Alcohols F322 1

ALCOHOLS

Aliphatic • general formula CnH2n+1OH - provided there are no rings

• named as substituted alkanes by removing the final -e and adding -ol
• for isomers the position of the OH is given a number - propan-1-ol / propan-2-ol

Aromatic • in aromatic alcohols, the OH must be attached directly to a benzene ring

• an OH on a side chain of a benzene ring behaves as a typical aliphatic alcohol.

OH CH3 CH2OH
OH
Q.1 Which of the structures is/are
classified as phenols?

Structures • alcohols are classified according to the environment of the OH functional group
• chemical behaviour, especially with oxidation, often depends on the structure

H H C C
H C OH C C OH C C OH C C OH
H H H C
methyl primary secondary tertiary

1° 2° 3°

Physical properties
Boiling point Increases with molecular size due to increased van der Waals’ forces. Alcohols
have higher boiling points than similar molecular mass alkanes due to the added
presence of inter-molecular hydrogen bonding. More energy is required to
separate the molecules.
C
Mr bp / °C C
ethanol C2H5OH 46 +78 O
propane C3H8 44 -42 O H
H
intermolecular hydrogen
bonding in alcohols
Boiling point also increases for “straight” chain isomers.
Greater branching = lower inter-molecular forces.

bp / °C
butan-1-ol CH3CH2CH2CH2OH 118
butan-2-ol CH3CH2CH(OH)CH3 100
2-methylpropan-2-ol (CH3)3COH 83

H
Solubility Low molecular mass alcohols are miscible with water
C
O
due to hydrogen bonding between the two molecules. O H
H
Alcohols are themselves very good solvents, being able
intermolecular hydrogen
to dissolve a large number of organic molecules. bonding with water

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2 F322 Alcohols

PREPARATION OF ALCOHOLS

Laboratory • from haloalkanes - reflux with aqueous sodium or potassium hydroxide.

• from aldehydes - reduction with sodium tetrahydridoborate(III) - NaBH4.
• from alkenes - acid catalysed hydration using conc. sulphuric acid.

Industrial Fermentation
Reagent(s) GLUCOSE - from hydrolysis of starch
Conditions yeast
warm but no higher than 37°C
Equation C6H12O6 ——> 2 C2H5OH + 2 CO2

Direct hydration
Reagent(s) ETHENE - from cracking of fractions from distilled crude oil
Conditions • catalyst - phosphoric acid
• high temperature and pressure

Equation C2H4 + H2O C2H5OH

Q.2 List some advantages and disadvantages of the two major industrial methods.

Fermentation advantage(s) • CHEAP EQUIPMENT

• MADE FROM RENEWABLE RESOURCES - SUGARS

disadvantage(s) • SLOW REACTION

• IMPURE PRODUCT
• BATCH PROCESS - EXPENSIVE ON MANPOWER

Hydration advantage(s) • FAST REACTION

• CONTINUOUS PROCESS - CHEAPER MANPOWER
• PURE PRODUCT

disadvantage(s) • MADE FROM A NON-RENEWABLE RESOURCE - OIL

• EXPENSIVE EQUIPMENT

Uses ethanol •
•
•

methanol • fuel, added to petrol to improve combustion properties

• solvent
• a feedstock for important industrial processes

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Alcohols F322 3

CHEMICAL PROPERTIES

General Lone pairs on the oxygen atom makes alcohols Lewis Bases (lone pair donors).
They can use a lone pair to • pick up protons
• behave as nucleophiles.

Elimination Reagent conc. sulphuric acid (H2SO4) or conc. phosphoric acid (H3PO4)
Conditions reflux 180°C
Product alkene
Equation e.g. C2H5OH(l) ———> CH2 = CH2(g) + H2O(l)
Mechanism

H H H H H H
H H
HO HO
H C C H C C H2O H C C H C C H
H H H H
H H H H H

Step 1 protonation of the alcohol using a lone pair on oxygen

Step 2 loss of a water molecule to generate a carbocation
Step 3 loss of a proton (H+) to give the alkene

H H
Note 1 There must be a hydrogen atom on a carbon HO
atom adjacent the carbon with the OH on it C C

H H

Note 2 Alcohols with the OH in the middle of a chain

H H
have two ways of losing water. In Step 3 of the
mechanism, a proton can be lost from either side C C C
H
of the carbocation. This can give a mixture of H H

alkenes from unsymmetrical alcohols

Elimination
Method 2 Conditions Pass vapour over a heated catalyst of pumice or aluminium oxide

Q.3 Butan-2-ol reacts with concentrated sulphuric acid to give THREE isomeric alkenes.
What are they and how are they formed?

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4 F322 Alcohols

Oxidation of Alcohols

Provides a way of differentiating between primary, secondary and tertiary alcohols.

Reagents include acidified potassium dichromate(VI) or potassium manganate(VII)

Primary Easily oxidised to aldehydes and then to carboxylic acids.

e.g. CH3CH2OH(l) + [O] ——> CH3CHO(l) + H2O(l)

then CH3CHO(l) + [O] ——> CH3COOH(l)

• it is essential to distil off the aldehyde before it gets oxidised to the acid
• the alcohol is dripped into a warm solution of acidified K2Cr2O7
• the aldehyde has a low boiling point - no hydrogen bonding - it distils off
• if it didn’t distil off it would be oxidised to the equivalent carboxylic acid
• to oxidise an alcohol straight to the acid you would reflux the mixture

DISTILLATION REFLUXING
gives an gives a
ALDEHYDE CARBOXYLIC ACID

compound formula intermolecular bonding boiling point

ETHANOL C2H5OH HYDROGEN BONDING 78°C
ETHANAL CH3CHO DIPOLE-DIPOLE 23°C
ETHANOIC ACID CH3COOH HYDROGEN BONDING 118°C

Secondary Easily oxidised to ketones

e.g. CH3CHOHCH3(l) + [O] ——> CH3COCH3(l) + H2O(l)

N.B. On prolonged treatment with a powerful oxidising agent they can be further
oxidised to a mixture of acids with fewer carbon atoms than the original alcohol.

Tertiary Not oxidised under these conditions. They do break down with vigorous oxidation

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Alcohols F322 5

Combustion Alcohols make useful fuels

e.g. C2H5OH(l) + 3O2(g) ——> 2CO2(g) + 3H2O(l)

• have high enthalpies of combustion

• do not contain sulphur so there is less pollution
• can be obtained from renewable resources

Esterification Reagent(s) carboxylic acid + strong acid catalyst (e.g conc. H2SO4 )
Conditions reflux
Product ester
Equation e.g. CH3CH2OH(l) + CH3COOH(l) CH3COOC2H5(l) + H2O(l)
ethanol ethanoic acid ethyl ethanoate

An advantage of concentrated H2SO4 is that it is also a dehydrating agent and

removes water as it is formed causing the equilibrium to move to the right and thus
increasing the yield of ester.

Q.4 Name these esters; HCOOC2H5

CH3COOCH3

CH3CH2COOCH3

Complete the equations;

+ HCOOC2H5 + H2O

+ CH3COOCH3 + H2O

+ CH3CH2COOCH3 + H2O

CH3CH2CH2OH + CH3CH2COOH +

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6 F322 Alcohols

IDENTIFYING ALCOHOLS USING INFRA RED SPECTROSCOPY

BOND COMPOUND ABSORBANCE RANGE

O-H alcohols broad 3200 cm-1 to 3600 cm-1
O-H carboxylic acids medium to broad 2500 cm-1 to 3500 cm-1
C=O ketones, aldehydes strong and sharp 1600 cm-1 to 1750 cm-1
esters and acids

Differentiation Compound O-H C=O

ALCOHOL YES NO
ALDEHYDE / KETONE NO YES
CARBOXYLIC ACID YES YES
ESTER NO YES

ALCOHOL Wavelength (microns)

2.5 3 4 5 6 7 8 9 10 12 15

O-H absorption .00 .00

.10 .10

.20 .20
Absorbance

.40 .40

.80 .80

4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600
-1
Frequency , cm

Wavelength (microns)
ALDEHYDE 2.5 3 4 5 6 7 8 9 10 12 15

.00 .00

C=O absorption .10 .10

.20 .20
Absorbance

.40 .40

.80 .80

4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600
-1
Frequency , cm

CARBOXYLIC ACID Wavelength (microns)

2.5 3 4 5 6 7 8 9 10 12 15

O-H absorption .00 .00

C=O absorption .10 .10

.20 .20
Absorbance

.40 .40

.80 .80

4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600
-1
Frequency , cm

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Alcohols F322 7

INDUSTRIAL PREPARATION OF ETHANOL - SUMMARY

FERMENTATION

Reagent(s) GLUCOSE - from hydrolysis of starch

Conditions yeast
warm but no higher than 37°C

Equation C6H12O6 ——> 2 C2H5OH + 2 CO2

• LOW ENERGY PROCESS

• USES RENEWABLE RESOURCES - PLANTS
• SIMPLE EQUIPMENT

• SLOW
• PRODUCES IMPURE ETHANOL
• BATCH PROCESS

HYDRATION OF ETHENE

Reagent(s) ETHENE - from cracking of fractions from distilled crude oil

Conditions catalyst - phosphoric acid

high temperature and pressure

Equation C2H4 + H2O ——> C2H5OH

• FAST

✔ •
•
PURE ETHANOL PRODUCED
CONTINUOUS PROCESS

• HIGH ENERGY PROCESS

✘ •
•
EXPENSIVE PLANT REQUIRED
USES NON-RENEWABLE FOSSIL FUELS TO MAKE ETHENE

USES • ALCOHOLIC DRINKS

• SOLVENT - industrial alcohol / methylated spirits (methanol is added)
• FUEL - used as a petrol substitute in countries with limited oil reserves

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