Alcohol, Phenol and Ethers 1239

20. (b) 5-10 % methyl and remaining ethanol is called methylated

spirit. It is also known as denatured alcohol because it is unfit
for drinking.
CH 2

H 2C CH–OH OH
21. (a) or

General introduction of alcohol, Phenol & Ethers H 2C CH 2

OH CH 2

23. cyclohexanol
(a) 5% aqueous solution of phenol at room temperature is called
2. (d) O2 N NO 2 as carbolic acid.
25. (b) Glycols are dihydric alcohols (having two hydroxyl groups).
Ethylene glycol is the first member of this series.
C H 2 OH
NO 2
2, 4, 6-trinitrophenol or picric acid |
CH 2 OH
4. (d) CH 2  CH  CH 2 Glycerol is trihydric alcohols. (Ethylene glycol)
| | | 26. (a) Methanol is also referred as wood alcohol or wood spirit or
OH OH OH wood naphtha as the earliest method for its preparation was by
OH destructive distillation of wood.
34. (b) Ether is basic because lone pairs of electrons are present on
CH 3 
5. (a) oxygen atom, R  O  R .


Hydroxy toluene 39. (a) Thio alcohol is known as mercaptans.

(c) % of C   100
Mass of C
6. Mass of substance

12 Preparation of alcohol, Phenol and Ethers

CCl 4   100  7.79 %
154
1. (c) Hydration of alkenes
72
C6 H 6 Cl6   100  24.74 %  
291 CH 2  CH 2  H HSO 4  CH 3  CH 2  HSO 4
24
CH 2OH  CH 2OH   100  38.70 % . CH 3  CH 2 HSO 4 2 CH 3  CH 2  OH  H 2 SO 4
H O
62 Boil
OH
Fermentation of sugars:
7. (c) OH o-dihydroxy benzene or catechol. C12 H 22 O11  H 2 O   C 6 H 12 O 6  C 6 H 12 O 6
Invertase

Glucose Fructose

CH 2  OH C 6 H 12 O 6  2C 2 H 5 OH
Zymase
 2CO 2
| Glucose or Fructose
8. (b) CH  OH
| 2. (c) CH 2  CH 2   CH 3  CH 2  HSO 4 
H 2 SO 4
 
Hydrolysis

CH 2  OH
CH 3 CH 2  OH  H 2 SO 4
one secondary and two primary alcoholic groups.
11. (b) Carbinol is CH 3 OH (Methanol). 3. (b) Hydroboration oxidation (Industrial preparation of alcohol)
1
12. (c) – OH group is attached to primary carbon. 3 CH 3 CH  CH 2  B2 H 6  (CH 3 CH 2CH 3 )3 B
Dry

OH 2 ether

13. (c) (CH 3 CH 2CH 3 )3 B   3CH 3CH 2CH 2  OH

H 2 O2

O2 N NO 2
4. (c) CH 2  CH 2  CH 3 MgI  CH 2  CH 2 
| |
O CH OMgI
3
NO 2 I
Picricacid)
acidor
is 2,
phenolic while others are non phenolic. CH 3  CH 2  CH 2  OH  Mg
(Picric 4, 6-trinitrophenol Propyl alcohol OH
15. (c) Butanal CH 3  CH 2  CH 2  CHO , an aliphatic aldehyde.
5. (d) Starch  Alcohol
Enzymes
OH
6. (c) Coconut oil + Alkali  Soap + Glycerol
It is a saponification reaction.
16. (b) 7. (c) C 6 H 12 O 6   2C 2 H 5 OH  2CO 2
Zymase

Glucose or Fructose Ethyl alcohol

Cyclohexanol is a secondary alcohol because  OH group is CH 3 CH 2 Cl

linked to 2 o carbon.
8. (d) 
Cl 2
18. (b) C2 H 5 OH and CH 3  O  CH 3 are isomers. Light / heat

Benzyl chloride
 1240 Alcohol, Phenol and Ethers
CH 2  OH 24. (c) C12 H 22 O11  H 2O   2C6 H12 O6 .
Maltase

Maltose (from yeast) Glucose


 aq . NaOH
 NaCl 26. (d) Grignard reagent reacts with compounds containing multiple
bonds like
Benzyl alcohol C  O, C  S, CN.
28. (d) Acetone reacts with Grignard’s reagent to give tertiary alcohol.
9. (a) 2(C 6 H 10 O 5 )n  nH 2 O 
Diastase
n (C12 H 22 O11 )
Starch (from germinated barley) Maltose (CH 3 ) 2 C  O  CH 3 MgBr   (CH 3 ) 3 C  OH
H 2O

C12 H 22 O11  H 2 O 

 2 C 6 H 12 O 6Maltase ter- butyl alcohol
(from yeast) Glucose
29. (b) C 2 H 5 MgBr  H 2 C  CH 2  H 2O

C 6 H 12 O 6   2C 2 H 5 OH  2CO 2
Zymase
(from yeast) O
10. (b)
N  N  Cl OH C2 H 5 CH 2 CH 2 OH  MgBr(OH )
( A)
 SO Na n - butyl alcohol
11. (c) + H 2 O  + N 2  HCl 3 OH

30. (a)  

NaOH
12. (c) CH 3 COOH  4 H   CH 3 CH 2OH  H 2O
LiAlH4
H

/ H 2O

H Phenol
13. (b) C  O   CH 2  O  MgI 
CH 3 MgI
 
Hydrolysis
H | N = N – Cl OH
CH 3
I 31. (b)  H 2O 
Boil
 N 2  HCl
CH 3  CH 2  OH  Mg
OH
Phenol
H
CHO CHO CH 2OH COONa 32. (b) C  O  C 2 H 5 MgI  CH 2  O  MgI
H |
C2 H 5
14. (b) +  
conc.
+
NaOH I
   C2 H5  CH 2  OH or C 3 H 7 OH  Mg
Hydrolysis

N  N  Cl OH OH
Br
35. (d) RMgBr O2  R  OMgBr   R  OH  Mg
hydrolysis
Grignard Alcohol OH
15. (d) + H 2O 
 dil.
 N 2  HCl reagent
H 2 SO 4
39. (b) C6 H12 O6   2C2 H 5 OH  2CO 2
Zymase

Glucose
16. (c) C2 H5 ONa  IC2 H5  C2 H5 OC2 H5  NaI
OH OH During fermentation CO 2 gas is eliminated.
40. (c) C2 H5  NH 2  HNO2  C2 H5 OH  N 2  H 2O
17. (b)  CHCl 3  3 NaOH 
 3 NaCl  2 H 2O
CHO CH 2  OH

 
LiAlH
41. (b) 4

18. (c) HCHO  HCHO   CH 3 OH 

Conc. KOH
HCOOK
Methyl alcohol Potassium formate
Benzyldehyde Benzyl alcohol
It is cannizzaro’s reaction.
CuO  ZnO Cr2 O 3
19. (d) Alcohol Benzene  Soluble 42. (a) CO  H 2  CH 3 OH
(dry) 573 K , 200 atm Methanol

(Alcohol) R  OH  Na  R  ONa  H 2 CH 3
CH 3  CH  C  H 2 O 2 
H SO 4
43. (a)
21. (c) CO  H 2  H 2  CH 3 OH Cr2 O 2 / ZnO CH 3 Markowniko ff rule
  672 K , 200 atm 2 methyl 2 butene
water gas
CH 3
O O CH 3  CH 2  C
|| || | CH 3
C C OH
23. (c) O  
Conc .
O + H 2O 2 methyl butan - 2 - ol
C H 2 SO 4 C
|| OH
O |
H H CH 3 CH  CH 2  H 2 O   CH 3  CH  CH 3
H 2 SO 4

propene Markowniko ff rule propene - 2-ol

44. (c) CH 3 CONa  Br  CH 3  CH 3  O  CH 3  NaBr

OH OH Dimethyl ether
(symmetrical ether)
Phenolphthalein
OH OH
 Alcohol, Phenol and Ethers 1241
CH 3 CH 3    H 2 C  CH 2  NaCl  CO 2
[ NaHCO 3 ]
| | | |
CH 3  C  O  Na  CH 3 Br  CH 3  C  OCH 3  NaBr OH OH
| | (Ethylene glycol)
CH 3 CH 3
Methyl ter- butyl ether CH 3
(unsymmetr ical ether) |

OH 57. (b) CH 3  C  O  Na  Cl  CH 3 
O-R |
CH 3
 RX    HX
Alkali 2, 2 dimethyl sodium ethoxide
45. (c)
CH 3
|
46. (b) C 2 H 5 Br  C 2 H 5 ONa   C 2 H 5  O  C 2 H 5
 NaBr
CH 3  C  O  CH 3  NaCl
Sod. ethaoxide diethyl ether |
CH 3
47. (c) RX  RONa  R  O  R  NaX Methyl - t butyl ether
Ether
It is a Williamson’s synthesis reaction. O O  MgI
|| |
48. (b) Williamson’s synthesis –
58. (c) CH 3  C  OC 2 H 5  CH 3 MgI  CH 3  C  OC 2 H 5
CH 3  CH 2  ONa  Cl  CH 2  CH 3  Ethyl methyl ester |
CH 3
CH 3  CH 2  O  CH 2  CH 3
49. (a) Dehydration of alcohols gives ethers. OH Br
|  Mg
50. (b) 2C 2 H 5 Br  Ag 2 O  C 2 H 5  O  C 2 H 5  2 AgBr 
 CH 3  C  O C 2 H 5 
Hydrolysis OH
Dry |
CH 3
If we take moist Ag2O then alcohol is formed
CH 3
Ag2O  H 2O  2 AgOH C  O  C 2 H 5 OH
CH 3
C2 H5 Br  AgOH  C2 H5 OH  AgBr
Ethyl alcohol
Acetone

51. (d) CH 3 OCH 3   CH 3 OCH 2 Cl

Cl 2 / hv 59. (b) NaBH 4 and LiAlH4 attacks only carbonyl group and
Methoxymet hane  Chlorodime thyl ether reduce it into alcohol group. They do not attack on double
(Lower ether)
bond.
   CH 3 OCH 2 CH 3
CH 3 MgBr
C6 H 5  CH  CHCHO  
4 NaBH
 MgBr(Cl ) Methoxyeth ane
(Higher ether) cinnamic aldehyde

O CH 3 C6 H 5  CH  CH .CH 2OH
|| | cinnamic alcohol
52. (a) CH 3  C  Br   CH 3  C  OH
(i) Excess- CH 3 MgI
60. (b,c) CH 2  CH 2  H 2 O  [O]  CH 2  CH 2
alk. KMnO 4
Acetyl bromide (ii)Saturated NH 4 Cl |
CH 3 | |
2 - methyl 2- propanol OH OH
Glycol
53. (d) When chlorine is passed in boiling toluene, substitution inside
chain takes place and benzyl chloride is obtained which on CH 2  CH 2  H 2 O 
 CH 3  CH 2  OH
Conc. H 2 SO 4

hydrolysis give benzyl alcohol. Ethene Ethanol

CH CH Cl CH OH 61. (a) Wood 

 Wood gas  Tar  Charcoal
Destructive
3 2 2
distillation

Cl2 H.OH  CH 3 OH  CH 3 COOH

+ HCl (wood alcohol) (vinegar)
CH NH 2 2
CH OH2

toluene Benzyl chloride Benzyl alcohol

54. (a) 2C 6 H 5 CHO  NaOH  C6 H 5 CH 2 OH  C6 H 5 COONa
Benzaldehyde (Benzyl alcohol)
62. (d)  HNO 2  + N 2  H 2O
55. (c) Ethanal with CH 3 MgBr gives propanol-2 (after hydrolysis)
and with C2 H 5 OH , it gives acetal. 64. (a) C 6 H 6 O   CH 3 I  C 6 Hl5 OCH 3  I 
OMgBr 
CH 3 CHO  CH 3 MgBr  CH 3 CH 

H

Acetaldehyde CH 3
OH Properties of alcohol, Phenol and Ethers
CH 3 CH
CH 3
2 propanol 1. (c) CH 3  OH  CH 3 Mg  X  CH 4  CH 3O  Mg  X
OC 2 H 5 4. (c) C 2 H 5 OH    CHI 3 (yellowppt)
NaOH / I2
CH 3 CHO  2C 2 H 5 OH   CH 3 CH
dry HCl
Iodoform test
OC 2 H 5
Acetal CH 3 OH    No ppt
NaOH / I2

56. (a) H 2 C  CH 2  HOCl  H 2 C  CH 2 OH 5. (a) CH 3  CH 2  CH 2  OH    CH 3 CH 2COOH

Oxidation
Ethylene (hypochloro us ) |
X Y
Cl
Ethylene chlorohydr ine Since on oxidation same no. of carbon atoms are obtained in as
therefore alcohol is primary

NH 2
N C

(A)
 1242 Alcohol, Phenol and Ethers
8. (b) + 3 KOH  CHCl 3  + 3 KCl  3 H 2O
(Y )
N N OH

C 2 H 5 OH  Cl 2   CH 3 CHO 
Ca (OH )2

Cl 2
Anhyd . ZnCl  HCl
(Z) Acetaldehyde 25. (c) (CH 3 )3 C  OH  HCl 2
CCl 3 CHO   CHCl 3
Ca (OH )2 (CH 3 )3 C  Cl  H 2 O 3 o reacts immediately
Chloral chloroform
Anhyd . ZnCl  HCl
OH
(Y )
(CH 3 )3 CH  OH  HCl 2
NO 2 NO 2 (CH 3 )2 CH  Cl  H 2O 2 o reacts after 5 min.
Conc. HNO 3
2,4,6-trinitrophenol Anhyd . ZnCl  HCl
OH Conc. H 2 SO 4 (TNP) CH 3 CH 2CH 2  OH  HCl 2 

12. (b)
CH 3 CH 2 CH 2  Cl  H 2 O 1 o reacts only on heating.
NO 2
26. (b) C2 H 5 OH  R  Mg  X  RH  C2 H 5 OMgX
OH OH Alkane
NO 2 C3 H7 OH  R  Mg  X  RH  C3 H7 OMgX
dil.HNO 3
+ O
|| H OH
30. (d) C +
OH OH OH NO 2 OH
conc. H SO 4 O
NO 2 2 
 C H OH
14. (c) || O
||
O C
NO 2 Phthalic
NO 2 anhydride Phenol O
Cl Increasing acidic character
C
15. (c) N  N  Cl  H NH 2


H
 N N NO 2  HCl
273 K
OH OH
p  Aminoazobe nzene (yellow ppt.)
CH 2 OH Phenolphthalein
CH 2  OH CH 2  I CH 2 33. (c) |  HIO4  2 HCHO  HIO3  H 2 O
| | ||
P4  I 2
16. (b) CH  OH 
 CH  I  CH
I CH 2 OH
| Small amount | 2 |
CH 2 OH CH 2  I CH 2  I
Unstable Allyl iodide 35. (b) CH 2 OH CH 2 I
|  PI3  |  CH 2  CH 2
 I2
CH 2  OH CH 2  I CH 2 OH CH 2 I
| |
18. (c) C H  OH   CH  I 
3 HI
 36. (a) R  OH  (NH 4 )2 Ce (NO 3 )6  Ce (NO 3 )6 (ROH )9  2 N  14 NO 3
I3 H 2O
| | 2 alcohol Cerric amm. nitrate yellow ppt.
CH 2  OH CH 2  I
37. (d) C2 H 5  O  C2 H 5  O2  CH 3  CH (OOH)  O  C2 H 5
hv
o
CH 2 CH 3 CH 3 25 C
|| || |
CH 
 CH  I 
HI
 CH
I
38. (a) H 2 SO 4  H  HSO 4 
| | 2 ||
CH 2  I CH 2  I CH 2 
C 2 H 5 OH  H    C 2 H 5  O  H
Protonatio n
19. (d) HOOC  COOH  HCOOH  CO 2 Glycerol
of alcohol 
Decarboxylation
H
HCOOH  Fehling solution Cu 2O  CO 2  H 2O OH OH Protonated alcohol

Red ppt. Nitro group is electron with-

NO 2 drawing. Hence, increases
21. (b) Glycerol undergoes extensive hydrogen bonding due to the 39. (c)
presence of 3 –OH groups. As a result the glycerol molecules acidic nature.
are highly associated and thus it has high viscosity.
Al2 CO 3
CH 2  OH CH 2 43. (d) CH 3 CH 2 OH 
 CH 2  CH 2  H 2 O
(X )

| || 350 o C
22. (b) CH  OH   CH  2 H 2 O
conc.
| H 2 SO 4 | ONa OCO 2 Na OH
CH 2  OH CHO
Acrolein
COONa
44. (a)   
CO 2 , 400 K
 
Rearr.
23. (a) CH 3  CH  CH 3    CH 3  C  CH 3
Oxidation
3 7 atm
| KMnO 4 ||
OH O
Acetone o
C 2 H 5 HSO 4 
110 C
H 2O
OH 
24. (b) N  Cl  H OH  Ethyl hydrogen sulphate

o
137 C
C 2 H 5 OH
H SO2 4
C2 H 5  O  C2 H 5  H 2 O
Diethyl Ether

p-hydroxyazobenzene o
C2 H 4  H 2 O
170 C

Ethene
 Alcohol, Phenol and Ethers 1243
61. (d) Due to hydrogen bonding.
45. (c) 62. (a) C2 H 5 OH 
Pt
CH 3 CHO
air

63. (c) CH 3  CH 2  OH   CH 2  CH 2  H 2O

Conc. H 2 SO 4
170 o C
CH 3 66. (b) Tertiary alcohol readily reacts with halogen acid
|   
CH 3 CH 3
46. (b) CH 3  C   CH 3  CH  CH 3 CH 2  CH 3
|  |
CH 3 Methyl CH 3  C  OH  CH 3  C   OH 
3 o 2o 1o Carbonium ion
 |

CH 3 CH 3
47. (c) Alcohols having less number of carbon atoms are more soluble
in water. Presence of 3 alkyl group increases electron density on
48. (a) C2 H5 OH  Na  C2 H5 ONa 3 o carbon atom. Hence OH group is easily removed. After
the removal of OH group 3 o carbonium ion is formed
2C 2 H 5 OH   C 2 H 5  O  C 2 H 5  H 2 O
Conc.
which is most stable
H 2 SO 4
(d) CH 3 CH 2CH 2OH   CH 3 CH  CH 2
conc. H 2 SO 4
Cl Cl 67.
160 180 o C
| |
Dark
CH 3  CH  O  CH  CH 3 
 CH 3  CH  CH 2 
Br2
  CH 3  C  CH
Alc . KOH
|
--dichlorodiethyl ether | Propyne
Br Br
50. (a) Cl
C2 H 5 O  C2 H 5 68. (b) Lower alcohols are soluble in all solvents.
2

O
||

Light
CCl 3  CCl 2  O  CCl 2  CCl 3 69. (c) CH 3  CH  CH 2  CH 3 
 CH 3  C  CH 2 CH 3 [O ]
|
C 2 H 5 OH  PCl5  C 2 H 5 Cl  POCl3  HCl
Perchlorod iethyl ether
51. (d) OH
(A) (B) 70. (b) Due to the resonance stabilisation of phenoxide ion.
C 2 H 5 Cl  KCN  C 2 H 5 CN  KCl 73. (a) R  CH 2  CH 2  OH   
Conc. H 2 SO 4
o
1 o alcohol 170 C
(B) Hydrolysis
R  CH  CH 2  H 2O
C2 H 5  COOH Alkene

OH OH OH OH 74. (a) R - CH 2 OH 

 R  CHO  H 2
Cu

1o alcohol
52. (c) R  CH  R 
 R  C R  H2
Cu
| ||
OH O
NO 2 2 o alcohol
CH 3
NO 2
CH 3 OH 2 2 
  HCOOH
K Cr O
75. (c) 7
53. (b) Higher alcohols are stronger and have bitter taste. H 2 SO 4

54. (c) Order of reactivity with alkali metal (e.g.-Sodium) follows the
CH 3 CH 2OH 2 2 
  CH 3 COOH
K Cr O
76. (a) 7
order 1o  2o  3 o .
77. (a) Lucas test is used for the distinction of primary secondary and
1 tertiary alcohols.
56. (c) CH 3 OH  Na  CH 3 ONa  H2
1 mole 1 mole 2
1 / 2 mole
( 23 gms) OH NH 2
57. (d) 3CH 3CH 2CH 2CH 2  OH  PBr3 
ZnCl
3CH 3 CH 2 CH 2 CH 2  Br  H 3 PO3 78. (a) + NH 3 
2
 + H 2O
o
300 C
58. (a) CH 3OH  Cl2  No reaction 80. (a) A compound that undergoes bromination easily is phenol. Due
to presence of – OH group the ring becomes much more active
CH 3 OH  HCl   CH 3 Cl  H 2O
ZnCl 2
in substitution reactions. The bromination occurs due to
3CH 3OH  PCl3  3CH 3Cl  H 3 PO3 availability of electrons on ortho and para position.
CH 3OH  PCl5  CH 3Cl  POCl3  HCl 81. (c) o-Nitrophenol has intramolecular H-bonding.
59. (d) CH 3  CH  CH 3 
 CH 3  C  CH 3 [O ]
84. (b) C2 H 5 OH gives iodoform test having -hydrogen atom while
| ||
OH O CH 3 OH does not give due to the absence of -hydrogen
atom.
OH OH
85. (c) Phenol has higher boiling point than toluene because of
Br hydrogen bonding.
Br
Br water
60. (c) 2
 87. (b) CH 3  CH  CH 2  aq. KOH  CH 3  CH 2  CH 2OH
Propene  1 Propanol  1
Phenol
Br 88. (d) C2 H 5 OH  PCl5  C2 H 5 Cl   C2 H 5 CN
KCN

2,4,6 tribromophenol
or white ppt. HCl / H2O

C6 H 5 COOH
 1244 Alcohol, Phenol and Ethers

 3Br2  
water
 3 HBr

In aqueous solution phenol ionizes to give phenoxide ion. Due to

89. (b) LiAlH4 + ether, is reducing agent. the presence of negative charge on oxygen the benzene ring is
OH highly activated and hence trisubstituted product is obtained.
NH 2
105. (d) C 2 H 5 OH   CH 3 COOH
CrO 3

Ethyl alcohol Aceticacid

97. (b)  NH 3  
ZnCl 2
 H 2O
107. (d) C 2 H 5 OH 
 C 2 H 4  H 2 O
Conc . H 2 SO 4

Aniline Ethanol 170 o C Ethane

  
         
: O H O H O H O H O H     O H     O  H

98. (a) .. .. 108. (b)

Oxygen atom of OH group acquires positive

.. charge. OH O
H H
| | 109. (a)  + H
H  C  OH HC
| ||
99. (c) HO  C  H  
4

KHSO
C  Phenol Phenoxide ion
| ||
H  C H C H 110. (c) (a) CH 3  CH  CH 3    CH 3  C  CH 3
Oxidation
| | ||
|
OH OH OH O
Glycerol Unstable
Conc . H 2 SO 4
(b) CH 3  CH 2  OH    CH 2  CH 2  H 2 O
H o
180 C
|
HC CH
2 (d) 2CH 3CH 2OH  2 Na  2CH 3  CH 2  ONa  H 2
|| ||
CH or CH 112. (b) Carbylamine reaction
|| | 
C H CHO CHCl 3  CH 3 NH 2  3 KOH  CH 3 N  C  3 KCl  3 H 2 O
alc. Methyl
|| Acrolein
isocyanide
O
113. (a) Secondary alcohol on dehydrogenation gives acetone
K 2 Cr2 O7
100. (d) CH 3  CH  CH 3  CH 3  C  CH 3
|
H 2 SO 4
|| CH 3  CH  CH 3 
 CH 3  C  CH 3  H 2
Cu
300 0 C
OH O | ||
OH O
  CHI 3  CH 3 COONa
NaOH
114. (a) CH 3  C H  CH 3  CH 3  C  CH 3
[O ]
I2 Yellow ppt | ||
OH OH O
OH
NO 2 118. (d) C2 H 5 OH  [O]  CH 3 CHO  CH 3 COOH .
O2 N OH
101. (d) conc. HNO 3  H 2 SO 4
OH
(conc.) OH

 
POCl
119. (a) + 3
H 2O
NO 2 COOH COOC6 H 5
Picric acid Salicylic acid Phenol Salol
102. (c) Phenol is weaker acid than carbonic acid
Phenyl salicylate
C6 H 5 OH H 2 CO 3 CH 3 COOH
OH OH OH
Ka  10  8  10 10 , Ka  10 7 , Ka  10  5
103. (a) OH OH OH 120. (c) (i)  Br2 
CS 2 Br + o- and p-
bromophenol
Br Phenol
104. (b)  Br2 
CS 2
+
Br
o -bromophenol OH OH
Br
p -bromophonol Br Br
In presence of non-polar solvent (CS 2 ) the ionization of
phenol is suppressed. The ring is slightly activated and hence (ii)  3 Br2  + 3HBr
(aq )
mono substitution occurs.
Phenol
On the other hand with Br2 water phenol forms 2,4,6- Br
tribromo phenol. 2, 4, 6-tribromophenol
OH In aq. solution phenol ionize to give phenoxide in which highly
OH activates benzene ring and give trisubstituted product while in
Br Br presence of CS 2 an inert solvent phenol is unable to ionize

Br
 Alcohol, Phenol and Ethers 1245
due to which benzene ring is slightly activated. Hence, 138. (d) 

Zn
   
Conc. H 2 SO 4
monosubstituted product is obtained. Distillation Conc. HNO 3

122. (d) Traces of water from ethanol is removed by reacting with Mg

metal. NO 2 NH — NH
CH 2  OH
| COOH o


Zn
123. (a) CH  OH  |   CH 2  CH  CH 2  OH
260 C NaOH
| COOH Allylalcohol
CH 2  OH Nitrobenzene Hydrazobenzene
Glycerol OH OH
COOH
Al 2 O 3 140. (b) + CCl 4  4 KOH  + 4 KCl  2 H 2O
C2 H5 OC2 H5  H 2O
Diethyl ether
125. (c) 250 o C Salicylic acid
C 2 H 5 OH
141. (a) C 6 H 12 O 6   2C 2 H 5 OH  2CO 2
Zymase
Al 2 O 3 Glucose Ethyl alcohol
C2 H 4  H 2 O
144. (a) C2 H 5 OH  NH 3 
 C2 H 5 NH 2  H 2OAl2 O3
C Ethene
250 o NaOH
126. (b) CH 3  CH  OH   CHI 3 1
I2 Yellow ppt 145. (b) CH 3 OH  O2   HCHO  H 2O
Cu
2
146. (a) CH 3 COOH  C2 H 5 OH  CH 3 COOC 2 H 5  H 2O
Ethyl acetate
1-phenyl ethanol
147. (a) CH 3 CH 2OH  CH 3 CHO  CH 3 COOH
Oxi. Oxi.
Iodoform test is given by compounds in which CH 3  CH  o
| 1 alcohol Ammonical
A
OH AgNO3
or CH 3  CH  group is present.
OH || OH Silver Mirror
O
Br 150. (b) CH 3 CH 2  OH  HO  CH 2  CH 3 2 
4
 Conc. H SO
140 o C
CH 3 CH 2  O  CH 2  CH 3  H 2O
127. (c)  3Br2  3 HBr Diethyl ether
Br   
   
: O H O H O H O H
1 mole 3 moles 1 mole ..
94 grams of phenol reacts with 480 gms. of Br 2 . 151. (b) ..

480 Rate of electrophillic substitution reaction. . in phenol is faster

2 gm. of phenol —  2  10.22 gms. than in benzene because presence of  OH group increases
94
electron density at o- and p- positions.
128. (b) 2C2 H5 OH  2 Na  2C2 H5 ONa  H 2 OH OH
OH
130. (a) CH 3 COOH  CH 3 OH  CH 3 COOCH 3  H 2 O
Esterification 152. (b) + HNO 3  NO 2 +
(dil)
131. (b) CH 3 OH has highest boiling point because of hydrogen
bonding.
NO
H O
2

O OH
132. (b) H C CH OH o- and p- nitrophenol
OH O
Br Br
Formic acid forms dimer due to which strangth of H  bond 153. (b)  3Br2  + 3HBr
increases Hence, boiling point increases.
133. (c) Lower members are soluble in water and solubility decreases
with increasing molecular mass because hydrophobic character
Br
increases. 2,4,6 – tribromophenol
155. (b) Secondary alcohol on dehydrogenation gives acetone
135. (d) Alcohols can not be dried using anhydrous CaCl2 because it CH 3  CH  CH 3 
 CH 3  C  CH 3  H 2
Cu

| 300 0 C ||
forms an addition compound CaCl2 .4 CH 3 OH .
OH O
CH 3
156. (c) C 2 H 5 OH    CHI 3
NaOH / I2

137. (b) Presence of methyl group increases electron density CH 3 COCH 3    CHI 3
NaOH / I2

at o- and p- positions. Hence, it undergoes nitration

readily. CH 3 OH    No reaction.
NaOH / I2

157. (d) 2,4,6 Trinitro toulene (TNT) CH 3

OH
O2 N NO 2

NO 2
 1246 Alcohol, Phenol and Ethers

177. (c)  CH 2 N 2  
HBF4
N 2

180. (c) Alcohol is soluble in water due to H-bonding

CH 2  OH CH 2  ONO 2
| |      
159. (c) CH  OH  3 HNO 3 
2

4
 CH  ONO 2  3 H 2 O
Conc. H SO
O  H     O  H    O  H
| H 2 SO 4 | | | |

CH 2  OH CH 2  ONO 2 R H R
Glycerol trinitrate Alcohol Water

CH 2  OH CH 2  O  CO  COOH 183. (c) CH 3CH 2  OH  2Cl2  CCl 3  CHO

| COOH o |
160. (a) CH  OH  |   CH  OH
110 C
  Oxidation will occur with chlorination of methyl group.
 H 2O  CO
| COOH | 2
(d) CH 3 CHO 
CH 2  OH CH 2  OH 185.  CHI 3
NaOH/I 2

Glycerol mono - oxolate

CH 3 CH 2 OH    CHI 3
NaOH / I2
Yellow
CH 2  O  CO  H CH 2  OH ppt.
| | CH 3  CH  CH 3   
NaOH / I2
CHI 3
CH  OH    CH  OH
Hydrolysis |
| | OH
CH 2  OH CH 2  OH
Glycerol mono - formate  C6 H 5  CH 2  OH    No yellow ppt.
NaOH / I2

HCOOH 186. (c) Benzyl alcohol and cyclohexanol are not acidic while phenol and
Formic acid
m-chlorophenol are acidic due to presence of electron
163. (b) C 2 H 5 OH  CH 3 COOH  
H 2 SO 4
withdrawing groups like  NO 2 ,  Cl,  CN increases the
Esterification
acidic character of phenols. Hence, m-chlorophenol is more
CH 3 COOC 2 H 5  H 2 O
Ethyl acetate
acidic than phenol.
187. (b) Three, these are
OH CH 3CH 2OCH 2CH 3 (I), CH 3OCH 2CH 2CH 3 (II)
and CH 3OCH (CH 3 )2 (III). Here I and II, I and III
165. (a)  Zn   
Distillation
+ ZnO. are pairs of metamers.
189. (c) CH 3 OCH 3 and C2 H 5 OCH 3 are gases while C2 H 5 OC2 H 5
     
166. (b) Hydrogen bonding : O  H .... O  H ..... O  H (b.p. 308 K) is low boiling liquid.
  
R H R 190. (a) C2 H 5 OC2 H 5    2C2 H 5 I 
Red P / HI
  2C2 H 6
Red P / HI

Alcohol Water Alcohol Cleavage of Reduction Ethane

ethers
CH 2 CH 2 191. (d) C2 H 5 OC2 H 5  O2  CH 3  CH  O  C2 H 5
|
HO OH Fuming
167. (c) +  O  OH
HO OH H 2 SO 4 Ether peroxide

CH 2 CH 2 192. (a) C 2 H 5 OC 2 H 5  HI  C 2 H 5 OH  C 2 H 5 I
Ethylene glycol
O – CH2 5 OH
CH 2 CH 2
O O  2 H 2O
193. (a)  HBr   C2 H 5 Br
CH 2 CH 2
168. (b) Tertiary carbonium ion is the most stable and it will be given R OH
196. (d) R  C  O  R OH  
Dry HCl
C
by dehydration of tertiary alcohol. | H OR 
169. (d) CH 3 CH 2 OH    CH 3 CH 2 O   H 
Heterolytic
H
bond fission Dry HCl ROH
170. (b) C 2 H 5 OH is soluble in water due to H-bonding.
173. (b) When ethanol dissolves in water then emission of heat and R OR 
C
contraction in volume. H OR 
175. (a) Azeotropic distillation method – Acetal
Rectified spirit + Benzene + water 198. (b) CH 3  O  CH 3  2 HI  2CH 3 I  H 2 O
 Fractional distillation 199. (b) Only alkyl aryl ethers e.g., C6 H 5 OCH 3 undergoes
First fraction at 331.8 K is ternary azeotrope electrophilic substitution reactions.
( H 2 O 7.4% + Benzene 74% + alcohol 18.5%) 200. (a) CH 3COCl  C2 H5 O  C2 H5  No reaction
Second fraction 341.2 K is a binary azeotrope O – CH 3 OH
(Benzene 67.7% + Alcohol 32.2%)
Last fraction at 351K is absolute alcohol. 201. (b)  HI  
Heat
 CH 3 I
Br
176. (a) CH 3  O  H  C 2 H 5 MgBr  C 2 H 6  Mg R ..
BF3
Methyl alcohol Ethyl magnesium
OCH 3
Ethane
202. (c) R  O  R   O :  BF3
bromide
R
Etherate
OH O  CH 3

Anisole
 Alcohol, Phenol and Ethers 1247
203. (d) Due to inter-molecular hydrogen bonding in alcohols boiling
point of alcohols is much higher than ether.
205. (b) CH 3  OCH 3 does not have replaceable H  atom.
CH 3 CH 2 OH
| COOH |
206. (a) CH 3  C  O  CH 3  H 2  CH 3 I  (CH 3 )3 COH 215. (a) |  CHOH  
 HCOOH  CO 2 
380 K
| | Formic acid
COOH CH 2 OH
CH 3 oxalic acid
Glycerol
CH 3 CH (OH )CH 2 CH 3   
Conc. H SO
207. (b) 2 4
CH 2 OH CH 2 OCO CH 2
CH 3 CH  CHCH 3 COOH | | | ||
 2 CO 2
(C 4 H 8 )
|  CHOH  CHO CO  CH
| | |
COOH CH 2 OH CH 2 OH CH 2 OH
CH 3 CHOHCH 2 CH 3  CH 3 COCH 2 CH 3
[O ]
oxalic acid
Glycerol Dioxalin Allylalcohol
2  Butanol Butanone
Butanone gives both an oxime and positive iodoform test, Thus at 530 K allyl alcohol is formed.
therefore, the original compound is 2-butanol. CH 2OH
208. (b) CH 2 OH  2 PCl5  CH 2 Cl  2 POCl3  2 HCl 216. (c) | anh. ZnCl2

 H 2O
 CH 3CHO
| | CH 2OH Acetaldehyde
CH 2 OH CH 2 Cl 217. (d) Ethyl alcohol give positive iodoform test (i.e. yellow ppt. with
Ethylene glycol 1, 2 dichloroethane
I 2 and NaOH)
209. (b) C2 H 5 OH (ethanol) is a very weak acid hence it does not react
with NaOH. However it reacts with metallic sodium. CH 3 CH 2 OH  4 I 2  6 NaOH 
210. (b) Methanol has high boiling point than methyl thiol because CHI 3  5 NaI  CH 3 COONa  3 H 2 O
there us intermolecular hydrogen bonding in methanol and no yellow ppt.
hydrogen bonding in methyl thiol. 218. (d) Tertiary alcohols react fastest with hydrogen halides 2 methyl
O O propan-2-ol is a tertiary alcohol.
|| || 219. (a) When benzoic acid reacts with ethyl alcohol in the presence of
CH 2 OH CH 2 O  C  C OH sulphuric acid ethyl benzoate is formed. This is known as
| COOH 110 C
|
esterification.
211. (a) CHOH  |   C HOH
| COOH | C 6 H 5 COOH  C 2 H 5 OH  
H 2 SO 4
CH 2 OH oxalic acid CH 2 OH Benzoic acid Ethyl alcohol
Glycerol Glycerol acid oxalate
C 6 H 5 COOC 2 H 5  H 2 O
O Ethyl benzoate water
||
CH 2 O  C  H CH 3
|  
 CO 2
 
 C HOH 220. (a) Ph Mg Br  H  O  C  CH 3 
| Phenyl magnesium
CH 2 OH bromide CH 3
Glycerol monoformat e CH 3
212. (a) Formation of a yellow precipitate on heating a compound with
an alkaline solution of iodine is known as iodoform reaction.
Ph  H  CH 3  C  OMgBr
Methyl alcohol does not respond to this test. Iodoform test is CH 3
exhibited by ethyl alcohol, acetaldehyde, acetone, methyl ketone
221. (b) Mg  CH 3 I   CH 3 MgI
Dry ether
and those alcohols which possess CH 3 CH (OH )  group.
213. (b) In friedal craft acylation, aromatic compounds such as benzene, 222. (a) Ethyl alcohol on dehydration with conc. H 2 SO 4 at 170°C gives
phenol etc. undergo acylation with CH 3 COCl in the ethylene.
170 C
presence of anhydrous AlCl3 and gives ortho and para CH 3 CH 2 OH   CH 2  CH 2  H 2 O
Ethyl alcohol conc. H 2 SO 4 Ethylene
derivatives. Intermediate is CH 3 C   O (acylium ion) of this OH
|
reaction. 223. (d) CH 3  CH 2  CH  CH 3  
Dehydratio n
OH OH OH 2 butanol
COCH 3
CH 3  CH 2  CH  CH 2  CH 3  CH  CH  CH 3
+ CH3COCl  
3 AlCl
+ 1 butene (Major product) 2 butene

Acetyl 224. (b) Fats are esters of higher fatty acids with glycerol, hence on
Phenol chloride o-acetyl phenol alkaline hydrolysis they give back glycerol and sodium or
COCH 3 potassium salt of acid (this is called soap).
OH p-acetyl
CH 2OCOR CH 2OH
phenol | |
CHOCOR  3 NaOH  CHOH  3 RCOONa
+ CH3Cl and + CH3Cl | | (Soap)
In fact denotes friedel craft alkylation. CH 2OCOR CH 2OH
214. (a) This reaction is known as Reimer Tiemann reaction. Fat

OH O Na
– + OH CH 3
| |
CHCl 225. (c) CH 3  C  CH 3 
  CH 3  C  CH 2  H 2 O
Cu
CHCl 3  aq. NaOH
2

   
NaOH 0
| 300 C
CH 3
Phenol Intermediate
O Na
– +
OH
CHO CHO



H

Salicylaldehyde
 1248 Alcohol, Phenol and Ethers
OH O The protonated ether undergoes nucleophilic attack by halide
||
227. (c) CH 3  C OH  CH 3  C  OH  H 2 O ion ( X  ) and forms alkyl alcohol and alkyl halide
OH
+ CH + CH .... Br
If two or more OH groups are present on carbon atom then HC O
3
HC O
3

H H
3 3

it immediately looses water molecule and forms acid or

aldehyde. +Br  –

Two OH groups on the same carbon aldehyde is formed

transition state
OH
R  CH   R  C  O
OH  H 2 O | HC
3 OH
Unstable
H
Aldehyde  +CH Br
CH 3 CH 3 3

Three OH groups on the same carbon acid is formed. | |

OH 241. (a) H 3 C  C  OH   H 3 C  C  Cl

conc . HCl
| ZnCl 2 |
OH
RC OH   R  C
 H 2O
CH 3 CH 3
O t  butyl alcohol t  butyl chloride
OH acid

228. (d) H 2 SO 4 , Al2O3 and H 3 PO4 all can act as dehydrating 242. (a) N 2 Cl   H OH  
base

agent.
CH 2OH  CH 2  I  CH 2 I
| |  | NN OH
229. (b) CHOH  3 HI  CH  I  
 3 H 2O
 CH
 I2
|
CH 2OH  CH  I 
| ||
CH 2
p-hydroxy azobenzene
Glycerol
 2  Allyliodide (orange dye)
This is an example of coupling reaction
230. (a) H 3 C  CH 2  CH  CH 2  OH   
Conc. H 2 SO 4
243. (b) Reimer-Tiemann reaction involves the carbon carbon bond
| dehydratio n
CH 3
formation.
2 Methyl butanol OH OH
H 3 C  H 2 C  C  CH 2 CHO
|  CHCl 3   
NaOH , 340 K
CH 3
2 - Methyl butene OH
Major prod uct
CHO
233. (c) CH 3 CHO 

Cu
 CH 3 CH 2OH 2
3
 CH 2  CH 2
Al O
  
dil. HCl
   NaCl

O O salicylaldehyde
|| ||
234. (b)  C6 H 5  CH  CH 3
C 6 H 5  C  CH 3  LiAlH4
244. (a) This is Reimer-Tiemann reaction where the electrophile is
Acetopheno ne 2 o alcohol dichlorocarbene (: CCl 2 ) generated from chloroform by the
action of a base.
235. (d) C 2 H 5 OH    C 2 H 4  H 2 O
Conc H 2 SO 4
170 o C OH   CHCl 3 ⇌ HOH  : CCl 2  Cl   : CCl 2
236. (b) 245. (a) Phenols are much more acidic than alcohols but less so than
OH  + H2 O carboxylic acids or even carbonic acid. This is indicated by the
 
Conc . H 3 PO4
values of ionisation constants. The relative acidity follows the
order:
Because conc. H PO acts as a dehydrating agent.
3 4
Ka 10 5  10 7  10 10  10 14  10 18
RCOOH H 2CO 3 C6 H 5 OH HOH ROH
238. (c) C 2 H 5 OH 
 CHI 3 yellow ppt.
NaOH
I2

CH 3 OH   No reaction
NaOH Uses of alcohol, Phenol and Ethers
I2

239. (d) It is not acetaldehyde or acetone as does not react with 1. (a) Glycerol 
  Glyceryltrinitrate  Dynamite
3 HNO Absorbed on

hydrazine. It is not CH 3 OH as does not react with Na. 

Kieselguhr

Glyceryldinitrate
240. (a) The ether molecule gets protonated by the hydrogen of the
acid to form protonated ether or oxonium salt. air
3. (d) C 2 H 5 OH    CH 3 COOH
Acetobactoracetii
+: CH OCOCH 3
CH OCH CH O
3

H
3 3
3


 HBr   Br COOH
4. (b) Aspirin or Acetyl salicylic acid.

Protonated ether
 Alcohol, Phenol and Ethers 1249
 CH  OH  8. (c) Correct order of dehydration in alcohols 3° > 2° > 1°.
 2 
6. (a) n (HOOC COOH ) + n | 
  9. (a) Oxiran is ethylene oxide, CH 2  CH 2
 CH  OH 
 2  O
Terephthallic acid Ethylene glycol

10. (c) 6 CH 3  CH  CH 2  B 2 H 6  

H 2 O2

 C C  O  CH 2  CH 2  O  
 ||  CH 3  CH 2  CH 2 OH
 || 

 O O n 11. (d) Distinction between primary, secondary and tertiary alcohol is
Polyster done by all three methods : oxidation, Victormeyer and Lucas
9. (a) Ethylene glycol is added to lowering down the freezing point of test.
water so that it does not freeze. OH
10. (b) Power alcohol 80% petrol and 20% ethyl alcohol
12. (b)  
O 2 ,air
12. (d) Glucose   2C 2 H 5 OH  2CO 2
Zymase
V2 O5
(From yeast)
13. (a) o- and p-nitrophenols are separated by steam distillation
16. (d) Glycerol is not used as an antiseptic agent. because o-nitrophenol is steam volatile while p-isomer is not.
18. (c) Denaturing can also be done by adding 0.5% pyridine, 14. (b) Benzoic acid.
petroleum naptha, CuSO 4 etc.
R  O  R ' 2 
O / light
15. (a)
20. (b) A mixture of glyceryl trinitrate and glyceryl dinitrate when
absorbed on kieselgurh is called dynamite. C2 H 5  O  CH (CH 3 )  O  OH
22. (c) Tonics have generally contains ethyl alcohol.
(d) CH 3 OH  CH 3 OH 2  CH 3 OCH 3
H SO (Conc )
16. 4

23. (c) Due to presence of methyl alcohol in liquor.

CH 3 OH  C2 H 5 OH 24 CH 3 OC2 H 5
H SO (Conc )
24. (d) An anaesthetic.
25. (c) Groundnut oil.
C2 H 5 OH  C2 H 5 OH 24 C2 H 5 OC2 H 5
H SO (Conc )

27. (a) C3 H7 COOC 2 H 5  C3 H7 CH 2OHNa / C 2 H 5 OH

17. (b) IV > III > I > II.
Ethyl butyrate Butyl alcohol
CH 2  CH 2
28. (a) Glycol is used as an antifreeze for automobile radiators because 18. (a) Cyclic ethers are called epoxides.
it lowers down the melting point of water. O
19. (b) CH 3  CH  CH OH 
HBr

Critical Thinking Questions CH 3  CH 2  CH OH

|
CH CH
2 3
OH Br

1. (c) or will undergoes a Friedel Craft’s

20. (c) OCH 3 on KMnO4 oxidation does not give
alkylation on ortho or para position because of more electron
density. benzoic acid.
2. (c) CH 2  CH 2  RMgI  CH 2  CH 2  R  HOH 21. (c) Chromic anhydride in glacial acetic acid is the best reagent to
| convert pen-3-en-2-ol into pent-3-in-2-one.
OMgI | | | |
22. (a) C  C  H  C  C  H 2O
MgI(OH)  R  CH 2  CH 2  OH | | | |

3. (c) The liquids which decompose at its boiling point can be H OH H OH 2
Protonated
purified by vacuum distillation. Glycerol which decomposes at alcohol
its boiling point (–563K) can be distilled without
decomposition at 453K under 12mm Hg pressure.
| |  H | |
 C  C  C  C
4. (a) Liebermann’s reaction. | |
H
5. (a) 1 o alcohol  2 o alcohol  3 o alcohol carbonium ion
Boiling point of alcohols decreases as the number of branches In all cases intermediate is carbonium ion, and there may be 1,
increases.
2-hydride or 1, 2-methyl shift to form more stable carbonium
O-CH 3
OH ion.

6. (c)  HI   CH 3 I Assertion & Reason

7. (c) 3CH 2  CH 2  2 KMnO4  4 H 2 O  3. (a) It is correct that phenol is more reactive than benzene.
4. (c) It is correct that sodium phenoxide (sodium salt of phenol) and
CH 2  OH
3 |  2 KMnO2  2 KOH CO 2 on heating from sodium salicylate. This is known as
CH 2  OH Kolbe’s reaction. Ethanol does not respond to this reaction.
Glycol Therefore, assertion is true. But the reason that phenoxide ion
is more basic than ethoxide ion is not correct.
 1250 Alcohol, Phenol and Ethers
5. (c) Lucas reagent is a mixture of anhydrous ZnCl 2 and coc. HCl is stable tert-butyl cation, therefore, it undergoes dehydration
most readily than propanol.
used for the distinction of monohydric alcohol. Tertiary alcohols on
addition produce a precipitate immediately while secondary 20. (e) The ease of dehydration of alcohols can be explained on the
alcohols produce ppt. after 5 minutes. Primary alcohols do not basis of stability of the intermediate carbocation. Greater the
produce any precipitate. Therefore, assertion is true but reason is stability of the carbonation formed, greater will be the rate of
false. reaction. The order of stability of carbocation formed is
6. (a) Phenols on treatment with neutral FeCl3 solution produce CH 3 CH 3 H
| | |
purple colour, resorcinol contains phenolic group hence in  
CH 3  C H 3C  C CH 3  C 
treatment with FeCl3 solution it gives purple colour. Here | | |
both assertion and reason are correct and reason is a correct CH 3 H H
explanation of assertion. This is due to the electron releasing (+I) effect of the alkyl
7. (b) Glycerol is purified by distillation under reduced pressure group. Therefore the ease of dehydration of alcohols follows the
because it decomposes on heating below its melting point. It is order.
a trihydric alcohol. Here, both assertion and reason are true
Tertiary > secondary > primary alcohol.
but reason is not a correct explanation of assertion.
8. (a) Alcohols and phenols can be distinguished by treating with 21. (c) Benzoylation in phenols is usually carried out in the presence
NaOH. Phenols react with NaOH to produce sodium phenoxide of aqueous NaOH because benzoyl chloride is not readily
because phenols are acidic and alcohols are neutral. Both hydrolysed by alkalies.
assertion and reason are true and reason is correct explanation. 22. (b) In phenols, the lone pairs of electrons on the oxygen atom are
9. (b) Zeolites are shape-selective porous solid acid catalysts, their delocalised over the benzene ring due to resonance and hence are
catalytic activity originates from the presence of highly acidic not easily available for protonation. On the other hand, in alcohols,
the lone pairs of electrons on oxygen atom are localized due to the
Al  O (H )  Si hydroxyl in the framework.
absence of resonance and hence are easily available for ptotonation.

10. (a) C 6 H 5 CH 2 OCH 3 
H
 C 6 H 5 CH 2  CH 3 OH



I
C 6 H 7 CH 2 I
This can be explained on the basis of S N 1 mechanism. The
carbonium ion produced being benzylium ion. Since this type is
more stable than alkylium ion.
11. (c) Lower the value of pKa, more acidic will be the compound.
Acetic acid is more acidic than phenol. This indicates that
carboxylate ion should be more stable than the phenoxide ion
and it is clear that carboxylate ion has more equivalent
resonating structures than the phenoxide ion.
12. (a) The conversion of sugar into ethyl alcohol by yeast is called
alcoholic fermentation.
23. (c) p-Nitrophenolate ion is more stable than phenolate ion.
C12 H 22 O11  H 2O   C6 H12 O6  C6 H12 O6
Invertase

Glucose Fructose 24. (b) Nitrous acid gives nitrosomine ion ( NO  ) which attacks phenol
C6 H12 O6   2C2 H 5 OH  2CO 2
Zymase at less hindered p-position of form p-nitrosophenol which is a
Ethyl alcohol tautomer of p-benzoquinone monoxide.
13. (b) The tendency to show H-bonding decreases with increasing HO N=O O NOH
hydrophobic character of carbon chain. The hydrophobic
character of carbon chain increases with he length of carbon p-Nitrosophenol p-Benzoquinone monoxime
chain.
14. (e) Ethyl alcohol forms azeotropic mixture with water which distils 25. (c) Nucleophilic attack of phenolate ion through the ortho-carbon
with unchanged composition (about 75% ethanol) and thus
absolute alcohol cannot be obtained by simple distillation. atom occurs on CCl 4 to form an intermediate which on
hydrolysis gives salicylic acid.
15. (e) The dehydration of t-butanol involves the formation of 3°
carbocation which is more stable than 1° carbocation in n- 26. (a) Victor-Meyer’s test is used to distinguish primary, secondary
butanol. Thus, tendency to lose water becomes more in t- and tertiary alcohols.
butanol.
16. (c) A mixture of conc. HCl + anhyd. ZnCl 2 is called Lucas reagent.

17. (e) Electron withdrawing groups such as  NO 2 , – CN, –X,

increase the acidity. Greater the number of electron
withdrawing groups more is the acidic character i.e. 2, 4, 6-
trinitrophenol is more acidic than 4-nitrophenol.
18. (b) Phenols cannot be converted into esters by direct reaction with
carboxylic acids since phenols are less nucleophilic than
alcohols.
19. (b) Alcohol which forms the more stable carbocation undergoes
dehydration more readily. Since tert-butyl alcohol forms more
 Alcohol, Phenol and Ethers 1251

P rimary Secondary Tertiary

R R
RCH 2 OH CHOH
R R C  OH
HI HI
R HI
RCH 2 I R
CHI
R R
AgNO2
AgNO2
R CI
RCH 2 NO 2 R R AgNO2
CHNO 2
HONO
R
HONO R
R  C  NO 2 R v
C  NO 2 R C  NO 2
||
R |
R HONO
NOH NO
Nitrolic acid Pseudonitr ol
v
NaOH NaOH No reaction
NaOH

Blood red colour Blue colour Colourless

28. (b) Removal of two molecules of water gives a product which
tautomerises to yield acrolein-an , -unsaturated aldehyde.
29. (b) Depending upon whether the alkyl halide and the alkoxide ion
carry the same or different alkyl groups both symmetrical and
unsymmetrical ethers can be prepared by Williamsons
synthesis.
30. (c) Ethers being Lewis bases form etherates with Lewis acids.
31. (d) (CH 3 )3 CONa and CH 3 CH 2 Br react to form
(CH 3 )3 C  O  CH 2 CH 3 . Good yields of ethers are
obtained when primary alkyl halides are treated with alkoxides
derived from any alcohol. 1°, 2° or 3°.