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Alcohols
Alcohols
F322
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 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 OH CH2OH
Aromatic
Q.1
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 H
methyl
H OH C C OH H
primary
C C C OH H
secondary
C C C OH C
tertiary
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
C O H
C O H
ethanol propane
C2H5OH C3H8
Boiling point also increases for straight chain isomers. Greater branching = lower inter-molecular forces. bp / C 118 100 83
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
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F322
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 conc. 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
fuel, added to petrol to improve combustion properties solvent a feedstock for important industrial processes
methanol
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Alcohols
F322
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.
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 C H C H H
H C H C
H H H
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
C H
Note 2
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 with the OH in the middle of a chain 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 C
H C H
HO
Note 1
There must be a hydrogen atom on a carbon atom adjacent the carbon with the OH on it
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. 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 acidified K2Cr2O7 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
Secondary
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
Combustion e.g.
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) ethanol ethanoic acid
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
Complete the equations; + + + CH3CH2CH2OH + CH3CH2COOH HCOOC2H5 + CH3COOCH3 + H2O H2O + + H2O
CH3CH2COOCH3
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F322
Alcohols
Differentiation
Wavelength (microns)
2.5 .00 3 4 5 6 7 8 9 10 12 15 .00
.10
.10
.20
.20
.40
.40
.80
.80
1800
1600
1400
1200
1000
800
600
Frequency , cm
-1
2.5 .00
Wavelength (microns) 6 7
10
12
15 .00
.10
.10
.20
.20
.40
.40
.80
.80
1800
1600 Frequency , cm
1400
-1
1200
1000
800
600
Wavelength (microns)
2.5 .00 3 4 5 6 7 8 9 10 12 15 .00
.10
.10
.20
.20
.40
.40
.80
.80
1800
1600
1400
1200
1000
800
600
Frequency , cm
-1
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Alcohols
F322
Equation
HYDRATION OF ETHENE Reagent(s) Conditions ETHENE - from cracking of fractions from distilled crude oil catalyst - phosphoric acid high temperature and pressure C2H4 + H2O > C2H5OH
Equation
$
USES
HIGH ENERGY PROCESS EXPENSIVE PLANT REQUIRED USES NON-RENEWABLE FOSSIL FUELS TO MAKE ETHENE
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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