FACTFILE:

GCE CHEMISTRY
4.8 CARBOXYLIC ACIDS

Learning Outcomes
Students should be able to: Nomenclature of carboxylic acids
4.8.1 recall the structural formulae of carboxylic The functional group is called the carboxyl group
acids, including branched structures, with up and is drawn
to six carbon atoms in the main chain; O
C
4.8.2 explain the boiling points and solubility of O H
carboxylic acids by making reference to
intermolecular attractions; or is written –COOH. It is made of a carbonyl and
hydroxyl group.
4.8.3 recall that carboxylic acids can be prepared
from primary alcohols and aldehydes to The names are based on the carbon skeleton with
include practical details; the ending changed from –ane to – anoic acid.
IUPAC nomenclature rules state that the carboxyl
4.8.4 recall that carboxylic acids, or their salts, carbon in the COOH functional group is always
can also be formed by acid or base catalysed carbon number 1. Any substituents are numbered
hydrolysis of esters and nitriles; and based on this.

4.8.5 recall that carboxylic acids form salts with Some carboxylic acids are shown below:
sodium carbonate, sodium hydroxide and
ammonia.

HCOOH CH3CH2COOH CH3CH2CH(CH3)COOH

H H O H H H O
O
H C H C C C H C C C C
OH OH OH
H H H H CH3
methanoic propanoic 2-methylbutanoic
acid acid acid

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FACTFILE: GCE CHEMISTRY / 4.8 CARBOXYLIC ACIDS

The structure below is the skeletal formula for e.g.

3-hydroxy-4-methylhexanoic acid. This reaction can be used to test for the presence of
an acid.
OH O

OH

Physical properties
1. The boiling point is higher than that of the
corresponding alkane. This is because the
intermolecular forces between alkanes are
van der Waals’ forces but between carboxylic
acid molecules there are van der Waals’ and
hydrogen bonds which are stronger.

The boiling point is higher than that of the

corresponding alcohol. This is because each pair
of carboxylic acid molecules is held together
by 2 hydrogen bonds in a structure called a When solid sodium carbonate reacts with a
dimer. This doubles the size of the molecule and carboxylic acid, effervescence is observed as carbon
increases the van der Waals forces between the dioxide is produced.
dimers resulting in a higher boiling point.
O
δ-
H
δ+ δ-
O H 2. with bases
δ+
C
δ+
C δ- δ+ δ-
C C H Dimer acid  base → salt  water
O H O e.g.
H bond H
CH3COOH  NaOH → CH3COONa  H2O
2. Short chain carboxylic acids are soluble ethanoic sodium sodium water
(miscible) in water as the polar OH and O can acid hydroxide ethanoate
hydrogen bond with water. As the number
of carbon atoms in the chain increases the observations: The mixture warms up.
solubility decreases because the longer
hydrocarbon "tails" of the molecules get 3. with ammonia
between water molecules and break hydrogen
bonds CH3COOH  NH3 → CH3COONH4
ethanoic ammonia ammonium
acid ethanoate

Acid reactions of carboxylic acids observations: the smell of ammonia disappears.

Carboxylic acids take part in typical acid reactions When dibasic or tribasic acids react with excess
– with carbonates, metals and bases to form salts. reagent, then all of the COOH groups react.
The salts are - anoates

1. With carbonates and hydrogencarbonates

acid  carbonate → salt  carbon dioxide  water
e.g.
2CH3COOH  Na2CO3 → 2CH3COONa  CO2  H2O
ethanoic sodium sodium carbon water
acid carbonate ethanoate dioxide

acid + hydrogencarbonate → salt + carbon dioxide + water

CH3COOH  NaHCO3 → CH3COONa  CO2  H2O

ethanoic sodium sodium carbon water
acid hydrogencarbonate ethanoate dioxide

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FACTFILE: GCE CHEMISTRY / 4.8 CARBOXYLIC ACIDS

Reaction with phosphorus Preparation of carboxylic acids

pentachloride PCl5 1. From primary alcohols or aldehydes
PCl5 replaces an OH group with a Cl. A new organic For example:
substance called an acyl chloride RCOCl, is formed. CH3CH2OH  2[O] → CH3COOH  H2O
In addition POCl3, phosphorus(V) trichloride oxide ethanol ethanoic acid
and hydrogen chloride are produced.
Alternatively an aldehyde may be used to produce
For example: the corresponding acid.
CH3CH2COOH  PCl5 → CH3CH2COCl  POCl3  HCl
propanoic propanoyl
acid chloride For example:
CH3CHO  [O] → CH3COOH
Condition: room temperature ethanal ethanoic acid
Observation: mixture warms up, steamy/misty
• Add concentrated sulfuric acid to water in a pear
fumes of hydrogen chloride, solid disappears.
shaped/round bottomed flask.
Reduction reactions • Swirl the solution and cool the flask to dissipate
Carboxylic acids are reduced to aldehdyes and the heat and prevent spitting.
further reduced to primary alcohols. The reducing • Add potassium dichromate(VI) and swirl.
agent is lithium tetrahydridoaluminate(III) (lithal). • Add anti-bump granules to promote smooth
boiling.
CH3CH2COOH  2[H] → CH3CH2CHO  H2O • Add the alcohol slowly, to the acidified potassium
propanoic acid propanal
dichromate(VI) solution and cool in a water bath.
CH3CH2COOH + 4[H] → CH3CH2CH2OH + H2O
propanoic acid propan-1-ol • Heat the mixture under reflux. (reflux is the
repeated boiling and condensing of a reaction
Condition: If the aldehyde is required it is distilled mixture).
off, but prolonged refluxing with LiAlH4 in ether will • Distil off the acid.
produce the primary alcohol.

cold water out

condenser

A labelled diagram of reflux should

include

• Condenser in upright position

• Flask
cold water in • Heat source
• Water flowing correctly in condenser
pear-shaped • Anti-bumping granules
flask
• Any gaps at the joints or closed
anti-bumping apparatus will be penalised
granules

HEAT

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FACTFILE: GCE CHEMISTRY / 4.8 CARBOXYLIC ACIDS

retort stand A labelled diagram of distillation

thermometer should include
water out
condenser • Condenser in horizontal position
• Flask
flask
• Side arm connection
mixture to be distilled
anti-bumping water in • Thermometer
granules • Heat source
distillate
tripod stand
• Water flowing correctly through
HEAT
from the condenser
Bunsen burner
• Anti-bumping granules
• Any gaps at the joints or a closed
apparatus are penalised

2. From acid or base catalysed hydrolysis of For example, ethanenitrile would produce
esters ammonium ethanoate via ethanamide.
Hydrolysis is the breaking up of molecules by H2O H2O
CH3CN CH3CONH2 CH3COONH4
reaction with water. It is slow so often it is catalysed
by adding acid or base. An ester can be hydrolysed
Acid hydrolysis of nitrile
into an alcohol and a carboxylic acid.
CH3CN  2H2O  HCl CH3COOH  NH4Cl
using acid
Condition: reflux with dilute hydrochloric acid.
H(aq)
CH3COOCH2CH3  H2O CH3COOH  CH3CH2OH
ethyl ethanoate ethanoic acid ethanol To produce the carboxylic acid in this case, add
dilute hydrochloric acid or dilute sulfuric acid.
Condition: reflux with dilute hydrochloric acid
Base hydrolysis of nitrile
In the base catalysed reaction the salt of the acid
CH3CN  NaOH  H2O → CH3COONa  NH3
is formed, acid is then added to it to liberate the
free carboxylic acid. There are two advantages of
Condition: reflux with sodium hydroxide solution.
base hydrolysis:
• the reactions are one-way rather than reversible,
and
• the products are easier to separate.
CH3COOCH2CH3  NaOH → CH3COONa  CH3CH2OH
ethyl ethanoate sodium ethanoate ethanol

3. From acid or base catalysed hydrolysis of

nitriles
Nitriles are compounds which contain the –C N
functional group.

For example:
ethanenitrile CH3CN propanenitrile CH3CH2CN

Nitriles react with water in two stages

• first to produce an amide (-CONH2 functional

group),
• and then the ammonium salt of a carboxylic
acid. Credits
Image page 2: © Trevor Clifford Photography/Science Photo Library

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FACTFILE: GCE CHEMISTRY / 4.8 CARBOXYLIC ACIDS

Revision Questions

1 Which one of the following compounds reacts with propanoic acid to form propanoyl chloride?

A chlorine
B chloropropane
C hydrogen chloride
D phosphorus pentachloride [1]

2 Lauric acid, C11H23COOH, the main acid found in coconut oil, is also found in macadamia nuts.
It is a white solid at room temperature with a melting point of 45OC, and is insoluble in water.

a) Write the empirical formula for lauric acid.

[1]

b) Explain why ethanoic acid is soluble in water where as lauric acid is insoluble.

[3]

c) Describe a chemical test to prove that lauric acid is an acid.

[2]

d) Write an equation for the reaction of lauric acid with phosphorus pentachloride

[2]

e) Lauric acid can be reduced to the corresponding alcohol.

(i) Write an equation for the reduction using [H] to represent the reducing agent.

[2]

(ii) Name a suitable reducing agent.

[1]

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FACTFILE: GCE CHEMISTRY / 4.8 CARBOXYLIC ACIDS

3 a) Write equations for the reaction of

propanoic acid and magnesium

[1]

methanoic acid and sodium carbonate

[1]

butanoic acid and potassium hydroxide

[1]

b) Pyruvic acid shows both the reactions of a ketone and a carboxylic acid. Complete the
following flow sequences below showing the oranic product in each case.

NH2NH
PCl5
CH3COCOOH
excess
LiAlH4 HCN

[4]

© CCEA 2016 6