Centre for Higher Secondary Education Department of Chemistry

TOPIC 15C: CARBOXYLIC ACIDS

GRADE 12
SEMESTER 3/2023 Checklist
P
Students will be assessed on their ability to:

15.9 understand the nomenclature of carboxylic acids and be able to draw their structural,
displayed and skeletal formulae
15.10 understand that hydrogen bonding affects the physical properties of carboxylic acids,
in relation to their boiling temperatures and solubility
15.11 understand that carboxylic acids can be prepared by the oxidation of alcohols or
aldehydes and the hydrolysis of nitriles
15.12 understand the reactions of carboxylic acids with:
i lithium tetrahydridoaluminate(III) (lithium aluminium hydride) in dry ether
(ethoxyethane)
ii bases to produce salts
iii phosphorus(V) chloride (phosphorus pentachloride)
iv alcohols in the presence of an acid catalyst
Further suggested practicals:
i solubility of a range of carboxylic acids, aldehydes and ketones
ii preparation of carboxylic acids by the oxidation of alcohols and aldehydes
iii reactions of carboxylic acids given in 15.12 ii, iii and iv

15C - 1 CARBOXYLIC ACIDS AND THEIR PHYSICAL

SPECIFICATION
PROPERTIES OBJECTIVE 15.9 &
15.10

Carboxylic acids
Ø A carboxylic acid is an organic compound that contains a carboxyl group, -COOH.
Ø The functional group (carboxyl group) contains a hydroxyl group, OH (like the alcohols)
and a carbonyl group, C=O (like the aldehydes and ketones).
Ø These two functional groups affect each other and hence the reactions of carboxylic
acids are different from corresponding alcohols and carbonyl compounds.
Ø The general formula is RCOOH, where R can be a hydrogen atom, an alkyl group, or an
aryl group.
Ø For straight chain monocarboxylic acids, the general formula is CnH2nO2.

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Nomenclature
Ø The stem (eg: methan-, propan-) indicates the number of carbon atoms in the longest
chain including the carbon of the carboxyl group.
Ø This is followed by Suffix –oic acid.
Ø Acids that contain two carboxyl groups are known as dicarboxylic acids

EXERCISE 1

Name the following compounds

O BrO
OH CH3 CH CH2 C OH

Draw the displayed and skeletal formula for the following compounds
Hexanoic acid Methylpropanoic acid

2-hydroxypropanoic acid Ethanedioic acid

Physical properties
• Carboxylic acids have distinctive smells and sour tastes
• Bonding in carboxylic acid group is a combination of the C=O double bond in carbonyl
compounds and of the single bonds in alcohols, hence three polar bonds are present. This
means they have strong intermolecular forces and therefore high boiling temperatures
compared with other organic compounds of similar molar mass as shown in table 1.

Table 1
NAME FORMULA MOLAR MASS/ gmol-1 BOILING TEMPERATURE
Hexanoic acid CH3CH2CH2CH2CH2CH2COOH 116.2 205.7
Heptanol CH3CH2CH2CH2CH2CH2CH2OH 116.2 176
Heptanal CH3CH2CH2CH2CH2CH2CHO 114.1 153

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• Boiling temperatures also increase as the carbon chain length increases, as the London
forces increase between the non-polar group, as shown in table 2.

Table 2
NAME FORMULA MOLAR MASS/ gmol-1 BOILING TEMPERATURE
Methanoic acid HCOOH 46 101
Ethanoic acid CH3COOH 60 118
Propanoic acid CH3CH2COOH 74 141

• In the absence of a solvent such as water, the extent of hydrogen bonding in shorter chain
carboxylic acids allows the formation of dimers (double molecules).

*hydrogen bonding
represented by dashed lines
between 2 molecules of
ethanoic acid

• Several reactions of carboxylic acids involve the loss of H+, which produces the carboxylate
ion, COO- in which the two carbon-oxygen bonds are identical as shown below.

*The charge and double bond character are evenly distributed across both oxygen atoms in the
carboxylate ion.
• Carboxylic acids can also interact with water molecules by hydrogen bonding through both
the carbonyl and hydroxyl groups. Because of this they are more soluble in water than
alcohols, aldehydes and ketones of similar molecular weight.

-Hydrogen bonding between

ethanoic acid and water.
*hydrogen bonds are
represented by dashed lines

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• The solubility in water decreases with increasing chain length as the hydrocarbon part of
the molecules becomes larger.

London forces

• As the non-polar group gets bigger, London forces between the non-polar groups becomes
dominant over the hydrogen bonding between the acid and the water molecules.

CHECKPOINT (PAGE 123- TEXTBOOK)

Explain why hexanoic acid is much less soluble than ethanoic acid in water.

15C - 2 PREPARATION AND REACTIONS OF

SPECIFICATION
CARBOXYLIC ACIDS OBJECTIVE 15.11, 15.12
(i), (ii),(iii) & (iv)

Preparation
• Carboxylic acids can be prepared by two main methods.
1. The oxidation of either a primary alcohol OR an aldehyde.

Reagent: K2Cr2O7 + dil H2SO4

Condition: Heat under reflux
Reaction type: Oxidation
Observation: Solution turn from Orange to Green

Equation with alcohol:

CH3CH2OH + 2[O] ® CH3COOH + H2O

Equation with aldehyde:

CH3CHO + [O] ® CH3COOH

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 Centre for Higher Secondary Education Department of Chemistry

2. The hydrolysis of a nitrile.

I. Acid hydrolysis

Reagent: dil. HCl

Condition: Heat under reflux
Reaction type: Hydrolysis
Equation:
CH3CH2CN + 2H2O + H+ ® CH3CH2COOH + NH4+
Propanenitrile Propanoic acid

II. Alkaline hydrolysis

Reagent: dil. NaOH followed by dil. HCl

Condition: Heat under reflux
Reaction type: Hydrolysis
Equation:
CH3CH2CN + H2O + NaOH ® CH3CH2COO-Na+ + NH3
Propanenitrile Sodium propanoate

*To convert to the acid, a strong acid like dilute HCl can be added.
CH3CH2COO- + H+ ® CH3CH2COOH
Propanoate ion Propanoic acid

Reactions of Carboxylic Acids

REAGENT CONDITION OBSERVATION TYPE OF EQUATION
REACTION
Lithium
No CH3COOH + 4[H] ® CH3CH2OH + H2O
aluminium Dry ether Reduction
observation Product: primary alcohol
hydride/ LIAlH4
Sodium
hydroxide, Room No CH3COOH + NaOH ® CH3COONa + H2O
Neutralisation
NaOH (aqueous temperature observation Product: Carboxylate salts
alkali)
Phosphorous Steamy fumes
Anhydrous,
pentachloride, which turn CH3COOH + PCl5 ® CH3COCl+ POCl3 + H2O
room Halogenation
PCl5 damp blue Product: Acylchloride
temperature
litmus red
Alcohol
(e.g. ethanol) CH3COOH + CH3CH2OH ® CH3COOCH2CH3 +
and Conc. Heat Pleasant smell Esterification H2O
Sulfuric Product: Ester
acid(catalyst)

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*Test for COOH functional group

Test: Add to sodium carbonate or sodium hydrogen carbonate.

Observation: Effervescence of a colourless gas that turns lime water milky
Inference: Evolution of CO2 gas shows the presence of the acid.

Ø The above test is positive for any acid; it does not prove that a carboxyl group is
present. Therefore, a further test for the OH group is necessary in order to show that
a carboxylic acid is present.

Test: Add PCl5

Observation: Steamy fumes which turns damp blue litmus red.
Inference: HCl gas evolved, showing the presence of the OH group.
z

TOPIC 15D: CARBOXYLIC ACID DERIVATIVES: ACYL CHLORIDES

GRADE 12
SEMESTER 3/2022 Checklist
P

Students will be assessed on their ability to:

15.13 understand the nomenclature of acyl chlorides and esters and be able to draw their
structural, displayed and skeletal formulae
15.14 understand the reactions of acyl chlorides with:
i water
ii alcohols
iii concentrated ammonia
iv amines
15.15 understand the hydrolysis reactions of esters, in acidic and alkaline solution
15.16 understand how polyesters, such as terylene, are formed by condensation
polymerisation reactions.
Further suggested practicals:
i demonstration of the reactions of ethanoyl chloride given in 15.14 i, ii and iii
ii the preparation of esters such as ethyl ethanoate as a solvent or a pineapple
flavouring
iii hydrolysis of an ester

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15D - 1 CARBOXYLIC ACID DERIVATIVES: SPECIFICATION

OBJECTIVE 15.13,
ACYL CHLORIDES 15.14(i), (ii), (iii) & (iv).

• These are compounds in which the –OH in –COOH group is replaced with Cl.
• They have the general formula RCOCl
• Similar to carboxylic acids, they also have two functional groups including a carbonyl
carbon. However, they are not classified as carbonyl compounds either.

Nomenclature
• These are named as alkyl or aryl derivatives of acid. The ending –oic acid is replaced by -oyl
chloride.

EXERCISE 2

Name the following compounds

O O

CH3 CH2 C Cl Cl

Draw the structural formula of the following compounds

Ethanoyl chloride Pentanoyl chloride

Reactions of Acyl Chlorides

• Acid chlorides are attacked by nucleophiles as the carbon atom in RCOCl is electron-
deficient, since it is joined to two electronegative atoms.

REAGENT EQUATION (with ethanoyl chloride as an example) PRODUCT

Water CH3COCl + H-OH ® Carboxylic acid

Alcohol CH3COCl + CH3CH2-OH ® Ester

(e.g.: C2H5OH)

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CH3COCl + NH3 ®

Conc. NH3 Amide

NH3 + HCl ®
solution (details seen later)

CH3COCl + 2NH3 ®

N-substituted
Primary CH3COCl + CH3NH2 ® amide
(N, emphasizes that
Amines (RNH2)
an alkyl group is
attached to the N)
N, N-substituted
Secondary
CH3COCl + (CH3)2NH ® amide
Amines (R2NH)
)
No reaction.
Tertiary
With three alkyl groups, there is no H atom to react with Cl -
Amines (R3N)
to form HCl

SPECIFICATION
15D – 2 CARBOXYLIC ACID DERIVATIVES: ESTERS OBJECTIVE 15.13,
15.15

• Esters are carboxylic acid derivatives where OH in the COOH functional group is replaced
by –O-alkyl group.
• They are colourless liquids with relatively low boiling and melting temperatures and are
quite insoluble in water.
• They generally have pleasant smells and are present in perfumes, food flavourings, biofuels
and solvents.

Nomenclature
Esters are formed when either
• a carboxylic acid is reacted with an alcohol in the presence of a strong acid catalyst such
as sulfuric acid or hydrochloric acid,

OR
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Ø by the reaction between an acid chloride and an alcohol.

Hence when naming;

• The first part of the name comes from the alkyl group attached to O and
• the second part of the name from the alkyl group joined to C.
E.g.: methyl ethanoate

ethanoate
methyl

EXERCISE 3

Name the following compounds

(CH3)2CHCOOCH3 CH3COCH2COOCH2CH3.

Name the structural formula for the following compounds

Propylethanoate Ethylpropanoate Butylmethanote

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Reactions of esters
REACTION
REAGENT CONDITION EQUATION (with methyl ethanoate)
TYPE

H2O, Dilute
H2SO4 or HCl Warm CH3COOCH3 +H2O ⇌ CH3COOH + CH3OH Acid hydrolysis
(as a catalyst)

H2O, Dilute Alkaline

Warm CH3COOCH3 +NaOH ® CH3COO- +Na+ + CH3OH
NaOH hydrolysis

• In alkaline hydrolysis, the carboxylate salt is formed which can be converted to the
carboxylic acid by acidification with dilute HCl.
CH3COO- + H+ ® CH3COOH
• Acid hydrolysis is reversible while alkaline hydrolysis reactions go to completion.
[*Hydrolysis refers to breaking down of a compound using water.]

Saponification – an example of alkaline hydrolysis

• Saponification means ‘soap making’.
• Soaps use organic compounds obtained from vegetable and originally animal sources.
Vegetable oils contain large quantities of TRIGLYCERIDES.
• Triglyceride is an ester of long chain carboxylic acids and a triol. These are triesters, which
consist of a large ester molecule that can be hydrolysed to one alcohol and three carboxylic
acid molecules.
• An example of saponification, the hydrolysis of a triglyceride with sodium hydroxide to give
propane-1,2,3-triol(glycerol) and sodium octadecanoate (sodium stearate), is shown
below.

sodium
octadecanoate
Triglyceride Propane-1,2,3-triol (sodium stearate)

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15D - 3 CARBOXYLIC ACID DERIVATIVES:

SPECIFICATION
POLYESTERS OBJECTIVE 15.16

• Polymers can be made by addition or condensation polymerisation.

• A polyester is a polymer (a chain of repeating units) where the individual units are held
together by ester linkages.
• They have a wide range of uses including, different types of clothing, soft drink bottles,
food packaging etc.

Addition polymerization:
• Monomers join together and nothing is lost, (Refer to Topic 5, Book 1: IAS)
e.g. polymerisation of propene

Condensation polymerization
• In condensation polymerisation, a small molecule is formed when two monomers (usually
two different monomers) join together. The small molecule often is water, hence, the
term condensation reaction.
• However, hydrogen chloride maybe formed in some reactions instead of water if a dioyl
chloride is used instead of a dicarboxylic acid.

E.g. formation of the polymer Terylene.

[Monomers: ethane-1,2-diol & terephthalic acid.]

The reactive groups at both ends

continue reacting with other molecules
forming a long polymer chain.

Structure of the polymer

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• A dioyl chloride can be used instead of the dicarboxylic acid and the reaction occurs the same
way except the small molecule removed will be hydrogen chloride and not water.

*When showing polyester formation, remember that the H comes from the diol and the OH
from the dicarboxylic acid (or the Cl from the dioyl chloride), in the formation of the small
molecule.

CHECKPOINT (PAGE 133- TEXTBOOK)

1. Why is it not possible to make a polymer by reacting together molecules of
HOOCCH2COOH and CH3OH?
2. Draw the repeat unit of the polymer formed between the molecules of HOOCCOOH
and CH3CH(OH)CH(OH)CH3.
3. (a) The substance known as PHBV is a biodegradable polymer formed from
3-hydroxybutanoic acid and 3-hydroxypentanoic acid. Draw the repeat unit of the
polymer formed.

3- hydroxybutanoic acid 3-hydroxypentanoic acid

(b) Another polyester, PHB, is made from a single monomer, 3-hydroxybutanoic

acid. Draw a section of this polymer showing two repeat units.

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