TERM PAPER

CHE-101

“pseudo order ”

DOA:-26/8/10

DOR:-28/9/10

DOS: 6/11/10

SUBMITTED TO:- SUBMITTED BY:-

Ms. GEETIKA ARORA Mr. Nishant Kumar garg

Department Of chemistry, Roll no :- RE6001B35

Reg. No:-11006867

Section:-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

ABSTRACT

In physical chemistry,we study about the speed and the progress of chemical reaction in
CHEMICAL KINECTICS.It tells us about the concentration of the reactants at different time
with the reaction progress.Sometimes some reaction looks like the reaction of first and second
order but they actually not.These are termed as pseudo order.

Further this term paper also highlights few experiments with their complete mechanism for
complete understanding that what happens at pseudo order level.
 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

5. Importance of rate law

6. Pseudo chemical reaction
7. Kinetic experiments related to first order.
8. Collision theory of reaction rate (arrhenius theory of reaction rate)
9. Refrences

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

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 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=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=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:

=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

=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:

=k ’.dt …………..(3)

Integrating equation (3) gives:

lnc = −k'⋅t +C ……………. (4)

The 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

REFRENCES

1. WIKIPEDIA ;pseudo order search

2. PARDEEPS; new course chemistry OF P.N.KAPIL

3. Mc GRAW HILLS ;text book of chemistry OF RAYMOND CHANG