ANSWER SCHEME TUTORIAL SK025 SEMESTER 2

SK025
CHAPTER 8.0 : HYDROXY COMPOUNDS
CHAPTER 8.0 : HYDROXY COMPOUNDS UNIT 8.1 : NOMENCLATURE &
PHYSICAL PROPERTIES
UNIT 8.2 : CHEMICAL PROPERTIES
LEARNING OUTCOMES:
8.1: NOMENCLATURE
a) Draw the structures, classify and name the hydroxy compounds (parent chain ≤ C10) according to the IUPAC nomenclature.
8.2: PHYSICAL PROPERTIES OF ALCOHOLS
a) Analyse the physical properties:
i. boiling point
ii. solubility in water
8.3: PREPARATION OF ALCOHOLS
a) Explain the preparation of alcohol by:
i. fermentation
ii. hydration of alkenes
iii. hydrolysis of haloalkanes
iv. addition of Grignard reagents to carbonyl compounds
b) Outline the synthesis of alcohols.
8.4: CHEMICAL PROPERTIES OF ALCOHOLS
a) Explain the reactions of alcohol with reference to:
i. reaction with sodium
ii. esterification
iii. dehydration
iv. substitution reactions using HX, PX3, PX5 or SOCl2
b) Explain the oxidation reactions with KMnO4/H+, Cr2O72-/H+, CrO3+/H+ and PCC/CH2Cl2
c) Explain the identification tests to distinguish classes of alcohols using Lucas reagent, i.e. concentrated HCl/ZnCl2
d) Outline the synthesis of compounds related to reactions of alcohols.
e) Explain iodoform test,i.e. I2/OH- to identify methyl carbinol CH3CH(OH)

TUTORIAL QUESTIONS :

1. Classify following compounds as , and and give their IUPAC names.

(a) Br CH3 (d) O2N OH

Br CH C OH
CH3
(b) CH3 (e) CH2 CH3
CH3 CH2 C CH2 OH CH CH CH2 CH2 OH
CH2 CH2 CH3 CH3
(c) CH3 (f) H3C CH2 OH
C C
OH H H

ANS:
(a) 1,1-dibromo-2-methyl-2-propanol (3 alcohol)
(b) 2-ethyl-2-methyl-1-pentanol (1 alcohol)
(c) 1-methylcyclopentanol (3 alcohol)
(d) 3-nitrocyclohexanol (2 alcohol)
(e) 3-methyl-4-phenyl-1-hexanol (1 alcohol)
(f) cis-2-buten-1-ol (1 alcohol)

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2. The following names are incorrect. Draw the structural formulae and give the correct
IUPAC names.
(a) 4-butanol
(b) 1,1-dimethyl-2-cyclopentanol
(c) 6-methyl-3-ethylcyclohexanol
(d) 7-chloro-4-heptanol

ANS:
H3C CH3
a) CH3CH2CH2CH2OH b)
OH
1-butanol

2,2-dimethylcyclopentanol

OH
c) H3C
d) CH3CH2CH2CH(OH)CH2CH2CH2Cl

1-chloro-4-heptanol
CH2CH3

5-ethyl-2-methylcyclohexanol
3. Arrange the following compounds in increasing order of boiling point. Explain your
answer.
(a) 1,2-ethanediol, n-butane, 1-propanol, 1,3-propanediol
(b) (CH3)2CHCH2OH, (CH3)2CH(CH2)2CH2OH, (CH3)2CH(CH2)3CH2OH

ANS:
(a) n-butane  1-propanol  1,2-ethanediol  1,3-propanediol
Compound Molecular weight Number of OH group
1,3-propanediol 76 2
1,2-ethanediol 62 2
1-propanol 60 1
n-butane 58 0
Boiling point increases with the increase in the number of hydrogen bond and the
increase in the strength of van der Waals forces. Van der Waals forces increase along
with the increase in molecular weight or size. Hydrogen bonding is stronger than van
der Waals forces.

1,3-propanediol and 1,2-ethanediol can form the same number of hydrogen bond due
to the presence of two OH groups in the compound but 1,3-propanediol has stronger
van der Waals forces than 1,2-ethanediol. Therefore it has the highest boiling point.

1-propanol has only one OH group and has fewer number of hydrogen bond. n-butane
has the lowest boiling point because it cannot form hydrogen bond and only van der
Waals forces exist between n-butane molecules.

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(b) (CH3)2CHCH2OH (CH3)2CH(CH2)2CH2OH  (CH3)2CH(CH2)3CH2OH
For alcohol with one OH group, the boiling point increases as the strength of van der
Waals forces increases. The bigger the molecular weight or size the stronger the van
der Waals forces.

(CH3)2CH(CH2)3CH2OH has the highest boiling point because it has the biggest
molecular weight (Mr = 100), followed by (CH3)2CH(CH2)2CH2OH (Mr = 86) and
(CH3)2CHCH2OH has the lowest boiling point because it has the smallest molecular
weight (Mr = 58).

4. Arrange the compounds in each set in decreasing order of solubility in water. Explain
your answer.
(a) ethanol, 1-pentanol, 1-hexanol
(b) hexane, 1-hexanol, 1,2-ethanediol

ANS:
(a) ethanol  1-pentanol  1-hexanol

solubility in water will decreases with the increase in molecular weight because the
hydrophobic area (alkyl group) becomes bigger.
1-hexanol has the lowest solubility because it has the biggest molecular weight (Mr =
86), followed by 1-pentanol (Mr = 72) and ethanol has the highest solubility because
it has the smallest molecular weight (Mr = 58).

(b) 1,2-ethanediol  1-hexanol  hexane

1,2-ethanediol is the most soluble because it has two OH groups, therefore it can form
more hydrogen bonding with water per molecule compared to hexanol that has only
one OH group. Whereas, hexane does not has any OH group present in the compound
and it cannot form hydrogen bonding with water. Therefore it is insoluble in water.

5. Draw the structural formulae of A to D in the following equations.

(a) O +
H3O
CH3 C CH2 CH CH3 + CH3 CH2 MgBr A B
CH3
(b) +
H2O, H
C
(aq)
(c) (CH3)2CHCH2Cl + NaOH  D

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ANS:
- + OH H3C
(a) O MgBr CH3
A: B:
H3C C CH2 HC CH3 H3C C CH2 CH CH3

H2C CH3 H2C CH3

(b) C : (c) (CH3)2CHCH2OH

OH

6. Write the complete equation for each of the following reactions.

(a) 2-butanol heated with acidified KMnO4 solution
(b) 2-propanol heated with concentrated H2SO4
(c) 2-methyl-1-propanol heated with acidified K2Cr2O7 solution
(d) methanol reacts with PCl5
(e) glacial ethanoic acid heated with 2-propanol in the presence of concentrated
H2SO4
(f) 1-hexanol reacts with PCC/CH2Cl2
(g) cyclopentanol reacts with SOCl2 in the presence of pyridine

ANS:
KMnO4, H+,
(a) CH3CH(OH)CH2CH3 CH3COCH2CH3 + H2O

(b) CH3CH(OH)CH3 conc.H2SO4 CH2=CHCH3 + H2O

(c) CH3CH(CH3)CH2(OH) K2Cr2O7, H+, CH3CH(CH3)COOH

(d) CH3OH + PCl5 CH3Cl + POCl3 + HCl

(e) CH3CH(OH)CH3 + CH3COOH conc.H2SO4 CH3COOCH(CH3)2

(f) CH3(CH2)4CH2OH PCC/CH2Cl2 CH3(CH2)4CHO

pyridine
(g) OH + SOCl2 Cl + SO2 + HCl

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CHAPTER 8.0 : HYDROXY COMPOUNDS
7. Show the preparation of
(a) propanone from 2-bromopropane (b) 1,2-dibromoethane from ethanol

ANS:

NaOH(aq) KMnO4, H+
(a) CH3CHBrCH3 CH3CH(OH)CH3 CH3COCH3

conc.H2SO4 Br2,CH2Cl2
(b) CH3CH2OH CH2=CH2 CH2BrCH2Br

8. The structural formula of alcohol A is given below:

OH CH2 CH3
CH3 CH2 CH CH CH2 CH CH3
CH3

(a) Give the IUPAC name of A.

(b) Is A optically active? Explain your answer.
(c) Classify alcohol A as 1, 2 or 3.
(d) Give the major product of the dehydration of A.
ANS:

(a) 4,6-dimethyl-3-octanol.
(b) Compound A is optically active because it has chirality centre. Chirality centre is
marked as (*). It has the ability to rotate plane-polarised light.

HO H H2C CH3
* * *
H3C CH2 C C CH2 C CH3
H CH3 H

(c) Secondary alcohol.

(d)
H2C CH3 H2C CH3

H3C CH2 CH C CH2 C CH3 H3C CH2 CH2 C CH C CH3

CH3 H or CH3 H

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CHAPTER 8.0 : HYDROXY COMPOUNDS
9. Give a chemical test to distinguish between
(a) 2-methyl-1-propanol and 2-methyl-2-propanol
(b) 1-butanol and 2-propanol
(c) benzene and cyclohexanol
(d) 2-methyl-2-butanol and 2-butanol
ANS:

(a) Use Lucas reagent (ZnCl2/ HCl (conc))

(10) : (CH3)2CHCH2OH + ZnCl2/HCl (conc) No observable change
Observation: No observation change within 10 minutes
(30) : (CH3)3COH + ZnCl2/ HCl (conc) (CH 3)3CCl + H2O
Observation: cloudiness appears immediately
(b) Use Lucas reagent (ZnCl2/ HCl (conc))
(1o)CH3CH2CH2CH2OH + ZnCl2/ HCl (conc) No observable change
Observation: No observation change within 10 minutes
(2o)CH3CH(OH)CH3 + ZnCl2/ HCl CH3CH(Cl)CH3 + H2O
Observation: Cloudiness appears within 5 minutes
(c) Use K2Cr2O7/H+ and heated
K2Cr2O7, H+, No observable change

Observation : Orange solution remain unchange.

OH K2Cr2O7, H+, O

Observation: orange solution changes to green

(d) OH
I2,NaOH No observable change
H3C CH2 C CH3
CH3

Observation: No observable changes

OH O
I2,NaOH - + CHI 3
H3C CH2 CH CH3 H3C CH2 C O Na +yellow precipitate
Observation: Yellow precipitate formed.

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10. Compound P is an alcohol. Upon oxidation with acidified KMnO4 solution, a ketone, Q is
formed. P reacts with PBr3 to give R which is then purified and refluxed in dry ether along
with Mg metal to form a Grignard reagent, S. S is treated with Q followed by acidic
hydrolysis to yield 3,4-dimethyl-3-hexanol. Identify P, Q, R and S. Write all the equations
for reactions involved.

ANS:

OH O
H3C C CH2 CH3
P= H3C CH CH2 CH3 Q=

R= H3C CH CH2 CH3 S= H3C CH CH2 CH3

Br MgBr

H3C CH CH2 CH3 KMnO4, H+

H3C C CH2 CH3

OH
O
(P) (Q)
PBr3
H3C CH CH2 CH3 H3C CH CH2 CH3

OH Br
(P) (R)
dry ether
H3C CH CH2 CH3 + Mg H3C CH CH2 CH3
reflux
Br MgBr
(Q) (S)
CH3 CH3

H3C CH CH2 CH3 + H3C C CH2 CH3 H3O+

H3C CH2 CH C CH2 CH3
MgBr
O OH
(Q) 3,4-dimethyl-3-hexanol
(S)

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CHAPTER 8.0 : HYDROXY COMPOUNDS

11. An alcohol C4H10O which has several isomers gave the following observations:
I Isomer L gives negative result with Lucas reagent and forms butanoic acid when
oxidised with acidified potassium dichromate solution.
II Isomer M is optically active and gives positive result with I2/NaOH.
III Isomer N reacts instantly with Lucas reagent but does not decolourise acidified
solution of potassium permanganate.
Explain the above observations and suggest the structural formulae of isomers L, M
and N.

ANS:

i) CH3CH2CH2CH2OH HCl/ ZnCl2(conc) No observable change

(L)
Observation: no cloudy solution formed

CH3CH2CH2CH2OH K2Cr2O7, H+, CH3CH2CH2COOH

Observation: orange solution changes to green

Isomer L is primary alcohol because it gives negative result with Lucas reagent and it
forms carboxylic acid when oxidized with acidified K2Cr2O7.

ii) I2/ NaOH - +

H3C CH2 CH CH3 H3C CH2 C O Na
OH
+ CHI3
O
(M)
Observation: Yellow precipitate is formed
Isomer M is optically active because it has a chirality centre (*) and it gives positive
result towards iodoform test due to the presence of methyl alcohol group.
iii) OH Cl

H3C C CH3 HCl/ ZnCl2(conc) H3C C CH3

CH3 CH3
(N)
Observation: Solution turns cloudy immediately
OH

H3C C CH3 KMnO4, H+ No observable change

CH3
(N)
Observation: purple colour of solution retained
Isomer N a tertiary alcohol because it is reactive towards Lucas reagent and cannot be
oxidised

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CHAPTER 8.0 : HYDROXY COMPOUNDS
CHAPTER 8.0 : HYDROXY COMPOUNDS UNIT 8.3 : PHENOL
LEARNING OUTCOMES:
8.5: PHENOL
a) Compare the acidity of phenol, alcohol and water.
b) Explain the chemical properties of phenol with reference to:
a. reaction with sodium
ii. reaction with sodium hydroxide
iii. identification tests using (i) FeCl3 solution and (ii) bromine water.

TUTORIAL QUESTIONS :

1. Give the IUPAC name for each of the following compounds.

(a)
HO OH

(b) CH3
CHCH3

HO
(c) NO2

O2N OH

NO2
(d) - +
O Na

ANS:
(a) 1,4-benzenediol @ p-dihydroxybenzene.
(b) m-isopropylphenol
(c) 2,4,6-trinitrophenol
(d) sodium phenoxide

2. Draw the structural formulae of the following compounds.

(a) 2-bromo-6-nitrophenol
(b) 5-chloro-2-methylphenol
(c) 4-tert-butyl-2,6-difluorophenol
(d) 4-amino-2,5-dichlorophenol

ANS:

Br Cl
(a) (b)

OH OH

NO2 CH3

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CHAPTER 8.0 : HYDROXY COMPOUNDS
F Cl
CH3
(c) CH3 (d)
HO H2N OH
CH3
F
Cl
3. The structural formula of X is shown below.
OH

CH2 CH2 CH2 OH

Draw the structural formula of the product formed when X reacts with
(a) sodium
(b) aqueous sodium hydroxide
(c) phosphorus pentachloride
(d) propanoic acid refluxed with traces of concentrated sulfuric acid

ANS:
(a) - + (b) - +
O Na O Na

- +
CH2CH2CH2O Na CH2CH2CH2OH

(c) OH (d) OH

O
CH2CH2CH2Cl CH2CH2CH2OCCH2CH3

4. Explain the following observations:

(a) Phenol is soluble in aqueous solution of sodium hydroxide but cyclohexanol is
not.
(b) Ethanol reacts with iodine in aqueous solution of sodium hydroxide to produce
yellow precipitate but 1-propanol does not.

ANS:

+ -
HO Na O
sodium phenoxide
(a)
+ NaOH (aq) + H2O

Phenol is more acidic than cyclohexanol. So phenol can react with a base to yield
sodium phenoxide which is a soluble salt.

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CHAPTER 8.0 : HYDROXY COMPOUNDS
NaOH
(b) CH3CH2OH + 3I2 CHI3 + HCOO-Na+

yellow precipitate
NaOH
CH3CH2CH2OH + 3I2 no observable change

Yellow precipitate is produced by ethanol because it has methyl alcohol group

whereas 1-propanol does not have the group.

5. Compound Y, C7H8O, is insoluble in water, dilute HCl and aqueous NaHCO3 but
dissolves in dilute aqueous NaOH. When Y is treated with bromine water, it is
converted rapidly into a compound with molecular formula C7H5OBr3.
(a) Suggest the structural formula of Y.
(b) Write all the equations involved.
(c) Give one confirmatory test for Y.

ANS:
OH

(a) CH3

3-methylphenol - +
OH O Na
(b)
+ NaOH(aq)
CH3 CH3

OH OH
Br Br
+ Br2/H2O
CH3 CH3
Br

(c) confirmatory test

OH OH

+ FeCl3
CH3 CH3
FeCl3
Y
purple complex

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CHAPTER 8.0 : HYDROXY COMPOUNDS

OBJECTIVE QUESTIONS:
1. Which of the following alcohol gives 2-methylpropanoic acid when it is oxidized?
A. 1-Butanol
B. 2-Butanol
C. 2-Methyl-1-propanol
D. 2-Methyl-2-propanol

2. When compound X, which is optically active, is warmed with chromic acid, an optically
inactive compound Y is formed. Y does not react with alkaline iodine. X is
A. (CH3)2CHCH2OH
B. C6H5-CH(OH)CH2CH3
C. CH3CH2CH2CH(OH)CH3
D. CH3CH2CH(OH)CH2CH3

3. Compound V gives the following observations:

 It gives positive triiodomethane test.
 It evolves white fumes when reacted with SOCl2.
 It decolourises purple colour of hot acidified KMnO4 solution.
Compound V is
A. CH3CH2OH
B. (CH3)3COH
C. CH3COCH2CH3
D. HOCH2C(CH3)2CH3

4. The reaction below is classified as

(CH3)3COH + HBr  (CH3)3CBr + H2O
A. oxidation
B. reduction
C. substitution
D. condensation

5. Which of the following statement is NOT true about an alcohol?

A. Methanol is the simplest alcohol.
B. Alcohol is more polar than haloalkane.
C. Ethanol can be prepared by fermentation.
D. Solubility of alcohol in water increases with number of carbon atoms.

6. When bromine is added to phenol, the brown colour of bromine is decolourised and a white
precipitate of 2,4,6-tribromophenol is formed. This is an example of
A. electrophilic addition
B. free radical substitution
C. electrophilic substitution
D. nucleophilic substitution

7. 2-butanol is ______ soluble in water compared to propanoic acid ;

2-butanol is ______ soluble in watter than 2-methylbutane.
A. more,more B. more, less
C. less,more D. less,less

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8. Arrange the following compounds in order of increasing boiling point.

I HOCH2CH2OH
II CH3CH2CH2OH
III CH3CH(OH)CH3
IV HOCH2CH2CH2OH

A. II < III < IV < I

B. III < II < I < IV
C. I < IV < III < II
D. II < III < I < IV

9. Phenol and phenylmethanol differ in their reaction with

A. propene.
B. aqueous iron(III) chloride.
C. sodium
D. magnesium

10. 1-Butanol can be differentiated from 2-butanol by using

A. alkaline iodine
B. phosphorus(V) chloride
C. acidified potassium dichromate solution
D. Brady’s solution

11. Oxidation of 2-pentanol produces compound X. X gives

A. negative reaction with Tollen’s reagent.
B. decolourisation of solution with bromine water.
C. positive reaction with schiff’s reagent.
D. gas that turned lime water milky

12. Which of the following compound(s) could be formed by the dehydration of 1-butanol?
A. 2-Butene
B. 1,3-Butadiene
C. 2-Methyl-1-propene
D. butanone

13. Compound X, C4H10O, can be oxidized to C4H8O2 by acidified potassium permanganate

solution. X could be
A. (CH3)2CHCH2OH
B. CH3CH2CH(OH)CH3
C. CH3CH(OH)CH2CH3
D. (CH3)3C(OH)

14. Which of the following reagents can be used to distinguish between phenol and phenyl
methanol?
A. PCl5
B. KCN
C. KMnO4, H+, 
D. 2,4-DNPH

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