Chemical Kinetics 24-25

CHEMICAL KINETICS
The branch of chemistry which deals with the study of reaction rates and their mechanisms is
called chemical kinetics
The factors which affect reaction rates are:
1) Concentration
2) Pressure
3) Temperature
4) Catalyst
Rate of a Chemical Reaction
The speed of a reaction or the rate of a reaction can be defined as the change in concentration of
a reactant or product in unit time. To be more specific, it can be expressed in terms of:
(i) the rate of decrease in concentration of any one of the reactants, or
(ii) the rate of increase in concentration of any one of the products.

Consider a hypothetical reaction, assuming that the volume of the system remains constant.
R→P
One mole of the reactant R produces one mole of the product P. If [R]1 and [P]1and [R]2 and [P]2
are the concentrations of R and P respectively at time t1 and t2 then,
Δt = t2 - t1
Δ[R] = [R]2 -[R]1
Δ [P] = [P]2-[P]1
The square brackets in the above expressions are used to express molar concentration.
Rate of disappearance of R
= Decrease in concentration of R = Δ[R]

Time taken Δt
Rate of appearance of P
= Increase in concentration of P = Δ[P]

Time taken t Δt
Since, Δ[R] is a negative quantity (as concentration of reactants is decreasing), it is multiplied

with –1 to make the rate of the reaction a positive quantity.
The above equations represent the average rate of a reaction, r
Average rate depends upon the change in concentration of reactants or products and the time
taken for that change to occur.
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:
OR
In partial pressures: atm s-1
Instantaneous Rate of a Reaction
To express the rate at a particular moment of time we determine the instantaneous rate. It is
obtained when we consider the average rate at the smallest time interval say dt ( i.e. when Δt
approaches zero).
rav = Δ[R] = Δ[P]

Δt Δt
As Δt 0, rinst = d[R] = d[P]

dt dt
10
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Factors Influencing Rate of a Reaction
1. Dependence of Rate on Concentration
Consider a general reaction
aA + bB ⇌ cC + dD
where a, b, c and d are the stoichiometric coefficients of reactants and products.
The rate expression for this reaction is Rate = [A]x [B]y where exponents x and y may or may not
be equal to the stoichiometric coefficients (a and b) of the reactants. Above equation can also be
written as Rate = k [A]x [B]y
-d[R] = k [A]x [B]y
dt
This form of equation is known as differential rate equation.
Rate law is the expression in which reaction rate is given in terms of molar concentration
of reactants with each term raised to some power, which may or may not be same as the
stoichiometric coefficient of the reacting species in a balanced chemical equation.
Order of a Reaction
The sum of powers of the concentration of the reactants in the rate law expression is called the
order of that chemical reaction.
The reactions taking place in one step are called elementary reactions. When a sequence of
elementary reactions (called mechanism) gives us the products, the reactions are called complex
reactions.
Molecularity of a Reaction
The number of reacting species (atoms, ions or molecules) taking part in an elementary
reaction, which must collide simultaneously in order to bring about achemical reaction is
called molecularity of a reaction.
Integrated Rate Equations

Zero Order Reactions: Zero order reaction means that the rate of the reaction is proportional to
zero power of the concentration of reactants.
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Consider the reaction,
Comparing with equation of a straight line, y = mx+c, if we plot [R] against t, we get a straight
line with slope = -k and intercept equal to [R]0
–1
Further simplifying:
Example of zero order reaction:

The decomposition of ammonia on platinum surface at high pressure follows zero order kinetics.
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First Order Reactions
In this class of reactions, the rate of the reaction is proportional to the first power of the
–1
concentration of the reactant R. For example,
Comparing equation (4.9) with y = mx + c, if we plot ln [R] against t (Fig. 4.4) we get a straight
line with slope = –k and intercept equal toln [R]0The first order rate equation (4.10) can also be
written in the form
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If we plot a graph between log [R]/[R] vs t, (Fig. 4.5), the slope = k/2.303
Hydrogenation of ethene is an example of first order reaction.
All natural and artificial radioactive decay of unstable nuclei take place by first order kinetics.
Let us consider a typical first order gas phase reaction

A(g) B(g) + C(g)
Let pi be the initial pressure of A and pt the total pressure at time‘t’. Integrated rate equation for
such a reaction can be derived as:
Total pressure pt = pA + pB + pC (pressure units)
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Half Life Of A Reaction
The half-life of a reaction is the time in which the concentration of a reactant is reduced to one
half of its initial concentration. It is represented as t½.
It is clear that for a zero order reaction, t½ is directly proportional to the initial concentration of
the reactants and inversely proportional to the rate constant.
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Pseudo First Order Reaction
The order of a reaction is sometimes altered by conditions. Consider a chemical reaction
between two substances when one reactant is present in large excess. During the hydrolysis of
0.01 mol of ethyl acetate with 10 mol of water, amounts of the various constituents at the
beginning (t = 0) and completion (t) of the reaction are given under
Temperature Dependence of the Rate of a Reaction

It has been found that for a chemical reaction with rise in temperature by 100, the rate constant is
nearly doubled.
It is also called pre-exponential factor. It is a constant at a specific temperature.
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The energy required to form this intermediate, called activated complex (C), is known as activation
energy (Ea). The figure is obtained by plotting potential energy vs reaction coordinate. Reaction
coordinate represents the profile of energy change when reactants change into products.
According to Maxwell – Boltzmann Distribution curve, the distribution of kinetic energy may be
described by plotting the fraction of molecules (NE/NT) with a given kinetic energy (E) vs kinetic
energy. Here, NE is the number of molecules with energy E and NT is the total number of
molecules.
Distribution curve showing energies among gaseous molecules
Distribution curve showing temperature dependance of rate of a reaction
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The peak of the curve corresponds the kinetic energy possesssed by maximum fraction of
molecules.
Increasing the temperature of the substance increases the fraction of molecules, which collide with
energies greater than Ea. It is clear from the diagram that in the curve at (t + 10), the area showing
the fraction of molecules having energy equal to or greater than activation energy gets doubled
leading to doubling the rate of a reaction.
In the Arrhenius equation, k = Ae-Ea/RT, e-Ea/RT represents the fraction of molecules having energy
equal to or greater than activation energy.
k1 and k2 are the rate constants at temperatures T1 and T2 respectively.
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Effect Of Catalyst
A catalyst is a substance which alters the rate of a reaction without itself undergoing any permanent
chemical change.
For example, MnO2 catalyses the following reaction so as to increase its rate considerably
MnO2
2KClO3 2KCl + 3O2
The action of the catalyst can be explained by intermediate complex theory. According to this
theory, a catalyst participates in a chemical reaction by forming temporary bonds with the
reactants resulting in an intermediate complex. This has a transitory existence and decomposes to
yield products and catalyst.
It is believed that the catalyst provides an alternate pathway or reaction mechanism by reducing
the activation energy between reactants and products and hence lowering the potential energy
barrier as shown in the figure below.
Collision Theory of Chemical Reactions

For a bimolecular elementary reaction
A+B Products
rate of reaction can be expressed as:
where ZA-B represents the collision frequency of reactants, A and Band e-Ea/RT represents the fraction
of molecules with energies equal to or greater than Ea. Comparing this equation with Arrhenius
equation, we can say that A is related to collision frequency ZA-B.
This equation predicts the value of rate constants fairly accurately for the reactions that involve
atomic species or simple molecules but for complex molecules significant deviations are
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observed. The reason could be that all collisions do not lead to the formation of products. The
collisions in which molecules collide with sufficient kinetic energy (called threshold energy*) and
proper orientation, so as to facilitate breaking of bonds between reacting species and formation of
new bonds to form products are called as effective collisions.
Diagram showing molecules having proper and improper orientation
To account for effective collisions, a factor, P called orientation factor or steric factor is
introduced in the equation. It accounts for proper orientation of molecules.
………………………………………………………………………………………………………..
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CHEMICAL KINETICS

The factors which affect reaction rates are:

Rate of a Chemical Reaction

(i) the rate of decrease in concentration of any one of the reactants, or

(ii) the rate of increase in concentration of any one of the products.

= Decrease in concentration of R = Δ[R]

= Increase in concentration of P = Δ[P]

Since, Δ[R] is a negative quantity (as concentration of reactants is decreasing), it is multiplied

In partial pressures: atm s-1

Instantaneous Rate of a Reaction

rav = Δ[R] = Δ[P]

As Δt 0, rinst = d[R] = d[P]

Integrated Rate Equations

Example of zero order reaction:

concentration of the reactant R. For example,

Let us consider a typical first order gas phase reaction

Temperature Dependence of the Rate of a Reaction

It is also called pre-exponential factor. It is a constant at a specific temperature.

Distribution curve showing energies among gaseous molecules

Distribution curve showing temperature dependance of rate of a reaction

k1 and k2 are the rate constants at temperatures T1 and T2 respectively.

Collision Theory of Chemical Reactions

Diagram showing molecules having proper and improper orientation

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