Predicting the Strength of Acid / Base

The stronger the acid, the weaker will be its conjugate base.
(The larger the pKa of the conjugate acid, the stronger the base)

Can we predict the relative basicity of two bases ?

Predicting the Strength of Acid / Base

The stronger the acid, the weaker will be its conjugate base.
(The larger the pKa of the conjugate acid, the stronger the base)
Can we predict the direction of equilibrium of the following reactions?

Predicting the Strength of Acid / Base

The stronger the acid, the weaker will be its conjugate base.
(The larger the pKa of the conjugate acid, the stronger the base)
The relationship between structure (size) and acidity
FHO-

Cl-

s
e
s
a
re
c
In
y
it
il
b
ta
S

Br-

B
a

HS-

I-

HSe-

The extent of electron delocalization (overall size) of the

corresponding conjugate bases may correlate with the acidity.

Predicting the Strength of Acid / Base

The stronger the acid, the weaker will be its conjugate base.
(The larger the pKa of the conjugate acid, the stronger the base)
The relationship between electronegativity and acidity

Predicting the Strength of Acid / Base

The stronger the acid, the weaker will be its conjugate base.
(The larger the pKa of the conjugate acid, the stronger the base)
The relationship between structure / electronegativity and acidity

Predicting the Strength of Acid / Base

The stronger the acid, the weaker will be its conjugate base.
(The larger the pKa of the conjugate acid, the stronger the base)
The relationship between structure / hybridization and acidity

*The higher the s-character, the higher is the carbons electronegativity.

H

H
C C

H C C H
H

H
H

C C
H

Acidity Increases
H
H C C

C C
H

Basicity Increases

C C
H

The Strength of Acid / Base: pKa

The Strength of Acid / Base: Inductive Effect

Inductive Effect: propagation of bond polarity through -bond

network (decrease with the distance)

The Strength of Acid / Base: Resonance Effect

requires energy
for the change
endothermic

Resonance Effect: stabilization of the system by having resonance

structures (increase with the # of equivalent resonance structures)

pKa vs. G (Standard Free-Energy Change)

requires energy
for the change
endothermic

G = RT ln Keq

pKa = log Ka

G = 2.303RT (log Ka)

= 2.303 (8.314x10-3 kj/molK)
x (273+25)K (log Ka)
= (5.7 kj/mol) x 4.75
= 27.1 kj/mol
Resonance Effect: stabilization of the system by having resonance
structures (increase with the # of equivalent resonance structures)

Organic Compounds as Bases

carboxylic and and alcohol as acids

carboxylic as a base

H
O

O
H
H3C

Cl

H
H3C

Cl-

The Strength of Acid / Base: pKa

Mechanism for Organic Reactions

Why acidbase?

Step 1

Many reactions in organic chemistry are:

either acidbase reaction themselves
or involves acidbase reaction at some stage

Mechanism for Organic Reactions

Why acidbase?

Many reactions in organic chemistry are:

either acidbase reaction themselves
or involves acidbase reaction at some stage

Step 1

Step 2

Step 3

Acid / Base in Nonaqueous Solution

Leveling Effect: No stronger base than OH- can exist in water.

Synthesis of Tritium-labeled Compound