KINETIC AND NON-KINETIC METHODS OF

STUDY OF REACTION MECHANISMS.

Dr.K.RAJARAJAN.M.Sc;M.Phil;Ph.D.
Assistant prof. of chemistry,
Rajah Serfoji Govt. College,
Thanjavur-613 005.
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1. AIMSAND OBJECTIVES
2. INTRODUCTION
3. KINETIC AND THERMODYNAMICS
CONTROL OF A REACTION
4. MICROSCOPIC REVERSIBILITY
5 HAMMONDS POSTULATE
6.KINETIC AND NON-KINETIC
METHODS OF STUDY OF REACTION
MECHANISMS

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KINETIC METHODS - PRIMARY AND
SECONDARY KINETIC ISOTOPIC
EFFECT
NON-KINETIC METHODS OF STUDY OF
REACTIONMECHANISM

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Identification of products:
Identification of the intermediate:
Isotopic labeling
Stereo Chemistry evidences
Stereo Chemical Method

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AIMS AND OBJECTIVES
The aim is to motivate and enable a
comprehensive knowledge on kinetic and non-
kinetic methods of study of reaction mechanisms
to the students.
On successful completion of this lesson the
student should have:
Understood the kinetic and non-kinetic methods
of study of reaction mechanisms

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INTRODUCTION
Under reversible reaction conditions the ratio of possible
products is determined by the relative stability of each
product, measured by its standard free energy (DG0). The
composition of the equilibrium mixture does not depend
on how fast (DG) each product is formed in the reaction.
This is termed thermodynamic (or equilibrium) control.
On the other hand when the quantity of each
product is formed and is not a function of the relative
stability (DG0) of each product, one calls it kinetic control
reaction.

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KINETIC AND THERMODYNAMICS CONTROL
OF A REACTION
A given set of the reaction at the given condition,
some times two products may formed
i.e., two isomeric products. As a mixture in such a
reaction one product is called kinetically
controlled and the other one is called
thermodynamically controlled product.

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The one which has high activation energy is more stable
product and this product is thermodynamically controlled
product. The one has low activation energy is less stable
product
this product is kinetically controlled products.
(i). Both the steps are irreversible then the product will contain
more C.
(ii). If both the steps are reversible and if the reaction is
stopped before the equilibrium attain
then also we get more kinetic controlled product C.
(iii). If both the steps are reversible and the equilibrium is
reached, then we get the B which is
thermodynamic controlled product is formed.
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MICROSCOPIC REVERSIBILITY
In a reversible reaction the forward and reverse
reactions must follow the same
mechanism. This phenomenon is called the principle of
microscopic reversibility.
Example:
In the dehydration of an alcohol, an olefin is format via.
a carbonium ion intermediate, as
a consequence of the principle of the microscopic
reversibility, the reverse reaction i.e., the acid
catalyzed hydration of olefin to alcohol, must involve
the same carbonium ion.
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 HAMMONDS POSTULATE
For any single reaction step, the geometry of the
transition state resembles to the side to
which it is closer in energy.
Example (i):
In the exothermic reaction the energy of transition
state is closer to reactant. So the
geometry of transition state resembles as reactant.

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Example (ii):
In SN1 reaction, there will be two transition
state, energy of these transition state are
closer
to intermediate so the geometry of transition
state resembles as intermediate.

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Methods that are used to determine to
Reaction Mechanism:
(i) Kinetic Methods
(ii) Non-Kinetic Methods

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KINETIC METHODS
PRIMARY AND SECONDARY KINETIC
ISOTOPIC EFFECT
This will observed if the C-H bond cleavage takes
place in a slow step mechanism.
Isotopic substitution will give acceptable charges,
i.e., the rate of the reaction

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This reaction can be catalyzed by both
an acid and a base.
The rate of the reaction depend on,
(i) Catalyst (ii) Reactant (iii) Independent
of Br2

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First let us assume step (i) is slow and step (ii) is fast. The
rate constant for the nitration of benzene is KH. The rate
constant for the nitration of benzene is KH. The rate
constant for the nitration of deuterated benzene is KD.

The step (ii) alone involves the C-H bond breaking. Here
in this case KH=KD there is kinetic isotopic effect.
If we consider the (ii), i.e., step (ii) as fast and (ii) as rate
determining then KH is not equal to KD. But the
experimental result shows that KH/KD = 1. There is no
isotopic effect.

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The kinetic isotopic effect shows that the first
step is the rate determining step and it does
not involve the C-H bond breaking. In some of
the reaction the C-H bond breaking is not the
rate determining step.
But there will be isotopic effect,
even though the C-H bond breaking is not
involved in the determining step. This effect is called
the secondary kinetic isotopic effect.

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NON-KINETIC METHODS OF STUDY OF
REACTIONMECHANISM
Non-Kinetic method involves the following
steps.
a) Identification of product
b) Identification of intermediate
c) Isotopic labeling
d) Stereo chemical evidences:

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Identification of products
The most fundamental basis for mechanistic
speculation i.e., the identification of the
products, without such intermediate we cant be
sure which reaction actually occurs under the
given conditions.
This should account for all the products, relative
proportion of the product and also the
product formed by the side reaction

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Identification of the intermediate
Among the most concrete evidence obtained about
the mechanism of the reaction is that
provided by the actual isolation and identification of
one or more intermediates from the
reactions mixtures.
(i) Isolation of an intermediate
It is sometimes possible to isolate an intermediate
from a reaction mixture by stopping the
reaction after a short time or by use of very mild
conditions

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Carbon has two isotopes C14 is the radio active so
we label the C in RCOO- is RC14OO but in the
product C14 is present in alkylcyanide.

Eg: Ester hydrolysis whether it is acid catalysis and

basic catalysis in involves two types cleavage.

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O18 in the products is found out by the help
of mass spectrum i.e., the acid and the
alcohol are analysed and the heavy isotope
O18 is present in the acid i.e., confirms the
acyloxygen cleavage present.
Stereo Chemical evidences

Olefins undergo addition because the double bond

is rich in electron. It is a univalence atom so we add 2
atoms.

(i) Two atoms are added simultaneously this is called

constructed mechanism.
Whether cis or trans isomer, carbonium ion
intermediate is formed means because of single
bond is capable of free rotation and the two acids
i.e., maleic and fumaric acid leads to the same
product because the bulky COOH groups in the
maleic acid intermediate and hindrance and it
forms the intermediate of trans isomer.
If it is bromium ion intermediate means the rotation is not
possible.

If it is cyclic bromonium ion intermediate means the

intermediate obtained by cis and trans isomers are not
identical. So the products are different i.e., it retained the
stereo chemistry of the reactant.
Stereo Chemical Method
Organic substance exhibits in stereo isomerism i.e.,
geometrical isomerism and optical isomerism in the case
of optical isomerism the starting material is in meso
active or racemic form, after the reaction is completed
then also we have to see the nature or seterochemistry
of the product.