CHAPTER

11 REACTION KINETICS

Animation 11.1: Spectrometer

Source & Credit: eLearn
 11 REACTION KINETICS [Link]

11.0.0 INTRODUCTION

It is a common observation that rates of chemical reactions differ greatly. Many reactions,
in aqueous solutions, are so rapid that they seem to occur instantaneously. For example, a white
precipitate of silver chloride is formed immediately on addition of silver nitrate solution to sodium
chloride solution. Some reactions proceed at a moderate rate e.g. hydrolysis of an ester. Still other
reactions take a much longer time, for example,the rusting of iron, the chemical weathering of
stone work of buildings by acidic gases in the atmosphere and the fermentation of sugars.
The studies concerned with rates of chemical reactions and the factors that affect the rates of
chemical reactions constitute the subject matter of reaction kinetics. These studies also throw light
on the mechanisms of reactions. All reactions occur in single or a series of steps. If a reaction
consists of several steps, one of the steps will be the slowest than all other steps. The slowest step
is called the rate determining step. The other steps will not affect the rate. The rates of reactions
and their control are often important in industry. They might be the deciding factors that determine
whether a certain chemical reaction may be used economically or not. Many factors influence the
rate of a chemical reaction. It is important to discover the conditions under which the reaction will
proceed most economically.

Animation 11.2: Kinetics

Source & Credit : [Link]

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11.1.0 RATE OF REACTION

During a chemical reaction, reactants are converted into products. So the concentration of
the products
increases with the corresponding decrease in the concentration of the reactants as they are being
consumed.

Animation 11.3: RATE OF REACTION

Source & Credit : blobs

The situation is explained graphically in Fig.(11.1) for the reactant A which is changing irreversibly
to the product B.
The slope of the graph for the reactant or the product is the steepest at the beginning. This
shows a rapid decrease in the concentration of the reactant and consequently, a rapid increase in
the concentration of the product. As the reaction proceeds, the slope becomes less steep indicating
that the reaction is slowing down with time. It means that the rate of a reaction is changing every
moment. The following curve for reactants should touch the time axis in the long run. This is the
stage of completion of reaction. The rate of a reaction is defined as the change in concentration of
a reactant or a product divided by the tim e taken for the change.

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Fig. (11.1) Change in the concentration of reactants and products with time for the reaction
A→B

The rate of reaction has the units of concentration divided by time. Usually the concentration
is expressed in mol dm-3 and the time in second, thus the units for the reaction rate are mol dm-3s-1.
change in concentration of the substance
Rate of reaction =
time taken for the change

For a gas phase reaction, units of pressure are used in place of molar concentrations. It follows
from the above graph that the change in concentration of the reactant A or the product B is much
more at the start of reaction and then it decreases gradually.

So the reaction rate decreases with time. It never remains uniform during different time periods. It
decreases continuously till the reaction ceases.

mol dm-3
Rate of reaction = = mol dm-3 s-1
seconds

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11.1.1 Instantaneous and Average Rate

The rate at any one instant during the interval is called the instantaneous rate. The rate of
reaction between two specific time intervals is called the average rate of reaction.
The average rate and instantaneous rate are equal for only one instant in any time interval. At first,
the instantaneous rate is higher than the average rate. At the end of the interval the instantaneous
rate becomes lower than the average rate. As the time interval becomes smaller, the average rate
becomes closer to the instantaneous rate.
The average rate will be equal to the instantaneous rate when the time interval approaches
zero. Thus the rate of reaction is instantaneous change in the concentration of a reactant or a
product at a given moment of time.
dx
Rate of reaction =
dt

Where dx is a very small change in the concentration of a product in a very small time interval
dt. Hence, dx/dt is also called rate of change of concentration with respect to time.
The rate of a general reaction, A → B , can be expressed in terms of rate of disappearance of
the reactant A or jthe rate of appearance of the product B. Mathematically,

-d[A] d[B]
Rate of reaction = = +
dt dt

Where d[A] and d[B] are the changes in the concentrations of A and B, respectively. The
negative sign in the term indicates a decrease in the concentration of the reactant A. Since the
concentration of product increases with time, the sign in rate expression involving the change of
concentration of product is positive.

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Animation 11.4: Average and Instantaneous Rate of Change

Source & Credit : brilliant

11.1.2 Specific Rate Constant or Velocity Constant

The relationship between the rate of a chemical reaction and the active masses, expressed as
concentrations, of the reacting substances is summarized in the law of mass action. It states that
the rate of reaction is proport ional to the active mass of the reactant or to the product of active
masses if more than one reactants are involved in a chemical reaction.

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For dilute solutions, active mass is considered as equal to concentration. By applying the law of
mass action to a general reaction.

aA + bB → cC + dD

Rate of reaction = k [A]a [B]b

This expression is called rate equation. The brackets [ ] represent the concentrations and the
proportionality constant k is called rate constant or velocity constant for the reaction.

If [A] = 1 mol dm-3 and [B] = 1 mol dm-3

Rate of reaction = k × 1a × 1b = k

Hence the specific rate constant of a chemical reaction is the rate of reaction when the
concentrations of the reactants are unity. Under the given conditions, k remains constant, but it
changes with temperature.

Animation 11.5: Velocity Constant

Source & Credit : wikia

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11.1.3 Order of Reaction

For a general reaction between A and B where ‘a’ moles of A and ‘b’ moles of B react to form ’c’
moles of C and ’d’ moles of D.

aA + bB → cC + dD

We can write the rate equation as:

a b
R =k [A] [B]

The exponent ’a’ or ‘b’ gives the order of reaction with respect to the individual reactant. Thus
the reaction is of order ‘a’ with respect to A and of order b with respect to B. The overall order
of reaction is (a+b). The order of reaction is given by the sum of all the exponents to which the
concentrations in the rate equation are raised. The order of reaction may also be defined as the
number of reacting molecules, whose concentrations alter as a result of the chemical change.
It is important to note that the order of a reaction is an experimentally determined quantity
and can not be inferred simply by looking at the reaction equation. The sum of the exponents in
the rate equation may or may not be the same as in a balanced chemical equation. The chemical
reactions are classified as zero, first, second and third order reactions. The order of reaction provides
valuable information about the mechanism of a reaction.

Animation 11.6: Rate and Order of Reac-

tion
Source & Credit : [Link]

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Examples of Reactions Showing Different Orders

1. Decomposition of nitrogen pentoxide involves the following equation.

2N 2O5 (g) → 2N 2O 4 (g) + O2 (g)

The experimentally determined rate equation for this reaction is as follows:

Rate = k[N 2O5 ]

This equation suggests that the reaction is first order with respect to the concentration of N2O5.
2. Hydrolysis of tertiary butyl bromide

CH 3 CH 3

CH 3 C Br + H 2O → CH 3 C OH + HBr

CH 3 CH 3

The rate equation determined experimentally for this reaction is

Rate = k[(CH 3 )3CBr]

The rate of reaction remains effectively independent of the concentration of water because,
being a solvent, it is present in very large excess. Such type of reactions have been named as
pseudo first order reactions.
3. Oxidation of nitric oxide with ozone has been shown to be first order with respect to NO and
first order with respect to O3. The sum of the individual orders gives the overall order of reaction as
two.
NO(g)+O3 (g) → NO2 (g)+O2 (g)

Rate = k[NO][O3 ]

4. Consider the following reaction

2FeCl3 (aq) + 6KI(aq) → 2FeI 2 (aq) + 6KCI(aq) + I 2

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This reaction involves eight reactant molecules but experimentally it has been found to be a
third order reaction.

Rate = k[FeCl3 ][KI]2

This rate equation suggests that the reaction is, in fact, taking place in more than one steps.
The possible steps of the reaction are shown below.

slow
FeCl3 (aq) + 2KI(aq)  → FeI 2 (aq) + 2KCI(aq) + Cl − (aq)

fast
2KI(aq) + 2Cl- (aq) → 2KCl(aq) + I 2 (s)

5. The order of a reaction is usually positive integer or a zero, but it can also be in fraction or can
have a negative value. Consider the formation of carbon tetrachloride from chloroform.

CHCl3 ()+Cl 2 (g) → CCl 4 ()+HCl(g)

Rate = k[CHCl3 ][Cl 2 ]1/2

The sum of exponents will be 1 + 1/2= 1.5, so the order of this reaction is 1.5.
From the above examples, it is clear that order of reaction is not necessarily depending upon
the coeffients of balanced equation. The rate equation is an experimental expression. A reaction
is said to be zero order if it is entirely independent of the concentration of reactant molecules.
Photochemical reactions are usually zero order.

11.1.4 Half Life Period

Half life period of a reaction is the time required to convert 50% of the reactants into products.
For example, the half life period for the decomposition of N2O5 at 45°C is 24 minutes.
It means that if we decompose 0.10 mole dm-3 of N2O5 at 45 °C, then after 24 minutes 0.05
mole dm-3 of N2O5 will be left behind. Similarly after 48 minutes 0.025(25%) mole dm-3 of N2O5 will
remain unreacted and after 72 minutes (3 half times) 0.0125 (12.5%) mole dm-3 of N2O5, will remain
unreacted.

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Decomposition of N2O5 is a first order reaction and the above experiment proves that the
half-life period of this reaction is independent of the initial concentration of N2O5. This is true for all
92 U has a half-life of 7.1x10 or 710 million
first order reactions. The disintegration of radioactive 235 8

years. If one kilogram sample disintegrates, then 0.5 kg of it is converted to daughter elements in
92 U , 0.25kg disintegrates in the next 710 million years. So, the
710 million years. Out of 0.5 kg of 235
half-life period for the disintegration of a radioactive substance is independent of the amount of
that substance.
What is true for the half-life period of first order reactions does not remain true for the
reactions having higher orders. In the case of second order reaction, the half-life period is inversely
proportional to the initial concentration of the reactant. For a third order reaction, half life is
inversely proportional to the square of initial concentration of reactants. Briefly we can say that

1 0.693
[t1/2 ]1 ∝ , scince[t 1/2 ]1 =

ao k

1 1
[t1/2 ]2 ∝ a 1
, scince[t1/2 ]2 =
ka

1 1.5
[t1/2 ]3 ∝ 2
, scince[t1/2 ]3 =
a ka 2

Where [t1/2 ]1 , [t1/2 ]2 , and [t1/2 ]3 are the half-life periods for 1st,
2nd and 3rd order reactions respectively and ‘a’ is the initial
concentration of reactants. In general for the reaction of nth
order:
1
[t1/2 ]n ∝
a n-1

The half-life period of any order reaction is, thus, inversely

proportional to the initial concentration raised to the power Animation 11.7: Half Life
one less than the order of that reaction. So, if one knows the Source & Credit : askiitians
initial concentration and half-life period of a reaction, then
order of that reaction can be determined.

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Example 1:

Calculate the half-life period of the following reaction when the initial concentration of HI is
0.05 M.
2HI(g) � H 2 (g) + I 2 (g)

The value of rate constant k = 0.079 dm3 mol-1 s-1 at 508 °C and rate expression is

Rate = k[HI]2

Solution:

According to the rate expression it is a second order reaction. The half life paired of a second
order reaction is

  1 1
 t 1  = 2-1 =
ka ka
 2  2

Putting the values of k and a.

  1 1 1
So, t 1  = = 3 -1 -1 -3
= sec.
 2 2 k x a (0.079dm mol s )(0.050moldm ) 0.079 x 0.05

 
 t 1  = 253sec Answer
 2  2

So, in 253 seconds, the half of HI i.e., 0.05/2=0.025 moles is decomposed.

11.1.5 Rate Determining Step

Finding out the rate equation of a reaction experimentally is very useful. Actually it gives us
an opportunity to look into the details of reaction. Rate equation of example (4) in article 11.1.3
showed clearly that the reaction is taking place in more than one steps. There are many such
reactions in chemistry which occur in a series of steps.

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If a reaction occurs in several steps, one of the steps is the slowest. The rate of this step
determines the overall rate of reaction. This slowest step is called the rate determining or rate
limiting step. The total number of molecules of reacting species taking part in the rate determining
step appear in the rate equation of the reaction.

Let us consider the following reaction

NO 2 (g) + CO(g) → NO(g) + CO2 (g)

The rate equation of the reaction is found to be

Rate = k[NO 2 ]2

This equation shows that the rate of reaction is independent of the concentration of carbon
monoxide. In other words the equation tells us that reaction involves more than one steps and
two molecules of NO2 are involved in the rate determining step. The proposed mechanism for this
reaction is as follows.

slow
NO 2 (g) + NO 2 (g)  → NO3 (g) + NO(g) (rate determining step)

fast
NO3 (g) + CO(g) → NO2 (g) + CO2 (g)

The first step is the rate determining step and

NO3 which does not appear in the final balanced
equation, is called the reaction intermediate.
The reaction intermediate has a temporary
existence and it is unstable relative to the
reactants and the products. This is a species
with normal bonds and may be stable enough
to be isolated under special conditions. This
reaction is a clear example of the fact that a
balanced chemical equation may not give
any information about the way the reaction
Animation 11.8: Rate Determining Step
actually takes place. Source & Credit : 800mainstreet

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11.2.0 DETERMINATION OF THE RATE OF A CHEMICAL REACTION

Determination of the rate of a chemical reaction involves the measurement of the concentration
of reactants or products at regular time intervals as the reaction progresses. When the reaction
goes on, the concentrations of reactants decrease and those of products increase. The rate of a
reaction, therefore, is expressed in terms of the rates at which the concentrations change.

∆C mol dm-3
Rate of reaction = =
∆t seconds

-3 -1
=mol dm s

Suppose, the concentration of a reactant of any chemical reaction changes by 0.01 mol dm-3
in one second, then rate of reaction is, 0 .01 mole dm-3 s-1.
Rate of a chemical reaction always decreases with the passage of time during the progress of
reaction. To determine the rate of reaction for a
given length of time, a graph is plotted between
time on x-axis and concentration of reactant on
y-axis whereby a curve is obtained.
To illustrate it, let us investigate the
decomposition of HI to H2 and I2 at 508°C.
Table(11.1) tells us that the change in
concentration of HI for first 50 seconds is 0.0284
mol dm-3 but between 300 to 350 sec, the
decrease is 0.0031 mol dm3. By using the data, a
graph is plotted as shown in Fig (11.2). The graph
is between time on x-axis and concentration of
HI in mol dm-3 on y-axis. Since HI is a reactant,
so it is a falling curve. The steepness of the
concentration-time curve reflects the progress
of reaction. Greater the slope of curve near the Fig.(l1.2) T he change in the HI concentration with time for the
start of reaction, greater is the rate of reaction. reaction 2HI(g) � H (g) + I (g) at 508°C.
2 2

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Table (11.1) Change in

concentration of HI with regular
intervals 2HI(g) � H 2 (g) + I 2 (g)
Concentration of Time (s)
HI (mol dm-3)
0.100 0
0.0716 50
0.0558 100
0.0457 150
0.0387 200
0.0336 250
0.0296 300
0.0265 350

In order to measure the rate of reaction, draw a tangent say, at 100 seconds, on the curve and
measure the slope of that tangent. The slope of the tangent is the rate of reaction at that point
i.e., after 100 seconds. A right angled triangle ABC is completed with a tangent as hypotenuse. Fig.
(11.2) shows that in 110 sec, the change in concentration is 0.027 mole dm-3, and hence the
0.027mol dm-3
Slope or rate =
110 sec

-4 -3 -1
=2.5x10 mol dm s

Animation 11.9: Chemical Reaction Rates

Source & Credit : crescentok

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This value of rate means that in a period of one sec in 1 dm3 solution, the concentration of HI
disappears by 2.5 x 10-4 moles, changing into the products.
The right angled triangle ABC can be of any size, but the results for the rate of reaction will be
the same.
If we plot a graph between time on x-axis and concentration of any of the products i.e H2 or I2,
then a rising curve is obtained. The value of the tangent at 100 seconds will give the same value of
rate of reaction as 2.5 x 10-4 mol dm-3S-1.
The change in concentrations of reactants or products can be determined by both physical
and chemical methods depending upon the type of reactants or products involved.

11.2.1 Physical Methods

Some of the methods used for this purpose cure the following: In these methods, a curve has
to be plotted as mentioned in 11.2.0. The nature of the curve may be rising for products and falling
for reactants. Anyhow, the results will be same for the same reaction under the similiar conditions.

Animation 11.10: Electrical Conductivity of materials focused on polymer

Source & Credit : wikidot

(i) Spectrometry

This method is applicable if a reactant or a product absorbs ultraviolet, visible or infrared

radiation. The rate of reaction can be measured by measuring the amount of radiation absorbed.

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(ii) Electrical Conductivity Method

The rate of a reaction involving ions can be studied by electrical conductivity method. The
conductivity of such a solution depends upon the rate of change of concentration of the reacting
ions or the ions formed during the reaction. The conductivity will be proportional to the rate of
change in the concentration of such ions.

(iii) Dilatometric Method

This method is useful for those reactions, which involve small volume changes in solutions.
The volume change is directly proportional to the extent of reaction.

(iv) Refractrometric Method

This method is applicable to reactions in solutions, where there are changes in refractive
indices of the substances taking part in the chemical reactions.

(v) Optical Rotation Method

In this method, the angle through which plane polarized light is rotated by the reacting mixture
is measured by a polarimeter. The extent of rotation determ ines the concentration of optically
active substance. If any of the species in the reaction mixture is optically active, then this method
can be followed to find out the rate of reaction.

11.2.2 Chemical Method

This is particularly suitable for reactions in solution. In this method, we do the chemical
analysis of a reactant or a product.
The acid hydrolysis of an ester (ethyl acetate) in the presence of a small amount of an acid is
one of the best examples.

+
H (catalyst)
CH 3COOC2 H 5 () + H 2O() �� �� �� �� �� ��
�� CH 3COOH() + C2 H 5OH()

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In case of hydrolysis of an ester, the solution of ester in water and the acid acting as a catalyst
are allowed to react. After some time, a sample of reaction mixture is withdrawn by a pipette
and run into about four times its volume of ice cold water. The dilution and chilling stops the
reaction. The acid formed is titrated against a standard alkali, say NaOH, using phenolphthalein as
an indicator.
The analysis is repeated at various time intervals after the start of reaction. This would provide
an information about the change in concentration of acetic acid formed during the reaction at
different time intervals. The different concentrations of acetic acid are plotted against the time
whereby a rising curve is obtained as shown in Fig (11.3).

Fig. (11.3 ) Measurement of rate of ester hydrolysis

The slope of the curve at any point will give the rate of reaction. Initially, the rate of reaction is high
but it decreases with the passage of time. When the curve becomes horizontal, the rate becomes
zero.
If we plot the graph for decreasing concentrations of CH3COOC2H5, then falling curves
are obtained as shown in Fig.(11.2) If we have any laboratory technique to record the changing
concentration of ester or alcohol, we can measure the rate of the reaction. This is a pseudo first
order reaction. Actually water being in large excess in comparison to ester does not affect the rate
and we think that water is not taking part in the reaction.

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Animation 11.11: Chemical Method

Source & Credit : fg-a

11.3. ENERGY OF ACTIVATION

For a chemical reaction to take place, the particles atoms, ions or molecules of reactants must
form a homogeneous mixture and collide with one another. These collisions may be effective or
ineffective depending upon the energy of the colliding particles. When these collisions are effective
they give rise to the products otherwise the colliding particles just bounce back. The effective
collisions can take place only when the colliding particles will possess certain amount of energy
and they approach each other with the proper orientation. The idea of proper orientation means
that at the time of collision, the atoms which are required to make new bonds should collide with
each other. The minimum amount of energy, required for an effective collision is called activation
energy.
If all the collisions among the reacting species at a given temperature are effective in forming
the products, the reaction is completed in a very short time. Most of the reactions, are, however,
slow showing that all the collisions are not equally effective.

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Let us study a reaction between molecules A2 and B2 to form a new molecule AB. If these
molecules will have energy equal to or more than the activation energy, then upon collisions their
bonds will break and new bonds will be formed. The phenomenon is shown in Fig. (11.4)

Fig. (11.4) Collisions of molecules, formation of activated complex and formation of products

Activated complex is an unstable combination of all the atoms involved in the reaction
for which the energy is maximum. It is a short lived species and decomposes into the products
immediately. It has a transient existence, that is why it is also called a transition state.
When the colliding molecules come close to each other at the time of collision, they slow
down, collide and then fly apart. If the collision is effective then the molecules flying apart are
chemically different otherwise the same molecules just bounce back.
When the molecules slow down just before the collision, their kinetic energy decreases and
this results in the corresponding increase in their potential energy. The process can be understood
with the help of a graph between the path of reaction and the potential energy of the reacting
molecules. Fig. (11.5a,b)
The reactants reach the peak of the curve to form the activated complex. Ea is the energy of
activation and it appears as a potential energy hill between the reactants and the products. Only,
the colliding molecules with proper activation energy, will be able to climb up the hill and give the
products. If the combined initial kinetic energy of the reactants is less than Ea, they will be unable
to reach the top of the hill and fall back chemically unchanged.
This potential energy diagram can also be used to study the heat evolved or absorbed during
the reaction. The heat of reaction is equal to the difference in potential energy of the reactants and
the products. For exothermic reactions, the products are at a lower energy level than the reactants
and the decrease in potential energy appears as increase in kinetic energy of the products Fig.
(11.5a). For endothermic reactions, the products are at higher energy level than the reactants and
for such reactions a continuous source of energy is needed to complete the reaction Fig. (11.5b).

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Fig. (11.5) A graph between path of reaction and the potential energy of the reaction

The energy of activation of forward and backward reactions are different for all the reactions.
For exothermic reactions the energy of activation of forward reaction is less than that of backward
reaction, while reverse is true for endothermic reactions. Energy of activation of a reaction provides
a valuable information about the way a reaction takes place and thus helps to understand the
reaction.

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Animation 11.12: Activation Energy and Spontaneous reactions

Source & Credit : thompsona

11.4 FINDING THE ORDER OF REACTION

The order of a reaction is the sum of exponents of the concentration terms in the rate
expression of that reaction.

It can be determined by the following methods.

(i) Method of hit and trial
(ii) Graphical method
(iii) Differential method
(iv) Half life method
(v) Method of large excess
Here we will only discuss half-life method and the method of large excess.

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Animation 11.13: Determination of Order of a Reaction

Source & Credit : askiitians

11.4.1 Half Life Method

As mentioned earlier, half life of a reaction is inversely proportional to the initial concentration
of reactants raised to the power one less than the order of reaction.
1
Therefore, (t1/2 ) n ∝
a n-1

Let us perform a reaction twice by taking two different initial concentrations ‘a1’ and ‘a2’ and
their half-life periods are found to be t1 and t2 respectively.

1 1
t1 ∝ n-1
and t2 ∝
a1 a 2 n-1

n-1
t1  a 2 
Dividing the two relations: =
t 2  a1 

t1 a 
Taking log on both sides: log =(n-1)log  2 
t2  a1 

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Animation 11.14: Half Life

Source & Credit : wikipedia

t 
log  1 
t
n− 1 =  2 
a 
log  2 
 a1 

t 
log  1 
Rearranging n= 1 +  t2 
a 
log  2 
 a1 

So, if we know the two initial concentrations and two half life values we can calculate the order of
reaction (n).

Example 2:

In the thermal decomposition of N2O at 760 °C, the time required to decompose half of
the reactant was 255 seconds at the initial pressure of 290 mm Hg and 212 seconds at the initial
pressure of 360 mmHg. Find the order of this reaction.

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Solution:

The initial pressures of N2O(g) are the initial concentrations.

Data a1 = 290mm Hg t1 = 255 seconds

a 2 = 360mm Hg t 2 = 212 seconds

Formula used

t 
log  1 
t
n = 1 +  2 
a 
log  2 
 a1 

Putting the values in the above equation

 255 
log 
n= 1 +  212 
 360 
log 
 290 

0.0802
n = 1+
0.0940

n = 1 + 0.85 = 1.85 ≈ 2

1.85 is close to 2, hence the reaction is of second order.

11.4.2 Method of Large Excess

In this method, one of the reactants is taken in a very small amount as compared to the rest
of the reactants. The active masses of the substances in large excess remain constant throughout.
That substance taken in small amount controls the rate and the order is noted with respect to that.
The reason is that a small change in concentration of a substance taken in very small amount
affects the value of rate more appreciably. The hydrolysis of ethyl acetate as mentioned earlier
shows that water being in large excess does not determine the order.

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In this way, the reaction is repeated by taking rest of the substances in small amounts one by
one and overall order is calculated. The method will be further elaborated in article 11.5.2.

11.5. FACTORS AFFECTING RATES OF REACTIONS

All those factors which change the number of effective collisions per second, affect the rate
of a chemical reaction. Some of the important factors are as follows.

Animation 11.15: FACTORS AFFECTING

RATES OF REACTIONS
Source & Credit : askiitians

11.5.1 Nature of Reactants

The rate of reaction depends upon the nature of reacting substances. The chemical reactivity
of the substances is controlled by the electronic arrangements in their outermost orbitals. The
elements of I-A group have one ejectron in their outermost s-orbital. They react with water more
swiftly than those of II-A group elements having two electrons in their outermost s-orbital. Similarly,
the neutralization and double decomposition reactions are very fast as compared to those reactions
in which bonds are rearranged. Oxidation-reduction reactions involve the transfer of electrons and
are slower than ionic reactions.

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11.5.2 Concentration of Reactants

The reactions are due to collisions of reactant molecules. The frequency with which the
molecules collide depends upon their concentrations. The more crowded the molecules are, the
more likely they are to collide and react with one another. Thus, an increase in the concentrations
of the reactants will result in the corresponding increase in the reaction rate, while a decrease in
the concentrations will have a reverse effect. For example, combustion that occurs slowly in air (21
% oxygen) will occur more rapidly in pure oxygen.
Similarly, limestone reacts with different concentrations of hydrochloric acid at different rates.
In the case of a gaseous reactant, its concentration can be increased by increasing its pressure.
Therefore, a mixture of H2 and Cl2 will react twice as fast if the partial pressure of H2 or Cl2 is
increased from 0.5 to 1.0 atmosphere in the presence of excess of the other component.
The effect of change in concentration on the rate of a chemical reaction can be nicely
understood from the following gaseous reaction.

2NO(g) + 2H 2 (g) → 2H 2O(g) + N 2 (g)

Animation 11.16: Reactants

Source & Credit : giphy

In this reaction, four moles of the reactants form three moles of the products, so the pressure
drop takes place during the progress of reaction. The rates of reaction between NO and H2 at
800°C are studied by noting the change in pressure. The following Table (11.2 ) has been obtained
experimentally for the above reaction.

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Table (11.2) Effect of change in

concentrations of reactants on
the rate of reaction
[NO] in [H2] in Initial rate
(mol dm-3) (mol dm-3) (atm min-1)
0.006 0.001 0.025
0.006 0.002 0.050
0.006 0.003 0.075
0.001 0.009 0.0063
0.002 0.009 0.025
0.003 0.009 0.056

Table (11.2)shows the results of six experiments. In the first three experiments the concentration
of H2 is increased by keeping the concentration of NO constant. By doubling the concentration of
H2, the rate is doubled and by tripling the concentration of H2, the rate is tripled. So, the rate of
reaction is directly proportional to the first power of concentration of H2.

Rate ∝ [H 2 ]

In the next three experiments, the concentration of H2 is kept constant. By doubling the concentration
of NO, the rate increases four times and by tripling the concentration of NO the rate is increased
nine times. So, the rate is proportional to the square of concentration of NO.

Rate ∝ [NO]2

The overall rate equation of reaction is,

Rate ∝ [H 2 ][NO]2

or Rate = k[H 2 ]1[NO]2

Hence, the reaction is a third order one. This final equation is the rate law for this reaction.
It should be kept in mind that rate law cannot be predicted from the balanced chemical equation.
This set of experiments helps us to determine the order of reaction as well.

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The possible mechanism consisting of two steps for the reaction is as follows:
(i) slow
2NO(g) + H 2 (g)  → N 2 (g) + H 2O2 (g) (rate determining)

(ii) fast
H 2O 2 (g) + H 2 (g) → 2H 2O(g)

The step (i) is slow and rate determining.

Animation 11.17: Concentration of Reactants

Source & Credit : socratic

11.5.3 Surface Area

The increased surface area of reactants, increases the possibilities of atoms and molecules of
reactants to come in contact with each other and the rates enhance. For example, AI foil reacts with
NaOH moderately when warmed, but powdered AI reacts rapidly with cold NaOH and H2 is evolved
with frothing.
2AI + 2NaOH + 6H 2O → 2NaAI(OH) 4 + 3H 2

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Similarly, CaCO3 in the powder form reacts with dilute H2SO4 more efficiently than its big
pieces.

Animation 11.18: Surface Area

Source & Credit : darelhardy

11.5.4 Light

Light consists of photons having definite

amount of energies depending upon
their frequencies. When the reactants
are irradiated, this energy becomes
available to them and rates of reactions
are enhanced. The reaction of CH4 and
Cl2 requires light. The reaction between
H2 and Cl2 at ordinary pressure is
negligible in darkness, slow in daylight,
but explosive in sunlight. Similarly, light
is vital in photosynthesis, and the rate is
influenced by light.
Animation 11.19: Light
Source & Credit : wikipedia

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11.5.5 Effect of Temperature on Rate of Reaction

The collision theory of reaction rates convinces us that the rate of a reaction is proportional to
the number of collisions among the reactant molecules. Anything, that can increase the frequency
of collisions should increase the rate. We also know, that every collision does not lead to a reaction.
For a collision, to be effective the molecules must possess the activation energy and they must also
be properly oriented. For nearly all chemical reactions, the activation energy is quite large and at
ordinary temperature very few molecules are moving fast enough to have this minimum energy.
All the molecules of a reactant do not possess the same energy at a particular temperature.
Most of the molecules will possess average energy. A fraction of total molecules will have energy
more than the average energy. This fraction of molecules is indicated as shaded area in Fig.(11.6).
As the temperature increases, the number of molecules in this fraction also increases. There
happens a wider distribution of velocities. The curve at higher temperature T2 has flattened. It shows
that molecules having higher
energies have increased and
those with less energies have
deceased. So, the number of
effective collisions increases
and hence the rate increases.
When the temperature of the
reacting gases is raised by
10K, the fraction of molecule
with energy more than Ea
roughly doubles and so the
reaction rate also doubles.
Arrheinus has studied the
quantitative relationship
between temperature, energy
of activation and rate constant
of a reaction. Fig. (11.6) Kinetic energy distributions for a reaction mixture at two different
temperatures. The size of the shaded areas under the curves are proportional
to the total fraction of the molecules that possess the minimum activation energy.

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Animation 11.20: Effect of Temperature on Rate of Reaction

Source & Credit : dynamicscience

11.5.6 Arrhenius Equation

Arrhenius equation explains the effect of temperature on the rate constant of a reaction. The
rate constant ‘k’ for many simple reactions is found to vary with temperature.
According to Arrhenius:

k=Ae ........ (1)

-Ea/RT

So, ‘k’ is exponentially related to activation energy (Ea) and temperature (T). R is general gas
constant and e is the base of natural logarithm. The equation shows that the increase in temperature,
increases the rate constant and the reactions of high activation energy have low ’k’ values.

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The factor ‘A’ is called Arrhenius constant and it depends upon the collision frequency of the reacting
substances. This equation helps us to determine the energy of activation of the reaction as well.
For this purpose, we take natural log of Arrhenius equation, which is expressed as n . The base of
natural log is e and its value is 2.718281.
Now, take natural log on both sides

nk = n(Ae-Ea/RT )

or nk = nA + ne-Ea/RT

-E
or nk = nA + ne
RT

Since ne = 1 (log of a quantity with same base is unity)

-E a
Therefore nk = + nA ........... (2)
RT

The equation (1) is the equation of straight line, and from the slope of straight line Ea can be
calculated. In order to convert this natural log into common log of base 10, we multiply the n term
with 2.303.
-E a
2.303 log k = + 2.303 log A (The base of common log is 10)
RT

Dividing the whole equation by 2.303

-E a
log k = + log A ........... (3)
2.303RT

This equation (3) is again the equation of straight line resembling.

y = -mx + c
Where ‘m’ is slope of straight line and ‘c’ is the intercept of straight line. Temperature is inde-
pendent variable in this equation while rate constant k is dependent variable. The other factors like
Ea, R and A are constants for a given reaction.

1
When a graph is plotted between T on x-axis and log k on y-axis, a straight line is obtained
with a negative slope. Actually, E a has negative sign so the straight line has two ends in second and
RT
fourth quadrants, Fig. (11.7).

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Fig. (11.7) Arrhenuis plot to calculate the energy of activation

The slope of the straight line is measured by taking the tangent of that angle θ which
this straight line makes with the x-axis. To measure the slope, draw a line parallel to
-E a
x-axis and measure angle θ . Take tan θ which is slope. This slope is equal to
2.303R
.

-E a
Slop =
2.303 R

Therefore E a = -Slop x 2.303 R ..........(4)

The straight lines of different reactions will have different slopes and different ‘Ea’ values. The
units of slope are in kelvins (K).
J mol-1
Since Slop = =K
2.303 JK -1mol-1

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Animation 11.21: Arrhenius Equation

Source & Credit : wps

Example 3:

A plot of Arrhenius equation Fig (11.8 ) for

the thermal decompositions of N2O5 is shown
in the following figure. The slope is found to be
-5400 K. Calculate the energy of activation of
this reaction.

Solution:

(i) The reaction is

N 2O5 � 2NO 2 + 1/2O 2

Fig. (11.8) Arrhenius plot for decomposition of N2O5

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Slope of the straight line = -5400 K

Equation used, Ea = -slope x 2.303 R
R = 8.3143JK-1mol-1
Putting the values,
Ea =-(-5400K)x 2.303 x 8.3143JK-1mol-1
Ea= +103410 J mol-1
Ea = 103.410 kJ mol-1
Hence, the decomposition of N2O needs 103.4kJmol-1 energy more than the average energy
to cross the energy barrier Fig.(11.9)

Fig. (11.9) Potential energy diagram of N2O5 decomposition

11.6 CATALYSIS

A catalyst is defined as a substance which alters the rate of a chemical reaction, but remains
chemically unchanged at the end of the reaction. A catalyst is often present in a very small proportion.
For example, the reaction between H2 and O2 to form water is very slow at ordinary temperature,
but proceeds more rapidly in the presence of platinum. Platinum acts as a catalyst. Similarly, KClO3
decomposes much more rapidly in the presence of a small
amount of MnO2. HCl is oxidised to Cl2 in the presence of CuCl2.

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CuCl2
4HCl+O2  → 2H 2O+2Cl 2

The process, which takes place in the presence of a catalyst, is called catalysis. A catalyst
provides a new reaction path with a low activation energy barrier, Fig.(11.10). A greater number of
molecules are now able to get over the new energy barrier and reaction rate increases.

Fig. (11.10) Catalyzed and uncatalyzed reactions.

Animation 11.22: CATALYSIS

Source & Credit : [Link]

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Types of Catalysis

(a) Homogeneous Catalysis

(b) Heterogeneous Catalysis

(a) Homogeneous Catalysis

In this process, the catalyst and the reactants are in the same phase and the reacting system
is homogeneous throughout. The catalyst is distributed uniformly throughout the system. For
example:
(i). The formation of SO3 (g) from SO2 (g) and O2 (g) in the lead chamber process for the manufacture
of sulphuric acid, needs NO (g) as a catalyst. Both the reactants and the catalyst are gases.

NO(g)
2SO 2 (g) + O2 (g) �� �� �� ��
�� 2SO3 (g)

(ii). Esters are hydrolysed in the presence of H2SO4. Both the reactants and the catalyst are in the
solution state.

+
H O
CH 3COOC2 H 5 (aq) + H 2O() �� ��H��3SO��
�4 � CH 3COOH(aq) + C2 H 5OH(aq)
2

(b) Heterogeneous Catalysis

In such systems, the catalyst and the reactants are in different phases. Mostly, the catalysts
are in the solid phase, while the reactants are in the gaseous or liquid phasse. For example:
(i). Oxidation of ammonia to NO in the presence of platinum gauze helps us to manufacture
HNO3.

Pt(s)
4NH 3 (g) + 5O 2 (g) �� �� �� �� 4NO(g) + 6H 2O(g)

(ii) Hydrogenation of unsaturated organic compounds are catalysed by finely divided Ni, Pd or Pt.

CH 2 = CH 2 (g) + H 2 (g) �� ��Ni(s)

�� ��� CH 3 - CH 3 (g)

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11.6.1 Characteristics of a Catalyst

There are many types of catalysts with varying chemical compositions, but the following
features are common to most of them.
1. A catalyst remains unchanged in mass and chemical composition at the end of reaction. It may
not remain in the same physical state. MnO2 is added as a catalyst for the decomposition of
KClO3 in the form of granules. It is converted to fine powder at the end of reaction. It has been
found in many cases that the shining surfaces of the solid catalyst become dull.
2. Sometimes, we need a trace of a metal catalyst to affect very large amount of reactants. For
example, 1 mg of fine platinum powder can convert 2.5 dm3 of H2 and 1.25 dm3 of O2 to water.
Dry HCl and NH3 don’t combine, but in the presence of trace of moisture, they give dense white
fumes of NH4Cl. Thousands of dm3 of H2O2, can be decomposed in the presence of 1 g of colloidal
platinum.
3. A catalyst is more affective, when it is present in a finely divided form. For example, a lump of
platinum will have much less catalytic activity than colloidal platinum. In the hydrogenation of
vegetable oils finely divided nickel is used.
4. A catalyst cannot affect the equilibrium constant of a reaction but it helps the equilibrium to be
established earlier. The rates of forward and backward steps are increased equally.
5. A catalyst cannot start a reaction, which is not thermodynamically feasible. It is now considered
that a catalyst can initiate a reaction. The mechanism of a catalysed reaction is different from
that of an uncatalysed reaction.

For example:

(i) The presence of CO as an impurity with hydrogen decreases the catalytic activity of catalyst in
the Haber’s process for the manufacture of NH3.
(ii) The manufacture of H2SO4 in the contact process needs platinum as a catalyst. The traces of
arsenic present as impurities in the reacting gases makes platinum ineffective. That’s why arsenic
purifier is employed in the contact process.

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11.6.2 Activation of Catalyst

Such a substance which promotes the activity of a catalyst is called a promotor or activator. It
is also called “catalyst for a catalyst”. For example :
(i) Hydrogenation of vegetable oils is accelerated by nickel. The catalytic activity of nickel can be
increased by using copper and tellurium.

Animation 11.23: Characteristics of a Catalyst

Source & Credit : logilent

(ii) In Haber’s process for the manufacture of ammonia, iron is used as a catalyst. If small amounts
of some high melting oxides like aluminum oxide, chromium oxide or rare earth oxides are added,
they increase the efficiency of iron.

Negative Catalysis

When the rate of reaction is retarded by adding a substance, then it is said to be a negative
catalyst or inhibitor. For example, tetraethyl lead is added to petrol, because it saves the petrol
from pre-ignition.

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Autocatalyst

In some of the reactions, a product formed acts as a catalyst. This phenomenon is called auto-
catalysis. For example:
(i) When copper is allowed to react with nitric acid, the reaction is slow in the beginning. It gains the
speed gradually and finally becomes very fast. This is due to the formation of nitrous acid during
the reaction, which accelerates the process.
(ii) The reaction of oxalic acid with acidified KMnO4 is slow at the beginning, but after sometimes,
MnSO4 produced in the reaction makes it faster.
2+
Mn
2KMnO 4 + 3H 2SO 4 + 5(COOH) 2  → K 2SO 4 + 2MnSO 4 + 10CO 2 + 8H 2O

Animation 11.24: Activation of Catalyst

Source & Credit : dynamicscience

11.6.3. Enzyme catalysis

Enzymes are the complex protein molecules and catalyze the organic reactions in the living
cells. Many enzymes have been identified and obtained in the pure crystalline state. However, the
first enzyme was prepared in the laboratory in 1969. For example:

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(i) Urea undergoes hydrolysis into NH3 and CO2 in the presence of enzyme urease present in
soyabean.

O
�
Urease
H2N C NH 2 +H 2O  → 2NH 3 +CO 2

(ii) Concentrated sugar solution undergoes hydrolysis into glucose and fructose by an enzyme
called invertase, present in the yeast.

Inertase
C12 H 22O11 + H 2O → C6 H12O6 + C6 H12O6

(iii) Glucose is converted into ethanol by the enzyme zymase present in the yeast.

Zymase
C6 H12O6  → 2C2 H 5OH + 2CO2

Enzymes have active centres on their surfaces. The molecules of a substrate fit into-their
cavities just as a key fits into a lock Fig. (11.11). The substrate molecules enter the cavities, form the
complex, reactants and the products get out of the cavity immediately. Michaulis and Menter(1913)
proposed the following mechanism for enzyme catalysis

E + S � ES → P + E

Where
E = enzyme, S = substrate (reactant)
ES = activated complex, P = product

Fig. (11.11) Lock and key model of enzyme catalysis

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Animation 11.25: Enzyme catalysis

Source & Credit : kth

11.6.4 Characteristics of Enzyme Catalysis

The role of enzyme as catalysts is like inorganic heterogeneous catalysts. They are unique in
their efficiency and have a high degree of specificity. For example:
(i) Enzymes are the most efficient catalysts known and they lower the energy of activation of a
reaction.
(ii) Enzymes catalysis is highly specific, for example, urease catalyses the hydrolysis of urea only
and it cannot hydrolyse any other amide even methyl urea.

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(iii) Enzyme catalytic reactions have the maximum rates at an optimum temperature.
(iv) The pH of the system also controls the rates of the enzyme catalysed reaction and the rate
passes through a maximum at a particular pH, known as an optimum pH. The activity of enzyme
catalyst is inhibited by a poison.
(v) The catalytic activity of enzymes is greatly enhanced by the presence of a co-enzyme or activator.

Animation 11.26: Characteristic of Enzyme

Source & Credit : tdmu

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KEY POINTS

1. The studies concerned with rates of chemical reactions and factors that affect the rates of chemical
reactions and the mechanism of reactions constitute the subject matter of reaction kinetics.
2. The rate of a reaction is the change in the concentration of a reactant or a product divided
by the time taken for the reaction. The rate of reaction between two specific time intervals
is called the average rate of reaction. While the rate at any one instant during the interval is
called the instantaneous rate. Rate constant of a chemical reaction is rate of reaction when the
concentrations of reactants are unity.
3. Order of reaction is the sum of exponents of the concentation terms in the rate expression
of a chemical [Link] exponents in the expression may or may not be different from
the coefficients of the chemical equation. Order of a reaction may be zero, whole number or
fractional.
4. Half life period of a reaction is the time required to convert 50% of the reactants into products.
Half-life period of any reaction is inversely proportional to the initial concentration raised to the
power one less than the order of that reaction.
5. The step which limits how fast the overall reaction can proceed, is known as the rate determining
step.
6. Determination of the rate of a chemical reaction involves the measurement of the concentration
of reactants or products at regular time intervals during the progress of reaction. The change
in concentration of reactants and products can be determined by both physical and chemical
methods.
7. The effective collisions between the colliding species will take place only when the reactant
molecules possess minimum amount of energy, which is called the energy of activation. Moreover,
proper orientation is also necessary.
8 . All those factors, which change the number of effective collisions per second, affect the rate of
chemical reaction. Some of the important factors are, nature and concentration of reactants,
surface area, light, and temperature and catalyst.
9. A catalyst is a substance, which alters the rate of a chemical reaction, but itself remains chemically
unchanged at the end of reaction. The process when the catalyst and the reactants are in the
same phase is said to be a homogenous catalysis. In case of heterogeneous catalysis, the catalyst
and the reactants are in different phases. A substance, which promotes the activity of a catalyst,
is called promoter or activator. In certain reactions, a product formed acts as a catalyst, the
phenomenon is called auto-catalysis.
10. Enzymes are the complex protein molecules, which catalyze the reactions in the living cells.

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EXERCISE

Q.1 Multiple choice questions.

(i) In zero order reaction, the rate is independent of

a) temperature of reaction. (b) concentration of reactants,
c) concentration of products (d) none of these
(ii) If the rate equation of a reaction 2A + B → products is, rate =k[A]2 [B], and A is present in large
excess, then order of reaction is
a) 1 (b) 2 (c) 3 (d) none of these
(iii) The rate of reaction
a) increases as the reaction proceeds.
b) decreases as the reaction proceeds.
c) remains the same as the reaction proceeds.
d) may decrease or increase as the reaction proceeds.
(iv) With increase of 10°C temperature the rate of reaction doubles. This increase in ate of reaction
is due to:
a) decrease in activation energy of reaction.
b) decrease in the number of collisions between reactant molecules.
c) increase in activation energy of reactants.
d) increase in number of effective collisions.
(v) The unit of the rate constant is the same as that of the rate of reaction in
(a) first order reaction. (b) second order reaction.
(c) zero order reaction. (d) third order reaction.

Q.2 Fill in the blanks with suitable words.

(i) The rate of an endothermic reaction_______ with the increase in temperature.

(ii) All radioactive disintegration nuclear reactions are of________ order
(iii) For a fast reaction the rate constant is relatively and half - life is ______ .
(iv) The second order reaction becomes______ if one of the reactants is in large excess.
(v) Arrhenius equation can be used to find out________of a reaction.

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Q.3 Indicate true or false as the case may be.

(i) The half life of a first order reaction increases with temperature.
(ii) The reactions having zero activation energies are instantaneous.
(iii) A catalyst makes a reaction more exothermic.
(iv) There is difference between rate law and the law of mass action.
(v) The order of reaction is strictly determined by the stoichiometry of the bdanced equation.

Q4. What is chemical kinetics? How do you compare chemical kinetics with clemical equilibrium
and thermodynamics.

Q5. The rate of a chemical reaction with respect to products is written with positive sign, but with
respect to reactants is written with a negative sign. Explain it with reference to the following
hypothetical reaction.

aA + bB → cC + dD

Q6 . What are instantaneous and average rates? Is it true that the instantaneousrate of a reaction at
the beginning of the reaction is greater than average rate and beomes far less than the average
rate near the completion of reaction?

Q7. Differentiate between

(i) Rate and rate constant of a reaction

(ii ) Homogeneous and heterogeneous catalyses
(iii) Fast step and the rate determining step
(iv) Enthalpy change of reaction and energy of activation of reaction

Q8. Justify the following statements

(i) Rate of chemical reaction is an ever changing parameter uner the given conditions.
(ii) The reaction rate decreases every moment but rate constant ‘k’ of the reation is a constant
quantity, under the given conditions.
(iii) 50% of a hypothetical first order reaction completes in one hour. The renaming 50% needs
more than one hour to complete.
(v) The radioactive decay is always a first order reaction.

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(iv) The unit of rate constant of a second order reaction is dm3 mol-1s-1, but the uit of rate of reaction
is mol dm-3s-1S.
(vi) The sum of the coefficients of a balanced chemical equation is not neessarily important to give
the order of a reaction.
(vii ) The order of a reaction is obtained from the rate expression of a reaction anthe rate expression
is obtained from the experiment.

Q9. Explain that half life method for measurement of the order of a reaction can help us to measure
the order of even those reactions which have a fractional order.

Q10. A curve is obtained when a graph is plotted between time on x-axis and concentration on
y-axis. The measurement of the slopes of various points give us the instantaneous rates of
reaction. Explain with suitable examples.

Q11. The rate determining step of a reaction is found out from the mechanism of that reaction.
Explain it with few examples.

Q12. Discuss the factors which influence the rates of chemical reactions.

Q.13. Explain the following facts about the reaction.

2NO(g) + 2H 2 (g) → 2H 2O(g) + N 2 (g)

(i) The changing concentrations of reactants, change the rates of this reaction.
(ii) Individual orders with respect to NO and H2 can be measured.
(iii) The overall order can be evaluated by keeping the concentration of one of the substances
constant.

Q14. The collision frequency and the orientation of molecules are necessary conditions for
determining the proper rate of reaction. Justify the statement.

Q.15. How does Arrhenius equation help us to calculate the energy of activation of a reaction?

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Q16. Define the following terms and give examples

(i) Homogeneous catalysis (ii) Heterogeneous catalysis
(iii) Activation of a catalyst (iv) Auto-catalysis
(v) Catalytic poisoning (vi) Enzyme catalysis

Q17. Briefly describe the following with examples

(i) Change of physical state of a catalyst at the end of reaction.
(ii) A very small amount of a catalyst may prove sufficient to carry out a reaction.
(iii) A finely divided catalyst may prove more effective.
(iv) Equilibrium constant of a reversible reaction is not changed in the presence of a catalyst.
(v) A catalyst is specific in its action.

Q18. What are enzymes? Give examples in which they act as catalyst. Mention the characteristics
of enzyme catalysis.

Q19. In the reaction of NO and H2, it was observed that equimolecular mixture of gases at 340.5
mm Hg pressure was half changed in 102 seconds. In another experiment with an initial pressure
of 288 mm of Hg, the reaction was half completed in 140 seconds. Calculate the order of reaction.
(Ans:2.88)
Q20. A study of chemical kinetics of a reaction
[A] [B] Rate
A + B → Products 1.00 0.15 4.2 x 10-6
2.00 0.15 8.4 x 10-6
gave the following data at 25 °C. Calculate the rate law. 1.00 0.2 5.6 x 10-6

(Ans: second order)

Q21. Some reactions taking place around room temperature have activation energies around 50kJ
mol-1.
-E

(i) What is the value of the factor e RT

at 25oC ?

(Ans: 1.72x10-9)

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(ii) Calculate this factor at 35 °C anat 45 0C and note1 the increase in this factor for every 10 0C
rise in temperature.
(Ans:3.31x10-9)

(iii) Prove that for every 10°C rise in of temperature, the factor doubles and so rate constant also
doubles.
(Ans:6.12x10-9)

Q22. H2 and I2 react to produce HI. Following data for rate constant at Temp. Rate constant
various temperatures (K) have been collected. (K) (cm3 mol-1 s-1) (K)
500 6.814 x 10-4
1
(i) Plot a graph between on x-axis and log k on the y-axis. 550 2.64 x 10-2
T
600 0.56 x 100
(ii) Measure the slope of this straight line and calculate the energy for 650 7.31 x 100
activation of this reaction. 700 66.67 x 100

(Ans: 8326.32,160.6kJmol-1)

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