Chemical Kinetics

Feasibility of a reaction under given conditions can be

predicted on the basis of Gibbs energy. Based on this fact, the extent
to which reaction proceeds can be explained with the help of
equilibrium constant.

The speed with which chemical reaction proceeds can only be

explained by branch of chemistry called chemical kinetics.
Kinetics means movement.

The study of kinetics not only explains the speed of the reaction but
also describes the condition, which affects the rate of reaction.

Mechanism of reaction: The study of rates of reactions helps us to

understand the pathways from reactants to products, which is called
mechanism of reaction.

Rate of a chemical reaction: In our daily life we experience various

chemical reactions with varying rates. Some reactions are rapid and
some are slow.

The reactions involving ionic species are fast e.g. neutralization of

acid by base and mixing of silver nitrate and sodium chloride to form
silver chloride (ppt.).

In these reactions, only ions are involved and no bonds are broken.
Therefore these are fast.

There are some reactions, which are extremely slow e.g. rusting of
iron. However there are some reactions, which occur, in a measurable
time and their rates can be measured easily in the lab e.g.

1) Hydrolysis of an ester in the presence of sodium hydroxide

2) Decomposition of hydrogen peroxide

3) Inversion of cane sugar to give glucose and fructose

 4) Decomposition of nitrogen (V) oxide

The rate of chemical reaction is a measure of the speed with which

the reactants are converted into products. It may also be defined as
the change in any one of the reactants or products per unit time.

Consider an equation, R → P where one mole of reactant R produces

one mole of product P. Then the rate of reaction may be expressed in
either of the following two ways:

1. The rate of disappearance or decrease in concentration of R

(reactant)

Rate of reaction = decrease in concentration of R / time taken

2. The rate of increase in concentration of P (product)

Rate of reaction = increase in concentration of P / time taken

If [R] 1 and [P] 1 are the concentrations of R and P respectively at time

t1 and [R] 2 and [P] 2 at t2 then,
Where square brackets express the molar concentration and ∆[R] and
∆[P] are the change on concentration of R and P during the time
interval ∆t. Then the rate of reaction may be expressed as:

It may be noted that in case of concentration of reactants minus (-)

sign is used which shows the decrease in concentration of reactant
with time.

The above rate is also called the average rate of reaction.

It has the dimensions of concentration / time.
In the above example stoichiometric coefficients of the reactants and
products are same.

Therefore the rate at which the concentration of R decreases will

be the same as the concentration of P increases.

Taking the example of PCl5

Reactions involving different stoichiometric coefficients

Consider the reaction A + B → 2C

In this case one mole of A combines with one mole of B and forms 2 moles of C.
It means that the rate of disappearance of A and B are the same but rate of
appearance of C must be twice the rate of disappearance of A and B. Thus,
To get unique value of the reaction rate, we divide the rate of reaction
defined with any of the reactants or products by the stoichiometric
coefficients of that reactant or product involved in that reaction.

For example, for the decomposition of gaseous nitrogen pentaoxide (N2O5) as:

1)
Similarly, for the reaction:
For a gaseous reaction at constant temperature, concentration is
directly proportional to the partial pressure of a species and hence
rate can also be expressed as the rate of change in partial pressure of
reactants or products.

Average rate and instantaneous rate

The rate expression given so far gives the average rate of reaction
over the time interval (∆t), which can be expressed as

Rate = change in concentration / time interval = ∆x /∆t

This concept is similar to the mechanical speed. But in case of

reactions, the rate depends on the concentration of the reactants. As
the reaction proceeds, the concentration of the reactant decreases.
Thus the rate of reaction may not be constant in the time interval in
which we measure. Thus, rate of a reaction cannot be determined by
simply dividing the total change in concentration by time taken as in
case of mechanical speed.

On the other hand, the rate of a reaction may be expressed at a

particular moment of time. Thus rate of a reaction may be defined as
the rate of change of concentration of any one of the reactants or
products at a given time. Such type of reactions are called
instantaneous rate. For this purpose, the time interval (t) is made as
small as possible so that rate of reaction remains almost constant
during that time interval.

Mathematically, instantaneous rates may be expressed as –d[R]/dt or

d [P]/dt instead of - ∆[R] / ∆t or - ∆[P] / ∆t .Here d[R] or d[P]
represents very small changes in the concentration of Ror Pin very
small interval of time,dt. Thus, average rate approaches the
instantaneous rate as ∆t becomes smaller and smaller i.e.,

In general, if dx represents very small change in concentration of any

species during the very small change of time, dt, the rate of the
reaction may be expressed as

Rate = dx/dt

For general reaction,

Instantaneous rate of some reactions;

1)
2)

3)

Experimental measurement of reaction rate

The rate of any reaction is measured by plotting a graph between the

concentrations of any of the reactants or products as a function of
time. To explain this, let us consider a reaction i.e. decomposition of
dinitrogen pentaoxide. It decomposes in the presence of carbon
tetrachloride.

This reaction can be easily studied by measuring the concentration of

N2O5 at various time intervals. To measure concentration at different
time intervals we must know the increase in the pressure of the
reaction mixture at different time intervals.

From the measured values of the pressure, the partial pressure of

N2O5 is calculated and then the molar concentration of N2O5 can be
calculated. The values of molar concentration of N2O5 at 318K art
different time are given below.

Then graph is plotted between the concentration of N2O5 and time

and rate of reaction is measured by measuring the change in the
concentration with time.
Measurement of average rate of reaction

Calculation of average rate of a reaction

The average rate of reaction is measured by noting the concentration

of reactants at two different time intervals t1 & t2.Then average rate is:
From the above equation, it is clear that concentration of reactant
decreases that is represented by negative sign.

Calculation of instantaneous rate of reaction

As we know that rate of a reaction is changing constantly so, it is

more appropriate to measure the instantaneous rate. It gives the rate
at a specific instant of time. It is determined by drawing a tangent to
the curve at a point corresponding to the given time. Then the slope
of the tangent will give the instantaneous rate of a reaction. The slope
can be determined by extending the tangent to intersect both the
axes.
Measurement of instantaneous rate of a reaction

In the above graph distance OA along the ordinates gives the change
in concentration. (dx) while the distance along the abscissa OB gives
the corresponding change in time (dt).

The ratio OA/OB ordx/dt gives the slope of the tangent Thus,

Instantaneous rate of reaction = OA/OB =dx/dt