Table of Contents

Non elementary reaction:-............................................................................................................... 2

Free Radicals:- ............................................................................................................................ 2

Molecules:- ................................................................................................................................. 2

Transition Complexes:-............................................................................................................... 2

Chain Reactions:- ........................................................................................................................ 3

Non chain Reactions:- ................................................................................................................. 3

Types of mechanisms:- ................................................................................................................... 3

Free radicals, chain reaction mechanism:- .................................................................................. 3

Molecular intermediates, nonchain mechanism:- ....................................................................... 4

Transition complex, nonchain mechanism:- ............................................................................... 4

Non elementary reaction:-
A non elementary reaction is one whose stoichiometry does not
match its kinetics. For example,

This non match shows that we must try to develop a multistep reaction model to explain the
kinetics.

Free Radicals:-
In chemistry, a radical (more precisely, a free radical) is an atom, molecule, or
ion that has unpaired valence electrons or an open electron shell, and therefore may be seen as
having one or more "dangling" covalent bonds.

For example: In chemical equations, free radicals are frequently denoted by a dot placed
immediately to the right of the atomic symbol or molecular formula as follows

Chlorine gas can be broken down by ultraviolet light to form atomic chlorine radicals.

Molecules:-
Consider the consecutive reactions

Ordinarily these are treated as multiple reactions. However, if the intermediate R is highly reactive
its mean lifetime will be very small and its concentration in the reacting mixture can become too
small to measure. In such a situation R may not be observed and can be considered to be a reactive
intermediate.

Transition Complexes:-
The numerous collisions between reactant molecules result in a wide
distribution of energies among the individual molecules. This can result in strained bonds, unstable
forms of molecules, or unstable association of molecules which can then either decompose to give
products, or by further collisions return to molecules in the normal state. Such unstable forms are
called transition complexes.

Chain Reactions:-
In chain reactions the intermediate is formed in a first reaction, called the
chain initiation step. It then combines with reactant to form product and more intermediate in the
chain propagation step. Occasionally the intermediate is destroyed in the chain termination step.
Thus,

Reactant → (Intermediate)* Initiation

(Intermediate)* + Reactant → (Intermediate)* + Product Propagation

(Intermediate)* →Product Termination

The essential feature of the chain reaction is the propagation step. In this step the intermediate is
not consumed but acts simply as a catalyst for the conversion of material.

Non chain Reactions:-

In the non chain reaction the intermediate is formed in the first reaction
and then disappears as it reacts further to give the product. Thus,

Reactants → (Intermediates)*

(Intermediates)* →Products

Types of mechanisms:-
Free radicals, chain reaction mechanism:-
The reaction

H2 + Br2 → 2HBr

with experimental rate

1
𝐾1 [𝐻2 ][𝐵𝑟2 ]2
𝑟𝐻𝐵𝑟 =𝐾
2 +[𝐻𝐵𝑟]/[𝐵𝑟2 ]
can be explained by the following scheme which introduces and involves the intermediates H and
Br,

Br2 → 2Br. Initiation and termination

Br· + H2 →HBr + H· Propagation

H· + Br2 → HBr + Br· Propagation

Molecular intermediates, nonchain mechanism:-

The general class of enzyme-catalyzed
fermentation reactions

A → R

is viewed to proceed with intermediate (A. enzyme)* as follows:

A + enzyme → (A. enzyme)*

(A. enzyme)* → R + enzyme

In such reactions the concentration of intermediate may become more than negligible.

Transition complex, nonchain mechanism:-

The spontaneous decomposition of azomethane

(CH2)3N→CH6 + N2

exhibits under various conditions first-order, second-order, or intermediate kinetics. This type of
behavior can be explained by postulating the existence of an energized and unstable form for the
reactant, A*. Thus,

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