19 Carboxylic Acids and Derivatives

Naming Carboxylic acids

H H
These have the ending -oic O
If there are carboxylic acid groups on both ends of the
acid but no number is
chain then it is called a - dioic acid
necessary for the acid group H C C C
as it must always be at the O O
Ethanedioic acid
end of the chain. The H H
O H
C C
numbering always starts from
the carboxylic acid end Propanoic acid HO OH Note the e in this name

Solubility in Water

Acidity The smaller carboxylic (up to C4) H
 
The carboxylic acid are only weak acids acids dissolve in water in all O H O
in water and only slightly dissociate, but proportions but after this the solubility 
H3C C
they are strong enough to displace rapidly reduces. They dissolve   H
carbon dioxide from carbonates. because they can hydrogen bond to 

O H O
the water molecules.
H
CH3CO2H(aq) CH3CO2-(aq)+ H+(aq)

Delocalisation
The delocalised ion has equal C-O bond lengths. If
The carboxylic acid salts are stabilised by delocalisation, which delocalisation did not occur, the C=O bond would be shorter
makes the dissociation more likely. than the C-O bond.

O O The pi charge cloud has delocalised O

delocalised and spread out. The delocalisation
H3C C H3C C
makes the ion more stable and H3C C
OH O therefore more likely to form.
O

Strength of carboxylic acids

O O Increasing chain length pushes

delocalised electron density on to the COO- ion,
H3C CH2 C H3C CH2 C
making it more negative and less
OH O stable. This make the acid less
strong.
Alkyl groups electron releasing
Propanoic acid less acidic than ethanoic acid

Cl O Cl O Electronegative chlorine atoms

H C C delocalised withdraw electron density from the
H C C COO- ion, making it less negative
OH and more stable. This make the acid
H O
H more strong.
Chlorine electron withdrawing chloroethanoic acid more acidic than ethanoic acid

O H H
O O OH In a dibasic acid the second HO2C- group
C C C C C C - withdraws electron density from the
COO- ion, making it less negative and
H O H O H H O OH
H more stable and weakens the O-H bond.
This make the acid more strong.
HO2C- group electron withdrawing

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Methods of preparing carboxylic acids
Full Oxidation of Primary Alcohols

Reaction: primary alcohol  carboxylic acid Observation: the

Reagent: potassium dichromate(VI) solution and dilute sulphuric acid orange dichromate
Conditions: use an excess of dichromate, and heat under reflux: (distill off ion (Cr2O72-) reduces
product after the reaction has finished) to the green Cr 3+ ion

H H H H H
O

H C C C O H + 2 [O] H C C C + H2O

H H H O H
H H

CH3CH2CH2OH + 2[O]  CH3CH2COOH + H2O

propan-1-ol Propanoic acid

Oxidation of Aldehydes

Reaction: aldehyde  carboxylic acid H H O H H O

Reagent: potassium dichromate (VI) solution and H C C C + [O]  H C C C
dilute sulphuric acid.
Conditions: heat under reflux H H H H H O H

Full Equation for oxidation RCHO + [O]  RCOOH

3CH3CHO + Cr2O72- + 8H+  3 CH3COOH + 4H2O + 2Cr3+

Hydrolysis of Nitriles
Reaction: Nitrile  carboxylic acid
Reagent: dilute hydrochloric/ sulphuric acid.
Conditions: heat under reflux

CH3CH2CN + H+ + 2H2O  CH3CH2COOH + NH4+

The Reactions of Carboxylic Acids

Salt formation reactions of carboxylic acids

Carboxylic acids can form salts with metals, alkalis and
carbonates.
acid + metal (Na)  salt + hydrogen The effervescence caused by production of CO2
2CH3CO2H + 2Na  2CH3CO2-Na+ + H2 with carboxylic acids with solid Na2CO3 or
aqueous NaHCO3 can be used as a functional
acid + alkali (NaOH)  salt + water group test for carboxylic acids
CH3CO2H + NaOH  CH3CO2-Na+ + H2O

acid + carbonate (Na2CO3)  salt + water + CO2

2CH3CO2H + Na2CO3  2CH3CO2-Na+ + H2O + CO2

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 Esterification
H H O H Esters have two parts
Carboxylic acids react with alcohols, in the to their names, eg
presence of a strong acid catalyst, to form H C C C O C H methyl propanoate.
esters and water. H H H
H+ The bit ending in –anoate The bit ending in –yl comes from
Carboxylic Acid + Alcohol Ester + water comes from the carboxylic the alcohol that has formed it
acid and includes the C in and is next to the single bonded
the C=O bond. oxygen.

H H H O H H
O The reaction is reversible. The
H+ reaction is quite slow and needs
+ H C C O H H C C O C C H + H2O
H3C C heating under reflux, (often for
OH H H H H H several hours or days). Low yields
(50% ish) are achieved. An acid
CH3CO2H + CH3CH2OH CH3CO2CH2CH3 + H2O catalyst (H2SO4) is needed.
Ethanoic acid Ethanol Ethyl Ethanoate

Reduction of carboxylic acids to alcohols

Lithium tetrahydridoaluminate (LiAlH4) is a
Carboxylic acids will be reduced to primary alcohols
strong reducing agent
H H O H H H
Reagents: LiAlH4 In dry ether
Conditions: Room temperature and pressure H C C C + 4[H] H C C C O H + H2O

Type of reaction: Reduction H H O H H H H

Propanoic acid Propan-1-ol
Role of reagent: Reducing agent

Reaction of carboxylic acid with phosphorous (V) chloride

Reaction: carboxylic acid  acyl chloride This reaction with PCl5 (phosphorous(v)chloride)
Reagent: PCl5 phosphorous(v)chloride can be used as a test for carboxylic acids. You would
Conditions: room temp observe misty fumes of HCl produced.

CH3COOH + PCl5  CH3COCl + POCl3 + HCl

O O
+ PCl5  + POCl3 + HCl
H3C C H3C C
OH Cl

Oxidation of methanoic acid O O It forms carbonic acid

(H2 CO3 ) which
Carboxylic acids cannot be oxidised by using H C + [O]  H O C decomposes to give
oxidising agents but methanoic acid is an O H O H CO2 + H2O
exception as its structure has effectively an
aldehyde group. It can be oxidised by Fehling’s
solution and Tollen’s Reagent

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Oxidation of ethanedioic acid
Ethanedioic acid can be oxidised by potassium manganate (VII). The
The reaction between MnO4- and
ethanedioic acid is oxidised to carbon dioxide gas. This reaction can be
C2O42- is slow to begin with (as
done as a quantitative titration.
the reaction is between two
negative ions). To do as a titration
Ox H2C2O42-  2CO2 + 2H+ + 2e- the conical flask can be heated to
Red MnO4-(aq) + 8H+(aq) + 5e-  Mn2+ (aq) + 4H2O 60o C to speed up the initial
Overall 2MnO4-(aq) + 6H+(aq) + 5C2O42-(aq)  10CO2(g) + 2Mn2+(aq) + 8H2O(l) reaction.

Relative acidities of carboxylic acids, phenols and alcohols

Carboxylic acids are acidic enough to react with sodium, sodium hydroxide, and O
sodium carbonate. As mentioned earlier the carboxylic acid salts are stabilised by
delocalisation, which makes the formation of the salts more likely. Delocalisation H3C C
spreads out the negative charge which makes it more stable
O
2CH3CO2H + 2Na  2CH3CO2-Na+ + H2
CH3CO2H + Na  CH3CO2-Na+ + H2

Phenols are very weakly acidic. They are weaker acids than carboxylic acids.
Phenols will react with sodium metal and sodium hydroxide, but are not strong
enough an acid to react with sodium carbonate. In phenol the lone pair of
electrons on the oxygen is delocalised with the electron charge cloud of the
arene ring. The delocalised bonding stabilises the formation of the phenoxide
ion. The delocalisation is less effective than that in a carboxylate ion

-
OH + Na O Na+ + ½ H2

-
OH + NaOH O Na+ + H2O

sodium phenoxide

Alcohols have almost no acidity. The do not react with sodium hydroxide or sodium
carbonate. They can react with sodium metal.
There is no delocalisation within an alcohol so the formation of a stable ethoxide
ion from ethanol is not possible except with the reaction with sodium. The negative
charge stays on the oxygen atom which makes it very unstable

2CH3CH2OH + 2Na  2CH3CH2O -Na+ + H2

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Carboxylic acid derivatives: Acyl Chlorides
Acyl Chlorides
Acyl chlorides are The Cl groups are classed as good leaving
O
much more reactive groups (to do with less effective delocalisation.)
CH3 C than carboxylic acids This makes acyl chlorides more reactive than
carboxylic acids and esters
Cl
ethanoyl chloride

Reaction with water Reaction with alcohol

Change in functional group: acyl chloride  Change in functional group: acyl chloride  ester
carboxylic acid Reagent: alcohol
Reagent: water Conditions: room temp.
Conditions: room temp.
RCOCl (l) + CH3CH2OH  RCO2CH2CH3 + HCl (g)
RCOCl (l) + H2O  RCO2H + HCl (g)
O H O H H
O O CH 3 C + CH3CH2OH  H + HCl
C C O C C H
CH3 C + H2O  CH3 C + HCl (g) Cl H H H
Cl OH
Observation: Steamy white fumes of HCl are
Observation: Steamy white fumes of HCl
given off
are given off

This reaction for making esters is much better than using

carboxylic acids as the reaction is much quicker and it is
not a reversible reaction

Reaction with phenol

Change in functional group: acyl chloride  ester

Reagent: phenols
Conditions: room temp.
O
O C
 + HCl
OH + C O
Cl

phenol Benzoyl Phenyl

chloride benzoate

Reaction with ammonia

Reaction with primary amines

Change in functional group: acyl chloride  Change in functional group: acyl chloride 
primary amide secondary amide
Reagent: ammonia Reagent: primary amine
Conditions: room temp. Conditions: room temp.

RCOCl (l) +2NH3  RCONH2 + NH4Cl (s) RCOCl +2CH3NH2  RCONHCH3 + CH3NH3+Cl-
O O O
O + CH3NH3+Cl-
CH3 C + 2NH3  CH3 C + NH4Cl (s) CH3 C + 2CH3NH2  CH3 C NH CH3
Cl NH2 Cl
N-methylethanamide
Observation: white smoke of NH4Cl is given off

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 Nucleophilic Addition Elimination Mechanism

Oδ- :O - O
O
CH3 C δ+ + +
H3C C OH H3 C C OH CH3 C
Cl δ-
:OH H H OH
Cl
H

Relative ease of hydrolysis

Acyl chlorides hydrolyse at room temperature with both water and sodium hydroxide. The carbon in the acyl
chloride is particularly electron deficient as it is attached to two electronegative atoms (O and Cl) so it
attractive to nucleophiles such as water. Also the C-Cl bond is weakest in the acyl chloride

H H
Alkyl halogenoalkanes will undergo nucleophilic substitution hydrolysis
H C C H reactions to produce alcohols . They won’t do this at room temperature
H Cl though so are less reactive than acyl chlorides. The carbon attached to the Cl is
positive due to the electronegativity difference but is less positive than the
carbon in the acyl chloride. They will hydrolyse if heated with water or sodium
Cl
hydroxide.

Aryl halogenoalkanes will not undergo nucleophilic substitution hydrolysis

reactions. The delocalisation in the benzene ring will extend to include the
lone pairs on the Cl. This strengthens the C-Cl bond and stops it from breaking
chlorobenzene

Hydrolysis of esters Esters can be hydrolysed and split up by either heating with acid or with sodium hydroxide.

i) with acid
This reaction is the reverse reaction of ester formation. When an ester
reagents: dilute acid (HCl)
is hydrolysed a carboxylic acid and an alcohol are formed.
conditions: heat under reflux
H+
This reaction is reversible and does not
CH3CH2CO2CH2CH3 + H2O CH3CH2CO2H + CH3CH2OH
give a good yield of the products.
ethyl propanoate

ii) with sodium hydroxide

reagents: dilute sodium hydroxide CH3CH2CO2CH3 + NaOH  CH3CH2CO2- Na+ + CH3OH
conditions: heat under reflux methyl propanoate sodium propanoate methanol

The carboxylic acid salt product is the anion of the carboxylic acid.
This reaction goes to completion. The anion is resistant to attack by weak nucleophiles such as alcohols, so the
reaction is not reversible.

Uses of Esters
Esters can have pleasant smells
Esters are sweet smelling
compounds that can be used in For use in perfumes they need to be non toxic, soluble in solvent such as
perfumes and flavourings. ethanol, volatile (turns into gas easily), and not react with water.

Although polar, they do not form hydrogen bonds (reason: there is no

Esters can be used as solvents for
hydrogen bonded to a highly electronegative atom)
polar organic substances thus, they have much lower b.p. than the hydrogen-bonded carboxylic acids
Ethyl ethanoate is used as a solvent they came from. They are also almost insoluble in water
in glues and printing inks
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