1

r __J

. (1 MarkJ
Very Short Answer Questions
1. Explain why phenols do not undergo substitution of
the -O H gro up like alco hols ?
hanol. Wh y?
2. The dipole mom ent of phenol is smaller than that of met
3. Wh y are ethers insoluble in water?
hols. Wh y?
4. Am ong HI, HBr, and HCl, HI is most reactive toward alco
5. Wh at is absolute alcohol?
6. Wh at is denatured alcohol?
thesize lert-butyl ethy l ether.
7. Nam e the alkyl halide and sodium alkoxide used to syn
henol. Why?
8. Ortho-nitrophenol is more acidic than ortho-methoxyp
rbonate solution. Why?
9. Phenol is an acid, but it does not react with sodium bica
10. Wh y rectified spirit cannot be converted into abso
lute alcohol by sim ple dist illat ion?
11. Diethyl ether does not react with sodium. Explain.
In Kol be reac ~on , inst ead of phen ol, phen oxid e ion is treated with carb on diox ide. Why?
12.
13. Suggest a reagent for the following conversion:
OH OH
►

14. How would you convert ethanol to ethene?

15. Draw the structure of 2,6-dimethylphenol.
ty of ethoxyethan •th
16. How ·do you account for the miscibili
. . e w1 water.
 Is Phenols, and Ethers
AICOhO ' .
fffij
~ g e the following compounds in decreasing -order of.acidity: H2O, ROH, HC _CH
, out of o-nitrophenol and p-nitrophenol, which is more volatile? Explain.
18
, suggest a reagent for conversion of ethanol to ethanoic acid. ·
19
20, Lower alcohols are soluble in water, higher alcohols ·are not. Why?
1
• ,

21• Arrange the following in order of decreasing acid strength: ·cH3OH, H2O, C6H5OH. ·. .
22. Of the two hydroxy organic compo~d s ROH and R'OH, the first one is_basic and the oth~ is acidic
in behavior. How is R different from R'?
23, How will you know whether a given OH group is alcoholic or phenolic in nature?
24, Arrange the following in decreasing order of their acidic character: ·'

(i) CH,oH --@--o H (ii) o,N --@- -oH (iii) c,H,OH - .

25. What is the order of dehydration of primary, secondary, and tertiary alcohols?

Short Answer Questions (2, 3 Marks)

1. Arrange the following sets of compounds in order of their incre_asing boiling points:
(i) Pentan-1-ol, butan-1-ol, butan-2-ol, ethanol, propan-1-ol, methanol
(ii) Pentan-1-ol, n-butane, pentanal, ethoxyethane.
2. Give the major products that are formed by heating each of the following ·ethers with Ill:
CH3
I
. (i) CH3 -CH2 - CH- CH2 - 0 - CH2 -CH3

CH3
I
(ii) CH3·-CH-C
2 H2 - 0 - C - CH2 - CH3
I
CH3

(ih) 0-CH,- ◊--o

3· Ethers can be prepared by
Williamson synthesis in which 'an alkyl halide is reacted with sodium
alkoxide. Di-tert-butyl ether cannot be prepared by this method. Explain. ·
4· How will the
following conversions be carried out? 1
-

(i) Propene to propan-2-ol

(ii) Ansisole to phenol (write the reaction only) .
5
· ~cohols react both as nucleophiles and electrophiles. Write one reaction of each type and describe
its mechanism.
6
· How.would you carry out the following conversions?
(i) Ethyl magnesium chloride to propan-1-ol.
(ii) Benzyt chloride to benzyl alcohol.
 7. Explain the mechanism of the following reactions:
(i) Addition of Grignard reagent to the carbonyl group of a compound forming an adduct fi
0 0
by hydrolysis. · • , 1I wed
(ii) Acid-catalyzed dehydration of an alcohol forming an alkene.
(iii) Acid-catalyzed hydration of an alkene forming an alcohol.
8. Explain the following observations:
(i) The boiling point of ethanol is higher than that of methoxymethane.
(ii) Phenol is.more acidic than ethanol.
(iii) o- and p-nitrophenols are more acidic than phenol.
9. Why is the reactivity of all the three classes of alcohols with cone. HCI and ZnCI2 (Lucas reag• l
di:ffierent?

-
10. The carbon--oxygen bond in phenol is slightly stronger than that in methanol. Why? -
11. How would you obtain the following products?
(i) Picric acid (2,4,6-trinitrophenol) from phenol
(ii) 2-Methylpropene from 2-Methylpropanol
12. How would you obtain the following?
(i) Benzoquinone from phenol
(ii) 2-Methylpropan-2-ol from methylmagnesium bromide
(iii) Propan-2-ol from propane
_13. (i) Give a chemical test to distinguish between the following pairs of compounds.
OH OH

(a)() C) md

I I A

(ii) Arrange the following_ compounds in increasing order of acidity and give a suitable explanation:
Phenol, o-nitrophenol, o-cresol
14. Give chemical tests ~o distinguish between compounds in each of the following pairs: -
(i) Phenol and benzyl al~ohol ; ) 01'
(ii) Butan·}-ol and 2-methylpropan-2-ol
15. Which is a.stronger acid: phenol or cresol? Explain.
,. 11'lr.
16. Giv~ the mechanism of preparation of ethoxyethane from ethanol. · , , cH ,
17. Name the reagents used in the following conversions:
.. (i;·
(ii A primary alcohol to an aldehyde (ii) Butan-:2,-one to butan-2-ol
_,. '..m
(iii) Phenol to 2,4,6-trib~omophenol ·

Long Answer Questions

l. (a) Discuss the following named reactions: .
(i) Discuss reaction . (ii) Clemmensen reduction
. . . . fltlenol1,, and EtNn . . .,
________,. .......;;;.;.._--===-....:..========-=--------
(Itl How ~kl you obtrun tbe foilo"1!lg7
(f) Bul..l ~ ftom ethanal (II) Butanoic acid from buunol
(I() BcnmK acid from dhylbenteoe
J. (a) Give dlcmK.a.l tes~ to distingui• between the folloWUlg:
(I) Bcnm,c aad and dhy1 bet\ma~
(II) Bcnaldd'eyde and acctophfflone
(I,) Complete each syntbe5t~ by givmg miPi~ n:agen~ or products in the following:

(I) (XCOOH s::

COOH
 ALCOHOLS1 PHENOLS AND ET
1 HERS
•Very Short Answer Questions
' (1 Mark)
1. Th e C- -0 bon d ~ phenols has . '
soine double bon d character due ' '
easily cleaved by nucleophile. In to res.o nan ce an~. h~nc~ cannot be
contrast, the C- -0 bon d in alcoho
can be easily cleaved by nucleophi ls is a pur e single QO~d and ~ence
le. . .
2. In phenol, the C- -0 bon d is les . . '
s polar due to the electron-witl:idr
as in methanol, the C- -0 bon d is aw hlg effect of ben zen e ring, where
more po lar due to the electron-rel -
3. Ethers are insoluble in water eas ing eff ect of the -C ~ group.
because due to the big ger size of
ethers fails to form intermolecular the alk yl gro ups , the oxy gen atom in
H-bonds with water.
4. HI has the low est bon d dissoc •
iation energy due to longer bon d
S. Absolute alcohol is 100% eth len gth . Th at is wh y it is mo st reactive.
yl alcohol.
6. Alcohol is made unfit for .dri '
nking by mixing sorn~ copper sul
· denatured alcohol. fate and pyr idi ne in it. Th is is cal
· led
7. Eth yl bro mi de and sodium tert
-butoxide.
8. Ortho-nitrophenol is more-acid
ic than ortho-methoxyphenol bec
drawing, wh ich increases the aci ause the nitro gro up is ele ctr on wit
dic character, whereas --O CH h-
decreases the acidic character: 3
group is ele ctr on releasing, which
9. -Ph eno l is a we ake r acid than
carbonic acid (1¾CO ) and hence
bicarbonate. 3 does not liberate CO fro m sodium
2
10. Rectified spirit containing 95%
ethyl alcohol and 5% water forms
at a constant temperature of 351.13 an azeotropic mi xtu re, wh ich dis
K. tils
11. Since diethyl ether does not con
tain an active hydrogen attached to
it does not rea ct wit h sodium. oxy gen like alc oho ls and phenol
s,
12. Phenoxide ion is more reactiv
e tha n phenol toward electrophi
undergoes electrophilic substituti lic aromatic sub stit uti on and hen
on wit h carbon dioxide, wh ich is ce
13. Cr 0 , pyridine, and HC l (pyrid a we ak electrophile.
3 iniuni chlorochromate). '
14• CH CH OH con e. H 2 SO 4 .
3 2 443 K CH2 = CH2 + H 2O
Ethanol Ethene L >
i .. . ,> ..

l~
.
. OH ,
'i •
'

15. CH3 CH3 ~ , l

. _.

.16. Th is is bec aus e of intermole

cular hyd rog en bon din g bet we en
17• Hi O> RO H> HC == CH , ether and wa ter mo lec ule .

18. o-Nitrophenol is mo re volatil

e bec_ause of intramolecular hyd
intermolecular hyd rog en bon din rog en bon din g bu t in p-n itro phe
g is present. · · nol ,
19. Cr 03, pyridine, ~d HC l (pyridini .
um chlorochromate).
Alcohols, Phenols, and Ethers
20. Lowe r alcohols can form H-bonds with water, whereas ·highe
fjf j•
r alcohols canno t due to a large r hydro -
carbo n part.
21. C;J5OH > J\O > CH OH
3
_22. R is an alkyl group, whereas R' is an aryl group .
23. Phenolic OH group gives blue or viole t coloration with neutr
al FeCl3 , while alcoholic OH group does
not. .
24. (ii)> (iii) > (i).
25. Tertiary alcohols > Secondary alcohols > Primary alcohols.

Short Answer Questions (2, 3 Marks)-

1. (i) Meth anol< ethan ol< propan-1-oi < butan-2-ol < butane -1-ol
< pentan-1-ol.
· (ii) n-Bu tane < ethoxyethane < pentanal < pentan-1-ol.
2. (i) CH3 - CH2 - CH- CH OH + CH CH 1
2 3 2
I
CH3

(iii) Q-cH,I Q-oH +

3. In tert-butyl halid es, elimination is favored over substitutio
n, so alkene is the only reacti on produ ct
and ether is not forme d.
CH3 , : CH3
I - + · · I .
CH -CH -Br + CH - ON a- CH ---+- CH - C = CH
3 3 3 3 2 + NaBr + CH3-C - OH
I I I
CH3 CH3 CH3
(tert-Butyl bromide) (2-methylprop-l~ene)
4. (i) CH- CH= CH +H- 0S0 H(conc.)~C H -CH -H SO4
-CH3 H~ CH -CH -CH
3 2 3 3
I 2 , .:\ 3 I 3
0S03H OH
lsopropyl hydrogen sulphate Propan-2-ol
. O-C H3 OH

(ii) 0
Anisol e
+HI
373 K ►
u
,,,l
Phenol
+CH
3
-· 1
.
5. Alcoh ols as nucleophiles: The 0--~ bond is broke n when
alcoh ols react as nucle ophil es.
H
•~• --.;:::o+- +I I I
..
R- O-H C- ---+- R - 0 - C.- ---+- R - 0-C -+ H+
/ •• . 1
I
 Answers and Solutions to Practice Exercises
as electrophiles.
Alcohols as electrophiles: The C-0 bond is b~oken when alcohols react
Protonated alcohols react in this manner.
•• +
R-C H2- R-H +Ir -+ R-C H2-R H2
0+
Br+ CH2 -OH2 -+
I ••
R

0 OMgCl
II &- + I /
6. (i)H -C- H +CH3 -CH2 - . MgC l-+ H-C -H
Forma ldehyd e . Ethyl magp.esium
I. I

. chloride CH2 -CH3

.
' / OH
CH3 -CH2 -CH2 -OH + Mg '-..
Propan-1-ol Cl
CH2 -Cl CH2 -OH
1•

(ii) @+KOH(~ ~@+KC!

Benzy l chlorid e · Benzyl alcohol
\

7. (i) Step I: Nucleophilic addition of Grignard reagent to carbonyl-group. I• ,.

·, 6+ 6-- 6-- 6+ '-.. - + ~
C= O+ R-M g-X -. C-O Mg -X .l

/ ' - - /. ✓, I '

R
Adduct

Step II: Hydrolysis

""'C-O-+
Mg -X H 20 ""'- . ,)
/I --- ✓1
C=O H+M g(OH
I
)X
•.
. 'I

R
R

. t .
(ii) CH3 -CH2 -OH

Mechanism
Step I: Formation ofpro tonat ed alcohols
H H H H H
I I .~ Fast I I I
H-C -C- O-H +H • ., H-C -C- O-H
I I .. I I ••
H H H H
Ethyl oxoniu m ion
Ethyl alcohol
Alcohols, Phenols, and Ethers .
. fjffj
Slep II: Formation of carbocation: It is the slowest step and hence the rate detennining step
H H H H H ' ' .
I I I+ Fast I ·I .
H-cl -cl -R-H .. ► . H-c-c+ + H20
.I I
H H H ·H
Ethyl oxonium ion Ethyl carbocation

Step III: Formation of ethylene by elimination of a proton

H H ·
I I H H
H-c-c+ .. 111 · "c=c/ + ir
I
H H
I H
./ "H
Ethyl carbocation Ethylene
To drive the equilibrium to the right, ethylene is removed as it is fonned.
+
H "-c=C/.
. /I I"
H OH
Mechanism
Step I: Protonation of alkene to form carbocation by electrophilic attack of H3O+. ·
•• + • ·+
Hi,.Q + H _. H30
. H H-
' ./ ~+ . . I +/ ••
"c=C + H...L-U -H .. ., -C-C + H2Q
./ '--- .. I · "
I .

Step II: Nuclephilic attack of water on ~arbocation..

H H H

1 - C ~-- ~ -~ - ~-.6
+-H
-.T- ':- -. I I .. 2..

Step m: Deprotonation to form an alcoh'ol.

H H :OH
H . I 1 ·

.· cl-cl_ Ol:l..HQ0 --+ -c-c-+H30 +

-I .. 2
.. I I ..
8. (i) Ethanol undergoes intermolecular hydrogen bonding due to the presence of a hydrogen attached
to oxygen atom. As a result, ethanol exists as associat~d molecules and hence has higher boiling
point than ethoxy ethane, which does not fonn hydrogen bonds. _
(ii) Phenol is stronger acid than ethanol because the phenoxide ion left after the release of proton is
stabilized by resonan~e, but ethoxide ion is not. Moreover, ethoxide ion is destabilized by the +I
effect of ethyl group. ~
(iii) Due to the -I effect or-R effect of the - NO2 group, the resulting phenolate ion is more stable than
phenoxide ion. Therefore, o- and p-nitrophenols are more acidic than phenol.
9. An alcohol reacts with cone. HCl and ZnC12 (Lucas reagent) to give carbocation. The more stal,\ . ·
the carbocation, the faster is the reaction.
 Answers and Solutions to Practice Exercises
10. This is due io the fact that
(i) in phenol, conjugation of unshared electron pair over oxygen with aromatic ring results in partial
double bond character in carbon-oxygen bond. . ·· ·
(ii) in phenol, oxygen is attached to a sp2-hybridized carbon atom, while in methanol, it is attached to
3
an sp -hybridized
' . carbon atom . .The bond formed between oxygen and sp -hybridized carbon is
2

more stable than that formed between oxygen and sp3-hybridized carbon. ,
OH . OH

A
OH

cone:H,~o.. s0,H cone. HNO, o,N

· 11. (i)
U , N02

Phenol
. N0
2

. Phenol-2,4- Picric acid

disulphonic acid
CH3 CH3 ?H3
I SOCl2 I:. SOCl2
(ii) CH3- CH-CH20H ► CH3- CH- CH2- Cl-------- CH3- C-. CH2
2-Methyl propanol 2-Methyl propene
OH

12. (i)©
Phenol
-0
· Benzoquinone

0 ~~ · 00
- I I ~ :. ·
1-
. C,-CH ~H20 . . · ,.;. ., .· . .
(ii) cH - ~ H3M~r-+ CH3-
3 ·_ I · 3 .~ ., CH3- CH3
Propanone Methyl magnesmm CH . CH
bromide 3 3
2-Methyl propan-2-ol

TH-
+ .. ·. . .
(iii) CH3- CH .CH2 + H20 Marlc~~o~ _C HJ-
·_ CH2 ..·
Propane addition ,. . OH
Propan-2-ol . ·: ,'. ''

13. (i) (a)

Ph . l . ives violet col~ration whh FeC13 solution, while cyclohexanol do~s not.
eno g . 3- . . . . -·. ·. · . · · .

6C6HsOH . + F~Cl3 ....... [Fe(0~6H5)6] . + 3ir + 1. ·. ~!IS

· Phenol Violet coioration :· , · · • J

OH

FeCl3
____ , •
,..► No violet coloration

Cyclohexanol
'"' nhols. Phenol~, ·and Ethers
(b) ~sop ropy l alco hol whe n wanned with NaO I
f jffj
(ljN aOH ) give s yelJo w prec ipita te of iodoform;
m cont rast benz yl alco hol does not resp ond to iodo
form test
CH 3 - CH - CH, +N.o1• CH, -CH -
I
OH =Nal
H;O

O
II
CH +JN■OI
J - 3N•OH r
CH - C- C- J
3 3

+NaOI - CH, - COON•

CH 2OH
. CHJ3

6
Jodoform
~
(Yel low ppt.)
I ~ . . NaOl • No yellow ppt.
(U) Incre asing orde r of acid ity: o-cre sol < phen ol
< o-nit roph enol
In subs titut ed phen ols. the pres ence of elect ron-w
ithdr awin g grou ps enha nce the acid ic stren gth
of phen ol, whe reas elect ron- relea sing grou ps decr
ease the acid ic stren gth of phen ol.
14. (1) Phen ol give s a viole t colo ratio n with FeCl
3
solut ion, whil e benz yl alco hol does not.
6CJ l 50H + feC l ➔ [(C~H 0)le J3- + 3HCI + 3H~
3 5
(Vio let colo ratio n)
(lJ) Bunm -2-o l when wan ned with NaO I (1/
NaO H) give s yello w prec ipita te of iodo form , whil
2-me thylp ropa n-2-o l does not give this tesL e
OH
I -+
CH 3CH 2CHC HJ + 41 2 + 6NaO H --4+ CHl + CHJCH
1 2 C00 Na + 5Nal + 5H2 0
lodof onn
(CH 3)CO H + 12 + NaO H ~ No reaction
IS. All the creso ls are weak er acid s than phenols.
Meth yl grou p has +I effec t (pos itive indu ctive effec
well as hype rcon juga tion effoc t, but the hype rcon t) as
juga tion effec t pred omin ates over the the +I effec
Sinc e both these effocts incre ase the elect ron dens t.
acid s than phen ols.
ity in the 0-H bond , all the creso ls weak are
er
As bype rcon juga tion effec t can oper ate only throu
gh ortho• and para -pos ition s and not throu gh meta
posit ions, therefore, meta-cresol is a stron ger acid -
than ortho- and para-cresols. How ever , due to the
stron ger +I effoct ar on/Jo -pos ition than at para -pos
ition (+I effect decr ease s with distance), ortho•
creso l is a weak er acid than para -cres ol. Thus , the
orde r of acidi c stren gth in incre asing orde r is as
follows:
ortho-cresol < para -cres ol < meta -cres ol < phen ol
H
-.c H 3CH 2 -(JI -
-~e
16. (l) CH - CH 2 - QH +H
3 H

•• e/
H
(ii) CH - CH - Q;+ CH3 - CH - e
0, _. CH 3 -C H- O- CH2 -CH +H 0
) 2
I~ 2
,H I 3 2
H H
(ill) CH -
3
CH 2 -fJ -
CD
CH.2 - CH 3 _. CH 3CH 2-
••
R- CH 2 -CH 3 + H
+

H
l!!I~~~• Answers an d Solutions to Practice Exercises
Pf? ~
17. (i) Pyridinium chlorochromate (C 5H5N+HCr03Cl) or cu1573 K
(ii) LiAIH/ether (iii) Br/H20
(5 Marks)
Long Answer Questions . . . .
· ·
l. (a) (i) Cannizzaro reaction: Aldehydes _that do not ha~e;:
tionation reactions on treatment with concentrate a a 1 0
tt
-hydrogen atom undergo d1spropor-
give a mixture of carboxylic acid
.
salt and alcohol,
2HCHO Cone. NaOH HCOONa + CH3 -OH
Formaldehyde Sodium formate Methyl alcoh?l d d 1 • , •

. f Id h des and ketones 1s re uce to CH2

(ii) Clemmensen reduction: The carbonyl group O . a ed~ dr hloric acid.
group on treatment with zinc ,amalgam and conc~n~ate Y 0 ~ ., ·. . •.
. . . . ._ - H) Zn-Hg ........._ H0
,I I
/
C-0 + 4( HCl .. CH2 +. 2
cone. · /
Aldehyde or Ketone
.I
,. · OH
I , . .-
(b) (i) CH CHO •d=il_._N=aO=Hz CH CH- CH CHO~CH3_< :;H= CHCHO
3 3 2
Ethanal , .. But-2-enal
; I

(ii) CH CH CH CH OH cr03-H2804 -CH CH CH COOii .i

3 2 2 2 3 2 2
Butan-1-ol Butanoic acid
·-+ · . .

!_OK H,o• . !.OH

(iii)

Ethyl benzene
.v - - - - .u .' Benzoic 'acid · ; · · ·• , · ·
I .

,,
•

2. (a) (i) Benzoic acid, on wannmg with sodi~ hydrogen carbonate; gives brisk ~ffervesceri.ce of CO
2
gas, while ~thyl benzoate does not respond to this test. · ·
• :. I . ~~~~COOR ~ +'Na~C03 _
. i c6~-coot~. + ,CO2 t·+H~O
Benzoic acid ' ; Brisk effervescence
(ii) Iodoform test: Acetophertone ·being. a methyl ketone, on treatment with i /NaOH · undergoes
. iodoform reaction to give yellow precipitate of iodoform but benzaldehyd~ do~s il~t.
. C6H5COCH3 + 3Na01:...+ C 6H5COONa+ CH13 + 2Na0H :, . +
Acetophenone ._
. lodoform · .
(Yellow ppt.)
I I

(b) (i)(( ' ~

COOR

·cooH
Heat '( (
- COCl
. · - + SO +HCI
2
,

-
COCI r