12ChF322 Alcohols

Alcohols
Candidates should be able to: (a) explain, in terms of hydrogen bonding, the water solubility and the relatively low volatility of alcohols; (b) describe the industrial production of ethanol by: (i) fermentation from sugars, ie from glucose, (ii) the reaction of ethene with steam in the presence of an acid catalyst; (c) outline, for alcohols: (i) the use of ethanol in alcoholic drinks and as a solvent in the form of methylated spirits, (ii) the use of methanol as a petrol additive to improve combustion and its increasing importance as a feedstock in the production of organic chemicals; (d) classify alcohols into primary, secondary and tertiary alcohols; (e) describe the combustion of alcohols; (f) describe the oxidation of alcohols using acidified dichromate ions,Cr2O72/H+ (ie K2Cr2O7/H2SO4), including: (i) the oxidation of primary alcohols to form aldehydes and carboxylic acids; the control of the oxidation product using different reaction conditions, (ii) the oxidation of secondary alcohols to form ketones, (iii) the resistance to oxidation of tertiary alcohols; (g) describe the esterification of alcohols with carboxylic acids in the presence of an acid catalyst; (h) describe elimination of H2O from alcohols in the presence of an acid catalyst and heat to form alkenes.

General
The functional group is -OH The homologous series has general formula CnH2n+1OH The names end in ol, with a number if needed to indicate where on the carbon skeleton the OH group is located. When more than one OH group is present the name ends in diol or triol etc. as shown below. Note that when there is more than one OH group the 'e' is not dropped from the name just before the numbers, whereas the the 'e' is dropped when there is only one OH group. e.g. propan-2-ol
H H H H C C C H H O H H

ethane-1,1-diol
H O H H C C H O H H

propane-1,2,3-triol
H H H H C C C H O O O H H H

Physical Properties
Solubility trend Alcohols are miscible (solids which dissolve are soluble, liquids which dissolve are miscible) with water but as the hydrocarbon chain gets longer their solubility gets less. Explanation: When methanol or ethanol mix with water, the hydrogen bonds between water molecules are disrupted but just as many new hydrogen bonds to C2H5OH or CH3OH are formed. With longer chain alcohols, although the -OH group can still form hydrogen Page 1

12ChF322 Alcohols bonds to water, the longer alkyl chain disrupts the hydrogen bonding between other water molecules. There are not strong intermolecular forces between the alkyl chains and the water molecules because the alkyl chains are essentially non-polar. Volatility trend ethanol propan-1-ol butan-1-ol (boiling points OC) 325 compared to propane 371 butane 390 pentane 231 (similar length) 271 309

Explanation: Hydrogen bonding between alcohols reduces their volatility (ease of separating molecules into gas phase). The intermolecular forces between alcohol molecules are therefore much stronger than in alkanes of equivalent size and shape. Diols and triols can form more hydrogen bonds (because they have more OH groups) leading to greater intermolecular forces and increased viscosity, density and boiling points.

Production of ethanol in industry

There are two processes used: Fermentation: Exothermic reaction which provides yeast with energy for its metabolism, using sugars such as glucose. (Anaerobic respiration) C6H12O6(aq) 2C2H5OH(aq) + 2CO2(g) The reaction does not require oxygen (anaerobic process) so air is excluded to prevent oxidation of the ethanol to undesirable compounds such as aldehydes. Fermentation stops when the ethanol concentration reaches ~15% by volume because the ethanol kills the yeast. This is a batch process. The ethanol must be separated from the rest of the solution by distillation. Hydration of ethene: Industrial methylated spirit is ethanol which has been adulterated with poisonous methanol so it is not drinkable. A foul tasting purple dye is often added too. In this way the taxes on ethanol for drinking are avoided, and the alcohol can be sold for other purposes more cheaply. Industrially ethanol is made by the addition reaction of steam to ethene in the presence of a phosphoric acid catalyst (see notes on alkenes) at elevated temperature and pressure.

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12ChF322 Alcohols

Uses of Alcohols Fuels - alcohols have high enthalpies of combustion Ethanol is used as a biofuel, and methanol as a fuel additive to improve combustion. Unleaded petrol contains about 5% methanol (to improve combustion) and 15% of MTBE, an ether made from methanol Solvents (e.g. methylated spirits) - Alcohols contain a polar hydroxyl group and a non-polar hydrocarbon chain, so they mix with many other polar and non-polar compounds. Methanol and ethanol will also dissolve some ionic compounds making them very useful solvents Drinks - alcoholic drinks provide us with valuable nutrients such as minerals and vitamins as well as a source of energy - but also affect behaviour in well known ways when abused. Methanol is an important feedstock in the production of organic chemicals. Practical techniques Refluxing heating a reaction mixture to continually vaporize and recondense it, preventing volatile components from escaping while keeping the temperature high to increase reaction rate

Distillation separating a component from a reaction mixture because it has a lower boiling point than the rest of the mixture. Involves evaporating the component then condensing it and collecting it separately.

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12ChF322 Alcohols Reactions of alcohols Reaction with carboxylic acids formation of esters When an alcohol is warmed with a carboxylic acid in the presence of an acid catalyst, an ester is formed. e.g. when ethanol reacts with ethanoic acid, ethyl ethanoate is the ester product.

CH3CH2OH + CH3COOH
H H H C C O H H H H O O H C C H H

CH3COOCH2CH3
H H H H O H C C H H H C C O

H2O
H O H

How it works: The H- from the alcohol's OH group and the OH from the carboxylic acid are removed to make water. The O from the alcohol joins to the C=O of the carboxylic acid to form an ester link. The reaction mixture needs to be refluxed because the reaction is fairly slow. The reaction is REVERSIBLE and at equilibrium there will be products and reactants both present. Distillation is used to remove the impure ester from the reaction mixture, before purification. The name of the ester formed takes the first part from the alcohol (alkyl-) and the second from the carboxylic acid (-alkanoate). Hence methanol and propanoic acid form methyl propanoate:

Esters have fruity smells and are found naturally in fruits. Butyl butanoate pineapple 3-methylbutyl ethanoate pear ethyl 2-methylbutanoate - apple Esters are used to make artificial flavourings and perfumes. Combinations of esters can be used to mimic some of the more complex mixtures found in nature. Check your understanding: i) Using displayed formulae, write an equation for the reaction between butanoic acid and ethanol in the presence of an acid catalyst ii) name the ester formed in this reaction

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12ChF322 Alcohols Combustion Alcohols are fully oxidised to H2O and CO2 on combustion. Ethanol burns with a pale blue flame - hard to see in sunlight making alcohol a dangerous fuel since it is also volatile. e.g. C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l)

Check your understanding: iii) Write a balanced symbol equation, including state symbols, to show the complete combustion of propan-2-ol in excess oxygen. Dehydration to form alkenes Alcohols can be dehydrated, eliminating water, when heated in the presence of an acid catalyst. Hot (170OC) concentrated sulphuric acid can be used: e.g. C2H5OH(g)
H H H C C H H O H

H2C=CH2(g) +
H H C C H H

H2O(g)
H O H

How it works: The OH group is removed from one C atom, and an H group is removed from an adjacent carbon these form water. A double bond forms between the two carbons. Note that it doesn't work if there isn't a hydrogen on the carbon adjacent to the one with the OH group. Check your understanding: iv) What would be produced when pentan-2-ol vapour is treated in this way ? Note that if the alcohol is asymmetrical then there are TWO possible products, depending on which H is removed along with the OH group

or
OH

H2O

Oxidation reactions When heated with acidified aqueous potassium dichromate(VI), alcohols are oxidised (dichromate ions are powerful oxidising agents) with the alcohol becoming a carbonyl compound. The products are different depending on the structure of the alcohol. There has to be an -H on the same carbon as the -OH otherwise there is no reaction.

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12ChF322 Alcohols We describe alcohols as PRIMARY, SECONDARY or TERTIARY depending on the number of carbon atoms attached to the carbon with the OH group. A primary alcohol
H H H H C C C H O H H H
H H C H H C H H

has only one other carbon attached to the carbon with the OH group.

A secondary carbon with A tertiary alcohol

H O

alcohol has two carbons attached to the the OH group has three carbons attached to the carbon with the OH group.

H H H H C H H C C C H H H O H

Check your understanding: Draw displayed formulae, then classify the following alcohols as primary, secondary or tertiary v) 3-methylpentan-1-ol vi) hexan-3-ol vii) cyclobutanol viii) 3-methylpentan-2-ol ix) 3-methylpentan-3-ol The oxidising agent can be shown in the reaction as [O], simplifying the equations. Primary alcohols are oxidized to form aldehydes
H H H C C O H H H

+ [O]

H H C C H

O H

H2O

ethanal (an aldehyde)

conditions: warm with acidified sodium/potassium dichromate(VI)

additionally we sometimes see the instruction to distil off the product as it is formed. Secondary alcohols are oxidized to form ketones
H H H H C C C H H O H H

+ [O ]

H O H H C C C H H H

+ HO 2

p ro p a n o n e (a k e to n e )

conditions: heat with acidified sodium/potassium dichromate(VI)

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12ChF322 Alcohols Tertiary alcohols are not oxidized in this way (since there's no H attached to the C with the OH group) Aldehydes are further oxidised to carboxylic acids on stronger heating and reflux with excess acidified dichromate(VI).
H H C C H H O
H O O H

+ [O]

H C C

ethanoic acid (a carboxylic acid)

conditions: heat with excess acidified sodium or potassium dichromate(VI)

. Ketones do not react further even with prolonged refluxing with an excess of the reactants. Check your understanding: x) Complete the table showing oxidation reactions of different alcohols:
Name: Pentan-1-ol Type: Primary Pentan-2-ol 2-methylbutan-2-ol Conditions: Heat with excess acidified sodium dichromate Heat with acidified sodium dichromate Heat with acidified sodium dichromate Product: Hexanoic acid Functional group: Aldehyde

Alcohol

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12ChF322 Alcohols

Answers to "Check your understanding" questions:

i) Using displayed formulae, write an equation for the reaction between butanoic acid and ethanol in the presence of an acid catalyst
H H H C C O H H H

H H H C C C C H H H H

H O

H H H H

H H H C C C C H H H H

H C C O

+ H2O

ii) iii)

name the ester formed in this reaction Ans: ethyl butanoate Write a balanced symbol equation, including state symbols, to show the complete combustion of propan-2-ol in excess oxygen. CH3CH(OH)CH3(l) + 4 O2(g) 3 CO2(g) + 4 H2O(l) (or displayed formula) (or all x2)

iv)

What would be produced when pentan-2-ol vapour is dehydrated using an acid catalyst ?

Ans: the OH group would be removed, along with an H from either the first or the third carbon atoms, giving water and either pent-1-ene or pent-2-ene.
OH

or

+ H2O

Classify the following alcohols as primary, secondary or tertiary v) 3-methylpentan-1-ol H H H

H H C H H HO C C C C C H H H H H H

Primary

vi)

hexan-3-ol

H H H H H H H C C C C C C H H H O H H H H

Secondary

vii)

cyclobutanol

H H H C C O H H C C H H H

Secondary

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12ChF322 Alcohols viii) 3-methylpentan-2-ol

H H H H H C H H H C C C C C H H O H H H H

Secondary

ix)

3-methylpentan-3-ol

H H H H H C H H H C C C C C H H H O H H H

Tertiary

x)

Complete the table showing oxidation reactions of different alcohols:

Type: Primary Primary Secondary Tertiary Conditions: Warm with acidified sodium dichromate Heat with excess acidified sodium dichromate Heat with acidified sodium dichromate Heat with acidified sodium dichromate Product: Pentanal Hexanoic acid Pentan-2-one No reaction Functional group: Aldehyde Carboxylic acid Ketone Alcohol

Name: Pentan-1-ol Hexan-1-ol Pentan-2-ol 2-methylbutan-2-ol

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