ALCOHOLS

At the end of this chapter, students should be able

to:
Draw the structures, classify and name the hydroxy
compounds according to IUPAC nomenclature
Explain physical properties of alcohol.
Explain the reaction of alcohol:
1. Formation of halogenoalkanes
2. Reactions with sodium
3. Oxidation
4. Dehydration
5. Esterification

Explain the identification tests to distinguish

classes of alcohols using:

Lucas reagent
2. KMnO4/H+ or Cr2O72-/H+
1.

INTRODUCTION
Hydroxy compounds include aliphatic alcohols,

phenols and aromatic alcohols.

Aliphatic alcohols are organic compounds with
at least one hydroxy (-OH) group attached to
the alkyl group.
Functional group hydroxy (-OH) group.
General formula: CnH2n+1OH

IUPAC Nomenclature
Find the longest carbon chain containing

the carbon with the -OH group.

Drop the -e from the alkane name, add -ol.
Number the chain, starting from the end
closest to the -OH group.
Number and name all substituents. =>

Name these:
CH3
CH3

CH CH2OH

2-methyl-1-propanol

OH
CH3

CH CH2CH3
2-butanol

CH3
CH3

OH

C OH
CH3

2-methyl-2-propanol

Br

CH3

3-bromo-3-methylcyclohexanol
=>

Classification
Primary: carbon with OH is bonded to one other carbon.
Secondary: carbon with OH is bonded to two other

carbons.
Tertiary: carbon with OH is bonded to three other
carbons.
Aromatic (phenol): -OH is bonded to a benzene ring.
H
CH 3
CH 3
CH3-C-OH CH3-C-OH CH3-C-OH
H
H
CH 3
Ethanol
2-propanol
2-methyl-2propanol
Primary (1o)
secondary (2o)
tertiary (3o)
alcohol
alcohol
alcohol

Physical Properties
Alcohols are polar compounds
H
O
H

C
H

they interact with themselves and with other

polar compounds by dipole-dipole interactions

Dipole-dipole interaction: the attraction

between the positive end of one dipole and

the negative end of another

Physical Properties
Hydrogen bonding:
bonding when the positive end

of one dipole is an H bonded to F, O, or N

(atoms of high electronegativity) and the
other end is F, O, or N

the strength of hydrogen bonding in water is

approximately 21 kJ (5 kcal)/mol
hydrogen bonds are considerably weaker
than covalent bonds
nonetheless, they can have a significant
effect on physical properties

Hydrogen Bonding

Physical Properties
In relation to alkanes of comparable size

and molecular weight, alcohols

have higher boiling points
are more soluble in water

The presence of additional -OH groups in a

molecule further increases solubility in

water and boiling point
Solubility of alcohols in water decreases
with increasing carbon number

REACTIONS
Formation of halogenoalkanes
Reactions with sodium
Oxidation
Dehydration
Esterification

Formation of
Halogenoalkanes
Reagent: Hydrogen halide (HX) or phosphorus
halide (PX3 or PX5) or SOCl2
1.With hydrogen halide
- the alcohol is refluxed with NaX and
concentrated H2SO4 (to produce HX)
- eg: NaCl + H2SO4
HCl + NaHSO4
C2H5OH + HCl
C2H5Cl + H2O
- most suitable for chlorides and bromides
-

2. With phosphorus halide & sulphur dichloride oxide.

- iodoalkanes can be made by warming a alcohol

with a mixture of red phosphorus and iodine.
- phosphorus (III) iodide is first formed which then
reacts with alcohol
2P + 3I2
2PI3
3CH3OH + PI3
3CH3I + P(OH)3
- chloroalkanes can be made by reacting alcohols
with phosphorus (III) chloride, PCl 3, phosphorus (v)
chloride, PCl5, or sulphur dichloride oxide, SOCl 2.
CH3CH2OH +PCl5
CH3CH2Cl + HCl + POCl3
CH3CH2OH + SOCl2
CH3CH2Cl + HCl + SO2

Reaction with sodium

Alcohols react with sodium to give hydrogen

gas
Eg: C2H5OH + Na

C2H5O-Na+ + 1/2H2
sodium ethoxide

-observation: sodium sinks and bubbles of

H2(g) evolved.

Oxidation
Reagent : acidified K2Cr2O7 ( or acidified KMnO4)
Condition: heat or reflux
Observation: orange aq. K2Cr2O7 turns green ( due to

formation of Cr3+ ions)

or purple aq. KMnO4 decolourised (due to formation of Mn2+
ions).
Primary alcohols
- are oxidised to aldehydes an then to carboxylic acids
CH3CH2OH + [O]
CH3CHO(ethanal) + H2O
Cr2O72-/H+
reflux
CH3COOH
(ethanoic acid)

Secondary alcohols
- Are oxidised to ketones
Eg:
H
Cr2O72-/H+
CH3-C-CH3 + [O]
CH3C=O + H2O
OH
reflux
CH3
propanone
Tertiary alcohols
- are not oxidised
- Bcoz tertiary alcohols do no have any hydrogen
atom to be removed from the carbon atom to which
the OH group is attached
Thus, oxidation is used to distinguish primary,
secondary, and tertiary alcohols.

Dehydration
Reagent: excess concentrated H2SO4
Condition: heat at about 170oC
Product: alkenes

excess c. H2SO4
Eg: CH3CH2OH
CH 2=CH2 + H2O
ethanol
heat at 170oC
ethene
If excess ethanol is used & the temperature is
kept about 140oC, ether is produced instead
of ethene
c. H2SO4

2CH3CH2OH
ethanol (excess)

CH3CH2OCH2CH3 + H2O
heat at 140oC

ethoxyethane (ether)

Esterification
Reagent: carboxylic acid or acyl halide
Product: sweet-smelling ester
1. With carboxylic acid
- condition: reflux in the presence of a small amount of

concentrated H2SO4
Eg: CH3CH2O + CH3C=O
H
OH
ethanol

ethanoic acid

CH 3C=O
+ H 2O
OCH 2CH3
ethyl ethanoate

- Concentrated H2SO4 is added as a catalyst

it also helps to increase the equilibrium yield of ester by

removing the H2O formed and so, shifts the equilibrium
to the right.

2. With acyl halide

- condition: room temperature

eg:
CH3CH2O + CH3C=O
CH3C=O
+ HCl
H
Cl
OCH2CH3
ethanol

ethanoyl chloride

ethyl ethanoate

- this reaction is very much faster than that

with carboxylic acid because ethanoyl
chloride is very reactive.

Identification tests to
distinguish classes of alcohols
1.

Lucas reagent

no visible reaction: primary

solution turns cloudy in 3-5 minutes:

secondary
solution turns cloudy immediately
2.

KMnO4/H+ or Cr2O72-/H+ (discussed in oxidation

reaction)