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Acid-Base Catalysis

ContentsGeneral

mechanisms of acid and base catalyzed


reactions,
Rates of acid and base catalyzed reactions,
Bronsted catalysis correlation of reaction rates with
acidity functions

Bronsted Acid-Base
Catalysis
In Bronsted acid-Base catalysis a

proton or
hydroxide becomes involved in the reaction
mechanism, lowers the energy of the transition
state(s), accelerate the reaction, and is
regenerated at the end of the reaction.

Types:
Specific catalysis
General

catalysis

Specific catalysis
The

specific acid is defined as the protonated


form of the solvent in which the reaction is being
performed.

Examples: In water, the specific acid is hydronium


(H3O+).
In acetonitrile, the specific acid is
CH3CNH+.
The specific base is defined as the conjugate
base of solvent.
Examples: In water- hydroxide,
Acetonitrile: -CH2CN.

Specific-

acid catalysis refers to a


process in which the reaction rate
depends upon the specific acid, not
upon other acids in the solution.

Specific-

base catalysis refers to a


process in which the reaction rate
depends upon the specific base, not
upon other bases in the solution.

The mathematics of Specific


Ex.
Water (H2O)
catalysis

If the acid catalysts is involved in an equilibrium prior to the


rate-determining step, and it is not involved in the ratedetermining step, then the kinetics of the reaction will
depend solely upon the concentration of the specific acid.

This is true even if an added acid (such as acetic acid) is


involved in protonating the reactant.

The reason for this is that when a prior equilibrium is


established, the concentration of RH + determines the rate of
reaction.

The concentration of RH+ depends upon the pH and the pKa


of the RH+, and does not depend upon the concentration of
the acid HA that was added to the solution.

Kinetics plots of specific


catalysis

General catalysis

Lets consider the case where the proton is involved in the ratedetermining step, not in a prior equilibrium.

This leads very different experimental observations, and a


phenomenon called general catalysis.

When an acid is involved in the rate-determining step, we have


general acid catalysis, and when base is involved in the ratedetermining step, we have general-base catalysis.

The terms general and specific often gets confused.

The term general refers to the fact that any acid or base we
add to the solution will affect the rate of the reaction, and hence
the catalysis is quite general.

The term specific refers to the fact that just one acid or base,
that from the solvent, affect the rate. The catalysis is therefore
specific.

Mathematics of general
catalysis

Mechanism