Alcohols

Chemistry Unit 2
C. Bailey Polack
 ALCOHOLS

O
H

Learning
Outcomes
2.6. Describe selected chemical reactions of
alcohols: with KMnO4/H+, K2Cr2O7/H+;
carboxylic acid, conc.H2SO4; I2, NaOH
(iodoform test)
 Alcohols
⦿ All alcohols belong to a family of organic
compounds which contain the –OH group of
atoms.
⦿ This group of atoms is called the hydroxyl group
⦿ Most alcohols are colourless liquids with a strong
smell.
⦿ The members of the alcohol homologous series
have the following features:
1. They have the general formula: CnH2n+1OH,
2. They have a hydroxyl functional group, –OH.
3. Their names end with ‘-ol’.
4. The formula of each member differs from the
previous one by –CH2.
Homologous Series of Alcohols
1. Explain why methanol is a liquid at r.t.p
Methanol RMM(32)
Propane RMM (44)
Butane RMM (58)

2. Explain why alcohols are soluble in water

3. Does solubility of alcohols changes when

RMM increases in the homologous series?
 Different types of Alcohols

Primary (1º) Secondary (2º ) Tertiary (3º)

H CH3 CH3
│ │ │
CH3─C─OH
CH3─C─OH CH3─C─OH
│ │ │
H H CH3

1C 2C 3C
attached attached attached
to C-OH to C-OH to C-OH
 Alcohols
Chemical Reactions

Reaction with a reactive metal like sodium

Combustion

C2H5OH(l) + 3O2(g) 🡪 2CO2(g) + 3H2O(l)

 Alcohols
Chemical Reactions

Oxidation

H+/K2Cr2O7
[O]
+ H 2O

During the reaction, the K2Cr2O7 solution is

reduced and the solution turns from orange to
green in colour.
Acidified KMnO4 oxidized primary alcohols similar
to K2Cr2O7
• The exact reaction, however, depends on the
type of alcohol, i.e. whether it is primary,
secondary, or tertiary, and on the conditions.
 Oxidation of 1° Alcohols
In the oxidation [O] of a primary alcohol 1°, one H is
removed from the –OH group and another H from
the C bonded to the –OH. ( this is incomplete
oxidation and occurs with limited oxidizing agent)

PRIMARY ALCOHOL ALDEHYDE

OH O
│ ║
CH3─C─H CH3─C─H + H2O
│
H
ethanol ethanal
 Try
• Oxidation of propanol with a small amount of
potassium dichromate
When writing the formulae of aldehydes in a
condensed way write CHO and not COH
e.g.CH3CH2CHO
Full Oxidation of Primary Alcohols
• In the full oxidation [O] of a primary alcohol
1°,the aldehyde formed would be oxidized
to an acid. ( you don’t have to show intermediate)
 Try
• Oxidation of propanol with excess potassium
dichromate
 Oxidation of 2° Alcohols
The oxidation of 2° alcohols is similar to 1°, except that a
ketone is formed. There is no further oxidation of this
product

SECONDARY ALCOHOL KETONE

OH O
│ ║
CH3─C─CH3 CH3─C─CH3 + H2O
│
H
2-propanol 2-propanone
 Oxidation of 3° Alcohols

Tertiary 3° alcohols cannot be oxidized.

TERTIARY ALCOHOL NO REACTION

OH
│
CH3─C─CH3 no product
│
CH3 no H on the C-OH to oxidize
2-methyl-2-propanol
 Alcohols
Esterification

Alcohols react with carboxylic acids to form

sweet smelling compounds known as esters.
The esterification reaction involves heating
under reflux and use of catalyst(conc. H2SO4). It
is a condensation reaction. It is reversible

conc H2SO4

reflux
 Alcohols
Dihydration
Ethanol is heated with an excess of concentrated
sulphuric acid at a temperature of 170°C.

170oC

If ethanol vapour is heated at 450 °C and pass over

aluminium oxide powder (Al2O3) , the ethanol is
essentially cracked to give ethene and water vapour.
The acid catalysts normally used are either
concentrated sulphuric acid or concentrated
phosphoric acid, H3PO4
 Alcohols

Iodoform Test
THE IODOFORM REACTION NaOH/I2
The triiodomethane (iodoform) reaction can be used
to identify the presence of a CH3CHR(OH) group in
alcohols. A positive result is the appearance of a
very pale yellow precipitate of triiodomethane
(previously known as iodoform) - CHI3. A positive
result is given by an alcohol containing the grouping:
 Iodoform Test
•Ethanol is the only
primary alcohol to give
the triiodomethane
(iodoform) reaction.
•If "R"is a hydrocarbon
group, then you have a
secondary alcohol. Lots
of secondary alcohols
give this reaction, but
those that do all have a
methyl group attached to
the carbon with the -OH
group. E.g. Propan-2-ol
•No tertiary alcohols give
the triiodomethane
(iodoform) reaction.
 Alcohols
Lucas Test
Lucas test in alcohols is a test to differentiate
between primary, secondary and tertiary
alcohols. It is based on the difference in
reactivity of the three classes of alcohols with
hydrogen
halides.                                                                      
               

PRIMARY no visible reaction

SECONDARY solution turns cloudy in 3-5 minutes
TERTIARY solution turns cloudy immediately,
and/or phases separate
The test is usually conducted at room temperature.
 OXIDATION ETHANAL
Cr2O7-2 Dilute H+
(GENTLE)

OXIDATION Conc. ETHANOIC

-
MnO4 ACID
(VIGOROUS) H2SO4 /hot

Conc.
ETHANOL DEHYDRATION H2SO4 or ETHENE
H3PO4 or 4400C
Al2O3/heat

Carboxilic ETHYLETHANOATE
ESTERIFICATION H+/ reflux
acid

IODOFORM TEST NaOH/I2 warm TRIIODOMETHANE