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Questions/ Exercises
1.

1 gram charcoal adsorbs 100 mL of 0.5 M acetic acid to form a mono layer and thereby the
molarity of acetic acid is reduced to 0.49 M. Calculate the surface area of the charcoal adsorbed
by each molecule of acetic acid. Given surface area of charcoal = 3.01 102m2/g.
(Ans. 5.0 10-19m2)

Hence, the surface area of charcoal adsorbed by one molecule of acetic acid:

2. When 100 mL of

oxalic acid solution is added to 2.0 g of active charcoal, the molarily of

oxalic acid is reduced to

(Ans. 1.55 g)

. Calculate the acetic acid adsorbed by 1g of charcoal.

Hence, the oxalic acid adsorbed by one gram of charcoal:

3.
A graph between log (x/m) and log p is a straight line at an angle of 45 o with intercept on the yaxis (log K) equal to 0.3010. Calculate the amount of the gas adsorbed per gram of the
adsorbent under a pressure of 0.4 atmosphere.

(Ans. 0.8 g)

Rate of a Chemical Reaction

Like speed of a motor car (i.e. the change in position or distance covered in a unit time), the
speed or rate of a chemical reaction can be defined as ?the change in concentration of a
reactant or a product in unit time.?
We know that as the reaction proceeds towards equilibrium, the concentration of any one of the
reactants decreases and consequently the concentration of any one of products increases. So,
rate of reaction may be expressed in terms of rate of disappearance of any one of reactant or rate
of appearance of any one of the product.
Let us consider the following reaction,

The rate of disappearance of reactants and the rate of appearance of product can be expressed
as:

Where, [A], [B] and [C] are the change in molar concentrations of A, B and C respectively in
the time interval t .
?ve sign with reactants indicates that its concentration decreases with time while +ve sign with
the product indicates the increase in its concentration with time.

Since the time can be expressed in minutes, hours, days or years (for radioactive reactions), the
unit of rate of reaction may change accordingly. For gaseous reactions, concentration is
expressed in partial pressures, hence the unit of rate of reaction is atm S -1.
Instantaneous rate of reaction: Above expression of rate only describes the average rate of
reaction which cannot be used to predict the rate of a reaction at a particular instant.
?Instantaneous rate of reaction(rinst) is the rate at a particular moment of time.? To
determine rinst we consider the average rate (rav) in the smallest time interval dt (when
Mathematically, for a reaction

Fig. Illustration of average rate and instantaneous rate of reaction

).

Example 1: The decomposition of N2O5 in CCl4 at 318K takes place according to the following
equation,

The initial and final concentrations of N2O5 in a time interval of 184 minutes are 2.33 mol L-1 and
2.08 mol L-1. Calculate the rate of this reaction in terms of hours, minutes and seconds. Also find
out the rate of production of NO2 during this period.

Solution:

Integrated Rate Equations

In order to relate the concentrations of reactants at different times with the rate constant, the
differential rate equation is integrated. As a result, we get an equation which is called integrated
rate equation. As per the syllabus, we shall determine the integrated rate equations for zero and
first order in the following sections:
(i) Zero Order Reactions
In zero order reactions, the rate of reaction is independent of the concentration of the reactants
i.e. change in concentration of the reactants has no effect on the rate of reaction.
Examples of zero order reactions:
Zero order reactions occur under special conditions like enzyme catalyzed reactions and the
reactions occurring on the surfaces of metals.

This is the integrated rate equation for zero order which relates the rate constant with the
concentration of reactant.

As the equation [A] = -kt + I, corresponds to straight line equation, y = mx + c, the plot of [A] vs
t(time) is found to be straight line with the slope (-k) and intercept equal to [A] 0.

(ii) First Order Reaction

In first order reaction, the rate of reaction is proportional to the first power of the concentration of
the reactant.

For Example,

This is the first order integrated rate equation which relates the rate constant (k) with the
concentration of the reactants.
Since the equation ln [A] = -kt + ln[A]0 Corresponds to straight line equation y = mx + c, we get a
straight line with slope = -k and intercept = ln [A]0 . When a plot of ln[R] against t (time) is drawn.
From above equation, we get

So, the plot of log[A]0/[A] against t, also gives a straight line with slope

In a gaseous reaction at constant temperature, concentration is directly proportional to the partial

pressure of a reacting species.
For a first order gas phase reaction,

Orde
r
0

Reaction
Type

Differential
rate law

Straight line
Integrated rate law
plot

Half life

Units of k

We can also find out the integrated rate equations for 2nd and 3rd order reaction,

Example 2. Decomposition of a gas is of first order reaction. It takes 80 minutes for 80% of the
gas to be decomposed when its initial concentration is 8 10-2 mole/litre. Calculate the rate
constant or specific reaction rate.
Solution: For First order reaction, integrated rate equation is given by