TERM PAPER

CHE-101
“ENZYM KINETICS”
DOA:-26/8/10
DOR:-28/9/10
DOS: 6/11/10
SUBMITTED TO:-
SUBMITTED BY:-
Ms. GEETIKA ARORA Mr.
Vivek Kumar
Department Of chemistry, Roll no :-
40
 Reg.
No:-11000518
Secti
on:-E6001

ACKNOWLEDGMENTS

This is a humble effort to express our sincere gratitude

towards those who have guided and helped us to complete this
project.
A project reported is major milestone during the study
period of a student. We could have faced many problems but our
teachers’ kind response to our needs and requirement, their
patient approach and their positive criticism helped us in making
our project. Very warm thanks to our project-in-charge “MS.
GEETIKA ARORA MAM” with her support and constant
encouragement AND LPU LIBRARY it was not very easy
without whose support to finish our project.
With the motivation of our parent it was very easy to
finish our project successfully and satisfactorily in short span of
time.
NISHANT KUMAR GARG
 CONTENTS

1. Introduction
2. Rates, rate laws and rate constant
3. Rate of reaction
4. Rate laws and rate constants
• simple rate laws
• First order
• Second order reaction

1. Importance of rate law

2. Pseudo chemical reaction
3. Kinetic experiments related to first order.
4. Collision theory of reaction rate (arrhenius theory of reaction rate)
INTRODUCTION

Kinetics is the study of the rates of chemical processes in an effort to understand

what it is that influence these rates and to develop theories which can be used to
predict them.

CHEMICAL KINECTICS is the area of chemistry concerned with the speeds,or

rates,at which a chemical reaction occurs.
Kinectics refers to the rates of the reaction,or chemical reaction rate,which is the
change in the concentration of the reactant or a product with time.
 RATES, RATE LAWS AND RATE CONSTANTS

In this Section we will introduce the language and terms used to describe
the rates of chemical reactions. At this stage we will not be concerned with
the theory of reactions or mechanisms, but just stand back and describe the
overall rates.

Rate of reaction
The rate is defined as change in concentration of the reactant and product with
respect to time.
Generally,
Reactants=products
Assume,
A+B=C

Rate=-Δ[A]Δt

Rate=-Δ[B]Δt

Rate=Δ[C]Δt

We can talk about the rate of formation or loss of any species – reactant,
intermediate or product. It is, however, important to specify which species
we are talking about. The rate can be positive or negative: a positive rate
means that the concentration is increasing with time e.g. a product; a
negative rate means that the concentration is falling with time e.g. a
reactant.
The rate may vary with time (and concentration), so it is usual to define
the rate over a very small time, . We think of the rate as the derivative of
concentration with respect to time

Rate=Δ[Concentration]Δt
Rate laws and rate constants
Experimentally it is found that rates depend on the concentrations of the
species involved in the reaction equation (and sometimes on the
concentrations of species which do not appear at first sight to be involved!).
The relation between the rate and these concentrations can often be
expressed mathematically in the form of an equation called a rate law.
Some rate laws are very simple and some are very complicated. A rate law
may be determined experimentally (Section 4) or may be the result of a
theoretical prediction, or both.
THE rates law expresses the relationship of the rate of a reaction to the rate
constant and the concentration of the reactants raised to some powers .

aA+Bb=Cc+Dd

rate=k[A]a[B]b

where k is constant, characteristic of a particular reaction, called the rate

constant or the rate coefficient. The powers a, b ... are also constants: a is
the order with respect to A, b is the order with respect to B.

Simple rate laws

First order
A first order rate law is one in which the rate is proportional to the
concentration raised to the power 1 (hence "first")
A=PRODUCTS

Rate=Δ[A]Δt

Rate=k[A]

is called a first order rate constant. The rate equation, and the reaction
it describes, is said to be first order in A or it is said that the order with
respect to A is one. As the units of r are concentration time–1 and the units
of [A] are concentration, the units of RATE in first order reaction are found as
time–1.
Second order reaction
A=PRODUCTS

Rate=Δ[A]Δt

Rate=k[A]2
A second order reaction has the concentration raised to the power of 2
is called a second order rate constant. The rate equation, and the
reaction it describes, is said to be second order in A, or the order with
respect to A is two. The units of k2nd are found to be conc.–1 time–1.

IMPORTANCE of rate law.

1. If we know the rate law and the constants in it we can use this to predict
the rate for any set of conditions (concentrations). The rate law is thus a
very succinct and practical way of expressing the rate. You might use this,
for example, in a model of the atmosphere or in predicting the rate of an
enzyme catalysed reaction.
2. The form of the rate law can tell us something about the mechanism of
the reaction. This is a point which we will consider in more detail below.
3. Knowing the rate law enables us to separate the concentration
dependence from the underlying, fundamental effect which is the size of the
rate constant.

PSEUDO CHEMICAL REACTION

Consider the general reactions...
A+B=PRODUCTS
In which order with respect to each reactants is 1 that the overall order of reaction
is 2.
The rate law is
Rate=k[A][B]
however one of the react is present in large excess.,e.g.,one of the reactant may be
solvent ,its concentration will remain almost constant.
In that case,the rate of the reaction depend only on the concentration of the reaction
present in smallar amount.Theus,the reaction becomes a first order reaction.

There are some reactions which appear to be second order but in fact
these are first order reaction with respect to the different reactants i.e.
Now, if one of the reactant is present in high concentration (solvent) then there is
very little change in its concentration. In other words the concentration of that
reactant remains practically constant during the reaction. For example,
If [A] = 0.01 M and that of solvent water [B] = 55.5 M, the concentration of B
changes only from 55.5 to 55.49 M even after the completion of the reaction.
Under such conditions, the rate of the given reaction will be according to first order
reaction
The reaction therefore, behaves as a first order reaction not a second
order reaction.

Some examples are

1) Pseudo reaction can be explained by taking an example of hydrolysis
of ethyl acetate:
The molecularity of the reaction is two because it involves two reacting species,
ethyl acetate and water. But the concentration of ethyl acetate changes during the
reaction while the concentration of water remains constant since it is present in
such large excess.
CH3COOC2H5 + H2O= CH3COOH+C2H5OH

According to reaction equation the absolute changes [A] and [B] have the same
magnitude. Since the initial amount of A is smaller, the effect on the concentration
and the reaction rate is much greater for A as for B

You can illustrate this with some numerical values:

Let initial concentartions be [A]₀ = 1 and [B]₀=100
At the instant where half of A has reacted away:
[A] = 0.5 and [B]= 99.5
So [B] has changed only by 0.5% while [A] changed by 50%.
Compare reaction rate to intial rate
r = k·0.5·[A]₀·0.995·[B]₀ = 0.4975·k·[A]₀·[B]₀ = 0.4975·r₀
You can see, that the drop in reaction rate is almost entirely determined by the
change of [A], because the relative change in concentration of A is much larger.

Therefore you can ingnore the change of concentration in [B]

thorughout the reaction, if B is in large excess:
[B] ≈ [B]₀
The rate equation simplifies to:
r = k'·[A]
where k' = k·[B]₀
So you can describe reaction kinetics by a pseudo 1st order rate law.

Kinetic Experiments RELATED TO FIRST ORDER.

• Bromination of Reactive Aromatics
• Fading of Triphenylmethane Dyes
• Fading of Phenolphtalein in Alkaline Solution
The bromination of acetanilide, 4-nitrophenol and diphenylether is based on a
second order reaction:

-Δ[Br]Δt =k.[Ar][Br]
If the initial concentration of the aromatic reactant (Ar) is much larger than the
bromine concentration, the concentration of Ar will not change appreciably during
the course of the reaction The concentration of the aromatic reactant in excess
remains (essentially) constant. Thus the rate’s dependence on bromine can be
isolated and the rate law can be written

Δ[Br]Δt=k’[Br] where k’=k[Ar]……….(2)

Equation (2) represents the differential form of the rate law. Integration of this
equation and determination of the integration constant C produces the
corresponding integrated law.
Substituting [Br] = c into equation (2) yields:
-Δ[c]c=k ’.dt ………………..(3)
Integrating equation (3) gives:
lnc = −k'⋅t +C ……………. (4)
sThe constant of integration C can be evaluated using boundary conditions. At t =
0 the
concentration of bromine is C0.
Therefore:
C = lnC0 …………….. (5)
Accordingly is obtained:
lnc = lnc0− k'⋅ t …………………… (6)
or
C=C0 e-k’.t ………………… ⋅ (7)
The decrease in the bromine concentration can be followed by photometric
measurement.

COLLISION THEORY OF REACTION RATE (ARRHENIUS

THEORY OF REACTION RATE)
A collision between high energy molecules overcomes the forces
of repulsion and brings the formation of an unstable molecule
cluster, called the activated complex. The life span of an
activated complex is very small. Thus, the activated complex
breaks either into reactants again or new substances, i.e.,
products. The activation energy (Ea) depends upon the nature of
chemical bonds undergoing rupture and is independent of
enthalpies of reactants and products. The energy changes during
exothermic and endothermic reactions versus the progress of the
reaction