THE ROMAN RIDGE SCHOOL

AS/A Level
Founded 2002
Chemistry U6
 TOPIC: ALCOHOLS
SUB-TOPICS:
Formation of alcohols
Reactions of alcohols

AIMS:
To examine properties and reactions of alcohols
To explore iodoform reaction
SUCCESS CRITERIA: I can …
Classify alcohols
Describe the reactions of alcohols
Describe iodoform reaction
Use chemical reactions to differentiate between alcohols
 Classification of Alcohols
Aliphatic • general formula CnH2n+1OH - provided there are no rings
• the OH replaces an H in a basic hydrocarbon skeleton

Aromatic • in aromatic alcohols (or phenols) the OH is attached directly to the ring
• an OH on a side chain of a ring behaves as a typical aliphatic alcohol

The first two compounds are

classified as aromatic alcohols
(phenols) because the OH group
is attached directly to the ring.
 Classification of Alcohols
Primary, secondary and tertiary

A chain of carbon atoms can be represented by R when drawing the structure.

This is referred to as an R group.

⚫ Primary (1°) alcohols have one R group

attached to the carbon to which the OH
group is attached.

⚫ Secondary (2°) alcohols have two R

groups attached to the carbon to which the
OH group is attached.

⚫ Tertiary (3°) alcohols have three R

groups attached to the carbon to which the
OH group is attached.
Naming alcohols
Alcohols with three or more carbon atoms display positional isomerism. The number
of the carbon to which the hydroxyl groups is attached is written before the –ol.

propan-1-ol propan-2-ol
 Physical Properties of Alcohols
1. Volatility: Aliphatic alcohols with less than 12 carbon atoms and lower aryl
alcohols are liquids at room temperature.

Example CH3CH2OH CH3OCH3 CH3CH2CH3

Mr 46 46 44
Boiling Point/oC 78.5 -24 -42

This is due to the presence of intermolecular

hydrogen bonding in alcohols.

Hydrogen Bonding
 Physical Properties of Alcohols
2. Solubility: Lower alcohols are soluble in water because they form hydrogen
bonds with water molecules.
δ+
δ- δ+

δ+
δ+

δ-

δ+

δ-

δ+
 Reactions of Alcohols
1. Combustion
• Alcohols burn to give CO2 and H2O.

Example: C2H5OH + 3O2 2CO2 + 3H2O

With a good supply of air, ethanol burns with a pale blue (non-luminous) flame.

With a limited supply of air, ethanol burns with a yellow (luminous) flame
and some soot (carbon) is also formed.
 Reactions of Alcohols
2. Substitution to give halogenoalkanes
Reagent: hydrogen halide (HX) or phosphorus halide (PX3 or PX5) or SOCl2.

• With hydrogen halide:

The alcohol is refluxed with NaX and concentrated H2SO4 (to produce HX ).

NaCl + H2SO4 HCl + NaHSO4

Example:
C2H5OH + HCl C2H5CI + H2O

• With phosphorus halide:

Alcohols react with PI3 (prepared in situ by mixing red phosphorus and iodine)
to give iodoalkanes.

Example: 3C2H5OH + PI3 3C2H5l + H3PO3

 Reactions of Alcohols
• With phosphorus halide:
Alcohols react with PCl5 (at room temperature) to give chloroalkanes.

Example: C2H5OH + PCl5 C2H5Cl + POCl3 + HCl

• With thionyl chloride (SOCl2):

SOCl2 is useful for producing chloroalkanes. The other products are gases
and escape from the solution.

Example: C2H5OH + SOCl2 C2H5Cl + SO2 + HCl

 Reactions of Alcohols
3. Reaction with sodium
• Alcohols react with sodium to give hydrogen gas.

𝟏
Example: C2H5OH + Na C2H5O-Na+ + H2
𝟐

4. 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).
 Reactions of Alcohols
4. Oxidation
Primary alcohols are oxidised to aldehydes and then to carboxylic acids.

Cr2O72-/H+ + H2O
CH3CH2OH + [O] reflux
Ethanol
Ethanal
mixture of
alcohol, water out
dilute sulfuric
[O]
acid and
potassium
dichromate(VI)
aldehyde
water in

ice Ethanoic acid

heat
 Reactions of Alcohols
4. Oxidation
Secondary alcohols are oxidised to ketones.
H
Cr2O72-/H+
CH3 C CH3 + [O] + H2O
reflux
OH
Propan-2-ol Propanone

Tertiary alcohols are not oxidised.

 Reactions of Alcohols
5. Dehydration to alkenes
• Condition: heat + Al2O3, porous pot or pumice as catalyst
• Product: alkenes

H H H H H H
Al2O3
ceramic wool soaked H C C C H H C C C H
Heat
in ethanol ethene gas H
H H OH
+ H2O
Propene
Propan-1-ol

aluminium
oxide
H H H H H H
Al2O3 H C C H
H C C C H C
water Heat
H OH H Propene H
Propan-2-ol + H2O
 Reactions of Alcohols
5. Dehydration to alkenes
If the carbon chain is four or more carbons in length and the -OH is not attached to a terminal
carbon, a mixture of positional isomers may be formed.

OH
but-1-ene

Butan-2-ol

but-2-ene
 Reactions of Alcohols
6. Ester formation
• Reagent: carboxylic acid or acyl halide
• Product: sweet-smelling ester
• With carboxylic acid:
Condition: reflux in the presence of a small amount of concentrated H2SO4

Ethanol
Ethanoic acid Ethyl ethanoate
 Reactions of Alcohols
6. Ester formation
• With acyl halide:
Condition: room temperature

Ethanol
Ethanoyl chloride Ethyl ethanoate

This method can be used to prepare phenate esters.

Ethanoyl chloride Phenol

Phenyl ethanoate
 Reactions of Alcohols
7. Tri-iodomethane (iodoform) reaction
• Reagent: aqueous iodine and aqueous NaOH
• Condition: warm
• Observation: yellow crystals of CHI3 formed.
• Only alcohol with CH3CH(OH)- group gives yellow crystals of CHI3 when
warmed with alkaline aqueous iodine.
 REVIEW AND REINFORCEMENT

Classify alcohols
Describe the reactions of alcohols
Describe iodoform reaction
Use chemical reactions to differentiate between alcohols