SUBTOPIC: CARBOXYLIC ACIDS

Functional group:

R- COO-H
1) Family: carboxylic acid
2) Name of functional group: carboxyl

Uses
1) Found in fruits, milk and ants

a. Short chain carboxylic acids

1. citric acid (citrus fruits),
2. tartaric acid (grape),
3. oxalic acid (soursop)
4. Butyric acid (Butter)
5. Lactic acid (Sour milk, muscle)
6. Methanoic acid (Red ants)

b. Long chain carboxylic acids(fatty acids)

1. Palmitic acid (Palm oil)
2. Oleic acid (olive)

Nomenclature
Carboxylic acids with 1 carboxyl group
1) Identify parent chain, which is the longest continuous carbon chain containing carboxyl/carboxy
group
2) No need to designate the position of Carboxyl group because it would always assume position
number one.

3) Eg:

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Carboxylic acids with 2 carboxyl groups
Dicarboxylic acids

Physical properties
-Use relative strength of secondary interactions to explain the trend in physical properties.

1) Boiling point/melting point

- Carbonyl group is an electron-withdrawing group and it would cause the carboxyl group
in carboxylic acid to be more polar than hydroxyl group in alcohol.

- Therefore carboxylic acids can form stronger hydrogen bonds with other carboxylic acid
molecules.

- Require a lot of heat/ high temperature to break stronger hydrogen bonds, hence have
high bp/mp

- Hence Carboxylic acids have much higher bp than alcohols due to the formation of
stronger hydrogen bonds which are formed between carboxylic acid molecules.

Carboxylic acids Alcohols

Compounds MW Bp (oC) Compounds MW Bp (oC)
Methanoic acid 46 100.5 Ethanol 46 78.3
Ethanoic acid 60 118 1-Propanol 60 97.2
Propanoic acid 74 141 1-Butanol 74 117.7
Butanoic acid 88 164 1-Pentanol 88 138.0

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 - The bps of esters are much lower than their isomeric acids due to presence of hydrogen
bondings in acids.
- In esters, only DDI is possible btw esters groups. Thus, lower bp of esters

Esters Carboxylic acids

Compounds MW Bp (oC) Compounds MW Bp (oC)
Methyl methanoate 60 31.5 Propanoic acid 60 97.2
Methyl Ethanoate 74 57 Butanoic acid 74 117.7

- Dicarboxylic acids have much higher bp/mp because they can form extensive (many)
hydrogen bonds with other dicarboxylic acid molecules. Hence require much higher temp
to break many strong hydrogen bonds between carboxylic acids molecules.

2) Solubility in water
Carboxylic acids with 1 carboxyl group
-Lower carboxylic acids (carboxylic acids with small molar mass) are very soluble in
water because water molecules can completely surround the carboxylic acid molecules.
Carboxylic acid molecules, which contain very polar carboxyl/carboxyl group, can form
strong hydrogen bonds with very polar water molecules.

Diagram:

-Higher carboxylic acids (carboxylic acids with big molar mass) have low solubility in
water because even though they contain very polar carboxyl groups, long non-polar
hydrocarbon chain outweighs the polarity of carboxyl group rendering the whole
carboxylic acid molecule as less polar or non- polar. Consequently, carboxylic acid
molecules cannot form strong hydrogen bonds with very polar water molecules. Hence,
they are less soluble in water. Example: oleic acid, palmitic acid. These are known as
fatty acids because they do not dissolve in water due to their long hydrocarbon chains.

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 Dicarboxylic acids
-very soluble in water despite their molecular size
-they have many very polar carboxyl groups in one molecule
-can form extensive strong hydrogen bonds with very polar water molecules, hence
very soluble in water.

Carboxylate ions
-Very soluble in water in all proportions because they can form ion-dipole interaction
with very polar water molecules.
-carboxylate ions are much more soluble in water compared to carboxylic acids
- Diagram:

3) Taste
- Sour

4) Odour
- Lower carboxylic acids have sharp irritating pungent odour because of low volatility
- Higher carboxylic acids have little odour because of higher volatility

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Chemical reactions
Preparation of carboxylic acids
1) From primary alcohols
a. carboxylic acid could be prepared from oxidation of primary alcohol in the presence of
excess oxidant such as acidified potassium dichromate or potassium permanganate
solution
b. Primary alcohol and excess acidified potassium dichromate are placed in the round
bottom flask and then heated under reflux

Equation:

Eq: R-OH (l) à R-COOH (l)

Cr2O72- (aq)à Cr3+ (aq)

c. The purposes of reflux are to prevent the volatile compounds from escaping the reaction
mixture and to speed up the rate of reaction.
d. Anti-bumping granules are added into heating mixture to promote even heat distribution
and to prevent the compounds from splashing out .

Diagram:

2) From aldehydes
a. Carboxylic acid could also be prepared from aldehyde by heating aldehyde and oxidant
such as acidified potassium dichromate solution under reflux

Equation:

Eq: R-CHO (l) à R-COOH (l)

Cr2O72- (aq)à Cr3+ (aq)

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 3) Acidic hydrolysis of esters

Weak acids
1) Carboxylic acids are weak acids.
2) Proton donors
3) Partially ionize in water to produce low concentration of hydrogen ions
4) Calculate pH by using the following formula
a. pH= - log 10 con of H+ (in mol/L)

Neutralisation reactions
1) Sodium hydroxide aqueous solution(NaOH)
a. Sodium hydroxide aqueous solution reacts with carboxylic acid to form carboxylate salt
and water

Balanced chemical equation:

R-COO-H(aq) + NaOH(aq) à RCOONa(aq) + H2O(l)

Eg: CH3CH2COOH + NaOH à CH3CH2COONa + H2O

2) Sodium carbonate aqueous solution (Na2CO3)

a. Sodium carbonate aq. solution reacts with carboxylic acid to form carboxylate salt, water
and carbon dioxide

2 RCOOH(aq) + Na2CO3(aq) à 2RCOONa(aq) + CO2(g) +H2O

Eg:

2CH3CH2COOH(aq) + Na2CO3(aq) à 2CH3CH2COONa(aq) + CO2(g) + H2O(l)

-Observe effervescence of CO2 gas

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 3) Sodium bicarbonate aqueous solution (NaHCO3)
a. Sodium bicarbonate reacts with carboxylic acid producing sodium carboxylate salt, CO2
and water

RCOOH(aq) + NaHCO3(aq) à RCOONa(aq) + CO2(g) + H2O(l)

Eg:

CH3CH2COOH(aq) + NaHCO3(aq) à CH3CH2COONa(aq) + CO2(g) + H2O(l)

-Observe effervescence of CO2 gas

Applications in drugs
1) Aspirin and ibuprofen are carboxylic acids that are used as pain relieving drugs

2) Drugs with analgesic properties such as aspirin (acetyl salicylic acid) and ibuprofen don’t dissolve
in water because they have large non-polar hydrocarbon portions.
3) Some people have problem to swallow tablets, so to ease this problem, water soluble aspirin or
ibuprofen is created.
4) In a tablet form, Aspirin or ibuprofen is mixed with sodium bicarbonate.
5) Upon contact with water, acid-base reaction takes place
a. Chemical equation:

2) Once in the stomach, carboxylate ion reacts with hydrogen ion ( HCl in stomach) to convert
carboxylate ion back into carboxylic acid
a. Chemical equation

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3) Then absorb into blood stream.