CARBOXYLIC ACIDS

What are carboxylic acids?

Carboxylic acids are compounds which contain a -COOH group.

Salts of carboxylic acids

Carboxylic acids are acidic because of the hydrogen in the -COOH group. When the acids form salts, this is lost and replaced by a metal. Sodium ethanoate, for example, has the structure:

Physical properties of carboxylic acids

The physical properties (for example, boiling point and solubility) of the carboxylic acids are governed by their ability to form hydrogen bonds.

Boiling points
propan-1-ol ethanoic acid CH3CH2CH2OH CH3COOH 97.2C 118C

The boiling points of carboxylic acids of similar size are higher still. The higher boiling points of the carboxylic acids are still caused by hydrogen bonding, but operating in a different way. In a pure carboxylic acid, hydrogen bonding can occur between two molecules of acid to produce a dimer.

 This immediately doubles the size of the molecule and so increases the van der Waals dispersion forces between one of these dimers and its neighbours - resulting in a high boiling point.

Solubility in water
In the presence of water, the carboxylic acids don't dimerise. Instead, hydrogen bonds are formed between water molecules and individual molecules of acid. The carboxylic acids with up to four carbon atoms will mix with water in any proportion. The solubility of the bigger acids decreases very rapidly with size. This is because the longer hydrocarbon "tails" of the molecules get between water molecules and break hydrogen bonds. In this case, these broken hydrogen bonds are only replaced by much weaker van der Waals dispersion forces.

1. MAKING CARBOXYLIC ACIDS - by oxidising primary alcohols or aldehydes Primary alcohols are oxidised to carboxylic acids in two stages - first to an aldehyde and then to the acid

 Starting from the primary alcohol, you could combine these into one single equation to give:

Eg :

2. Making carboxylic acids by hydrolysing nitriles What are nitriles? Nitriles are compounds which contain -CN attached to a hydrocarbon group. Some common examples include:

Converting the nitrile into a carboxylic acid There are two ways of doing this, both of which involve reacting the carbon-nitrogen triple bond with water. This is described as hydrolysis of nitriles The two methods produce slightly different products - you just have to be careful to get this right.

Acid hydrolysis
The nitrile is heated under reflux with a dilute acid such as dilute hydrochloric acid. A carboxylic acid is formed. For example, starting from ethanenitrile you would get ethanoic acid. The ethanoic acid could be distilled off the mixture.

Alkaline hydrolysis
The nitrile is heated under reflux with an alkali such as sodium hydroxide solution.

To liberate the weak acid, ethanoic acid, you just have to supply hydrogen ions from a strong acid such as hydrochloric acid.

The acidity of the carboxylic acids

The carboxylic acids are acidic because of the hydrogen in the -COOH group. In solution in water, a hydrogen ion is transferred from the -COOH group to a water molecule. For example,

 No more than about 1% of the acid has reacted to form ions at any one time. These are therefore weak acids.

RCOOH + H2O
Relatively less stable

RCOO- + H30+
relatively more stable

The pH of carboxylic acid solutions

The pH depends on both the concentration of the acid and how easily it loses hydrogen ions from the -COOH group. Ethanoic acid is typical of the acids where the -COOH group is attached to a simple alkyl group. Typical lab solutions have pH's in the 2 - 3 range, depending on their concentrations.

Reactions of the carboxylic acids

1. With metals Carboxylic acids react with the more reactive metals to produce a salt and hydrogen.

2. With metal hydroxides These are simple neutralisation reactions and are just the same as any other reaction in which hydrogen ions from an acid react with hydroxide ions.

3. With carbonates and hydrogencarbonates In both of these cases, a salt is formed together with carbon dioxide and water. For carbonates:

For hydrogencarbonates:

 The full equation is:

4. With ammonia

colourless solution of ammonium ethanoate.

5. With amines Amines are compounds in which one or more of the hydrogen atoms in an ammonia molecule have been replaced by a hydrocarbon group such as an alkyl group. Simple primary amines include :

For example, ethanoic acid reacts with methylamine to produce a colourless solution of the salt methylammonium ethanoate.

ESTERIFICATION OF CARBOXYLIC ACIDS

What are esters? Esters have a hydrocarbon group of some sort replacing the hydrogen in the -COOH group of a carboxylic acid. A common ester - ethyl ethanoate

A few more esters

Making esters
Esters are produced when carboxylic acids are heated with alcohols in the presence of an acid catalyst. The catalyst is usually concentrated sulphuric acid.

Uses of esters
Used as taste enhancers, flavourings and preservatives Excellent solvents for many organic compounds (drugs, antibiotics, etc) Production of polyesters

REDUCTION OF CARBOXYLIC ACIDS

The reducing agent Lithium tetrahydridoaluminate(III), (lithium aluminium hydride), LiAlH4

 The reaction happens in two stages - first to form an aldehyde and then a primary alcohol.

CONVERTING CARBOXYLIC ACIDS INTO ACYL CHLORIDES (ACID CHLORIDES) nucleophilic substitution reaction Replacing -OH by -Cl

1. Replacing the -OH group using phosphorus(V) chloride, PCl5 Phosphorus(V) chloride is a solid which reacts with carboxylic acids in the cold to give steamy acidic fumes of hydrogen chloride. It leaves a liquid mixture of the acyl chloride and a phosphorus compound, phosphorus trichloride oxide (phosphorus oxychloride) - POCl3.

2. Replacing the -OH group using phosphorus(III) chloride, PCl3 Phosphorus(III) chloride is a liquid at room temperature. Its reaction with a carboxylic acid is less dramatic than that of phosphorus(V) chloride because there is no hydrogen chloride produced.

3. Replacing the -OH group using sulphur dichloride oxide (thionyl chloride) Sulphur dichloride oxide (thionyl chloride) is a liquid at room temperature and has the formula SOCl2.

THE DECARBOXYLATION OF CARBOXYLIC ACIDS AND THEIR SALTS In decarboxylation, the -COOH or -COONa group is removed and replaced with a hydrogen atom.

 The solid sodium salt of a carboxylic acid is mixed with solid soda lime, and the mixture is heated.

For example, benzene can be made by heating soda lime with solid benzoic acid (benzenecarboxylic acid), C6H5COOH.

Uses of Carboxylic Acids in Industry

Methanoic acid and ethanoic acid are used to coagulate rubber latex Methanoic acid is also used in textile dyeing and in leather tanning Ethanoic acid is use in the food industry as vinegar. It is used in the manufacturing industry to produce vinyl acetate (CH3COOCH=CH2) Vinyl acetate is polymerised to form polymer, polyvinyl acetate plastic (PVA)

Uses of Carboxylic Acids in Industry

Manufacture of nylon Preservatives in foodstuffs Preparation of medicines