CONTENT

 Introduction to catalysis

 Introduction to acid catalysis

 Examples

 Hydrolysis of an ester

 Acid catalyzed dehydration of ethanol

 Electrophilic Substitution of Benzene

 Nitration of Benzene

 Halogenation of Benzene

 Formation of arenium ion

 Types of Acid Catalysis

 General acid catalysis

 Special acid catalysis

 Graphs

 Comparison of General and specific acid catalysis

 Advantages and disadvantages of acid catalysis

 ACID CATALYSIS
INTRODUCTION

Catalyst:
A catalyst is a substance that

 Increases the rate of a chemical reaction, without being consumed in

reaction itself.

 Can lower activation energy, required for a reaction to occur, thus

increasing the speed of reaction.

 Provides an alternative pathway for reaction, which requires less

energy to proceed.

 Decreases the time to reach equilibrium.

 May be enzyme or metal.

Catalysis:
The ability of as species to speed up the rate at which the reaction proceeds.

To act as a catalyst, a substance must meet following criteria:

 It should be specific in action. A particular catalyst works for one reaction; it
may not work for any other reaction.

 If different catalysts are used for the same reactant, then products may
change.

 It must alter the pathway.

 It should be cheap (long lifetime).

 It should be inert/non-reactive with other reactants.

  It should be non-flammable

 It should be environment friendly or non-toxic or eco-friendly.

 It should be easy to separate.

 It should remain unchanged in mass and chemical composition at the end of

reaction.

 It may not remain in the same physical state.

 It must be present in a sufficient quantity to be effective.

 It is more effective when it is present in finely divided form.

 It must be able to interact with reactants in a way that stabilizes the

transition state of reaction.

Acid Catalysis
An acid catalyst increases the rate of a reaction by donating a proton to a
reactant.

In acid catalysis a chemical reaction is catalyzed by an acid.

Bronsted–Lowry Acid–Base theory:

 The acid is the proton (hydrogen ion, H+) donor

 The base is the proton acceptor.

Lewis Acid-Base Concept:

 The acid is electron pair acceptor.

 The base is electron pair donor.

Two types of acid sites are recognized

 Bronsted acid
  Lewis acid

 Mineral acids such as H2 SO4, HF and AlCl3 are widely used in the industry.

 The US petroleum refining industry alone uses ~ 2.5 M tons of and H2 SO4 ~
5000 tons of anhydrous HF annually.

 Out of 127 acid and base catalyzed commercial processes listed in 1999
(Tanabe & Hölderich, Appl.Catal. A, 181 (1999) 399) 10 were based on basic
catalysts & 14 based on acid-base catalysts.

EXAMPLES

 Hydrolysis of an ester

 Acid catalyzed dehydration of ethanol

 Electrophilic Substitution of Benzene

 Nitration of Benzene

 Halogenation of Benzene

 Formation of arenium ion

Hydrolysis of an ester

 The rate of hydrolysis of an ester is markedly increased by an acid catalyst

(H+).

 Donation of a proton to, and removal of a proton from, an electronegative

atom such as oxygen are fast steps.

 Therefore, the reaction has two slow steps:

 formation of the tetrahedral intermediate

 collapse of the tetrahedral intermediate.

  A catalyst must increase the rate of a slow step because increasing the
rate of a fast step will not increase the rate of the overall reaction.

EXPLANATION

 The acid increases the rates of both slow steps of this reaction.

 It increases the rate of formation of the tetrahedral intermediate by

protonating the carbonyl oxygen, thereby increasing the reactivity of the
carbonyl group.
  We have seen that a protonated carbonyl group is more susceptible to
nucleophilic attack than an unprotonated carbonyl group because the
protonated carbonyl group is more electrophilic.

 In other words, the protonated carbonyl group is more susceptible to

nucleophilic attack.

 Increasing the reactivity of the carbonyl group by protonating it is an

example of providing a way to convert the reactant into a less stable (i.e.,
more reactive) species.

1st Slow Step

Acid-catalyzed first slow step Uncatalyzed first slow step

 The mechanism for the acid-catalyzed hydrolysis of an ester shows that the
reaction can be divided into two distinct phases:

 Formation of a tetrahedral intermediate

 collapse of a tetrahedral intermediate.

 There are three steps in each phase.

 Notice that in each phase, the first step is a fast protonation step, the second
step is a slow catalyzed step that involves either breaking a pi-bond or
forming a pi-bond

 The last step is a fast deprotonation step (to regenerate the catalyst).
2nd Slow Step

Acid-catalyzed second slow step Uncatalyzed second slow step

 The acid increases the rate of the second slow step by changing the basicity
of the group that is eliminated when the tetrahedral intermediate collapses.

 In the presence of an acid, methanol 1pKa+ of CH3O+H2 = -2.52 is

eliminated.

 In the absence of an acid, methoxide ion 1pKa of CH3OH = 15.72 is

eliminated.

 Methanol is a weaker base than methoxide ion, so it is more easily

eliminated.

Acid catalyzed dehydration of ethanol

Step I: Protonation of ethanol

Step II: Formation of carbocation

Step III: Elimination of a proton

Note: The acid used in Step I is released in Step III. To drive the equilibrium to the
right, ethene is removed as it is formed.

Electrophilic Substitution of Benzene

1. Generation of electrophile:

In the presence of Lewis acid, generation of electrophile takes place. As the Lewis acid accepts
the electron pair from the attacking reagent.

2. Formation of arenium ion:

The electrophile generated attacks on the benzene ring to form a positively charged
cyclohexadienyl cation better called an arenium ion containing one sp3 hybridized
carbon atom. The positive charge is effectively distributed over three carbon atoms
by resonance which makes it partially stable.
3. Removal of positive charge from the carbocation intermediate:

The arenium ion finally loses its proton from sp3 hybridized carbon to a Lewis base restoring the
aromaticity.

1. Nitration of Benzene

Benzene reacts with nitric acid at 323-333k in presence of sulphuric acid to form nitrobenzene.
This reaction is known as nitration of Benzene.
2. Sulphonation of Benzene

Sulphonation of benzene is a process of heating benzene with fuming sulphuric acid

(H2SO4 +SO3) to produce benzenesulphonic acid. The reaction is reversible in nature.

3. Halogenation of Benzene

Benzene reacts with halogens in the presence of Lewis acid like FeCl3, FeBr3 to form aryl
halides. This reaction is termed halogenation of benzene.

Types of Acid Catalysis

 There are 2 types of catalysis:

 General acid catalysis

 Specific acid catalysis

General Acid Catalysis Specific Acid Catalysis

The proton is transferred to the reactant The proton is fully transferred to the reactant
(according to Brownsted-Lowery Concept) (according to Brownsted-Lowery Concept)
during the slow step of the reaction. before the slow step of the reaction begins.

Pair of electron is accepted (according to Pair of electron is accepted (according to

Lewis Concept) during the slow step of the Lewis Concept) before the slow step of the
reaction. reaction begins.
The reagent is involved in a rate determining The rate of the reaction depends on the
proton transfer equilibrium. protonation equilibrium of the reagent;
proton transfer is not rate determining.

The catalytic effect depends on the The catalytic effect is independent:

concentration of the different proton donors
present in the reaction mixture  of the concentration

 of the specific structure

of the different proton donors in the reaction

mixture.

In a general-acid-catalyzed reaction, the In a specific-acid-catalyzed reaction, the

transition state has a partially transferred transition state has a fully transferred proton.
proton.
When acids other than the hydronium ion Specific acid catalysis occurs when a
accelerate the reaction rate, this is known as hydronium H3O+ ion catalyzes a reaction
general acid catalysis. that is determined solely by the pH, rather
than the buffer concentration.
As the reaction rate increases with increasing
buffer concentration at a constant pH and ionic
strength in solution, general acid-base catalysis
is demonstrated, with a greater increase with a
buffer that contains a more concentrated acid or
base portion. Since the concentration of
hydronium or hydroxide ions does not change
(the pH remains constant), the reaction must be
catalyzed by the buffer.

In specific-acid-catalyzed attack by water

In general-acid-catalyzed attack by water on a on a carbonyl group, the nucleophile
carbonyl group, the carbonyl group becomes attacks a fully protonated carbonyl group
protonated as the nucleophile attacks it.
 In specific-acid-catalyzed collapse of a
In general-acid-catalyzed collapse of a tetrahedral intermediate, a fully protonated
tetrahedral intermediate, the leaving group leaving group is eliminated.
picks up a proton as the group is eliminated.

The term" specific" refers to the fact that

The term "general" refers to the fact that any just one acid or base, that from the solvent,
acid or base we add to the solution will affect affects the rate.
the rate of the reaction.
The kinetic expression contains [H3O+], as
The concentration of the acid (or its conjugate the definition of specific-acid-catalysis
base) that results from addition of an acid to implies. Hence, the reaction rate depends on
the reaction vessel does affect the rate of the the pH.
reaction.

If the acid catalyst is involved in an

equilibrium prior to the rate-determining
step, and it is not involved in the rate-
determining step, then the kinetics of the
reaction will depend solely upon the
concentration of the specific acid.
Advantages of Acid Catalysis
Faster Reaction Rates:

Acid catalysts can significantly increase the rate of chemical reactions by lowering
the activation energy required for the reaction to occur. This means that reactions
that would otherwise occur slowly or not at all can proceed at a much faster rate.

Selectivity:

Acid catalysts can promote selective reactions, where specific products are formed
over others, by affecting the reaction pathway. This is particularly useful in
industries where specific products are required.

Mild Reaction Conditions:

Many acid-catalyzed reactions can be carried out at relatively mild temperatures

and pressures, which reduces the energy and resources required for the reaction.
This can lead to lower costs and fewer environmental impacts.

Compatibility:

Acid catalysts are compatible with a wide range of reaction conditions and
substrates, making them versatile tools for many different types of reactions.

Simplified Reaction Mechanisms:

Acid catalysts can simplify reaction mechanisms, reducing the number of steps
required to achieve the desired products. This can make reactions more efficient
and easier to optimize.

Disadvantages of acid catalysis

Selectivity:

Acid catalysis can sometimes lack selectivity, leading to the formation of

unwanted byproducts that can reduce the yield and efficiency of the process.

Safety concerns:

Working with strong acids can be hazardous and requires careful handling, which
can pose safety concerns for workers.

Cost:

The use of strong acids can be expensive and can increase the overall cost of the
process.
 REFERENCE
1. https://slideplayer.com/slide/9035353/
(Basic Concepts)
2. March's Advanced Organic Chemistry: Reactions, Mechanisms, and
Structure
(Electrophilic substitution reaction of benzene)
3. https://www.britannica.com/science/acid-base-catalysis
(Bronsted-Lowery and Lewis concept)
4. https://en.wikipedia.org/wiki/Acid_catalysis#:~:text=In%20acid%20catalysi
s%20and%20base,are%20esterifications%20and%20aldol%20reaction
(Specific and General acid catalysis)
5. https://www.chemistrysteps.com/ester-hydrolysis-acid-and-base-catalyzed-
mechanism/
(Hydrolysis of Ester)
6. https://chemistnotes.com/organic/acid-base-catalysis-general-vs-specific/
7. https://www.quora.com/Catalysts-What-is-the-difference-between-general-
acid-catalysis-and-specific-acid-catalysis
8. Chat GPT (Advantages and disadvantages)