Alcohols

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ALCOHOLS
Classification 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 by a number - propan-1-ol and propan-2-ol in aromatic alcohols (or phenols) 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 CH2 OH OH

Aromatic

Q.1

Which of the structures is/are classified as phenols?

CH3

Structural differences

alcohols are classified according to the environment of the OH functional group chemical behaviour, especially with oxidation, often depends on the structural type
H H C H
methyl

H OH C C H
primary

C OH C C H
secondary

C OH C C C
tertiary

OH

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. Mr 46 44 bp / C +78 -42

ethanol propane

C2H5OH C3H8

C O H

C O H

Boiling point also increases for straight chain isomers. Greater branching = lower inter-molecular forces. bp / C 118 100 83

intermolecular hydrogen bonding in alcohols

butan-1-ol butan-2-ol 2-methylpropan-2-ol

CH3CH2CH2CH2OH CH3CH2CH(OH)CH3 (CH3)3COH

Solubility

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

C O H

H O H

intermolecular hydrogen bonding with water

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Alcohols

PREPARATION OF ALCOHOLS
Laboratory from haloalkanes from aldehydes from alkenes - reflux with aqueous sodium or potassium hydroxide. - reduction with sodium tetrahydridoborate(III) - NaBH4. - acid catalysed hydration using concentrated sulphuric acid.

Industrial

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

Direct hydration Reagent(s) Conditions ETHENE - from cracking of fractions from distilled crude oil catalyst - phosphoric acid high temperature and pressure C2H4 + H2O C2H5OH

Equation

Q.2
Fermentation

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

advantage(s)

CHEAP EQUIPMENT MADE FROM RENEWABLE RESOURCES - SUGARS SLOW REACTION IMPURE PRODUCT BATCH PROCESS - EXPENSIVE ON MANPOWER

disadvantage(s)

Hydration

advantage(s)

FAST REACTION CONTINUOUS PROCESS - CHEAPER MANPOWER PURE PRODUCT MADE FROM A NON-RENEWABLE RESOURCE - OIL EXPENSIVE EQUIPMENT

disadvantage(s)

Uses

ethanol

methanol

added to petrol to improve combustion properties of unleaded petrol solvent used as a feedstock for important industrial processes fuel

Alcohols

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CHEMICAL PROPERTIES General Lone pairs on the oxygen atom of alcohols make them Lewis Bases (lone pair donors). They can use a lone pair to pick up protons behave as nucleophiles.

Elimination

Reagent Conditions Product Equation Mechanism

H H C H HO H

conc. sulphuric acid (H2SO4) or conc. phosphoric acid (H3PO4) reflux 180C alkene e.g. C2H5OH(l) > CH2 = CH2(g) + H2O(l)

H H C H

H C H HO H H2O H

H H C H C H H H C C H H H

C H

Step 1 Step 2 Step 3

protonation of the alcohol using a lone pair on oxygen loss of a water molecule to generate a carbocation loss of a proton (H+) to give the alkene
H
H C H HO H C H C H

Note 1

There must be a hydrogen atom on a carbon atom adjacent the carbon with the OH on it

Note 2

Alcohols with the OH in the middle of a chain can have two ways of losing water. In Step 3 of the mechanism, a proton can be lost from either side of the carbocation. This can give a mixture of alkenes from unsymmetrical alcohols

H C H

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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Alcohols

Oxidation of Alcohols
Provides a way of differentiating between primary, secondary and tertiary alcohols The usual reagents are acidified potassium dichromate(VI) or potassium manganate(VII)

Primary

Easily oxidised to aldehydes and then to carboxylic acids. e.g. then CH3CH2OH(l) + [O] CH3CHO(l) + [O] > > CH3CHO(l) + H2O(l) 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 the oxidising agent - acidified K2Cr2O7 because the aldehyde has a low boiling point - no hydrogen bonding - it distils off if it didnt distil off it would be oxidised to the equivalent carboxylic acid to oxidise an alcohol straight to the acid you would reflux the mixture compound ETHANOL ETHANAL ETHANOIC ACID formula C2H5OH CH3CHO CH3COOH intermolecular bonding HYDROGEN BONDING DIPOLE-DIPOLE HYDROGEN BONDING boiling point 78C 23C 118C

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 very vigorous oxidation

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

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Esterification Reagent(s) Conditions Product Equation

carboxylic acid + strong acid catalyst (e.g conc. H2SO4 ) reflux ester e.g. CH3CH2OH(l) + CH3COOH(l) CH3COOC2H5(l) + H2O(l)

One 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.

Sodium

Reagent(s) Conditions Product Equation

sodium room temperature sodium alkoxide and hydrogen e.g. 2CH3CH2OH(l) + 2Na(s) > 2CH3CH2ONa(alc) + H2(g) sodium ethoxide

Alcohols are organic chemistrys equivalent of water; water reacts with sodium to produce hydrogen and so do alcohols. The reaction is slower with alcohols than with water. Alkoxides are white, ionic crystalline solids e.g. CH3CH2O Na+

Bromination

Reagent(s) either or Conditions Product Equation reflux haloalkane

conc. hydrobromic acid HBr(aq) sodium (or potassium) bromide and conc. sulphuric acid

e.g. C2H5OH(l) + conc. HBr(aq)

>

C2H5Br(l) + H2O(l)

Mechanism The mechanism starts off in a similar way to the dehydration (protonation of the alcohol and loss of water) but the carbocation (carbonium ion) is attacked by a nucleophilic bromide ion in step 3.

Step 1 Step 2 Step 3

protonation of the alcohol using a lone pair on oxygen loss of a water molecule to generate a carbocation (carbonium ion) a bromide ion behaves as a nucleophile and attacks the carbocation

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Alcohols

IDENTIFYING ALCOHOLS USING INFRA RED SPECTROSCOPY

INFRA RED SPECTROSCOPY Chemical bonds vibrate at different frequencies. When a infra red (IR) radiation is passed through a liquid sample of an organic molecule, some frequencies are absorbed. These correspond to the frequencies of the vibrating bonds. Most spectra are very complex due to the large number of bonds present and each molecule produces a unique spectrum. However the presence of certain absorptions can be used to identify functional groups. BOND O-H O-H C=O COMPOUND alcohols carboxylic acids ketones, aldehydes esters and acids ABSORBANCE broad medium to broad strong and sharp RANGE 3200 cm-1 to 3600 cm-1 2500 cm-1 to 3500 cm-1 1600 cm-1 to 1750 cm-1

Differentiation

Compound ALCOHOL ALDEHYDE / KETONE CARBOXYLIC ACID ESTER

O-H YES NO YES NO

C=O NO YES YES YES

Wavelength (microns)
2.5 3 4 5 6 7 8 9 10 12 15 .00

BUTAN-1-OL O-H absorption

Absorbance

.00

.10

.10

.20

.20

.40

.40

.80

.80

4000 3600 3200 2800 2400 2000

1800

1600

1400 -1

1200

1000

800

600

Frequency , cm

Wavelength (microns)
2.5 .00 3 4 5 6 7 8 9 10 12 15 .00

Absorbance

PROPANOIC ACID O-H absorption C=O absorption

.10

.10

.20

.20

.40

.40

.80

.80

4000 3600 3200 2800 2400 2000

1800

1600

1400 -1

1200

1000

800

600

Frequency , cm

Wavelength (microns) 2.5 3 4 5 6 7 8 9 10 12 15 .00

ETHYL ETHANOATE C=O absorption

Absorbance

.00

.10

.10

.20

.20

.40

.40

.80

.80

4000 3600 3200 2800 2400 2000

1800

1600 Frequency , cm

1400
-1

1200

1000

800

600

Alcohols

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INDUSTRIAL PREPARATION OF ETHANOL - SUMMARY FERMENTATION

Reagent(s) Conditions GLUCOSE - from hydrolysis of starch yeast warm but no higher than 37C C6 H12 O6 > 2 C2 H5 OH + 2 CO2

Equation

LOW ENERGY PROCESS USES RENEWABLE RESOURCES - PLANTS SIMPLE EQUIPMENT

SLOW PRODUCES IMPURE ETHANOL BATCH PROCESS

HYDRATION OF ETHENE
Reagent(s) Conditions ETHENE - from cracking of fractions from distilled crude oil catalyst - phosphoric acid high temperature and pressure C2 H4 + H2 O > C2 H5 OH

Equation

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