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 CHAPTER

13 Hydrocarbons

13.2 Alkanes (d) the eclipsed conformation of ethane is more

stable than staggered conformation, because
1. Which of the following alkane cannot be made in eclipsed conformation has no torsional strain.
good yield by Wurtz reaction? (NEET-I 2016)
(a) n-Hexane (b) 2, 3-Dimethylbutane
6. In the following the most stable conformation of
(c) n-Heptane (d) n-Butane
n-butane is
(NEET 2020)
CH3 CH3
2. The alkane that gives only one monochloro H CH3 H H
product on chlorination with Cl 2 in presence of
(a) (b)
diffused sunlight is H H
(a) 2,2-dimethylbutane (b) neopentane H H CH
3
(c) n-pentane (d) isopentane. H
(Odisha NEET 2019) H3 C H3C
CH 3 H
3. Hydrocarbon (A) reacts with bromine by (2010)
substitution to form an alkyl bromide which by (c) H (d) H
Wurtz reaction is converted to gaseous hydrocarbon H H H
H H H3C
containing less than four carbon atoms. (A) is
(a) CH CH (b) CH2 CH2 7. Liquid hydrocarbons can be converted to a mixture
(c) CH3 — CH3 (d) CH4 (NEET 2018) of gaseous hydrocarbons by
4. With respect to the conformers of ethane, which of (a) oxidation
the following statements is true? (b) cracking
(a) Bond angle changes but bond length remains (c) distillation under reduced pressure
same. (d) hydrolysis. (2010)
(b) Both bond angle and bond length change. 8. Which of the following conformers for ethylene
(c) Both bond angle and bond length remain same. glycol is most stable?
(d) Bond angle remains same but bond length OH OH
changes. (NEET 2017) OH
5. The correct statement regarding the comparison of (a) (b)
staggered and eclipsed conformations of ethane, is H
H H
(a) the eclipsed conformation of ethane is more H HH
stable than staggered conformation even though OH
the eclipsed conformation has torsional strain OH OH
(b) the staggered conformation of ethane is more H
stable than eclipsed conformation, because (c) OH
(d)
staggered conformation has no torsional strain HO
(c) the staggered conformation of ethane is less H HH H H
stable than eclipsed conformation, because H
staggered conformation has torsional strain (Mains 2010)
98
9. Dihedral angle in staggered form of ethane is
(a) 0° (b) 120° (b)
(c) 60° (d) 180° (2000)
10. Which of the following reaction is expected to
readily give a hydrocarbon product in good yields?
C H OH
(a) CH CH Cl2 (b) (CH ) CHCl 2 5 (c)
3 3 h3 2
Electrolysis I2
(c) RCOOK Oxidation (d) RCOOAg
(d) (NEET 2019)
(1997)
11. In the commercial gasolines, the type of
hydrocarbons which are more desirable is 17. The most suitable reagent for the following
conversion, is
(a) linear unsaturated hydrocarbon
(b) toluene
(c) branched hydrocarbon
(d) straight-chain hydrocarbon. (1997)
(a) Hg2+/H+, H2O (b) Na/liquid NH3
12. The most stable conformation of n-butane is
(c) H2, Pd/C, quinoline (d) Zn/HCl (NEET 2019)
(a) gauche (b) staggered
(c) skew boat (d) eclipsed. (1997) 18. Which of the following compounds shall not
produce propene by reaction with HBr followed by
13. Which of the following is used as an antiknocking
elimination or direct only elimination reaction?
material?
H2 C CH2
(a) Glyoxal (b) Freon
(a) C
(c) T.E.L. (d) Ethyl alcohol (1996) H2
14. Reactivity of hydrogen atoms attached H2
to different carbon atoms in alkanes has the order (b) H3 C C CH2OH
(a) tertiary > primary > secondary (c) H2C C O
(b) primary > secondary > tertiary H2
(c) both (a) and (b) (d) H3 C C CH2Br (NEET-II 2016)
(d) tertiary > secondary > primary. (1993) 19. The compound that will react most readily with
gaseous bromine has the formula
13.3 Alkenes (a) C3 H6 (b) C2 H2
(c) C4 H10 (d) C2 H4 (NEET-II 2016)
15. An alkene on ozonolysis gives methanal as one of
the product. Its structure is 20. In the reaction with HCl, an alkene reacts in
CH2 CH2 CH3 accordance with the Markovnikov’s rule to give
CH CH CH3
a product 1-chloro-1-methyl-cyclohexane. The
(a) (b) possible alkene is
CH2 CH3

CH2 CH CH2 CH2CH2CH3 (a) (A) (b) (B)

(c) (d) CH3

(NEET 2020)
(c) (A) and (B) (d) (2015)
16. An alkene A on reaction with O3 and Zn H2O gives
propanone and ethanal in equimolar ratio. Addition
21. Which of the following is not the product of
of HCl to alkene A gives B as the major product. The
structure of product B is dehydration of ?
OH

(a) (a) (b)

Hydrocarbons 99
R R R H
(c) (a) (b)
(d) (2015) H H R H
R R
22. In the following reaction (c) R R (d)
R H R R
(R = alkyl substituent)
(2005)
27. Reaction of HBr with propene in the presence of
The major product is peroxide gives
(a) isopropyl bromide (b) 3-bromopropane
(a) (c) allyl bromide (d) n-propyl bromide.
(2004)
CH 3
28. The compound, CH3 C CH CH 3 on reaction
with NaIO4 in the presence of KMnO 4 gives
(b) (a) CH3COCH3
(b) CH3COCH3 + CH3COOH
(c) CH3COCH3 + CH3CHO
(d) CH3CHO + CO2 (2003)
(c)
29. Geometrical isomers differ in
(a) position of functional group
(d) (b) position of atoms
(2012) (c) spatial arrangement of atoms
(d) length of carbon chain. (2002)
30. In preparation of alkene from alcohol using Al 2O3
23. Which of the following compounds will exhibit cis-
which is the effective factor?
trans (geometrical) isomerism? (a) Porosity of Al2O3
(a) Butanol (b) 2-Butyne (b) Temperature
(c) 2-Butenol (d) 2-Butene (2009) (c) Concentration
24. H3C – CH– CH CH2 + HBr A (d) Surface area of Al2O3 (2001)
CH3 31. Which reagent converts propene to 1-propanol?
A (predominantly) is (a) H2O, H2SO4
(a) CH 3–CH–CH–CH 3 (b) B2H6, H2O2, OH–
(c) Hg(OAc)2, NaBH4/H2O
Br CH3
(d) Aq. KOH (2000)
(b) CH3 CH CH CH3
32. Which is maximum stable?
CH3 Br (a) 1-Butene
(c) CH3 – CH– CH 2 – CH2 Br (b) cis-2-Butene
CH3 (c) trans-2-Butene
(d) All have same stability. (2000)
Br
33. 2-Butene shows geometrical isomerism due to
(d) CH3 – C – CH2CH3 (2008) (a) restricted rotation about double bond
CH3 (b) free rotation about double bond
25. Which of the compound with molecular formula (c) free rotation about single bond
C5H10 yields acetone onozonolysis? (d) chiral carbon. (2000)
(a) 3-Methyl-1-butene (b) Cyclopentane 34. 2-Bromopentane is heated with potassium ethoxide
(c) 2-Methyl-1-butene (d) 2-Methyl-2-butene in ethanol. The major product obtained is
(2007) (a) trans-2-pentene (b) 1-pentene
26. Which one of the following alkenes will react faster (c) 2-ethoxy pentane (d) 2-cis-pentene.
with H2 under catalytic hydrogenation conditions? (1998)
 100
Hypochlorous (b) CH CH > CH2 CH2
35. In a reaction, CH2 CH2 M
acid
CH2OH > CH3—C CH > CH3—CH3
R
(c) CH3—CH3 > CH2 CH2
CH2 OH > CH3—C CH > CH CH
where, M = Molecule and R = Reagent. M and R are (d) CH2 CH2 > CH3—CH CH2
(a) CH3CH2OH and HCl > CH3—C CH > CH CH
(b) CH 2 CH2 and heat (NEET 2017)
(c) CH 3 CH2 Cl and NaOH
44. Predict the correct intermediate and product in the
(d) CH2Cl – CH2OH and aq. NaHCO3. (1997)
following reaction :
36. The reaction, H2O, H2SO4
CH2 CH – CH3 + HBr  CH3CHBr – CH3 is H3 C — C CH Intermediate
HgSO4 (A)
(a) electrophilic substitution
(b) free radical addition  Product
(B)
(c) nucleophilic addition (a) ,
(d) electrophilic addition. (1996)
37. Which of the following has zero dipole moment? (b) ,
(a) 1-Butene (b) 2-Methyl-1-propene
(c) cis-2-Butene (d) trans-2-Butene (1996)
38. One of the following which does not observe the (c) ,
anti-Markownikoff’s addition of HBr, is
(a) pent-2-ene (b) propene (d) ,
(c) but-2-ene (d) but-1-ene. (1994)
39. Reduction of 2-butyne with sodium in liquid (NEET 2017)
ammonia gives predominantly 45. The pair of electrons in the given carbanion,
(a) cis-2-butene (b) no reaction CH3C C–, is present in which of the following
(c) trans-2-butene (d) n-butane. (1993) orbitals?
40. The restricted rotation about carbon carbon double (a) sp2 (b) sp
bond in 2-butene is due to (c) 2p (d) sp3 (NEET-I 2016)
(a) overlap of one s and sp2-hybridized orbitals 46. In the reaction
(b) overlap of two sp2-hybridized orbitals (i) NaNH /liq. NH
(c) overlap of one p and one sp2-hybridized orbitals H C CH 2
(ii) CH3CH2Br
3
X
(d) sideways overlap of two p-orbitals. (1993) (i) NaNH2/liq. NH3
Y,
41. Which one of the following can exhibit (ii) CH 3 CH2 Br
cis-trans isomerism? X and Y are
(a) CH3 – CHCl – COOH (a) X = 2-butyne, Y = 2-hexyne
(b) H – C C – Cl (b) X = 1-butyne, Y = 2-hexyne
(c) ClCH CHCl (c) X = 1-butyne, Y = 3-hexyne
(d) ClCH2 – CH2Cl (1989) (d) X = 2-butyne, Y = 3-hexyne. (NEET-I 2016)
47. Which of the following organic compounds has
13.4 Alkynes same hybridization as its combustion product
42. In the following reaction, (CO2)?
red hot iron tube (a) Ethane (b) Ethyne
H3C – C  CH  873
K 
 A,
(c) Ethene (d) Ethanol (2014)
the number of sigma() bonds present in the
48. In the following reaction :
product A, is SO4
(a) 21 (b) 9 HC CH H2 ‘P’
Hg 2+
(c) 24 (d) 18
Product ‘P’ will not give
(Odisha NEET 2019) (a) Tollens’ reagent test
43. Which one is the correct order of acidity? (b) Brady’s reagent test
(a) CH CH > CH3—C CH (c) Victor Meyer test
> CH2 CH2 > CH3—CH3 (d) Iodoform test. (Karnataka NEET 2013)
Hydrocarbons 101

49. Which of the following reagents will be able to 55. When acetylene is passed through dil. H2SO4 in the
distinguish between 1-butyne and 2-butyne? presence of HgSO4, the compound formed is
(a) NaNH2 (b) HCl (a) acetic acid (b) ketone
(c) O2 (d) Br2 (Mains 2012) (c) ether (d) acetaldehyde. (1999)
50. Considering the state of hybridization of carbon 56. The cylindrical shape of an alkyne is due to
atoms, find out the molecule among the following (a) two sigma C – C and one  C – C bonds
which is linear? (b) one sigma C – C and two  C – C bonds
(a) CH3 — CH CH — CH3 (c) three sigma C – C bonds
(b) CH3 — C C — CH3 (d) three  C – C bonds. (1997)
(c) CH2 CH — CH2 — C CH Reagent
57. R – CH2 – CCl2 – R R–CC–R
(d) CH3 — CH2 — CH2 — CH3 (2011)
The reagent is
51. Base strength of (a) Na (b) HCl in H2O
(c) KOH in C2H5OH (d) Zn in alcohol. (1993)
is in the order of 58. A compound is treated with NaNH2 to give sodium
(a) (i) > (iii) > (ii) (b) (i) > (ii) > (iii) salt. Identify the compound.
(c) (ii) > (i) > (iii) (d) (iii) > (ii) > (i) (2008) (a) C2H2 (b) C6H6
(c) C2H6 (d) C2H4 (1993)
52. Predict the product C obtained in the following
reaction of 1-butyne. 59. The shortest C–C bond distance is found in
HI (a) diamond (b) ethane
CH
3
CH
2
C CH+ HCl B (c) benzene (d) acetylene. (1991)
C
60. Acetylenic hydrogens are acidic because
I
(a) CH3 CH2 CH2 C H (a) sigma electron density of C – H bond in
acetylene is nearer to carbon, which has 50%
Cl s-character
I (b) acetylene has only open hydrogen in each
(b) CH3 CH2 CH CH2Cl carbon
(c) acetylene contains least number of hydrogens
I among the possible hydrocarbons having two
(c) CH3CH2 C CH3 carbons
(d) acetylene belongs to the class of alkynes with
Cl molecular formula, CnH2n–2. (1989)
(d) CH3 CH CH2CH2 I (2007)
61. Which is the most suitable reagent among the
Cl following to distinguish compound (3) from rest of
53. Products of the following reaction : the compounds?
CH C CCH CH (i) O3 (1) CH3 – C C – CH3
3 2 3
(ii) hydrolysis
(2) CH3 – CH2 – CH2 – CH3
are (3) CH3 – CH2C CH
(a) CH3COOH + CO2 (4) CH3 – CH CH2
(b) CH3COOH + HOOCCH2CH3 (a) Bromine in carbon tetrachloride
(c) CH3CHO + CH3CH2CHO (b) Bromine in acetic acid
(d) CH3COOH + CH3COCH3 (2005) (c) Alk. KMnO4
54. When CH CH CHCl is treated with NaNH , the (d) Ammoniacal silver nitrate (1989)
3 2 2 2
product formed is 13.5 Aromatic hydrocarbons
(a) CH3 – CH CH2 (b) CH3 – C CH 62. Among the following the reaction that proceeds
NH2 through an electrophilic substitution is
(c) CH CH CH
3 2
NH2 (a)
Cl
(d) CH3CH2CH (2002)
NH2
102
67. Consider the nitration of benzene using mixed
(b) N2Cl Cl + N2 conc. H2SO4 and HNO3. If a large amount of KHSO4
is added to the mixture, the rate of nitration will be
(c) (a) unchanged (b) doubled
(c) faster (d) slower.
(NEET-I 2016)
68. The oxidation of benzene by V2O5 in the presence of
(d) air produces
(a) maleic anhydride
(b) benzoic acid
(NEET 2019) (c) benzaldehyde
(d) benzoic anhydride. (2015)
63. Which of the following can be used as the halide
component for Friedel–Crafts reaction? 69. What products are formed when CH3
(a) Chlorobenzene (b) Bromobenzene the following compound is treated
(c) Chloroethene (d) Isopropyl chloride with Br 2 in the presence of FeBr3?
(NEET-II 2016) CH3
CH3 CH3
64. In which of the following molecules, all atoms are Br
coplanar? and
(a)
CH3 CH3
Br
(a) (b)
CH3 CH3
(b) Br Br
and
(c) CH3 CN CH3 CH3
CH3 C C CN (d)
CH3 CH3
(NEET-II 2016) (c) Br
65. In pyrrole the electron density is maximum on and
4 3 CH3 CH3
5 2 Br
N1
CH3 CH3
H
(a) 2 and 3 (b) 3 and 4 (d) and
(c) 2 and 4 (d) 2 and 5 CH3 Br CH3
(NEET-II 2016) Br (2014)
66. In the given reaction,
70. Some meta-directing substituents in aromatic
HF substitution are given. Which one is most
P
0 °C deactivating?
the product P is (a) — COOH (b) — NO2
(c) — C N (d) — SO3H
(NEET 2013)
(a) (b)
71. Which of the following compounds will not undergo
Friedel-Crafts reaction easily?
(a) Nitrobenzene (b) Toluene
(c) Cumene (d) Xylene (NEET 2013)
(c) (d) 72. Which of the following chemical system is non
aromatic?
(a) (b)
(NEET-II 2016)
Hydrocarbons 103

(b) CH3 – CH CH2 + C6H6

(c) (d)
S (c) H2C CH2 + C6H6
(Karnataka NEET 2013) (d) H3C – CH3 + C6H6 (2004)
73. Among the following compounds the one that is 80. Which one of the following is a free-radical
most reactive towards electrophilic nitration is substitution reaction?
(a) benzoic acid (b) nitrobenzene
CH3 Boiling CH2Cl
(c) toluene (d) benzene. (a) + Cl2
(2012, 1992)
74. The reaction of toluene with Cl2 in presence of FeCl3 (b)
gives X and reaction in presence of light gives Y.
Thus, X and Y are CH2Cl + AgNO CH2NO2
(a) X = benzal chloride, (c) 2

Y = o-chlorotoluene
(d) CH3CHO + HCN → CH3CH(OH)CN (2003)
(b) X = m-chlorotoluene,
Y = p-chlorotoluene 81. The correct order of reactivity towards the
(c) X = o- and p-chlorotoluene, electrophilic substitution of the compounds aniline
Y = trichloromethyl benzene (I), benzene (II) and nitrobenzene (III) is
(d) X = benzyl chloride, (a) III > II > I (b) II > III > I
Y = m-chlorotoluene. (2010) (c) I < II > III (d) I > II > III (2003)
75. Benzene reacts with CH3Cl in the presence of 82. Increasing order of electrophilic substitution for
anhydrous AlCl3 to form following compounds
(a) chlorobenzene (b) benzyl chloride CH3
(c) xylene (d) toluene. (2009)
76. Nitrobenzene can be prepared from benzene by (I) (II)
using a mixture of conc. HNO3 and conc. H2SO4. In
the mixture, nitric acid acts as a/an OCH3 CF3
(a) acid (b) base
(c) catalyst (d) reducing agent. (III) (IV)
(2009)
(a) IV < I < II < III (b) III < II < I < IV
77. Which one of the following is most reactive towards
(c) I < IV < III < II (d) II < III < I < IV
electrophilic attack?
(2000)
83. In Friedel-Crafts reaction, toluene can be prepared
(a) (b) by
(a) C6H6 + CH3Cl (b) C6H5Cl + CH4
(c) C6H6 + CH2Cl2
(c) (d) (d) C6H6 + CH3COCl (2000)
(2008) 84. In Friedel-Crafts alkylation, besides AlCl3 the other
78. The order of decreasing reactivity towards an reactants are
electrophilic reagent, for the following would be (a) C6H6 + CH3Cl (b) C6H6 + CH4
(i) benzene (ii) toluene (c) C6H6 + NH3 (d) C6H6 + CH3COCl
(iii) chlorobenzene (iv) phenol (1999)
(a) (ii) > (iv) > (i) > (iii) 85. Which of the following compounds will be most
(b) (iv) > (iii) > (ii) > (i) easily attacked by an electrophile?
(c) (iv) > (ii) > (i) > (iii) OH Cl
(d) (i) > (ii) > (iii) > (iv) (2007) (a) (b)
79. Using anhydrous AlCl3 as catalyst, which one of the CH3
following reactions produces ethylbenzene (PhEt)? (c) (d)
(a) H3C – CH2OH + C6H6 (1999, 1998)
104

86. Which one of these is not compatible with arenes? 89. The reactive species in the nitration of benzene is
(a) Electrophilic additions (a) NO3+ (b) HNO 3
(b) Delocalisation of -electrons (c) NO (d) NO– (1994)
2 2
(c) Greater stability
90. Which is the correct symbol relating the two Kekule
(d) Resonance (1998)
structures of benzene?
87. Among the following compounds (I-III) the correct
(a) (b)
order of reaction with electrophile is
(c) (d) (1993)
91. Select the true statement about benzene amongst
the following
(a) because of unsaturation benzene easily
undergoes addition
(a) I > II > III (b) I = II > III (b) there are two types of C – C bonds in benzene
(c) II > III > I (d) III < I < II (1997) molecule
88. Electrophile in the case of chlorination of benzene (c) there is cyclic delocalisation of -electrons in
in the presence of FeCl3 is benzene
(a) Cl (b) FeCl3 (d) monosubstitution of benzene gives three
(c) Cl +
(d) Cl– (1996) isomeric products. (1992)

ANSWER KEY
1. (c) 2. (b) 3. (d) 4. (c) 5. (b) 6. (b) 7. (b) 8. (d) 9. (c) 10. (c)
11. (c) 12. (b) 13. (c) 14. (d) 15. (c) 16. (d) 17. (c) 18. (c) 19. (a) 20. (c)
21. (a) 22. (a) 23. (d) 24. (d) 25. (d) 26. (a) 27. (d) 28. (b) 29. (c) 30. (b)
31. (b) 32. (c) 33. (a) 34. (a) 35. (d) 36. (d) 37. (d) 38. (c) 39. (c) 40. (d)
41. (c) 42. (a) 43. (a) 44. (c) 45. (b) 46. (c) 47. (b) 48. (c) 49. (a) 50. (b)
51. (b) 52. (c) 53. (b) 54. (b) 55. (d) 56. (b) 57. (c) 58. (a) 59. (d) 60. (a)
61. (d) 62. (c) 63. (d) 64. (a) 65. (d) 66. (c) 67. (d) 68. (a) 69. (c) 70. (b)
71. (a) 72. (d) 73. (c) 74. (c) 75. (d) 76. (b) 77. (a) 78. (c) 79. (c) 80. (a)
81. (d) 82. (a) 83. (a) 84. (a) 85. (a) 86. (a) 87. (a) 88. (c) 89. (c) 90. (d)
91. (c)

Hints & Explanations

1. (c) : Wurtz reaction is used for the preparation of Na/dry ether
Br2/hv Wurtz reaction
higher alkanes containing even number of C-atoms. 3. (d) : CH4 CH3 Br CH 3 CH3
(A)
Thus this reaction cannot be used for the preparation of (Less than 4
caron atoms)
n-heptane.
2. (b) : In chlorination of alkanes, hydrogen is replaced 4. (c) : Conformers of ethane have different dihedral
angles but same bond angle and bond lengths.
by chlorine. In neo-pentane, only one type of hydrogen
Angle of rotation or angle
is present, hence replacement of any hydrogen atom will 5. (b) :
of torsion or dihedral angle
give the same product.

neo-pentane
Hydrocarbons 105

Magnitude of torsional strain depends upon the angle of CH2 CH CH2 CH2 CHO
rotation about C—C bond. Staggered form has the least (i) O3
15. (c) :
torsional strain and the eclipsed form has the maximum + HCHO
torsional strain. So, the staggered conformation of ethane (ii) Zn/H2 O Methanal
is more stable than the eclipsed conformation.
16. (d) :
6. (b) : The anti-conformation is the most stable CH3
conformation of n-butane as in this, the bulky methyl HCl
CH3 C CH CH3 CH3 C CH2 CH3
groups are as far apart as possible thereby keeping steric
repulsion at a minimum. CH3 Cl
7. (b) : The process of cracking converts higher (A) (B)

alkanes into smaller alkanes and alkenes. This process O3 Zn/

H2O
can be used for production of natural gas.
8. (d) : The conformation (d) is most stable because of CH3 C CH3 + CH3 C H
intermolecular H-bonding. O O
9. (c) : The staggered form of ethane has the following Addition of HCl to an alkene (A) will take place according
structure and the dihedral angle is 60°, which means ‘H’ to Markownikoff’s rule.
atoms are at an angle of 60° to each other.
H2, Pd/C
H3C CH3
H 17. (c) : CH3 C CCH3
quinoline CC
H H H H
. 60° 18. (c) :
cis-2-Butene

H H
H H2 C CH 2 HBr CH3 CH 2 CH2 Elimination
10. (c) : When an aqueous solution of sodium or C Br
potassium salt of carboxylic acid is electrolysed, H2 H CCH CH 3 2
hydrocarbon is evolved at anode. HBr Elimination
CH3CH2CH2OH H3C–CH CH2
2RCOOK E  2RCOO
lectrolysis
Oxidation
 2K  
Anode Cathode Br O
At anode : 2RCOO – 2e  R – R + 2CO2
– –
HBr
Alkane
CH2 C O H2 C C OH H3C C Br
11. (c) : The branching of chain increases the octane CH3CH2CH2Br Elimination CH3CH CH2
number of a fuel. High octane number means better fuel.
12. (b) : Newman projections for n-butane are 19. (a) : Rate of free radical substitution with Br2(g)
depends upon the stability of free radical. Propenyl free
H 3C H3C H3 C
CH3 radical is allylic free radical which is more stable.
H H H CH3

H
H H H H H H H 20. (c) :
CH 3 H
staggered eclipsed skew or gauche

The staggered conformation has minimum repulsion

between the hydrogen atoms attached tetrahedrally
21. (a) :
to the two carbon atoms. Thus, it is the most stable
conformation.
13. (c) : Tetraethyl lead (C2H5)4Pb, is used as an
antiknocking agent in gasoline used for running
automobiles.
14. (d) : The reactivity of H-atom depends upon the
stability of free radicals, therefore reactivity of H-atom
follows the order : 3º > 2º > 1º.
106
(i) O3
CH3 H (d) H3C C CH CH3
3O (ii) Zn/H 2 O2
22. (a) : CH3 C CH CH2
CH3 O
CH3 2-Methyl-2-butene
CH3 CH3 OH H3 C C CH3CHO
OH
CH3 C CH CH3 CH3 C CH CH3 Acetaldehyde
CH3
CH3 CH3 Acetone
1° carbocation (Minor product)
(less stable) 26. (a) : The relative rates of hydrogenation decrease
with the increase of steric hindrance. Most stable the
OH alkene, slowly it undergoes hydrogenation to give the
OH product. Least substituted alkene is less stable and more
CH3 C CH CH 3 CH3 C CH CH3
reactive.
CH3 CH3 CH3 CH3 Order of stability is :
3° carbocation
(more stable)
Major product
R R R R R H
CC CC C C >
23. (d) : Cis-trans isomerism is exhibited by compounds R R R H R H
having C C, C N and N N groups, due to
restricted rotation around the double bond. Among
the given options, only 2-butene exhibits geometrical
isomerism.
Hence, alkene which will react faster with H2 is that
H3 C CH3 H CH3 whichRis most unstable.
C C C C R fast
H H H3C H + H /Pt R CH CH R
cis-form trans-form C C 2 2 2
24. (d) : H H
3 3 27. (d) : The formation of n-propyl bromide in presence
H of peroxide can be explained as follow :
CH3 C CH CH2 CH3 C CH CH3
H H Step 1 : Peroxide undergoes fission to give free radicals.
2° carbocation R – O – O –R 2R– O
(less stable)
Step 2 : HBr combines with free radical to form bromine
CH3 CH3 free radical.
Br
CH3 C CH2CH3 CH3 C CH2 CH3 R–O + HBr R– OH + Br
Br 3° carbocation
(more stable)
·
Step 3 : Br attacks the double bond of the alkene to form
Major product a more stable free radical.
(2-Bromo-2-methylbutane) Br
25. (d) : (a) H C CH CH CH 2
(i) O3
. . 2 (1° free radical, less stable)
CH3CH –CH
3 (ii) Zn/H2O2 CH CH CH .
CH3 3 2 + Br
CH3 –CH– CH2 Br
3-Methyl-1-butene
(2° free radical, more stable)
Step 4 : More stable free radical attacks on HBr.
CH3CHCH2Br + HBr CH3CH2CH2Br + Br
n-Propyl bromide
(i) O3 Step 5 : Br + Br Br2
(b) no reaction
(ii) Zn/H2O2
CH3 CH 3
Cyclopentane NaIO4
(i) O3 28. (b) : CH3 C CH CH3 CH3 – C O
(c) H3C CH2 C CH2 KMnO4
(ii) Zn/H2O2
CH3 CH3 COOH
2-Methyl-1-butene 29. (c) : Geometrical isomers are those isomers which
possess the same molecular and structural formula but
differ in the arrangement of atoms or groups in space due
to hindered rotation around the double bonded atoms.
Hydrocarbons 107

30. (b) : Temperature is an effective factor because at 40. (d) : C C,

different temperature it forms different products.
Al2O3, 620 K
CH3CH2OH CH2 CH2 H  bond H
–H 2O

This is intramolecular dehydration. At lower temperature, C C

 bond
intermolecular dehydration takes place between two H H
molecules of alcohol and ether will be formed.
31. (b) : Propene adds to diborane (B 2H6) giving an Restricted rotation is due to sideways overlap of two
addition product. The addition compound on oxidation p-orbitals.
gives 1-propanol. Here addition of water takes place 41. (c) :
according to anti-Markownikoff’s rule.
H3C
32. (c) : C C H (trans-2-butene)
H CH3 1, 2-Dichloroethene exhibits cis-trans (geometrical)
This is most stable as the repulsion between two methyl isomerism.
red h ot iron tu be
groups is least. 42. (a) : CH3—C  CH  873
K 
33. (a) : Due to restricted rotation about double bond,
2-butene shows geometrical isomerism. There are 21  bonds.
H3C H 43. (a) : Alkanes, alkenes and alkynes follow the
H H
C C C C following trend in their acidic behaviour :
H CH3 H C CH3 sp sp sp2 sp2 sp3 sp3
(trans) 3 (cis) HC CH > H2C CH2 > CH3— CH3
34. (a) : This is because sp-hybridised carbon is more
electronegative than sp2-hybridised carbon which is
further more electronegative than sp3-hybridised carbon.
Hence, in ethyne proton can be released more easily than
CH2OH aq. NaHCO3 CH2OH ethene and ethane.
35. (d) : CH CH2 + HOCl
2
CH2Cl CH2OH Among alkynes the order of acidity is :
Therefore, M = CH2Cl—CH2OH and HC CH > CH3—C CH > CH3—C C— CH3
R = aq. NaHCO3 This is due to +I effect of — CH3 group.
36. (d) : In this reaction, HBr undergoes heterolytic 44. (c) : In case of unsymmetrical alkynes addition of
fission as HBr  H+ + Br– H2O occurs in accordance with Markownikoff’s rule.

Br–
CH – CHBr– CH
3 3
This is an example of electrophilic addition reaction.
37. (d)
38. (c) : In case of but-2-ene (CH3 – CH CH – CH3) sp sp
both double bonded carbons are identical. Therefore, it 45. (b) : CH3 C C –
does not observe the anti-Markownikoff’s addition of Thus, pair of electrons is present in sp-hybridised orbital.
HBr.
46. (c) :
39. (c) : Reduction of non-terminal alkynes with Na in
liq. NH3 at 195 - 200 K gives trans-2-butene.
Na in liq. NH3 CH 3 H
CH3 – C C – CH3 195 – 200 K C C
H CH3
trans-But-2-ene
(Birch reduction)
108
2SO4
5 55. (d) : CH CH + H2O dil. H CH CH—OH
47. (b) : C2H2  O2   2CO2  H 2 O Acetylene
HgSO4 2
2
Both ethyne and CO2 have sp-hybridisation. CH3—C—H
sp sp sp
O
OCO HC CH Acetaldehyde

56. (b) : In alkyne, two carbon atoms constituting

48. (c) :
the triple bond are sp-hybridised.Carbon undergoes sp-
hybridisation to form two sp-hybrid orbitals. The two
2p-orbitals remain unhybridised. Hybrid orbitals form
one sigma bond while two -bonds are formed by
unhybridised orbitals.
Acetaldehyde does not give Victor Meyer test. 57. (c) : A powerful base is needed to carry out second
49. (a) : Terminal alkynes (1-butyne) react with NaNH2 dehydrohalogenation reaction e.g., hot alcoholic KOH
to form sodium acetylide and evolve hydrogen but 2- solution or alkoxide ion.
butyne do not. 58. (a) : Alkynes react with strong bases like NaNH2 to
50. (b) : CH3 – C C – CH3 form sodium acetylide derivative known as acetylides.
– +
In case of sp3 hybridised carbon, bond angle is 109° 28; H– C C– H + NaNH 2 H– C CNa + 1/2H 2
sp2 hybridised carbon, bond angle is 120° and sp 59. (d) : Shortest C– C distance (1.20 Å) is in acetylene.
hybridised carbon, bond angle is 180°.
So, only is linear.

60. (a) : H C C H

51. (b) : 


Conjugate base of the given acid : The formation of C – H bond in acetylene involves sp-
hybridised carbon atom. Since s-electrons are closer to
the nucleus than p-electrons, the electrons present in a
bond having more s-character will be more closer to the
Conjugate base of stronger acid is weaker and vice-versa. nucleus. In alkynes s character is 50%, the electrons
52. (c) : CH3 CH2 C CH + HCl constituting this bond are more strongly bonded by the
carbon nucleus. Thus, acetylenic C-atom becomes more
I
HI electronegative in comparison to sp2, sp3 and hence the
CH3 CH2 C CH2 CH3 CH2 C CH3 hydrogen atom present on carbon atom ( C – H) can
be easily removed.
Cl Cl
61. (d) : All the three reagents except ammoniacal
(B) (C)
AgNO3 reacts with 1, 2 and 4 compounds. The
According to Markownikoff’s rule, during
hydrohalogenation to unsymmetrical alkene, the compound 3 possessing the terminal alkyne only reacts
negative part of the addendum adds to less hydrogenated with ammoniacal AgNO3 and thus can be distinguished
from 1, 2 and 4 compounds.
(i.e. more substituted) carbon atom.
62. (c) : The attacking species in the reaction given
53. (b) : On ozonolysis, higher alkynes form diketones +
which are further oxidised to dicarboxylic acid. in option (c) is an electrophile i.e., Cl. Therefore, it is an
O electrophilic substitution reaction.
CH3C C–CH2CH3+ O3 CH3– C C–CH2CH3 63. (d) : Friedel–Crafts reaction :
CH(CH3 )2
O O CH3
H2O H2O2 Anhyd. AlCl3
+ CH3 CH Cl
CH3C 2CH3 Isopropyl chloride 
Benzene Cumene
O O CH3 COOH + CH3CH2COOH
Chlorobenzene, bromobenzene and chloroethene are
NaNH2
54. (b) : CH3CH2CHCl2 CH3C CH not suitable halide components as C–X bond acquires
Hydrocarbons 109

some double bond character due to resonance of lone CH3

(no substitution occurs here)
pair of electrons with -bond. Br2
2
64. (a) : Biphenyl is coplanar as all C-atoms are sp FeBr 3
hybridised. CH3
1,3-Dimethylbenzene
65. (d) : Pyrrole has maximum electron density on (m-Xylene)
2 and 5. It generally reacts with electrophiles at the C-
2 or C-5 due to the highest degree of stability of the CH3 CH3
Br
protonated intermediate.
H H
CH3 CH3
Y Y
+H Br
4 3 N
H+ N
H 4- Bromo-1,3-dimethyl 6-Bromo-1,3-dimethyl
5 2 benzene benzene
(I) (II) (major) (minor)
N1 +H
H 70. (b) : —NO2 is most deactivating due to – I and – M
H HH H
N+ Y N Y + N Y effect.
H H H 71. (a) : Nitrobenzene is strongly deactivated, hence
(III) (IV) (V)
will not undergo Friedel-Crafts reaction.
More stable ion 72. (d) : The molecules which do not satisfy Huckel rule
Attack at position 3 or 4 yields a carbocation that is a or (4n + 2)-electron rule are said to be non-aromatic.
hybrid of structures (I) and (II). Attack at position 2 or 5 The compound (d) has total 4e–. It does not follow
yields a carbocation that is a hybrid not only of structures (4n + 2) rule. So, it is non-aromatic compound.
(III) and (IV) (analogous to I and II) but also of structure 73. (c) : As the +I effect increases reactivity towards
(V). The extra stabilization conferred by (V) makes this
electrophilic reactions increases and as –I or –M effect
ion the more stable one. Also, attack at position 2 or 5 is increases, reactivity towards electrophilic reactions
faster because the developing positive charge is decreases. Thus, the order is
accommodated by three atoms of the ring instead of only
two.
+ +
66. (c) : H (from HF)
Addition reaction +
H
Friedel–Cra s
alkylation 74. (c) : The reaction of Cl2, in presence of FeCl3, with
toluene yields a ring substitution product.
67. (d) : Mechanism of nitration is : CH3 CH3 CH3
HNO3 + 2H2SO4  NO+2+ 2HSO–4+ H3O+ Cl
If a large amount of KHSO4 is added then conc. of HSO4– Cl2/FeCl3
ions increases and the reaction will be shifted in backward
Cl
direction hence, the rate of nitration will be slower. (X)
68. (a) : CHCOOH In presence of sunlight, free radical reaction takes
+9 O V2O5 , 773 K
2 2 –2CO2 , –H2O
CHCOOH place.
O
Maleic acid CH3 CH2Cl CHCl2 CCl3
Cl2 /h
CHC  Cl2 /h Cl2 /h
O
CHC
–H2 O

(Y)
O
Maleic anhydride 75. (d) : This is Friedel-Crafts alkylation.
CH3
69. (c) : — CH3 group is o,p-directing. Because of
crowding, no substitution occurs at the carbon atom AlCl3
+ CH3Cl
between the two — CH3 groups in m-xylene, even though
two — CH 3 groups activate that position. Benzene Toluene
110

Mechanism: CH 3Cl + AlCl3  AlCl4– + CH3+ substitution. While — CH3 and — OCH3 are electron-
Lewis acid Electrophile donating group which favours electrophilic substitution
CH3 in the benzene ring at ‘ortho’ and ‘para’ positions. The
CH3
+ AlCl – +I effect of — OCH3 is more than — CH3, therefore the
+ CH3 H 4 correct order for electrophilic substitution is
CF3 CH3 OCH3
Toluene
+ AlCl3 + HCl
< < <
76. (b) : (IV) (I) (II) (III)

83. (a) : In Friedel-Crafts reaction toluene is obtained

by the action of CH3Cl on benzene in presence of AlCl3.
77. (a) : Groups like, — Cl and — NO2 shows –I effect.
–I groups attached to the benzene ring decrease the CH3
electron density and hence less prone to electrophilic AlCl3
+ CH3Cl + HCl
attack. — OH not only shows –I effect but also +M
effect which predominates the –I character and electron Toluene
density is increased in the benzene ring which facilitates 84. (a) : In Friedel-Crafts reaction, an alkyl group is
electrophilic attack. introduced into the benzene ring in presence of a Lewis
78. (c) : Benzene having any activating group i.e., acid (AlCl3) catalyst. The reaction is
— OH, — R undergoes electrophilic substitution easily CH3
AlCl3
as compared to benzene itself. Thus, toluene and phenol + CH3Cl + HCl
undergo electrophilic substitution easily. Chlorine due to Benzene Toluene
–I-effect deactivates the ring. So, it is difficult to carry out 85. (a) : — OH, — Cl and — CH groups in benzene
the electrophilic substitution in chlorobenzene. Hence, 3

the order is C6H5OH > C6H5CH3 > C6H6 > C6H5Cl. are ortho, para directing groups. But among these
— OH group is strongly activating while — CH3 is weakly
79. (c) : C6H5H + H2C == CH2 activating and — Cl is deactivating. Thus, phenol will be
most easily attacked by an electrophile.
C6H5 CH2 CH
CH3 CH2 3
86. (a) : Arenes undergo electrophilic substitution
80. (a) : heat reactions and are resistant to addition reactions, due to
.
+H
delocalisation of -electrons. These are also stabilized by
Benzyl free radical
Energy resonance.
Cl 2 2Cl 87. (a) : In structure III, withdrawal of electrons by
sunlight
—NO2 causes decrease in reaction rate while in structure I,
CH2 . CH2Cl there is electron releasing effect by — OCH3 group which
+ Cl
accelerates the reaction.
The order of reactivity towards electrophile is :
NH2 NO2 I > II > III
81. (d) : 88. (c) : Cl2 + FeCl3  FeCl4– + Cl+
I III 89. (c) : Nitronium ion (NO+) is2 an electrophile that
II
— NH2 group is electron donating hence increases actually attacks the benzene ring.
electron density on ring. Benzene is also electron rich due 90. (d) : Benzene shows Kekule structures which are
to delocalisation of electrons. — NO2 group is electron resonating structures and these structures are separated
withdrawing hence, decreases electron density on ring. by a double headed arrow ().
Thus, correct order for electrophilic substitution is 91. (c) : Due to resonance all the C – C bonds in
I > II > III. the benzene possess same nature and the resonating
82. (a) : Due to –I effect of F atom, —CF3 on benzene structures are obtained because of the delocalisation of
ring, deactivates the ring and does not favour electrophilic -electrons.

