Chemistry - 2

1
C
CHEMISTRY
h apter
ontents
01. HALOALKANES & HALOARENES 3
02. ALCOHOL, PHENOL & ETHERS 32
03. ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 65
04. ALIPHATIC & AROMATIC AMINES 110
05. BIOMOLECULES 145
® SAMPLE QUESTION PAPER (2020-21) 164

2
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CBSE
ALLEN
HALOALKANES & HALOARENES
l Haloalkanes (Alkyl halides) are halogen derivatives of alkanes with general formula [CnH2n+1X],
(X = F, Cl, Br or I)
l Haloarenes (Aryl halides) are halogen derivatives of arenes with general formula Ar – X.
l Since halogen is more electronegative then C, hence C – X bond is polar.
d+ d–
–C–X
l Named Reactions :
(a) Sandmeyer Reaction :
+
NH 2 N2 X – X
NaNO2+HX Cu2X2
273–278 K
+ N 2 (X = Cl, Br)
(b) Finkelstein Reaction :
R - X + NaI ¾¾¾¾
dry acetone
® R - I + NaX (X = Cl, Br)
(c) Swartz Reaction :
CH3 – Br + AgF ® CH3 – F + AgBr
Instead of Ag – F, other metallic fluoride like Hg2F2, CoF2 or SbF3 can also be used.
(d) Wurtz Reaction :
2R - X + 2Na ¾¾¾ ¾
dry ether
® R - R + 2NaX
node06\B0B0-BA\Kota\Board Material\Chemistry\CBSE\CBSE Booklet\English\Updated booklet-21\New Pattern CBSE Booklet\Part wise boocklet\Part 2\03_OC\01_Haloalkanes & Haloarenes
(e) Wurtz-Fitting Reaction :
X R
dry
+ 2Na + R – X ether + 2NaX
(f) Fitting Reaction :
X
dry
2 + 2Na ether + 2NaX
biphenyl or
diphenyl
l Nucleophilic Substitution Reactions :
1 d+ d–
Nu C–X C – Ni + X
1
haloalkane
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(a) Substitution nucleophilic bimolecular (SN ) : 2
1. 1° haloalkane
2. Bimolecular, 2nd order
3. One step
l Order of reaction : 1° > 2° > 3°
l Deciding factor : Steric hinderance
(a) Substitution nuclephilic unimolecular (SN1) :
CH3
(CH3)3 CBr ¾¾¾¾

Step I
¬¾¾¾ ®
¾ Å + BrΘ
H 3C CH3
CH3
Step -II
Å + –OH ¾¾¾¾¾
(nucleophile)
®
H3C CH3 Fast
Planar carbocation
1. 3° haloalkane
2. Unimolecular, 1st order
3. Two steps
Order of reactivity : 3° > 2° > 1°
Deciding factor : Stability of carbo cation
Allylic éë CH 2 = CH - C H 2 ùû and benzylic éë C 6 H 5 C H 2 ùû halides undergo reaction via SN1 mechanism

Å Å
as the corresponding carbo cations are resonance stabilized.

l Aryl halides are much less reactive towards nucleophilic substitution reactins than haloalkanes.
l Halogen is deactivating but o, p-direction in electrophilic substitution reaction of haloarenes.
l Important Nucleophilic substitution reactions of Alkyl halide
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+ –
NaOH
R–OH + NaX
+–
KOH
R–OH + KX
AgOH
R–OH + AgX
Ag2O
R–OH + AgX
Moist
H2 O
R–OH + HX
D
– +
R–ONa
R–OR + NaX (Williamson ether synthesis reaction)
ether
O
– + O
R–C–OAg
R–C–OR + AgX
ester
+ –
Åd 1d NaI
R–X R–I + Nax (Finkelstein reaction)
Acetone
CH3X, R-CH2X, R2CHX, R3CX AgF
R–F + AgX (Swarts reaction)
Åd 1d
H–NH2 + –
S N1 R–NH2 + HX ® RNH3X KOH R–NH2 + KX + H2O
1°amine
HÅd
1d
S N2 R–N H + – KOH
R2NH + HX ® R2NH2X R 2NH + KX + H2O
2°amine
1dÅd
R2NH + –
R3N + HX ® R3NHX KOH R3N + KX + H2O
3°amine
R3N + –
R4NX
Tetra Alkyl Ammonium Halide
2H
R–H + HX
LiAlH4 Alkane
KCN
R–CºN
Alkyl cyanide
AgCN
R–N=C
Alkyl isocyanide
+–
KO–N=O R–O–N=O
Alkyl nitrite
O
AgNO2
R–N
O
Nitroalkane
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l Electrophilic Substitution Reaction 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 D
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
(Minor) CH3
(5) Friedel Craft reaction (Major)
(Acetylation) Cl Cl
COCH3
CH3COCl
+
anhyd AlCl 3
2-Chloroacetophenone
(Minor) COCH3
(Major)
l Markownikoff's rule—Haloalkanes are also prepared by the action halogen acid (HX) on alkene.
The reaction follows Markownikoff's rule, that states the negative part of the reagent goes to the carbon
bearing less number of hydrogen atoms.
l Alkyl halides are slightly soluble in water because they do not form H-bonds with water.
l Due to better symmetry of para isomers as compared to ortho and isomers, para isomers have high
melting points as compared to their ortho and meta isomers.
l Chiral chirality—An object or molecule which is non-suprimposable on its mirror image is called
chiral and the property is called chirality.
l A chiral or asymmetruic carbon—is that, in which all the four valencies are satisfied by four different
groups. Such a carbon bearing molecule is generally optically active.
l racemic mixture—An equimolar mixture of two enantiomers (d and l-forms) is called racemic
mixture. It is represented as dl of ± forms and will be optically inactive. The process of converting
d of l-form of an optically active compound into racemic mixture (dl) is called recemisation.
l In electrophilic substitution reactions, Cl, Br etc. are ortho/para directing groups and direct the incoming
group to ortho and para positions.
l haloarenes are less reactive than haloalkanes towards nucleophilic substitution rections, due to resonace
2
effect (double bond character between C–Cl bond), sp -hydridisation of C bearing halogen atom and
instability of phenyl cation.
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EXERCISE-1 NCERT IMPORTANT QUESTION
1. Why is sulphuric acid not used during the reaction of alcohols with KI ?
Ans. In the presence of sulphuric acid (H2SO4), KI produces HI
2KI + H2SO4 ¾® 2KHSO4 + 2HI
Since H2SO4 is an oxidizing agent, it oxidizex HI in I2
2HI + H2SO4 ¾® I2 + SO2 + H2O
As a result, the reaction between alcohol and HI to produce alkyl iodide cannot occur.
So in place of H2SO4 a non oxidising acid such as H3PO4 is used.
2. Among the isomeric alkanes of molecular formula C5H12, identify the one that on photochemical
chlorination yeilds.
(i) A single monochloride
(ii) Three isomeric monochlorides
(iii)Four isomeric monochlorides
CH3 CH3
Cl2
Ans. (i) CH3–C–CH3 CH 3–C–CH 2–Cl
CH3 CH3
Neopentane (C 5H12)
gives only one monochloride
CH3–CH2–CH2–CH2 (I)
|
Cl
Cl2
(ii) CH3–CH2–CH2–CH2–CH3
CH3–CH2–CH2–CH–CH 3 (II)
n-Pentane Cl
Gives three monochloride
CH3–CH2–CH–CH2–CH 3 (III)
Cl
CH3
CH3–CH–CH2–CH2–Cl
(1)
CH3
a
CH3 CH3–CH–CH–CH 3
a b c d Cl2 (2)
(iii) CH3–CH–CH2–CH3 Cl
Iso Pentane CH3
Gives four monochloride
CH3–CH–CH2–CH3
(3)
Cl
CH3
CH2–CH–CH2–CH3
(4)
Cl
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3. Draw the structure of major monohalo products in each of the following reactions :
OH CH2CH3 Br2, heat or
(i) + SOCl2 (ii) UV light
O2N
CH2OH heat CH3
(iii) + HCl (iv) + HI
HO
heat
(v) CH3CH2Br + NaI (vi) + Br2
UV light
Ans. (i)
(ii)
(iii)
(iv)
(v)
(vi)
4. Identify A, B, C, D, E, R and R1 in the following :
dry ether H 2O
(i) Br + Mg A B
dry ether
(ii) R – Br + Mg C D2 O CH3CHCH3
D
CH3 CH3
Na ether Mg H2 O
(iii) CH3––––––––––CH3
1
R –X D E
CH3 CH3
Ans. (i)
CH3
Dry ether D2O
(ii) RBr + Mg CH3–CH–MgBr CH3–CH–CH3
(C)
D
(iii) Therefore, the compounds R – Br is
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Therefore, compound D is
And, compound E is
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.
The reactions involved in the question are :

Cl2 No reaction
dark
Cl
sun Cl2
ligh
t
Cyclopentane
Mono chlorocyclopentane (C5H 10)

6. 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 D
CH3–CH2–CH=CH2
Peroxide
CH3–CH2–CH2–CH2–Br
NaI
CH3–CH2–CH2–CH2–I
dry acetone
(ii) CH3–CH2–CH2–CH2–Cl + NaI (Finkelstein reaction) CH3–CH2–CH2–CH2–I + NaCl
(iii)
7. 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-methyllcyclohexane
(ii) 2-Chloro-2-methyllbutane
(iii) 2,2, 3-Trimethyl-3-bromopentane
Br CH3 Alc. NaOH/KOH

CH3
OR C 2H 5ONa
Ans. (i) + HBr
OR
(C2H 5OH+NaOH) (Only one alkene)
CH3 CH3
Alc. NaOH/KOH
(ii) CH3–––CH2–––C–––CH3 –HCl
CH3–––CH=C–––CH3
Cl 2-Methyl-2-butene (major)
+
CH3
CH3–––CH2–––C=CH2
2-Methyl-1-butene (minor)
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CH3 Br Alc. NaOH/KOH CH3

OR C 2H 5ONa
(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-dimethylbut-1-ene (II) (minor)
8. Write the structure of the major organic product in each of the following reactions.
ace to ne
(i) CH3 CH2 CH2 Cl + Nal ¾¾¾¾®
heat (ii) ( CH3 )3 CBr + KOH ¾¾¾¾
ethanol
heat ®
(iii) CH3 CH(Br)CH2 CH3 + NaOH ¾¾¾

water
¾
® (iv) CH3 CH2Br + KCN ¾¾¾¾¾
aq.acetone
®
(v) C6H5ONa + C2H5Cl ¾¾® (vi) CH3CH2CH2OH+SOCl2 ¾¾®
(vii) CH3CH2CH = CH2 + HBr ¾¾¾¾

Peroxide
® (viii) CH3CH=C(CH3)2 + HBr ¾¾®
Ans. (i)
(ii)
water
(iii) CH3CH(Br)CH2CH3 + NaOH ¾¾¾ ® CH3CH(OH)CH2CH3 + NaBr
(iv) CH3CH2Br + KCN ¾¾¾¾¾

aq.ethanol
® CH3CH2CN + KBr
(substitution )
Nucleophilic
(v) C6 H5 ONa + C2H5 Cl ¾¾¾¾¾ ¾

® C6 H5 - O - C2H5 + NaCl
(synthesis )
William son ' s
(vi) CH3CH2CH2OH + SOCl2 ¾¾® CH3CH2CH2Cl + SO2 + HCl
(vii) CH3CH2CH = CH 2 + HBr ¾¾¾¾¾¾¾ Peroxide

¾
® CH 3CH2CH2CH2 - Br
(
Anti - Markovnikov ' s
addition )
(viii)
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9. Write the mechanism of the following reaction :
EtOH - H2 O
nBuBr + KCN ¾¾¾¾¾ ® nBuCN
Ans. The given reaction is :
EtOH - H2 O
nBuBr + KCN ¾¾¾¾¾ ® 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 C 3H 5
C3H5 –
C–Br NC C Br NC—C + Br
H H
H H H H
10. 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 µ Steric hindrance
Br Br
CH3CH2CH2CH2CH2 – Br > CH3CH2CH2CHCH3 > CH3CH2CCH3

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

CH3 CH 3
1-Bromo-3-methylbutane 2-Bromo-3-methylbutane 2-Bromo-2-methylbutane
(1°) (2°) (3°)

Since steric hindrance in alkyl halides increases in the order of 1° < 2° < 3°, the increasing order
of reactivity towards SN2 displacement si 3° < 2° < 1°.
Reactivity towards SN2 is
1-Bromo-2-methylbutane > 2-Bromo-3-methylbutane > 2-Bromo-2-methylbutane
CH3 CH 3 CH 3
(iii) CH3–CH2–CH2–CH2–Br CH3– CH–CH2–CH2–Br CH3– CH2–CH–CH2– Br CH3–C–CH2–Br
1-Bromobutane (1°) 1-Bromo-3-methylbutane (1°) 1-Bromo-2-methylbutane (1°) CH 3
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.
11. Out of C6H5CH2Cl and C6H5CHClC6H5, which is more easily hydrolysed by aqueous KOH ?
Ans. C6H5 CHCl C6H5 (more reactive)
+
(i) C6H5–CH2–Cl –Cl– C6H5–CH 2 (Less stable intermediate)
Benzyl chloride (1°) 1° carbocation
Cl
+
(ii) C6H5–CH–C6H5 –Cl
– C6H5–CH–C6H5 (More stable intermediate)
Chlorodiphenylmethane 2° carbocation
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12. 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 b-carbon. So
R–Cl + Aq. KOH ¾¾® R–OH + KCl
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 b-carbon of the alkyl chloride and form an alkene
by eliminating a molecule of HCl.
R - CH 2 - CH2 - Cl + KOH (alcoholic) ¾¾® R - CH = CH2 + KCl + H2 O
Alkyl chloride Alkene
13. Identify the chiral molecule in the following pair :
(i) (ii)
Cl Cl
Ans. (i)
14. (a) Draw the structures of major monohalo products in each of the followings reactions:
PCl5
(i) CH2OH
(ii) CH2–CH = CH 2 + HBr
(b) Which halogen compound in each of the following pairs will react faster in SN2 reaction :
(i) CH3Br or CH3I
(ii)(CH3)3 C – Cl or CH3 –Cl
Ans. (a) (i) CH2Cl (ii) CH2–CH – CH3

Br
(b) (i) CH3Br (ii) CH3–Cl
15. 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.
Ans. (I) SN2 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
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16. Write IUPAC name of the following compounds -
Cl
CH3
(a) CH3–C–—CH–CH3 (b) (c) CH3–CH–CH2—CH–CH3
CH3
CH3 Cl Br Cl
Cl
Ans. (a) 2-Chloro-3,3-dimethylbutane (b) 1,4-dichloro-2-methylbenzene

(c) 2-bromo-4-chloropentane
17. Give reasons for the following
(i) Ethyl iodide undergoes SN2 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) Iodie 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 double bond character while in CH3–X, C–X bond is a single bond.
18. What happens when bromine attacks
CH2 = CH – CH2 – C º CH
Ans. CH2 = CH – CH2 – C = C – Br
Br
19. (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

I Cl
or
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.
H3C 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.
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20. How would you differentiate between SN1 & SN2 reaction mechanism of substitution reaction ? Give
one ex. of each.
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.
21. (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
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 double bond character between C & Cl, C
is sp2 hybridised so more electronegative thus Cl – is not
replaced easily
–Cl :
:
+Cl :
:
+ Cl :
:
:
Cl : : Cl :
:
22. Write the IUPAC name of following compound.

H CH3
H
H
H Br
Ans. 3-bromo-2-methyl prop-1-ene
23. Which one in the following pairs undergoes SN1 substitution reaction faster and why
Cl
Cl or
(i)
Cl
or Cl
(ii)
Cl
Ans. (i) tertiary halide reacts faster than sec. halide tertiary carbocation intermediate.
Cl
(ii) reacts faster because of greater stability of secondary carbocation than primary
24. Complete reaction :

CH3
(i) + HI ? (ii) CH3CH2CH=CH2 + HBr ¾® ?
CH3
Ans. (i) I (ii) CH3–CH2–CH–CH3
Br
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25. Suggest a possible mechanism for the reaction n BuBr + KCN ¾® n-BuCN
C3H5 C3H5
Ans. C–Br NC C Br
H H H
H
C3H5 –
NC—C + Br
H
H
26. 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
REASONING :
1. Chlorobenzene is less reactive than chloromethane
Ans. In chlorobenzene, each carbon atom of benzene ring is sp2 hybridised and is electron withdrawing.
Chlorine atom donates a lone pair of electron and acquire positive charge. The negative charge is
delocalised on ortho and para position by resonance.
Å Å Å
:
:
Cl Cl Cl Cl Cl
: : : :
Q Q
Q
C-Cl bond acquires partial double bond character and larger amount of energy is required to break C-
Cl bond in chlorobenzene and therefore is less reactive than haloalkane towards nucleophilic
substitution reaction.
2. Haloalkanes react with KCN to form alkyl cyanide as main product while AgCN form isocyonide.
+KCN
R–CN + KX
R–X +AgCN
R–N=C + AgX
Ans. KCN is, predominantly ionic compound and provide cyanide ion : C º N && in solution. The attack
mainly takes place through lone pair of electron on carbon atom due to high electron density and
not through nitrogen atom since C-C bond is more stable than C-N bond. AgCN is mainly a
covalent compound therefore, nitrogen donates electron pair forming isocyanide as the main
product.
3. Grignard Reagent is prepared under anhydrous conditions.
Ans. In Grignard Reagent, the carbon-magnesium covalent bond is highly polar with carbon atom of
alkyl or aryl group withdrawing electrons from electropositive magnesium and magnesium halogen
bond is also ionic
d- d++ d-
R - Mg- X . So Grignard reagent is highly reactive, and react with any source of proton to give
hydrocarbons.
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R – Mg – X + H2O ® R – H + Mg(OH)X
4. Why is Wurtz Reaction is carried in dry ether.
Ans. CH 3 Br + 2Na + Br - CH 3 ¾¾¾¾

dry other
® CH3 – CH3+2NaBr
Sodium metal is sensitive towards air and moisture forming :

4Na + O2 ® 2Na2O
2Na + 2H2O ® 2NaOH + H2
So reaction is carried in dry ether to avoid air and moisture.
5. SN1 reactions are favoured in protic solvent.
Ans. It involves C-X bond breakage for which the energy required is obtained through solvation of
halide ion with the protons of protic solvent like H2O, alcohol etc.
6. Tertiary halides donot undergo SN2 mechanism.
Ans. In SN2 reaction, the nucleophile attacks to the carbon atom from the opposite side of halide atom.
Three alkyl groups cause a steric hinderance to the approach of nucleophile.
7. Although chlorine atom is an electron withdrawing group yet it is ortho and para directing in
electrophilic aromatic substitution reactions.
Ans. Chlorine withdraws electrons through inductive effect and releases electrons through resonance.
Through inductive effect, chlorine destabilises the intermediate carbocation formed during the
electrophilic substitution. Reactivity is thus controlled by the stronger inductive effect and
orientation is controlled by resonance effect.
CHEMICAL TEST :
III. Difference between Alkyl Halide and Aryl Halide
Cl
(i) Chemical Test Chloroethane (C2H5Cl) Chlorobenzene
White precipitate of AgCl

(1) Add aq NaOH + AgNO 3 No change
is formed which is soluble
excess of NH 4OH
C2H5Cl + NaOH (aq) ¾® C2H5OH + NaCl

NaCl + AgNO3 ¾® AgCl (white ppt) + NaNO3
(ii) Test Chloroethane CH3CH2Cl Bromoethane CH3CH2Br
(1) Add aq NaOH + AgNO 3 White ppt (AgCl) Creamy yellow ppt (AgBr)
(2) Add NH4OH in both White ppt get dissolved Yellow ppt dissolved partly
test tube in NH 4OH in NH4OH
16 E
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CH2Cl Cl
(iii) Test Benzyl chloride Chlorobenzene
(1) Add aq NaOH + AgNO 3 White ppt of AgCl is formed which is No change
soluble in excess of NH4OH
NAME REACTIONS :
1. 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 ¾¾¾¾¾
Dry acetone
® 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)
2. 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 ¾® H3C – F + AgX
(X = Cl, Br)
Note: Finkelstein Reaction and Swarts Reaction are known as halogen exchange reaction.
3. 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.
CH3Br + 2Na + BrCH 3 ¾¾¾¾

dry ether
® CH 3 - CH 3 + 2NaBr
Bromomethane Ethane
C2 H 5 Br + 2Na + BrC 2 H 5 ¾¾¾¾

dry ether
® CH 3CH 2 CH 2 CH 3
Bromoethane n - Butane
4. Wurtz-Fittig Reaction
A mixture of an alkyl halide and aryl halide gives an alkylarene when treated with sodium in dry ether
and is called Wurtz-Fittig reaction.
X R
Ether
+ Na + RX + Na X
5. Fittig 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 Fittig reaction.
X
Ether
2 + Na + 2NaX
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6. Friedel-Crafts alkylation Reaction
When benzene is treated with an alkyl halide in the presence of anhydrous aluminium chloride,
alkylbenzene is formed.
CH3
Anhyd. AlCl 3
+ CH3Cl + HCl
Toluene
(13.75)
C2H5
Anhyd. AlCl 3
+ C2H5Cl + HCl
Ethylbenzene
Cl Cl Cl
CH3
Anhyd. AlCl 3
+ CH3Cl
1-Chloro-2-methylbenzene CH3
(Minor)
(Major)
OCH3 OCH3 OCH3

CH3
Anhyd. AlCl 3
+ CH 3Cl CS 2 +
Anisole 2-Methoxytoluene CH3

(Minor)
4-Methoxytoluene
(Major)
MECHANISM :
Mechanism of SN1 & SN2 :
Ans. (a) Substitution nucleophilic bimolecular (SN2)
The reaction between CH3Cl and hydroxide ion to yield methanol and chloride ion follows a second
order kinetics, i.e., the rate depends upon the concentration of both the reactants.
(b) Substitution nucleophilic unimolecular (SN1)

SN1 reactions are generally carried out in polar protic solvents (like water, alcohol, acetic acid,
etc.). The reaction between tert-butyl bromide and hydroxide ion yields tert-butyl alcohol and
follows the first order kinetics, i.e., the rate of reaction depends upon the concentration of only
one reactant, which is tert- butyl bromide.
(CH3)3CBr + –OH (CH3)3COH + Br–
2-Bromo-2- methylpropane 2-Methylpropane-2-ol
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It occurs in two steps. In step I, the polarised C—Br bond undergoes slow cleavage to produce a
carbocation and a bromide ion. The carbocation thus formed is then attacked by nucleophile in step
II to complete the substitution reaction.
CH3
(CH3)3 CBr ¾¾¾¾

Step I
¬¾¾¾ ®
¾ Å + BrΘ
H 3C CH3
CH3
Å + –OH ¾¾¾¾
Step II
® (CH3 )3COH
H 3C CH3
Step I is the slowest and reversible. It involves the C–Br bond breaking for which the energy is obtained
through solvation of halide ion with the proton of protic solvent. Since the rate of reaction depends
upon the slowest step, the rate of reaction depends only on the concentration of alkyl halide and not
on the concentration of hydroxide ion.
IMPORTANT CONVERSIONS :
1. How will you bring about the following conversion ?
(i) Ethanol to but-1-yne (ii) Propene to 1-nitropropane (iii) Toluene to benzyl alcohol
(iv) Ethanol to ethyl fluoride (v) Bromomethane to propanone
(vi) But-1-ene to but-2-ene
(vii) 1-Chlorobutane to n-octane (viii) Benzene to biphenyl
Ans. (i) CH3CH2 OH ¾¾¾¾¾¾
SOCl .Pyridine Na–C ºCH
® CH3CH2Cl ¾¾¾¾¾
2
® CH3 – CH2 – C º CH
Ethanol Chloroethane
(ii) CH3 - CH = CH2 + HBr ¾¾¾¾

Peroxide
® CH3 - CH2 - CH2Br ¾¾¾¾
AgNO
® CH 3 - CH2 - CH2NO 2 2
Pr opene 1 -Bromppropane 1 -Nitropropane
(iii)
PCl 5 AgF
(iv) CH3–CH2–OH CH3–CH2– Cl CH3–CH2– F
Ethanol Chloroethane Ethyl fluoride
KCN (alc) CH 3–MgBr Hydrolysis

(v) CH3 – Br CH3 – CN CH3–C=NMgBr + CH3–C=O
Bromomethane Acetonitrile H3O
CH3 CH3
Propanone
Br
HBr KOH (alc).D
(vi) CH3CH2CH=CH2 (Markovnikov CH3CH2CHCH3 –HBr
CH3CH2=CHCH3
2-Bromobutane 2-Butene
But-1-ene addition)
dry ether
(vii) 2CH3CH2CH2CH2–Cl + 2Na –2NaCl CH3CH2CH2CH2CH2CH2CH2CH3
1-Chlorobutane n-Octane
Br
Br2/Fe Na
(viii) dark Dry ether + 2NaBr
Benzene Bromobenzene Diphenyl
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2. How the following conversions can be carried out ?
(i) Propene to propan-1-ol (ii) 1-Bromopropane to 2-bromopropane
(iii) Benzene to 4-bromonitrobenzene (iv) Benzyl alcohol to 2-phenylethanoic acid
(v) Ethanol to propanenitrile (vi) Aniline to chloro benzene
(vii) 2- Chlorobutane to 3, 4-dimethylhexane
(viii) 2-Methyl-1-propene to 2-chloro-2-methyl propane
(ix) Ethyl chloride to propanoic acid (x) But-1-ene to n-butyliodide
(xi) 2-Chloropropane to 1- propanol (xii) Isopropyl alcohol to iodoform
(xiii) Chlorobenzene to p-nitrophenol (xiv) 2-Bromopropane to 1-bromopropane
(xv) Chloroethane to butane (xvi) tert-Butyl bromide to isobutyl bromide
(Nucleophilic
HBr/Peroxide substitution)
Ans. (i) CH3–CH=CH2 (Ani-Markovnikov
CH3–CH2–CH2–Br
Aq KOH/D
CH3–CH2–CH2–OH
addition) 1°-Bromopropane Propan-1-ol
Propene
Markovnikov Br
KOH(alc)/D addition
(ii) CH3–CH2–CH2–Br (Dehydrohalogenation)
CH3–CH=CH2
HBr
CH3–CH–CH3
1-Bromopropane Propene 2-bromopropane
Br Br
Br2/FeBr3 HNO3/H2SO 4
(iii) Dark (Nitration)
Benzene Bromobenzene NO2
4-Bromonitrobenzene
2 1
CH2OH CH2Cl CH2CN CH2COOH
PCl5 KCN, Aq. ethanol (Hydrolysis)
(iv) +
H /H2O
Benzyl alcohol Benzyl cryanide 2-Phenylethanoic acid
(v) CH3 - CH2 - OH ¾¾¾¾

redP / Br KCN,Aq.ethanol
® CH 3 - CH2 - Br ¾¾¾¾¾¾
2
® CH3 - CH2 - CN
Ethanol Bromoethane Propanenitrile
(vi)
Cl CH 3 CH3
2Na/dry ether
(vii) 2CH3–CH–CH2–CH3 (Wurtz reaction) CH3–CH2–CH–CH–CH2–CH3 + 2NaCl
2-chlorobutane 3, 4-dimethylhexane
CH3 CH 2
HCl
(viii) CH3–C=CH2 (Markovnikov
CH3–C–CH3
2-Methyl-1-propene addition) Cl
2-chloro-2-methylpropane
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KCN aq. etharol (Hydrolysis)
(ix) CH3–CH2–Cl (nucleophilic CH3–CH2–CN CH3–CH2–COOH
H +/H2O
substitution) Propanenitrile Propanoic acid
Ethylchloride
Finkelstein
HBr/Peroxide reaction
(x) CH3–CH2–CH=CH2 (Anti-Markovnikov
CH3–CH2–CH2–CH2–Br
Nal/dry acetone
CH3–CH2–CH2–CH2—I
addition) Bromobutane n- Butyl iodide
But-1-ene
Cl
KOH(alc)/D (i) B2H6
(xi) CH3–CH–CH3 (Dethydrohalogenation)
CH3–CH=CH 2 CH3CH2CH2OH
(ii) H2O 2 + NaOH
2-Chloropropane Propene 1-Propanol
HBr/Peroxide (Anti-Markovnikov
addition)
Aq. KOH/D
CH3– CH2–CH2–OH (Nucleophilic
CH3–CH2–CH2–Br
1-Propanol substitution) 1-Bromopropane
OH O O
CrO3 NaOI
(xii) CH3–CH–CH3 (Oxidation)
CH3–C–CH 3 CH3–C–ONa + CHI3
(Iodoform reaction)
Propanone Iodoform
Isopropyl alcohol (NaOH + I2)
(xiii)
Br (Anit-Markovnikov
KOH(alc)/D addition)
(xiv) CH3–CH–CH3 Dehydrohalogenation CH3–CH=CH2+HBr CH3–CH 2–CH 2–Br
Propene HBr/peroxide
2-Bromopropane 1- Bromopropane
(xv) CH3CH2 - Cl ¾¾¾¾¾¾

2Na / dryether
( Wurtz reaction ) ® CH3 - CH2 - CH2 - CH3
Chloroethane Butane
Br
(xvi) CH3–C–CH3 KOH(alc)/D HBr/Peroxide
Dehydrohalogenation
CH3–C=CH2 (Anit-Markovnikov
CH3–CH–CH2–Br
CH3 CH3 addition) CH3
Tert-Butylbromide 2-Methylpropene Isobutyl bromide
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WORD PROBLEMS :
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-bulyl bromide and
isobutyl bromide.
(i) CH3–CH2–CH2–CH2–Br (ii) 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.
2Na / dry ether
2CH 3CH2CH2CH2Br ¾¾¾¾¾¾
(Wurtz reaction )
® CH 3CH2CH2CH2CH2CH2CH2CH3 + 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)/D
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)
CH 3–C–CH3
CH3 CH3
2-Methylpropene (b) 2-Bromo-2-methylpropane (c)
(an isomer of (a))
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EXERCISE-2 PREVIOUS YEARS QUESTION
1. Read the given passage and answer the questions number 1 to 5 that follow : 1× 5 = 5
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. (CBSE 2020)
(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
2. 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 / sp 3 hybridised carbon in cyclohexyl chloride whereas sp 2 carbon in
chlorobenzene.
3. Among all the isomers of molecular formula C4H9Br, identify :
(a) the one isomer which is optically active. (CBSE 2019)
(b) the one isomer which is highly reactive towards SN 2 .
(c) the two isomers which give same product on dehydrohalogenation with alcoholic KOH.
[3]
Ans. (a) CH3CH2CH(Br)CH3
(b) CH3CH2CH2CH2Br
(c) (CH3)3Br and (CH3)2CHCH2Br
4. Out of Chlorobenzene and p-nitrochlorobenzene, which one is more reactive towards nucleophilic
substitution reaction and why ? [1]
(CBSE 2019)
Ans. p-nitrochlorobenzene undergoes nucleophilic substitution reaction faster than chlorobenzene due
to resonance effect.
5. Out of chlorobenzene and benzyl chloride, which one gets easily hydrolysed by aqueous NaOH
and why ? (CBSE 2018)
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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 p-Bond of benzene due to which partial double bond character
develop & it reduce its reactivity.
6. (a) Identify the chiral molecule in the following pair : (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/D
(c) +
(major) (minor)
X
X
7. Out of and , which is an example of vinylic halide? (CBSE 2017)
X
Ans.
8. The following compounds are given to you : (CBSE 2017)

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 b-elimination reaction.
Ans. (i) 1–Bromopentane (ii) 2–Bromopentane (iii) 2–Bromo–2–methylbutane
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9. Write the major monohalo product(s) in each of the following reactions: (CBSE 2016)
CH2–CH=CH2
UV light Peroxide
(i) +Br2 ? (ii) +HBr ?
CH2OH
Heat
(iii) +HCl ?
OH
Br
CH2–CH2–CH2Br CH2Cl
Ans. (i) (ii) (iii)
HO
10. Which of the following two reactions is SN2 and why ? (CBSE 2016)
C2H5 C2H5
Y
H H
(i) (ii) X CH3 Y CH3
Retantion
Ans. (i) Inversion of configuration
11. Which would undergo SN2 reaction faster in the following pair : (CBSE 2015)
C6H5 – CH2 – CH2 – Br and C 6H 5 – CH – CH3
Br
Ans. C6H5–CH2CH2–Br
12. How do you convert the following : (CBSE 2015)
(i) Prop-1-ene of Propan-2-ol (ii) Bromobenzene to 2-bromoacetophenone
(iii) 2-bromobutane to But-2-ene
+
H2O/H
Ans. (i) CH3–CH=CH2 CH3–CH(OH)–CH3
Br Br O
CH3COCl/Anhy AlCl3 C–CH3
(ii) D
Br
KOH(Alc)
(iii) CH3–CH 2–CH–CH3 CH3–CH=CH–CH3 (or any other correct method)
13. What happens when (CBSE 2015)
(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.
Acetone
Ans. (i) C2H5Cl + NaI C 2H5I + NaCl
Dry ether
(ii) Cl + 2Na + Cl D
+2NaCl
D
(iii) CH3Cl + KNO2 CH3–ONO + KCl
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EXERCISE-3 R AC E
Type 1 : Passage question 1 :-
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.
(i) When anisole is treatest with HI the product obtained is?
(a) Phenol & methyl iodide
(b) Iodobenzene & methanol
(c) Methyl iodide & methyl alcohol
(d) Phenol & methyl alcohol
(ii) Name the instrument used for measuring the angle by which the plane polarised light is rotated.
(a) (b) Polarimeter
(c) Polariser (d) None of these
(iii) Predict the major product formed when 2-Bromopentane reacts with alcoholic KOH.
(a) Pent-1-ene (b) Pent-2-ene
(c) Pentane (d) But-1-ene
(iv) The conversion of an alkyl halide into an alcohol by aqueous NaOH is classified as
(a) a dehydrohalogenation reaction
(b) a substitution reaction
(c) an addition reaction
(d) a dehydration reaction
Type 2 : Assertion and Reason :-
Question 2 to 6 :- Note:- In the following questions a statement of assertion followed by a reason
. choose the correct answer out of the following choices –
(A) both assertion and reason are true , and reason is the correct explaining of the assertion
(B) both assertion and reason are true but reason is not the correct explaining of the assertion
(C) Assertion is not true but reason is true
(D) Both assertion and reason are false
2. Assertion : Aryl iodides can be prepared by reaction of arenes with iodine in the presence of an
oxidising agent.
Reason : Oxidising agent oxidises I2 into HI.
3. Assertion : It is difficult to replace chlorine by –OH in chlorobenzene in comparison to that in
chloroethane.
Reason : Chlorine-carbon (C—Cl) bond in chlorobenzene has a partial double bond character
due to resonance.
4. Assertion : Phosphorus chlorides (tri and penta) are preferred over thionyl chloride for the
preparation of alkyl chlorides from alcohols.
Reason : Phosphorus chlorides give pure alkyl halides.
26 E
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5. Assertion : KCN reacts with methyl chloride to give methyl isocyanide.
Reason : CN¯ is an ambident nucleophile.
6. Assertion : Presence of a nitro group at ortho or para position increases the reactivity of
haloarenes twowards nucleophilic substitution.
Reason : Nitro group, being an electron withdrawing group decreases the electron density
over the benzene ring.
Type 3 : Multiple choice quation (one correct answer) (Queations 7 to 16):-
7. In the reaction R – OH + PBr3 ¾® RBr. The number of moles of alcohol that may be converted in
to akyl-bromide by one mole of PBr3 is
1
(i) 1-mole (ii) 2-moles (iii) 3-moles (iv) mole
3
8. A equimolar mixture of methyl iodide and ethyl iodide is heated with sodium and dry ether. The
number of possible alkane product is
(i) one (ii) two (iii) three (iv) four
9. The major product formed in the following reaction
CH 3
|
CH 3 - C - CH - CH 3 + HBr ¾¾
®
| |
CH 3 OH
(i) (CH3)3CCHBrCH3
(ii) (CH3)3CCH = CH2
(iii) (CH3)2CBrCH(CH3)2
(iv) (CH3)2C = C(CH3)2
10. Toluene reacts with a halogen in the presence of iron (III) chloride giving ortho and paral halo
compounds. The reaction is
(i) Electrophilic elimination reaction (ii) Electrophilic substitution reaction
(iii) Free radical addition reaction (iv) Nucleophilic substitution reaction
11. Which reagent will you use for the following reaction?
CH3CH2CH2CH3 ¾® CH3CH2CH2CH2Cl + CH3CH2CHClCH3
(i) Cl2 / UV light (ii) NaCl + H2SO4
(iii) Cl2 gas in dark (iv) Cl2 gas in the presence of iron in dark
12. The order of reactivity of following alcohols with halogen acids is ___________.
CH 3
|
(a) CH3CH2 — CH2 — OH (b) CH3CH2 - CH - OH (c) CH 3 CH 2 - C - OH
| |
CH 3 CH 3
(i) (a) > (b) > (c) (ii) (c) > (b) > (a) (iii) (b) > (a) > (c) (iv) (a) > (c) > (b)
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13. Which of the following is halogen exchange reaction?
(i) R X + NaI ¾® RI + NaX
C=C + HX C–C
(ii)
H X
ZnCl2
(iii) R – OH + XH ¾¾¾¾
® R–X+H O
2
CH3 CH3 CH3
Fe
(iv) + X2 +
dark X
X
14. Arrange the following compounds in increasing order of their boiling points.
CH 3
|
CH3
CH – CH2Br H3 C - C - CH 3
(a) (b) CH3CH2CH2CH2Br (c) |
CH3
Br
(i) (b) < (a) < (c) (ii) (a) < (b) < (c) (iii) (c) < (a) < (b) (iv) (c) < (b) < (a)
15. 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?
(i) Cl¯ (ii) Cl+ (iii) AlCl3 (iv) [AlCl4]¯
16. A primary alkyl halide would prefer to undergo _____________.
(i) SN1 reaction (ii) SN2 reaction (iii) a–Elimination (iv) Racemisation
Answer key :
Q. No. 1 (i) (ii) (iii) (iv) 2 3 4 5 6 7 8
Ans. a b b b A A C C A iii iii
Q. No. 9 10 11 12 13 14 15 16
Ans. iii ii i ii i iii ii ii
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EXERCISE-4 MOCK TEST
1. Write the IUPAC name of following compound. [1]
H CH3
H
H Br
H
X
X
2. Out of and , which is an example of vinylic halide? [1]
3. Which would undergo SN2 reaction faster in the following pair : [1]
C6H5 – CH2 – CH2 – Br and C 6H 5 – CH – CH3
Br
4. Which one of the following compound is more easily hydrolysed by KOH & Why. [2]
CH3CHClCH2CH3 or CH3CH2Cl
5. Write the structure of the product when chlorobenzene is treated with methyl chloride in the
presence of sodium metal and dry ether. [2]
6. Complete reaction : [2]
CH3
(i) + HI ? (ii) CH3CH2CH=CH2 + HBr ¾® ?
7. Write a chemical test to distinguish between [2]

(a) Chlorobenzene & benzyl chloride (b) Chloroform & CCl4
8. Suggest a possible mechanism for the reaction n BuBr + KCN ¾® n-BuCN [3]
9. Give reasons for the following [3]

(i) Ethyl iodide undergoes SN2 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.
10. 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
11. 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 PCl5
(iii) +HCl ? (iv) CH2OH
OH
(v) CH2–CH = CH2 + HBr
E 29
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MOCK TEST SOLUTIONS
1. 3-bromo-2-methyl prop-1-ene
X
2.
3. C6H5 – CH2CH2 – Br
4. CH3CHClCH2CH3 is more reactive than CH3CH2CH2CH2Cl as the former one gives more stable
carbocation intermediate.
H3C H H3C H – HC
H
C OH
+ 3
CCl C— OH
H3CCH2 H3CCH2 H3CH2C
Cl CH3
Na
5. + CH3–Cl
dry ether
Toluene
CH3
6. (i) I (ii) CH3–CH2–CH–CH3
Br
7. (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.
C3H5 C3H5
8. C–Br NC C Br
H H H
H
C3H5 –
NC—C + Br
H
H
9. (i) Iodide is better leaving group because of its larger size than bromide therefore ethyl idoide under
goes SN2 reaction faster than ethyl bromide.
30 E
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ALLEN
(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.
H O/H +
10. (i) CH 3 - CH = CH 2 ¾¾¾¾®
2
CH 3 - CH(OH) - CH 3
Br Br O
CH3COCl/Anhy AlCl3 C–CH3
(ii)
D
Br
|
KOH (Alc)
(iii) CH 3 - CH 2 - CH - CH 3 ¾¾¾¾¾ ® CH 3 - CH = CH - CH 3 (or any other correct method)
Br CH2Cl
CH2–CH2–CH2Br
11. (i) (ii) (iii)
HO
(iv) CH2Cl (v) CH2–CH – CH3

Br
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ALCOHOL, PHENOL & ETHER
l Hydroxyl (–OH) derivatives of alkane are called alcohols.
l Alcohols are classified as 1°, 2° and 3°.
l –OH group is attached to sp3 hybridized carbon, Alcohols further may be monohydric, dihydric and
polyhydric on the basis of OH grpup.
l Phenols : Compounds containing –OH group bound directly to benzene ring.
CH3
OH CH3 CH3
OH
OH OH
Common Name Phenol o-Cresol m-Cresol p-Cresol
IUPAC Name Phenol 2-Methylphenol 3-Methylphenol 4-Methylphenol
OH
OH OH
OH
OH OH
Common name Catechol Resorcinol Hydroquinone or quinol
IUPAC Name Benzene-1,2-diol Benzene-1,3- diol Benzene-1,4- diol
l Strucutres : Oxygen atom is sp hybridised and tetrahedral geometry of hybrid atomic orbitals ROH
3
bond angle depends upon the R group. R–O–H angle for CH3–OH is 108.9°.
H
s-Bond
node06\B0B0-BA\Kota\Board Material\Chemistry\CBSE\CBSE Booklet\English\Updated booklet-21\New Pattern CBSE Booklet\Part wise boocklet\Part 2\03_OC\02_Alcohol, phenol & Ethers
H C 142 pm 96 pm
108.9°
H H
l Isomerism :
(i) Functional isomerism
(ii) Chain isomerism
(iii) Positional isomerism
l General methods of preparation :
(i) Acid catalysed hydration of alkenes :
OH
dil. H 2SO 4
CH3–CH=CH2+H2O CH3–CH–CH 3
(ii) Hydroboration oxidation :
-
® (CH3–CH2–CH2)3B ¾¾¾ ® CH3–CH2–CH2OH +H3BO3
OH
3CH3–CH=CH2 + ½B2H6 ¾¾¾
D.E.
H O 2 2
(iii) From carbonyl compounds with Grignard’s reagent :
R R OMgBr R OH Br
C = O + R–MgBr ¾¾¾
Dry
® C H 3O + C + Mg
ether H R ¾¾¾ ® H R OH
H
Formaldehyde gives 1° alcohol and ketones gives tertiary alcohol.
32 E
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(iv) By reduction of carbonyl compounds :
RCHO + 2H ¾¾
Pd
® RCH2OH
H H
C=O + 2H ¾¾¾
NaBH 4
® CH2OH
R R
R R
C=O + 2H ¾¾¾ ® CH2OH
NaBH 4
R R
(v) By reduction of ester with LiAlH4 or Na/C2H5OH :
O
R–C–OR' + 4H ¾¾¾
LiAlH 4
® R–CH2OH + R¢ – OH
(vi) By hydrolysis of esters :
O

conc.
R–C–O–R' + H 2O R–C–OH + R¢–OH
H 2SO 4
(vii) From alkyl halidcs :

R–X + KOH(aq) ¾® R–OH + KX
(viii) By reduction of acids and their derivatives :
R–COOH ¾¾¾
LiAlH
® RCH2OH4
R–COCl + 2H2 ¾¾
Ni
® R.CH2OH + HCl
(ix) From 1° amines :
R–NH2 ¾¾¾¾ ® ROH

NaNO 2
H O+ N 2 2
l Physical properties :
Intermolecular H-bond is found in between the molecules of alcohol and phenols due to which their
boiling points and solubility in water increases.
l Chemical properties :
[A] These reaction in which cleavage of O – H bond
1. Acidic nature of phenol
Ar – OH + 2Na ¾® Ar – O – Na + H2
Phenol due to acidic nature, react with NaOH alcohol not.
C6 H5 OH + NaOH ¾® C6 H5 ONa + H2 O
2. Esterification
R/Ar – OH + R' – C – OH R/Ar – OH + R' – C + H2O

C C
Alcohol/Carboxylic ester
Phenol acid
E 33
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[B] Those reaction in which cleavage of C – O bond.
1. Lucus Reagent [Anhydrous ZnCl2 + conc. HCl]
Tertiary alcohol + Lucus reagent ¾® immediate reaction
Secondary alcohol + Lucus reagent ¾® reaction after 5 minutes
Primary alcohol + Lucus reagent ¾® No reaction at room temperature.
2. Dehydration : On heating alcohol at 170 °C temperature in the preoence of conc. H2SO4 alkene
is formed.
conc. H2SO4
– C – C– > C = C < + H2O
alkene
H OH
3. Oxidation : Alcohol an oxidation form carbonyl compounds which on further oxidation give
carboxylic acid.
Nucleo-philic substitution reactions in phenol – OH group is orthopara directing.
Dill. HNO 3
o and p-nitrophenol
+
conc. HNO3
2,4,6 trinitrophenol
conc. H2SO4
Phenol Br 2 water (Picric acid)
Kolbe RX 2,4,6 tribromophenol
salicyclic acid
Riemer
salicyddehyde
Tiemann reaction
l Ether : Alkoxy derivatives of alkanes are called ether. Also known as anhydride of alcohols.
Formation of etiher :
1. By dehydration of alcohol
2CH 3CH2 OH ¾¾¾
413K
H2SO4
® C 2 H 5 - O - C 2 H 5 + H 2O
2. Williamson reaction :
R–X + R '– O – Na ¾¾® R - O - R ' + NaX

alkyl Sodium ether Sodium
salt of alkoxid halide
3. Chemical Properties of Ether :

R – O – R + H – X ® R – X + R – OH
R – OH + H – X ® R – X + H2O
l Ethers are dialkyl derivatives of waler or monoalkyl derivatives of alcohols with formula.
l Ethers arc relatively inert and hence are used as solvents.
l 100% elhanol is known as absolute alcohol.
l 95% ethanol is called rectified spirit.
l A mixture of 20% ethanol and 80% gasoline is known as power alcohol.
l Iodoform test is used for distinguishing compounds having the groups
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O OH
CH3–C– or CH3–CH–
l Presence of EWGs increase the acid strength of phenols while ERGs or EDGs decrease the acid
strength.
EWG : –NO2, –X, –CN, –COOH etc.
EDG or ERG : –R, –OR, –OH, –NH2 etc.
l 3° alcohols are resistant to oxidation due to lack of a-hydrogen.
l Intermolccular H-bonds of p- and m-nitrophenol increases water solubility/acid strength while
intramolecular H-bonds in o-nitrophenol decreases these properties.
l In the reaction of alkyl aryl ether (anisole) with HI, the products are always alkyl halide and phenol
because O–R bond is weak than O–Ar bond which has partial double character due to resonance.
l C–O–C bond in ether is bent and hence the ether is always polar molecule even if both alkyl groups
are identical.
Reaction of Alcohol :
(NSR) Na +
CH3CH2—ONa
O
O
CH3—C—OH
CH3—C—O—CH 2—CH 3
Conc. H2SO 4
O
O
(CH3—C)2O
CH3—C—O—CH 2—CH 3
HCl/ZnCl2
CH3—CH2Cl
Lucas Reagent
CH3—CH2—OH
HBr or CH3—CH2—Br
NaBr + H 2SO 4 [3° R—O—H ® Alkene]
NH3 CH3—CH 2—NH2

Al2O3
PCl5
Cl—CH 2—CH 3+POCl3
PCl3
Cl—CH2—3CH3+H3PO3
PBr3
Br—CH2—3CH3 + H 3PO3
SOCl2
Cl—CH 2—CH 3+SO 2+HCl
H2SO4/D/140°C
CH3—CH2—O—CH 2—CH3
Conc. H2SO 4
CH2=CH2
170°C
E 35
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DEHYDROGENATIONS :
OH OH C H3
Reagent H3C CH 2 CH 2 CH 2 H 3 C CH 2 CH CH 3 H3C–C–OH
1° Alcohol 2° Alcohol CH3

3° Alcohol
O O
PCC/PDC Anhy. CrO3 H3C CH2 CH2 C H H3C CH2 C CH3 No reaction
Å O O
K 2Cr 2O7/H No reaction
KMnO 4/H /OH/D
+ H3C–CH2–CH–C–OH H3C–C–OH+CH3–C–OH
Jones Reagent O
O O CH3
Cu/500°C || || |
H 3C–CH 2–CH 2–C–H CH3–CH2–C–CH3 H3C–C=CH2
Lucas Reagent No reaction within five min. Immediately

HCl/ZnCl2
Preparation of Phenol :
SO3Na OH
(i) NaOH
(ii) HÅ
PHENOL
N2+Cl¯ OH
H2O/D
PHENOL
MgBr OH
O2/60°C/D
H2O/H+
PHENOL
CH3
|
H3C–C–H OH
(i) O2
Å
(ii) H /H2O
–(CH3COCH3) PHENOL
36 E
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Reactions of Phenol :
O
|| O
||
H3C–C–Cl O–C–CH3
NH2
NH3
ZnCl2/300°C
FeCl3 3+
3HCl + [(Ph3O)6Fe]
Neutral Volet colour
NaHCO3
No effervescence
OH
–
ONa+
NaOH
Na2CO3
PHENOL
–
ONa+ O–CH3
NaOH CH3I
H
Zn
D
Cl
PCl5 (Ph–O)3PO
+
(major)
E 37
Chemistr y
ALLEN
OH O
conc. HNO3 + H2SO4 O2N NO2
+
NO2 O
(major)
OH O
125°C CO2/NaOH C–OH Kolbes
Schimdt
H+ Reaction
OH
NaOH
OH N=N
Å
N NCl¯
PHENOL
Ac
OH O O
CO2/NaOH C–OH AcCl C–OH
125°C O
Asphin
Na2Cr2O7
O O
H2SO4
OH
Br2 Br Br
2,4,6-Tribromophenol
H2O
Br
OH OH
OH Br2 Br
+
CS2
Br
PHENOL OH OH
conc. H2SO4 SO3¯H conc. O2N NO2
100°C HNO3
SO3H NO2
O
CHCl3 OH
C
NaOH H Remer Tiemann Reaction
38 E
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1. Show how are the following alcohols prepared by the reaction of a suitable Grignard reagent on
methanal ?
CH2OH
(i) CH3–CH–CH2OH (ii)
CH3
Ans. (i)
MgBr CH2OMgBr CH2OH

H2O
(ii) H–C–H + + Mg(OH)Br
O
Methanal Cyclohexylmagnesium Cyclohexylmethanol
bromide
2. Write structures of the products of the following reactions
O O
NaBH4
(i) CH 3 - CH = CH2 ¾¾¾¾
H O/H +
(ii) CH2 – C–O–CH3
® 2
H
NaBH4
(iii) CH3–CH2–CH–CHO
CH3
+
H 2O/H
Ans. (i) CH3–CH=CH2 CH3–CH–CH3
Propane OH
Propan-2-ol
O OH
CH2–C–OCH3 CH2–C–OCH3
(ii) NaBH4
O HÅ O
Methyl (2-oxocyclohexyl) Methyl (2-hydroxycyclohexyl)

ethanoate ethanoate
NaBH 4
(iii) CH3–CH2–CH–CHO H
Å CH3–CH2–CH–CH2OH
CH3 CH3
2-Methylbutanal 2-Methylbutan-l-ol
3. Ortho and para nitrophenols are more acidic than phenol. Draw the resonance structures of the
corresponding phenoxide ions.
– –
O O O O O
! Q
Ans.
!
(Resonance structure of the phenoxide ion)
E 39
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ALLEN
O O O O O O
Q Q
+ + + +
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— Q + O
—
—
O
Q
(Resonance structures of o-nitrophenoxide ion)

It can be observed that the presence of nitro groups increases the stability of phenoxide ion.
4. 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.
5. Predict the products of the following reactions :
OC2H5
(i) CH 3–CH2–CH2–O–CH3+HBr ¾® (ii) + HBr
OC 2H5 Conc.H SO
HI
(iii) 2 4
Conc.HNO 3 (iv) (CH3 )3 C - OC2H5 ¾¾ ¾

®
Ans. (i) CH 3 - CH 2 - CH2 - O- CH3 + HBr ¾¾® CH 3 - CH2 - CH2 - OH + CH3 - Br (S N 2)

n - propylmethyl ehter Pr opanol Bromomethane
OC2H5 OH
(ii) + HBr + C2H5Br
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)
HI
C - OC2 H 5 ¾¾
(iv) (CHtert3 -)3Butyl ¾
® (CH 3 )3 C - I + C 2 H5 OH (S N 1)
ethyl ether tert - Butyliodide Ethanol
40 E
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6. 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
7. Write the equation of the reaction of hydrogen iodide with :

(i) 1-propoxypropane
(ii) Methoxybenezene and
(iii) Benzyl ethyl ether
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
Methoxy benzene Phenol
CH2–O–C2H5 CH2l
(iii) + HI + C2H5–OH
Benzyl ethyl ether Benzyl iodide Ethanol
8. Write the equations involved in the following reactions:

(i) Reimer – Tiemann reaction
(ii) Williamson’s ether synthesis.
–+ –+
OH ONa ONa
CHCl3 + aq.NaOH CHCl2 NaOH
CHO
Ans. (i)
+
Intermediate H
OH
CHO
Salicylaldehyde
E 41
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(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 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.
9. Write the mechanism of the following reaction:
HBr
CH3CH2OH CH3CH2Br + H2 O
Ans. (i) Formation of protonated alcohol :
H H H H H
Fast
H – C – C – O – H + H+ ¾¾¾
® H – C – C – O+ –– H
H H H H
Ethanol Protonated alcohol
(ii) Formation of carbocation :
H H H H H
Slow
H – C – C – O+ – H ¾¾¾ ® H – C – C+ + H2O
H H H H
H H H H
(iii) H – C – C++ Br– ¾¾
® H – C – C–Br
H H H H
10. Rearrange the following compounds in the increasing order of their boiling points:
CH3 - CHO, CH3 - CH2 - OH, CH3 - CH2 - CH3
Ans. CH3 - CH2 - OH > CH3 - CHO > CH3 - CH2 - CH3
11. Explain the mechanism of the following reaction:
+
CH3 - CH2 - OH ¾¾¾
H
443K
® CH2 = CH2 + H2O
Ans. Mechanism : The dehydration of ethanol involves the following steps :
(i) Formation of protonated alcohol :
H H H H H
Fast +
H – C – C – O – H + H+ ¾¾¾ ® H–C–C–O –H
H H H H
42 E
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H H H H H
H – C – C – O+ – H ¾¾¾
Slow
® H – C – C+ + H2O
H H H H
(iii)Formation of ethene :
H H
H H
H – C – C+ ¾¾
®
H
C=C
H
+ H+
H H
12. Explain the mechanism of acid catalysed hydration of an alkene to form corresponding alcohol.
Ans. Step I : Protonation of alkene to form carbocation by electrophilic attack of H3O+.
H2O + H+ ¾® 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 H H
Å Slow Å
H–C–C–O–H H – C – C + H 2O
H H H H
13. Explain the following behaviours :
(i) Alcohols are more soluble in water than the hydrocarbons of comparable molecular masses.
(ii) Ortho-nitrophenol is more acidic than ortho-methoxyphenol.
Ans. (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.
14. How would you convert ethanol to ethene?
Ans. Mechanism : The dehydration of ethanol involves the following steps :
(i) Formation of protonated alcohol :
H H H H H
Fast
H – C – C – O – H + H+ ¾¾¾ ® H – C – C – O+ – H
H H H H
H H H H H
Slow
H – C – C – O+ – H ¾¾¾ ® H – C – C+ + H2O
H H H H
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(iii) Formation of ethene :
H H
H H
H – C – C+ ¾¾ ® C=C + H+
H H
H H
15. How would you obtain the following:
(i) Benzoquinone from phenol
(ii) 2-Methylpropane-2-ol from methylmagnesium bromide
(iii) Propane-2-ol from propene
Ans. (i) Benzoquinone from phenol
OH O
Na2Cr 2O 7
H 2SO 4
O
Phenol benzoquinone
CH3 CH3 Br
H2O/H +
(ii) CH3 MgBr + CH3 C CH3 ® CH3 C CH3 CH3 C CH3 + Mg
Methyl
Magnessium O OMgBr OH OH
bromide Propanone 2-Methypropane-2-ol
Br OH
HBr Aq. KOH
CH3 CH = CH2 CH3 – CH – CH 3 -KBr CH3 CH CH3
Propane 2-Bromopropane Propane-2-ol
or 2-Propanol
16. How would you convert following:
(i) Phenol to benzoquinone
(ii) Propanone to 2-methylpropan-2 ol
(iii)Propene to propan-2-ol
OH O
Ans. (i) K2Cr2O 7

H 2SO 4
O
Phenol benzoquinone
CH3 CH3
CH3 H2O
(ii) C = O + CH3MgBr ® [CH3– C– OMgBr] CH3 C OH + Mg (OH) Br
CH 3
Propanone CH3 CH3
2-methyl propan-2-ol
H+
(iii) CH3 CH = CH2 + H2O CH3– CH – CH3
propene
OH
propan-2-ol
44 E
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17. Explain the following observations :
(i) The boiling point of ethanol is higher than that of methoxymethane.
(ii) Phenol is more acidic than ethanol.
(iii) ortho– and para-nitrophenols are more acidic than phenol.
Ans. (i) The boiling point of ethanol is higher than that of methoxymethane due to the presence of hydrogen
bonding in alcohols.
(ii) Since the phenoxide ion left after the removal of a proton is stabilized by resonance where as
alkoxide ion is not which is left after the removal of a proton found alcohol.
(iii)o & p-nitrophenols are more acidic then phenol due to –M effect of NO2 at from ortho &
+
para position make the ejections of H easity & secondly stabilized the conjugate base.
REASONING :
1. Phenol is acidic in nature.
Ans. In phenol each atom of benzene ring is sp2 hybridised and is electron withdrawing. Oxygen atom
donates a pair of electron to the ring and acquire positive charge which facilitate the donate ion of
proton.
OH O–
H2O
+ H3O+
The Phenoxide ion (conjugate base) is stabilised by resonance.

– –
O O O O O
Q Q
1
2. Which is more acidic, p-nitrophenol or phenol? Explain why?
Ans. p-nitrophenol is more acidic. Any electron withdrawing group like –NO2 withdraws the electron
density away from oxygen atom of phenoxide ion and this results in further delocalisation of
negative charge and stabilisation of phenoxide ion. Hence, electron withdrawing groups favour
the ionisation of substituted phenol to give more and more of H+ ions.
3. Cresol (C6H5OCH3) is less acidic than phenol.
Ans. Cresol is less acidic than phenol. Any electron releasing group like - CH3, releases the electron
density over oxygen atom and destabilises, it resulting in decrease in ionisation of cresol. So
cresol is less acidic than phenol.
4. Ethers are insoluble in water.
Ans. Ethers cannot form Hydrogen bonds with water because it is less polar than water and cannot
break hydrogen bonds formed between H2O molecules.
5. Boiling points of ethers are lower than isomeric alcohols.
Ans. Boiling points of ethers are lower than isomeric alcohols due to lack of intermolecular hydrogen
bonding in ethers whereas alcohol molecules are associated through strong hydrogen bonds.
6. Ethers are polar in nature even if both alkyl groups are identical.
Ans. Ethers have non-linear structure. Each of the two C-O bonds are polar. Net dipole moment is the
vector sum of dipole moments of both the bond dipoles.
.:
O
.
R R
E 45
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7. o-nitrophenol is volatile while p-nitrophenol is not.
H
O O
N
O N O H O N O H
O
O O
o-nitrophenol
(intramolecular H-bonding) p-nitrophenol
(intermolecular H-bonding)
o-nitrophenol is steam volatile due to intramolecular hydrogen bonding while p-nitrophenol is less
volatile due to intermolecular hydrogen bonding.
8. Phenyl methyl ether reacts with HI to form phenol and methyl iodide not iodobenzene and methanol.
O–CH3 OH
+ HI + CH3I
(a) In phenyl methyl ether, the carbon atoms of phenyl group are sp2 hybridised and there is a partial double bond
character in phenyl carbon-oxygen bond. Hence, C6H5–O bond is stronger than CH3–O.
Therefore, the attack of I– on the alkyl carbon of C6H5–O–H3C occurs and breaks the CH3–O-bond
to form phenol and iodomethane.
(b) Benzene ring offers a steric hinderance to I- to attack at C6H5–O-bond.
9. Phenoxide ion has more number of resonating structure than carboxylate ion but carboxylic acid is a
stronger acid than phenol.
Ans. The phenoxide ion has non-equivalent resonance structures in which negative charge is at less
electronegative carbon atom of phenoxide ion.
The carboxalate ion has two equivalent resonance structures in which negative charge is more
effectively delocalised over two electronegative oxygen atoms. In phenoxide ion, the negative charge
is less effectively delocalised over one oxygen atom and less electronegative carbon atom of phenoxide
ion. Thus, the carboxylate ion is more stabilised than phenoxide ion. Therefore, carboxylic acids are
more acidic than phenols.
CHEMICAL TEST :
I. Primary, Secondary and Tertiary alcohol
Test 1º Alcohol 2º Alcohol 3º Alcohol
(i) (1) Add Lucas reagent No change Turbidity appears Turbidity appears
(Conc. HCl + Anhyd. ZnCl2) within 5 minutes immediately
Lucas Test
Lucas test is based on Kinetics of the reaction. 3º alcohols react at the fastest rate.
CH3 CH3
anhydrous
H3C–C–OH + H Cl H3C–C–Cl + H2O
ZnCl2
CH3 CH3
(3º alcohol)
(Turbidity appears immediately)
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H3 C anhydrous H3 C
CHOH + HCl CHCl + H2O
H3 C ZnCl2 H3 C
(2º alcohol)
(Turbidity appears with in 5 minutes)

anhydrous
CH3CH2OH + HCl ZnCl2
No change appears
(1º alcohol)
(ii) Organic compound + Lucas reagent
Test Propan-1-ol Propan-2-ol

OH
CH3CH2CH2OH CH3–CH–CH3
(1) Lucas Test No change Turbidity appears within
Add Lucas Reagent 5 minutes.
(Conc. HCl + Anhydrous ZnCl2)
(2) Iodoform Test No change Yellow precipitate of CHl3
Add (I2 + NaOH)
OH
Heat CHl3 + CH 3COONa + 5NaI + 5H 2O
6NaOH + 4I2 + CH3CHCH3
(Yellow ppt)
Test Ethanol Propan-2-ol

(iii) (1) Add Lucas Reagent

No change Turbidity within 5 minutes
II. Difference between Alcohol and Phenol
OH
Test Ethanol Phenol
(i) (1) Add (I2+NaOH) and heat Yellow ppt. of CHl3 No change
(2) Add neutral FeCl3 No change Violet Colouration
3C6H5OH + FeCl3 ¾® (C6H5O)3Fe + 3HCl

Ferric phenoxide
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OH
Propan-2-ol
Test Phenol
CH3–CH(OH)CH 3
FeCl3 test : Violet colour No change

(1) Add Neutral FeCl3 colour of Br2 decolourised No change
(2) Add Bromine water
OH OH
(ii) Br Br
H3 O
+ 3Br
–3HBr
Br
(White ppt)
NAME REACTIONS :
1. 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 is formed. This reaction is
known as Reimer - Tiemann reaction.
– + – +
OH O Na O Na OH
CHCl2 CHO CHO
CHCl3 + aq NaOH NaOH H+
Intermediate Salicylaldehyde
2. 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+
2-Hydroxybenzoic acid
(Salicylic acid)
3. Friedelcraft reaction of anisole

(A) Alkylation
OCH3 OCH3 OCH3
CH3
Anhyd.AlCl3
+CH3Cl CS2 +
Methyl
chloride
Anisole CH3
2-Methoxytoluene 4-Methoxytoluene
(Minor) (Major)
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(B) Acetylation
OCH3 OCH3 OCH3

COCH3
Anhyd.AlCl3
+ CH3COCl +
Ethanoyl
Anisole chloride
COCH3
2-Methoxy- 4-Methoxy
acetophenone acetophenone
(Minor) (Major)
4. Wilhamson ether synthesis reaction

Åd d –Å ..
R – X + R – ONa R–O
.. – R + NaX
Alkyl halide Sodium Ether
alkoxide
MECHANISM :
1. Mechanism of preparation of Alkene to Alcohol :
+
H
C=C + H2O C C
H OH
OR
CH2=CH2 + H2O CH3–CH2–OH

OR
+
H
CH3CH = CH2 + H2O CH3—CH —CH 3
—
OH
Ans. The mechanism of the reaction involves the following three steps:
Step 1: 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 2: Nucleophilic attack of water on carbocation.
H H H
— —
— —
— —
—
+
: :
+
—C—C + H2O —C—C—O —H
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Step 3: Deprotonation to form an alcohol.
: — —
H OH
:
H H
— —
—
— —
— — +
—C—C— + H3O
+
: :
—C—C—O —H + H2O
2. Mechanism of preparation of Ethene from Ethanol :
Ans. The mechanism of the reaction invovles the following three steps :
Step 1: Formation of protonated alcohol.
H H H H H
+ Fast
H—C—C—O+—H
: :
H—C—C—O—H + H :
H H H H
(Ethyl oxonium ion)
Step 2: Formation of carbocation: It is the slowest step and hence, the rate determining step of the
reaction.
H H H H H
+ Slow
H—C—C—O —H H—C—C++H2O
:
H H H H
Step 3: Formation of ethene by elimination of a proton.
H H H— H
H—C—C+ — C=C + H+
H H
H H Ethene
The acid used in step 1 is released in step 3. To drive the equilibrium to the right, ethene is
removed as it is formed.
3. When 3-methylbutan-2-ol is treated with HBr, the following reaction takes place :
Br
HBr
CH3–CH–CH–CH 3 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
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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 hydrogen shift
H
+ +
CH3–C–CH–CH 3 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
4. Mechanism of preparation of Ethanol to Ethoxyethane : 2C2H5OH C2H5OC2H5

Ans. The mechanism of the reaction invovles the following three steps :
H
+
Step (i) : CH3—CH2—O—H H
: :
: :
CH3—CH2—O+—H
H +
Step (ii) : CH3CH2—O: + CH3—CH2—O
+ CH3—CH2—O—CH2CH3 + H2O
:
H H
H
+
Step (iii) : CH3CH2— O —CH2CH3® CH3CH2—O—CH2CH3 + H+
H
5. Mechanims of an Ether with concentrated HI starts with protonation of ether molecule.
CH3–O–C2H5 + HI ¾® CH3I + C2H5OH
Ans. The reaction of an ether with concentrated HI starts with protonation of ether molecule.
Step 1:
H
: :
: :
CH3—O—CH2CH3 + H—I CH3—O+—CH2CH3 + I–
The reaction takes place with HBr or HI because these reagents are sufficiently acidic.
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Step 2:
6. Mechanism of preparation of tert butyl iodide
Ans. Step-1 :
CH3 CH3
.. Å !
H–I + H
CH—C—O—CH
3 .. 3 CH—C
3 O
.. +I
CH3 CH3 CH 3
CH3 CH3
+ Slow Å
Step-2 : CH—C—O—CH
3
H
3 CH—C
3 + CH3 OH
CH3 CH3
CH3 CH3
I-
Å Fast
CH3 —C + CH3 — C— I
CH3 CH3
7. Mechanism of 1-propoxypropane synthesised from propan-1-ol :
H+
2CH3CH2CH2–OH CH3CH 2CH 2–O–CH2CH2CH3
Propane-1-ol 1-Propoxypropane
Ans. The mechanism of this reaction involves the following three steps :
Step 1 : Protonation
H
H+ +
CH3CH2CH2–O–H CH3CH 2CH2–O –H
Propane-1-ol
Step 2 : Nucleophilic attack
+ H +
CH3CH2CH2–O + CH3–CH2–CH2–O CH3CH2CH2–O–CH2–CH2–CH3
H
H H
+
H2O
Step 3 : Deprotonation
+ +
CH3CH2CH2–O–CH3CH2CH2 CH3CH2CH2 – O – CH2CH2CH3 + H
H 1-Propoxypropane
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1. (a) Out of t-butyl alcohol and n-butanol, which one will undergo acid catalyzed dehydration faster
and why ? (CBSE 2020)
(b) Carry out the following conversions : [1×3=3]
(i) Phenol to salicylaldehyde
(ii) t-butylchloride to t-butyl ethyl ether
(iii) Propene to Propanol
OR
(a) Give the mechanism for the formation of ethanol from ethene. [2]
(b) 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
Ans. (a) Tert-butyl alcohol, because it forms more stable 3º carbocation than 1º carbocation.
(b)
OH OH
OH OH
H CHO
Cl NaOH CH –H2O
(i) + Cl – CH + OH
Cl NaOH – HCl
– 2NaCl Salicyaldehyde
C2H 5Cl
(ii) (CH3)3CCl + NaOH (aq) ¾® (CH3)3COH ¾® (CH3)3CONa (CH3)3COC2H5
B2H6 (3NaOH + 3H2O 2)

(iii) CH3CH = CH2 (CH3 – CH2 – CH2 –)3B CH3 – CH2 – CH3
|
OH
OR
(a) Step 1 : 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 2 : Nucleophilic attack of water on carbocation

H H H
| .. | | |+
–C–C+ +H2O
.. –C–C–O –H
| | |
Step 3 : Deprotonation to form an alcohol.
..
H H H :OH
| | | | |
+
–C–C–O –H – C – C – + H+
| | | |
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(b) (i) (K2Cr2O7 + H2SO4) (Na2Cr2O7 + H2SO4)
(ii) Br2 in CH3COOH
(iii) Br2 aq./Bromine water
2. (a) Give equations of the following reactions : [5]
(i) Phenol is treated with conc. HNO3.
(ii) Propene is treated with B2H6 followed by H2O2/OH–. (CBSE 2019)
(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
OR
(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]
OH OH
O2N NO2
conc. HNO3
Sol. (a) (i) (picric acid)
NO2
(ii) CH3–CH=CH2+(½B2H6) (CH3–CH2–CH2–)3B

–
H2O 3H2O2,OH
3CH3–CH2–CH2–OH
CH3 CH3
(iii) CH3–C–ONa + CH3Cl CH3–C–O–CH3
CH3 CH3
(b) On heating with (NaOH + l2), 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
OR
CH3 CH3
CH2–CH CH3–C–O–O–H OH
+
O2 H
(a) (i) H2O
+ CH3COCH3
SO3H OH
(i) NaOH
(ii) +
(ii) H
+ –
N2Cl OH
H2O
(iii) +N2+HCl
OH
O2N
(b)
CH3
NO2
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OH ONa OH
COOH
NaOH (i) CO2
(c) (ii) H+
(Salicylic acid)
3. Write the IUPAC name of the following : (CBSE 2018)

CH3
CH3 – C – CH – CH3
C2H5 OH
CH3
Ans. CH3 — C — CH — CH 3 Þ
C2H 5 OH
4. Write the structures of the main products in the following reactions : (CBSE 2018)
O
NaBH4 CH = CH2
CH2–C–OCH3 +
H
(i) (ii) + H2O
O
OC2H5
(iii) + HI
O OH
NaBH4
CH2—C—OCH 3 CH2—C—OCH3
Ans. (i)
O O
CH=CH 2 CH–CH3
H+
(ii) + H 2O
OH
(iii)
5. Write the IUPAC name of the following compound : (CBSE 2017)

CH = CH – CH 2 – OH
Ans. 3-phenyl-prop-2-en-1-ol
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6. (a) Arrange the following compounds in the increasing order of their acid strength :(CBSE 2017)
p-cresol, p-nitrophenol, phenol
(b) Write the mechanism (using curved arrow notation) of the following reaction :
+ +
CH2 = CH2 ¾¾¾ H O
® CH3 – CH 2 + H2O
3
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) (ii)
H3C CH3 H3C CH3
7. Give reasons for the followings : (CBSE 2017)
(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. (i) Due to the resonance, the electron pair of nitrogen atom gets delocalised towards carbonyl
group/ resonating structures.
(ii) Because of +I effect in methylamine electron density at nitrogen increases whereas in aniline
resonance takes place and electron density on nitrogen decreases / resonating structures.
(iii) Due to protonation of aniline/formation of anilinium ion
8. Write the chemical equations involved in the following reactions: (CBSE 2016)
(i) Kolbe's reaction (ii) Friedal- Crafts acetylation of anisole.
OH ONa OH
COOH
NaOH (i) CO2
Ans. (i) (ii) H+
(Salicylic acid)
OCH3 OCH3 OH
COCH3
Anhyd. AlCl3
(ii) +CH3COCl +
COCH3
9. How do you convert: (CBSE 2016)

(i) Phenol to toluene (ii) Formaldehyde to Ethanol
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OH CH3
Anhyd. AlCl3
Ans. (i) +Zn
CH3Cl
H 2O/H+
(ii) HCHO+CH3MgX CH3CH2OMgX CH3CH2OH
10. Give reasons for the following: (CBSE 2016)
(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
CH 3OH.
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.
11. Write the IUPAC name of the given compound : (CBSE 2015)
CH3
CH3 C CH2 OH
CH3
Ans. 2,2–Dimethylpropan–1–ol
12. Give reasons for the following : (CBSE 2015)
(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.
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
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EXERCISE-3 R AC E
In phenol –OH group directly attached to sp2 hybridised carbon of benzene ring acts as a 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 benzine ring. As a result of
••
resonance, the oxygen atom acquires a partial positive charge. This weakens the –OH bond and
thus facilitates the release of a proton.
(i) Which one is stronger acid
(a) phenol (b) alcohol (c) Cresol (d) None of these
(ii) Phenol can be distinguished from ethanol by the reactions with _________.
(a) Br2 /CS2 (b) Na
(c) Neutral FeCl3 (d) All the above
(iii) Which of the following reactions will not give phenol?
Cl NH2
(a) fusion with NaOH at 300 atm (b) (i) NaNO2 / HCl
(ii) H2O / H +
(ii) H2O (Warming)
Cl
(i) Oleum
(c) (ii) NaOH (heating) (d) (i) NaOH (aq.) / 298 k / 1atm
(iii) H+ (ii) HCl
CH 3
|
(iv) The correct IUPAC name of CH 3 - C - CH 2 CH 3 is
|
OH
(a) tert-butyl alcohol (b) 2,2-Dimethylpropanol

(c) 2-Methylbutan-2-ol (d) 3-Methylbutan-3-ol
Question 2 to 6 :- Note:- In the following questions a statement of assertion followed by a reason
. choose the correct answer out of the following choices –
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2. Assertion : p-nitrophenol is more acidic than phenol.
Reason : Nitro group helps in the stabilisation of the phenoxide ion by dispersal of negative
charge due to resonance
3. Assertion : Boiling points of alcohols and ethers are high.
Reason : They can form intermolecular hydrogen-bonding.
4. Assertion : Ethanol is a weaker acid than phenol.
Reason : Sodium ethoxide may be prepared by the reaction of ethanol with aqueous NaOH.
5. Assertion : Phenol forms 2, 4, 6 – tribromophenol on treatment with Br2 in carbon disulphide at
273K.
Reason : Bromine polarises in carbon disulphide.
6. Assertion : Phenols give o- and p-nitrophenol on nitration with conc. HNO3 and H2SO4 mixture.
Reason : — OH group in phenol is o–, p– directing.
7. Alkene is obtained when an alcohol is passed over heated Cu. The alcohol is:
(i) CH3–CH2–OH (ii) CH3–CH–OH
CH3
CH3 CH3
(iii) CH 3–C–OH (iv) C6H 5–CH–CH 2–OH
CH3
8. What is the correct order of reactivity of alcohols in the following reaction?

ZnCl
R–OH + HCl ¾¾¾¾
2
® R–Cl + H2O
(i) 1° > 2° > 3° (ii) 1° < 2° > 3°
(iii) 3° > 2° > 1° (iv) 3° > 1° > 2°

9. Monochlorination of toluene in sunlight followed by hydrolysis with aq. NaOH yields.
(i) o-Cresol (ii) m-Cresol
(iii) 2, 4-Dihydroxytoluene (iv) Benzyl alcohol
10. CH3CH2OH can be converted into CH3CHO by ________.
(i) catalytic hydrogenation
(ii) treatment with LiAlH4
(iii) treatment with pyridinium chlorochromate
(iv) treatment with KMnO4
11. The process of converting alkyl halides into alcohols involves ___________.
(i) addition reaction (ii) substitution reaction
(iii) dehydrohalogenation reaction (iv) rearrangement reaction
12. IUPAC name of m-cresol is ___________.
(i) 3-methylphenol (ii) 3-chlorophenol
(iii) 3-methoxyphenol (iv) benzene-1,3-diol
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13. Which of the following species can act as the strongest base?
(i) !OH (ii) !OR
!O
(iii) !OC6H5 (iv)
NO2
14. Which of the following compounds will react with sodium hydroxide solution in water?
(i) C6H5OH (ii) C6H5CH2OH
(iii) (CH3)3COH (iv) C2H5OH
15. Which of the following is most acidic?
(i) Benzyl alcohol (ii) Cyclohexanol
(iii) Phenol (iv) m-Chlorophenol
16. Which of the following reagents can not be used to oxidise primary alcohols to aldehydes?
(i) CrO3 in anhydrous medium.
(ii) KMnO4 in acidic medium.
(iii) Pyridinium chlorochromate.
(iv) Heat in the presence of Cu at 573K.
Answer key :
Q. No. 1 (i) (ii) (iii) (iv) 2 3 4 5 6 7 8
Ans. a c c d A A D D A iii iii
Q. No. 9 10 11 12 13 14 15 16
Ans. iv iii ii i ii i iv ii
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1. Write the IUPAC name of the following compound : [1]
CH = CH – CH 2 – OH
2. Write the structure of the major product obtained from dinitration of 3-methylphenol. [1]
3. How would you convert following: [1]
Phenol to benzoquinone
4. Boiling point of ethanol is higher than that of dimethyl ether. Why ? [2]
5. Anisole on reaction with HI gives phenol and CH3–I as main products and not iodobenzene and
CH3OH. Why ? [2]
6. Explain the following observations : [2]
(i) Phenol is more acidic than ethanol.
(ii) o– and p-nitrophenols are more acidic than phenol.
7. Write the equations involved in the following reactions: [2]
(i) Reimer – Tiemann reaction
(ii) Williamson’s ether synthesis.
8. Explain the mechanism of acid catalysed hydration of an alkene to form corresponding alcohol. [3]
9. Write the structures of the main products in the following reactions: [3]
O
NaBH4
(i) CH2–C–OCH3 ?
O
CH = CH2
+
H
(ii) + H2O ?
OC2H5
(iii) + HI ?
10. How can you obtain Phenol from (i) Cumene, (ii) Benzene sulphonic acid [3]
11. (a) Give equations of the following reactions : [5]
(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
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MOCK TEST SOLUTIONS
1. 3-phenyl-prop-2-en-1-ol
OH
O2N
2.
CH3
NO2
OH O
3. K2Cr2O7
H2SO4
O
Phenol benzoquinon
4. (a) Due to intermolecular hydrogen bonding.

(b) o-nitrophenol is steam volatile due to intramolecular hydrogen bonding while p-nitrophenol is less
volatile due to intermolecular hydrogen bonding.
5. 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.
6. (i) Since the phenoxide ion left after the removal of a proton is stabilized by resonance where as alkoxide
ion is not which is left after the removal of a proton found alcohol.
(ii) o & p-nitrophenols are more acidic then phenol due to –M effect of NO2 at from o & p position
make the ejections of H+ easity & secondly stabilized the conjugate base.
–+ –+
OH ONa ONa
7. (i) CHCl+ CHCl2 CHO
3 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 on the alkyl halide. Better results are obtained
in case of primary alkyl halides.
CH3 CH3
– +
CH–CH–
3 O Na + CH3 – Br CH–3 O–CH–CH 3 + NaBr
If the alkyl halide is secondary or tertiary, then elimination competes over substitution.
62 E
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8. Step I : Protonation of alkene to form carbocation by electrophilic attack of H3O+.
H2O + H+ ¾® 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– + H3O+
O OH
NaBH4
CH—C—OCH CH—C—OCH
9. (i) 2 3 2 3
O O
CH – CH2 CH – CH3
H+
(ii) + H2O OH
OC2H5 OH
(iii) + HI + C2H5 – I
CH3 CH3
CH–CH
2 CH–C–O–O–H
3 OH
10. (i) O2 H
+
+CH2 COCH 3
H 2O
SO3H OH
(ii) (i) NaOH
+
(ii) H
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OH OH
O2 N NO2
conc. HNO 3
11. (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
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ALDEHYDE, KETONE AND CARBOXYLIC ACID
l Aldehydes, ketones, catboxylic acids and Iheir derivatives are commonly called as carbonyl compounds
l In Rosemund's reduction, poisoning of Pd with BaSO4 prevent reduction of R–CHO to R–CH2OH.
l In the reaction of toluene with CrO3, acetic anhydride is used to protect benzaldehyde by forming
benzylidenediacetate to avoid its oxidation to benzoic acid.
l Order of reactivity of aldehydes and ketones towards nucleophilic addition is :
(i) HCHO > CH3CHO > CH3CH2CHO.
(ii) HCHO > RCHO > RCO R.
(iii) ArCHO > Ar COR > Ar CO Ar
l Benzaldehyde does not reduce Fehling's reagent.
l Aldehydes and ketones w ith atleast one a-H atom get condensed in presence of a base. This is
known asAldol condensation.
l Aldol condensation involves carbanion as intermediate.
l Aldehydes with no a-H atoms under Cannizzaro's reaction.
l Ketones react with dihydric alcohols to form cyclic ketals
l Monocarboxylic acids having (C12-C18) carbon atoms, are called fatty acids.
l Boiling points of carboxylic acids is greater than corresponding alcohols.
l Presence of EWGs enhances the acidic character of carboxylic acids.
l –COOH group is m-directing in electrophilic substitution reactions
l Compounds containing –CHO group are named as carbaldehydes if –CHO groups are three or more
l Isomerism : Chain, position and functional.
l Structure of –CHO group sp2-hybridised.
node06\B0B0-BA\Kota\Board Material\Chemistry\CBSE\CBSE Booklet\English\Updated booklet-21\New Pattern CBSE Booklet\Part wise boocklet\Part 2\03_OC\03_Aldehydes, Ketones and Carboxylic Acids
l General Methods of Preparation :

(i) Controlled oxidation of 1º alcohols :
(ii) Dehydration of 1º alcohols :

RCH2OH RCHO + H2
(iii) From Rosemund reaction/reduction :
RCOCI + H2 RCHO + HCI
(iv) Hydration of alkyncs :
CHºCH [CH=CH–OH] CHCHO

(v) Reductive ozonolysis of alkencs :
R–OH = CH–R 2RCHO + H2O2
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(vi) From salts of fatty acids :
(RCOO)2Ca + (HCOO)2Ca 2RCHO + 2CaCO3

(vii) Stephen's reduction of nitrile compounds :
R–CºN [R–CH=NH HCl] RCHO + NH4Cl

(viii) Hydrolysis of germinal halides :
Cl OH
aq. KOH
R–CH R–CH RCHO + H2O
Cl OH
(ix)From Gngnard's reagent:
H–CºN + R–MgX H– =X–MgX RCHO + NH3 + Mg(OH)X
l General Methods of Preparation of Ketones only

(i) Dehydrogcnation of 2º alcohols
O
Cu
R–CHOH–R 573 K R–C–R + H2
(ii) Hyration of alkynes
OH O
H2O Tautomerism
R–C CH R—C = CH2 R–C–CH3
1% HgSO4
40% H2SO4
O
R R (i) O2
(iii) C=C 2R–C–R + H2O2
(ii) H2 O / Zn
R R
(iv) From Grignard's reagents :
R'
R¢ MgX + R–CºN ® H3O
+
R–C=N–MgX R–C=O + NH3 + Mg(OH) X

R'
(iv) From acid chlorides
RCOCl + R2Cd ® 2R– –R¢ + CdCl2

l Physical Properties :
HCHO is a gas at normal temperature Formalin is 40% as solution of HCHO.
Due to polarity they have high values of boiling point Solubility in water is only for lower members
66 E
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l Reactivity :
(i) + I effect of alkyl groups decreases the +ve charge on carbonyl carbon.
(ii) Steric hindrance : Bulky group hinder approach of nucleophile.
(iii)a-hydrogen atom is acidic due to resonance.
l Vinegar is 8 to 10% solution of CH3COOH
l a-hydrogen atoms in carboxylic acid are acidic in nature and can be easily replaced by halogen atoms
in HVZ reaction.
l Relative acid strength of RCOOH > HOH > ROH > HCºCH > NH3. It is because a strong acid has
weak conjugate base.
Preparation of Aldehyde & Ketone both :
K2Cr2O7/H 2SO4
R–OH
(1°,2°)
PCC
R–OH
(1°,2°)
Cu or Ag
R–OH
(1°,2°) 300°C
O3
R–CH=CH–R RCHO
H2O/Zn
RCOR
aq. KOH
RCH2CHCl2
H2SO4
RCºCH
Hg+2
BH3/THF
RCºCH
H2O2/OH
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Preparation of Aldehyde only :
DIBAL-H
RCN H2O
RCOOR DIBAL-H
H2O
RCOCl H2/Pd
(Rosenmund BaSO4
Reduction)
(i) SnCl2/HCl
RCN
(Stephen's Reduction) (ii) H2O
(CH3CO)2O/CrO3 RCHO
Ar–CH3
H3O /D
+ ArCHO
CrO2Cl2
Ar–CH3
(Etard reduction) H3O+
Cl2/hn
Ar–CH3
+
H3O
CO+HCl
anhyd AlCl3
(Gatterman Koch
aldehyde synthesis)
Preparation of Ketone only :

R'MgX
RCN
H2O
R2'Cd RCOR'
RCOCl
ArCOR'
R2'COCl
anhyd. AlCl3
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Reaction of Aldehyde & Ketone :
Metal/H2
CH–OH
or LiAlH4
or NaBH4
or Na+C2H 5OH
(i) N2H4 Wolf kishner

CH2
(ii) OH/D reduction
Zn–Hg/HCl Clemmensen's
CH2 reduction
Red P/HI CH2

Z=–H,–R,–OH,–NH2
–NH –NHCONH2
H2N–Z
C=N–Z –NH NO2
NO2
PCl5 or SOCl2 Cl
C
Cl
HCHO H2O OH (Partial
C hydrolysis)
CONH2
R
C=O HCN OH 2H2O/H
Å
C
OH (Complete
H (NAR)
C
CN
COOH hydrolysis)
R
LiAlH4 OH
C=O C
CH2NH2
R
NaHSO3 OH [Bisulphite compound
C
SO3Na (White crystalline)]
ROH/H+ OH ROH/H+ OR
C C
OR OR
(Hemi-acetal) (Acetal)
RMgX OH
C (Alcohol)
R
Aldol Reaction (Aldehyde or ketone with aH) :
dil. NaOH D
(i) 2CH3CHO CH 3–CH–CH2–CHO CH3–CH=CH–CHO
–H2O
(Aldol condensation product)
OH
Aldol
CH3 CH3
dil. NaOH D
(ii) 2CH3COCH3 CH3–C–CH2COCH3 CH3–C=CH–COCH3
–H2O (Aldol condensation product)
OH
Ketol
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Cannizzaro reaction (Aldehyde with no aH)
conc. NaOH
2HCHO D
CH3OH+HCOO–Na+
Tests
Tollen’s test :
RCHO + 2[Ag(NH3)2]+ + 3 –OH ¾® RCOO– + 2Ag + 2H2O + 4NH3
(Given by Aliphatic and aromatic aldehyde)
Fehling’s test:
RCHO + 2Cu+2+ 5 –OH ¾® RCOO– + Cu2O + 3H2O
(Given by Aliphatic aldehyde) (Red-Brown ppt.)
Carboxylic Acid :
Preparation :
K2Cr2O7/HÅ
H3C–CH2–OH Å
KMnO4/H
H3OÅ
H3CºN
D
CrO3 + H2SO4
CH3CH2–CH2
|
OH
O
|| H3OÅ
H3C–C–NH2 O
D ||
O H3C–C–OH
|| H3O
Å
O
H3C–C–OEt
or NaOH ||
H3C–CH2–C–OH
O
|| H3O
Å
H3C–C–Cl
O O
|| || H3O
Å
H3C–C–O–C–CH3
O NaOH or
|| (NaOH+I2)
H3C–C–CH3
(Haloform test) CHI3
+
O=C=O/H3O
CH3MgBr
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Reactions :
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71
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TEST
Tollen’s Reagent
O
||
H–C–OH Ag¯ + CO2 + H2O
Fehling Solution
O
||
2CuO
H–C–OH Cu2O¯ + CO2 + H2O
red ppt
R COOH
(1) KmNO4–KOH
Å
(2) H
R[1°/2° Alkyl group

C=C, CºC, CH2–OH, CHO, COCH3 etc]
COOH
Conc. HNO3+conc. H2SO4
NO2
COOH
Friedel craft reagent NO
reaction
COOH
Br2 + FeBr3
Br
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1. Arrange the following compounds in increasing order of their boiling points.
CH3 CHO, CH3 CH2OH, CH3OCH3, CH3CH2 CH3
Ans. CH 3 CH2 CH 3 < CH 3 OCH3 < CH3 CHO < CH3 CH2 OH
non polar more polar H - bond i ng
2. Arrange the following componds in increasing order of their reactivity in nucleophilic addition reactions.
(i) Ethanal, Propanal, Propanone, Butanone.
(ii) Benzaldehyde, p-Tolualdehyde, p-Nitrobenzaldehyde, Acetophenone.
Hint : Consider steric effect and electronic effect.
Ans. Reactivity of carbonyl compound µ (+)ve charge on sp2 C
O O O O
C C C C
(i) CH3 H CH3CH2 H CH 3 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
O
CHO CH3 CHO
C
(ii) CH3
NO2 CHO
p-Nitrobenzaldehyde p-Tolualdehyde Benzaldehyde Acetophenone
more – I less – I +I of –CH 3
–I group on >C = O inreases (+)ve charge so reactivity order is

Acetophenone < p-tolualdehyde < Benzaldehyde < p-Nitrobenzaldehyde
3. 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 + NH2 – C – NH – NH2
O
C
+
CH3 H
(iv) + CH3CH2NH2
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O N–OH
Ans. (i)
+
H + H2O
+ HO – NH2
O2N
O O2N NNH NO2
(ii) + NH2 – NH NO2 + H2O
O O
H+
(iii) R – CH = CH – CHO + NH2 – C – NH – NH2 R – CH = CH – CH = N – NH – C – NH2 +H O
2
O H3C
C C = N – CH2CH3
+
CH3 H
(iv) + CH3CH2NH2 + H2O
4. 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
KMnO 4 – KOH H3O+
Ans. (i) D
Ethylbenzene Benzoic acid
COCH3 COOK COOH

KMnO 4 – KOH H3O+
(ii) D
Acetophenone Benzoic acid
O
Br MgBr C COOH
Mg O=C=O H3O +
(iii) dry ice
OMgBr
Ether
Bromobenzene Benzoic acid
CH=CH2 COOK
KMnO 4 – KOH H 3O+
COOH
(iv) + HCOOK
D
Phenylethene
5. 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
NO2 N–OH
Ans. (i) CH=NNH NO2 (ii)
O
OCH3 NNH–C–NH2
(iii) CH3–CH (iv)
OCH3
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CH2–CH 2
OH OH
H2C CH2 +
O O O
Å
(v) H3C – CH2 – C – CH2 – CH2 – CH3 H
–H2O CH3–CH2–C–CH2–CH2–CH3
H OH H
(vi) HÅ H–OH
C –H 2O C=O +
H H–O–CH3
H OCH3
6. 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 C H + C H
Ph–MgBr H 3O
Ans. (i)
Ph Hydrolysis Ph
Cyclohexane- Cyclohexylphenylcarbinol
carbaldehyde
CH=O
(ii) +
+ 2[Ag(NH3)2] + 3OH
–
Cyclohexane- Tollen's reagent

carbaldehyde O
–
C–O
+ 2Ag + 4NH3 + 2H2O
Silver mirror
Cyclohexane-
carboxylate ion
O
CHO O
(iii) pH 3.5 CH=NNH–C–NH2 + H2O
+ H2NNH–C–NH2
weak acid
Semicarbazide
Cyclohexane- Cyclohexanecarbaldehyde
carbaldehyde semicarbazone
OC2H5
CHO H OC2H5
Dry HCl gas C OC H + H O
(iv) + 2 5 2
H
Cyclohexane- H OC2H5
carbaldehyde Ethanol (Excess) Cyclohexanecarbaldehyde
diethyl acetal
CH3
CHO Zn/Hg–HCl
(v) (clemmensen
reduction)
Cyclohexane- Methylcyclohexane
carbaldehyde
7. 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
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Ans. Aldehydes and ketones having at least one a-hydrogen undergo aldol condensation (ii), (v), (vi), (vii)
gives aldol condensation.
Aldehydes (only) having no a-hydrogen undergo Cannizzaro reactions. (i), (iii), (ix) gives cannizzaro
reaction.
Compound (iv) is a ketone having no a-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
(ii) 2CH3CH2CH2—CH—CHO dil. NaOH
CH3
2-Methylpentanal
CH3
CH3CH2CH2—CH—CH—C—CH2CH2CH3
CH3 OH CHO
O
dil NaOH
(v) 2 O
OH
Cyclohexanone
O OH CH3
dil NaOH
2 C—CH2CH3 C—CH—C
(vi)
CH2 O
1-Phenylpropanone
CH3
OH CHO
dil NaOH
(vii) 2 CH2CHO CH2—CH—CH
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
8. Write structural formulas and names of four possible aldol condensation products 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.
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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)
9. 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) CH3CH2 CH(Br)COOH, CH3CH(Br)CH2COOH, (CH 3 )2 CHCOOH, CH3 CH2CH2 COOH
[Acid strength]
(c) Benzoic acid, 4-Nitrobenzoic acid, 3,4–Dinitrobenzoic acid, 4–Methoxybenzoic acid
[Acid strength]
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
10. Complete each synthesis by giving missing starting material, reagent or products.
CH2CH3 COOH
KMnO4 SOCl2
(i) KOH, heat
(ii) heat
COOH
H2NCONHNH2
C
(iii) C6H5CHO (iv)
O [Ag(NH 3)2]+
CHO
NaCN/HCl
(v) (vi)
CHO COOH
C6H5CHO
dil.NaOH (i) NaBH4
(vii) + (viii) CH3COCH2COOC2H5 (ii) H+
CH3CH2CHO
CrO3
(ix) OH (x) CH2 CHO
(i) O 3
(xi) (ii) Zn-H 2O O
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CH2CH3 COOK
KMnO4
Ans. (i) KOH, heat
Ethylbenzene Potassium benzoate
COOH SOCl2
COCl
(ii)
COOH COCl
Phthalic acid Phthaloyl chloride
O
(iii) C6H5CHO + H2NCONHNH2 C6H5CH = NHHC–NH2 + H2O
Benzaldehyde Semicarbazide Benzaldehyde semicarbazone
O
COCl C
+ Anhyd AlCl 3
(iv) + HCl
F.C. acylation
Benzene Benzoyl chloride Benzophenone
O [Ag(NH3)2]+ O
(v) CHO COOH + 2Ag
4-Oxocyclohexanecarbaldehyde 4-Oxocyclohexanecarboxylate Silver mirror
anion
OH
CHO CH
NaCN/HCl CN
(vi) COOH COOH
2-Formylbenzoic acid 2-[1-Hydroxycyanomethly]
benzoic acid
C6H5CHO
Benzaldehyde
dil.NaOH 3 2 1
(vii) + C6H5CH=C–CHO
CH3CH2CHO CH3
Propanal 2-Methyl - 3 - phenyl
pro - 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
Cyclohexanol Cyclohexanone
CHO
½ B 2H6 H2O2/OH
—
PCC
(x) CH2 CH2 B CH2OH
3
Methylenecyclohexane Cyclohexanecarbaldehyde
(i) O3
(xi) 2 O
(ii) Zn-H2O
Cyclohexylidene cyclohexane Cyclohexanone
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11. Write the structure of 2-hydroxybenzoic acid.
COOH
Ans. OH
12. (a) Write the products formed when CH3CHO reacts with the following reagents:
(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
dil NaOH
(iii) CH3CHO CH3—CH—CH2—CHO
Ethanal 3-Hydroxybutanal
(b) (i) NaHCO3 test: Benzoic acid being an acid produces brisk effervescence with NaHCO3 solution
while ethylbenzoate does not.
C6H5COOH + NaHCO3 ® C6H5 COONa + CO2 + H2 O

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 :
CH3–C–CH3
Propanone gives iodoform test but propanal (CH3–CH2–CHO) does not.
O
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–BaSO4
Benzaldehyde
NaOH
(ii) HCHO + HCHO CH3OH + H COONa
Methanal Methanol
(c) CH3 CH2 –CH2 –CO–CH3
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13. (a) How will you convert the following :
(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) CH 3 – C – CH3 conc. HCl
?
O
Pd – BaSO4
(ii) CH3 – C – Cl + H2 ?
O
COOH
(iii) Br2 / FeBr3 ?
(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 /H 2

(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.
OR
(a) (i) CH3–CH2–CH3
(ii) CH3–CHO
COOH
(iii)
Br
(b) (i) F–CH2–COOH
(ii) CH3 COOH
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14. Write the IUPAC name of the following :
O
CH 3–CH 2–CH=CH–C–H
Ans. Pent-2-ene-1-al
15. (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
(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 D
Ans (a) (i) CH3CH 2CH2CH 2 OH ¾¾¾¾¾¾
(ii)dilute H SO
® CH 3CH 2 CH 2COOH
4
2
2
4
O
(i)KMnO 4 / KOH, D
(ii) Me C–Me ¾¾¾¾¾¾
(ii) diluteH 2SO4
® HOOC COOH
4-Methylacetophenone Benzene-1,4-dicarboxylic acid

[Terephthalic acid]
OR
(i) Iodoform test given by propanone. It gives yellow ppt of CHI3.
I2 + NaOH
H3C–C –CH3 CH3–C –ONa + CHI3 (yellow ppt)
O O
(ii) Tollen's test given by benzaldehyde. It gives silver mirror ppt.

CHO COOH
+ 2Ag (silver mirror)

+
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
16. (a) Illustrate the following name reactions:
(i) Cannizzaro’s reaction
(ii) Clemmensen reduction
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(b) How would you obtain the following:
(i) But-2-enal from ethanal
(ii) Butanoic acid from butanol
(iii) Benzoic acid from ethylbenzene
Ans. (a) (i) Bute–2– enal from ethanal
O (i) dil O
NaOH
CH3 – C – H CH3 – CH = CH – C – H
Ethanal (ii) D But – 2 – enol
(Reaction is known as Aldol condensation)
OH O
KMnO4
(ii) CH3 – CH2 – CH2 – CH2 CH3 – CH2– CH2 – C –OH
Butanol H+ Butanoic acid
CH 2–CH 3 O = C – OH
KMnO4/OH
(iii) Oxidation
Ethanal Benzoicacid
17. (a) Give chemical tests to distinguish between the following :

(i) Benzoic acid and ethyl benzoate.
(ii) Benzaldehyde and acetophenone.
(b) Complete each synthesis by giving missing reagents or products in the following:
COOH
SOCl2
(i) heat
COOH
H 2NCONHNH 2
(ii) C6H 5 CHO
(iii) CH2 CH2OH
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 + H2 O
Benzoic acid Sod. Benzoate
C6 H5COOC 2 H5 ¾¾¾¾¾¾¾
NaHCO3 SOLUTION
® No effervescence due to evolution of CO2 gas.
® Iodoform test: Ethylbenzoate on boiling with excess of NaOH solution gives ethyl alchohol which
on heating with iodine gives yellow ppt. iodoform.
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C6 H 5 COOCH 2 CH3 + NaOH ¾¾¾
Boil
® C 6 H 5COONa + CH 3CH 2 OH
Ethyl benzoate Sod. benzoate Ethyl alcohol
CH 3CH 2 OH + 4I 2 + 6NaOH ¾¾¾

heat
® H COONa + CHI 3 + 5NaI + 5H 2O
Ethanol Sod. 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.
C6 H 5 COOCH3 + 3 NaOI ® C6 H 5 COONa + CHI 3 ¯ + 2NaOH

Acetophenone Sodium Iodoform
benzoate (Yellow ppt)
C6 H5 COC 6 H 5 ¾¾¾
NaOI
® No yellow ppt. of CHI3
O
COOH COCl
SOCl2
(b) (i) heat
(ii) C6H5–CH = N – NH – C –NH 2
COOH COCl
Phthalic acid Phthyaloyl Chloride
B2H6
(iii) CH2 H2O 2 /NaOH CH2OH
18. (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) bromobenzene to benzoic acid
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– CH3
Ethanal HCl
Ethane
O
Zn–Hg
CH3– C – CH3 CH3– CH2–CH3
Propanone HCl Propane
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(ii) Cannizzaro’s reaction: Aldehydes which do not contain any a- 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
NaOH – +
(2) –C–H+ –C–H – CH2 + – C – O Na
50%
OH
OH O CH2CH3 COOH
–
CrO 3, H 2SO4 KMnO4/OH
(b) (i) (ii)
Cyclohexanol Cyclohexan-1-one Ethylbenzene Benzoic acid
Br Mg Br COOH
Mg/dry ether (i) Dry ice, (ii) H3+O

(iii) Grignard reaction
Bromobenzene Phenylmagnesium Benzoic acid

bromide
19. (a) Illustrate the following name reactions:
(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 a-halogenated acids. This is known as Hell-Volhard-Zelinsky
(HVZ) reacation. The reaction is given by aliphatic acids having a-hydrogen./ Bromine reacts
smoothyl.
Re d P
CH3CH2 COOH + Br2 ¾¾¾¾ UV light
® 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.
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CH3 NH2NH2 CH3 KOH/ethylene glycol CH3
C=O C = NNH2 CH2 + N2
CH 3 –H2O CH3 heat CH3
Acetone Propane
O
Conc. HCl Br 2-NaOH
CH3 CH2 CN CH3 CH2 C NH2 CH 3 CH 2 NH 2
(b) (i) Partial hydrolysis
Ethyl cyanide Propionamide Ethylamine
HONO K2Cr2O 7/H2SO4

CH3 CH2 OH CH3 COOH
–N2, –H 2O Oxidation
Ethanol Ethanoic acid
K2Cr2O 7/H 2SO 4

(ii) CH3 CH2 CH2 CH2 OH Oxidation
CH3 CH2 CH2 COOH
Butan-1-ol Butanoic acid
CH3 COOH
(iii) (i) KMnO4 + KOH

(ii) H 2O
Mythylbenzene Benzoic acid
20. (a) Write chemical equations to illustrate the following name bearing reactins :
(i) Cannizzaro's reaction
(ii) Hell-Volhard-Zelinsky reaction

(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
NaOH
Ans. (a) (i) HCHO + HCHO CH3 OH + H COONa
Methanal Methanol
Re d P
(ii) CH3 COOH + Cl2 ¾¾¾¾
UV light
® Cl CH2 COOH + HCl
acetic acid Chloro acetic acid
O
|| Tollen's reagent
(b) (i) CH3 – CH2 – C – H silver mirror is formed
Propanal
O
||
CH3 – C – CH3 Tollen's reagent No reaction
Propanone
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(ii) Acetophenone Benzophenone
+ve iodoform test –ve Iodoform Test
O
CH3– C –
O
I2/NaOH
C
O
I2/NaOH
CHI3+ – C – O– Na+
Iodoform No Reaction
yellow ppt
(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 ® (C6H5 COO)3Fe + 3HCl
Benzoic acid Buff coloured ppt.
21. (a) How will you bring about the following conversions :
(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
CrO3
OH
Dil NaOH
|
CH3CH2OH CH3 – CH – CH2 – CHO
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)
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(b) The relevant equations for all the reactions involved may be explained as follows :
O Butyl butanoate
dil. H2SO4
CH3CH2CH2 . COCH2CH2CH3 CH3CH2CH2OH + CH3CH2CH2CH2OH
Hydrolysis
A(m. f. C 8H 16O 2) B(Butanoic acid) C(Butane-1-ol)
(K2Cr2O7 + H2SO4)
CH3CH 2CH2OH Oxidation CH3CH 2CH2CH2COOH
(Butane-1-ol) B(Butanoic acid)
Dehydration
CH3CH2CH2OH (–H2O) CH 3CH2CH=CH2
C(Butane-1-ol) D(But-1-ene)
Therefore, (A) Butyl butanoate, (B) Butanoic acid, (C) Butan-1-ol, (D) But-1-ene
22. (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
conc. NaOH
Ans. (a) (i) HCHO + HCHO ¾¾¾¾¾ ® 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
D
(b) (i) Propanal Propanone

Give +ve Test with Tollen’s Give –ve Test with Tollen's Reagent
Reagent, Fehling solution Fehling solution. Benedict solution.
(ii) Phenol & Benzoic acid

Benzoic acid given alteruences with NaHCO3 where as phenol does not give any alteruencese
(envolved CO2)
O = C – OH O = C – O –Na +
+ NaHCO 3 + H2O + CO2
OH
+ NaHCO 3 No Reaction
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23. (a) An organic compound A contains 69.77% carbon, 11.63% hydrogen 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 sodium 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
Ans. (a) Pentan-2- one
CH3 CH2 CH2 C CH3
O
(b) (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)
NaOI
C6H5COC6H5 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 + 3H2 O
Ethanal (yellow ppt.)
NaOI
CH3CH2CHO No yellow ppt of CHI3
Propanal
REASONING :
1. Aldehydes are more reactive towards nucleophiles than ketones.
Ans. (a) Sterically, the presence of two large substituents in ketones hinders the approach of nucleophile
to carbonyl carbon as compared with aldehydes having only one such substituent.
(b) The two alkyl groups in ketones are electron releasing and release the electron density over
carbonyl carbon, thus reduces the electrophilicity of carbonyl carbon more effectively than in aldehyde
which has only one alkyl group.
2. Cyclohexanone forms cyanohydrin in good yield but 2,2,6-trimethyl cyclohexanone does not.
d+ d– OH
Ans. O+H–CN
CN
H3C CH3
d+ d–
O+H–CN No reaction
CH3
(a) The three methyl groups are electron releasing and increase the electron density over carbonyl
carbon atom thus reduces its electrophilicity.
(b) Three methyl groups causes steric hinderance to nucleophilic attack the carbonyl carbon of
C=O group.
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3. During the preparation of an ester from a carboxylic acid and an alcohol in the presence of an acid
catalyst, ester is removed as fast as it is formed.
+
H
Ans. RCO OH+H OR1 RCOOR1 + H2O
Both esterification and hydrolysis of ester are catalysed by acid, the reaction is reversible and an
equilibrium is established, so ester or water is removed to favour the forward reaction, as per Le
Chatelier’s principle.
4. pKa of chloroacetic acid is less than that of acetic acid or chloroacetic acid is a stronger acid than
acetic acid.
O
Ans.
O
Any electron releasing group like CH3 increases the electron density over carboxylate anion
(–COO–). The stability of the conjugate base is reduced and hence, H+ cannot be donated easily.
Thus, it decreases the acid strength of carboxylic acid.
Any electron withdrawing group like Cl, F, NO2 etc. withdraws the electron density away from
COO– and spreads it and thus stabilises the carboxylate ion by delocalisation of negative charge.
Thus, it increases the acid strength of carboxylic acid.
CHEMICAL TEST :
I. Primary, Secondary and Tertiary alcohol
(iv) Test Enthanol ( C 2 H 5OH ) Pr opan - 1 - ol ( CH 3CH 2 CH 2OH )

(1) Add (I 2 + NaOH)and heat Yellow ppt of iodoform ( CHl3 ) is formed Nochange
6NaOH + 4I2 + CH3CH2OH ¾® CHI 3 + HCOONa + 5NaI + 5H 2 O

( yellow ppt. )
(v) Test Ethanol ( CH3CH 2 OH ) Methanol ( CH3OH )

Add (I2 / NaOH) and heat Yellow pracipitate of CHI3 is formed Nochange
IV. Difference between Aldehyde and Ketone
O
(i) Test Acetaldehyde CH3CHO Acetone H3C–C–CH3
(1) Add Fehling's reagent Brown red precipitate No change
is formed
CH3CHO + 2Cu + 5OH ¾® CH3COO + Cu2O (red brown) + 3H2O
2+ –
(2) Add Tollen's reagent Silver mirror is formed No change
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(ii)
Test Acetaldehyde CH3CHO Formaldehyde HCHO
Add I2+NaOH and heat No change

4NaOH + 3I 2 + CH 3CHO ¾® CHI3 + HCOONa + 3NaI + 3H 2O
(iii) Test Ethanal (CH3CHO) Benzaldehyde (C6H6CHO)
(1) Add I 2+NaOH No change

(2) Add Fehling's reagent Red ppt of Cu2O No change
(iv) Test Pentan-3-one Pentan-3-one

O O
CH3–C–CH 2CH 2CH 3 CH3CH2–C–CH2CH3
(1) Add I 2+NaOH and heat Yellow ppt. (CHI3) is formed No change
O
4NaOH + 3I2 + CH3 – C – CH2 CH2CH3 ¾®CHI3 + CH3CH2CH 2COONa + 3NaI + 3H2O
(Yellow ppt.)
Acetophenone Benzophenone
(v) Test
COCH3 O
C
(1) Add I 2 + NaOH Yellow iodoform (CHI3) No change
COCH 3 COONa
4NaOH + 3I2 + CHI3 + + 3NaI + 3H2O
(2) Add NaHSO 3 White ppt No change

O OH
C–CH3 + NaHSO3 ¾® C–SO3– Na+
CH3
V. Difference between Different-Different Carboxylic Acid
(i) Test Formic acid (HCOOH) Acetic acid (CH3COOH)
(1) Tollen's reagent Silver mirror (Ag) is formed No change
HCOOH + [Ag(NH3) 2] + + 2OH ¾® CO 2 + Ag + 2H 2O + 2NH 3
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VI. Difference between Phenol and Carboxylic Acid
Phenol (White solid) Benzoic acid (White solid)

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

(2) Add NaHCO3 (aq) No change Effervescence of CO 2
C 6H 5COOH + NaHCO 3 ¾® C 6H 5COONa + CO 2 + H2O
IX. Difference between Ketone and Carboxylic Acid

(i)
Test CH3COCH3 acetone acetic acid CH3COOH
(1) Add l2+NaOH + heat Yellow ppt of iodoform (CHI3) No change
4NaOH + 3l2 + CH3COCH3 ® CHI3 + CH 3COONa + 3Nal + 3H2O
(2) Add NaHCO3 No change Effervescence of CO 2
CH3COOH + NaHCO3 ® CH3COONa + H2O + 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 CO 2
NAME REACTIONS :
1. Friedel-Crafts acylation reaction
The reaction of benzene with an acyl halide or acid anhydride in the presence of Lewis acids
(A lCl 3) yields acyl benzene.
COCH 3
Anhyd. AlCl 3
+ CH3COCl D + HCl
Acetylchloride
Acetophenone
COCH3
Anhyd. AlCl 3
+ (CH3CO)2O D + CH3COOH
Acetic anhydride
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Cl Cl O Cl
O
Anhyd. AlCl 3 CH3
+ H3C–C–Cl +
(Minor) O CH3
(Major)
OCH3 OCH3 OCH3

COCH3
Anhyd. AlCl 3
+ CH3COCl +
Ethanoyl
chloride 2-Methoxy- COCH3
acetophenone
4-Methoxy-
(Minor)
acetophenone
(Major)
2. 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
3. Stephen reaction
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.
+
RCN + SnCl2 + HCl ¾¾

® RCH = NH ¾¾¾
H3 O
® RCHO
4. 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
5. 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
Benzene Benzaldehyde
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6. Clemmensen Reduction The carbonyl group of aldehydes and ketones is reduced to CH2 group on
treatment with zinc- amalgam and concentrated hydrochloric acid. This is known as Clemmensen
reduction.
Zn-Hg
C=O CH2 + H2O (Clemmensen reduction)
HCl
7. 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)
8. 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 ¾¾
® RCO O + 2Ag + 2H 2O + 4NH 3
Silver Mirror
9. 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 + 2Cu 2+ + 5O H ¾¾
® RCO O + Cu 2O + 3H 2O
Re d - brown ppt
10. 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 D CH3–CH=CH–CHO
Ethanal –H2O But-2-enal
OH (Aldol condensation product)
(Aldol)
3-Hydroxybutanal
CH3 CH3
Ba(OH)2 D
2CH3–CO–CH3 CH 3–C–CH 2CO–CH3 CH3–C=CH–CO–CH3
–H2O
Propanone OH
(Ketol) 4-Methylpent-3-en-2-one
4-Hydroxy-4-methylpentan-2-one (Ketol condensation product)
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(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. D But-2-enal
CH3CH2CHO CH3
CH3–CH=C–CHO + CH3CH2–CH=CHCHO
CH3
2-Methylbut-2-enal Pent-2-enal
11. Cannizzaro reaction:
Aldehydes which do not have an a-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
12. 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.
Electrolysis
2CH3COO- Na + + 2H 2 O ¾¾¾¾¾¾ ® CH 3 – CH 3 + 2CO 2 + H 2 + 2NaOH
Sodium acetate
13. Hell-Volhard-Zelinsky (HVZ )reaction.

Carboxylic acids having an a-hydrogen are halogenated at the a-position on treatment with
chlorine or bromine in the presence of small amount of red phosphorus to give a-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
a–Halocarboxylic acid
MECHANISM :
1. Mechanism of esterification of carboxylic acids :
R– –OH + R¢–OH R– –OR¢ + H2O
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OH
+ H
O H+ R' ¾ OH +
Ans. R ¾ C R¾C R ¾ C ¾ O ¾ R'
OH O ¾ R'
Carboxylic acid OH H
Tetrahedral intermediate
Proton
transfer
+
OH OH
O –H+ –HOH
R¾C R ¾C R ¾ C ¾ O ¾ R'
O ¾ R' O ¾ R' +
Ester Protonated ester OH
H
1. 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
Å
AlCl 3 KMnO4 H
Ans. (i) + CH3–Cl CH3OH
(ii) In above reaction if

COOH COOH
HNO3
+ H 2SO 4
(Nitration) NO2
CH3 CH3 COOH

CH3Cl/
Anhyd. AlCl 3 HNO3/H2SO4 KMnO 4–KOH D
(iii) (Friedel-Craft (Nitration) H 3O+
alkylation)
Benzene NO2 NO2
(Major) p-Nitrobenzoic acid
CH3 CH2Br CH2CN CH2COOH

CH3Cl/
+
Anhyd.AlCl 3 Br2 and hv Alc. KCN,D H /H 2O
(iv)
Benzene Toluene Benzylbromide Benzylcyanide Phenylacetic aicd
(v)
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2. 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 a-Hydroxyphenylacetic acid
O OH
NaBH4 conc.H2SO 4
Ans. (i) CH3–C–CH3 CH3–CH–CH3 D CH3–CH=CH2
Propene
(ii)
(iii)
(iv)
O
CHO COOH COCl + Anhyd.AlCl3 C
HNO3 SOCl2
(v) (Oxidation) (Friedel-Craft acylation)
Benzaldehyde Benzophenone
OH
Br MgBr H3C–CH
Mg/dry ether (i) CH3CHO
(vi) (ii) H2O
Bromobenzene 1-Phenylethanol
(vii)
CHO OH OH
+
HCN H /H 2O
(viii) C6H5–CH–CN C6H5–CH–COOH
a-Hydroxyphenylacetic acid
Benzaldehyde
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WORD PROBLEMS :
1. 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)
2. An alkene ‘A’ (Mol. formula C5H10) on ozonolysis gives a mixture of two compounds ‘B’ and ‘C’.
Compound ‘B’ gives positive Fehling test and also forms iodoform on treatment with I2 and NaOH.
Compound ‘C’ does not give Fehling test but forms iodoform. Identify the compounds A, B and C.
Write the reaction for ozonolysis and formation of iodoform from B and C.
Ans.
Other isomers of ‘A’ will not give products corresponding to the given test.
3. An aromatic compound ‘A’ (Molecular formula C8H8O) gives positive 2,4-DNP test. It gives a yellow
precipitate of compound ‘B’ on treatment with iodine and sodium hydroxide solution. Compound
‘A’ does not give Tollen’s or Fehling test. On drastic oxidation with potassium permanganate it forms
a carboxylic acid ‘C’ (Molecular formula C7H6O2), which also formed along with the yellow
compound in the above reaction. Identify A, B and C and write all the reactions involved.
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Ans.
4. Write down functional isomers of a carbonyl compound with molecular formula C3H6O. Which
isomer will react faster with HCN and why ?
Ans.
Compound I will react faster with HCN due to less steric hinderance and electronic reasons than II.
No, It is a reversible reaction. Hence equilibrium is established.
–
Addition of acid inhibits the reaction because the formation of CN ions is prevented.
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1. Iodoform test in not given by [1]

(CBSE 2020)
(A) Ethanol
(B) Ethanal
(C) Pentan-2-one
(D) Pentan-3-one
Ans. (D)
2. 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)
3. What happens when
(a) Propanone is treated with methylmagnesium bromide and then hydrolysed, and
(b) benzene is treated with CH3COCl in the presence of anhydrous AlCl3 [1 × 2 = 2]
Ans. (a) (CH3)3C-OH/tertiary butyl alcohol is formed.
(b) C6H5COCH3/acetophenone is formed
4. Write structures of main compounds A and B in each of the following reactions : [2]
(a) C6 H 5 COOH ¾¾¾
PCl
5 ® A ¾¾¾¾¾¾
2 H / Pd - BaSO
4®B (CBSE 2019)
(i)CH MgBrZn(Hg)/conc.HCl
(b) CH 3 CN ¾¾¾¾¾
3
+
® A ¾¾¾¾¾¾¾ ®B
(ii) H3O
Ans. (a) A = C6H5COCl B = C6H5CHO

(b) A = CH3COCH3 B = CH3CH2CH3
5. (a) Give reasons : [3]
(i) Benzoic acid is a stronger acid than acetic acid. (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 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.
6. Write structures of main compounds A and B in each of the following reactions : [2]
(a) PCC
CH 3CH 2 OH ¾¾¾ CH3OH / dry HCl(g)
® A ¾¾¾¾¾¾¾ ®B (CBSE 2019)
NaOI
(b) C6 H5COCH3 ¾¾¾® A + B
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Ans. (a) A® CH3CHO ; B® CH3–CH–OH
OCH3
NaOI
(b) C6 H5COCH3 ¾¾¾® CHI3 + C6 H5 – COONa
7. How do you convert the following ? (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 :-
Å
O O MgX
(Grignard reagent)
CH3 – C – H + CH3 – Mg X ® CH3 – CH H O/H+ CH 3 – CH – OH
2
CH3 CH3
(Ethanol) (Adduct)
CrO3
O
CH 3 – C – CH 3
Propanone
(b) Toluene to Benzoic Acid ®

CH3 COOK COOH
KMnO 4
–KOH/D 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.
8. (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). (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 ?
O
Ans. (a) (A) ® CH3 – CH2 – CH2 – CHO (B) ® CH3 – C – CH2 – CH3
CH3 O
(C) (D) CH3 – CH2 – CH2 – CH3
CH3 – CH – C – H
(b) B is ketone, so it will be less reactive towards nucleophilic addition reaction, with HCN due
to + I effect & steric hinderance
(Inductive)
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9. (a) Write the product(s) in the following reactions : (CBSE 2017)
O
(i) + HCN ¾® ?
COONa
(ii) + NaOH ¾¾¾
CaO
D
®?
(a) DIBAL -H
(iii) CH3 – CH = CH – CN ¾¾¾¾¾
(b) H O
® ?2
(b) Give simple chemical tests to distinguish between the following pairs of compounds :
(i) Butanal and Butan-2-one (ii) Benzoic acid and Phenol
OR
(a) Write the reactions involved in the following :
(i) Etard reaction (ii) Stephen reduction
(b) How will you convert the following in not more than two steps :
(i) Benzoic acid to Benzaldehyde (ii) Acetophenone to Benzoic acid
(iii) Ethanoic acid to 2-Hydroxyethanoic acid
OH
CN
Ans. (a) (i)
(ii)
(iii) CH3 – CH = CH – CHO

(b) (i) Tollen's reagent test : Add ammoniacal solution of silver nitrate (Tollen's Reagent) in
both the solutions. Butanal gives silver mirror whereas Butan–2–one does not.
(ii) Add neutral FeCl3 in both the solutions, phenol forms violet colour but benzoic acid does not.
OR
(a) (i) Etard reaction
CH 3 CH(OCrOHCl2)2 +
CHO
CS2 H3O
+CrO2Cl2
Tolueoe Chromium complex Benzaldehyde

Or
CH 3 CHO
(i) CrO2Cl2, CS2
+
(ii) H3O
Tolueoe Benzaldehyde
(ii) Stephen reaction

+
H3O
RCN + SnCl2 + HCl ¾¾® RCH = NH RCHO
Or
(i) CrO2Cl2, CS2
RCN RCHO
(ii) H3O+
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(b) (i)
COOH COCl CHO
SOCl2 Resonmund's
reduction
Pd/BaSO 4
Benzoic Benzoyl Benzaldehyde
acid chloride
(ii)
COCH3 COONa COOH
+
I2/NaOH H 3O
Acetophenone Sodium benzoate Benzoic

acid
Cl2/P KOH(Aq)
(c) CH3COOH CH2COOH CH 2COOH
Cl OH
10. (a) Write the structures of A, B, C and D in the following reactions: (CBSE 2016)
(i) SnCl2–HCl dil..NaOH heat

CH3CN A B C
(i) H2O
HCN
D
(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]
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11. (a) Write the chemical reaction involved in Etard reaction. (CBSE 2016)
(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 ¾¾¾¾¾¾2.H 2O
®
(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

CS2 H3O+
Ans. (a) +CrO2Cl2
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
12. Predict the products of the following reactions : (CBSE 2015)
(a)KMnO 4 / KOH
(i) CH 3 - C = O ¾¾¾¾¾¾¾
H 2 N - NHCONH 2
®? (ii) C 6 H 5 - CH 2 - CH 3 ¾¾¾¾¾¾¾
(b)H +
®?
|
CH 3
COOH
(iii) conc.HNO 3 / H 2SO 4
¾¾¾¾¾¾¾¾ ®
Ans. (i) CH3–C=N–NH–CO–NH2 (ii) C6H5–COOH

CH3
COOH
(iii)
NO2
13. Write the reagents used in the following reactions : (CBSE 2015)
(i) C6 H5 - CO - CH 3 ¾¾
?
® C 6 H 5 - CH 2 - CH 3
(ii) CH3 - COOH ¾¾

?
® CH 3 - COCl
Ans. (i) Zn-Hg, HCl or H2N–NH2 & KOH/Glycol , D

(ii) PCl5 / PCl3 / SOCl2 (Any one)
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EXERCISE-3 RACE
Read the given passage and answer the following questions.
Aldehydes and ketones containing atleast one a-H atom undergo a reaction in the presence of dilute
alkali as catalyst to form b-hydroxy ketols. When two different aldehydes or ketones combine them
mixture of four products are formed, then reaction is called cross-aldol condensation.
(i) Which of the following compounds do not undergo aldol condensation?
(a) CH3 — CHO (b) CH2 – CHO
CH 3
O |
(c) || (d) CH - C - CHO
3
CH 3 - C - CH 3 |
CH 3
(ii) When aldols readily lose water the product formed.

(a) a, b-unsaturated carbonyl compound
(b) a, g-unsaturated carbonyl compound
(c) a-unsaturated carbonyl compound
(d) b-unsaturated carbonyl compound
(iii) When benzaldehyde reacts with CH3CHO in presence of dilute NaOH the product formed-
(a) 2-hydroxy-3-phenylpropanal (b) 3-hydroxy-3-phenylpropanal
(c) 3-hydroxy-2-phenylpropanal (d) 3-phenylpropanal
(iv) When benzaldehyde reacts with Conc. NaOH the product formed -
(a) Sodiumbenzoate & benzylalcohol (b) Sodium acetate & benzylalcohol
(c) Sodiumbenzoate & methylalcohol (d) Sodium acetate & sodium alkoxide
Question 2 to 6 :- Note:- In the following questions a statement of assertion followed by a reason . choose
the correct answer out of the following choices –
2. Assertion : Formaldehyde is planar molecule.
Reason : It contains sp2 hybridised carbon atom.
3. Assertion : Compound containing – CHO group are easily oxidised to corresponding carboxylic acids.
Reason : Carboxylic acids can be reduced to alcohols by treatment with LiAlH4.
4. Assertion : The a-hydrogen atom in carbonyl compound is less acidic.
Reason : The anion atom is reasonance stabilised.
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5. Assertion : Aromatic aldehydes and formaldehyde undergo Cannizaro reaction.
Reason : Aromatic aldehydes are almost as reactive as formaldehyde.
6. Assertion : Aldehydes and ketones, both react with Tollen’s reagent to form silver mirror.
Reason : Both, aldehydes and ketones contain a carbonyl group.
7. Which of the following compounds does not reduce fehling's solution?
(i) C6H5 CHO (ii) CH3CHO (iii) CH3 COCH2OH (iv) HCOOH
8. The approprite reagent for transformation
O
CH2 – CH3
CH3 ¾®
HO
HO
(i) Zn – Hg, HCl (ii) NH2 – NH2, OH¯

(iii) H2 / NI (iv) NaBH4
9. In the following sequence of reactions
AlCl3
Zn,Hg
+ CH3CH2COCl ¾¾¾® X ¾¾¾¾¾¾ ® Y
conc.HCl, heat
The product (Y) is :

(i) PhCOCH2 CH3 (ii) PhCHOHCH2CH3
(iii) PhCH2CH2CH3 (iv) PhCH = CHCH3
10. How many stereoisomers are possible for the product formed the condensation of benzaldehyde with
acetaldehyde by the action of hot concentrated NaOH?
(i) Two (ii) Three (iii) Four (iv) None of these
11. Cannizzaro's reaction is not given by
CHO CHO
(i) (ii) (iii) HCHO (iv) CH3CHO

CH3
12. Which of the following compounds is most reactive towards nucleophilic addition reactions?
O O O O
|| || || ||
(i) CH 3 - C - H (ii) CH3 - C - CH3 (iii) C–H (iv) C – CH3
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13. The correct order of increasing acidic strength is _____________.
(i) Phenol < Ethanol < Chloroacetic acid < Acetic acid
(ii) Ethanol < Phenol < Chloroacetic acid < Acetic acid
(iii) Ethanol < Phenol < Acetic acid < Chloroacetic acid
(iv) Chloroacetic acid < Acetic acid < Phenol < Ethanol
14. The reagent which does not react with both, acetone and benzaldehyde.
(i) Sodium hydrogensulphite (ii) Phenyl hydrazine
(iii) Fehling’s solution (iv) Grignard reagent
15. In Clemmensen Reduction carbonyl compound is treated with _____________.
(i) Zinc amalgam + HCl (ii) Sodium amalgam + HCl
(iii) Zinc amalgam + nitric acid (iv) Sodium amalgam + HNO3
16. Iodoform test is not given by
(i) Ethanol (ii) Ethanal (iii) Pentan-2-one (iv) Pentan-3-one
Answer key :
Q. No. 1 (i) (ii) (iii) (iv) 2 3 4 5 6 7 8
Ans. d a b a A B C D D i ii
Q. No. 9 10 11 12 13 14 15 16
Ans. iii i iv i iii iii i iv
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1. Write the structure of 2-Hydroxybenzoic acid. [1]
2. Arrange the following in the increasing order of their reactivity towards nucleophilic addition reaction:
CH3–CHO, C6H5COCH3, HCHO [1]
3. Write the product in the following reaction. [1]
1.(i - Bu)2 AlH
CH3CH2CH=CH–CH2CN ¾¾¾¾¾¾2.H 2O
®
4. 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]
5. 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.
6. Why pKa of Cl–CH2–COOH is lower than the pKa of CH3COOH ? [2]
7. Write the chemical equations to illustrate the following name reactions: [2]
(i) Rosenmund reduction (ii) Cannizzaro's reaction
8. (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 ? [3]
9. 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

10 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
D
11. Write the product(s) in the following reactions : [5]
O
(i) + HCN ¾® ?
COONa
(ii) + NaOH ¾¾¾
CaO
D
®?
(a ) DIBAL -H
(iii)CH3 – CH = CH – CN ¾¾¾¾¾
(b) H O
®?2
H 2 N - NHCONH 2
(iv) CH 3 - C| = O ¾¾¾¾¾¾¾® ?
CH 3
(a)KMnO 4 / KOH
(v) C 6 H 5 - CH 2 - CH 3 ¾¾¾¾¾¾¾
(b)H +
®?
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MOCK TEST SOLUTIONS
COOH
1. OH
2. C6H5COCH3 < CH3CHO < HCHO
3. CH3CH2CH = CH – CH2CHO
4. A : CH3COCH3
B : CH3CH2CHO
5. (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.
6. Stronger –I effect of Cl , stronger acid less pka / strong electron withdrawing power of Cl.
COCl CHO
H2
7. (i) Pd–BaSO4
Benzaldehyde
NaOH
(ii) HCHO + HCHO CH3OH + HCOONa
Methanal Methanol
O
||
8. (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)
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COOH COCl CHO
9. (i) SOCl 2 Resonmund's

reduction
Pd/BaSO 4
Benzoic Benzoyl Benzaldehyde
acid chloride
COCH3 COONa COOH
(ii) I 2 /NaOH H 3O +
Acetophenone Sodium benzoate Benzoic

acid
CH3 KMnO COOK COOH

4
(iii) –KOH/D H3O

+
Benzoic acid
OH
|
10. A : CH3CHO B : CH 3 - CH - CH 2 CHO
OH
|
C : CH3 – CH = CH – CHO D : CH 3 - CH ...CN
OH
CN
11. (i)
(ii)
(iii) CH3 – CH = CH – CHO
(iv) CH 3 - C = N - NH - CO - NH 2
|
CH 3
(v) C6H5–COOH
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ALIPHATIC & AROMATIC AMINES
l Amines are alkyl and/or aryl derivatives of .
l Functional groups of 1°, 2° and 3° amines are respectively as given below :
l Gabriel phthalimide synthesis can't be used for the preparation of 2° and 3° amines. It gives aliphatic
primary amine only.
l Hofmann's bromamide reaction gives 1º amines having one carbon atom less than parent primary
amide.
l The order of basic strength of aliphatic amines is
(i) (a) Aliphatic amines are known as amino alkanes ;
(b) Aliphatic amines are more basic than . i.e., CH3NH2 > NH3
(ii) In aqueous solution medium, the order is 2º > 1° > 3º (for–CH3 group) and 2º > 3º > 1° for –C2H5 group.
(iii) In non-aqueous medium or gaseous phase, the order is 3º > 2° > 1°.
l Basic strength of aromatic amines :
(i) Aromatic amines are weaker bases than
(ii) ERGs like –CH3,–OR,–NH2 etc. increase basic strength while EWGs like –NO2, –CN etc.
decrease the basic strength The effect of substituents is more at para positions and less at meta position.
l Basic strength of amines is expressed in terms of Kb or pKb.
l 1º, 2° and 3° amines can be distinguished by Hinsberg's test.
l Hinsberg's reagent is benzenesulphonyl chloride (C6H5SO2Cl).
l 3º amines like trimethylamine are used as insect attractants
l Carbylamine lest only given by 1º amines.
l 1º amines give effervescence with HNO2.
l –NH2 group in aniline is o- and p-directing and is highly activating in nature.
l Acylation of aniline is done before subjecting it to nitration or halogenation.
l Aliphatic diazonium salts are very unstable and do not exist while aromatic salts are relatively stable.
l Arenediazonium salts are highly reactive compounds and reactivity is due to excellent leaving ability
of diazo group as N2 gas.
node06\B0B0-BA\Kota\Board Material\Chemistry\CBSE\CBSE Booklet\English\Updated booklet-21\New Pattern CBSE Booklet\Part wise boocklet\Part 2\03_OC\04_Aliphatic & Aromatic Amines
Preparation :
NH3(Excess)
H3C–CH2–X
–HX
(Aminolysis)
O
C (i) NH3
Gabriel
Phthalimide O
Synthesis
(ii) KOH, CH3–I
C (iii) H2O, H
+
[NSR] O
CH3NH2
Na(Hg)/EtOH RCH2NH 2
R–CºN
H2/Ni or LiAlH4/Et 2O R–NH2
O
Hoffmann ||
Bromamide Br2, KOH
H3C–C–NH2
Degradation H2O, HO¯
Fe/HCl or H2/Pd
R–NO2
or Sn/HCl
or SnCl2 + HCl
110 E
CBSE
ALLEN
Reaction :
HCl +
R–NH3 Cl¯
CH3Br R–NHCl3
Alkylation
CH3COCl
CH3NH2 Base (Acylation)
R–NHCl3
RCH2 NH2
R–NH2 CHCl3, KOH
N–NC
(Carbylamine test)
+
HNO2/H
R–OH
[But CH3–NH2®CH3–O–CH3]
N–R
Test
Reagent R–NH2(1°) R2NH(2°) R3N(3°) NH2
R–N–SO2–Ph O
Ph–SO2Cl | soluble ||
(Hinsberg H R2N–S–Ph No reaction NH–SO2–Ph
reagent) NaOH
!
O Na OH
[R–N–SO2–Ph]Na+ Insoluble
ANILINE
Preparation
NO2
Sn/HCl or Fe/HCl
Reduction
OH NH2
NH3/ZnCl2/300°C
O=C–NH2
Br2/KOH
Hofmann Bromoamide
Degradation
E 111
Chemistr y
ALLEN
Reaction of aniline:
O
|| O
C–Cl ||
NH–C
Base
Schotten Baumann Reactions
CHCl3 +
N ºC¯
KOH
Carbylamine Test
NH2
Br Br
Br2/H 2O
or Br2/CS2
Br
NH2 O NHCOCH3 NHCOCH3 NH2

||
!
(CH3–C)2O HNO3, H2SO4 OH or
Pyridene 288 K HÅ
(Group Protection)
NO2 NO2
NH2 NH2 NH2

Conc. HNO3 NO 2
+ +
Conc. H2SO4 NO2
[51%] [47%] [2%]
NO2
O NH2 NH2
||
(i) H3C–C–Cl NO2
+ +
(ii) HNO3+H2SO4/H3O
(Group Protection) NO2
Å
NH2 NH3
(1) Conc. H2SO4
(2) 453-473K
!
SO3H SO3
Friedel crafts reagent

No reactions
112 E
CBSE
ALLEN
Benzene Diazonium Chloride:
Reactoin :
OH
N=N OH
NH2
N=N H2N
H
NH–CH3 |
N=N N–CH3
OH OH
NH2 N=N
Cl
CuCl / HCl
CuBr / HBr Br
CN
CuCN/KCN
CN
+ Cu/HCl
NH2 NaNO2/HCl NºNCl¯
(0°–5°C)
Cu/HBr Br
C2H5OH/D
or H3PO2/D
OH
+
H2O / H
283 K
KI I
HBF4 F
D
+
N2BF4
HBF4 NaNO2 NO2
Cu/D
E 113
Chemistr y
ALLEN
1. Arrange the following in increasing order of their basic strength :

(i) C2H5NH2, C6H5NH2, C6H5CH2NH2 and (C2H5)2NH
(ii) C2H5NH2, (C2H5)2 NH, (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
2. 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)2NH and CH3NH2
(iii) In increasing order of basic strength :
(a) Aniline, p-nitroaniline and p-toluidine
(b) C6H5NH2, C6H5 NHCH3, C6H5CH2NH2
(iv) In decreasing order of basic strength in gas phase :
C2H5NH2, (C2H5)2NH, (C2H5)3N and NH3
(v) In increasing order of boiling point :
C2H5 OH, (CH3 )2NH, C2H5NH2
(vi) In increasing order of solubility in water :
C6H5NH2, (C2 H5)2NH, C2H5 NH2
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
3. Complete the following reactions :
(i) C6H5NH2 + CHCl3 + alc. KOH ¾®
(ii) C6H5N2Cl + H3PO2 + H2O ¾®
(iii) C6H5NH2 + (conc.) H2SO4 ¾®
(iv) C6H5N2Cl + C2H5OH ¾®
(v) C6H5NH2 + (aq.) Br2 ¾®
(vi) C6H5NH2 + (CH3CO)2O ¾®
( i ) HBF
(vii) C6H5N2Cl ¾¾¾¾¾¾ 4
( ii) NaNO / Cu,D
2
®
114 E
CBSE
ALLEN
Heat
Ans. (i) C6H5NH2 + CHCl3 + 3KOH (alc.) C6H5N = C
(Carbylamine reaction)
Aniline Phenyl isocyanide
(offensive smell)
(ii) C6H5N+2Cl–+ H3PO2 + H2O C6H6 + N2 + H3PO3+HCl

Benzenediazonium Benzene
Chloride
+
(iii) C6H5NH2 + H2SO4 (Conc.) C6H5NH 3HSO 4
—
Anilinium hydrogen
Aniline sulphate
Reduction
(iv) 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
O
O
H3C—C CH3COOH
(vi) C6H5NH2 + O or Pyridine
C6H5–NH–C–CH3 + CH 3COOH
H3C—C
(Acetylation)
O
Aniline Acetic anhydride Acetanilide
+ HBF 4 + – NaNO 2/Cu

(vii) C6H5N2Cl— C6H5 N2BF4 C6H5 NO2 + BF3 + NaF
Heat
Benzene diazonium
Benzenediazonium Nitrobenzene
Chloride
tetra fluoroborate
4. Write the IUPAC name of following.

(i) CH3CH2CN (ii) CH – CH – CN (iii) CH3CH2NC (ii) CH – CH – NC
CH3 CH3
Ans. (i) Propane nitrile (ii) 2-methyl propane nitrile
(iii) Ethyl Carbylamine (iv) isopropyl carbylamine
5. Write the preparation methods of Cyanides
Ans. (i) From alkyl halides : R—X + KCN ¾® R—CN + KX
(ii) From amides
CH3CONH2 ¾¾¾ P2O 5
® CH3CN + H2O
(Ethyl Nitrile)
CH3CONH2 + SOCl2 ¾® CH3CN + SO2 + HCl
(iii) From carboxylic acids :

D D
CH3COOH + NH3 ¾® CH3COONH4 ¾¾ ® CH3CONH2 ¾¾ ® CH3CN + H2O
Acetamide Methyl cynide
E 115
Chemistr y
ALLEN
6. Write the preparation methods of Iso-cyanides :
Ans. (i) Carbylamine reaction :
R NH2 + CHCl3 + 3KOH (alc.) ¾® R –NC + 3KCl + 3H2O
Chloroform Carbylamine
(ii) C2H5Br + AgCN ¾® C2H5NC + AgBr
Ethyl carbil Amine
7. Write the Physical Properties of Cyanides and Iso-cyanides.

Ans. (i) Physical state, colour and odour : The lower alkyl cyanides and isocyanides are colourless
liquids but the higher members are crystalline slids. Alkyl cyanides have generally pleasant
odours but alkyl isocyanides have very unpleasant odours.
(ii) Boiling points : Both –CN and –NC groups are highly polar. As a result, they have strong
intermolecular dipole-dipole interactions and hence have higher boiling points than the alkyl
halides of comparable molecular masses. Alkyl isoyanides usually have lower boiling points
than their corresponding alkyl cyanides. This is due to the reason that alkul isocyanides have
lower dipole moments (~3D) as compared to those of alkyl cyanides (~4D).
(iii) Solubility : Alkyl cyanides are more soluble than alkyl isocyanides because of hydrogen bonding.
However, solubility decreases with increase in molecular mass.
R–CºN.......H
O–H.......NºC–R
8. Write the Chemical Properties of Cyanides

Ans. (i) Hydrolysis :
(a) Complete hydrolysis
+
O +
O
H2O/H H2O/H
CH3CN ¾¾¾® CH3–C–NH2¾¾¾® CH3–C–OH+NH3
(Methyl cyanide) (Acetamide) (Acetic acid)
(b) Partial hydrolysis

O O
NaOH NaOH
CH3CN ¾¾¾® CH3–C–NH2¾¾¾® CH3–C–ONa+NH3
(Methyl cyanide) (Acetamide) (Sodium acetate)
(ii) Reduction :
Na + C 2H5OH
RCN +4[H] ¾¾¾¾¾¾ ® RCH2NH2
LiAlH 4
RCN + 4[H] ¾¾¾¾ ® RCH2NH2
(iii) With Grinard Reagent :

CH3
CH3 H2O/H
+
ether
CH3CN + CH3MgBr ¾¾¾® ¾¾¾® CH 3 – C = O + Mg(OH)Br + NH3
CH3 – C = NMgBr
116 E
CBSE
ALLEN
9. Write the Chemical Properties of Iso-cyanides
Ans. (i) Hydrolysis : Alkyl isocyanide form primary amine and formic acid during complete hydrolysis
in acidic medium.
+
H /H O
CH3 NC ¾¾¾® 2
CH3–NH2+HCOOH
(ii) Reduction :
Na + C2 H5OH
RN ®
= C + 4[H] ¾¾¾¾¾¾ ® RNHCH3
2° amine
10. The conversion of primary aromatic amines into diazonium salts is known as .......
Ans. Diazotization
11. Account for the following:
(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.
OR
Give the structures of A,B and C in the following reactions:
Sn + HCl NaNO2 + HCl H2 O
(i) C6H 5NO2 A B C
273 K
+
H2O/H NH3 Br2 + KOH
(ii) CH3CN A B C
D
Ans. (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.
+
C6 H5 NH2 + AlCl 3 ¾¾® C6 H5 N H2 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 Et2 NH > Et3 N > EtNH 2
is order of Kb.
E 117
Chemistr y
ALLEN
OR
+
(i) (A) C6H5NH2 (B) C6H5N º NCl
—
(C) C6H5OH
Aniline Benzenedizonium Phenol
Chloride
O
(ii) (A) CH3COOH (B) CH3—C—NH2 (C) CH3–NH2
Propanoic acid Ethanamide Methanamine
12. Write the main products of the following reactions :

(i) CH3CH2NH2 ¾¾¾
HNO
0ºC
® ? 2
(ii) S – Cl + H – N – C 2H 5 ?
O H
O
N–H CH3– C – Cl
(iii) H Base ?
O
O N – C – CH3
Ans. (i) CH3 CH 2 OH (ii) S – N – C2H 5 (iii) H
O H
13. Describe the following giving the relevant chemical equation in each case :
(i) Carbylamine reaction
(ii) Hofmann's bromamide reaction
Ans. (i) R–NH2 + CHCl3 + 3KOH ¾¾¾
Heat
® R–NC + 3HCl + 3H2O
O
(ii) R–C–NH2 + Br2 + 4NaOH ¾® RNH2 + Na2CO3 + 2NaBr + 2H2O
14. Complete the following reaction equations :
(i) C6H5N2Cl + H3PO2 + H2O ¾®
(ii) C6H5NH2 + Br2(aq.) ¾®
Ans. (i) C6H6 + N2 + H3PO3 + HCl
NH2
Br Br
(ii) + 3HBr
Br
2,4,6 Tribromoaniline
15. Rearrange the following in an increasing order of their basic strengths:
C6H5NH2, C6H5N(CH3)2, (C6H5)2NH and CH3NH2 .
Ans. (C6H5)2 NH < C6 H5 NH2 < C6 H5 N(CH3)2 < CH3NH2
118 E
CBSE
ALLEN
16. State reasons for the sollowing:
(i) pKb value for aniline is more than that for methylamine.
(ii) Ethylamine is soluble in water whereas aniline is not soluble in water.
(iii) Primary amines have higher boiling points than tertiary 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, hydrocarbon part, the extent of H - bonding decreases considerably and hence
aniline is insoluble in water.
(iii) Primary amines (RNH2) has two hydrogen atoms on the N atom and therefore, form intermolecular
hydrogen bonding.
R R R
N H N H N H
H H H
Tertiary amines (R3N) do not have hydrogen atoms on the nitrogen atom and therefore, these do
not from hydrogen bonds. As a result of hydrogen bonding in primary amines, they have higher
boiling points than tertiary amines of comparable Molecular mass.
17. Give the chemical tests of distinguish between the following pairs of compounds :
(i) Ethylamine and Aniline
(ii) Aniline and Benzylamine
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 ¾¾¾¾ ® C 2 H 5 OH + N 2 + H 2O
Ethyla min e Ethylalcohol
Aniline with HNO2 at 273-278 K followed by treatment with an alkaline solution of b naphthol
when a brilliant yellow, orange or red coloured dye is obtained.
NH 2
273-278K
+ HONO + HCl N+ NCl- + 2H 2O
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.
HONO
C6 H 5 CH 2 NH2 ¾¾¾
HCl
® [C 6 H 5 CH 2 - N + º NCl - ] ¾¾¾
H2 O
® C 6 H 5 CH 2 OH + N 2 + HCl
Benzyla min e 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
E 119
Chemistr y
ALLEN
18. Identify A and B in each of the following processes:
(i) CH 3CH 2Cl ¾¾¾
NaCN
® A ¾¾¾¾
reduction
Ni / H
®B
2
(ii) C6 H5NH 2 ¾¾¾¾¾

NaNO / HCl2
® A ¾¾¾¾
C H NH
OH
®B 6 5
-
2
NaCN reduction
Ans (i) CH3CH2Cl CH3CH2C N CH3CH2CH2NH2
Chloroethane propanenitrile propan-1-amine
(A) (B)
NaNO2/HCl C6H5NH 2
(ii) C6H5NH2 C6H5 – N2 Cl
+ -
OH
-
Benzene diazonium
Chloride (A)
N=N NH2
p-Aminoazobenzene
(B)
19. Arrange the following compounds in an increasing order of basic strengths in their aqueous
solutions :
NH3, CH3NH2, (CH3)2NH, (CH3)3 N
Ans. The order of basic strength of methyl substituted amines in aqueous solution is.
(CH3)2NH > CH3 NH2 > (CH3)3 N > NH3
20. Complete the following reaction equations :
O
(i) R–C–NH2 ¾¾¾
LiAlH4
H 2O
® (ii) C6H5N2Cl + H3PO2 + H2O ® (iii) C6H5NH2 + Br2(aq) ®
O
Ans. (i) R–C–NH2 ¾¾¾
LiAlH4
H 2O
® R–CH2–NH2
(ii) C6H5 N2Cl + H3 PO2 + H2O ® C6H6 + N2 + H3PO3 + HCl
NH 2
Br Br
(iii) C6H5NH2 + Br2(aq) ® + 3HBr
Br
21. Account for any two of the following:
(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.
+ – –
OH
RNH2 + HCl ® RNH3Cl RNH2 + H2 O
(b) The nitro compounds are highly polar molecules because nitro compounds is a strong electron
withdrawing group
O
C N
+
O-
120 E
CBSE
ALLEN
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
+
NH2
+
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.
REASONING :
1. There are two –NH2 groups in semicarbazide but only one is involved in the formation of
semicarbazones.
Ans. C = O + H2 N NHCONH2 ¾® C = NNHCONH2 + H2O
The lone pair of electrons on –NH2 nearer to is delocalised over oxygen atom and therefore, this
–NH2 group is not available as nucleophile. The –NH2 group not involved in resonance, will act as a
nucleophile.
–
O O O
Å +
H2 N–C–NHNH2 « H2N = C – NHNH2 « H2N – C = N – NH2
2. Amines are higher boiling compounds than hydrocarbons but lower boiling than alcohols of comparable
molecular masses.
Ans. Boiling points of amines and alcohols are higher than those of hydrocarbons of comparable molecular
masses due to intermolecular hydrogen bonding in amines and alcohols.
R R R R
N–H N–H O–H O–H
H H
Hydrogen bonds in amines are weaker than those present in alcohols. This is because oxygen is more
electronegative than nitrogen, so boiling points of amines are lower than those of alcohols of comparable
molecular masses. The intermolecular forces in hydrocarbons are weak van der Waals forces due to
which hydrocarbons have lower boiling points than amines or alcohols.
3. Boiling point of isomeric tertiary amines are lower than those of primary amines.
Ans. Boiling points of isomeric tertiary amines are lower than those of primary amines due to the lack of
intermolecular hydrogen bonding which exists in primary amines.
4. Observed Kb order is :
(C2H5 )2 NH<(C2H5)3N<C2H5NH2<NH3
(CH3)2NH>CH3 NH2 >(CH3)3N>NH3
Ans. (a) In gaseous phase, where solvent factor is missing, larger the number of electron releasing groups,
more basic is the amine (positive inductive effect) as they release the electron cloud over N-atom and
lone pair of electrons can be donated easily. The Kb order should be: teritary amine > secondary
amine > primary amine.
E 121
Chemistr y
ALLEN
(b) In aqueous phase, the substituted ammonium cations get stabilised not only by electrons releasing
effect of alkyl groups (+I) but also by solvation with water molecules via hydrogen bonding. In case
the alkyl group is bigger than CH3 group, there will be steric hinderance to H–bonding resulting in
less stabilisation of substituted ammonium cation.
Combining these factors (i) Inductive effect stabilisation of substituted ammonium cations via H-bonding. (ii)
steric hinderance of bigger alkyl group to H-bonding. The order of basic strength is as given above.
5. Aniline is a weaker base than CH3NH2.
Ans. In aniline, each C-atom of benzene ring is sp2 hybridised and is electron withdrawing. Nitrogen atom
donates a lone pair of electrons to the ring and acquire (+) charge. The negative charge is delocalised
on ortho and para position by resonance.
+ + +
:
:
NH2 NH2 NH2 NH2 NH2
– –
–
So due to delocalisation, the lone pair of electrons on benzene ring is not available for donation and
therefore, aniline is weaker base than C H 3NH2 where CH3 is an electron releasing group and increases
electron availability on N-atom which can be donated easily.
6. Methylamine in water react with ferric chloride to precipitate hydrated ferric oxide.
Ans. Methylamine in water behaves as a base to form OH– ions which react with FeCl3 to form hydrated ferric oxide.
CH3 NH2 H–OH
Methylamine Water
Due to e-releasing effect of –CH3 group, methylamine is more basic than water. Therefore, in water,
methylamine produces OH– ions by accepting H+ ions from water.
+
CH3–NH2 + H–OH®CH3– NH3 + OH–
Ferric chloride (FeCl3) dissociates in water to form Fe +3 & Cl– ions.
FeCl3 ® Fe3+ + 3Cl–
Then, OH– ion reacts with Fe3+ ion to form a precipitate of hydrated ferric oxide
2Fe3+ + 6OH– ® Fe2O3.3H2O
(Hydrated ferric oxide)
7. –NH2 is ortho and para directing in aromatic electrophilic substitution reactions but aniline on nitration
give a substantial amount of meta-nitro aniline.
NH2 NH2 NH2 NH2
Conc.HNO3
NO2
+ +
Conc. H2SO4
NO 2
Aniline NO2
(51%) (47%) (2%) è
æ
+
NH3 +
In strongly acidic medium aniline is protonated to form anilinium ion æ in which – NH 3 group,
+ acts as meta directing.
+ +
è
:
C6 H5NH2 + H HSO4– C 6H5NH3 HSO4–

+
:
NH2 NH3 NH2
+ NO 2
+H
NO2
122 E
CBSE
ALLEN
Å !
NH2 NH3HSO 4
+ H2SO 4 ¾¾®
Lewis acid
Lewis base Anilinium hydrogen
sulphate
(m–directing)
8. Aniline does not undergo Friedel–Craft reaction

Ans. 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 NH2AlCl3
+ AlCl3 + HCl
Lewis
Lewis Salt
acid
base
9. Aromatic primary amines cannot be prepared by Gabriel’s phthalamide synthesis.
Ans. Aryl halides do not undergo nucleophilic substitution reaction with the anion formed by phthalamide
because of partial double bond character of C—X bond of aryl halide.
CHEMICAL TEST :
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
+
SO2NNa
SO 2 Cl + H HNCH3 ¾¾ NaOH
® SO 2 NHCH 3 ¾¾
–HCl
® CH3
OH –
soluble
Soluble in base
CH3 CH3
N H + Cl SO2 ¾¾ ® SO 2 N
– HCl
OH –
¾¾ ® No reaction
NaOH
CH3 CH3
(insoluble in Base)
E 123
Chemistr y
ALLEN
Test Methanamine Dimethyl Amine

(CH3 NH2 ) (CH 3 NHCH3 )
(ii)
(1) Add Hinsberg reagent White ppt (soluble White ppt insoluble in
C6 H5SO2Cl in NaOH ) NaOH (aq.)
(2) Add CHCl3 + KOH(alc.) Foul odour of No change
isocyanide
CH3NH2 + CHCl3 + 3KOH ® CH3 - N =r C + 3KCl + 3H2O
NH2 NHCH 3
(iii) Test Aniline N-methyl-aniline
(1) Add Hinsberg reagent White ppt solution in White ppt insoluble in
(C6H5SO2Cl) NaOH NaOH
C6H5SO2Cl + H2NC6H5 ¾® C6H5SO2 ¾ NHC6H5 ¾¾®

–
OH
NaOH
C6H5SO2 N Na
C 6H 5
(2) Add CHCl3 + KOH (alc) Foul odour of isocyanide No change

NH2 N=C
+ HCCl 3 + 3KOH ® + 3KCl + 3H 2O
VIII. Difference between Aliphatic and Aromatic
NH2
(i)
Test Aniline Methylamine (CH3NH2)
(1) Add Br2/H 2O Colour of Br2 (aq.) No change

decolourised
NH2
NH2
Br Br
+ 3Br2(aq) ® + 3HBr
Br (Colourless)
124 E
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IX. Difference between Ketone and Carboxylic Acid
(iii) NH2 NH2

Test
(Aniline)
Cyclohexylamine
(1) Add NaNO 2 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.
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 + N 2 + CuX
+ –
ArN2X
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 ¾¾
® Ar - N 2 BF4 ¾¾¾
Heat
® Ar - F + BF3 + N 2
Fluoroboric acid
4. 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 125
Chemistr y
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.
5. 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–NH 2 + Na2CO3 + 2NaBr + 2H 2O
6. 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 ¾¾¾
Heat
® R - NC + 3KCl + 3H 2O
Note: Secondary and tertiary amines do not show this reaction and is used as a test for primary amines.
7. 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)
(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
O C 2H5 O C2H5
N,N-Diethylbenzenesulphonamide (insoluble in alkali)
126 E
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(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.
8. 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
NºN Cl + H
–
OH N=N OH + Cl + H2O
p-Hydroxyazobenzene (orange dye)
Similarly the reaction of diazonium salt with aniline yields p-aminoazobenzene.

–
+ – OH
NºN Cl + H NH2 N=N NH2 + Cl– + H2O
p-Aminoazobenzene
(yellow dye)
1. 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
Ans. (i) CH3COOH ¾¾¾¾
NH / D
® CH3CONH2 ¾¾¾¾¾¾¾¾¾¾Br / KOH
Hoffmann bromamide reaction ¾
3
® CH3NH2 2
Ethanoic acid ethanamide
®CH3 ( CH2 ) 4 CONH2 ¾¾¾¾ ®CH3 ( CH2 )4 NH2

P.H.( Partial hydrolysis )
(ii) CH3 (CH)4 CN ¾¾¾¾¾¾¾ ¾ Br /KOH
¾ 2
Hexanenitrile 1-pentanamine
KCN ( alc )
(iii) CH 3OH ¾¾¾
PCl
® CH3 Cl ¾¾¾¾
5 H O / dil.HCl
® CH3CN ¾¾¾¾¾ ® CH3COOH 2
Methanol Ethanenitrile Ethanoic acid
O
® CH 3 COOH ¾¾¾® CH3C–NH2 ¾¾¾ ® CH3 - NH2
Br2
(iv) CH 3 - CH 2 - NH 2 ¾¾¾¾¾¾
® CH 3 CH 2 - OH ¾¾¾ HNO 2
or KOH
[O] NH 3
D
( NaNO 2 + HCl )
(v) CH 3COOH ¾¾¾¾®

+
LiAlH P +I KCN H O/ H
Re duction
CH 3CH 2OH ¾¾¾ ® CH 3CH2 I ¾¾¾
4
- KI
® CH3CH2CN ¾¾¾¾ ® CH 3CH 2COOH
2 2
Ethyliodide Ethylcyanide Pr opanoic acid
(vi) CH3 NH2 ¾¾¾¾¾

HNO
- N ,- H O 2
P+I
® CH3 OH ¾¾¾ 2
2
KCN
® CH3 I ¾¾¾
- KI
Na / C H OH
® CH3 CN ¾¾¾¾¾
Reduction
® CH3 CH2 NH2
2 2 5
Methyliodide Ethanamine
(vii) CH3 NO2 ¾¾¾¾

Sn / HCl CHCl + KOH
® CH3 NH2 ¾¾¾¾¾ Na + C H OH
® CH 3 NC ¾¾¾¾¾
Reduction
® CH 3 NHCH3
3 2 5
Dimethylamine
(viii) CH3CH2COOH ¾¾¾

NH
D
® CH 3CH2CONH2 ¾¾¾¾
Br / KOH
¾
® CH2CH2NH2
3 2
Propanoic acid Propanamide
K2 Cr2O7 / H2 SO4
¾¾¾¾¾
HNO2
- N2 ,- H2O
® CH 3CH2OH ¾¾¾¾¾¾ ¾
® CH 3COOH
Ethanol Ethanoic acid
E 127
Chemistr y
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2. 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
+
N º NCl
—
NO2 NH2 CN COOH
(i) Fe/HCl NaNO 2/HCl CuCN/KCN H3OÅ

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

Chloride
NO2 NO2 NH2

Conc.HNO3
+Conc.H 2SO4 Br2/Fe Sn + HCl
(ii) 333 K
Br Br
Benzene Nitrobenzene m-Bromoaniline
m-Bromonitrobenzene
N2Cl OH
NaNO2/HCl Boiling
273-278 K dil H2SO4
Br Br
m-Bromophenol
COOH COCl CONH2 NH2
PCl5 2NH3 Br2 + KOH

(iii) -NH 4Cl
Benzoic acid Benzoyl Chloride Benzamide Aniline
+ –
NH2 NH2 N=NBF4 F
Br Br Br Br Br Br
Br2/H2O NaNO 2/HBF 4 Heat
(iv) 273-278 K
Aniline
Br Br Br
2,4,6-Tribromonoaniline 2,4,6-Tribromo fluoro benzene
CH2Cl CH2CN CH2CH2NH2
KCN (alc). Heat LiAlH 4

(v) –KCl
Benzyl Chloride Phenyl ethanenitrile 2-Phenyl ethanamine
Cl Cl Cl
Conc. HNO3
+ Conc. H2SO 4 Sn/HCl
(vi) Nitrotion (Reduction)
Chlorobenzene
NO2 NH2
P-Nitro chlorobenzene p-Chloro aniline
(Major isomer)
128 E
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NH2 NHCOCH3 NHCOCH3 NH2
(CH3CO) 2O/CH3COOH Br2/CH 3COOH H 2O/OH —

(vii)
Aniline Acetanilide
Br Br
p-Bromo acetanilide p-Bromo aniline
(Major product)
+ —
CONH2 NH2 N2Cl
Br2/NaOH NaNO2/HCl
(viii) Heat 273-278 K
Diazotisation
Benzamide Aniline Benzene diazonium
Chloride
CH3
H3PO2–H 2O/Cu, Heat CH3Cl/Anhyd.AlCl3
Benzene Toluene
+ —
NH2 N2Cl
NaNO 2/HCl H3PO2–H2O/Cu, Heat CH 3Cl/Anhyd. AlCl 3

(ix) 273-278 K
Aniline Benzene diazonium Benzene

Chloride
CH3 CH2Cl CH2OH
Cl 2(1 mole),hv KOH (aq.)

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

NaOH + Br
–
® B ¾¾¾¾¾ ®C
NaCN
(i) CH3CH2I ¾¾¾® A ¾¾¾¾¾¾ OH
Partial hydrolysis
2
NH +
(ii) C6H5N2Cl ¾¾¾®
CuCN H O/ H
A ¾¾¾¾ ® B ¾¾¾
D
®C 2 3
LiAlH HNO
KCN
(iii) CH3CH2Br ¾¾¾ ® A ¾¾¾¾ ® B ¾¾¾
0° C
¾
®C 4 2
+
(iv) C6H5NO2 ¾¾¾¾
Fe / HCl
® A ¾¾¾¾¾
NaNO + HCl
273K
® B ¾¾¾¾
H O/ H
D
2
®C 2
NaOBr NaNO / HCl

(v) CH3COOH ¾¾¾
NH
D
® A ¾¾¾¾ ® B ¾¾¾¾¾
3
® C 2
C H OH
(vi) C6H5NO2 ¾¾¾¾
Fe / HCl
® A ¾¾¾
HNO
273K
® B ¾¾¾¾® C
¾ 2 6 5
E 129
Chemistr y
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O
NaOH + Br2
Ans. (i) CH3CH2I
—
NaCN OH
CH3CH2CN CH3—C—NH2 CH3–NH2
Partial hydrolysis
Iodoethane Propanenitrile (A) Ethanamide (B) Methanamine (C)
CuCN H2O/HÅ NH3 Heat

(ii) C6H5N2Cl C6H5CN
hydrolysis
C6H5COOH C6H5COONH4 C6H5CONH2
Benzenediazonium Cyanobenzene Benzoicacid (B) Benzamide (C)
Chloride (A)
(iii)
Fe/HCl NaNO 2/HCl + H2O/H+

(iv) C6H5NO2 C6H5NH2 C6H5N º NCl— Heat
C6H5OH
Nitrobenzene Aniline (A) Benzenedizonium Phenol (C)
Chloride (B)
(v)
Fe/HCl HNO2 + C6H 5OH

(vi) C6H5NO2 C6H5NH2 C6H5N º NCl
—
N=N OH
273 K
Nitrobenzene Aniline (A) Benzenediazonium
Chloride (B) p-Hydroxyazo benzene (C)
4. How will you carry out the following conversions :-

(a) Toluene ¾® p-toluidine (b) p-toluidine diazonium chloride ¾® p-toluic acid
(c) nitrobenzene ¾® acetanilide (d) acetanilide ¾® p-nitroaniline
(e) (f)
(g) (h)
(i)
130 E
E
(f)
(e)
(c)
Ans. (a)
(d)
(b)
ALLEN
CBSE
131
Chemistr y
ALLEN
(g)
(h)
(i)
WORD PROBLEMS :
1. 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.
(i) (aq.) NH3 Br2 + KOH
Ans. C6H5COOH Heat
C6H5CONH2 C6H5NH2
Benzoic aicd (A) Benzamide (B) Aniline (C)
m.f. = C7H 7NO mf = C 6H 7N
2. A hydrocarbon ‘A’, (C4H8) on reaction with HCl gives a compound ‘B’, (C4H9Cl), which on reaction
with 1 mol. of NH3 gives compound ‘C’, (C4H11N). On reacting with NaNO2 and HCl followed by
treatment with water, compound ‘C’ yields an optically active alcohol, ‘D’. Ozonolysis of ‘A’ gives
2 moles of acetaldehyde. Identify compounds ‘A’ to ‘D’. Explain the reactions involved.
132 E
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Ans.
Addition of HCl has occurred on ‘A’. This implies ‘A’ is an alkene.
Cl in compound ‘B’ is substituted by NH2 to give ‘C’.
‘C’ gives a diazonium salt with NaNO2/HCl that liberates N2 to give

optically active alcohol. This means that ‘C’ is an aliphatic amine. Number
of carbon atoms in amine is same as in compound ‘A’.
Since product of ozonolysis of compound ‘A’ are CH3–CH=O and O=CH–CH3. The compound ‘A’ is
CH3 –CH=CH–CH3 .
On the basis of structure of ‘A’ reactions can be explained as follows :
3. A colourless substance ‘A’ (C6H7N) is sparingly soluble in water and gives a water soluble compounds
‘B’ on treating with mineral acid. On reacting with CHCl3 and alcoholic potash ‘A’ produces an
obnoxious smell due to the formation of compound ‘C’. Reaction of ‘A’ with benzenesulphonyl
chloride gives compound ‘D’ which is soluble in alkali. With NaNO2 and HCl, ‘A’ forms compound
‘E’ which reacts with phenol in alkaline medium to give an orange dye ‘F’. Identify compounds ‘A’
to ‘F’.
Ans.
E 133
4.
134
4.
Chemistr y
Ans. 1. Sn–HCl
2.
3. H2O / H+
5. H3PO2 / H2O
Predict the reagent or the product in the following reaction sequence.
ALLEN
E
CBSE
ALLEN
1. Out of the following, the strongest base in aqueous solution is

(A) methylamine (B) Dimethylamine [1]
(C) Trimethylamine (D) Aniline (CBSE 2020)
Ans. (B)
2. Give the structures of A and B in the following sequence of reactions : (CBSE 2020)
NH 3 NaOBr
(a) CH3COOH ¾¾¾
D
® A ¾¾¾ ®B
Fe/HCl NaNO 2 + HCl
(b) C6 H5 NO2 ¾¾¾® A ¾¾¾¾¾
0°-5° C
®B
+
(c) C6 H 5 N +2 Cl - ¾¾¾
CuCN
D
H 2O/H
® A ¾¾¾¾ ®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
(a) (i) Add ice cold (NaNO2 + HCl) followed by phenol or b -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
3. Arrange the following in decreasing order of basic character : [1]

C6H5NH2, (CH3)3N, C2H5NH2 (CBSE 2019)
Ans. (CH3)3N > C2H5NH2 > C6H5NH2
4. Complete the following reactions : [3]

CN
(a) H2 / Ni (CBSE 2019)
CH3
Br H3PO2+H2O
(b)
+
N2Cl–
CH2–NH2
(c) Ethanolic KOH
+ CHCl3
E 135
Chemistr y
ALLEN
OR
How do you convert the following : [3]
(a) N-phenylethanamide to p-bromoaniline
(b) Benzene diazonium chloride to nitrobenzene
(c) Benzoic acid to aniline
CH2NH2
Ans. (a)
CH3
Br
(b)
CH2NC
(c)
OR
O O
H–N–C–CH3 H–N–C–CH 3 NH2
– +
Br2 OH or H
(a) CH3COOH
Br Br
+ –
N2+Cl
–
N 2BF 4 NO2
NaNO2
(b) +HBF4 Cu,D
Fluoroboric
acid
COOH CONH2 NH2

NH3 Br2/KOH
(c) Heat
Benzoic acid Benzamide Aniline
5. Arrange the following in increasing order of pKb values : (CBSE 2019)

C6H5CH2NH2, C6H5NHCH3, C6H5NH2 [1]
Ans. C6H5CH2NH2 < C6H5NHCH3 < C6H5NH2
6. Arrange the following in decreasing order of solubility in water : [1]
(C2H5)2NH, C2H5NH2, C6H5NH2 (CBSE 2019)
Ans. (C2H5)2NH > C2H5NH2 > C6H5NH2
7. (a)Write the reactions involved in the following : (CBSE 2018)
(i) Hoffmann bromamide degradation reaction
(ii) Diazotisation
(iii) Gabriel phthalimide synthesis
136 E
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ALLEN
(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.
OR
(a) Write the structures of the main products of the following reactions :
NH2
(CH3CO)2O (CH3) 2NH

(i) (ii) SO2Cl
Pyridine
(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
Ans. (a) (i) Hoffmann Bromamide degradation reaction :
O
D
R – C – NH2 + Br2 + 4NaOH R – NH2 + Na2CO3 + 2NaBr + 2H2O
(ii) Diazotisation
273–278 K Å
C6H5NH2 + NaNO2 + 2 HCl C6H5NH2 Cl
D
Aniline Aromatic diazonium
(iii) Gabriel phthalimide synthesis
O O
C C CO
Alc. KOH –KBr
NH N N–C2H 5
C2H5Br/D
C C CO
n-ethyl phthalimide
O O
(Potassium pthalimide)
H2 O OH–/D
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.
Å Å Å Å
NºN N=N N=N N=N
Å Å
E 137
Chemistr y
ALLEN
OR
O
NH2 NH–C–CH3
O
(CH3CO)2 O
(a) (i) ¾¾¾¾¾ ¾
® + CH 3–C–CH3
Pyridine
SO2Cl O
(ii) (CH ) NH S N CH3

¾¾¾¾¾
3 2 ®
O CH3
N, N–dimethyl benzenesulphonamide
Å
N2 Cl CH CH OH
(iii) ¾¾¾¾¾®
3 2 + N2 + HCl + CH3CHO
(b) Test to distinguish aniline & N, N-dimethyl aniline
(c) Increasing order

C2 H5 - NH 2 < C6 H5 NH - CH 3 < C6 H5 - NH 2
8. Give reasons for the followings : (CBSE 2017)
(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. (i) Due to the resonance, the electron pair of nitrogen atom gets delocalised towards carbonyl
group/ resonating structures.
(ii) 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.
(iii) Due to protonation of aniline/formation of anilinium ion
9. Write the IUPAC name of the given compound: (CBSE 2016)
CH3–NH–CH2–CH–CH3
CH3
Ans. N-methyl-2-methylpropanamine / 2-methyl-N-methylpropanamine
10. Write the structures of A, B and C in the following reactions: (CBSE 2016)
(i) C6H5— COO–NH4+ ¾¾
D Br2 / KOH
® A ¾¾¾¾¾
CH 3COCl / pyridine
® B ¾¾ ¾¾¾ ¾¾¾ ®C
NaNO2 / Cu Sn / HCl CHCl 3 + alc.KOH

(ii) C6H5 N 2+ BF4- ¾¾¾¾¾
D
® A ¾¾¾¾ ® B ¾¾¾¾¾¾¾ ®C
138 E
CBSE
ALLEN
Ans. (i) A : C6 H5 CONH2
B :C6 H5 NH2
C : C6 H5 NHCOCH3
(ii) A : C6 H5 NO2
B : C6 H5 NH2
C : C6H5 NC
11. 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 : (CBSE 2015)
Br2+KOH NaNO2+HCl CuCN
(C7H7ON) A C6H5NH2 B C
273 K
CHCl3+NaOH H2O
D E
+
NºNCl
–
CONH2 CN N C OH
Ans. A =
B= C= D= E=
12. (a) Write the structures of the main products when aniline reacts with the following reagents : (CBSE 2015)
(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
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)
E 139
Chemistr y
ALLEN
EXERCISE-3 R AC E
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
(i) Which is most basic
(a) (C2 H5)2 NH (b) C6 H5 CH2NH2 (c) C6H5 NH2 (d) C2 H5NH2
(ii) Which is most basic
(a) C6H5 NH2 (b) (C2H5)2NH (c) C2H5 NH2 (d) (C2H5)3 N
(iii) Which is most basic
(a) C6 H5 CH2 NH 2 (b) C6 H5NH2 (c) (CH3)2NH (d) (CH3)3 N
(iv) Which is most basic
(a) C2H5 NH2 (b) (C2H5)2NH (c) (C2H5)3 N (d) NH3
(i) both assertion and reason are true , and reason is the correct explaining of the assertion
2. Assertion : Hoffmann's bromide reaction is given by pri. amines
Reason : Primary amines are more basic than sec. amines
3. Assertion : Acylation of amines gives a monosubstituted product wheres alkylation of amines gives
polysubstituted product.
Reason : Acyl group sterically hinders the approach of further acyl groups.
4. Assertion : N-Ethylbenzenesulphonamide is soluble is alkali.
Reason : Hydrogen attached to nitrogen in sulphonamide is strongly acidic.
5. Assertion : Acetanilide is less basic than aniline.
Reason : Acetylation of aniline results in decrease of electron density on nitrogen.
6. Assertion : Aromatic 1° amines can be prepared by Gabriel Phthalimide Synthesis.
Reason : Aryl halides undergo nucleophilic substitution with anion formed by phthalimide.
140 E
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7. Propanamide on reaction with bromine in aqueous NaOH gives:
(i) Propanamine (ii) Ethanamine
(iii) N-Methyl ethanamine (iv) Propanenitrile
8. Which of the following synthetic method will result in a primary amine?
(i) Gabriel's phthalimide synthesis (ii) Hoffmann bromide reaction
(iii) Reduction of nitrate (iv) All of these
9. Which of the following is a 3° amine?
(i) 1-methylcyclohexylamine (ii) Triethylamine
(iii) tert-butylamine (iv) N-methylaniline
10. Indicate which nitrogen compuond amongst the following would undergo Hoffmann reaction
(i.e. reaction with Br2 and strong KOH) to furnish the primary amine (R – NH2)
(i) RCONHCH3 (ii) RCOONH4 (iii) RCONH2 (iv) R – CONHOH
11. Aniline reacts with concentrated HNO3 to give
NH2 NH2 NH2

NO2
(i) H2N NH2 (ii) , and
NO2
NO2
NO2
(iii) O O (iv)
12. Amongst the following, the strongest base in aqueous medium is ____________.
(i) CH3NH2 (ii) NCCH2NH2 (iii) (CH3)2 NH (iv) C6H5NHCH3
13. Methylamine reacts with HNO2 to form _________.
(i) CH3 – O – N = O (ii) CH3 – O – CH3 (iii) CH3OH (iv) CH3CHO
14. In the nitration of benzene using a mixture of conc. H2SO4 and conc. HNO3, the species which
initiates the reaction is __________.
(i) NO2 (ii) NO+ (iii) NO2+ (iv) NO2¯
15. Reduction of aromatic nitro compounds using Fe and HCl gives __________.
(i) aromatic oxime (ii) aromatic hydrocarbon
(iii) aromatic primary amine (iv) aromatic amide
16. Acid anhydrides on reaction with primary amines give ____________.
(i) amide (ii) imide (iii) secondary amine (iv) imine
Answer key :
Q. No. 1 (i) (ii) (iii) (iv) 2 3 4 5 6 7 8
Ans. a b c c D A A A D ii iv
Q. No. 9 10 11 12 13 14 15 16
Ans. ii iii ii iii iii iii iii i
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1. Write the IUPAC name of the given compound: [1]
CH3–NH–CH2–CH–CH3
CH3
2. S – Cl + H – N – C 2H 5 ? [1]
O H
O
N–H CH3– C – Cl
3. H Base ? [1]
4. Give a simple chemical test to distinguish between Aniline and N, N-dimethylaniline. [2]
5. Although –NH2 is o/p directing group, yet aniline on nitration gives a significant amount of
m-nitroaniline. [2]
6. Write the reactions involved in the following : [2]
(i) Hofmann bromamide degradation reaction
(ii) Gabriel phthalimide synthesis
7. (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 Br2 + KOH
8. CH3CN A B C [3]
D
9. Write the structures of the main products when aniline reacts with the following reagents : [3]
(i) Br2 water (ii) HCl (iii) (CH3CO)2O/pyridine
10. 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.
11. 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 : [5]
Br2+KOH NaNO2+HCl CuCN
(C7H7ON) A C6H5NH2 B C
273 K
CHCl3+NaOH H2O
D E
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MOCK TEST SOLUTIONS
1. N-methyl-2-methylpropanamine / 2-methyl-N-methylpropanamine
O
2. S – N – C2H5
O H
N – C – CH3
3.
H
4. Test to distinguish aniline & N, N-dimethyl aniline
O O
– HCl
S – Cl + H – NH S – NH
O O
Hinsberg Aniline Product
reagent
O N(CH3)2
S – Cl
+ No reaction
O
Benzene sulphonamide N, N–dimethyl aniline
5. Due to protonation of aniline/formation of anilinium ion.

6. (i) Hoffmann Bromamide degradation reaction :
O
D
R – C – NH2 + Br2 + 4NaOH R – NH2 + Na2CO3 + 2NaBr + 2H2O
(ii) Gabriel phthalimide synthesis

O O
C C CO
Alc. KOH – KBr
NH N C2H5
C2H5Br/D
C C CO
e-ethyl pthalimide
O O
(Potassium pthalimide)
H2O OH¯ / D
COOH
C2H5 – NH2 +
ethanamide COOH
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7. (a) C6H5CH2NH2 < C6H5NHCH3 < C6H5NH2
(b) (C2H5)2NH > C2H5NH2 > C6H5NH2
O
||
CH 3 - NH 2
8. (A) CH3 COOH (B) CH3 - C - NH 2 (C)
Pr opanoic acid Methana mine
Ethanamide
NH2
Br Br NH3+Cl¯
O
9. (i) (ii) (iii) NH – C – CH3
Br
10. (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.
+
C6 H 5 NH 2 + AlCl 3 ¾¾
® 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) 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 3N > EtNH 2 is
order of Kb.
+
CONH2 N º NCl¯ CN NºC OH
11.
A= B= C= D= E=
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BIOMOLECULES
l Biomolecules are complex substances which form the basis of human life. They are also responsible
for their growth, maintenance and their ability to reproduce. Carbohydrates, proteins, fats vitamins,
enzymes, hormones etc. are called biomolecules.
l Carbohydrates : These are optically active polyhydroxy aldehydes or ketones or the compounds
which produce these on hydrolysis.
l Classification :
(i) Monosaccharides : Those carbohydrates which cannot be hydrolyscd into further simpler
carbohydrates E.g., glucose, fructose, galactose etc.
(ii) Disaccharides : Those carbohydrates which produces two monosaccharides on hydrolysis
Eg . sucrose, maltose and lactose.
(iii) Oligosaccharides : Those carbohydrates which give two to ten monosaccharides on hydrolysis.
(iv) Polysaccharides : Those carbohydrates which on hydrolysis give large number of
monosaccharides hydrolysis E.g., starch, cellulose, glycogen.
l Sugar : Carbohydrates which are sweet in taste.
(i) Reducing sugars : Those which reduce Fehling's or Tollen’s reagent due to availability of free
aldehydic groups Eg. glucose, fructose, galactose.
(ii) Non-reducing sugars : Those which do not reduce Fehling's or Tollen’s reagent they do not
have free aldehydic group. E.g., sucrose.
l Glucose : It is a monosaccharide with molecular formula C6H12O6.
l Preparation :
(i) From sucrose :
(only from sucrose)
node06\B0B0-BA\Kota\Board Material\Chemistry\CBSE\CBSE Booklet\English\Updated booklet-21\New Pattern CBSE Booklet\Part wise boocklet\Part 2\03_OC\05_Biomolecules
(ii) From starch :

(C6H10O5)n + nH2O ® C12H22O11 + H2O ® 2C6H12O6
glucose
l Structure :
Fischer structure :
(+) glucose has 'D' configuration as shown :
CHO
H–C–OH
HO–C–H
H–C–OH
H–C–OH
CH2OH
D-(+)-glucose
‘D’-means –OH group on first chiral ‘C’ from the bottom is on right hand and (+) means it is
dextrorotary i.e., it rotates plane polarized light towards right.
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l Reactions of glucose :
HI
CH3–(CH2 )4CH3 n-hexane
NH2 OH
CH=NOH
(CHOH)4
CH2OH glucose oxime
Br2
WaH 6
COOH
(CHOH)4
CHO
CH2OH gluconic acid
(CHOH)4
HNO3
CH2OH COOH
glucose (CHOH)4
COOH saccharic acid
(CH3 CO)2 O
CHO
(CHOCOCH 3)4
CH2OCOCH3 glucose pentaacetate
OH
HCN
CH
CN
(CHOH)4
CH2OH glucose cyanohydrin
l Objections against open chain structure of glucose

The open chain structure was unable to explain the following reactions :
(a) It does not give the 2, 4-DNP test, Schiff's test and does not form the hydrogensulphide product
withNaHSO3.
(b) The pentacetate of glucose does not react with NH2OH, indicating the absence of free aldehydic
group
(c) Glucose exist in 2 different crystalline forms a and b forms. These arc called anomers. They
differ inoptical rotation, they also differ in melting point
After which a close chain (cyclic) structure of glucose was proposed by Haworth.
* Anomers are isomers which have a different configuration at C-l functional group c-atom
l Glycosidic linkage : The linkage between two monosaccharide units through oxygen is called the
glycosidic linkage.
l Proteins : These are macro molecules made up of amino acids joined by amide linkage ( CONH ) is
called as peptide linkage. These are required for growth and development of the body.
l Amino acids : These contain an amino (–NH2) and an acidic (–COOH) group and are therefore
amphoteric in nature. In solution they exist in the form of zwitter ion (a dipolar ion).
Essential and non-essential amino acids : The amino acids which are essential for health but cannot
be synthesis by the body are called essential amino acids. They are ten in number while the remaining
10 which the human body can synthesis are called non-essential amino acids.
Zwitter ion : The dipolar structure of amino acids is called internal salt of Zwitter ion.
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l Classilication
Fibrous Protein Globular Protein
Polypeptide chains run parallel or anti-

Chains of polypeptide coil around to give a
(i) parallel and held together by hydrogen and (i)
spherical shape.
disulphide bonds
Usually soluble in water, eg. insulin,
Generally insoluble in water e.g., keratin, thyroglobin, albumin, haemoglobin and
(ii) (ii)
collagen, myosin, fibroin. fibrinogen gets converted into fibrous protein
fibroin on clotting of blood
l Structure and shape of protein

Primary structure Secondary structure Tertiary structure Quaternary structure
The specific sequence It is the shape in which Represents overall folding Protein can be composed
of amino acids in the the long polypeptide chain of the polypeptide chain of two or more polypeptide
polypeptide chain Change can exist It is of two types: It gives rise to the fibrous chains called sub-units
in amino acids sequence -helix and -pleated or globular molecular The spatial arrangement
changes the protein These structures arise due shapes. Forces stabilizing of these sub-units with
completely. They have to regular folding of the the 2° and 3º structures respect to each other is
covalent bonds. back bone of the are hydrogen bonds, quaternary structure of
polypeptide chain due to disulphide linkages, van the protein.
H-bonding between the der Waal's and electrostatic
C=O and –NH– groups forces of attraction
of the peptide bond
l Native state of protein : The parental state or the natural state in which the protein is found.
l Denaturation of protein : Destruction of the native state of protein is denaturation. It can he brought by physical
and chemical methods. The 2° and 3° structures are destroyed, only 1° structure is retained.
l Nucleic acids : These are biomolecules which are long chain polymers of nucleotides. They are of
two types.
(i) Deoxyribonucleic acid (DNA)
(ii) Ribonucleic acid (RNA)
l Nuceloside = Base + Sugar
Nucleotide = Base + Sugar + Phosphate
l DNA RNA
(i) Double helical (i) Single stranded
(ii) Sugar is 2-deoxyribose (ii) Sugar is ribose
(iii) Bases A.T.G.C (iii) Bases A. U, G.C
(iv) Property of replication (iv) Do not replicate
(v) It is responsible for transmission (v) Helps in protein biosynthesis
of heredity character
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1. Glucose or succrose 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. 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
NH4OH
(CHOH)4 (CHOH)4
CH2OH CH2OH
Glucose Glucose Oxime
But pentaacetate of D-glucose does not react with NH2OH. This is because pentaacetate does not
form an open chain structure.
1 1
CH=NOH CH=O CHOH CHOCOCH3
H 2 2
OH HOH2C OH H OHO H OCOCH3
–H2O 3 5(CH3CO) 2O 3
HO H HO H HO H CH3OCO H
NH2OH –5CH3 COOH
H OH 4 H 4 OCOCH O
H OH H OH 3
H OH 5 5
H OH H H
6 6
CH2OH CH2OH CH2OH CH2 OCOCH3
a - glucose pentaacetate
Glucose oxime Glucose a - glucose + b - glucose +
(open chain form) b - glucose pentaacetate
No oxime
3. 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)
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.
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4. 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 b-D-2-deoxyribose
and phosphoric acid are obtained as products.
5. 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.
6. 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.
7. 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.
8. 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.
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 D
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
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(iii) On being treated with HNO3, D-glucose get oxidised to give saccharic acid.
CHO COOH
HNO3
(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. (1) 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.
(2) The pentaacetate of glucose does not react with hydroxylamine. This indicates that a
free –CHO group is absent from glucose.
(3) Glucose exists in two crystalline forms –µ and b. The µ - form (m.p. = 419 K) crystallises
from a concentrated solution of glucose at 303 K and the b-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
H2 N—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.
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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) a - helix structure
(ii) b-pleated sheet structure
(i) a - Helix structure
In this structure, the –NH– group of an amino acid residue forms H-bonds with the C=O group of
the adjacent turn of the right-handed screw (a-helix).
C
O
C
C
O
HO H
CN
N
O H
C
HC N
O
O H
N NH
H N
N
a - helix structure
(ii) b-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
H RCH N
C=O
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 N H RCH
C RCH N C=O
C= RCH
=C
b - pleated sheet structure
14. What type of bonding helps in stabilising the a -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 µ-helix help in stabilising the helix.
15. Differentiate between globular and fibrous proteins.
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Ans. Fibrous protein Globular protein
1. It is a fibre-like structure formed by the The polypeptide chain in this protein in folded
polypeptide chain. These proteins are hold around itself, giving rise to a spherical
together by strong hydrogen and disulphide structure.
bonds.
2. It is usually insoluble in water. It is usually soluble in water.
3. Fibrous proteins are usually used for structural All enzymes are globular proteins. Some
purposes. For example, keratin is present in hormones such as insulin are also globular
nails and hair; collagen in tendons; and myosin proteins.
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 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.
18. 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.
19. 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
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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
20. 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.
21. 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 molecules is The sugar moiety in RNA molecules is b-D
b-D-2 deoxyribose. ribose.
2. DNA contains thyamin (T). It does not RNA contains uracil (U). It does not contain
contain Uracil (U). thymine (T).
3. The helical structure of DNA is double- The halical structure of RNA is single-
stranded. stranded.
The functional differencess between DNA and RNA are as follows :
DNA RNA
1. DNA is the chemical basis of hereidity. RNA is not responsible for heredity.
2. DNA molecules do not synthesise proteins, Proteins are synthesised by RNA molecules
but transfer coded message for the synthesis in the cells.
of proteins in the cells.
22. 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)
23. Define the following terms:
(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
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O
— 5' O
O —P—O—H2C Base
O— 4' 1'
HH HH
3' 2'
OH OH
Structure of a nucleotide
(ii) a-D-glucose and b-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
24. Write the structure of the product obtained when glucose is oxidised with nitric acid.
COOH
Ans. Saccharic acid (dicarboxylic acid) (CHOH)4
COOH
25. What is essentially the difference between a-glucose and b-glucose ? What is meant by pyranose
structure of glucose ?
Ans. The six membered cyclic structure of glucose is called pyranose structure.
6 6
CH2OH CH2OH
O O
H 5 H H 5 OH
H H
4 1 4 1
OH H OH H
HO 3 2 OH HO 3 2 H
H OH H OH
a – D glucose b – D glucose
26. Explain what is meant by the following:
(i) peptide linkage
(ii) pyranose structure of glucose = ?
Ans. (i) Proteins are the polymers of a-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.
6 6
CH2OH CH2OH
O O
H 5 H H 5 OH
H H
4 1 4 1
(ii)
OH H OH H
HO 3 2 OH HO 3 2 H
H OH H OH
27. Write the main structural difference between DNA and RNA. Of the four bases, name those which
are common to both DNA and RNA.
Ans. DNA is double stranded a-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).
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28. 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.
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.
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.
29. Name the four bases present in DNA. Which one of these is not present in RNA ?
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).
30. What happens when D-glucose is treated with the following regents ?
(i) HI (ii) Bromine water (iii) HNO3
Ans. (i) On prolonged heating with HI, D-glucose forms n-hexane.
CHO
HI, D
(CHOH)4 CH 3–CH 2–CH 2–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
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1. Assertion (A): Sucrose is a non-reducing sugar. (CBSE 2020)

Reason (R) : Sucrose has glycosidic linkage. [1]
Ans. (ii) Both assertion (A) and reason (R) are correct statements, but Reason(R) is not the correct explanation
of the Assertion (A)
2. Give the plausible explanation for the following : (CBSE 2020)
(a) Glucose doesn't give 2,4-DNP test. [1×3=3]
(b) The two strands in DNA are not identical but are complementary.
(c) Starch and cellulose both contain glucose unit as monomer, yet they are structurally different.
Ans. (a) Because the -CHO group in glucose is involved in hemiacetal formation and thus is not free/due
to cyclic structure of glucose -CHO group is not free.
(b) Because the hydrogen bonds are formed between specific pairs of bases.
(c) Starch is a polymer of -glucose while cellulose is a polymer of -glucose
3. What is the basic structural difference between starch and cellulose ? [1]
OR
Write the products obtained after hydrolysis of DNA. (CBSE 2019)
Ans. Starch is a polymer of a-glucose whereas cellulose is a polymer of b-glucose.
OR
2-deoxyribose + nitrogen containing heterocyclic base + phosphoric acid
4. (a) What are the products of hydrolysis of maltose ? [3]
(b) What type of bonding provides stability to a-helix structure of protein ? (CBSE 2019)
(c) Name the vitamin whose deficiency causes pernicious anaemia.
OR
Define the following terms : [3]
(a) Invert sugar
(b) Native protein
(c) Nucleotide
Ans. (a) Glucose + Glucose
(b) Hydrogen bonding
(c) Vitamin-B12
OR
(a) Hydrolysis of sucrose brings a change of a sign of rotation from dextro(+) to laevo(–) and the
product is named as invert sugar.
(b) Protein found in biological system with unique three dimesion structure and biological activity
is called native protein.
(c) A unit formed by the combination of nitrogenous base, sugar and phosphate. (CBSE 2019)
5. What is the difference between amylose and amylopectin ? [1]
OR
Write the products obtained after hydrolysis of lactose.
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Ans. Amylose is a straight chain polymer whereas amylopectin is a branched chain polymer.
OR
The hydrolysis of lactose gives b-D-galactose and b-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
b - D - galactose b - D - glucose
6. Define the following with an example of each : (CBSE 2018)

(a) Polysaccharides
(b) Denatured protein
(c) Essential amino acids
OR
(a) Write the product when D-glucose reacts with conc. HNO3.
(b) Amino acids show amphoteric behaviour. Why ?
(c) Write one difference between a-helix and b-pleated structures of proteins.
Ans. (a) Polysaccharides ® The compound that have large no. of monosaccarides unit on hydrolysis.
Eg ® 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
OR
(a)
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(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
(a-amino acid)
NH2
:
(c) 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 b-pleated all peptide chains are stretched out to nearly extensions & then laid side by side which
are held together by intomolecular hydrogen bonding.
7. (a) Which polysaccharide component of carbohydrates is commonly present in bread ? (CBSE 2017)
(b) Write the two types of secondary structures of proteins ?
(c) Give two examples of water soluble vitamins ?
Ans. (a) Starch
(b) a-Helix and b-pleated sheets
(c) Vitamin B/B1/B2/B6/C (any two)
8. (i) Write one reaction of D-Glucose which cannot be explained by its open chain structure. (CBSE 2016)
(ii) What type of linkage is present in Nucleic acids ?
(iii) Give one example each for water-soluble vitamins and fat-soluble vitamins?
Ans. (i) Sodium Hydrogen Sulphite reaction/ Pentaacetate of glucose does not react with Hydroxylamine/
Schiff’s test (any one)
(ii) Phosphodiester linkage
(iii) Fat soluble - Vitamin A/D /E/ K
Water soluble - Vitamin B /C
9. (i) Which one of the following is a disaccharide : (CBSE 2015)
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.
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
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EXERCISE-3 R AC E
Glucnose in an aldohexose. It can occur freely as well as in combined from in the nature. It is present
in sweet fruits and honey. Is is also present in quantities in ripe grapes. As glucose is an aldohexose,
it consist of six C-atoms and an aldehyde group. It is the most abundant organic compound on the
earth and used as an immediate source fo energy for all metabolic reactions in the animals.
(i) 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.
(ii) 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 hydroxylamine.
(d) Glucose is oxidised by nitric acid to gluconic acid.
(iii) When glucose is treated with Br2 / water-
(a) Gluconic acid (b) Saccharic acid (c) acetic acid (d) None of these
(iv) The another name given to glucose is
(a) aldoheptose (b) ketohexose (c) pentose (d) dextrose
(iii) Assertion is not true but reason is true
(iv) Both assertion and reason are false
2. Assertion : Glycine must be taken through diet.
Reason : It is an essential amino acid.
3. Assertion : D (+) – Glucose is dextrorotatory in nature.
Reason : ‘D’ represents its dextrorotatory nature
4. Assertion : All naturally occurring a-aminoacids except glycine are optically active.
Reason : Most naturally occurring amino acids have L-configuration.
5. Assertion : The two strands in double strand helix structure of DNA are complementary to each
other.
Reason : Disulphide bonds are formed between specific pairs of bases.
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6. Assertion : Glucose reacts with hydroxylamine to form an oxide and also adds a molecule of
hydrogen cyanide to give cyanohydrin.
Reason : The carbonyl group is present in the open chain structure of glucose.
7. Curding of milk is an example of
(i) breaking of peptido linkage (ii) hydrolysis of lactose
(iii) breaking of protien into amina acids (iv) denaturation of protein
8. Proteins are found to have two different types of secondary structures viz. a-halix and b-Pleated sheet
structure, a-helix structure of protein is stablized by:
(i) peptide bonds (ii) Vander Walles forces
(iii) Hydrogen bonds (iv) Dipole-dipole interactions
9. Nucleic acids are the Polymers of:
(i) Nucleosides (ii) Nucleotides (iii) Bases (iv) Sugars
10. Each Polypeptide in protein has amino acids linked with each other in a specific sequence. This
sequence of amino acids is said to be_________:
(i) Primary structure of proteins (ii) Secondary structure of proteins
(iii) tertiary structure of proteins (iv) Quaternary structure of propetins
11. DNA and RNA contains four bases each. Which of the following bases is not present in RNA?
(i) Adenine (ii) Uracil (iii) Thymine (iv) Cytosine
12. Amino acids are
(i) acidic (ii) basic (iii) amphoteric (iv) neutral
13. An a-helix is a structural feature of
(i) Sucrose (ii) Polypeptides (iii) Nucleotides (iv) Starch
14. Peptide linkage is present in
(i) Carbohydrates (ii) Vitamins (iii) Proteins (iv) Rubber
15. Dinucleotide is obtained by joining two nucleotides together by phosphodiester linkage. Between
which carbon atoms of pentose sugars of nucleotides are these linkages present?
(i) 5¢ and 3¢ (ii) 1¢ and 5¢ (iii) 5¢ and 5¢ (iv) 3¢ and 3¢
16. Proteins can be classified into two types on the basis of their molecular shape i.e., fibrous proteins and
globular proteins. Examples of globular proteins are :
(i) Fibrin (ii) Keratin (iii) Albumin (iv) Myosin
Answer key :
Q. No. 1 (i) (ii) (iii) (iv) 2 3 4 5 6 7 8
Ans. c c b d D C A A B iv iii
Q. No. 9 10 11 12 13 14 15 16
Ans. ii i iii iii iii iii i iii
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1. What is the difference between acidic amino acid and basic amino acid? [1]
2. What type of bonding provides stability to a-helix structure of protein ? [1]
3. What type of linkage is present in Nucleic acids ? [1]
4. Write the two types of secondary structures of proteins ? [2]
5. Write one difference between a-helix and b-pleated structures of proteins. [2]
6. Amino acids show amphoteric behaviour. Why ? [2]
7. What are essential and non-essential amino acids? Name one of each type. [2]
8. Write the main structural difference between DNA and RNA. Of the four bases, name those which
are common to both DNA and RNA. [3]
9. What is essentially the difference between a-glucose and b-glucose ? What is meant by pyranose
structure of glucose ? [3]
10. What happens when D-glucose is treated with the following regents ? [3]
(i) HI
(ii) Bromine water
(iii) HNO3
11. Define the following terms: [5]
(i) Nucleotide
(ii) Anomers
(iii) Native protein
(iv) Denatured protein
(v) Essential amino acids
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MOCK TEST SOLUTIONS
1. 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.
2. Hydrogen bonding
3. Phosphodiester linkage
4. a-Helix and b-pleated sheets.
5. 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 b-pleated all peptide chains are stretched out to nearly extensions & then laid side by side which
are held together by intermolecular hydrogen bonding.
6. 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 (a-amino acid)
NH2
7. 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.
8. DNA is double stranded a-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).
9. The six membered cyclic structure of glucose is called pyranose structure.
6 6
CH2 OH CH2 OH
O O
H 5 H H H5 OH
H
4 1 4 1
OH H OH OH H H
HO 3 2 HO 3 2
H OH H OH
10. (i) On prolonged heating with HI, D-glucose forms n-hexane.

CHO
HI, D
(CHOH) 4 CH3–CH2–CH2–CH2–CH2–CH3
n-Hexane
CH2OH
D-Glucose
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(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 COO
HNO3
(CHOH)4 (CHOH)
Oxidation
CH2OH COO
D-glucose D-saccharic
11. (i) A unit formed by the combination of nitrogenous base, sugar and phosphate.
(ii) a-D-glucose and b-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
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CBSE SAMPLE QUESTION PAPER : 2020-21
CHEMISTRY (THEORY)
MM : 70 Time : 3 Hours
General Instructions. Read the following instructions carefully.
(a) There are 33 questions in this question paper. All questions are compulsory.
(b) Section A: Q. No. 1 to 2 are case-based questions having four MCQs or Reason Assertion type
based on given passage each carrying 1 mark.
(c) Section A: Question 3 to 16 are MCQs and Reason Assertion type questions carrying 1 mark each
(d) Section B: Q. No. 17 to 25 are short answer questions and carry 2 marks each.
(e) Section C: Q. No. 26 to 30 are short answer questions and carry 3 marks each.
(f) Section D: Q. No. 31 to 33 are long answer questions carrying 5 marks each.
(g) There is no overall choice. However, internal choices have been provided.
(h) Use of calculators and log tables is not permitted.
Section-A (Objective Type)

Objective Type Questions
1. Read the passage given below and answer the following questions: (1x4=4)
node06\B0B0-BA\Kota\Board Material\Chemistry\CBSE\CBSE Booklet\English\Updated booklet-21\New Pattern CBSE Booklet\Part wise boocklet\Part 2\Sample Paper
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 utilizes
oxygen or air as the ultimate, stoichiometric oxidant, producing water as the only by-product
A wide range of primary, secondary, allylic, and benzylic alcohols can be smoothly oxidized 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.
The following questions are multiple choice questions. Choose the most appropriate answer:
(i) The Copper based catalyst mention in the study above can be used to convert:
(a) propanol to propanonic acid (b) propanone to propanoic acid
(c) propanone to propan-2-ol (d) propan-2-ol to propanone
(ii) The carbonyl compound formed when ethanol gets oxidised using this copper-based catalyst can
also be obtained by ozonolysis of:
(a) But-1-ene (b) But-2-ene (c) Ethene (d) Pent-1-ene
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OR
Which of the following is a secondary allylic alcohol?
(a) But-3-en-2-ol (b) But-2-en-2-ol (c) Prop-2-enol (d) Butan-2-ol
(iii) 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' respectively 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
(iv) 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
2. Read the passage given below and answer the following questions: (1x4=4)
The amount of moisture that leather adsorbs or loses is determined by temperature, relative humidity,
degree of porosity, and the size of the pores. Moisture has great practical significance because its amount
affects the durability of leather, and in articles such as shoes, gloves, and other garments, the comfort
of the wearer. High moisture content accelerates deterioration and promotes mildew action. On the
other hand, a minimum amount of moisture is required to keep leather properly lubricated and thus
prevent cracking.
The study indicates that adsorption of moisture by leather is a multi-molecular process and is
accompanied by low enthalpies of adsorption. Further 75-percent relative humidity the adsorption is
a function of surface area alone. Untanned hide and chrome-tanned leathers have the largest surface
areas. The leathers tanned with the vegetable tanning materials have smaller surface areas since they
are composed of less hide substance and the capillaries are reduced to smaller diameters, in some cases
probably completely filled by tanning materials. This process of tanning occurs due to mutual
coagulation of positively charged hide with negatively charged tanning material. The result of the study
indicated that untanned hide and chrome-tanned leather adsorb the most water vapour.
2. In these questions (Q. No 5-8 , a statement of assertion followed by a statement of reason is given.
Choose the correct answer out of the following choices.
(a) Assertion and reason both are correct statements and reason is correct explanation for assertion.
(b) Assertion and reason both are correct statements but reason is not correct explanation for assertion.
(c) Assertion is correct statement but reason is wrong statement.
(d) Assertion is wrong statement but reason is correct statement.
(i) Assertion: Vegetable tanned leather cannot adsorb a large amount of moisture.
Reason: Porous materials have higher surface area.
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(ii) Assertion: Animal hide soaked in tannin results in hardening of leather.
Reason: Tanning occurs due to mutual coagulation.
(iii) Assertion: Adsorption of moisture by leather is physisorption.
Reason: It is a multimolecular process and is accompanied by low enthalpies of adsorption
(iv) Assertion: The vegetable tanning materials have smaller surface areas
Reason: The capillaries present in leather are reduced to smaller diameters
OR
Assertion: Leather absorbs different amount of moisture.
Reason: Some moisture is necessary to prevent cracking of leather.
Following questions (No. 3 -11) are multiple choice questions carrying 1 mark each:
3 Which of the following option will be the limiting molar conductivity of CH3COOH if the limiting
molar conductivity of CH3COONa is 91 Scm2mol–1? Limiting molar conductivity for individual ions
are given in the following table.
2 –
S.No. Ions Limiting molar conductivity/Scm mol
+
1 H 349.6
+
2 Na 50.1
+
3 K 73.5
–
4 OH 199.1
(a) 350 Scm2mol–1 (b) 375.3 Scm2mol–1
(c) 390.5 Scm2mol–1 (d) 340.4 Scm2mol–1
4. Curdling of milk is an example of:

(a) breaking of peptide linkage (b) hydrolysis of lactose
(c) breaking of protein into amino acids (d) denauration of proetin
OR
Dissachrides that are reducing in nature are:
(a) sucrose and lactose (b) sucrose and maltose
(c) lactose and maltose (d) sucrose, lactose and maltose
5. When 1 mole of benzene is mixed with 1 mole of toluene The vapour will contain: (Given : vapour
of benzene = 12.8kPa and vapour pressure of toluene = 3.85 kPa).
(a) equal amount of benzene and toluene as it forms an ideal solution
(b) unequal amount of benzene and toluene as it forms a non ideal solution
(c) higher percentage of benzene
(d) higher percentage of toluene
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6. Which of the following is the reason for Zinc not exhibiting variable oxidation state
(a) inert pair effect (b) completely filled 3d subshell
(c) completely filled 4s subshell (d) common ion effect
OR
Which of the following is a diamagnetic ion: (Atomic numbers of Sc, V, Mn and Cu are 21, 23, 25
and 29 respectively)
(a) V2+ (b) Sc3+ (c) Cu2+ d) Mn3+
7. Propanamide on reaction with bromine in aqueous NaOH gives:

(a) Propanamine (b) Ethanamine
(c) N-Methyl ethanamine (d) Propanenitrile
OR
IUPAC name of product formed by reaction of methyl amine with two moles of ethyl chloride
(a) N,N-Dimethylethanamine (b) N,N-Diethylmethanamine
(c) N-Methyl ethanamine (d) N-Ethyl ,N-methylethanamine
8. Ambidentate ligands like NO2! and SCN! are :

(a) unidentate (b) didentate (c) polydentate (d) has variable denticity
OR
The formula of the coordination compound Tetraammineaquachloridocobalt(III) chloride is

(a) [Co(NH3)4(H2O)Cl]Cl2 (b) [Co(NH3)4(H2O)Cl]Cl3
(c) [Co(NH3)2(H2O)Cl]Cl2 (d) [Co(NH3)4(H2O)Cl]Cl
9. Which set of ions exhibit specific colours? (Atomic number of Sc = 21, Ti = 22, V=23, Mn = 25,
Fe = 26, Ni = 28 Cu = 29 and Zn =30)
(a) Sxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxc3+, Ti4+, Mn3+ (b) Sc3+, Zn2+,
Ni2+ (c) V3+, V2+, Fe3+ (d) Ti3+, Ti4+, Ni2+
10. Identify A,B,C and D:
(a) A = C2H4, B = C2H5OH, C = C2H5NC, D = C2H5CN

(b) A = C2H5OH, B = C2H4, C = C2H5CN, D = C2H5NC
(c) A = C2H4, B = C2H5OH, C = C2H5CN, D = C2H5NC
(d) A = C2H5OH, B = C2H4, C = C2H5NC, D = C2H5CN
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11. The crystal showing Frenkel defect is :
In the following questions (Q. No. 12 - 16) a statement of assertion followed by a statement of
reason is given. Choose the correct answer out of the following choices.
(a) Assertion and reason both are correct statements and reason is correct explanation for assertion.
(b) Assertion and reason both are correct statements but reason is not correct explanation for assertion.
(c) Assertion is correct statement but reason is wrong statement.
(d) Assertion is wrong statement but reason is correct statement.
12. Assertion: The two strands are complementary to each other
Reason: The hydrogen bonds are formed between specific pairs of bases.
13. Assertion: Ozone is thermodynamically stable with respect to oxygen.

Reason: Decomposition of ozone into oxygen results in the liberation of heat
14. Assertion: Aquatic species are more comfortable in cold waters rather than in warm waters.
Reason:Different gases have different KH values at the same temperature
OR
Assertion: Nitric acid and water form maximum boiling azeotrope.
Reason: Azeotropes are binary mixtures having the same composition in liquid and vapour phase.
15. Assertion: Carboxylic acids are more acidic than phenols.

Reason: Phenols are ortho and para directing.
16. Assertion: Methoxy ethane reacts with HI to give ethanol and iodomethane
Reason: Reaction of ether with HI follows SN2 mechanism
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SECTION B
The following questions, Q.No 17 – 25 are short answer type and carry 2 marks each.
17. With the help of resonating structures explain the effect of presence of nitro group at ortho position
in chlorobenzene.
OR
Carry out the following conversions in not more than 2 steps:
(i) Aniline to chlorobenzene
(ii) 2-bromopropane to 1- bromopropane
18. A glucose solution which boils at 101.04ºC at 1 atm. What will be relative lowering of vapour pressure
of an aqueous solution of urea which is equimolal to given glucose solution? (Given: Kb for water
is 0.52 K kg mol-1)
19. (i) Write the electronic configuration iron ion in the following complex ion and predict its magnetic
behaviour :
[Fe(H2O)6]2+
(ii) Write the IUPAC name of the coordination complex: [CoCl2(en)2]NO3
OR
(i) Predict the geometry of [NiCN4]2–

(ii) Calculate the spin only magnetic moment of [Cu(NH3)4]2+ ion.
20. For a reaction the rate law expression is represented as follows:

Rate = k [A][B]1/2
i. Interpret whether the reaction is elementary or complex. Give reason to support your answer.
ii. Write the units of rate constant for this reaction if concentration of A and B is expressed in moles/L.
OR
The following results have been obtained during the kinetic studies of the reaction:
P + 2Q ® R + 2S
–1
Exp. Initial P(mol/L) Initial Q (mol/L) Init. Rate of Formation of R (M min )
–4
1 0.10 0.10 3.0 × 10
–4
2 0.30 0.30 9.0 × 10
–4
3 0.10 0.30 3.0 × 10
–4
4 0.20 0.40 6.0 × 10
Determine the rate law expression for the reaction.
21. The C-14 content of an ancient piece of wood was found to have three tenths of that in living trees.
How old is that piece of wood? (log 3= 0.4771, log 7 = 0.8540 , Half-life of C-14 = 5730 years )
E 169
Chemistry
ALLEN
22. When 3-methylbutan-2-ol is treated with HBr, the following reaction takes place:
Br
|
CH 3 - CH - CH - CH 3 ¾¾ ¾
HBr
® CH 3 - C - CH3 - CH3
| | |
CH 3 OH CH 3
Give a mechanism for this reaction.
!
23. Give the formula and describe the structure of a noble gas species which is isostructural with IF5
24. The following haloalkanes are hydrolysed in presence of aq KOH.

(i) 1- Chlorobutane (ii) 2-chloro-2-methylpropane
Which of the above is most likely to give (a)an inverted product (b) a racemic mixture:
Justify your answer.
25. Atoms of element P form ccp lattice and those of the element Q occupy 1/3rd of tetrahedral voids
and all octahedral voids. What is the formula of the compound formed by the elements P and Q?
SECTION C
Q.No 26 -30 are Short Answer Type II carrying 3 mark each.
26. Give reasons for the following:
i. Transition elements act as catalysts
ii. It is difficult to obtain oxidation state greater than two for Copper.
iii. CrO is basic but Cr2O3 is amphoteric.
OR
Observed and calculated values for the standard electrode potentials of elements from Ti to Zn in the
first reactivity series are depicted in figure (1):
FIGURE 1
170 E
CBSE
ALLEN
Explain the following observations:
i. The general trend towards less negative E° values across the series
ii. The unique behaviour of Copper
iii. More negative E° values of Mn and Zn
27. Arrange the following in increasing order of property specified:

i. Aniline, ethanamine, 2-ethylethanamine (solubility in water)
ii. Ethanoic acid, ethanamine, ethanol (boiling point)
iii. Methanamine, N, N dimethylmethanamine and N- methylmethanamine (basic strength in aqueous
phase)
OR
i. Give a chemical test to distinguish between N-methylethanamine and N,N-dimethylethanamine.
ii. Write the reaction for catalytic reduction of nitrobenzene followed by reaction of product so formed
with bromine water.
iii. Out of butan-1-ol and butan-1-amine, which will be more soluble in water and why?
28. A metal crystallizes into two cubic system-face centred cubic (fcc) and body centred cubic (bcc) whose
unit cell lengths are 3.5 and 3.0A respectively. Calculate the ratio of densities of fcc and bcc.
29. Three amino acids are given below:

Alanine CH3CH(COOH)(NH2) Aspartic acid HOOC–CH2CH(COOH)(NH2) and Lysine H2N-
(CH2)4-CH(COOH)(NH2)
i. Make two tripeptides using these amino acids and mark the peptide linkage in both cases.
ii. Represent Alanine in the zwitter ionic form.
30. i. Arrange the following in decreasing order of bond dissociation enthalpy
F2 , Cl2 , Br2 , I2
ii. Bi does not form pp-pp bonds. Give reason for the observation.
iii. Electron gain enthalpy of oxygen is less negative than sulphur. Justify
SECTION D
Q.No 31 to 33 are long answer type carrying 5 marks each.
31. (i) Answer the following questions: (2+3)
(a) Write the balanced chemical reaction for reaction of Cu with dilute HNO3.
(b) Draw the shape of ClF3
(ii) 'X' has a boiling point of 4.2K, lowest for any known substance. It is used as a diluent for oxygen
in modern diving apparatus. Identify the gas 'X'. Which property of this gas makes it usable as
diluent? Why is the boiling point of the gas 'X' so low?
E 171
Chemistry
ALLEN
OR
(i) Answer the following questions: (2+3)
(a) Arrange the following in the increasing order of thermal stability:
H2O, H2S, H2Se, H2Te
(b) Give the formula of the brown ring formed at the interface during the ring test for nitrate.
(ii) A greenish yellow gas 'A' with pungent and suffocating odour, is a powerful bleaching agent.
'A' on treatment with dry slaked lime it gives bleaching powder. Identify 'A' and explain the reason
for its bleaching action. Write the balanced chemical equation for the reaction of 'A' with hot and
concentrated NaOH.
32. An organic compound 'A' C8H6 on treatment with dilute H2SO4 containing mercuric sulphate gives
compound 'B'. This compound 'B' can also be obtained from a reaction of benzene with acetyl chloride
in presence of anhy AlCl3. 'B' on treatment with I2 in aq. KOH gives 'C' and a yellow compound
'D'. Identify A, B, C and D. Give the chemical reactions involved. (5)
OR
(i) Write the reaction for cross aldol condensation of acetone and ethanal.
(ii) How will you carry out the following conversions:
(a) Benzyl alcohol to phenyl ethanoic acid
(b) Propanone to propene
(c) Benzene to m-Nitroacetophenone
33. (i) State Kohlrausch law. (1+4)
(ii) Calculate the emf of the following cell at 298 K:
Al(s)/Al3+ (0.15M)//Cu2+(0.025M) /Cu(s)
(Given Eº(Al3+/Al) = –1.66 V, Eº(Cu2+/Cu) = 0.34V, log 0.15 = –0.8239, log 0.025 = –1.6020)
OR
(i) On the basis of E° values identify which amongst the following is the strongest oxidising agent
Cl2(g) + 2e– ® 2Cl– Eº = +1.36 V, (1+4)
MnO4– + 8H+ + 5e– ® Mn2+ + 4H2O Eº = +1.51 V
Cr2O72– + 14H+ + 6e– ® 2Cr3+ + 7H2O Eº = +1.33 V
172 E
CBSE
ALLEN
(ii) The following figure 2, represents variation of ( L m ) vs c for an electrolyte. Here L m is the
molar conductivity and c is the concentration of the electrolyte.
Figure 2
(a) Define molar conductivity
(b) Identify the nature of electrolyte on the basis of the above plot. Justify your answer.
(c) Determine the value of L om for the electrolyte.
(d) Show how to calculate the value of A for the electrolyte using the above graph.
E 173

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02. ALCOHOL, PHENOL & ETHERS 32

03. ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 65

04. ALIPHATIC & AROMATIC AMINES 110

05. BIOMOLECULES 145

® SAMPLE QUESTION PAPER (2020-21) 164

Guidelines for Chemistry

3. We already provide chapter wise key points, NCERT important question

syllabus is reduced in 2020-21 session and we have designed your course

(b) Finkelstein Reaction :

(e) Wurtz-Fitting Reaction :

(f) Fitting Reaction :

l Nucleophilic Substitution Reactions :

(CH3)3 CBr ¾¾¾¾

Allylic éë CH 2 = CH - C H 2 ùû and benzylic éë C 6 H 5 C H 2 ùû halides undergo reaction via SN1 mechanism

as the corresponding carbo cations are resonance stabilized.

4. Identify A, B, C, D, E, R and R1 in the following :

The reactions involved in the question are :

Mono chlorocyclopentane (C5H 10)

Br CH3 Alc. NaOH/KOH

CH3 Br Alc. NaOH/KOH CH3

(iii) CH3 CH(Br)CH2 CH3 + NaOH ¾¾¾

(v) C6H5ONa + C2H5Cl ¾¾® (vi) CH3CH2CH2OH+SOCl2 ¾¾®

(vii) CH3CH2CH = CH2 + HBr ¾¾¾¾

(iv) CH3CH2Br + KCN ¾¾¾¾¾

(v) C6 H5 ONa + C2H5 Cl ¾¾¾¾¾ ¾

(vi) CH3CH2CH2OH + SOCl2 ¾¾® CH3CH2CH2Cl + SO2 + HCl

(vii) CH3CH2CH = CH 2 + HBr ¾¾¾¾¾¾¾ Peroxide

CH3CH2CH2CH2CH2 – Br > CH3CH2CH2CHCH3 > CH3CH2CCH3

(ii) CH3CHCH2CH2Br > CH3CHCHCH3 > CH3CCH2CH3

(1°) (2°) (3°)

(ii) CH2–CH = CH 2 + HBr

Ans. (a) (i) CH2Cl (ii) CH2–CH – CH3

Ans. (a) 2-Chloro-3,3-dimethylbutane (b) 1,4-dichloro-2-methylbenzene

(iii)Which one under goes SN2 substitution reaction & Why

22. Write the IUPAC name of following compound.

24. Complete reaction :

Ans. CH 3 Br + 2Na + Br - CH 3 ¾¾¾¾

Sodium metal is sensitive towards air and moisture forming :

White precipitate of AgCl

C2H5Cl + NaOH (aq) ¾® C2H5OH + NaCl

(ii) Test Chloroethane CH3CH2Cl Bromoethane CH3CH2Br

CH3Br + 2Na + BrCH 3 ¾¾¾¾

C2 H 5 Br + 2Na + BrC 2 H 5 ¾¾¾¾

OCH3 OCH3 OCH3

Anisole 2-Methoxytoluene CH3

(b) Substitution nucleophilic unimolecular (SN1)

(CH3)3 CBr ¾¾¾¾

(ii) CH3 - CH = CH2 + HBr ¾¾¾¾

Pr opene 1 -Bromppropane 1 -Nitropropane

KCN (alc) CH 3–MgBr Hydrolysis

(v) CH3 - CH2 - OH ¾¾¾¾

(xv) CH3CH2 - Cl ¾¾¾¾¾¾

(i) CH3–CH2–CH2–CH2–Br (ii) CH3–CH–CH2–Br

Therefore, compound (a) is either n-butyl bromide or isobutyl bromide.

Thus, compound (d) is 2, 5–dimethylhexane,

Ans. (a) The chiral molecule.

8. The following compounds are given to you : (CBSE 2017)

7. Write a chemical test to distinguish between [2]

9. Give reasons for the following [3]

(v) CH2–CH = CH2 + HBr

(iv) CH2Cl (v) CH2–CH – CH3

(iii) From carbonyl compounds with Grignard’s reagent :

(vii) From alkyl halidcs :