H H H
H H H
4 1 4 1 4 1
O OH H OH H OH H O
H OH H OH H OH
–Link –Link
Amylopectin
2. Cellulose : Cellulose occurs exclusively in plants and it is the most abundant organic substance
in plant kingdom. It is a predominant constituent of cell wall of plant cells. Cellulose is a straight
chain polysaccharide composed only of -D-glucose units which are joined by glycosidic linkage
between C1 of one glucose unit and C4 of the next glucose unit.
HOH2C
O
O
OH
HOH 2C
O
O OH
OH
HOH2C
O
O OH
OH -links
O
OH
Cellulose
3. Glycogen: The carbohydrates are stored in animal body as glycogen. It is also known as animal
starch because its structure is similar to amylopectin and is rather more highly branched. It is
present in liver, muscles and brain. When the body needs glucose, enzymes break the glycogen
down to glucose. Glycogen is also found in yeast and fungi.
PROTEINS
The word protein is derived from Greek word, proteios, which means primary or of prime
importance. All proteins are polymers of -amino acids.
288 E
CBSE
ALLEN
AMINO ACIDS
Amino acids contain amino (–NH2) and carboxyl (–COOH) functional groups. Depending upon
the relative position of amino group with respect to carboxyl group, the amino acids can be
classified as and so on. Only -amino acids are obtained on hydrolysis of proteins.
They may contain other functional groups also.
Classification of Amino Acids :
Amino acids are classified as acidic, basic or neutral depending upon the relative number of
amino and carboxyl groups in their molecule.
1. Classification of Amino acids on the basis of position of –NH2 group.
On basis of position of –NH2 group amino acids are classified as -amino acid, -amino acid,
- amino acid etc.
(i)  - Amino acids :
 
CH2 COOH CH3 CH COOH
NH2 NH2
Glycine Alanine
(-Amino acetic acid) (-Amino propionic acid)
(ii)  - Amino acids :

 
CH2 CH2 COOH
NH2 -Amino propionic

acid
(iii)  – Amino acids :
  
CH2 CH2 CH2 COOH
NH2 -Amino butyric acid

2. Classification of Amino acids on the basis of number of –NH2 group and –COOH group.
(i) Neutral Amino acids :
CH2 – COOH CH2 – CH2 – COOH
NH2 NH2
Glycine Alanine
(ii) Acidic Amino acids :
O O O O
HO C CH C OH HO C CH2 CH C OH
NH2 NH2
Aspartic acid Glutamic acid
E 289
Chemistry
ALLEN
(iii) Basic Amino acids :
O
H2N (CH2)4 CH CH2 C OH
NH2
(Lysine)
ESSENTIAL AMINO ACID AND NON-ESSENTIAL AMINO ACIDS

1. Non-essential amino acids :
The amino acids, which can be synthesised in the body, are known as non-essential amino
acids.
2. Essential amino acids :
Those amino acids which cannot be synthesised in the body and must be obtained through diet,
are known as essential amino acids.
T Threonine V Valine
M Methionine I Isoleucine
L Leucine L Lysine
P Phenylalanine A Arginine
T Tryptophan H Histidine
NATURAL AMINO ACIDS
H O H O COOH
 –
H2N–C–C–OH H3N–C–C–O H2N H
R R R
Name of the amino Three Letter Symbol One Letter Code Structure of Amino
acids acids
O
1. Glycine Gly G H2N–CH–C–OH
H
O
2. Alanine Ala A H2N–CH–C–OH
CH3
O
3. Valine* Val V H2N–CH–C–OH

CH
H3 C CH3
290 E
CBSE
ALLEN
O
H2N–CH–C–OH
4. Leucine* Leu L
CH2

CH
H3 C CH3
O
H2N–CH–C–OH
CH
5. IsoLeucine* ILe I
CH2 CH3
CH3
O
H2N–CH–C–OH
6. Serine Ser S
CH2
OH
O
H2N–CH–C–OH
7. Threonine* Thr T
CH
H3C OH
O
H2N–CH–C–OH
8. Cysteine Cys C
CH2
SH
O
H2N–CH–C–OH
CH2
9. Methionine* Met M
CH2
S
CH3
O
10. Proline Pro P HN CH – C –OH
E 291
Chemistry
ALLEN
O
H2N–CH–C–OH
11. Phenylalanine* Phe F CH2

O
H2N–CH–C–OH
CH2
12. Tyrosine Tyr Y

OH
O
H2N–CH–C–OH
13. Aspartic acid Asp D CH2
C
O OH
O
H2N–CH–C–OH
14. Glutamic acid Glu E CH2
CH2
C
O OH
O
H2N–CH–C–OH
15. Aspargine Asn N CH

C
O NH2
O
H2N–CH–C–OH
16. Glutamine Glu O CH2

CH2
C
O NH2
292 E
CBSE
ALLEN
O
H2N–CH–C–OH
CH
17. Lysine* Lys K CH
CH
CH
H2N
O
H2N–CH–C–OH
CH2
18. Arginine* Arg R CH2
CH2
NH

C
H2N NH
O
H2N–CH–C–OH
CH2
19. Tryptophan* Try W
N–H

O
H2N–CH–C–
CH
20. Histidine* His H
N–H
N
PROPERTIES OF AMINO ACIDS
Amino acids are usually colourless, crystalline solids. These are water-soluble, high melting solids
and behave like salts rather than simple amines or carboxylic acids. This behaviour is due to the
presence of both acidic (carboxyl group) and basic (amino group) groups in the same molecule.

NH2 O NH3 O
R CH C OH R CH C O
-Amino acid Zwitter ion
E 293
Chemistry
ALLEN
In aqueous solution, the carboxyl group can lose a proton and amino group can accept a proton,
giving rise to a dipolar ion known as zwitter ion. This is neutral but contains both positive and
negative charges.
Note :
1. In zwitter ionic form, amino acids show amphoteric behaviour as they react both with acids
and bases.
2. Except glycine, all other naturally occurring -amino acids are optically active, since the
-carbon atom is asymmetric.
3. These exist both in –D-and–L-forms. Most naturally occurring amino acids have
L-configuration. L-Amino acids are represented by writing the –NH2 group on left hand side.
STRUCTURE OF PROTEINS :
Proteins are the polymers of -amino acids and they are connected to each other by peptide
bond or peptide linkage.
Chemically, peptide linkage is an amide formed between –COOH group and –NH2 group.
The reaction between two molecules of similar or different amino acids, proceeds through the
combination of the amino group of one molecule with the carboxyl group of the other. This
results in the elimination of a water molecule and formation of a peptide bond (–CO–NH–).
H O H O H O H O
| || | || –H2O | || | ||
H–N–CH2 – C – OH + H – N – CH – C –OH H–N–CH2 – C – N – CH – C –OH
| |
CH3 Peptide CH3
Glycine Alanine Bond
Glycylalanine [Gly-Ala]
CLASSIFICATION OF PROTEINS
1. Classification of proteins on the basis of molecular shapes :
Proteins can be classified into two types on the basis of their molecular shape.
(a) Fibrous proteins : When the polypeptide chains run parallel and are held together by
hydrogen and disulphide bonds, then fibre- like structure is formed. Such proteins are
generally insoluble in water.
Some common examples are keratin (present in hair, wool, silk) and myosin (present
in muscles), etc.
(b) Globular proteins : This structure results when the chains of polypeptides coil around to
give a spherical shape. These are usually soluble in water. Insulin and albumins are the
common examples of globular proteins.
2. Classification of proteins on the basis of structures and shapes :

Structure and shape of proteins can be studied at four different levels, i.e., primary, secondary,
tertiary and quaternary, each level being more complex than the previous one.
(i) Primary structure of proteins: Proteins may have one or more polypeptide chains. Each
polypeptide in a protein has amino acids linked with each other in a specific sequence and it is
this sequence of amino acids that is said to be the primary structure of that protein. Any change
in this primary structure (i.e., the sequence of amino acids) creates a different protein.
294 E
 CBSSE
ALLEN
A
Primary structure of o Protein

(ii) SSecondary structure of o proteins : The secon ndary structure of proteein refers to
o the shape in
wwhich a lonng polypeptiide chain caan exist. Th hey are founnd to exist iin two diffeerent types of
o
v -helix
sstructures viz. x and -pleeated sheet structure. These struuctures arisee due to thhe
rregular foldding of the backbone
b off the polypeeptide chain
n due to hyddrogen bond ding betweeen
C  and –
–NH- groups s of the pep
ptide bond.
||
O
((a) -Hellix is one of
o the mostt common ways
w in whhich a polyypeptide chaain forms all
a
possibble hydrogeen bonds bby twisting into a rig
ght handed screw (hellix) with thhe
NHH group off each aminno acid ressidue hydro
ogen bondedd to the C=O of an
a

adjaceent turn of the
t helix.
-Helix SStructure of
o Proteins
((b) In -sstructure alll peptide chhains are sttretched outt to nearly m
maximum extension
e annd
then laid side by side whichh are held toogether by in ntermolecullar hydrogen bonds. Thhe
structuure resemblles the pleaated folds of drapery and thereforre is known as -pleateed
sheet.
β‐Pleated Shheet Structure of Proteins
E 29
95
Chemistry
C
N
ALLEN
(iii) TTertiary strructure of proteins: T The tertiary structure off proteins reepresents ov
verall foldinng
oof the polyppeptide chaiins i.e., furth
ther folding of the seco
ondary struccture. It givees rise to tw
wo
mmajor moleccular shapes viz. fibrouus and globu ular.
TThe main forces whiich stabilisse the 2° and a 3° stru
uctures of pproteins arre hydrogeen
bbonds, disuulphide linkkages, van d der Waals and electro ostatic forcces of attracction.
(iv) QQuaternaryy structuree of protein ns : Some of the proteeins are com

mposed of two or morre
ppolypeptidee chains refeerred to as ssub-units. The
T spatial arrangemennt of these subunits
s witth
rrespect to eaach other iss known as qquaternary structure. A diagramm matic represeentation of all
a
tthese four sttructures is given in figgure.
DENATUR
D RATION OF F PROTEIINS :
Physiccal change likel change in temperaature or chem mical chang ge like channge in pH, the
t hydrogeen
bonds are disturbbed. Due to o this, globuuler unfold d and helix get uncoileed and protein loses its i
biologgical activityy. This is caalled denatuuration of prrotein. The coagulation
c n of egg whiite on boilinng
is a coommon exam mple of den naturation.
Another example is curdling g of milk wwhich is cau used due to the formatiion of lacticc acid by thhe
bacteriia present inn milk. Durring denatur uration secon ndary and tertiary
t struuctures are destroyed
d buut
primarry structure remains un nchanged.
Difference
D b
between Fib brous and Globular P Proteins :
F
Fibrous prootein Globularr protein
1. It is a fibree-like structture forme d by the The polyp peptide chaain in this protein inn
poolypeptide chain. These proteins are held folded aro ound itselff, giving rise to a
toogether by strong hydro ogen and dissulphide spherical structure.
2. It is usually insoluble
i in water. It is usually
y soluble inn water.
3. Fiibrous prooteins are usually uused for All enzym mes are gloobular proteeins. Somee
strructural puurposes. Forr example, kkeratin is hormones such as inssulin are also globularr
prresent in nails and hair; colllagen in proteins.
teendons; andd myosin in muscles.
296 E
CBSE
ALLEN
NUCLEIC ACIDS
It has been observed that nucleus of a living cell is responsible for the transmission of inherent
characters, also called heredity. The particles in nucleus of the cell, responsible for heredity, are
called chromosomes which are made up of proteins and another type of biomolecules called
nucleic acids. These are mainly of two types, the deoxyribonucleic acid (DNA) and ribonucleic
acid (RNA). Since nucleic acids are long chain polymers of nucleotides, so they are also called
polynucleotides.
CHEMICAL COMPOSITION OF NUCLEIC ACIDS :
Nucleic acids are colourless, complex and amorphous compound and are made of three units.
1. Pentose sugar
2. Nitrogenous bases
3. phosphoric acid
1. Pentose sugars : Two types of sugars have been isolated by carrying out the hydrolysis of
nucleic acids. These are -D-ribose and -D-2- deoxyribose. Both of them contain a five
membered hetrocyclic ring and are generally called pentose sugars.
5 5
HOH2C OH HOH2C O OH
O
4 1 4 1
H H H H
H H H 3 2
H
3 2
OH OH OH H
-D-ribose -D-2-deoxyribose
present in RNA present in DNA
2. Nitrogenous Bases : Two types of nitrogeneous bases present in nucleic acid i.e.
PURINES and PYRIMIDINES.
NITROGENEOUS BASES
PURINE PYRIMIDINES
It is made up of six membered It is single six membered
ring condensed with a five hetrocyclic ring with two nitrogen
membered ring. atom.
The bases derived from purine The bases derived from pyrimidine
are Adenine (A) and Guanine (G) are Thymine (T). Cytosine (C) and
Uracil (U)
(i) ADENINE
(ii) GUANINE (i) CYTOSINE
(ii) THYMINE
(iii) URACIL
E 297
Chemistry
C
N
ALLEN
Based
d on constitu
uent presen
nt, there arre two typees of nucleicc acid. Thes
ese are :
 Deoxyyribonucleic acid (DNA) : The baase constitu uents are :
Adeniine (A), Gu
uanine (G), Cytosine (CC), Thymin ne (T)
NH2 O N 2
NH O
C H3C C
N C N C
C C HC N C NH
N NH
HC HC
C C HC C HC C
N CH N C–NH2 N O
N N N O
H H H H
Adeniine (A) anine (G)
Gua Cyttosine (C) Thyminne (T)
 Ribon
nucleic acid
d (RNA) : The
T base coonstituents are :
Adeniine (A), Gu
uanine (G), Cytosine (C
C), Uracil (U).
(
NH2 O NH2 O
N C C C C
N
C N C NH HC N HC NH
HC HC
C CH C C–NH2 HC C HC C
N N N N O N O
H N
H H H
Adeniine (A) nine (G)
Guan Cyttosine (C) Urracil (U)
Bases : Adnine, Guanine
G annd Cytosinee are preseent in both DNA and RNA
Bases : Thyminee is present only in DN NA.
Base : Uracil is present
p onlyy in RNA.
Pentosse sugar, deeoxyribosee is present in DNA wh hile ribose is in RNA
3.PPhosphoricc Acid : In addition
a to bbases and sugars,
s phossphoric acidd as phosphaate is another
cconstituent of nucleic acid.
a
ARRANGE
A EMENT OF F CONSTO OTUENTS IN NUCLE EIC ACID :
These are in fact, three buildiing blocks iin nucleic acid.
 mbination of
A com o base and sugar in kn nown as nu ucleoside.
 A com
mbination of o base, sugar and phoosphates forrm nucleottides.
Nucleiic acid are polynucleo otides which h means th hat these arre polymerss of nucleottides.
Structure
S off Nucleis Acid
A :
Nuccleoside Nucleotid
de
Nittrogenous Nitrogenou
us
Base Base
Pentose Peentose
Phosphate Group
up

298 E
 CBSSE
ALLEN
A
Structture of Nuccleic Acids :-
A unitt formed byy the attach
hment of a base to 1' position off sugar is kn known as nu ucleoside. In
I
nucleoosides, the sugar
s carbo
ons are nummbered as 1'', 2', 3', etc.. in order too distinguissh these from
m
the basses. When nucleoside
n is linked too phosphoric acid at 5'--position off sugar moiety, we gett a
nucleootide.
 Nucleootides are jooined togeth

her by phossphodiester linkage bettween 5' andd 3' carbon atoms of thhe
pentosse sugar.
Distingu
uish betweeen Nucleosside and Nu
ucleotide
Nucleosid
de Nucleeotide
1. Nucleosidde is a comp
pound formeed by the 1. Nucleotides is a compound d formed by b
union of a nitrogen base
b with a pentose the un
nion of a nnitrogen basse, a pentosse
sugar. sugar and phosphhate.
2. It is a com
mponent of nucleotide.
n 2. Nucleotide is throough phosp
phorylation of
o
nucleo
oside.
3. It is slightlly basic in nature.
n 3. A nuccleotide is accidic in natu
ure.
A simpplified versiion of nucleeic acid chaain is as show
wn below Fig.
F
E 29
99
Chemistry
ALLEN
Primary Structure of DNA
Information regarding the sequence of nucleotides in the chain of a nucleic acid is called its
primary structure.
DNA is macro molecule which is formed by two polydeoxiribonucleotoide chain. Each

polydeoxiribonucleotoide joined by phosphodiester linkage.
O
5 CH2 O Base-I
4 1
H H H H
3 2
O OH
HO – P = O
O
5 CH2 O Base-II
4 1
H H H H
3 2
O OH
HO – P = O
Primary structure of DNA
Secondary Structure of DNA
Nucleic acids have a secondary structure also. James Watson and Francis Crick gave a double
strand helix structure for DNA. Two nucleic acid chains are wound about each other and held
together by hydrogen bonds between pairs of bases. The two strands are complementary to each
other because the hydrogen bonds are formed between specific pairs of bases.
Adenine forms hydrogen bonds with Thymine whereas Cytosine forms hydrogen bonds
with Guanine.
300 E
 CBSSE
ALLEN
A
5' 3'
G C–
–G
 A=T 
 T= A 
 A=T
 C=G
 G C 
 T=A 
–CG–
––T=A–
 G C
 A=T 
–T=A–
–A=T–
 T= A 
 C G 
G C–
–G
5' 3'

T=A CG
Note : In seconddary structu ure of RNA A, helices are present which arre only sing gle stranded.
Somettimes they foldf back onn themselve s to form a double heliix structure..
Different
D tyypes of RNA A found in the cell
(i) M Messenger RNA
R (m-RN NA)
(ii) R Ribosomal RNA
R (r-RN
NA)
(iii) T Transfer RNNA (t-RNA))
DIFFEREN
D NCE BETW WEEN DNA A AND RNA A
The sttructural differences between
b DNNA and RN NA are as follows
f :
DNA RNA
1. T The sugarr moiety in DN NA The su ugar moietty in RNA A moleculees is -D
mmolecules iss -D-2 deo oxyribose. ribose.
2. D DNA contaiins thyamin n (T). It do es RNA contains
c urracil (U). It does no ot contain
nnot contain Uracil
U (U). thyminne (T).
3. T The helicall structure of DNA is The helical structu ure of RNA is single-sttranded.
ddouble-strannded.
The fu unctional differencess
d s between DDNA and RNAR are as follows :
DNA RNA
1. D DNA is thhe chemiccal basis of RNA iss not respon nsible for heeredity.
hhereidity.
2. D DNA moleccules do no ot synthesiise Proteinns are synthesised by RRNA molecu ules in the
pproteins, butt transfer co
oded messagge cells.
ffor the synthhesis of prroteins in thhe
ccells.
E 30
01
Chemistry
ALLEN
BIOLOGICAL FUNCTIONS OF NUCLEIC ACIDS
DNA is the chemical basis of heredity and may be regarded as the reserve of genetic information.
DNA is exclusively responsible for maintaining the identity of different species of organisms
over millions of years. A DNA molecule is capable of self-duplication during cell division and
identical DNA strands are transferred to daughter cells. Another important function of nucleic
acids is the protein synthesis in the cell. Actually, the proteins are synthesised by various RNA
molecules in the cell but the message for the synthesis of a particular protein is present in DNA.
VITAMINS
They are organic compounds required in the diet in small amounts to perform specific biological
functions for maintenance of optimum growth and health of the organism. They are classified as
follows :
(i) Fat soluble vitamins : Vitamin A, D, E and K. They are stored in liver and adipose
(fat storing) tissues.
(ii) Water soluble vitamins : B group vitamins and vitamin C, they need to supplied regularly in
diet as they are excreted in urine and cannot be stored (except vitamin B12) in our body.
Vitamin Sources Deficiency diseases
(i) Vitamin-A Milk, cod liver oil, butter, Night blindness, xerophthalmia
(Retinol carrots, green leaves, tomatoes, (i.e. hardening of cornea of eye)
or eye vitamin) eggs, etc. and xerosis.
(ii) Vitamin-B1 Pulses, nuts, green vegetables, Beriberi (a disease of nervous

Thiamine or Aneurin Polished rice, yeast and egg system) and loss apetite.
yolk.
(iii) Vitamin - B2 Milk, meat, green vegetables Inflammation of tongue or dark
or Riboflavin and yeast. red tongue (glossitis), and
or Lactoflavin cheilosis (cracking or fissuring the
lips and corners of the mouth)
(iv) Vitamin-B6 Rice, bran, yeast, meat, fish, Specific dermatitis called
or Pyridoxine egg, yolk, maize, spinach and acrodynia, pellagra (shrivelled
or Adermine lettuce. skin) anaemia and convulsions.
(v) Vitamin-B12 Milk, liver, kidney and eggs. Inflammation of tongue, mouth
or cyanocobalamine etc. and pernicious anaemia.
(vi) Vitamin-C Citrus fruits, amla, (oranges, Scurvy and brittleness of bones,
or L-Ascorbic acid lemons), sprouted pulses, swelling and bleeding of gums
germinated grains and leafy and lossening of teeth.

vegetables.
(vii) Vitamin D Fish liver oil, cod liver oil, Rickets (softening and bending of
or Ergocal ciferol milk and eggs. bones) in children, controls Ca
(or antirachtic and P metabolism.
or sunshine)
302 E
CBSE
ALLEN
(viii) Vitamin-E Eggs, milk, fish, wheat germ, Sterility (loss of sexual power and
or ocopherols oil, cotton seed oil etc. reproduction)
(,  and )
or Antisterility factor
(ix) Vitamin-H (Biotin) Yeast, liver, Kidney and milk. Dermatitis, loss of hair and
paralysis.
(x) Vitamin-K Cabbage, alfalfa, spinach and Haemorrhage and lenthens time of
or Phylloquinones carrot tops. blood clotting.
or Antihaemorrhagic
(xi) Coenzyme Q10 Chloroplasts of green plants Low order of immunity of body
and mitochondria of animals against many diseases
ENZYMES
Enzymes are proteins that catalyse biological reactions. They are very specific in nature and
catalyse only a particular reaction for a particular substrate. Enzymes are usually named after the
particular substrate or class of substrate and sometimes after the particular reaction.
For example, enzymes used to catalyse the hydrolysis of maltose into glucose is named as
maltase.
Maltase
C12 H 22 O11   2C 6 H12 O 6
Maltose Glucose
Again, the enzymes used to catalyse the oxidation of one substrate with the simultaneous
reduction of another substrate are named as oxidoreductase enzymes.
The name of an enzymes ends with '–ase'.
Enzyme Reaction catalysed
(i) Invertase or sucrase Sucrose   Glucose + Fructose
(ii) Maltase Maltose   Glucose + Glucose
(iii) Lactase Lactose   Glucose + Galactose
(iv) Amylase Starch  n × Glucose
(v) Emulsin Cellulose  n × Glucose
(vi) Urease NH2CONH2  CO2 + 2NH3
(vii) Carbonic anhydrase
H2CO3   CO2 + H2O
(viii) Pepsin
Proteins  Amino acids
(ix) Trypsin
Proteins  Amino acids
(x) Nucleases
DNA or RNA  Nucleotides
(xi) DNA polymerase
Deoxynucleotide triphosphates DNA
(xii) RNA polymerase
Ribonucleotide triphosphates RNA
E 303
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ALLEN
HORMONES :
Hormones are molecules that act as intercellular messengers. These are produced by endocrine
glands in the body and are poured directly in the blood stream which transports them to the site
of action.
In terms of chemical nature, some of these are steroids, e.g., estrogens and androgens; some are
poly peptides for example insulin and endorphins and some others are amino acid derivatives
such as epinephrine and norepinephrine.
(a) Insulin in keeping the blood glucose level within the narrow limit. Hormone glucagon tends to
increase the glucose level in the blood. The two hormones together regulate the glucose level in
the blood.
(b) Epinephrine and norepinephrine mediate responses to external stimuli. Growth hormones and sex
hormones play role in growth and development. Thyroxine produced in the thyroid gland is an
iodinated derivative of amino acid tyrosine.
(c) Steroid hormones are produced by adrenal cortex and gonads (testes in males and ovaries in
females).
(d) Glucocorticoids control the carbohydrate metabolism, modulate inflammatory reactions and are
involved in reactions to stress.
(e) Testosterone is the major sex hormone produced in males. It is responsible for development of
secondary male characteristics (deep voice, facial hair. general physical constitution) and
estradiol is the main female sex hormon. It’s responsible for development of secondary female
charateristics and participates in the control of menstrual cycle.
(f) Progesterone is responsible for preparing the uterus for implantation of fertilised egg.
304 E
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ALLEN
1. Glucose or sucrose are soluble in water but cyclohexane or benzene (simple six membered ring
compounds) are insoluble in water. Explain.
Ans. A glucose molecules contains five –OH groups while a sucrose molecule contains eight –OH
groups. Thus, glucose and sucrose undergo extensive H-bonding with water.
Hence, these are soluble in water.
But, cyclohexane and benezene do not contain –OH groups. Hence, they cannot undergo H-
bonding with water and as a result, they are insoluble in water.
2. What are the expected products of hydrolysis of lactose ?
Ans. Lactose is composed of -D galactose and -D glucose. Thus, on hydrolysis, it gives -D
galactose and -D glucose.
6 6
CH2OH CH2OH
O O
HO H5 H H
5
OH
4 1 O 4 1
H OH H H OH H H
3 2 3 2
H OH H OH
 - D - Galactose  - D - Glucose
Lactose
C12H22O11 + H2O C6H12O6 + C6H12O6
Lactose D-(+)-Glucose D-(+)-Galactose
3. How do you explain the absence of aldehyde group in the pentaacetate of D-glucose ?
Ans. D-glucose reacts with hydroxylamine (NH2OH) to form an oxime because of the presence of
aldehydic (–CHO) group of carbonyl carbon. This happens as the cyclic structure of glucose
forms an open chain structure in an aqueous medium, which then reacts with NH2OH to give an
oxime.
CHO CH=N–OH
NH 2OH
(CHOH)4 (CHOH)4
CH2OH CH2OH
Glucose Oxime
But pentaacetate of D-glucose does not react with NH2OH. This is because pentaacetate does not
form an open chain structure.
4. The melting points and solubility in water of amino acids are generally higher than that of the
corresponding halo acids. Explain.
Ans. Both acidic (carboxyl) as well as basic (amino) groups are present in the same molecule of amino
acids. In aqueous solutions, the carboxyl group can lose a proton and the amino group can accept,
thus giving rise to a dipolar ion known as a zwitter ion.
O O
R—CH—C—O—H R—CH—C—O—
+
NH2 NH3
(Zwitter ion)
E 305
Chemistry
ALLEN
Due to this dipolar behaviour, they have strong electrostatic interactions within them and with
water, But halo-acids do not exhibit such dipolar behaviour.
For this reason, the melting points and the solubility of amino acids in water is higher than those
of the corresponding halo-acids.
5. Where does the water present in the egg go after boiling the egg ?
Ans. When an egg is boiled, the proteins present inside the egg get denatured and coagulate. After
boiling the egg, the water present in it is absorbed by the coagulated protein through H-bonding.
6. Why cannot vitamin C be stored in our body ?
Ans. Vitamin C cannot be stored in our body because it is water soluble. As a result, it is readily
excreted in the urine.
7. What products would be formed when a nucleotide from DNA containing thymine is
hydrolysed?
Ans. When a nucleotide from the DNA containing thymine is hydrolyzed, thymine, -D-2-
deoxyribose and phosphoric acid are obtained as products.
8. When RNA is hydrolysed, there is not relationship among the quantities of different bases
obtained. What does this fact suggest about the structure of RNA ?
Ans. A DNA molecule is double-stranded in which the pairing of bases occurs. Adenine always pairs
with thymine, while cytosine always pairs with guanine. Therefore, on hydrolysis of DNA, the
quantity of adenine produced is equal of that off thymine and similarly, the quantity of cytosine
is equal to that of guanine.
But when RNA is hydrolyzed, there is no relationship among the quantities of the different bases
obtained. Hence, RNA is single-stranded.
306 E
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ALLEN
1. What are monosaccharides ?

Ans. Monosaccharides are carbohydrates that cannot be hydrolysed further to give simpler units of
polyhydroxy aldehyde or ketone.
Monosaccharides are classified on the basis of number of carbon atoms and the functional group
present in them. Monosaccharides containing an aldehyde group are known as aldose and those
containing a keto group are known as ketose. Monosaccharides are further classified as triose,
tetrose, pentose, hexose, and heptose according to the number of carbon atoms they contain. For
example, a ketose containing 3 carbon atoms is called ketotriose and an aldose containing 3
carbon atoms is called aldotriose.
2. What are reducing sugars ?
Ans. Reducing sugars are carbohydrates that reduce Fehling's solution and Tollen's reagent. All
monosaccharides and disaccharides, excluding sucrose, are reducing sugars.
3. Write two main functions of carbohydrates in plants.
Ans. Two main functions of carbohydrates in plants are :
(i) Polysaccharides such as strach serve as storage molecule.
(ii) Cellulose, a polysaccharide, is used to build the cell wall.
4. Classify the following into monosaccharides and disaccharides.
Ribose, 2-deoxyribose, maltose, galactose, fructose and lactose
Ans. Monosaccharides :
Ribose, 2-deoxyribose, galactose, fructose
Disaccharides :
Maltose, lactose
5. What do you understand by the term glycosidic linkage ?
Ans. Glycosidic linkage refers to the linkage formed between two monosaccharide units through an
oxygen atom by the loss of a water molecule.
For example, in a sucrose molecule, two monosaccharide units,  - glucose and - fructose, are
joined together by a glycosidic linkage.
6
CH2OH
5 O 1
O
H H H HOH2C H
4 1 2 5
OH OH H O
3 2 H OH CH
6
2OH
Glycosidic 3 4
H linkage
OH OH H
- D - glucose  - D - fructose

Surcose
6. What is glycogen ? How is it different from starch ?

Ans. Glycogen is a carbohydrate (polysaccharide). In animals, carbohydrates are stored as glycogen.
Strach is a carbohydrate consisting of two components – amylose (15-20%) and amylopectin (80-85%).
However, glycogen consists of only one component whose structure is similar to amylopectin.
Also, glycogen is more branched than amylopectin.
E 307
Chemistry
ALLEN
7. What are the hydrolysis products of (i) sucrose and (ii) lactose ?
Ans. (i) On hydrolysis, sucrose gives one molecule of -D glucose and one molecule of -D-fructose.
CH2OH
O O
H H H HOH2C H
OH OH H O
H OH CH2OH
H OH OH H
Hydrolysis
CH2OH
O O
H H H HOH2C H
+
OH OH H OH HO H OH CH2OH
H OH OH H
- D - glucose - D - fructose
(ii) The hydrolysis of lactose give -D-galactose and -D-glucose.

CH2OH CH2OH
O O
OH H H H OH
O
H OH H H OH H H
H OH H OH
Hydrolysis
CH2OH CH2OH
O O
OH H OH H H OH
+
H OH H H OH OH H H
H OH H OH
- D - galactose - D - glucose
8. What is the basic structural difference between starch and cellulose ?

Ans. Starch consists of two components - amylose and amylopectin. Amylose is a long linear chain of
-D–(+)–glucose units joined by Cl – C4 glycosidic linkage (-link).
CH2OH CH2OH
O O
H H H H H H
4 1 4 1
O O O
OH H OH H
H OH H OH
-Link
Amylose
Amylopectin is a branched-chain polymer of –D–glucose units, in which the chain is formed

by C1– C4 glycosidic linkage and the branching occurs by C1– C6 glycosidic linkage.
308 E
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ALLEN
CH2OH CH2OH
O O
H H H H H H
4 1 4 1
O OH H O OH H O -Link
Branch at C6
H OH H OH 6 CH2OH
CH2
-Link O O
H H5 H H H H
4 1 4 1
O OH H O OH H O
H OH H OH
-Link
Amylopectin
On the other hand, cellulose is a straight-chain polysacchoride of -D-glucose units joined by

C1– C4 glycosidic linkage (-link).
HOH2C
O
HOH2C O
O
HOH2C O OH
O
O OH OH
-Link
O OH OH
-Link
OH
9. What happens when D-glucose is treated with the following reagents ?

(i) HI (ii) Bromine water
(iii) HNO3
Ans. (i) When D-glucose is heated with HI for a long time, n-hexane is formed.
CHO
Hl CH3–CH2–CH2–CH2–CH2–CH3
(CHOH)4 
n - hexane
CH2OH
D - glucose
(ii) When D-glucose is treated with Br2 water, D-gluconic acid is produced.
CHO COOH
Br2water
(CHOH)4 (CHOH)4
CH2OH CH2OH
D - glucose D-gluconic acid
(iii) On being treated with HNO3, D-glucose get oxidised to give saccharic acid.
CHO COOH
HNO 3
(CHOH)4 (CHOH)4
CH2OH COOH
D - glucose Saccharic acid
10. Eunmerate the reactions of D-glucose which cannot be explained by its open chain structure.
Ans. (a) Aldehydes give 2, 4-DNP test. Schiff's test, and react with NaHSO4 to form the hydrogen
sulphite addition prodcut. However, glucose does not undergo these reactions.
(b) The pentaacetate of glucose does not react with hydroxylamine. This indicates that a
free –CHO group is absent from glucose.
E 309
Chemistry
ALLEN
(c) Glucose exists in two crystalline forms – and . The  - form (m.p. = 419 K) crystallises
from a concentrated solution of glucose at 303 K and the -form (m.p.=423 K) crystallises
from a hot and saturated aqueous solution at 371 K. This behaviour cannot be explained by
the open chain structure of glucose.
11. What are essential and non-essential amino acids ? Give two examples of each type.
Ans. Essential amino acids are required by the human body, but they cannot be synthesised in the
body. They must be taken through food. For example : valine and leucine
Non-essential amino acids are also required by the human body, but they can be synthesised in
the body. For example: glycine, and alanine
(i) Peptide linkage
(ii) Primary structure
(iii) Denaturation
12. Define the following as related to proteins
(i) Peptide linkage
(ii) Primary structure
(iii) Denaturation
Ans. (i) Peptide linkage :
The amide formed between –COOH group of one molecule of an amino acid and –NH2
group of another molecule of the amino acid by the elimination of a water molecule is
called a peptide linkage.
Peptide
linkage
–H2O
H2N—CH—COOH + H2N—CH—COOH H2N—CH—CO—NH—CH—COOH
CH(CH3)2 CH3 CH(CH3)2 CH3
Valine Alanine Valylalanine (Val-Ala)
(ii) Primary structure :

The primary structure of protein refres to the specific sequence in which various amino
acids are present in it, i.e., the sequence of linkage between amino acids in a polypeptide
chain. The sequence in which amino acids are arranged is different in each protein. A
change in the sequence creates a different protein.
(iii) Denaturation :
In a biological system, a protein is found to have a unique 3- dimensional structure and a
unique biological activity . In such a situation, the protein is called native protein.
However, when the native protein is subjected to physical changes such as chage in
temperature or chemical change such as change in pH, its H-bonds are disturbed. This
disturbance unfolds the globules and uncoils the helix. As a result, the protein loss its
biological activity. This loss of biological activity by the protein is called denaturation.
During denaturation, the secondary and the tertiary structures of the protein get destroyed,
but the primary structure remains unaltered.
One of the examples of denaturation of proteins is the coagulation of egg white when an
egg is boiled.
310 E
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13. What are the common types of secondary structure of proteins ?
Ans. There are two common types of secondary structure of proteins :
(i)  - helix structure (ii) -pleated sheet structure
(i)  - Helix structure
In this structure, the –NH group of an amino acid residue forms H-bonds with the group of
the adjacent turn of the right-handed screw (-helix).
C
O
C
C
O
HO H
CN
N
O H
C
HCN
O
O H
N NH
H N
N
 - helix structure
(ii) -pleated sheet structure
This structure is called so because it looks like the pleated folds of drapery. In this
structure, all the peptide chains are stretched out to nearly the maximum extension and then
laid side by side. These peptide chains are held together by intermolecular hydrogen bonds.
N
RCH N
N
H C=O RCH
N H RCH
C=O
RCH N H C=O
C=O RCH N
N RCH
H O=C
RCH N H O=C
H C=O RCH
N H
N H C=O
RCH
RCH N H
C RCH N C=O
C= RCH
=C
- pleated sheet structure

14. What type of bonding helps in stabilising the -helix structure of proteins ?
Ans. The H-bonds formed between the –NH group of each amino acid residue and the C=O group of
the adjacent turns of the -helix help in stabilising the helix.
E 311
Chemistry
ALLEN
15. Differentiate between globular and fibrous proteins.
Ans.
Fibrous protein Globular protein
1. It is a fibre-like structure formed by the The polypeptide chain in this protein in
polypeptide chain. These proteins are hold folded around itself, giving rise to a spherical
together by strong hydrogen and disulphide structure.
2. It is usually insoluble in water. It is usually soluble in water.
3. Fibrous proteins are usually used for All enzymes are globular proteins. Some
structural purposes. For example, keratin is hormones such as insulin are also globular
present in nails and hair; collagen in proteins.
tendons; and myosin in muscles.
16. How do you explain the amphoteric behaviour of amino acids ?
Ans. In aqueous solution, the carboxyl group of an amino acid can lose a proton and the amino group
can accept a proton to gives a dipolar ion known as zwitter ion.
O O
R—CH—C—O—H R—CH—C—O—
+
NH2 NH3
(Zwitter ion)
Therefore, in zwitter ionic form, the amino acid can act both as an acid and as a base.
O O O
+ +
H H
R—CH—C—O— R—CH—C—O— R—CH—C—OH
OH +
OH +
NH2 NH3 NH3
Thus, amino acids show amphoteric behaviour.

17. What are enzymes ?
Ans. Enzymes are proteins that catalyse biological reactions. They are very specific in nature and
catalyse only a particular reaction for a particular substrate. Enzymes are usually named after the
particular substrate or class of substrate and some times after the particular reaction.
For example, enzymes used to catalyse the hydrolysis of maltose into glucose is named as
maltase.
Again, the enzymes used to catalyse the oxidation of one substrate with the simultaneous
reduction of another substrate are named as oxidoreductase enzymes.
The name of an enzymes ends with '–ase'.

18. What is the effect of denaturation on the structure of proteins ?
Ans. As a result of denaturation, globules get unfolded and helixes get uncoiled. Secondary and
tertiary structures of protein are destroyed, but the primary sturctures remain unaltered. It can be
said that during denaturation, secondary and tertiary-structured proteins get converted into
primary - structured proteins. Also, as the secondary and tertiary structures of a protein are
destroyed, the enzyme loses its activity.
312 E
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ALLEN
19. How are vitamins classified ? Name the vitamin responsible for the coagulation of blood.
Ans. On the basis of their solubility in water or fat, vitamins are classified into two groups.
(i) Fat-soluble vitamins : Vitamins that are soluble in fat and oils, but not in 'water, belong to
this group. For example: Vitamins A, D, E, and K
(ii) Water-soluble vitamins : Vitamins that are soluble in water belong to this group. For
example : B group vitamins (B1, B2, B6, B12, etc.) and vitamin C
However, biotin or vitamin H is neither soluble in water nor in fat.
Vitamin K is responsible for the coagulation of blood.
20. Why are vitamin A and vitamin C essential to us ? Give their important sources.
Ans. The deficiency of vitamin A leads to xerophthalmia (hardening of the cornea of the eye) and
night blindness. The deficiency of vitamin C leads to scurvy (bleeding gums).
The sources of vitamin A are fish liver oil, carrots, butter, and milk. The sources of vitamin C are
citrus fruits, amla, and green leafy vegatables.
21. What are nucleic acids ? Mention their two important functions.
Ans. Nucleic acids are biomolecules found in the nuclei of all living cells, as one of the constituents of
chromosomes. There are mainly two types of nucleic acids - deoxyribonucleic acid (DNA) and
ribonucleic acid (RNA). Nucleic acid are also known as polynucleotides as they are long-chain
polymers of nucleotides.
Two main functions of nucleic acids are :
(i) DNA is responsible for the transmission of inherent characters from one generation to the
next. This process of transmission is called heredity.
(ii) Nucleic acids (both DNA and RNA) are responsible for protein synthesis in a cell. Even
though the proteins are actually synthesised by the various RNA molecules in a cell, the
message for the synthesis of a particular protein is present in DNA.
22. What is the difference between a nucleoside and a nucleotide ?
Ans. A nucleoside is formed by the attachment of a base to l' position of sugar.
Nucleoside = Sugar + Base
5' O
HOH2C Base
4' 1'
HH HH
3' 2'
OH OH
Structure of a nucleoside
On the other hand, all the three basic components of nucleic acids (i.e., pentose sugar, phosphoric
acid, and base) are present in a nucleotide.

Nucleotide = Sugar + Base + Phosphoric acid
O
— 5' O
O —P—O—H2C Base
O
— 4' 1'
HH HH
3' 2'
OH OH
Structure of a nucleotide
E 313
Chemistry
ALLEN
23. The two strands in DNA are not identical but are complementary. Explain.
Ans. In the helical structure of DNA, the two strands are held together by hydrogen bonds between
specific pairs of bases. Cytosin forms hydrogen bond with guanine, while adenine forms
hydrogen bonds with thymine. As a result, the two strands are complementary to each other.
24. Write the important structural and functional differences between DNA and RNA.
Ans. The structural differences between DNA and RNA are as follows :
DNA RNA
1. The sugar moiety in DNA The sugar moiety in RNA molecules is -D
molecules is -D-2 deoxyribose. ribose.
2. DNA contains thyamin (T). It does RNA contains uracil (U). It does not contain
not contain Uracil (U). thymine (T).
3. The helical structure of DNA is The halical structure of RNA is single-stranded.
double-stranded.
The functional differencess between DNA and RNA are as follows :

DNA RNA
1. DNA is the chemical basis of RNA is not responsible for heredity.
hereidity.
2. DNA molecules do not synthesise Proteins are synthesised by RNA molecules in the
proteins, but transfer coded message cells.
for the synthesis of proteins in the
cells.
25. What are the different types of RNA found in the cell ?
Ans. (i) Messenger RNA (m-RNA)
(ii) Ribosomal RNA (r-RNA)
(iii) Transfer RNA (t-RNA)
26. What is hormones and write to its functions ?
Ans. Hormones are molecules that act as intercellular messengers. These are produced by endocrine
glands in the body and are poured directly in the blood stream which transports them to the site
of action.
In terms of chemical nature, some of these are steroids, e.g., estrogens and androgens; some are
poly peptides for example insulin and endorphins and some others are amino acid derivatives
such as epinephrine and norepinephrine.
(a) Insulin in keeping the blood glucose level within the narrow limit. Hormone glucagon
tends to increase the glucose level in the blood. The two hormones together regulate the
glucose level in the blood.
314 E
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ALLEN
(b) Epinephrine and norepinephrine mediate responses to external stimuli. Growth hormones and
sex hormones play role in growth and development. Thyroxine produced in the thyroid
gland is an iodinated derivative of amino acid tyrosine.
(c) Steroid hormones are produced by adrenal cortex and gonads (testes in males and ovaries
in females).
(d) Glucocorticoids control the carbohydrate metabolism, modulate inflammatory reactions
and are involved in reactions to stress.
(e) Testosterone is the major sex hormone produced in males. It is responsible for development
of secondary male characteristics (deep voice, facial hair. general physical constitution) and
estradiol is the main female sex hormon. It’s responsible for development of secondary
female charateristics and participates in the control of menstrual cycle.
(f) Progesterone is responsible for preparing the uterus for implantation of fertilised egg.
E 315
Chemistry
ALLEN
EXERCISE-3 EXEMPLAR
1. Glycogen is a branched chai polymer of a-D glucose units in which chain is formed by C1-C4
glycosidic linkage where as branching occurs by the formation of C1-C6 glycosidic linkage.
Structure of glycogen is similar to ….
(a) amylose (b) amylopectin (c) cellulose (d) glucose
Ans. (b)
2. Which of the following polymer is stored in the liver of animals ?
(a) amylose (b) cellulose (c) amylopectin (d) glycogen
Ans. (d)
3. Sucrose (cane sugar) is a disaccharide, One molecule of sucrose on hydrolysis gives ………
(a) 2 molecules of glucose
(b) 2 molecules of glucose + 1 molecule of fructose
(c) 1 molecule of glucose + 1 molecule of fructose
(d) 2 molecules of fructose
Ans. (c)
4. Which of the following pairs represents anomers ?
CHO CHO CHO CHO
(a) (b)
H OH HO H H OH HO H
HO H HO H HO H H OH
H OH H OH H OH HO H
H OH H OH H OH HO H
CH2OH CH2OH CH2OH CH2OH
(c) H OH HO H (d) H OH HO H
H OH H OH H OH HO H
O O O O
HO H HO H HO H H OH
H OH H OH H OH HO H
H H H H

Ans. (c)
5. Proteins are found to have two different types of secondary structures viz -helix and -pleated
sheet structure. -helix structure of protein is stabilised by :

(a) peptide bonds
(b) van der Waals, forces
(c) hydrogen bonds
(d) dipole-dipole interactions
Ans. (c)
316 E
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ALLEN
6. In disaccharides, if the reducing groups of monosaccharides, i.e, aldehydic or ketonic groups are
bonded, these are non-reducing sugars. Which of the following disaccharide is a non-reducing
sugar ?
CH2OH CH2OH
OH H OH
H
(a) H H
OH H OH H
O
OH OH
H OH H OH
CH2OH
OH HOH2C
H O H
H
(b) OH H
O H OH
OH CH2OH
H OH
OH H
CH2OH CH2OH
O HO O OH
(c) HO H H
OH H O OH H
H H H
H OH H OH
CH2OH CH2OH
O H O OH
(d) HO H H
OH H O OH H
HO H H
H OH H OH
Ans. (b)
7. Which of the following acids is a vitamin ?
(a) Aspartic acid (b) Ascorbic acid
(c) Adipic acid (d) Saccharic acid
Ans. (b)
8. Dinucleotide is obtained by joining two nucleotides together by phosphodiester linkage. Between
which carbon atoms of pentose sugars of nucleotides are these linkages present ?
(a) 5’ and 3’ (b) 1’ and 5’
(c) 5’ and 5’ (d) 3’ and 3’

Ans. (a)
9. Nucleic acids are the polymers of :
(a) nucleosides (b) nucleotides
(c) bases (d) sugars
Ans. (b)
E 317
Chemistry
ALLEN
10. Which of the following statements is not true about glucose ?
(a) It is an aldohexose (b) On heating with HI it forms n-hexane
(c) It is present in furanose form (d) It does not give 2,4-DNP test
Ans. (c)
11. Each polypeptide in a protein has amino acids linked with each other in specific sequence. This
sequence of amino acids is said to be ……….
(a) primary structure of proteins
(b) secondary structure of proteins
(c) tertiary structure of proteins
(d) quaternary structure of proteins
Ans. (a)
12. DNA and RNA contain four bases each. Which of the following bases in not present in RNA ?
(a) Adenine (b) Uracil (c) Thymine (d) Cytosine
Ans. (c)
13. Which of the following B group vitamins can be stored in our body ?
(a) Vitamin B1 (b) Vitamin B2
(c) Vitamin B6 (d) Vitamin B12
Ans. (d)
14. Which of the following bases is not present in DNA ?
(a) Adenine (b) Thymine
(c) Cytosine (d) Uracil
Ans. (d)
15. There cyclic structures of monosaccharides are given below which of these are anomers.
H OH HO H HO H
H OH H OH HO H
O O O
HO H HO H HO H
H OH H OH H OH
H H HO H
H
CH2OH CH2OH
CH2OH
(i) (ii)
(iii)
(a) 1 (b) 2 (c) 3 (d) 4

Ans. (a)
318 E
CBSE
ALLEN
16. Which of the following reactions of glucose can be explained only by its cyclic structure ?
(a) Glucose forms pentaacetate
(b) Glucose reacts with hydroxylamine to form an oxime
(c) Pentaacetate of glucose does not react with hydroxyl amine
(d) Glucose is oxidised by nitric acid to gluconic acid
Ans. (c)
17. Structure of disaccharide formed by glucose and fructose is given below. Identify anomeric
carbon atoms in monosaccharide units.
f
CH2OH a
e
OH HOH2C
H O H
d
H b
a e
OH H
O H OH
OH b CH2OH
c c d f
H OH
OH H
(a) ‘a’ carbon of glucose and ‘a’ carbon of fructose
(b) ‘a’ carbon of glucose and ‘e’ carbon of fructose
(c) ‘a’ carbon of glucose and ‘b’ carbon of fructose
(d) ‘f’ carbon of glucose and ‘f’ carbon of fructose
Ans. (c)
18. Three structures are given below in which two glucose units are linked. Which of these linkages
between glucose units are between C1 and C4 and which linkages are between C1 and C6 ?
H O H O OH H OH H O OH
H H H H
OH H O OH H OH H OH H
HO H H HO H
CH2OH
H OH H OH H HO H OH
H OO
O H
(I) OH H
CH2 O H
H OH H OH
H
OH H (III)
HO OH
H HO
(II)
(a) (A) is between C1 and C4, (B) and (C) are between C1 and C6
(b) (A) and (B) are between C1 and C4, (C) is between C1 and C6
(c) (A) and (C) are between C1 and C4, (B) is between C1 and C6
(d) (A) and (C) are between C1 and C6, (B) is between C1 and C4
Ans. (c)
E 319
Chemistry
ALLEN
19. Name the sugar present in milk. How many monosaccharide units are present in it ? What are
such oligosaccharides called ?
Ans. Sugar present in milk is known as lactose sugar. Two units of monosaccharides -D-galactose
and -D-glucose are linked together.
Hence, are known as disaccharides.
6 CH2OH
6 CH2OH
H 5 O O OH
H H 5
4 H
OH H1 O 4
OH H1
OH 2
H H
3 2
3
H OH H OH
-D-galactose -D-glucose
20. How do you explain the presence of all the six carbon atoms in glucose in a straight chain ?
Ans. Glucose on heating with HI produces n-hexane.
CHO
HI
(CHOH)4 
CH3– CH2– CH2– CH2– CH2– CH3
n-hexane
CH2OH
Glucose
This suggests that all the six carbon atoms of glucose are linked in a straight chain.
21. In nucleoside, a base is attached at 1’ position of sugar moiety. Nucleotide is formed by linking o
phosphoric acid unit to the sugar unit of nucleoside. At which position of sugar unit is the
phosphoric acid linked in a nucleoside to give a nucleotide ?
Ans. Phosphoric acid is linked at 5’-position of sugar moiety of nucleoside to give a nucleotide.
O
1
O—P–O—CH2 O Base
1 4’ 1’
O
H H
H 2’ H
OH OH
22. Name the linkage connecting monosaccharide units in polysaccharides ?
Ans. Glycosidic linkage connects monosaccharide units in polysaccharide.
CH2OH 6 CH2OH
5
OH O O OH
H H 5
4 H
OH H 1 O 4
OH H 1
OH H H
3 2 2
3
H OH H OH
Glycoside linkage in lactose
320 E
CBSE
ALLEN
23. Under what conditions glucose is converted to gluconic acid and saccharide acid ?
Ans. Glucose on oxidation with Br2/H2O produces gluoconic acid (six carbon carboxylic acid).
CHO COOH
Br2/H2O
(CHOH)4 (CHOH)4
CH2OH CH2OH
Gluconic acid
Glucose on oxidation with nitric acid produces saccharic acid. (dicarboxylic acid)
CHO COOH
HNO3
(CHOH)4 (CHOH)4
CH2OH COOH
Saccharide acid
24. Aldopentoses named s ribose and 2-deoxyribose are found in nucleic acids. What is their relative
configuration ?
5 5
CH2OH O OH HOCH2 O OH
Ans. 1 1
4 4
H OH H H
H 3 2 H H 3 2 H
OH OH OH H
-D-ribose -D-2-deoxyribose
In case of cyclic structure of saccharide, If –OH group present at second last carbon is present at
bottom side, then it is considered as D configuration (as shown below)
25. Amino acids can be classified as -, -, -, - and so on depending upon the relative position of
amino group with respect to carboxyl group. Which type of amino acids form polypeptide chain
in proteins ?
Ans. -amino acid forms polypeptide chain by elimination of water molecules.

 amino acid  R—CH—COOH
NH2
R O R
nR—CH—COOH—H2N—C H—C—NH—C H—COOH
NH2
peptide linkage
E 321
Chemistry
ALLEN
26. -helix is a secondary structure of proteins formed by twisting of polypeptide chain into right
handed screw like structure. Which type of interactions are responsible for making the -helix
structure stable ?
Ans. -helix is a secondary structure of proteins formed by twisting of polypeptide chain to right
handed screw like structure. Hydrogen bonds formed between —NH— group of amino acids in
one turn with the C = O groups of amino acids belonging to adjacent turn is responsible for
making the -helix structure stable.

27. During curdling of milk, what happens to sugar present in it ?
Ans. Curdling of milk is caused due to formation of lactic acid by the bacteria present in milk. It is an
example of denaturation of protein, i.e., when a protein is subjected is some physical or chemical
charges. Hydrogen bond get disturbed. Globules unfold and helix uncoil and protein loss its
biological acturty.
28. How do you explain the presence of give —OH groups in glucose molecule ?
Ans. Glucose on reaction with acetic anhydride produces glucose pentaacetate.
CHO CHO
Acetic anhydride
(CHOH)4 (CHOAc)4
CH2OH CHOAc
Glucose pentaacetate
This reaction explain presence of five –OH groups.

29. Why does compound (A) given below not form an oxime ?
AcO H
H OAc
AcO O
OH
H OAc
H
CH2OAc
(A)
Ans. Compound (A) does not form an oxime on reaction with NH2OH due to absence of CHO group
of C = O group.
30. Why must vitamin C be supplied regularly in diet ?

Ans. Vitamin C is water soluble hence, they are regularly excreted in urine and can not be stored in
our body, so, they are supplied regularly in diet.
31. Amino acids behave like salts rather than simple amines or carboxylic acids. Explain.
Ans. Amino acids have acidic COOH group as well as NH2 group hence, COOH looses its H to NH2,
hence they exist as Zwitter ion.
R—CH—COO–
NH3

Zwitter ion
322 E
CBSE
ALLEN
32. How do you explain the presence of an aldehydic group in a glucose molecule ?
Ans. Glucose on reaction with bromine water produces gluconic acid. This indicates the presence of
CHO group.
CHO COOH
Br2 / H2O
(CHOH)4 (CHOH)4
CH2OH CH2OH
Gluconic acid
33. Which monosaccharide units are present in starch, cellulose and glucose and which linkages link
these units ?
Ans. Monosaccharides units present in starch, cellulose and glucose can be determined by knowing the
product of their hydrolysis.
(i) Starch is a polysaccharide of -glucose in which two types of linkage are observed i.e.,
C1 – C6 and C1 – C4 glycosidic linkage.
(ii) Cellulose is a straight chain polysaccharide of -D-glucosine which glucose are linked
together by C1–C4 glycosidic linkage.
(iii) Glucose is a monosaccharide.
34. Describe the term D- and L-configuration used for amino acids with examples.
Ans. All naturally occurring -amino acids (except glycine) are optically active due to the presence of
chiral carbon atom. These have either D- or L-configuration. D-form means that, the amino
(–NH2) group is present towards the right hand side L-form shows the presence of —NH2 group
on the left hand side.
COOH COOH
H NH2 H2N H
CH3 CH3
D-alanine L-alanine
35. Coagulation of egg white on boiling is an example of denaturation of protein. Explain it in terms
of structural changes.
Ans. Denaturation of proteins Protein present in egg white has an unique three dimensional structure.
When it is subjected to physical changes like change in temperature i.e., no boiling, coagulation
of egg white occurs due to denaturation of protein.
During denaturation hydrogen bonds are disturbed due to this globules unfold and helix gets
uncoiled and protein looses its biological activity.
E 323
Chemistry
ALLEN
(MATCHING THE COLUMNS)
36. Match the vitamins given in Column I with the deficiency disease they cause given in Column II.
Column I Column II
(Vitamins) (Disease)
(A) Vitamin A (a) Pernicious anaemia
(B) Vitamin B1 (b) Increased blood clotting time
(C) Vitamin B12 (c) Xerophthalmia
(D) Vitamin C (d) Rickets
(E) Vitamin D (5) Muscular weakness
(F) Vitamin E (6) Night blindness
(G) Vitamin K (7) Beri-beri
(8) Bleeding gums
(9) Osteomalacia
Ans. A-3,6 ; B-7 ; C-1 ; D-8 ; E-4,9 ; F-5 ; G-2
37. Match the following enzymes given Column I with the reactions they catalyse given in
Column II.
Column I Column II
(Enzymes) (Reactions)
(A) Invertase (a) Decomposition of urea into NH3 and CO2
(B) Maltase (b) Conversion of glucose into ethyl alcohol
(C) Pepsin (c) Hydrolysis of maltose into glucose
(D) Urease (d) Hydrolysis of cane sugar
(E) Zymase (5) Hydrolysis of protein into peptides.
Ans. A-4 ; B-3 ; C-5 ; D-1 ; E-2

Note: In the following questions a statement of assertion followed by a statement of reason is given.
Choose the correct answer out of the following choices.
38. Assertion (A) : D(+)-Glucose is dextrorotatory in nature.
Reason (R) : ‘D’ represents its dextrorotatory nature.
Ans. (c)
324 E
CBSE
ALLEN
39. Assertion (A) : Vitamin D can be stored in our body.
Reason (R) : Vitamin D is fat soluble vitamin.
Ans. (a)
40. Assertion (A) : -glycosidic linkage is present in maltose.
Reason (R) : Maltose is composed of two glucose units in which C-1 f one glucose unit is linked
C-4 of another glucose unit.
Ans. (d)
41. Assertion (A) : All naturally occurring -aminoacids except glycine are optically active.
Reason (R) : Most naturally occurring amino acids have L-configuration.
Ans. (b)
42. Assertion (A) : Deoxyribose. C5H10O4 is not a carbohydrate.
Reason (R) : Carbohydrates are hydrates of carbon so compounds which follow Cx (H2O)y
formula are carbohydrates.
Ans. (b)
43. Assertion (A) : Glycine must be taken through diet.
Reason (R) : It is an essential amino acid.
Ans. (b)
44. Assertion (A) : In presence of enzyme, substrate molecule can be attacked by the reagent
effectively.
Reason (R) : Active sites of enzymes hold the substrate molecule in a suitable position.
Ans. (a)
E 325
Chemistry
ALLEN
(CARBOHYDRATES)
1. General formula for carbohydrates is:
(a) Cn H2n O2n  2 (b) Cx (H2 O)2x (c) C x (H 2 O)y (d) None of these
2. The commonest disaccharide has the molecular formula –
(a) C10 H18O9 (b) C10 H 20 O10 (c) C18 H 22 O11 (d) C12 H 22 O11
3. Molecular formula C6 H12 O6 is of –
(a) Glucose (b) Fructose (c) Both (a) and (b) (d) None of these
4. Sugars are :
(a) Optically active polyhydroxy aldehydes
(b) Optically active polyhydroxy ketones
(c) Optically active polyhydroxy aldehydes or ketones
(d) Polyhydroxy aldehydes or ketones which may or may not be optically active
5. Which is not monosaccharide?
(a) Glucose (b) Fructose (c) Galactose (d) All of these
6. If monosaccharide contains an aldehyde group, it is known as –
(a) Epimer (b) Osones (c) Osazone (d) Aldose
7. If a monosaccharide contains a ketogroup, it is known as –
(a) Ketose (b) Osones (c) Epimer (d) Osazone
8. Glucose contains –
(a) One CHO group (b) Five OH groups
(c) One primary alcoholic group (d) All are correct
(PROTEIN)
9. Insulin is:
(a) An amino acid (b) Protein (c) A carbohydrate (d) A lipid
10. Peptides are:
(a) Esters (b) Salts (c) Amides (d) Ketones
11. The proteins which are insoluble in water are:
(a) Fibrous proteins (b) Globular proteins
(c) Both (a) and (b) (d) None of these
12. Amino acids are :

(a) Liquids (b) Volatile solids
(c) Non-volatile crystalline compounds (d) Mixture of amines and acids
13. Proteins are hydrolysed by enzymes into –
(a) Dicarboxylic acids (b) Hydroxy acids
(c) Amino acids (d) Aromatic acids
326 E
CBSE
ALLEN
14. The functional group which is found in amino acid is :
(a) COOH group (b)  NH2 group (c)  CH 3 group (d) Both (a) and (b)
15. Metal present in blood is :
(a) Al (b) Mg (c) Cu (d) Fe
16. Proteins are built up of –
(a) Dicarboxylic acids (b) Amino acids
(c) Alcohols (d) Hydroxy acids
17. The helical structure of proteins is established by –
(a) Peptide bonds (b) Dipeptide bond (c) Hydrogen bond (d) Vander Waal's forces
(NUCLEIC ACID)
18. A nucleotide consists of –
(a) Base and sugar (b) Base and phosphate
(c) Sugar and phosphate (d) Base, sugar and phosphate
19. Which of the following is responsible for heredity character?
(a) DNA (b) RNA (c) Proteins (d) Hormones
20. The base adenine occurs in –
(a) DNA only (b) RNA only
(c) DNA and RNA both (d) Protein
21. The protein which maintains blood sugar level in the human body?
(a) Haemoglobin (b) Oxytocin (c) Insulin (d) Ptyalin
22. In DNA, the complementary bases are:
(a) Uracil and adenine; cytosine and guanine (b) Adenine and thymine; guanine and cytosine
(c) Adenine and thymine; guanine and uracil (d) Adenine and guanine; thymine and cytosine
23. Which substance is not present in nucleic acid?
(a) Cytosine (b) Adenine (c) Thymine (d) Guanidine
24. The structure of DNA is:
(a) Linear (b) Single helix (c) Double helix (d) Triple helix
25. DNA contains the sugar –
(a) Deoxyribose (b) Ribose (c) D-Fructose (d) D-glucose
26. The base present in DNA, but not in RNA is :
(a) Guanine (b) Adenine (c) Uracil (d) Thymine
ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. c d c c c d a d b c
Q. No. 11 12 13 14 15 16 17 18 19 20
Ans. a c c d d b c d a c
Q. No. 21 22 23 24 25 26
Ans. c b d c a d
E 327
Chemistry
ALLEN
Note: In the following questions a statement of assertion followed by a statement of reason is

given. Choose the correct answer out of the following choices.
1. Assertion (A) : A solution of sucrose in water is dextrorotatory. But on hydrolysis in the
presence of a little hydrochloric acid, it becomes laevorotatory.
Reason (R) : Sucrose on hydrolysis gives unequal amounts of glucose and fructose. As a result
of this change in sign of rotation is observed.
2. Assertion (A) : DNA molecules and RNA molecules are found only in the nucleus of a cell.
Reason (R) : On heating, the enzymes do not lose their specific activity.
3. Assertion (A) : Haemoglobin is an oxygen carrier.
Reason (R) : Oxygen binds as O2 to Fe of haemoglobin.
4. Assertion (A) : Glycosides are hydrolysed in acidic conditions.
Reason (R) : Glycosides are acetals.
5. Assertion (A) : Carboxypeptidase is an exopeptidase.
Reason (R) : It cleaves the N-terminal bond.
6. Assertion (A) : Sucrose is a non-reducing sugar.
Reason (R) : It has glycosidic linkage.
7. Assertion (A) : Maltose is a reducing sugar which gives two moles of D-glucose on hydrolysis.
Reason (R) : Maltose has a 1,4--glycosidic linkage.
8. Assertion (A) : In the iodometric titration, starch is used as an indicator.
Reason (R) : Starch is a polysaccharide.
9. Assertion (A) : Alpha ()-amino acids exist as internal salt in solution as they have amino and
carboxylic acid groups in near vicinity.
Reason (R) : H+ ion given by carboxylic group (–COOH) is captured by amino group (–NH2)
having lone pair of electrons.
10. Assertion (A) : Millon's test is a test for identification of proteins.
Reason (R) : Millon's reagent is a solution of mercurous nitrate and mercuric nitrate in nitric acid
containing little nitrous acid.
11. Assertion (A) : -pleated sheet structure of protein shows maximum extension.
Reason (R) : Intermolecular hydrogen bonding is present in them.

12. Assertion (A) : Fructose is a reducing sugar.
Reason (R) : It has a ketonic group.
13. Assertion (A) : All enzymes are made up of proteins and all proteins have three dimensional
structures.
Reason (R) : Secondary structures of protein are sequence of amino acids.
328 E
CBSE
ALLEN
14. Assertion (A) : Insulin is water soluble.
Reason (R) : Insulin is a globular protein.
15. Assertion (A) : Solubility of proteins is minimum at the isoelectric point.
Reason (R) : At isoelectric point, protein molecule behaves as a zwitter ion.
16. Assertion (A) : Nucleotides are phosphate esters of nucleosides.
Reason (R) : The various nucleotides in nucleic acids are linked either through purine or
pyrimidine bases.
17. Assertion (A) : Glycine must be taken through diet.
Reason (R) : It is non-essential amino acid.
18. Assertion (A) : D (+) – Glucose is dextrorotatory in nature.
Reason (R) : ‘D’ represents its dextrorotatory nature.
19. Assertion (A) : All naturally occurring -amino acids except glycine are optically active.
Reason (R) : Most naturally occurring amino acids have L-configuration.
20. Assertion (A) : Sucrose is a non-reducing sugar.
Reason (R) : The reducing groups of glucose and fructose are involved in glycosidic bond
formation.
21. Assertion (A) : Invert sugar is laevorotatory.
Reason (R) : Sucrose is dextrorotatory.
22. Assertion (A) : Maltose is a non-reducing sugar.
Reason (R) : The free aldehyde group is present at C1 of second glucose in solution.
23. Assertion (A) : Lactose is a disaccharide.
Reason (R) : Hydrolysis of lactose gives -D-galatose and -D-glucose.
ANSWER KEY
Q. No. 1 2 3 4 5 6 7 8 9 10
Ans. c d c d c a c b a b
Q. No. 11 12 13 14 15 16 17 18 19 20
Ans. b b d b a c d c b b
Q. No. 21 22 23
Ans. d d c
E 329
Chemistry
ALLEN
CASE BASED QUESTIONS
Case-I
Carbohydrates are optically active polyhydroxy aldehydes and ketones. They are also called
saccharides. All those carbohydrates which reduce Fehling's solution and Tollen's reagent are
referred to as reducing sugars. Glucose, the most important source of energy for mammals, is
obtained by the hydrolysis of starch. Vitamins are accessory food factors required in the diet.
Proteins are the polymers of -amino acids and perform various structural and dynamic functions
in the organisms. Deficiency of vitamins leads to many diseases. (4) [CBSE 2023]
(a) The penta-acetate of glucose does not react with hydroxylamine. What does it indicate?
Ans. It indicating the absence of free –CHO group.
(b) Why cannot vitamin C be stored in our body?
Ans. Because it is water soluble vitamin and readily excreted in urine.
(c) Define the following as related to proteins :
(i) Peptide linkage
(ii) Denaturation
Ans. (i) Peptide linkage :
The amide formed between –COOH group of one molecule of an amino acid and –
NH2 group of another molecule of the amino acid by the elimination of a water
molecule is called a peptide linkage.
Peptide
linkage
–H2O
(ii) Denaturation :
When a protein in it's native form, is subjected to physical change, like change in
temperature or chemical change like change in pH, the hydrogen bonds are disturbed.
Due to this, globules unfold and helix get uncoiled and protein loses its biological
activity. This is called denaturation of protein.
OR
(c) Define the following as related to carbohydrates:
(i) Anomers
(ii) Glycosidic linkage
Ans. (i) -glucose and -D-glucose which have configuration isomer at C1 carbon is known
as Anomers.
(ii) A linkage between two monosaccharides units through an oxygen atom is called
glycosidic linkage.
330 E
CBSE
ALLEN
Case - II
Carbohydrates are also called saccharides. If a monosaccharide contains an aldehyde group, it is
known as an aldose and if it contains a keto group, it is known as a ketose. Glucose is the
monomer of many of the larger carbohydrates, namely starch, cellulose. Carbohydrates are also
called saccharides. All monosaccharides whether aldose or ketose are reducing sugars. Frutose is
an important ketohexose. It is obtained along with glucose by the hydrolysis of diasaccharide,
sucrose, Polysaccharides contain a large number of monosaccharide units joined together by
glycosidic linkages. These are the most commonly encountered carbohydrates in nature. they
mainly act as the food storage or structural materials.
(a) What is the molecular formula of glucose ?
Ans.
(b) Write the reaction for the preparation of glucose from sucrose ?
Ans.
(c) Write the structural and functional differences between RNA and DNA.
Ans. Structural differences between DNA and RNA are :
(a) In DNA, the pentose sugar is -D-2-deoxyribose but in RNA it is -D-ribose.
(b) The pyrimidine bases in DNA are cytosine and thymine, while in RNA, these are
cytosine and uracil.
(c) DNA has double stranded -helix structure, while RNA has single stranded -helix
structure.
(d) Molecular mass of DNA is higher than that of RNA.
Functional differences between DNA and RNA are :
(a) DNA has unique property of replication, while RNA generally does not have this
proeprty.
(b) DNA controls the transmission of hereditary characters, while RNA controls protein
synthesis.
OR
(i) What are the different types of RNA found in cell ?
(ii) Name the sugar present in milk. How many monosaccharide units are oligosaccharides
called ?
Ans. (i) Three types of RNA present in the cell are :
(a) ribosomal RNA (r-RNA)
(b) messenger RNA (m-RNA)
(c) transfer RNA (t-RNA)
(ii) Sugar present in milk is known as lactose. Two units of monosaccharides, i.e., -D-
galactose and -D-glucose are linked together. Hence, such oligosaccharides are
known as disaccharides.
6 6
CH2OH
CH2OH
OH 5 O
H H 5 OH
4 H
OH H 1 O 4
OH H 1
H 3 2 H
3 2 OH
Glycoside
H OH linkage
H OH
-D-galactose
-D-glucose
Lactose
E 331
Chemistry
ALLEN
1. An  - helix is a structural feature of (1) [CBSE 2023]
(a) Sucrose (b) Polypeptides
(c) Nucleotides (d) Starch
Ans. (b)
2. Proteins are polymers of (1) [CBSE 2023]
(a) Nucleic acids (b) Amino acids
(c) Monosaccharides (d) Amines
Ans. (b)
3. When D-glucose reacts with HI, it forms (1) [CBSE 2023]
(a) Gluconic acid (b) n-hexane
(c) Saccharic acid (d) Iodohexane
Ans. (b)
4. Glucose is oxidized by Br2 water to give : [1] (CBSE Term-1_2022)
CHO COOH COOH COOH
(a) (CHOH)4 (b) (CHOH)4 (c) (CHOH)4 (d) (CHOH)4
COOH CH2OH COOH CH3
Ans. (b)
CHO COOH
Bromine water
(CH–OH)4 (CH–OH)4
[O]
CH2–OH CH2–OH
Gluconic acid
5. Which of the following is fibrous protein ? [1] (CBSE Term-1_2022)

(a) Albumin (b) Keratin (c) Insulin (d) Globin
Ans. (b) Keratin
Examples of fibrous proteins are keratin (present in hair, wool, skilk) and myosin. (present
in muscles).
6. -D-Glucopyranose and -D-Glucopyranose are [1] (CBSE Term-1_2022)
(a) Isomers which differ in configuration at C-5
(b) Geometrical isomers

(c) Functional isomers
(d) Anomers
Ans. (d)
The two cyclic hemiacetal forms of glucose differ only in the configuration of the –OH group of
C-1, called anomeric carbon. Such isomers i.e. -forms and -form, are called Anomers.
332 E
CBSE
ALLEN
7. Two among the three components of DNA are 2-deoxyribose and a nitrogen containing
heterocyclic base. The third component is : [1] (CBSE Term-1_2022)
(a) D-ribose (b) Thymine (c) Guanine (d) Phosphoric acid
Ans. (d)
The components of DNA are
Pentose sugar + Nitrogenous base + Phosphoric acid
8. Which one among the following bases is usually not present in RNA ? (1) (CBSE Term-1_2022)
(a) Uracil (b) Thymine (c) Adenine (d) Guanine
Ans. (b)
Base present in DNA AGCT
Base present in RNA  AGCU
9. Glucose on reaction with (CH3CO)2O forms glucose pentaacetate which confirms the presence of
[1] [CBSE Compartment 2021]
(a) –CHO group (b) –COOH group (c) Five –OH groups (d) A straight chain
Ans. (c)
CHO O O CHO O
(CH–OH)4 + 5CH3 –C–O – C– CH3 (CH–O–C–CH3)4 + 5CH3 COOH
  O
CH2–OH
CH2–O–C–CH3
Glucose penta acetate
Glucose react with acetic an hydride to form glucose penta acetic which shows that of a glucose
moleculer contain five –OH groups.
10. Name the unit formed by the attachment of a base to 1 position of sugar.
[1] (CBSE Compartment 2021)
Ans. Nucleoside
11. What are the products of hydrolysis of lactose? (1) [CBSE 2020]
Ans. Lactose is C12H22O11 a disaccharide with a glucose and a galactose unit present in pyranose form
so on hydrolyzing it we will obtain glucose and galactose.
12. Write the structure of the product obtained when glucose is oxidised with nitric acid.
(1) [CBSE 2020]
COOH
Ans. Saccharic acid (dicarboxylic acid) (CHOH)4
COOH
13. Name the four bases present in DNA. Which one of these is not present in RNA ?
(1) [CBSE 2019]

Ans. DNA contains four bases viz adenine (A), guanine (G), cytosine (C) and thymine (T). RNA also
contains four bases, first three bases are same as in DNA but the fourth one is uracil (U).
14. Write two main functions of carbohydrates in plants. (1) [CBSE 2018]
Ans. Main Functions of Carbohydrates in plants :
(i) Carbohydrates are used as storage molecules as starch in plants.
(ii) Cell wall of bacteria and plants is made up of cellulose.
E 333
Chemistry
ALLEN
15. Write two difference between DNA and RNA. (2) [CBSE 2023]
Ans. The structural differences between DNA and RNA are as follows :
DNA RNA
1. The sugar moiety in DNA The sugar moiety in RNA molecules is -D
molecules is -D-2 deoxyribose. ribose.
2. DNA contains thyamine (T). It does RNA contains uracil (U). It does not contain
not contain Uracil (U). thymine (T).
3. The helical structure of DNA is The helical structure of RNA is single-stranded.
double-stranded.
16. What are nucleic acids? Why two strands in DNA are not identical but are complementary?
(2) [CBSE 2023]
Ans. Nucleic acids are biomolecules found in the nuclei of all living cells, as one of the constituents of
chromosomes. There are mainly two types of nucleic acids - deoxyribonucleic acid (DNA) and
ribonucleic acid (RNA). Nucleic acid are also known as polynucleotides as they are long-chain
polymers of nucleotides.
In the helical structure of DNA, the two strands are held together by hydrogen bonds between
specific pairs of bases. Cytosin forms hydrogen bond with guanine, while adenine forms
hydrogen bonds with thymine. As a result, the two strands are complementary to each other.
17. (a) What is the difference between a nucleoside and nucleotide ?
(b) What products would be formed when a nucleotide from DNA containing thymine is
hydrolysed ? (2) [CBSE 2023]
Ans. (a) Nucleoside : A nucleoside has chemical composition that consists of a sugar and a base
without the phosphate group.
Nucleotide: The chemical composition of nucleotide consists of a phosphate group, a
sugar and a nitrogenous base.
(b) When a nucleotide from the DNA containing thymine is hydrolyzed, thymine,
-D-2-deoxyribose and phosphoric acid are obtained as products.
18. Define vitamins and classify them on the basis of their solubility. [2]
OR
Define proteins and classify them on the basis of their molecular shape. [2]
(CBSE Compartment 2021)
Ans. On the basis of their solubility in water or fat, vitamins are classified into two groups.
(i) Fat-soluble vitamins : Vitamins that are soluble in fat and oils, but not in 'water, belong to
this group. For example: Vitamins A, D, E, and K
(ii) Water-soluble vitamins : Vitamins that are soluble in water belong to this group. For
example : B group vitamins (B1, B2, B6, B12, etc.) and vitamin C
However, biotin or vitamin H is neither soluble in water nor in fat.
Vitamin K is responsible for the coagulation of blood.
334 E
CBSE
ALLEN
OR
Proteins : These are macro molecules made up of amino acids joined by amide linkage is called
as peptide linkage. These are required for growth and development of the body.
On the basis of their molecular shape, proteins are of two types.
(A) Fibrous Protein
(i) Polypeptide chains run parallel or anti- parallel and held together by hydrogen and
disulphide bonds.
(ii) Generally insoluble in water e.g., keratin, collagen, myosin, fibroin.
(B) Globular Protein
(i) Chains of polypeptide coil around to give a spherical shape.
(ii) Usually soluble in water, eg. insulin, thyroglobin, albumin, haemoglobin and
fibrinogen gets converted into fibrous protein fibroin on clotting of blood.
19. Write the main structural difference between DNA and RNA. Of the four bases, name those
which are common to both DNA and RNA. (2) [CBSE 2019]
Ans. DNA is double stranded -helix structure in which two strands are coiled spirally in opposite
directions. RNA has single stranded -helix structure. DNA contains four bases namely, adenine
(A), guanine (G), cytosine (C) and thymine (T).
20. Explain what is meant by the following: (3) [CBSE 2020]
(i) peptide linkage
(ii) pyranose structure of glucose
Ans. (i) Disaccharides onhydrolysis with dilute acids or enzymes yield two molecules of either the
same or different monosaccharides. The two monosaccharides are ionied together by an
oxide linkage formed by the loss of a water molecule. Such a linkage between two
monosaccharides units through oxygen atom is called glycosidic linkage.
(ii) Proteins are the polymers of -amino acids and they are connected to each other by peptide
bond or peptide linkage. Chemically, peptide linkage is an amide formed between –COOH
group and –NH2 groups.
21. Amino acids may be acidic, alkaline of neutral, How does this happen? What are essential and
non-essential amino acids? Name one of each type. (3) [CBSE 2020]
Ans. Amino acids are classified as acidic, basic or neutral depending upon the relative number of
amino and carboxyl groups in their molecule.
Equal number of amino and carboxyl groups makes it neutral; more number of amino thatn
carboxyl group makes it basic and more carboxyl groups as compared to amino groups makes it
acidic.
E 335
Chemistry
ALLEN
Essential amino acids : The amino acids which cannot be synthesised in the body and must be
obtained through diet, are known as essential amino acids.
Example: Valine, Leucine.
Non-essential acids : The amino acids, which can be synthesised in the body are known as
non-essential amino acids.
Example : Alanine, Aspartic acid.
22. What happens when D-glucose is treated with the following regents ? (3) [CBSE 2020]
(i) HI (ii) Bromine water (iii) HNO3
Ans. (i) On prolonged heating with HI, D-glucose forms n-hexane.
CHO
(CHOH)4 HI,  CH3–CH2–CH2–CH2–CH2–CH3

n-Hexane
CH2OH
D-Glucose
(ii) D-glucose gets oxidised to six carbon carboxylic acid (gluconic acid) on reaction with
brominewater
CHO
Br2 water
(CHOH)4 COOH
CH2OH (CHOH)4
D-glucose CH2OH
Gluconic acid
(iii) On oxidation with nitric acid, D-glucose yields a saccharic acid.
CHO COOH
HNO3
(CHOH)4 (CHOH)4
Oxidation
CH2OH COOH
D-glucose D-saccharic acid
23. (i) Which one of the following is a disaccharide :
starch, maltose, fructose, glucose
(ii) What is the difference between acidic amino acid and basic amino acid?
(iii) Write the name of the linkage joining two nucleotides. (3) [CBSE 2019]
Ans. (i) Maltose
(ii) In acidic amino acid more carboxyl groups as compared to amino groups are present & In
basic amino acid more number of amino than carboxyl groups are present
(iii) Phosphodiester linkage
336 E
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ALLEN
24. Define the following terms: (3) [CBSE 2019]
(i) Nucleotide
(ii) Anomers
(iii) Essential amino acids
Ans. (i) All the three basic components of nucleic acids (i.e., pentose sugar, phosphoric acid, and
base) are present in a nucleotide.
Nucleotide = Sugar + Base + Phosphoric acid
O
5' O
O——P—O—H2C Base
O — 4' 1'
HH HH
3' 2'
OH OH
Structure of a nucleotide
(ii) -D-glucose and -D-glucose which have configuration isomer at C1 carbon is known as
Anomers
(iii) Essential amino acids are required by the human body, but they cannot be synthesised in
the body. They must be taken through food. For example : valine and leucine
25. Shanti, a domestic halper of Mrs. Anuradha, fainted while mopping the floor. Mrs. Anuradha
immediately took her to the nearby hospital where she was diagnosed to be severely ‘anaemic’.
The doctor prescribed an iron rich diet and multivitamins supplement to her. Mrs. Anuradha
supported her financially to get the medicines. After a month, Shanti was diagnosed to be normal.
After reading the above passage, answer the following questions: (3) [CBSE 2019]
(i) What values are displayed by Mrs. Anuradha?
(ii) Name the vitamin whose deficiency causes ‘pernicious anaemia’.
(iii) Give an example of a water soluble vitamin.
Ans. (i) Mrs. Anuradha has shown care, responsibility and helping nature.
(ii) Iron
(iii) Vitamin B and Vitamin C
26. Define the following with an example of each : (3) [CBSE 2018]
(a) Polysaccharides
(b) Denatured protein
(c) Essential amino acids
Ans. (a) Polysaccharides  The compound that have large no. of monosaccarides unit on
hydrolysis.
Ex  Starch, Cellulose etc.
(b) Denatured protein  Due to the change in temperature on pH secondary & tertiary
structure are destroyed but primary structure remain intact.
Ex  Coagulation of egg white on boiling
(c) Essential amino acids  The amino acids which cannot be synthesised in the body &
must be obtanied through diet.
Eg  Valine, Leucine
E 337
Chemistry
ALLEN
27. (a) Which polysaccharide component of carbohydrates is commonly present in bread ?
(b) Write the two types of secondary structures of proteins ?
(c) Give two examples of water soluble vitamins ? (3) [CBSE 2018]
Ans. (a) Starch
(b) -Helix and -pleated sheets
(c) Vitamin B/B1/B2/B6/C (any two)
28. What is essentially the difference between -glucose and -glucose ? What is meant by pyranose
structure of glucose ? (3) [CBSE 2018]
Ans. The six membered cyclic structure of glucose is called pyranose structure.
6 6
CH2OH CH2OH
5 O 5 O
H H H OH
H H
4 1 4 1
OH H OH H
HO 3 2 OH HO 3 2 H
H OH H OH
 – D glucose  – D glucose
29. Carbohydrates are optically active polyhydroxy aldehydes and ketones. They are also called
saccharides. All those carbohydrates which reduce Fehling's solution and Tollen's reagent are
referred to as reducing sugars. Glucose, the most important source of energy for mammals, is
obtained by the hydrolysis of starch. Vitamins are accessory food factors required in the diet.
Proteins are the polymers of -amino acids and perform various structural and dynamic functions
in the organisms. Deficiency of vitamins leads to many diseases. (4) [CBSE 2023]
(a) The penta-acetate of glucose does not react with hydroxylamine. What does it indicate?
(b) Why cannot vitamin C be stored in our body?
(c) Define the following as related to proteins :
(i) Peptide linkage
(ii) Denaturation
OR
(c) Define the following as related to carbohydrates:

(i) Anomers
(ii) Glycosidic linkage
Ans. (a) It indicating the absence of free –CHO group.
(b) Because it is water soluble vitamin and readily excreted in urine.
338 E
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ALLEN
(c) (i) Peptide linkage :
The amide formed between –COOH group of one molecule of an amino acid and –NH2
group of another molecule of the amino acid by the elimination of a water molecule is
called a peptide linkage.
Peptide
linkage
–H2O
(ii) Denaturation :
When a protein in it's native form, is subjected to physical change, like change in
temperature or chemical change like change in pH, the hydrogen bonds are disturbed. Due
to this, globules unfold and helix get uncoiled and protein loses its biological activity. This
is called denaturation of protein.
OR
(i) -glucose and -D-glucose which have configuration isomer at C1 carbon is known as
Anomers.
(ii) A linkage between two monosaccharides units through an oxygen atom is called glycosidic
linkage.
30. Strengthening the Foundation: Chargaff Formulates His "Rules"
Many people believe that James Watson and Francis Crick discovered DNA in the 1950s.
In reality, this is not the case. Rather, DNA was first identified in the late 1860s by
Swiss chemist Friedrich Miescher. Then, in the decades following Miescher's discovery, other
scientists--notably, Phoebus Levene and Erwin Chargaff--carried out a series of research efforts
that revealed additional details about the DNA molecule, including its primary chemical
components and the ways in which they joined with one another. Without the scientific
foundation provided by these pioneers, Watson and Crick may never have reached their ground
breaking conclusion of 1953: that the DNA molecule exists in the form of a three-dimensional
double helix.
Chargaff, an Austrian biochemist, as his first step in this DNA research, set out to see whether
there were any differences in DNA among different species. After developing a new paper
chromatography method for separating and identifying small amounts of organic material,
Chargaff reached two major conclusions:
(i) The nucleotide composition of DNA varies among species.
(ii) Almost all DNA, no matter what organism or tissue type it comes from maintains certain
properties, even as its composition varies. In particular, the amount of adenine (A) is
similar to the amount of thymine (T), and the amount of guanine (G) approximates the
amount of cytosine (C). In other words, the total amount of purines
(A + G) and the total amount of pyrimidines (C + T) are usually nearly equal. This
conclusion is now known as "Chargaff's rule."
Chargaff’s rule is not obeyed in some viruses. These either have single- stranded DNA or
RNA as their genetic material.
E 339
Chemistry
ALLEN
Answer the following questions:
(a) A segment of DNA has 100 adenine and 150 cytosine bases. What is the total number of
nucleotides present in this segment of DNA?
Ans. A = 100 so T = 100
C = 150 so G = 150
Total nucleotides = 100 + 100 + 150 + 150 = 500
(b) A sample of hair and blood was found at two sites. Scientists claim that the samples belong
to same species. How did the scientists arrive at this conclusion?
Ans. They studied the nucleotide composition of DNA. It was the same so they concluded that
the samples belong to same species.
(c) The sample of a virus was tested and it was found to contain 20% adenine,
20% thymine, 20 % guanine and the rest cytosine. Is the genetic material of this virus (a)
DNA-double helix (b) DNA-single helix (c) RNA? What do you infer from this data?
Ans. A = T = 20%
But G is not equal to C so double helix is ruled out.
The bases pairs are ATGC and not AUGC so it is not RNA
The virus is a single helix DNA virus
OR
How can Chargaff’s rule be used to infer that the genetic material of an organism is
double- helix or single- helix?
Ans. According to Charagraff rule, all double helix DNA will have the same amount of A and T as
well as C will be same amount as G. If this is not the case then the helix is single stranded.
31. (a) Write the product when D-glucose reacts with conc. HNO3. (5) [CBSE 2019]
(b) Amino acids show amphoteric behaviour. Why ?
(c) Write one difference between -helix and -pleated structures of proteins.
(d) Write one reaction of D-Glucose which cannot be explained by its open chain structure.
(e) Give one example each for water-soluble vitamins and fat-soluble vitamins?
Ans. (a)
340 E
CBSE
ALLEN
(b) The amino acids contains both acidic –COOH group & basic –NH2 (amino) group in their
structure, due to which they can exist both as acid & base, this nature is called Amphoteric
nature
O
R – CH – C – OH (-amino acid)
NH2
:
(c) In -helix, a polypeptide chain form by all possible hydrogen bonds by twisting into a right
handed helical structure with –NH group of each amino acid.
In -pleated all peptide chains are stretched out to nearly extensions & then laid side by
side which are held together by intomolecular hydrogen bonding.
(d) Sodium Hydrogen Sulphite reaction/ Pentaacetate of glucose does not react with
Hydroxylamine/Schiff’s test (any one)
(e) Fat soluble - Vitamin A/D /E/ K
Water soluble - Vitamin B /C
E 341
Chemistry
ALLEN
PRACTICE TEST
SECTION-A
1. Deficiency of which vitamin causes osteomalacia? [1]
(a) Vitamin A (b) Vitamin D
(c) Vitamin K (d) Vitamin E
2. Which of the following statement is not true about glucose ? [1]
(a) It is an aldohexose. (b) It contains five hydroxyl groups.
(c) It is a reducing sugar. (d) It is an aldopentose.
3. Sucrose on hydrolysis gives : [1]
(a) -D-Fructose +-D-Fructose (b) -D-Glucose +-D-Fructose
(c) -D-Glucose + -D-Glucose (d) -D-Glucose + -D-Fructose
4. Which structure(s) of proteins remains(s) intact during denaturation process ? [1]
(a) Both secondary and tertiary structures (b) Primary structure only
(c) Secondary structure only (d) Tertiary structure only
5. The non-essential amino acid among the following is : [1]
(a) valine (b) leucine (c) alanine (d) lysine
Note: In the following questions a statement of assertion followed by a statement of reason is
given. Choose the correct answer out of the following choices.
6. Assertion (A) : The two strands in double strand helix structure of DNA are complementary to
each other.
Reason (R) : Disulphide bonds are formed between specific pairs of bases. [1]
7. Assertion (A) : Glucose reacts with hydroxylamine to form an oxime and also adds a molecule
of hydrogen cyanide to give cyanohydrin.
Reason (R) : The carbonyl group is present in the open chain structure of glucose. [1]
SECTION-B
8. Write the two types of secondary structures of proteins ? [2]
9. Write one difference between -helix and -pleated structures of proteins. [2]
10. Amino acids show amphoteric behaviour. Why ? [2]
11. What are essential and non-essential amino acids? Name one of each type. [2]
342 E
CBSE
ALLEN
SECTION-C
12. Write the main structural difference between DNA and RNA. Of the four bases, name those
which are common to both DNA and RNA. [3]
13. What is essentially the difference between -glucose and -glucose ? What is meant by pyranose
structure of glucose ? [3]
SECTION-D
14. Organic compounds containing amine as functional group are present in a vivid variety of
compounds, namely amino acids, hormones, neurotransmitters, DNA, alkaloids, dyes, etc. Drugs
including nicotine, morphine, codeine and heroin, etc. which have physiological effects on
humans also contain amino group in one form or another. Amines are basic because of the
presence of lone pair of electrons on nitrogen. Addition of nitrogen into an organic framework
leads to the formation of two families of molecules, namely amines and amides. As chemistry
students, we must appreciate the versatility of nitrogen. [1+1+2=4]
(a) What are the products of hydrolysis of maltose ?
(b) What type of bonding provides stability to -helix structure of protein ?
(c) What is the basic structural difference between starch and cellulose ?
OR
What is the difference between amylose and amylopectin ?
SECTION-E
15. Define the following terms: [5]
(i) Nucleotide
(ii) Anomers
(iii) Native protein
(iv) Denatured protein
(v) Essential amino acids
E 343
Chemistry
ALLEN
SECTION-A
1. b
2. d
3. d
4. b
5. c
6. c
7. a
SECTION-B
8. -Helix and -pleated sheets.
9. In a-helix, a polypeptide chain form by all possible hydrogen bonds by twisting into a right
handed helical structure with –NH group of each amino acid.
In -pleated all peptide chains are stretched out to nearly extensions & then laid side by side
which are held together by intermolecular hydrogen bonding.
10. The amino acids contains both acidic –COOH group & basic –NH2 (amino) group in their
structure, due to which they can exist both as acid & base, this nature is called Amphoteric nature
O
R – CH – C – OH (-amino acid)
NH2

11. Essential amino acids : The amino acids which cannot be synthesised in the body and must be
obtained through diet, are known as essential amino acids.
Example: Valine, Leucine.
Non-essential acids : The amino acids, which can be synthesised in the body are known as non-
essential amino acids.
Example : Alanine, Aspartic acid.
SECTION-C
12. DNA is double stranded -helix structure in which two strands are coiled spirally in opposite
directions.
RNA has single stranded a-helix structure. DNA contains four bases namely, adenine (A),
guanine (G), cytosine (C) and thymine (T).
13. The six membered cyclic structure of glucose is called pyranose structure.
6 6
CH2 OH CH2 OH
5 O 5 O
H H H OH
H H
4 1 4 1
OH H OH OH H
HO 3 2 HO 3 2 H
H OH H OH
 – D glucose  – D glucose
344 E
CBSE
ALLEN
SECTION-D
14. (a) 2 moles of -D-Glucose
(b) Intra molecular hydrogen bonding
(c) Starch is a polymer of -glucose whereas cellulose is a polymer of -glucose.
OR
Amylose is a straight chain polymer whereas amylopectin is a branched chain polymer.
SECTION-E
15. (i) A unit formed by the combination of nitrogenous base, sugar and phosphate.
(ii) -D-glucose and -D-glucose which have configuration isomer at C1 carbon is known as
Anomers
(iii) Protein found in biological system with unique three dimesion structure and biological
activity is called native protein.
(iv) Denatured protein  Due to the change in temperature on pH secondary & tertiary
structure are destroyed but primary structure remain intact.
Ex  Coagulation of egg white on boiling
(v) Essential amino acids are required by the human body, but they cannot be synthesised in
the body.
They must be taken through food. For example : valine and leucine
E 345
Chemistry
ALLEN
NAME REACTIONS
1. Sandmeyer Reaction :
The Cl , Br and CN nucleophiles can easily be introduced in the benzene ring of benzene
diazonium salt in the presence of Cu(I) ion. This reaction is called Sandmeyer reaction.
2. Gatterman Reaction :
Chlorine or bromine can be introduced in the benzene ring by treating the benzene diazonium
salt solution with corresponding halogen acid in the presence of copper powder. This is referred
as Gatterman reaction.
Cu/HCl
ArCl + N2 + CuX
+ –
ArN 2X
Cu/HBr ArBr + N2 + CuX
Note : The yield in Sandmeyer reaction is found to be better than Gattermann reaction.
3. Balz-Schiemann Reaction :
When benzenediazonium chloride is treated with fluoroboric acid, benzene diazonium
fluoroborate is precipitated which on heating decomposes to yield aryl fluoride.
 
Ar N 2 Cl   HBF4 
 Ar  N 2 BrF4 
Heat
 Ar  F  BF3  N 2
Fluoroboric acid
4. Finkelstein Reaction :
Alkyl iodides are often prepared by the reaction of alkyl chlorides/ bromides with NaI in dry
acetone. This reaction is known as Finkelstein reaction.

R – X + NaI  R – I + NaX
(X = Cl, Br)
Note : This reaction in forward direction can be favoured by precipitating NaX formed in dry
acetone (according to Le Chatelier’s principle)
346 E
CBSE
ALLEN
5. Swarts Reaction : Heating an alkyl chloride/bromide in the presence of a metallic fluoride such
as AgF, Hg2F2, CoF2 or SbF3 gives alkyl fluorides. The reaction is termed as Swarts reaction.
H3C – X + AgF  H3C – F + AgX
(X = Cl, Br)
Note : Finkelstein Reaction and Swarts Reaction are known as halogen exchange reaction.
6. Wurtz Reaction : Alkyl halides react with sodium in dry ether to give hydrocarbons containing
double the number of carbon atoms present in the halide. This reaction is known as Wurtz
reaction.
CH 3Br  2Na  BrCH 3 
dry ether
 CH 3  CH 3  2NaBr
Bromomethane Ethane
C 2 H 5 Br  2Na  BrC 2 H 5 
dry ether
 C2 H5  C2 H5
Bromoethane n  Butane
7. Wurtz-Fitting Reaction : A mixture of an alkyl halide and aryl halide gives an alkylarene when
treated with sodium in dry ether and is called Wurtz-Fitting reaction.
X R
Ether
+ Na + RX + Na X
8. Fitting Reaction : Aryl halides also give analogous compounds when treated with sodium in dry
ether, in which two aryl groups are joined together. It is called Fitting reaction.
X
Ether
2 + Na + 2NaX
9. Friedel-Crafts alkylation Reaction : When benzene is treated with an alkyl halide in the
presence of anhydrous aluminium chloride, alkylbenene is formed.
CH3
Anhyd. AlCl 3
+ CH3Cl + HCl
Toluene
(13.75)
C2H 5
Anhyd. AlCl 3
+ C2H5Cl + HCl
Ethylbenzene
Cl Cl Cl
CH3
Anhyd. AlCl 3
+ CH3Cl
1-Chloro-2-methylbenzene CH3
(Minor)
(Major)
OCH3 Cl OCH3
CH3
Anhyd. AlCl 3
+ CH3Cl CS2 +
2-Methoxytoluene CH3
(Minor)
4-Methoxytoluene
(Major)
Note : Aromatic carboxylic acids do not undergo Friedel-Crafts reaction because the carboxyl
group is deactivating and the catalyst aluminium chloride (Lewis acid) gets bonded to the
carboxyl group.
E 347
Chemistry
ALLEN
10. Friedel-Crafts acylation reaction : The reaction of benzene with an acyl halide or acid
anhydride in the presence of Lewis acids (AlCl3) yields acyl benzene.
COCH3
Anhyd. AlCl3
+ CH3COCl  + HCl
Acetylchloride
Acetophenone
COCH3
Anhyd. AlCl 3
+ (CH3CO)2O  + CH3COOH
Acetic anhydride
Cl Cl O Cl
O
Anhyd. AlCl3 CH3
+ H3C–C–Cl +
(Minor) O CH3
(Major)
OCH3 OCH3 OCH3

COCH 3
Anhyd. AlCl3
+ CH3COCl +
Ethanoyl
chloride 2-Methoxy- COCH 3
acetophenone
4-Methoxy-
(Minor)
acetophenone
(Major)
11 Reimer-Tiemann Reaction : On treating phenol with chloroform in the presence of sodium
hydroxide, a –CHO group is introduced at ortho position of benzene ring resulting
salicylaldehyde. This reaction is known as Reimer - Tiemann reaction.
– –
OH O Na+ O Na+ OH
CHCl2 CHO CHO
CHCl3 + aq NaOH NaOH H+
12. Kolbe’s Reaction : Phenol with sodium hydroxide gives sodium phenoxide ion which with
carbon dioxide in acidic medium results hydroxybenzoic acid (salicylic acid). This is known as
Kolbe’s reaction.
OH ONa OH
COOH
NaOH (i) CO2
(ii) H+
(Salicylic acid)
348 E
CBSE
ALLEN
13. Rosenmund Reduction : Acyl chloride (acid chloride) is hydrogenated over catalyst, palladium
on barium sulphate. This reaction is called Rosenmund reduction.
O
C CHO
Cl H2
Pd – BaSO4
Benzoyl chloride Benzaldehyde
14. Stephen reaction :


RCN  SnCl 2  HCl 

 RCH  NH 
H3 O
 RCHO
Nitriles are reduced to corresponding imine with stannous chloride in the presence of
hydrochloric acid, which on hydrolysis give corresponding aldehyde. This reaction is called
Stephen reaction.
15. Etard reaction : Chromyl chloride oxidizes methyl group to a chromium complex, which on
hydrolysis gives corresponding benzaldehyde. This reaction is called Etard reaction.
CH3 CH(OCrOHCl2)2 CHO
CS2 H3O+
+ CrO2Cl2
Toluene Chromium complex Benzaldehyde
16. Gatterman Koch Reaction : When benzene or its derivative is treated with carbon monoxide
and hydrogen chloride in the presence of anhydrous aluminium chloride or cuprous chloride, it
gives benzaldehyde or substituted benzaldehyde. This reaction is known as Gatterman-Koch
reaction.
CHO
CO, HCl
Anhyd. AlCl3/CuCl
Benzene Benzaldehyde
17. Clemmensen Reduction : The carbonyl group of aldehydes and ketones is reduced to CH2
group on treatment with zincamalgam and concentrated hydrochloric acid. This is known as
Clemmensen reduction.
Zn-Hg
C=O CH2 + H2O (Clemmensen reduction)
HCl
18. Wolff Kishner Reduction : The carbonyl group of aldehydes and ketones is reduced to CH2
group on treatment with hydrazine followed by heating with sodium or potassium hydroxide in
high boiling solvent such as ethylene glycol. This is known Wolff Kishner reduction.
NH2NH2 KOH/ethylene glycol
C=O C=NNH2 CH2 + N2
–H2O heat
(Wolff-Kishner reduction)
E 349
Chemistry
ALLEN
19. Tollens’ test : On warming an aldehyde with freshly prepared ammoniacal silver nitrate solution
(Tollens’ reagent), a bright silver mirror is produced due to the formation of silver metal. The
aldehydes are oxidised to corresponding carboxylate anion. The reaction occurs in alkaline
medium.
 
RCHO  2[Ag(NH 3 )2 ]  3O H 
 RCO O  2Ag  2H 2 O  4NH 3
Silver Mirror
20. Fehling’s test : Fehling reagent comprises of two solutions, Fehling solution A and Fehling
solution B. Fehling solution A is aqueous copper sulphate and Fehling solution B is alkaline
sodium potassium tartarate (Rochelle salt). These two solutions are mixed in equal amounts
before test. On heating an aldehyde with Fehling’s reagent, a reddish brown precipitate is
obtained. Aldehydes are oxidised to corresponding carboxylate anion. Aromatic aldehydes do
not respond to this test.
 
R  CHO  2Cu2   5O H 
 RCO O  Cu 2 O  3H 2 O
Re d  brown ppt
21. Aldol reaction : Aldehydes and ketones having at least one a-hydrogen undergo a reaction in the
presence of dilute alkali as catalyst to form b-hydroxy aldehydes (aldol) or b-hydroxy ketones
(ketol), respectively. This is known as Aldol reaction. The name aldol is derived from the names
of the two functional groups, aldehyde and alcohol, present in the products.
(i) Aldol condensation : The aldol and ketol readily lose water to give a, b-unsaturated carbonyl
compounds which are aldol condensation products and the reaction is called Aldol
condensation.
dil. NaOH
2 CH3–CHO CH3–CH–CH 2–CHO  CH3–CH=CH–CHO
Ethanal –H2O But-2-enal
OH (Aldol condensation product)
(Aldol)
3-Hydroxybutanal
(ii) Cross aldol condensation : When aldol condensation is carried out between two different
aldehydes and / or ketones, it is called cross aldol condensation. If both of them contain a-
hydrogen atoms, it gives a mixture of four products.
CH3CHO 1. NaOH CH3–CH=CH–CHO + CH3CH2–CH=C–CHO
+ 2.  But-2-enal
CH3CH2CHO CH3
CH3–CH=C–CHO + CH3CH2–CH=CHCHO
CH3
2-Methylbut-2-enal Pent-2-enal
350 E
CBSE
ALLEN
22. Cannizzaro reaction : Aldehydes which do not have an -hydrogen atom, undergo self
oxidation and reduction (disproportionation) reaction on treatment with concentrated alkali. In
this reaction, one molecule of the aldehyde is reduced to alcohol while another is oxidised to
carboxylic acid salt.
H O
H H
C=O + C=O + Conc. KOH H–C–OH + H–C
H H OK
H
Methanol Potassium formate
2 CHO + Conc. NaOH CH2OH + COONa
Benzaldehyde Benzyl alcohol Sodium benzoate
23. Kolbe electrolysis : An aqueous solution of sodium or potassium salt of a carboxylic acid on
electrolysis gives alkane containing even number of carbon atoms. It is decarboxylation reaction.
The reaction is known as Kolbe electrolysis.
2CH 3COO  Na   2H 2O
Sodium acetate
 Electrolysis
CH 3 – CH 3  2CO 2  H 2  2NaOH
24. Hell-Volhard-Zelinsky (HVZ )reaction : Carboxylic acids having an -hydrogen are

halogenated at the -position on treatment with chlorine or bromine in the presence of small
amount of red phosphorus to give -halocarboxylic acids. The reaction is known as Hell-
Volhard-Zelinsky reaction.
(i) X2/Red phosphorus
R–CH2–COOH (ii) H O R–CH–COOH
2
X
X = Cl, Br
–Halocarboxylic acid
25. Gabriel phthalimide synthesis : Gabriel synthesis is used for the preparation of pure primary
amines.
Phthalimide on treatment with ethanolic potassium hydroxide forms potassium salt of

phthalimide which on heating with alkyl halide followed by alkaline hydrolysis produces the
corresponding primary amine.
E 351
Chemistry
ALLEN
O O O
C KOH C – + R–X C
N–H NK N–R
C C C
O O O
Phthalimide N-Alkylphthalimide
O
O
C –
NaOH(aq) C ONa+
N–R – +
+ R – NH2
C ONa (1° amine)
C
O
O
Note : Aromatic primary amines cannot be prepared by this method because aryl halides do not
undergo nucleophilic substitution with the anion formed by phthalimide.
26. Hoffmann bromamide degradation reaction : An amide with bromine in an aqueous or
ethanolic solution of sodium hydroxide gives primary amines.
In this degradation reaction, migration of an alkyl or aryl group takes place from carbonyl carbon
of the amide to the nitrogen atom. The amine so formed contains one carbon less than that
present in the amide.
O
R–C–NH2 + Br2 + 4NaOH R–NH2 + Na2CO3 + 2NaBr + 2H 2O
27. Carbylamine reaction : Aliphatic and aromatic primary amines on heating with chloroform and
ethanolic potassium hydroxide form isocyanides or carbylamines which are foul smelling
substances. This reaction is known as carbylamines reaction or isocyanide test.
R  NH 2  CHCl3  3KOH 
Heat
 R  NC  3KCl  3H 2 O
Note : Secondary and tertiary amines do not show this reaction and is used as a test for primary
amines.
28. Hinsberg’s Test : Benzenesulphonyl chloride (C6H5SO2Cl), which is also known as Hinsberg’s
reagent, reacts with primary and secondary amines to form sulphonamides.
(i) The reaction of benzenesulphonyl chloride with primary amine yields N
ethylbenzenesulphonyl amide. The hydrogen attached to nitrogen in sulphonamide is strongly
acidic due to the presence of strong electron withdrawing sulphonyl group. Hence, it is soluble
in alkali.
O O
S–Cl + H–N–C2H5 S–N–C2H5 + HCl
O H O H
N-Ethylbenzenesulphonamide
(soluble in alkali)
352 E
CBSE
ALLEN
(ii) In the reaction with secondary amine, N,N-diethylbenzenesulphonamide is formed. Since
N, N-diethylbenzene sulphonamide does not contain any hydrogen atom attached to nitrogen
atom, it is not acidic and hence insoluble in alkali.
O O
S–Cl + H–N–C2H5 H3 C S–N–C2H5 + HCl
(insoluble in alkali)
O C2H 5 O C2H 5
N,N-Diethylbenzenesulphonamide
(iii) Tertiary amines do not react with benzenesulphonyl chloride.

Note : This test is used for the distinction of primary, secondary and tertiary amines and also for
the separation of a mixture of amines. However, these days benzenesulphonyl chloride is
replaced by p-toluenesulphonyl chloride.
29. Coupling Reactions : Benzene diazonium chloride reacts with phenol in which the phenol
molecule at its para position is coupled with the diazonium salt to form p-hydroxyazobenzene.
This type of reaction is known as coupling reaction.
–
+ – OH
NN Cl + H OH N=N OH + Cl– + H2O
p-Hydroxyazobenzene (orange dye)
Similarly the reaction of diazonium salt with aniline yields p-aminoazobenzene.

–
+ – OH
NN Cl + H NH2 N=N NH2 + Cl– + H2O
p-Aminoazobenzene
(yellow dye)
E 353
Chemistry
ALLEN
CHEMICAL TEST
0
I. Primary, Secondary and Tertiary alcohol
Test 1º Alcohol 2º Alcohol 3º Alcohol

(i)
(1) Add Lucas reagent No change Turbidity appears Turbidity appears
Anhyd. ZnCl
ZnCl22 + Conc. HCl within 5 minutes immediately
(ii) Carbonic compound + Lucas reagent

Test Propan-1-ol Propan-2-ol
OH
CH3CH2CH2OH CH3–CH–CH 3
(1) Lucas Test No change Turbidity appears within
Add Lucas Reagent 5 minutes.
(Anhydrous ZnCl2 + HCl)
(2) Iodoform Test No change Yellow precipitate of CHl3
Add I2 / NaOH
(iii)
Test Ethanol Propan-2-ol
(1) Add Lucas Reagent

No change Tubidity within 5 minutes
ZnCl2 + HCl)
(Anhydrous ZnCl2
(iv) Test Enthanol  C2 H5OH  Pr opan  1  ol  CH3CH 2CH 2OH 

(1) Add I2 / NaOHand heat Yellow iodo / form  CHl3  Nochange
(v) Test Ethanol  CH 3CH 2OH  Methanol  CH3OH 

(1) Add I 2 / NaOH and heat Yellow procipitateof CHI3 Nochange
(2) Addsalicylicacid Pleasant odour Odour of oilof wint er green
II. Difference between Alcohol and Phenol

(i) OH
Test Ethanol CH3CH2OH Phenol
(1) Add I2 / NaOH and heat Yellow ppt. of CHl3 No change

(2) Add neutral FeCl3 No change Violet Colouration
354 E
CBSE
ALLEN
(ii) OH
Propan-2-ol
Test Phenol
CH3–CH(OH)CH 3
(1) Add Neutral FeCl3 Violet colour No change

(2) Add Br2 / H2O colour of Br2 decolourised No change
III. Difference between Alkyl Halide and Aryl Halide

(i) Cl
Test Chloroethane (C2H5Cl) Chlorobenzene
(1) Add aq NaOH + AgNO 3 White precipitate of AgCl No change

soluble in Ammonia
(ii)
Test Chloroethane CH3CH2Cl Bromoethane CH3CH2Br
(1) Add aq NaOH + AgNO 3 White ppt (AgCl) Creamy yellow ppt (AgBr)
(2) Add NH 3 in both test tube White ppt get dissolved Yellow ppt dissolved partly
in NH3 in NH 3
(iii) CH2Cl Cl
Test Benzyl chloride Chlorobenzene
(1) Add aq NaOH + AgNO 3 White ppt soluble in No change

Ammonia
IV. Difference between Aldehyde and Ketone

(i) O
Test Acetaldehyde CH3CHO Acetone H3C–C–CH3
(1) Add Fehling's reagent Brown red precipitate No
(2) Add Tollen's reagent Silver mirror No
(ii)
Test Acetaldehyde CH3CHO Formaldehyde HCHO
(1) Add I2/NaOH and head Yellow ppt. iodoform (CHI3) No Change
(2) Add KMnO4/H2SO4 Smell of vinegar Efferescence of CO2
E 355
Chemistry
ALLEN
(iii)
Test Ethanal (CH3CHO) Benzaldehyde(C
(C66H56CHO)
CHO)
(1) Add I2/NaOH Yellow iodoform (CHI3) No change

(2) Add Fehling's reagent Red ppt of Cu2O No change
(iv)
Test Pentan-2-one
Pentan-3-one Pentan-3-one
O O
CH3–C–CH 2CH 2CH3 CH3CH2–C–CH2CH3
(1) Add I2/NaOH and heat Yellow ppt. (CHI3) No change
(v) Acetophenone Benzophenone

Test
COCH3 O
C
(1) Add I2/NaOH Yellow iodoform No Change
(2) Add NaHSO3 White ppt No
V. Difference between Different-Different Carboxylic Acid
(i)
Test Formic acid (HCOOH) Acetic acid (CH3COOH)
(1) Tollen's reagent Silver mirror (Ag) No change
VI. Difference between Phenol and Carboxylic Acid
(i) Phenol (White solid) Benzoic acid (White solid)

Test
OH COOH
(1) Add neutral FeCl3 Violet colour No change

(2) Add NaHCO3 (aq) No change Effervescence of CO2
VII. Difference between Primary, Secondary and Tertiary Amine
(i) Test Primary Amine Secondary Amine Tertiary

Amine
Hinsberg reagent White ppt soluble White ppt soluble No Change
C6H5SO2Cl in NaOH in NaOH
356 E
CBSE
ALLEN
(ii)
Test Methanamine Dimethyl Amine
(CH3NH2) (CH3NHCH3)
(1) Add Hinsberg reagent White ppt (soluble White ppt insoluble in
C6H5SO2Cl in NaOH) NaOH (aq.)
(2) Add CHCl3 + KOH(alc.) Four odour of No change
isocyanide
(iii) NH2 NHCH3
Test Aniline N-methyl-aniline
(1) Add Hinsberg reagent White ppt solution in White ppt insoluble in
(C6H5SO2Cl) NaOH NaOH
(2) Add CHCl3 + KOH Foul odour of No change
( l ) i id
VIII. Difference between Aliphatic and Aromatic
(i) NH 2
Test Aniline Methylamine (CH3NH2)
(1) Add Br2/H2O Colour of Br2 (aq.) No change

decolourised
IX. Difference between Ketone and Carboxylic Acid
(i)
Test CH3COCH3 acetone acetic acid CH3COOH
(1) Add l2/NaOH + heat Yellow iodoform (CHI3) No change

(2) Add NaHCO3 No Change Effervescence of CO2
(ii)
Test acetaldehyde CH3CHO acetic acid CH3COOH
(1) Add Fehling's reagent Red ppt. of Cu2O No change

(2) Add Tollens' reagent Silver mirror (Ag) No change
(3) Add NaHCO3 No change Effervescence of CO2
(iii)
NH2
NH2
Test
(Aniline)
Cyclohexylamine
(1) Add NaNO2 and HCl and N2 gas is liberated and no Stable diazonium salt is formed
then add phenol in colouration is observed. which reacts with phenol to form
presence of a base. orange dye.
E 357
Chemistry
ALLEN
CBSE SAMPLE PAPER
CLASS: XII
Session: 2023-24
Subject : Chemistry
Time : 3 Hrs. Max. Marks : 70
General Instructions :
1. There are 33 questions in this question paper with internal choice.
2. SECTION A consists of 16 multiple-choice questions carrying 1 mark each.
3. SECTION B consists of 5 short answer questions carrying 2 marks each.
4. SECTION C consists of 7 short answer questions carrying 3 marks each.
5. SECTION D consists of 2 case-based questions carrying 4 marks each.
6. SECTION E consists of 3 long answer questions carrying 5 marks each.
7. All questions are compulsory.
8. Use of log tables and calculators is not allowed.
SECTION – A
The following questions are multiple-choice questions with one correct answer. Each question
carries 1 mark. There is no internal choice in this section.
1. Which of the following solutions will have the highest conductivity at 298 K ?
(a) 0.01 M HCl solution (b) 0.1 M HCl solution
(c) 0.01 M CH3COOH solution (d) 0.1 M CH3COOH solution
O
A + B 
dil. NaOH
2. CH=CH–C
Identify A and B :
(a) A = 1-phenylethanal, B = acetophenone
(b) A = Benzophenone, B = formaldehyde
(c) A = Benzaldehyde, B = acetophenone
(d) A = Benzophenone, B = acetophenone

3. The vitamins which can be stored in our body are :
(a) Vitamin A, B, D and E
(b) Vitamin A, C, D and K
(c) Vitamin A, B, C and D
(d) Vitamin A, D, E and K
358 E
CBSE
ALLEN
4. What is IUPAC name of the ketone A, which undergoes iodoform reaction to give
CH3CH = C(CH3)COONa and yellow precipitate of CHI3 ?
(a) 3-Methylpent-3-en-2-one (b) 3-Methylbut-2-en-one
(c) 2,3-Dimethylethanone (d) 3-Methylpent-4-one
5. Which of the following is not correct ?
(a) In haloarenes, the electron pairs on halogen atom are in conjugation with -electrons of the
ring.
(b) The carbon-magnesium bond is covalent and non-polar in nature.
(c) During SN1 reaction, the carbocation formed in the slow step being sp2 hybridised is planar.
(d) Out of CH2=CH–Cl and C6H5CH2Cl, C6H5CH2Cl is more reactive towards SN1 reaction.
6. Match the properties with the elements of 3d series :
(i) Lowest enthalpy of atomisation (p) Sc
(ii) Shows maximum numbers of oxidation states (q) Mn
(iii) Transition metal that does not form coloured compounds (r) Zn
(s) Ti
(a) i-r, ii-q, iii-p (b) i-r, ii-s, iii-p (c) i-p, ii-q, iii-r (d) i-s, ii-r, iii-p
7. Which of the following statement is true ?
(a) Molecularity of reaction can be zero or a fraction
(b) molecularity has no meaning for complex reactions.
(c) molecularity of a reaction is an experimental quantity.
(d) reactions with the molecularity three are very rare but are fast.
8. In which of the following solvents, the C 4 H8 NH 3 X  is soluble :
(a) ether (b) acetone (c) water (d) bromine water

9. Which of the following observations is shown by 2-phenyl ethanol with Lucas reagent ?
(a) Turbidity will be observed within five minutes
(b) No turbidity will be observed
(c) Turbidity will be observed immediately
(d) Turbidity will be observed at room temperature but will disappear after five minutes.
10. If the initial concentration of substance A is 1.5 M and after 120 seconds the concentration of
substance A is 0.75 M, the rate constant for the reaction if it follows zero-order kinetics is :
(a) 0.00625 mol L–1s–1 (b) 0.00625 s–1
(c) 0.00578 mol L–1s–1 (d) 0.00578 s–1
E 359
Chemistry
ALLEN
11. Anisole undergoes bromination with bromine in ethanoic acid even in the absence of iron (III)
bromide catalyst:
(a) Due to the activation of benzene ring by the methoxy group
(b) Due to the de-activation of benzene ring by the methoxy group
(c) Due to the increase in electron density at ortho and para positions
(d) Due to the formation of stable carbocation
12. The trend of which property is represented by the following graph ?
19
18
17
Radius/nm
16
15
14
13
12
Sc Ti V Cr Mn Fe Co Ni Cu Zn
(a) ionization enthalpy (b) atomic radii
(c) enthalpy of atomization (d) melting point
For Visually Challenged Learners
12. Which of the following is not considered a transition element ?
(a) Scandium (b) Silver (c) Vanadium (d) Zinc
13. Given below are two statements labelled as Assertion (A) and Reason (R) :
Assertion (A) : Alcohols react both are nucleophilies and electrophiles.
Reason (R) : The bond between C–O is broken when alcohols react as nucleophiles.
Select the most appropriate answer from the options given below :
(a) Both A and R are true and R is the correct explanation of A.
(b) Both A and R are true but R is not the correct explanation of A.
(c) A is true but R is false.
(d) A is false but R is true.
Assertion (A) : Strong oxidising agents oxidise toluene and its derivatives to benzoic acids.
Reason (R) : It is possible to stop the oxidation of toluene at the aldehyde stage with suitable
reagents.
360 E
CBSE
ALLEN
Assertion (A) : Enzymes are very specific for a particular reaction and for a particular substrate.
Reason (R) : Enzymes are biocatalysts.
Assertion (A) : During electrolysis of aqueous copper sulphate solution using copper electrodes
hydrogen gas is released at the cathode.
Reason (R) : The electrode potential of Cu2+/Cu is greater than that of H+/H2
SECTION – B
This section contains 5 questions with internal choice in two questions. The following
questions are very short answer type and carry 2 marks each.
17. (a) Radioactive decay follows first-order kinetics. The initial amount of two radioactive
elements X and Y is 1 gm each. What will be the ratio of X and Y after two days if their
half-lives are 12 hours and 16 hours respectively.
(b) The hypothetical reaction P + Q  R is half order w.r.t. 'P' and zero order w.r.t. 'Q'. What
is the unit of rate constant for this reaction ?
18. A 5% solution of Na2SO4.10H2O (MW = 322) is isotonic with 2% solution of non-electrolytic,

non-volatile substance X. Find out the molecular weight of X.
19. (a) Arrange the isomeric dichlorobenzene in the increasing order of their boiling point and
melting points.
(b) Explain why the electrophilic substitution reactions in haloarenes occur slowly and require
more drastic conditions as compared to those in benzene.
E 361
Chemistry
ALLEN
20. (a) Out of p-tolualdehyde and p-nitrobenzaldehyde, which one is more reactive towards
nucleophilic addition reactions, why?
(b) Write the structure of the product formed when acetone reacts with 2,4 DNP reagent.
OR
Convert the following :
(a) Benzene to m-nitrobenzaldehyde
(b) Bromobenzene to benzoic acid
21. (a) DNA fingerprinting is used to determine paternity of an individual. Which property of
DNA helps in the procedure ?
(b) What structural changes will occur when a native protein is subjected to change in pH ?
SECTION – C
This section contains 7 questions with internal choice in two questions. The following
questions are short answer type and carry 3 marks each.
22. (a) Write the formula for the following coordination compound
Bis(ethane-1,2-diamine) dihydroxidochromium(III) chloride
(b) Does ionization isomer for the following compound exist ? Justify your answer.
Hg[Co(SCN)4]
(c) Is the central metal atom in coordination complexes a Lewis acid or a Lewis base ? Explain.
23. (a) Can we construct an electrochemical cell with two half-cells composed of ZnSO4 solution
and zinc electrodes ? Explain your answer.
(b) Calculate the  0m for Cl– ion from the data given below :
 0m MgCl2  258.6 Scm 2 mol1 and  0m Mg 2  106 Scm 2 mol1
(c) The cell constant of a conductivity cell is 0.146 cm–1. What is the conductivity of 0.01 M
solution of an electrolyte at 298 K, if the resistance of the cell is 1000 ohm ?
24. Write the name of the reaction, structure and IUPAC name of the product formed when :
(a) Phenol reacts with CHCl3 in the presence of NaOH followed by hydrolysis.
(b) CH3CH2CH(CH3)CH(CH3)ONa reacts with C2H5Br.
25. You are given four organic compounds "A", "B", "C" and "D". The compounds "A", "B" and "C"
form an orange — red precipitate with 2,4 DNP reagent. Compounds "A" and "B" reduce
Tollen's reagent while compounds "C" and "D" do not. Both "B" and "C" give a yellow
precipitate when heated with iodine in the presence of NaOH. Compound "D" gives brisk
effervescence with sodium bicarbonate solution. Identify "A", "B", "C" and "D" given the
number of carbon atoms in three of these cabron compounds is three while one has two carbon
atoms. Gvien an explanation for your answer.
362 E
CBSE
ALLEN
26. When sucrose is hydrolysed the optical rotation values are measured using a polarimeter and are
given in the following table :
S.No. Time (hours) Specific Rotation
1 0 +66.5°
2  –39.9°
(a) Account for the two specific rotation values.

(b) What is the specific name given to sucrose based on the above observation.
(c) One of the products formed during the hydrolysis of sucrose is a glucose, that reacts with
hydroxylamine to give compound A. Identify compound A.
27. An organic compound A with the molecular formula (+) C4H9Br undergoes hydrolysis to form
(±) C4H9OH. Give the structure of A and write the mechanism of the reaction.
28. The rate constants of a reaction at 200 K and 500 K are 0.02 s–1 and 0.20 s–1 respectively.
Calculate the value of Ea (Given 2.303 R = 19.15 JK–1 mol–1)
SECTION – D
The following questions are case-based questions. Each question has an internal choice and
carries 4 (1 + 1 + 2) marks each. Read the passage carefully and answer the questions that
follow.
29. Metal complexes show different colours due to d-d transitions. The complex absorbs light of
specific wavelength to promote the electron from t2g to eg level. The colour of the complex is due
to the transmitted light, which is complementary of the colour absorbed.
The wave number of light absorbed by different complexes of Cr ion are given below :
Complex Wavenumber of light Energy of light

absorbed (cm–1) absorbed
(kJ/mol)
[CrA6]3– 13640 163
[CrB6]3+ 17830 213
[CrC6]3+ 21680 259

[CrD6]3– 26280 314

(a) Out of the ligands "A", "B", "C" and "D", which ligand causes maximum crystal field
splitting ? Why ?
OR
Which of the two, "A" or "D" will be a weak field ligand ? Why ?
E 363
Chemistry
ALLEN
(b) Which of the complexes will be violet in colour ? [CrA6]3– or [CrB6]3+ and why ? [Given :
If 560 –570 nm of light is absorbed, the colour of the complex observed is violet.)
(c) If the ligands attached to Cr3+ ion in the complexes given in the table above are water,
cyanide ion, chloride ion and ammonia (not in this order)
Identify the ligand, write the formula and IUPAC name of the following :
(i) [CrA6]3– (ii) [CrC6]3+
30. The lead-acid battery represnts the oldest rechargeable battery technology. Lead acid batteries
can be found in a wide variety of applications including small-scale power storage such as UPS
systems, ignition power sources for automobiles, along with large, grid-scale power systems. The
spongy lead act as the anode and lead dioxide as the cthode. Aqueous sulphuric acid is used as an
electrolyte. The half-reactions during discharging of lead storage cells are :
Anode : Pb(s) + SO 24  (aq) PbSO4(s) + 2e–
Cathode : PbO2(s) + 4H+(aq) + SO 24 (aq) + 2e–  PbSO4(s) + 2H2O

There is no safey way of disposal and these batteries end - up in landfills, Lead and sulphuric
acid are extremely hazardous and pollute soil, water as well as air. Irrespective of the
environmental challenges it poses, lead-acid batteries have remained an important source of
energy.
Designing green and sustainable battery systems as alternatives to conventional means remains
relevant. Fuel cells are seen as the future source of energy. Hydrogen is considered a green fuel.
Problem with fuel cells at present is the storage of hydrogen. Currently, ammonia and methanol
are being used as a source of hydrogen for fuel cell. These are obtained industrially, so add to the
environmental issues.
If the problem of storage of hydrogen is overcome, is it still a "green fuel?" Despite being the
most abundant element in the Universe, hydrogen does not exist on its own so needs to be
extracted from the water using electrolysis or separated from carbon fossil fuels. Both of these
processes require a significant amount of energy which is currently more than that gained from
the hydrogen itself. In addition, this extraction typically requires the use of fossil fuels. More
research is being conducted in this field to sovle these problems. Despite the problem of no good
means to extract Hydrogen. It is a uniquely abundant and renewable source of energy, perfect for
our future zero-carbon needs.
(a) How many coulombs have been transferred from anode to cathode in order to consume one
mole of sulphuric acid during the discharging of lead storage cell?
(b) How much work can be extracted by using lead storage cell if each cell delivers about
2.0 V of voltage ? (1 F = 96500 C)
(c) Do you agree with the statement - "Hydrogen is a green fuel." Give your comments for and
against this statement and justify your views.
364 E
CBSE
ALLEN
OR
Imagine you are a member of an agency funding scientific research. Which of the following
projects will you fund and why ?
(i) Safe recycling of lead batteries
(ii) Extraction of hydrogen
SECTION – E
The following questions are long answer type and carry 5 marks each. Two questions have an
internal choice.
31. Attempt any five of the following :
(a) Which of the following ions will have a magnetic moment value of 1.73 BM.
Sc3+, Ti3+, Ti2+, Cu2+, Zn2+
(b) In order to protect iron from corrosion, which one will you prefer as a sacrificial electrode,
Ni or Zn ? Why? (Given standard electrode potentials of Ni, Fe and Zn are –0.25 V,
–0.44 V and –0.76 V respectively)
(c) The second ionization enthalpies of chromium and manganese are 1592 and 1509 kJ/mol
(d) Give two similarities in the properties of Sc and Zn.
(e) What is actinoid contraction ? What causes actinoid contraction ?
(f) What is the oxidation state of chromium in chromate ion and dichromate ion ?
(g) Write the ionic equation for reaction of KI with acidified KMnO4.
32. (a) What is the effect of temperature on the solubility of glucose in water ?
(b) Ibrahim collected a 10 mL each of resh water and ocean water. He observed that one
sample labelled "P" froze at 0°C while the other "Q" at –1.3°C. Ibrahim forgot which of the
two, "P" or "Q" was ocean water. Help him identify which container contains ocean water,
giving rationalization for your answer.
(c) Calculate Van't Hoff factor for an aqueous solution of K3[Fe(CN)6] if the degree of
dissociation () is 0.852. What will be boiling point of this solution if its concentration is
1 molal ? (Kb = 0.52 K kg/mol)
OR
(a) What type of deviation from Roult's Law is expected when phenol and aniline are mixed
with each other ? What change in the net volume of the mixture is expected ? Graphically
represent the deviation.
(b) The vapour pressure of pure water at a certain temperature is 23.80 mm Hg. If 1 mole of a
non-volatile non-electrolytic solute is dissolved in 100g water. Calculate the resultant
vapour pressure of the solution.
E 365
Chemistry
ALLEN
33. An organic compound with molecular formula C7H7NO2 exists in three isomic forms, the isomer
'A' has the highest melting point of the three. 'A' on reduction gives compound 'B' with molecular
formula C7H9N. 'B' on treatment with NaNO2/HCl at 0–5°C to form compound 'C'. On treating C
with H3PO2, it gets converted to D with formula C7H8, which on further reaction with CrO2Cl2
followed by hydrolysis forms 'E' C7H6O. Write the structure of compounds A to E. Write the
chemical equations involved.
OR
(a) Account for the following
(i) N-ethylbenzenesulphonyl amide is soluble in alkali.
(ii) Reduction of nitrobenzene using Fe and HCl is preferred over Sn and HCl.
(b) Arrange the following in :
(i) Decreasing order of pKb values
C6H5NH2, C6H5NHCH3, C6H5CH2NH2, CH3NH2, NH3
(ii) Increasing order of solubility in water
C2H5Cl, C2H5NH2, C2H5OH
(iii) Decreasing boiling point
CH3COOH, C2H5OH, CH3NH2, CH3OCH3
366 E
CBSE
ALLEN
CBSE SAMPLE PAPER SOLUTIONS
SECTION – A
1. (b) 0.1 M HCl solution, conductivity is higher for strong electrolyte, conductivity decreases with
dilution.
2. (c) A = Benzaldehyde, B = Acetophenone. This is an example of crossed Aldol condensation.
3. (d) Vitamin A, D, E and K. These are fat soluble vitamins.
4. (a) 3-Methylpent-3-en-2-one
5. (b) The carbon-magnesium bond is covalent and non-polar in nature.
6. (a) i-r, ii-q, iii-p
Zinc has no unpaired electrons in 3d or 4s orbitals, so enthapy of atomization is low
Mn = 3d54s2 shows +2, +3, +4, +5, +6 and +7 oxidation state, maximum number in 3d series.
7. (b) molecularity has no meaning for complex reactions.
8. (c) water
9. (b) No turbidity will be observed, given compound is a primary alcohol.
[R ]  [R]
10. (a) 0.00625 mol L–1s–1 for zero order k  0 = 1.5 – 0.75/120
t
11. (a) Due to the activation of benzene ring by the methoxy group.
12. (b) atomic radii
For Visually Challenged Learners
12. (d) Zinc
13. (c) A is true but R is false
14. (b) Both A and R are true but R is not the correct explanation of A.
15. (b) Both A and R are true but R is not the correct explanation of A.
16. (d) A is false but R is true.
SECTION – B
17. (a) For first order reaction
half life of X = 12 hours
2 days = 48 hours means 4 half lives, amount of X left = 1/16 of initial value
Half life of Y = 16 hours [½]
2 days = 48 hours means 3 half lives, amount left = 1/8 of initial value
Ratio of X : Y = 1 : 2 [½]
(b) b. mol1/2 L–1/2 s–1 as Rate = k[P]1/2 [1]
18. 1 = 2 [½]
iC1RT = C2RT [½]

3 5 2
 [½]
322 M
2  322
M= [½]
3 5
M = 42.9 g
E 367
Chemistry
ALLEN
19. (a) m-dichlorobenzene < o-dichlorobenzene < p-dichlorobenzene [½]
symmetrical structure and close packing in para isomer
ortho has a stronger dipole dipole interaction as compared to meta. [½]
(b) the halogen atom because of its –I effect has some tendency to withdraw lectrons from the
benzene ring. As a result, the ring gets somewhat deactivated as compared to benzene and
hence the electrophilic substitiion reactions in haloarenes occur slowly and require more
drastic conditions to those in benzene. [1]
20. (a) p-nitrobenzaldehyde is more reactive towards the nucleophilic addition reaction than
p-tolualdehyde as Nitro group is electron withdrawing in nature. Presence of nitro group
decrease electron density, hence facilitates the attack of nucleophile. Presence of
–CH3 leads to +I effect as –CH3 is electron releasing group. [1]
NO2 NO2
NHNH2 NH=C(CH3)2
(b) CH3COCH3 +
O2N O2N [1]
OR
CHO CHO
CO, HCl conc. HNO3

(a) AlCl3/CuCl conc. H2SO4
NO2
[1]
Br MgBr COOH
Mg i. O=C=O
(b)
dry ether ii. HOH
[1]
21. (a) Replication :
A sequence of bases on DNA is unique for a person and is the genetic material transferred
to the individual from the parent which helps in the determination of paternity. [1]
(b) During denaturation secondary and tertiary structures are destroyed but the primary
structure remains intact. [1]
SECTION – C
22. (a) [Cr(en)2(OH)2]Cl or [Cr(H2NCH2CH2NH2)2(OH)2]Cl [1]
(b) No, ionization isomers are possible by exchange of ligand with counter ion only and not by
exchange of central metal ion. [1]
(c) The central atom is electron pair acceptor so it is a Lewis acid. [1]
368 E
CBSE
ALLEN
23. (a) Yes, if the concentration of ZnSO4 in the two half cell is different, the electrode potential
will be different making the cell possible. [1]
(b)  0m (MgCl2 )   0m (Mg 2 )  2 0m (Cl )
258.6 = 106 + 2 0m (Cl )
 0m (Cl )  76.3 Scm 2 mol1 [1]
(c) Cell constant G* = k × R

k = G*/R = 0.146/1000 = 1.46 × 10–4 Scm–1 [1]
24. (a) Reimer Tiemann [½]
OH
CHO
2-Hydroxybenzaldehyde [½ + ½]
(b) Williamson synthesis, CH3CH2CH(CH3)CH(CH3)OC2H5

2-Ethoxy-2-methylpentane [½ + ½ + ½]
25. A, B and C contain carbonyl group as they give positive 2,4 DNP test
A and B are aldehydes as aldehydes reduce Tollen's reagent
C is a ketone, as it contains carbonyl group but does not give positive Tollen's test [½]
C is a methyl ketone as it gives positive iodoform test
B is an aldehyde that gives positive iodoform test [½]
D is a carboxylic acid
Since the number of carbons in the compounds A, B, C and D is three or two
B is CH3CHO as this is only aldehyde which gives a positive iodoform test [½]
The remaining compounds A, C and D have three carbons
A is CH3CH2CHO, C is CH3COCH3 and D is CH3CH2COOH [½ each]
26. (a) The reactant sucrose is dextrorotatory. On hydrolysis it give glucose dextrorotatory and
fructose which is leavoroatatory. The specific rotation of fructose is higher than glucose.
Sucrose is dextrorotatory but after hydrolysis gives dextrorotatory glucose and
laevorotatory fructose. Since the laevorotation of fructose (–92.4*) is more than

dextrorotation of glucose (+52.5*) the mixture is laevorotatory. [1]
(b) Invert sugar, The hydrolysis of sucrose brings about a change in the sign of rotation, from
dextro (+) to laevo (–) and the product is named as invert sugar. [1]
(c) Glucose [1]
E 369
Chemistry
ALLEN
CH=N–OH
(CHOH)4
CH2OH
27. C2H5–CH–CH3
Br
Mechaism
H H
Slow step
H3C—C—C2H5 C + Br1
H3C C2 H5
Br
H H H
Fast
C + OH1 H3C—C—OH + HO—C—CH3
H3C C2H5 C2H5 C2H5
k  Ea  1 1 
28. log  2     
 1
k 2.303R  T1 T2 
0.20 Ea  1 1 
log  
0.05 2.303R  200 500 

Ea  300 
log10   
19.15  200  600 
19.15  200  500
Ea =
300
Ea = 6383 J/mol [1+1+1]
SECTION – D
29. (a) D. Energy is directly proportional to the wave number. Maximum energy of light is
required for an electron to jump from t2g to eg in case of [CrD6]3– [½ + ½]
OR
A, The splitting caused in least in this case as the energy required for electron to jump from
t2g to eg., is minimum. [½ + ½]

(b) [CrB6]3+ wavelength of light absorbed is 1/17830 = 560 nm for the complex while
1/13640 = 733 nm for [CrA6]3– complex. [½ + ½]
(c) (i) [CrCl6]3–, Hexachloridochromate (III) ion [1]
(ii) [Cr(NH3)6]3+, Hexaamminechromium (III) ion [1]
A = Cl–, B = H2O, C = NH3, D = CN–
370 E
CBSE
ALLEN
30. (a) 2 mol e– (or 2F) have been transferred from anode to cathode to consume 2 mol of H2SO4
therefore, one mole H2SO4 requires oen faraday of electricity or 96500 coulombs.
(b) wmax = –nFE* = –2 × 96500 × 2.0 = 386000 J of work can be extracted using lead storage
cell when the cell is in use.
(c) Both yes and no should be accepted as correct answers depending upon what
explanation is provided.
Yes, Hydrogen is a fuel that on combustion gives water as a byproduct. There are no
carbon emissions and no pollutions caused.
However, at prsent the means to obtain hydrogen are electrolysis of water which use
electricity obtained from fossil fuels and increase carbon emission.
Inspite of the problems faced today in the extraction of hydrogen, we cannot disagree on
the fact that hydrogen is a clean source of energy. Further research can help in finding
solutions and greens ways like using solar energy for extraction of hydrogen. [2]
No, It is true that Hydrogen is a fuel that on combustion gives water as a byproduct. There
are no carbon emissions and no pollutions caused.
However, at present the means to obtain hydrogen are electrolysis of water which use
electricity obtained from fossil fuels and increase carbon emissions.
Hydrogen is no doubt a green fuel, but the process of extraction is not green as of today. At
present, looking at the process of extraction, hydrogen is not a green fuel. [2]
OR
(i) Lead batteries are currently the most important and widely used batteries. These are
rechargeable. The problem is waste management which needs research and awareness.
Currently, these are being thrown into landfills and there is no safe method of disposal or
recycling. Researching into safe method of disposal will reduce the pollution and health
hazards caused to a great extent.
(1 mark for importance, 1 for need for the research)
(ii) Fuel cell is a clean source of enegy. Hydrogen undergoes combustion to produce water.
The need of the hour is green fuel and hydrogen is a clean fuel. The current problem is
obtaining hydrogen. Research that goes into this area will help solve the problem of
pollution and will be a sustainable solution.

(1 mark for importance, 1 for need for the research)
SECTION – E
31. (a) Both Ti3+ and Cu2+ have 1 unpaired electron, so the magnetic moment for both will be
1.73 BM.
(b) Zn, it has a more negative electrode potential so will corrode itself in place of iron.
E 371
Chemistry
ALLEN
(c) Mn+ has 3d54s1 configuration and configuration of Cr+ is 3d5, therefore, ionisation enthalpy
of Mn+ is lower than Cr+.
(d) Sc and Zn both form colourless compound and are diamagnetic.
(e) The decrease in the atomic and ionic radii with increase in atomic number of actinoids due
to poor shielding effect of 5f electron.
(f) In both chromate and dichromate ion the oxidation state of Cr is +6.
(g) 10I   2MnO 4  16H   2Mn 2  8H 2 O  5I 2 [1 each, any 5]
32. (a) Addition of glucose to water is an endothermic reaction. According to Le Chat elier's
principle, on increase in temperature, solubility will increase.
(b) Q is ocean water, due to the presence of salts it freezes at lower temperature (depression in
freezing point)
(c) K3[Fe(CN)6] gives 4 ions in aqueous solution [½]
i = 1 + (n – 1)  [½]
i = 1 + (4 – 1) × 0.0852
i = 3.556 [½]
Tb = iKbm = 3.556 × 0.52 × 1 = 1.85 [1]
Tb = 101.85ºC [½]
OR
(a) Negative Deviation is expected when phenol and aniline are mixed with each other. The net
volume of the mixture will decrease, V < 0 due to stronger intermolecular interactions.
Vapour pressure 
PB
PA
XA = 1 Mole fraction XA = 0
XB = 0 XB = 1
P-X Diagram for Solutions showing Negative Deviation from Raoult's Law
[1]
(b) Relative lowering of vapour pressure = (P° – P) / P° = x2 [½]
x2 = n2 / n1
n2 = 0.1
n1 = 100/18
372 E
CBSE
ALLEN
x2 = 0.1/5.55 + 0.1 = 0.1 / 5.65 = 0.018 [½]
P° = 23.8 mm Hg
Relative lowering of vapour pressure = (23.80 –P) / 23.80 = 0.018 [½]
23.80 – P = 0.428 [½]
P = 23.80 – 0.428 = 23.37 mm Hg [1]
33. Compound "A" is p-methylnitrobenzene
Compound "B" is p-methylbenzenamine
Compound "C" is p-methylbenzenediazoiumchloride
Compound "D" – Toluene
Compound "E" – Benzaldehyde
The chemical reactions involved are
O
CH3 CH3 CH3 CH3 C—H
Sn/HCl NaNO2/HCl H3PO2 CrO2Cl2

0°C-5°C H3O+
NO2 NH2 N2Cl
A B C D E
(1 mark for correct identification of A, 1 each for identification and reaction of formation of B,
C, D and E from A)
OR
(a) (i) The hydrogen attached to N-ethylbenzene sulphonamide is acidic in nature. This is
due to the presence of strong electron withdrawing sulphonyl group. Hence, it is
soluble in alkali. [1]
(ii) Reduction with iron scrap and hydrochloric acid is preferred because FeCl2 formed
gets hydrolysed to release hydrochloric acid during the reaction. Thus, only a small
amount of hydrochloric acid is required to initiate the reaction. [1]
[1]
(b) (i) C6H5NH2 > C6H5NHCH3 > NH3 > C6H5CH2NH2 > CH3NH2
(ii) C2H5Cl < C2H5NH2 < C2H5OH [1]
(iii) CH3COOH > C2H5OH > CH3NH2 > CH3OCH3 [1]
E 373
Chemistry
ALLEN
IMPORTANT NOTE
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374 E

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CHEMISTRY

S.No. Content Page

01. HALOALKANES & HALOARENES (UNIT-10) 01 – 70

02. ALCOHOLS, PHENOLS & ETHERS (UNIT-11) 71 – 142

03. ALDEHYDES, KETONES & CARBOXYLIC ACIDS

04. AMINES (UNIT-13) 217 – 279

05. BIOMOLECULES (UNIT-14) 280 - 345

06. NAME REACTION 346 - 353

07. CHEMICAL TEST 354 – 357

08. CBSE SAMPLE PAPER WITH SOLUTIONS 358 – 374

"This booklet is colour coded for you convenience.

11. CH3 neo-Pentyl chloride 1-Chloro-2,2-Dimethylpropane

Alkyl halides Alkenyl halides Alkynyl halides Aryl halides

Mono halides Di halides Trihalides Tetra halides

I. Compounds containing II. Compounds containing

(a) Alkyl halide/Halo alkanes (a) Viniylic halides

(c) Benzylic halides

CH2— (Benzyl group) CH3

CH2 X Benzyl halide

+Cl2 n-propyl chloride

(Resonating structures of benzylic carbocation)

Mechanism : above reaction proceed in two steps:

Explanation of SN2 Reaction Mechanism

Types of reaction SN2 :

Difference between SN1 and SN2 reaction

SN1 reaction SN2 reaction

Unimolecular nucleophilic substitution Bimolecular nucleophilic substitution

2. It is first order reaction 2. It is second order reaction

Note (3): Substitution by Nitrite group (—ON=O)

STEREO CHEMICAL ASPECTS OF NSR:

high intensity Polarizer Polarimetry cell with Analyzer Detector

(1) Ordinary light: These waves vibrates equally in all directions.

Chiral objects NonChiral objects

A chiral molecule and its mirror image

C Obtained by rotating B by 180º C is superimposable on its mirror image A

Explain inversion, retention, and racemisation with suitable example.

H3C CH3 CH3

B = Base ; X = Leaving group

III. Reaction with metals

Example: (2) CH 3 Br  2Na  BrCH 3  CH 3  CH 3  2NaBr

C2 H 5 Br  2Na  BrC2 H 5 

Example: (4) CH3–CH–Br Na

Benzene Attacking Elecrophilic

GENERAL METHODS OF PREPARATION OF HALOARENE

Nitro benzene Aniline Benzenediazonium

 CH3Cl < CH3CH2Cl < CH3(CH2)2Cl < CH3(CH2)3Cl

3. Density : All arylhalides are heavier than water

(5) Freons: ChloroFlouroCarbon/CFCs

c=n C–1 =2–1=1 

(v) CH 3CH 2 I (vi)

(iii) CH3CHCH2CH2Br or CH3CH2CHCH2Br

Ans. (i) 2-Chloro-2-methylpropane (3°) 3° more stable

R – Br + Mg dry ether C D2O CH3CHCH3

Ans. (A) MgBr (B)

7. Write IUPAC names of the following:

Ans. (i) 4-Bromopent-2-ene (ii) 3-Bromo-2-methylbut-1-ene

(ii) CH3–CH2–CH = CH2 + HCl  

CH2– CH2– CH2– Br