REACTIONS OF ALCOHOLS

& ETHERS
1. Combustion (Extreme Oxidation)
alcohol + oxygen carbon dioxide + water
2 CH3CH2OH + 6 O2 4 CO2 + 6 H2O

2. Elimination (Dehydration)
H2SO4/100 C
alcohol alkene + water
H2SO4/100 C
CH3CH2CH2OH CH3CH=CH2 + H2O

3. Condensation
H2 SO4/140 C
excess alcohol ether + water
H2 SO4/140 C
2 CH3CH2OH CH3CH2OCH2CH3 + H2O
4. Substitution
Lucas Reagent
ZnCl2
alcohol + hydrogen halide alkyl halide + water
ZnCl2
CH 3CH2OH + HCl CH3CH 2Cl + H2O

This reaction with the Lucas Reagent (ZnCl2) is a qualitative

test for the different types of alcohols because the rate of the
reaction differs greatly for a primary, secondary and tertiary
alcohol.
The difference in rates is due to the solubility of the
resulting alkyl halides
Tertiary Alcohol turns cloudy immediately (the alkyl
halide is not soluble in water and precipitates out)
Secondary Alcohol turns cloudy after 5 minutes
Primary Alcohol takes much longer than 5 minutes to
turn cloudy
5. Oxidation
Uses an oxidizing agent such as potassium
permanganate (KMnO4) or potassium dichromate
(K2Cr2O7).
This reaction can also be used as a qualitative test
for the different types of alcohols because there is a
distinct colour change.
dichromate chromium 3+
(orange) (green)
permanganate manganese (IV) oxide
(purple) (brown)
Tertiary Alcohol not oxidized under normal conditions
CH 3
KMnO4
H 3C C OH
K2Cr2O7
NO REACTION
CH 3
tertbutyl alcohol

Secondary Alcohol ketone + hydrogen ions

H
O
KMnO4
H 3C C CH 3
K2Cr2O7 C + 2 H+
H3C CH 3
OH
propanone
2-propanol

Primary Alcohol aldehyde + water carboxylic acid + hydrogen ions

KMnO4 O H H KMnO4
O H H
CH 3CH2CH 2OH
K2Cr2O7
C C C H + H 2O C C C H + 2 H+
K2 Cr2O 7 HO H H
H H H
1-propanol
propanal propanoic acid
6. Acid-Base Reactions
Like water, alcohols can act as an acid or base,
depending on what it is reacting with.
When they react as an acid, the alkyl oxide ion
(R-CH2O-) is formed.
ethanol + sodium ethoxide ion + sodium ion + hydrogen
2 CH3CH2OH + 2 Na 2 CH3CH2O- + 2 Na+ + H2
When they react as a base, the alkyl oxonium ion
(R-CH2OH2+) is formed
ethanol + sulfuric acid ethyloxonium ion + bisulfate ion
CH3CH2OH + H2SO4 CH3CH2OH2+ + HSO4-
 Preparation of Alcohols
1. Hydration of an Alkene
H2 SO 4 / 100C
alkene + water alcohol
H H H
H2 SO4 / 100C
H2C CHCH3 + H2O H C C C H

H OH H

2. Oxidation of an Alkene
This reaction uses an oxidizing agent like KMnO4 or
K2Cr2O7 to produce a diol.
KMnO4
alkene + water "diol"
K2Cr 2O7
KMnO4 H H H
H2C CHCH3 + H2O H C C C H
K2Cr 2O7
OH OH H
 Reactions of Ethers
1. Ethers do not react with oxidizing or reducing
agents.
2. Combustion
ether + oxygen carbon dioxide + water
CH3-O-CH3 + 3 O2 2 CO2 + 3 H2O
3. Reaction with Concentrated

Binary Acids
ether + 2 binary acid 2 alkyl halides + water

CH 3OCH 2CH3 + 2 HCl H3CCl + ClCH2CH3 + H2O
4. Reaction with Atmospheric Oxygen
This is a slow reaction in which highly unstable
peroxides are formed
ether + oxygen peroxide
CH 3OCH 2CH3 + O2 H3COOCH2CH 3
 HOMEWORK
Pg 44 # 7-9
Pg 48 # 12, 13 of Practice
Pg 48 # 2-4, 6 of Section