5.

0
Alcohol

~ Organic compound with at least one hydroxyl group (OH) which act as
functioning group.

Alcohol has the general formula of CnH2n+1OH or sometimes CnH2n+2O.

The naming of alcohol end with ~ol.
5.1
Nomenclature of alcohol (naming & classifying alcohol)

The way of naming alcohol is similar to the way of naming alkene
[1] Find the longest carbon chain with OH in it, and name accordingly
[2] Identify the alkyl group that attached towards the parent chain and name
the alkyl
[3] Give the prefic of di- ; tri- or tetra based on how many similar alkyl attached
toward it
[4] Give the numbering of alkyl based on the carbon number based on alcohol

3-methylpentan-2-ol

4-methylpentan-1-ol
CH3CH2CH(CH3)CH2OH

2-methylbutan-1-ol
4-methylpentan-2-ol

3,4-dimethylheptan-4-ol

4-ethyl-2-methylhexan-2-ol
C(CH3)3CH(OH)CH2CH3

2,2-dimethylpentan-3-ol
3,3-dimethylbutan-2-ol

5-ethyl2,5-dimethylheptan-2-ol

5-ethyl-2-methylheptan3-ol
C(CH3)3CH2C(OH)(CH3)2

2,4,4-trimethylpentan-2-ol
3-ethyl-2,4-dimethylpentan-2-ol

Isomerism in alcohol.

Alcohol may exhibit structural isomerism and in some case, optical
isomerism. For example, butanol, C4H9OH, may have 5 different isomers


Practice : write out all the possible isomers for pentanol, C5H11OH

5.2
Physical properties of alcohol
(A)
Boiling point of alcohol

Similar to other organic compounds, the boiling point of alcohol increased
with number of carbon
Alcohol

CH3OH

C2H5OH

C3H7OH

C4H9OH

C5H11OH

C6H13OH

C7H15OH

C8H17OH

Boiling point oC

46

78

90

115

135

152

169

190

Boiling point
trend

BOILING POINT INCREASE DOWN HOMOLOGUS SERIES

increase

Similar to other organic compounds, the boiling point .
with the

number of carbon as the weak Van Der Waals forces increase with
molecular mass of the compound.

Though, the hydrogen bonding are weaker when goes down to homologous
series as the polarity of molecules as the decrease
number of carbon
increase.

Similar too, to other organic compound, alcohol with more branch has lower
boiling point than a straight-chain molecule

Molecules

Boiling point
(0C)

Butan-1-ol

Butan-2-ol

2-methylpropan-2-ol

117

99

82

Straight chain molecules have higher boiling point compare to branched

largerthan a
chain because straight chain molecule has a surface area

branched chain molecule. The more branches attached to the parent chain,
weaker between
the . the surfacesmaller
area ; the forces of attraction
lower
molecules ; the boiling point.


The number of the hydroxyl group in an organic compound is also one of the

major factor which contribute to its boiling point

Molecules
Boiling point
(0C)

Butan-1-ol

Butan-1,2-diol

Butan-1,2,3-triol

117

208

274

The boiling point of the alcohol increase with the number of OH. This is a
hydrogen
result caused by more ..
bond formed between OH of the

molecules. So the more the OH ; stronger the hydrogen bond ; higher the
boiling point.


Compare to alkane and haloalkane, alcohol has a higher boiling point

Compound

Ethanol (C2H5OH)

Propane
(C3H8)

Fluoroethane
(C2H5F)

Relative molecular
mass

46

44

48

Boiling point (oC)

78

4.2

Alcohol has the highest boiling point compare to other organic compound
hydrogen
because it forms strong ... bond
between the molecules.

Fluoroethane has a higher boiling point than propane as fluoroethane is a

polarand so, the weak forces are
. molecules
Van Derthan
Waals
stronger
propane since propane is a ... molecule.
Non-polar

B)Solubility of alcohol in water

Hydrogen bonding occur between alcohol molecules because of the
hydroxy
presence of .
group. This bring 2 important consequences
toward hydrogen where

It cause the boiling points of alcohol higher than those in alkanes
and haloalkanes

It cause lower alcohol (methanol and ethanol) to be completely
miscible with water.


Solubility decrease with the increase of number of carbon in alcohol. Butan-

1-ol and pentan-1-ol are slightly miscible with water and the rest become
more and more insoluble.

This is due to the non-polar properties of alkyl which attached to the OH,
directly influence the efficiency of hydrogen bond, causing the poplar
bonding to be more obvious than hydrogen bonding. (dipole-dipole
interaction between R- and R- are more obvious)

Ethanol is a good solvent for both polar and non polar solute because it
alkyl group and a polar group ()
hydroxyl
contain non polar (.)
in it. As a
result, ethanol is used as solvent in many industries

(C)
Acidity of alcohol

Alcohols are generally a weak acid. Table below shows the pKa value of some
alcohols and water
Compounds

Methanol
(CH3OH)

Ethanol
(C2H5OH)

Propan-1-ol
(C3H7OH)

Phenol
(C6H5OH)

p-methylphenol
CH3-C6H5OH

Water

pKa

15.5

16.0

18.0

10.0

11.0

14.0

As shown in the table above, alkyl-alcohol is weaker than phenyl-alcohol.

This is a result of the different effect of the group that attached to hydroxyl
group OH.
donating group whereas phenyl is an electron

Alkyl is an electron ....
withdrawing group.
..

Alcohol

Explanation
Ethanol dissociate in water according to the equation

+
CH3CH2OH
Ethanol

CH3CH2OH + H2O
CH3CH2O- + H3O+
Alkyl group, which is an electron donating group, donate electron
to O and caused the electron density of O in ROH increase. As a
result, O is more readily to accept proton, which makes the
equilibrium favours to left.
Phenol dissociate in water according to the equation

Phenol

C6H5OH + H2O
C6H5O- + H3O+
The phenyl group is an electron-withdrawing group, which
withdrawn the electron density from partially negative charge, ,
from O making O less readily to accept proton. As a result, O is
more readily to donate proton which makes equilibrium favour
more to right.

5.3
Chemical properties of alcohols
5.3.1
Preparation of alcohol in industries.

Alcohol can be prepared by a few methods in industries / laboratory
1. Fermentation
2. Hydration of alkene (see Chapter 2)
3. Hydrolysis of haloalkane (see Chapter 4)
4. Grignard reagent (see Chapter 4)
Name of
reaction

Reagent used
and condition

Equation

Fermentation
of glucose

Zymase enzyme

C6H12O6
2 CH3CH2OH + 2 CO2 Glucose

ethanol
carbon dioxide

Name of
reaction

Reagent used
and condition

Hydration of
alkene

Steam (H2O)
--------Phosphoric acid,
(H3PO4 )
At 300oC ; 60
atm
@
Concentrated H0
2SO4 at 80 C.

Hydrolysis of
haloalkane

NaOH (aq)
under reflux

Reaction of
Grignard
reagent

Aldehyde /
ketone with
H2SO4

Equation

1-chloropropane

sodium
Hydroxide

propan-1-ol

H 3O +

CH3CH2MgBr + CH3CH=O

CH3CH2CH(OH)CH3

5.4
Chemical reaction of alcohol

Aliphatic alcohol undergoes 2 types of reaction which involve ROH where :
Fission of O H

Fission of C O
Dehydration of alcohol
Reaction with hydrogen halide
Reaction with phosphorous halide
(PX5) or thionyl chloride, SOCl2

Formation of alkoxide
Formation of ester
Oxidation of alcohol

Name of reaction

Reagent used and

condition

Equation

Formation of
alkoxide

Sodium (Na)

2 CH3CH2OH + 2 Na
2 CH3CH2ONa+ + H2 (g)

Ethanol
sodium sodium ethoxide hydrogen

Esterification

Carboxylic acid
(RCOOH) catalysed
by conc. sulphuric
acid (H2SO4)

Ethanol

propanoic acid

ethyl propanoate

water

Name of
reaction

Reagent used and

condition

Oxidation of
alcohol

Acidified KMnO4 or
acidified K2Cr2O7 +
heat

Equation

propan-1-ol

propan-2-ol

Dehydration
(removal of
water)
from
alcohol

Excess conc.
H2SO4
at 1800C
or
Alumina (Al2O3) at
350oC

Halogenation of
alcohol

Phosphorous
pentachloride
(PCl5)

propanal

propanoic acid

propanone

CH3CH2CH2OH + PCl5

CH3CH2CH2Cl + POCl3 + HCl

(1)
Reaction with sodium metal

When sodium is added to alcohol, a white solid (sodium alkoxide)
formed and effervescences occur and hydrogen is released. Example :
2 CH3CH2CH2OH + 2 Na
2 CH3CH2CH2O-Na+ + H2
Propan-1-ol
sodium propoxide

Sodium alkoxide formed dissolve readily in water to form back alcohol
+ sodium hydroxide

The reaction is slower than when sodium reacts with water.

Reactivity decrease with the class increase 30 alcohol < 20 alcohol < 10
alcohol (less reactive)

Sodium hydroxide (NaOH) cannot react with aliphatic alcohol.
a) CH3CH(OH)CH3 + Na

Na+)CH + H2
CH
CH(O
3
3
b) C(CH3)2(OH)CH2CH3 + K

K+)CH CH + H2
C(CH
)
(O
3
2
2
3
c) CH3C(CH3)(OH)CH2CH3 + Na

CH3C(CH3)(ONa+)CH2CH3 + H2

(2)
Esterification : Formation of ester

When excess alcohol (ROH) react with carboxylic acid (RCOOH) and
catalysed by a few drops of concentrated sulphuric acid and heat under
reflux.

ROH + RCOOH
RCOOR + H2O
Alcohol

Carboxylic acid

Ester

CH3CH2OH
Ethanol

CH3COOH
Ethanoic acid

CH3CH2CH2OH
Propan-1-ol

CH3CH2CH2COOH
Butanoic acid

CH3CH2CH2CH2OH
Butan-1-ol

CH3CH2COOH
Propanoic acid

CH3CH2COOCH2CH2CH2CH3
butyl propanoate

H 2O

CH3CH2OH
Ethanol

CH3CH2COOH
Propanoic acid

CH3CH2COOCH2CH3
ethyl propanoate

H 2O

CH3COOCH2CH3
Ethyl ethanoate
CH3CH2CH2COOCH2CH2CH3
propyl butanoate

Water

H 2O

H 2O


Esterification can also be achieved by replacing carboxylic acid with alkanoyl

chloride
Example :

ethanol ethanoyl chloride

ethyl ethanoate hydrogen chloride

Note that in the reaction above, no acidic medium is required. Compare to
carboxylic acid, alkanoyl chloride is more reactive than carboxylic acid. Also,
the reaction produces a white fume of hydrogen chloride as side product.

(3)
Oxidation of alcohol

Using strong oxidising agent such as acidified potassium dichromate
[K2Cr2O7 / H+], alcohol can be oxidise to form carbonyl compound and
even to carboxylic acid.

Using different categories of alcohol, different type of carbonyl compounds
are formed.
Class

Example

10 alcohol
(methanol)

CH3OH

10 alcohol

CH3CH2CH2OH
propan-1-ol

20 alcohol

CH3CH(OH)CH3
propan-2-ol

30 alcohol

CH3C(CH3)(OH)CH3
2-methylpropan-2-ol

Reaction

No reaction


Note the following changes occur in the oxidation of alcohol

Oxidation of primary (10) alcohol will yield an aldehyde while

oxidation of secondary (20) alcohol will yield a ketone.

Aldehyde formed from 10 alcohol can be further oxidised to form
carboxylic acid. For the case of methanal, further oxidation of
methanal will yield carbon dioxide and water.

Tertiary (30) alcohol is not oxidised when react with strong oxidising
agent as it does not have H attached to the COH.

The differences in behaviour of alcohols toward oxidising agents
may be used to distinguish between 10 alcohol, 20 alcohol and 30
alcohol. So, this is consider a basic test to distinguish between the
class of alcohol used.

Alcohol

Product

CH3CH2CH2COOH

CH3CH2COCH3

No reaction

Alcohol

Product

CH3CH2COCH2CH3

C(CH3)3COOH

CH(CH3)2COCH3


In industries, oxidation of alcohol is carried under catalytic dehydrogenation,

where hydrogen is removed from the alcohol, forming aldehyde, ketone and
even an alkene.
Class

Example

10 alcohol

CH3CH2CH2OH
propan-1-ol

20 alcohol

CH3CH(OH)CH3
propan-2-ol

30 alcohol

CH3C(CH3)(OH)CH3
2-methylpropan-2-ol

Reaction

Note that, unlike oxidation using acidified potassium manganate (VII), here,

the side product is hydrogen gas. Furthermore, aldehyde and ketone formed
are not further oxidised.

(4) Dehydration of alcohol

Dehydration of alcohol is an elimination reaction where
water is removed from organic compound.

Dehydration of alcohol can be carried out under these
conditions :

Heating mixture of excess concentrated acid such as H2SO4 at 1800C

Passing alcohol vapour over aluminium oxide (Al2O3) as catalyst at

3000C.

Dehydrating 1o alcohol will yield only 1 product whereas

dehydrating 2o alcohol will yield 2 products.

Class

Example

10 alcohol

CH3CH2CH2OH
propan-1-ol

20 alcohol

CH3CH2CH(OH)CH3
butan-2-ol

30 alcohol

CH3CH2C(CH3)(OH)CH3
2-methylbutan-2-ol

Result

Propan-1-ol

propene


The major/minor products of the alkene formed followed Saytzeffs Rule

where alkene containing the greater alkyl is predominant. (H atom from a

lesser CH is preferably to be eliminated)

However, if excess alcohol react with concentrated H2SO4, ether is given off.

2 CH3CH2CH2OH
CH3CH2CH2OCH2CH2CH3 + H2O
Propan-1-ol
dipropyl ether

Same result is given off by using aluminium oxide (Al2O3). The ease of
dehydration increase in order from
10 alcohol < 20 alcohol < 30 alcohol.
Example : Write out the possible products for dehydration of these alcohols
1. CH3CH2CH(OH)CH2CH3

2. CH(CH3)2CH(OH)CH3

CH3CH2CH=CHCH3
3. C(CH3)3OH

+ C(CH3)2=CHCH3
CH(CH3)2CH=CH2
C(CH3)2=CH2

(5)
Halogenation of alcohol formation of haloalkane

As introduced in the earlier chapter, haloalkane can be prepared by adding
conc. hydrochloric acid (HCl) with the aid of zinc chloride, ZnCl2 to alkene.
This mixture is called as Lucas reagent.

Halogenation can also be carried out using halogen rich compound, such as
phosphorous (V) pentachloride (PCl5) or thionyl chloride (SOCl2).
CH3CH2CH2OH + HCl (conc)

CH3CH2CH2Cl + H2O
propan-1-ol
CH3CH2CH(OH)CH3 + PCl5

CH3CH2CH(Cl)CH3 + HCl + POCl3
butan-2-ol
CH3C(CH3)(OH)CH3 + SOCl2

C(Cl)(CH3)3 + HCl + SO2
2-methylpropan-2-ol


To prepare a bromoalkane, reagent used is concentrated hydrobromic

acid, HBr, catalysed by concentrated sulphuric acid

CH3CH2CH2OH + HBr (conc)

CH3CH2CH2Br + H2O
Propan-1-ol

5.4
Phenol and Aromatic alcohol
5.4.1 Manufacturing of phenol

There are 3 methods of making phenol.
#
The cumene process
#
The hydrolysis of chlorobenzene / diazonium salt
#
Alkali fusion with sodium benzenesulphonate
(1)
Synthesising phenol cumene reaction

Step 1 : Formation of cumene using benzene ring and propene.

Benzene

propene

Step 2 : Oxidation of cumene.

cumene


Step 3 : Decomposition by sulphuric acid : Migration of phenyl group

cumene hydroperoxide

phenol

propanone

(2)
Hydrolysis of chlorobenzene : Dow Process

Phenol has been process using Dow process widely in chemical industries. It
generally involve 2 steps.
Step 1 : Hydrolysis of chlorobenzene by NaOH to form phenoxide salt.

chlorobenzene

sodium phenoxide

Step 2 : Distillation of phenoxide salt mixed with hydrochloric acid.

Sodium phenoxide

phenol

(3)
Hydrolysis of diazonium salt

In laboratory, phenol is prepared by hydrolysis of diazonium salt.
Effervescence occur and a colourless gas is given out, along with the
white fume of hydrogen chloride

benzenediazonium chloride

water

phenol

The formation of azo will be discussed extensively when we are in

amine later part

5.5
Chemical reaction of phenol

The OH act as ring activating groups when attached to benzene. As a result,
it activates the rings and cause benzene to be more reactive. Consequently,
phenol is more reactive toward electrophilic substitution than benzene.
(1)

Halogenation of phenol

When bromine water is added to phenol at room temperature, brown colour of
bromine water decolourised and formed a white precipitate of 2,4,6tribromophenol.

(2)
Nitration of phenol

When concentrated nitric acid (HNO3) is used to react with phenol, it formed a
yellow crystalline solid of 2,4,6-trinitrophenol. This yellow crystal is used in dyeing
industries and make explosive

(3)
Reaction with iron (III) chloride, FeCl3

When a few drops of iron (III) chloride solution is added to phenol, a violetblue colouration produced. A methylphenol produce blue colour.

5.5

Chemical Test to distinguish between alcohols

Differentiate
Methanol
(CH3OH) and
other alcohol

Chemical test

Observation

Positive test : Methanol

Acidified
Purple colour of potassium manganate is decolourised.
potassium
Effervescence (Bubbling) occurs. Gas released turn lime water
manganate (VII) chalky
2 + H2O
Equation : CH3OH H2C=O
CO
Positive test : Ethanol
Add NaOH then iodine and heated gently. Pale yellow crystal of
Iodoform test
triiodomethane is formed.
Equation : CH3CH2OH + 4I2 + 6
CHI3 + 5 I- + HCOOPositive test : alkan-2-ol
Add NaOH then iodine and heated gently. Pale yellow crystal of
Iodoform test triiodomethane is formed.
Equation : RCH(OH)CH3 + 4 I2 + 6

CHI3 (s) + RCOO + 5 I + 5 H2O
[O]

Ethanol
(C2H5OH) and
other alcohol
Alkan-2-ol
(R-CHCH3)
OH
and other
alcohol

[O]

Phenol with
other
alkylalcohol

Positive test : Phenol

Add bromine water directly to phenol. The brown colour of
Bromine water bromine water is bleached instantly and a white precipitate is
formed.
Equation : refer above
Positive test : Phenol
Iron (III) chloride Add iron (III) chloride solution to phenol and a violet-blue
solution formed instantly.

CH3CH2CH2CH2CH2OH + HBr
CH3CH2CH2CH2CH2Br + H2O

Mol of 1-bromopentane formed = 15.0 / 5(12) + 11(1) + 80 = 0.09934 mol

Since only 60% ; mol of 1-bromopentane should be formed = 0.09934 x 100 / 60
mol = 0.1657 mol
Mass of pentan-1-ol required = 0.1657 x [ (5(12) + 12(1) + 16) ]
= 14.6 g (3.s.f. with unit)

Excess concentrated H2SO4 under reflux/ Al2O3 heated strongly

CH3CH2CH2CH2CH2OH
CH3CH2CH2CH=CH2 + H2O

KMnO4 / H+ or K2Cr2O7 / H+ under reflux

CH3CH2CH2CH2CH2OH + KMnO4 / H+
CH3CH2CH2CH2COOH + H2O
CH3COOH catalysed by conc. H2SO4 under reflux / CH3COCl
CH3CH2CH2CH2CH2OH + CH3COOH
CH3CH2CH2CH2OCOCH3 + H2O

100

Type of reaction : elimination reaction

Reagent : PCl5
Observation : White fume released by leaf alcohol while the other does not
Equation : CH3CH2CH=CHCH2CH2OH + PCl5

CH3CH2CH=CHCH2CH2Cl + POCl3 + HCl

C10H20O
alkene

156
alcohol

Citronellol : optical isomerism

Geraniol : geometrical isomerism

Observation : brown colour of aqueous bromine decolourised

Explanation : due to the presence of unsaturated C=C
Equation :

chlorine gas
Electrophilic aromatic substitution

neutralisation

Bromine water
white precipitate is formed
brown colour of bromine remain unchanged

Carbon attached with OH, that was surrounded by 1 carbon

secondary

primary

tertiary

orange
Isomer 3

green

(i) sodium metal

(ii) Br2 (aq)

(iii) NaOH(aq)

(iv) CH3COCl

(v)

hot acidified K2Cr2O7

(vi)

PCl5

B (pentan-2-ol)
B (pentan-2-ol)
A yellow precipitate is formed