Chemical Reaction

Engineering

Mechanism
of Reaction
PHARMACEUTICAL CHEMICAL ENGINEERING
Semester 4
Department of Chemical Engineering
Topics Single and Elementary
and
Multiple
Nonelemetary
Reactions
Reactions

Representation Representation
of an of a
Elementary Nonelementary
Reaction Reaction
Topics Kinetic Models The Types of
for Intermediates
Nonelementary
Reactions

Reaction Search for The

Schemes Reaction
Mechanism
 Single and Multiple Reactions

Examples: Single Reaction

A+RS When a single stoichiometric equation

and single rate equation are chosen to
represent the progress of the reaction

Multiple Reaction

ARS More than one stoichiometric equation

and kinetic expression are chosen to
represent the progress of the reaction
 Classification of Multiple Reactions

Examples:
Series Reactions
ARS

R A R Parallel Reactions:
Competitive & Side by Side
A or
S B S
A+BR More Complicated
R+BS
 Elementary Reaction

Consider a single reaction with stoichiometric equation

A+BR
Assumption:
 The rate-controlling mechanism involves the collision/interaction
of molecule A and B
 The number of collisions of molecules A and B is proportional to
the rate of reaction
 At a given temperature, the number of collision is proportional to
the concentration of the reactants
So, the rate of disappearance of A is given by

 The rate equation corresponds to a stoichiometric equation

 Nonelementary Reactions

The rate of production of HBr

 There is no direct correspondence between stioichiometry and

rate of reaction
 Kinetic Models for Nonelementary Reactions

Example of nonelementary reaction

A series of elementary steps to explain the kinetics:

 Types of Intermediates

Free Radicals
 Free atoms or larger fragments of stable molecules that
contain one or more unpaired electrons

DPPH Triphenylmethyl
 Types of Intermediates

Ions and Polar Substances

 Electrically charged atoms, molecules, or fragments of
molecules, such as

Molecules
 Consider the consecutive reactions
A  R S
 If the intermediate R is highly reactive  lifetime will be
very small and its concentration in the reacting mixture
can become too small to measure  R is reactive
intermediate
 Types of Intermediates

Transition Complexes

 Collisions between reactant molecules  wide

distribution of energies among the individual molecules
 Resulting strained bonds, unstable forms of molecules,
or unstable assocuation of molecules
 The molecules  decompose to give product, or by
further collisions return to molecule in normal state
 Reaction Schemes

Nonchain Reactions

 The intermediate is formed in the first reaction and

then disappears as it reacts further to give the product

Reactants  (Intermediates)*
(Intermediates)*  Products
 Reaction Schemes

Chain Reactions consist of 3 steps

 Initiation: the intermediate is formed in a first reaction

 Propagation: the intermediate then combines with
reactant to form product and more intermediate
 Chain termination: the intermediate is destroyed

Reactants  (Intermediates)* Initiation

(Intermediates)* + Reactant  (Intermediate)* + Product Propagation
(Intermediate)*  Product Termination
 Examples of Reaction Mechanism

Free radicals, chain reaction mechanism

 The reaction:

with experimental rate

can be explained by the following scheme which introduces

and involves the intermediates H* and Br*
Initiation and termination
Propagation
Propagation
 Examples of Reaction Mechanism

Molecular intermediates, nonchain reaction

mechanism
 The general class of enzyme-catalyzed fermentation
reaction:
A (with enzyme)
with experimental rate

Is viewed to proceed with intermediate (A.enzyme)* as

follows:
A + enzyme (A.enzyme)*
(A.enzyme)* R + enzyme
 Examples of Reaction Mechanism

Transition complex, nonchain reaction

mechanism
 The spontaneous decomposition of azomethane:
( 𝐶𝐻 3 )2 𝑁 2 → 𝐶 2 𝐻 6 + 𝑁 2 𝑜𝑟 𝐴 → 𝑅+𝑆

 This type of behavior can be explained by postulating

the existence of an energized and unstable form for the
reactant, A*.
A + A  A* + A Formation of energized molecule
A* + A  A + A Return to stable form by collision
A*  R + S Spontaneous decomposition into products
 Search for The Rate of Reaction

Example 2.1
 The reaction:
A+B AB

 Find the rate expression for the reaction

Solution

 1st assumption: elementary reaction

Rate of formation of AB: