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 / 100°C
alkene + water alcohol
H H H
H2 SO4 / 100°C
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