CHEMISTRY FOR NEET & AIIMS

HINTS & SOLUTIONS

EXERCISE - 1 13. (C) CH  CH  H 2  CH 2  CH 2
NEET LEVEL That is called addition reaction.

14. (D) When methane gas is treated with chlorine in the

1. (D) It is SN2 type of reaction.
presence of sunlight, one hydrogen of methane replaced
2. (C) by the chlorine atom and forms methyl chloride. The
mechanism involved in this reaction is free radical
3. Light
(C) Cl 2   2Cl mechanism. So it is an example of free radical substitution
reaction.
CH3 CH3Cl
15. (C) Due to OH– attack it is nucleophilic substitution.
Cl + H+
16. (A) Electron deficient species (in complete octet) acts
as an electrophile i.e. BCl3.
(Freeradical substitution)
4. (B) 17. (A) NO 2 is produced when conc. HNO3 reacts with
5. (A) It is nucleophilic substitution reaction which is in conc. H2SO4.
first order. HNO 3  H 2SO4  HSO4  NO 2  H 2 O
6. (C)
18. (D) Phenol will undergo electrophilic substitution more
7. (C)
readily than benzene.
8. (D)
19. (A) AlCl3 is lewis acid i.e., electron deficient compound.
9. (D) All cations are expected to act as Lewis acid since So it is electrophile.
they are electron deficient in nature. However cation
such as Na+, K+ etc. (Inert gas configuration) have a 20. (D) CH3O– is the strongest nucleophile which is capable
very little tendency to accept electrons. Therefore they of acting as donar of electon pair.
do not acts as lewis acids in friedel Craft's reaction.
21. (A) The phenyl ring having H - N< group is activated
10. (D) The process of nitration takes place as below while another one is deactivated due to  C  , so
||

HONO2  2H 2SO4 
H 3O  2HSO  
NO  O
4 2
(nitronium ion ) electrophilic aromatic bromination will occur at para
position with respect to H - N< group inactivated ring.
The electrophile responsible for nitration is NO 2 ion.
22. (D) The non reactivity of the chlorine atom in vinyl
11. (B) Dehydrohalogenation of an alkyl halide on presence chloride may be explained from the molecular orbital point
of alcoholic potash is an example of elimination reaction. of view as follows. If the chlorine atom has sp 2

R  CH 2 CH 2  Cl  KOH   hybridization the C - Cl bond will be a -bond and the
alc.
two lone pairs of electron would occupy the other two
RCH  CH 2  KCl  H 2 O sp2 orbitals. This would leave a p-orbital containing a
lone pair and this orbital could not conjugate with the 
12. (D) CH2 bond of the ethylenic link. Thus two M.O.S. will be
CH3 required to accommodate these four  electrons. Further
CH + HCl  Cl
CH more since chlorine is more electronegative than carbon,
Cl Cl the electron will tend to be found in the chlorine atom
(1, 1 dichloroet hane)
has now lost full control of the one pair and so, is less
It is addition reaction. negative than it would have been had there been no
Which is according to Markownikoff rule. conjugation. Since two carbon atoms have acquired a

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share in the lone pair, each atom acquires a small negative EXERCISE - 2
charge. Hence, owing to delocalisation of bonds
AIIMS LEVEL
(through conjugation), the vinyl chloride molecule has
an increased stability. Before the chlorine atom can be
1. (C) Reactivity towards H2O is proportional to stability
displaced by some other group the lone pair must be
of carbocation.
localised again on the chlorine atom. This requires energy
and so the chlorine is more firmly bound than has no 2. (C)
conjugation occurred.
3. (D) CH3 – CH2 – CH2 – CH2 – OH HBr  
CH2 – CH– Cl CH2 – CH– Cl CH3 – CH2 – CH2 – CH2 – Br
Unbranched 1º alcohol give SN2 reaction with HX.
23. (A) Nucleophiles are those substances which can
donate a pair of electrons. These can be neutral or 4. (A)
negative. The nucleophilic power depends on the
tendency of species to donate electrons. This is more, 5PCl
  
when an electron pushing group (+I group) is present.
Among the alkyl groups, those having higher number of
C-atoms will push more, hence ethyl > methyl. It is SN2 reaction

O Na
5. (D) CH3 – C  CH  CH3 – C  C–Na+
C2H5 > > S – H, CH3 > > C – O, CH3 >> NH2,
(+1) (+1) (+1) CH3 CH2 I
    CH3  C  C  CH2  CH3
CH5 + CH2 SN 2
(–1)
6. (C)
H O
–
24. (A) Conjugated acid of Cl is a stronger acid i.e., HCl. 2
AgNO 3

25. (B) Saytzeffs product.

7. (B) SN2 mechanism is a single step concerted process
26. (D) and proceed through transition state is formed.

27. (B) 8. (C) Rate of SN2  [R – X ] [Nu–]

28. (A) AlCl3 is electron deficient species thus it is a Lewis r2 

[3RX] 21 OH– 
=
acid. r1 [RX] [OH – ]
r2 = 1.5 r1
29. (D) Nucleophilicity  size (in a group).
9. (B)
30. (D) The nucleophilicity order is
O
||
> > > 10. (B) CH 3–CH 2– C – OCH3
31. (C) O
NaNH2 /  ||
32. (D)   
 CH3–CH2– C – NH2
 CH3ONa

33. (C) Weaker bases are better leaving group. 11. (C)
34. (A)
35. (C)

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12. (D)
24. (D) All the given species undergo nucleophilic
substitution reaction. This reactivity can be explained in
terms of the nature of (C – X) bond which is highly
polarised covalent bond due to large difference in the
 
electronegativities of carbon and halogen atoms.  C  X

25. (C) Increasing + I effect

(CH 3 )3 C  (CH3 ) 2 CH  CH3 CH 2  CH 3
13. (C) As steric hinderance increases on carbonyl group
the rate of nucleophilic addition reaction decreases. 26. (B) Reactivity  stability of intermediate carbocation

14. (C) CH3

15. (C) Ph–CH=CH2 Ph–C=CH–CH3
E E
16. (D) According to stability of carbocation. (I) (II)

17. (A) It is E2 reaction (anti elimination). CH3


Alc.KOH
 CH 3 — Ph – CH – CH2 Ph – C – CH – CH3
CH3 — CH — CH2 — CH3 

| (a) E (b) E
Cl
Ph – C = CH – CH3 CH2 = CH – NO2
CH=CH—CH3 E (III)
Ph (IV) E
18. (B)
 
19. (B) Ph – C – CH – CH 3 CH2 – CH – NO2
Ph E E
CH3 CH3 (c) (d)
OH Stability order c > b > a > d
H SO 4
20. (B) 2   Reactivity order III > II > I > IV
– H2 O
* *
27. (B) A is CH – CH – COOH
CH3 CH3 Br
Br

OH
28. (C) CH3 – CH = CH2 dil
H2SO4 CH3 – CH – CH3 (A)

OH
21. (C) -Hydrogen is absent. B2H6 H2O2
CH3 – CH = CH2 H2SO4
–
OH CH3 – CH2 – CH2 (B)
22. (B) If the dehydrohalogenation of an alkyl halide can A and B are not chain isomers. A and B are
yield more than one alkene, then according to the saytzeff isomers of CH3 – CH2 – O –CH3
rule, the main product is the most highly substituted
(i.e. mixed ether)
alkene.
Light
29. (B) CH 3 – CH 2  CH 2  CH 3  Br2  
–
HO OH
CH3 – CH2 – CH – Br
H H H H H2C = CHCH2CH3 CH 3
H–C–C–C–C–H 1 – butene (20%)
CH3CH = CHCH3
H Br H H 2 – butene (80%)
30. (B) Reactivity (ESR)  e– density in the ring

23. (D) Halogenation of alkanes takes place in presence of

light (sunlight or UV) or at elevated temperature via free
radical.

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Stability of alkene I > III > II
CH3 Reactivity A > C > B
(Maximum hyperconjugation)

3–H
EXERCISE - 3
P-1 (Matrix Match)
– 1. A  (r), B  (q), C  (s), D  (p)
Cl
31. (B) ( Due to +M/ +R of – Cl) 2. A  (q), B  (r), C  (s), D  (p)
3. A  p, q, B  q, r, C  p, q, s, D  (s)
– –

Reaction - A gives
CH3 Cl
Conc. HCl
32. (C) CH3 – C – CH2 – OH +ZnCl2 CH3 – C – CH2 – CH3
CH3 CH3 CH3

Reaction - B gives
–H2O H

Cl at 25°C gives CH3

CH3
 
CH3 – C – CH2 CH3 – C – CH2 – CH3
CH3 CH3
Reaction-C gives

CH3 CH3 OH
H2 SO4
33. (B) CH3 – C – CH2 – CH2 – OH CH3 – C = C – CH3 Reaction-D gives

CH3 CH3

–H2O H
EXERCISE - 3
CH3

P-2 (Assertion & Reason)
CH3 – C – CH2 – CH2
CH3 –H 1. (B) 2. (C) 3. (A) 4. (A)
CH3 CH3 5. (B) 6. (A) 7. (E) 8. (C)
 
CH3 – C – CH – CH3 CH3 – C – CH – CH3
CH3 CH3

H
34. (D) CH3 – C – CH2 CH3 – C = CH2
–HBr
CH3 CH3
(A) (I)

CH3 – CH2 – Br CH2 = CH2

–HBr
(B) (II)

CH3 – CH2– CH2– Br CH3 – CH = CH2

–HBr
(C) (III)

Reactivity of alkyl halide  stability of alkene

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9. (A) 10. (E) 11. (E) 12. (E) 4. (B) : Hybridisation of carbon = sp3 – number of  – bonds In CO2,
13. (E) 14. (E) 15. (A) 16. (A) (O  C  O) hybridisation of carbon = sp3–2 = sp
1 1
17. (A) 18. (E) 19. (A)
In ethyne or acetylene, C2H2,
EXERCISE - 4 2 3–2
P-1 (NEET/AIPMT) (H  C  C  H) hybridisation of carbon = sp = sp

5. (D) : Allylic and benzylic halides show high reactivity

1. (C) At higher temperature the reaction of toluene with
towards SN1 reaction. Further, due to greater stabilisation
chlorine is an example of free radical substitution.
of allyl and benzyl carbocations intermediates by
(I) Cl – Cl  2Cl Free radical (Initiation) resonance, primary allylic and primary benzylic halides
show higher reactivity in SN1 reaction than other simple
CH3 CH2 primary halides.

(a) + Cl  + HCl H
(Propagation)
H3C C CH CH2 Cl
CH3 CH2Cl H H
(II) +
(b) + Cl2  H3C C CH CH2 H3C C CH CH2
+ Cl +
2° -allyl cation 1° -allyl cation
Benzylic free radical is resonating stable

(III) Cl + Cl  Cl2 (termination) Hence. it undergoes nucleophilic reaction readily.

6. (B) : In SN1 reaction, there slight more inversion product

2. (A)
than retention product because SN1 reaction also depend
KOH
+
K + OH
– on shielding effect of the front side of the reacting carbon.
RX + OH– R – OH + X– 7. (C) : In keto-enol tautomerism, a carbonyl compound
Nucleophile with a hydrogen atom on its alpha-carbon rapidly
OH– is a stronger nucleophile than halogen. So it easily equilibrates with its corresponding enol.
replace the weaker nucleophile.
Nucleophiles are either negative charge or lone pair of
electrons bearing species, e.g. OH–, NH3 , etc.
O OH

3. (D) : Reactivity of carbonyl compounds towards R C CH2R' R C CHR'

nuclephilic addition reactions depends on the presence Ketone Enol

of substituted group.
Electron withdrawing (–I, –M) groups increase reactivity
towards nucleophilic addition reactions. Thus, correct 8. (D)
order is
O Cl
OH : CCl2 (Dichloro carbene)
H C Cl
CHO CHO CHO C CH3 –H2O
Cl –Cl
> > >

NO2(--I, --M) CH3 (+I)

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EXERCISE - 4 9. (D) :
P-2 (AIIMS)
1. (C) : (CH3)3CO– is a better base than a nucleophile. Hence
elimination occurs. The product formed is resonance
stabilised.
2. (C) : In methyl alcohol, F– ion is solvated but in DMSO
or CH3CN (aprotic solvent) F– ion is not solvated.
Unsolvated F– ion acts more efficiently as a nucleophile.

EtO
3. (B) : CH2 CH2 Br CHO CHO
-HBr

CH CH2
10. (B) : Br2 / CCl4
  Br
OCH3 OCH3
It is a primary bromide. So it will undergo elimination OH OH
either by E2 or ElcB. Since there is no deuterium exchange
in C2H5OD solvent, –OH group is more activating so attack of Br +
C – H bond is not broken to form carbanion. (electrophile) occurs at ortho position of –OH group
Hence the actural mechanism is E2 only. during ESR
H Br CH3 C6 H5
Ph C C H Ph CH CH2 + EtOH + Br
EtO H H
NaOH
11. (B) : H Br 
S 2
 H OH
4. (D) : Substituent with stron + R effect, +I effect and N
C 6 H5 CH3
weaker – I effect increases the basicity. Hence pKb
(R) (S)
decreases. Also, alkylamines are stronger bases than
arylamines. So, the order is (D). inversion of configuration
5. (A) : Weaker acids have higher pKa. – OCH3 at meta- 12. (D) : Assertion is false, because aryl halides do not
position exerts only –I effect, hence increases the acidity. undergo nucleophilic substitution under ordinary
– I effect order : – NO2 > – OCH3 > – Cl. conditions. This is due to resonance, because of which
– CH3 has + I effect. the carbon–chlorine bond acquires partial double bond
So order is (A). character, hence it becomes shorter and stronger and
thus cannot be replaced by nucleophiles. However
6. (A) Reason is true.
7. (D) : Larger the value of pKa, smaller will be its acidity.
Out of the four groups, –COOH, –NO2 and –CN are e– 13. (D)
withdrawing which makes benzoic acid more acidic
whereas –OCH3 is e– donating which reduces the acidity
(Makes H+ less easily available). pKa value increases if –
OCH3 is present at para-position of benzoci acid.
8. (B) : Lassaigne’s test is given by those nitrogenous
compounds in whic carbon is also present along with
nitrogen.
In NH2 – NH2.HCl, carbon is absent so it does not give
Lassaigne’s test.

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MOCK TEST
1. (C) 2. (B) 3. (A) 4. (A)
5. (B) 6. (B) 7. (B) 8. (D)
9. (A) 10. (C) 11. (B) 12. (D)
13. (B) 14. (C) 15. (C) 16. (B)
17. (C) 18. (C)
CH3
19. (B) Ph – CH = C – CH3 + HBr Peroxide

Br H CH3

CH3
Br
Ph – CH – CH – CH3
Br
intermediate

20. (D) H


CH3 OH H3C
CH3 CH3
H –H


 
H3C H3C
H
CH3 CH3

21. (C) Reactivity with Lucas reagent  Stability of

intermediate carbocation.

22. A  p, q, s; B  q; C  q, r, s; D  q, r
23. (D) 24. (A) 25. (A) 26. (A)
27. (A) 28. (D) 29. (C) 30. (D)

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