CHAPTER 19: CARBOXYLIC ACID AND THEIR DERIVATIVES

Physical Properties of Carboxylic Acid

Physical Properties of Carboxylic Acid

Boiling Point Solubility Acidity

Physical Explanation
properties
Boiling Point ● Boilong point of carboxylic acid depends on the strength of intermolecular forces between
molecules.
● The boiling point of carboxylic acid is higher than an alcohol, a ketone or an aldehyde (with Mr
that almost the same) because:

i. It exists as stable dimers that form hydrogen bond.

ii. Molecules in dimers are arranged closely packed, therefore the hydrogen bonds are relatively
strong.
iii. more energy is needed to overcome the intermolecular forces ,higher boiling point

Hydrogen bond in dimer

Dimers = the geometry of the carboxyl group
O H O allows for the formation of two hydrogen bonds
per molecule are known to exist predominately as
R C C R dimers
O H O
Hydrogen bond in dimer

Solubility Solubility - Ability to form bond with its solvent

Solubility in water

⮚ Carboxylic acids are soluble in water due to the formation of hydrogen bond between the water
molecules and carboxylic acid molecules.

Hydrogen Bonds

H
O H O H O
R C C R
O H O H O
H
⮚ The solubility of carboxylic acid in water is almost the same as alcohol.
 ⮚ Aliphatic carboxylic acids with C > 5 are insoluble in water. Size of R, alkyl group ↑, hydrophobic
area ↑.

⮚ Solubility decreases with relative Mr because of the bigger hydrophobic area

Mr , Hydrophobic area , Solubility

Hydrophobic area R OH Hydrophilic area

Aromatic Carboxylic Acid

⮚ Aromatic carboxylic acids are slightly soluble in water due to the huge aromatic ring.
⮚ Dicarboxylic acids are relatively more soluble since more hydrogen bonds are formed.

HOOC
HOOC COOH COOH COOH
CH2CH2 CH2 > H3C CH2 CH2 > H3C CH2 CH2 CH2 CH2 >

Solubility in organic solvent

⮚ Carboxylic acids are soluble in non polar solvent such as benzene due to the Van der Waals forces
between the benzene and alkyl group of carboxylic acids.

Van Der Waals forces

O H O
R C C R
O H O

Hydrogen Bond

Acidity ⮚ The acidity of carboxylic acid is influenced by:

a) Resonance effect
b) Inductive effect

⮚ Carboxylic acid is relatively a weak acid, however it is stronger than phenol & alcohol
 OH
O
H3C C OH > > H2O > R OH

Resonance effect

⮚ Carboxylic acids are more acidic due to the resonance stabilisation of the carboxylate ion.

⮚ The electrons in carboxylate ion are delocalised between two oxygen atoms, whereas in phenoxide
ion, the electrons are delocalized in the benzene ring.

Carboxylate ion :

O
-
R C O

O
R C OH + H2O

OH

+ H2O

R OH + H2O

Inductive effect

⮚ The C=O group in carboxylic acid is a electron-withdrawing group which reduce the electron
density of –OH, therefore the –OH bond becomes weaker.
+
⮚ Thus H is easily donated and carboxylic acid is more acidic than phenol.

Effect of a substituent group on the acidity of carboxylic acid

a) Electron Withdrawing Group (EWG)

⮚ Electron-withdrawing groups (e.g –NO ,-F,-Cl,-Br, -I ) reduce the electron density of –O—H.
⮚ Thus the O-H bond becomes weaker and H+ can be easily released.
⮚ The compound is said to be more acidic
 ⮚ Electron- Withdrawing Group (EWG) increases the acidity.

Example:
CH3CHCl-COOH and CH3CH2COOH

Solution :

⮚ Cl is an electron-withdrawing groups, therefore reduce the electron density of –OH.

+
⮚ Thus the O-H bond becomes weaker and H can be easily released.
⮚ Acidity :

⮚ Electron-withdrawing groups increase the acidity.

b) The electronegativity of electron withdrawing group (EWG) in the compound

Example:
CH3CHF-COOH and CH3CHCl-COOH

⮚ Both F and Cl are electron-attracting group.

⮚ The electronegativity of F > Cl
⮚ The electron density of –OH in CH3CHF-COOH is less, thus the –OH bond is weaker than in
+
CH3CHCl-COOH. Therefore, H is easily donated.

⮚ Acidity :

c) Number of electron withdrawing group (EWG) in the compound

Example:

CH3C(Cl)2-COOH and CH3CHCl-COOH

⮚ CH3C(Cl)2-COOH contains 2 Cl atoms that make the bond of –OH weaker than CH3CHCl-
+
COOH (with only one Cl atom). Thus, H is easily donated.

⮚ Acidity :

Remember : The inductive effect can be quite large of one or more strongly electron-
withdrawing groups(EWG) are present on the carbon atom
d) The position of electron withdrawing group (EWG) in the compound

Example:

CH3CH2CH(Cl)COOH and CH2(Cl)CH2CH2COOH

⮚ The distance between Cl atom and carboxyl group in CH 3CH2CHCl-COOH is nearer

compare to in CH2ClCH2CH2-COOH.

+
⮚ The –OH bond in CH3CH2CH(Cl)COOH is weaker than in CH2ClCH2CH2-COOH, so H is
easily donated.

⮚ Acidity :

Remember : The inductive effect is dependent on distance. The effect of electron-withdrawing

groups decrease as the substituent moves farther from the carboxyl

e) Electron Donating Group (EDG)

Example:

CH3COOH and CH3CH2COOH

⮚ -R is an electron –releasing group.

⮚ The size of –R group in CH3CH2COOH is larger than in CH3COOH, so CH3CH2- is a stronger

releasing group than CH3-.

+
⮚ The electron density of –OH in CH3CH2COOH increases and H is difficult to be donated.
⮚ Electron-Donating Groups (EDG) - reduce the acidity of a carboxylic acid.