Course Title: Organic Chemistry-I

Course code: CHM-553, CHM-507

Semester: MSc 1st , BS 5th

By: Dr. Maryam/ Dr. Umme Kalsoom

Assistant Professor
Department of Chemistry
GCWUF
Learning Objectives:

• The Various Factors Influencing the Acidity of Acids.

i. Strength of the H-A bond
ii. Electronegativity of A (anion)
iii. Factors stabilizing A- Compared with HA
iv. The Nature of the Solvent
Factors Influencing the Acidity of acid:

We will study the factors that lead to lower energy (stabilization) in the
conjugate base.

Stabilization of the
conjugate base
makes the acid
stronger.
 Factors Influencing the Acidity of acid:
Acidity of an organic compound, HA is influenced by the following factors.

i. Strength of the H-A bond

ii. Electronegativity of A (anion)
iii. Factors stabilizing A- Compared with HA
iv. The Nature of the Solvent
Factors Influencing the Acidity of acid:
i. Strength of the H-A Bond:

• Compounds having weaker H-A bond dissociate easily and behave as strong
acids.
• Thus, H2S is a stronger acid than H2O since S-H bond is weaker than O-H
bond.
• Similarly, HI is stronger acid than HF.
 Factors Influencing the Acidity of Acid:
ii. Electronegativity of A:

• As the bond to H becomes more polarized, H becomes more positive and the
bond is easier to break.
Factors Influencing the Acidity of Acid:

As the electronegativity decreases in the order: O˃N˃C, C=O unit due to its –R
effect enhances the electron affinity of carboxylic oxygen and makes a
carboxylic acid RCOOH more acidic than an alcohol ROH.
Factors Influencing the Acidity of Acid:
iii. Factors Stabilizing A-:

• It is a well known fact that acidity is measured by Ka (or pKa) of the acid in
aqueous medium, e.g.

• It is a thermodynamic requirement that the conjugate base A- should have a

greater influence on the acidity of HA.
• More stable the A- , the higher is the acidity of HA.
Factors Influencing the Acidity of Acid:

• Another suitable answer for the question “why RCOOH is stronger acid than
ROH” lies with the stability of their conjugate bases.
• The carboxylate ion RCOO- can reduce its charge density by resonance and
hence more stable than RO-, which has no scope for dispersion of its charge.

Two resonance structures more stable

Factors Influencing the Acidity of Acid:

• Phenol is more acidic than alcohols due to resonance stabilization of

phenoxide ion which is not possible in alkoxide.

Phenoxide ion

• With alcohols there is no such factor stabilizing alkoxide anion RO-, relative
to the alcohol itself, and alcohols are thus very much less acidic than
carboxylic acids.
Factors Influencing the Acidity of Acid:
iv. Effect of Solvent:

• Solvent also exerts a significant effect on compounds acidity. A polar protic

solvent like water stabilizes the conjugate base by solvation and shifts the
acid base equilibrium towards its formation.
• Water is an effective ionizing solvent due to its
(i) high dielectric constant (ε = 80), and
(ii) ion solvating ability.
 Factors Influencing the Acidity of Acid:

• Due to these particular features, water can solvate, and thereby stabilize, both
cations and anions. This effect is particularly marked with anions for
powerful “hydrogen –bonded” type solvation which is explained below.

• Hydrogen bond stabilizes both H3O+ and A- ions. Thus CH3COOH is a

good acid in H2O but not in hexane. Stabilization of CH3COO- (as well
as H+) takes place through hydrogen bonding in H2O.
Summary:
• Studied the various factors which effect the acidity of an organic compound,
HA .
• Also discussed the effect of the strength of the H-A bond on the acidity of
acid. Weaker the H-A bond stronger will be the acidity of HA.
• Greater the electronegativity of A (anion) stronger will be the acid.
• Factors stabilizing A- Compared with HA are studied. More stable the A- , the
higher is the acidity of HA.
• Also studied the effect of the nature of the solvent on the acidity.
Quiz:
• Justify the following statements.
i. Phenol is more acidic than ethanol.
ii. HI is stronger acid than HF.
iii. CH3OH is stronger base than CH3NH2.
iv. Acetic acid is stronger acid in water but not in hexane.
References:
• Bansal, R. K. 1990. A Text Book of Organic Chemistry. 2nd Edition, Wiley
Easteren Ltd.
• Haq Nawaz Bhatti. Advanced Organic Chemistry.