(CLASS XII) TUITION - CHEMISTRY

CHAPTER - 04
CHEMICAL KINETICS

The branch of Chemistry that deals with the rate of chemical reaction, factors affecting the rate and
the mechanism of a reaction is called Chemical Kinetics.
Rate of a Reaction
It may be defined as the change in concentration of a reactant or product in unit time.
For a hypothetical reaction R  P, the rate of reaction can be expressed by decrease in concentration
of reactants or by increase in concentration of products.
i.e., Rate of reaction = Rate of disappearance of R

Decreaseinconcentrationof R
r
Time taken

[R]
Or, r 
t

[Since, [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].
Or, Rate of reaction = Rate of appearance (formation) of P

Increase in concentration of P

Time taken

[P]
i.e., r
t
The above rate expressions are also called Average rate.
Units of Rate of reaction
If concentration is expressed in moles/L and time is in second, the unit of rate of reaction is mol/L/s.
General Expression for Rate
For a general reaction, aA  bB  cC  dD

1 [A] 1 [B] 1 [C] 1 [D]

rav    
a t b t c t d t

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Instantaneous Rate of reaction

The rate of reaction at a particular instant of time is called Instantaneous Rate of a reaction. Or, it is
the rate of a reaction when the time interval approaches zero.

d[H2 ] d[I2 ] ½ d[HI]

For the reaction, H2  I2  2HI,rinst    
dt dt dt

[H2 ] [I ] [HI]

And rav.     2 ½
t  t

Rate of Formation of Product and Rate of Disappearance of Reactant

When stoichiometric coefficient is 1 the average rate or instantaneous rate of reaction is equal to the
rate of formation of products or rate of disappearance of reactant.

eg : Consider Reaction N2  3H2 

 2NH3

d[N2 ]
Rate of disappearance of N2 =
dt

d[H2 ]
Rate of disappearance of H2 =
dt

d[NH3 ]
Rate of formation of NH3 =
dt

Graphical representation of Rate of Reaction

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Factors affecting rate of a reaction

The important factors which affect the rate of a chemical reaction are :

1. Nature of the reactants

2. Concentration of the reactants

3. Temperature

4. Pressure (for gaseous reaction only)

5. Effect of catalyst

6. Influence of radiation

Dependence of Rate of reaction on concentration

It is found experimentally that Rate of reaction is directly proportional to the concentration of reactants.
Thus for a general reaction, aA  bB  cC  dD,

Rate  [A]x [B]y

Or,   k [A]x [B]y [where x and y may or may not be equal to a and b)

In the above equation ‘k’ is a constant called rate constant or velocity constant or specific reaction
rate of the reaction. It is defined as the rate of the reaction when the concentration of each of the
reactants is unity.

Order of reaction

Order is the sum of the powers of the concentration terms of the reactants in the rate law. It
is an experimental quantity. It can have the values 0, 1, 2,3, ...... or a fraction. It is applicable to both
elementary and complex reactions.

For a general reaction, aA  bB  cC  dD;r  k [A]x [B]y , Order of the reaction = x + y

If the order of a reaction is zero, it is called zero order reaction, if it is one, it is called first order
reaction, if it is two, it is called second order reaction and so on.

Molecularity of a reaction

It is the total number of reacting species collides simultaneously in a chemical reaction. It is a

theoretical quantity. It cannot be zero or fractional. It can have values 1, 2, 3 etc. it is applicable only to
elementary reactions.

If the molecularity of a reaction is 1, it is called unimolecular reaction.

e.g. NH4NO 2  N2  2H2O

If the molecularity of a reaction is 2, it is called bimolecular reaction.

e.g. 2HI  HI  I2

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Difference between order and Molecularity of a reaction

Order Molecularity
It is the sum of the powers of the concentration It is the total number of reactant species collide
1
terms in the rate law expression simultaneously in a chemical reaction
2 It is an experimental quantity It is a theoretical quantity
3 It can be zero or fractional It cannot be zero fractional
It is applicable to both elementary and
4 It is applicable only to elementary reactions
complex reactions

Elementary and complex reactions

A reaction that takes place in a single step is called elementary reaction. While a reaction that occurs
in more than one step is called a complex reaction. In a complex reaction one of the steps is slower
than the other steps and this step is called the Rate determining step. The overall rate of the reaction
is controlled by this slowest step.
Consider the decomposition of hydrogen peroxide which is catalysed by iodide.
I
2H2 O2 
Alkaline Medium
 2H2 O  O2

This reaction takes place in two steps

1. H2O2  I 
 H2O  IO

2. H2O2  IO 
 H2O  I  O2
Here the first step is slower than the second. So it is the rate determining step (rds).
Unit of Rate constant

 products, rate  k[A]n

For an nth order reaction nA 

rate
Therefore, k =
[Concentration]n

mol / L / sec
Unit of k =  mol1 n n 1 s1
(mol / L)n

The units of rate constant for different ordered reactions are :

Reaction Order Unit of rate constant

-1 -1
Zero order reaction 0 Mol L s
-1
First order reaction 1 s
-1 -1
Second order reaction 2 Mol L s

Integrated Rate Law Equations

These are equations relating the rate of a reaction and concentration of reactants. Different ordered
reactions have different integrated rate law equations.
1. Integrated Rate law of Equation for a Zero Order Reaction

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Consider a zero order

R 
P

d[R]
The rate of expression for the above reaction is r  ...............(1)
dt
Rate law for the above reaction is r = k[R]0 = k .............(2)

d[R]
From equations (1) & (2), we can write  k
dt
Or, d[R] = –k.dt
Integrating the equation, we get
[R] = –kt + C ..................(3)
Where C is the constant of integration. To evaluate the value of C, consider the initial conditions. i.e.,
when t = 0, [R] = [R]0
Substitute these values in eqn. (3)
[R]0 = – k × 0 + C
C = [R]
Substituting in equation(3) we get
[R] = –Kt + [R]0
[R]0 – [R] = Kt

[R]0  [R]
K
t
This equation is of the form of a straight line, y = mx + c. So if we plot [R] against t, we get a straight
line with slope = –k and intercept equal to [R]0.

Example for zero order reaction is the decomposition of gaseous ammonia on a hot platinum surface
at high pressure.

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N2  H2 
 2NH3

2. Integrated Rate law Equation for a First order reaction

Consider a first order reaction, R 

P

The rate expression for the above reaction is r   d[R] ................(1)

dt

Rate law for the above reaction is r = k[R] ..................(2)

d[R]
From equations (1) & (2), we can write   k [R] ..................(3)
dt

d[R]
Or,   Kdt
[R]

On integrating the above equation we get,

n[R]   Kt  C ................(3)

Where ‘C’ is the constant of integration. To evaluate the value of C,

i.e., when t = 0, [R] = [R]0

Substitute these values in eqn. (3)

ln[R]0  K  0  C

Or, C = –ln[R]0

Substituting in equation (3), we get

n[R]  Kt  n[R]0 ...................(4)

n[R]0  n[R]  Kt

1 [R]
K  2.303 log 0
t [R]

This equation is known as integrated rate equation for a first order reaction.

From eqn. (4), n[R]   Kt  n[R]0

This equation is of the form y = mx + c, equation for a straight line. So if we plot a graph between ln[R]
against time, t we get straight line graph as follows :

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Half life of a reaction (t1/2)

The half-life of a reaction is the time taken for concentration of a reactant is reduced to one half of its
initial concentration.
1. Half life of a zero order reaction

[R]0  [R]
For a zero order reaction, k 
t

When t = t1/2, [R] = ½[R]0

On substituting these values in the above equation,

[R]0  ½[R]0
k
t1/2

[R]0
or, t1/2 
2k

i.e. half life of a zero order reaction is directly proportional to the initial concentration of the reactants
and inversely proportional to the rate constant.
2. Half life of a first order reaction

2.303 log[R]0
For a first order reaction, k 
t [R]

When t = t1/2, [R] = [R]0/2

Substitute these values in the above equation

2.303 log[R]0
k
t1/2 [R]0 / 2

2.303 2.303  0.3010

Or, t1/2  log2 
k k

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0.693
Or, t1/2 
k
Thus for a first order reaction, half-life period is constant, i.e., it is independent of initial concentration
of the reacting species.
Pseudo first order reaction
These are reactions which appear to follow higher order but actually follow first order kinetics. In
these reactions the concentration of one of the reactants is large excess and so its change in
concentration does not affect the rate of the reaction.
e.g. 1. Hydrolysis of ester (ethyl acetate)
2. Inversion of cane sugar
Rate of reaction and Temperature
Most of the chemical reactions are accelerated by increase in temperature. It has been found that for
a chemical reaction, when the temperature is increased by 10o, the rate of the reaction and the rate
constant is nearly doubled. The ratio of the rate constants of a reaction at two temperatures differing
by 10o is called temperature coefficient.

Rate constant of the reaction at (T+10) K

i.e., Temperature coefficient = Rate constant of the reaction at TK

The temperature dependence of the rate of a chemical reaction can be accurately explained by
Arrhenius equation. The equation is :

k = A eEa/RT ................(1)
Where A is a constant called the Arrhenius parameter or the frequency factor or the pre-exponential
factor. It is constant for a particular reaction. R is the universal gas constant and Ea is activation
energy measured in joules/mole (J mol–1)
According to Arrhenius, a chemical reaction occurs by the collision of reactant molecules. All the
molecular collisions are not effective. For effective collision, the colliding molecules should have a
minimum kinetic energy called activation energy. When such molecules collide, an unstable
intermediate called activated complex is formed, which decomposes to form products.

H2  I2  2HI

In a chemical reaction, all the molecules in the reacting species do not have the same kinetic energy.
Ludwig Boltzmann and James Clark Maxwell calculated the distribution of kinetic energy among the

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molecules. They plotted a graph between the fraction of molecules with a given kinetic energy against
kinetic energy. This plot known as Maxwell-Boltzmann distribution curve of molecular energies.

When the temperature is raised, the fraction of molecules with activation energy increases (almost
doubled).
In the Arrhenius equation the factor e-Ea/RT corresponds to the fraction of molecules that have
kinetic energy greater than Ea.
Taking logarithm on both sides of equation (1), we get
Ea
lnk   ln A
RT
This equation is of the form y = mx + c, equation for a straight line. So if we plot a graph between ln k
against 1/T, we get a straight line with slope = –Ea/R and they y-intercept in A.

If k1 is the rate constant at temperature T1 and k2 is the rate constant at temperature T2, then
Ea
lnk1    ln A .................(2) and
RT1

Ea
lnk 2    ln A .................(3)
RT2
Equation (2) – (3) gives,
Ea E
lnk 2  lnk1   a
RT1 RT2

k 2 Ea  1 1 
ln    
k1 R  T1 T2 

k2 Ea  1 1 
log    
k1 2.303R  T1 T2 

k2 Ea  T2  T1 
log   
k1 2.303R  T1 T2 

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Effect of Catalyst

A catalyst increases the rate of a chemical reaction by providing an alternate pathway or reaction
mechanism by reducing the activation energy between reactants and products.
Collision Theory
This theory was developed by Max Trautz and William Lewis. It is based on kinetic theory of gases.
According to this theory, the reactant molecules are assumed to be hard spheres and reaction is
occurred when molecules collide with each other. The number of collisions per second per unit
volume of the reaction mixture is known as collision frequency(Z).
Another factor which affects the rate of chemical reactions is activation energy. For a bimolecular
elementary reaction.
A  B  Products
Rate of reaction can be expressed as
Rate (r) = ZABe–Ea/RT
Where ZAB represents the collision frequency of reactants, A and B and e–Ea/RT represents the fraction
of molecules with energies equal to or greater than Ea.
A third factor which affects the rate of a chemical reaction is the proper orientation. To account for
this, a factor P called the probability or steric factor is introduced. So the above equation becomes :
Rate (r) = PZABe–Ea/RT
Thus, in collision theory activation energy and proper orientation of the molecules together determine
the criteria for an effective collision and hence the rate of a chemical reaction.

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Descriptive Questions
1. The order of a chemical reaction can be zero and even a fraction but molecularity cannot be zero or
a non-integer
i. What do you mean by the order of a reaction?
ii. What is the molecularity of a reaction?
iii. The conversion of molecules ‘A’ to ‘B’ follows second order kinetics. If the concentration of A is
increased to three times, how will it affect the rate of formation of ‘B’?
2. List out any three important differences between order and molecularity
3. What is the relation between Rate Constant and Half-Life Period of a first order reaction?
4. Half-Life Period of a first-order reaction is 20 seconds. How much time will it take to complete 90% of
the reaction?
5. Write the unit of rate constant ‘K’ of a reaction if the concentration is in mol L–1 and time in s. (order of
the reaction is two)
6. Express the rate of the following reaction in terms of reactants and products :

2HI  H2  I2
7. By deriving the equation for t½ of first order reaction, prove that it is independent of initial concentration
of its reacting species.

1 [R]
[Hint : For a first order reaction, k  2.303 log 0
t [R]

8. Indicate the order and molecularity of the reaction given below :

C12H22O11  H2O  C6H12O6  C6H12O6

9. Rate constant (K) of a reaction is 5 × 10–2s–1

Find the half life (t½) of the reaction
10. Define activation energy (Ea).

Multiple Choice Questions

1. When the rate of the reaction is equal to the rate constant, the order of the reaction is
1) Zero order 2) First order 3) Second order 4) Third order
2. A catalyst alters, which of the following in a chemical reaction?
1) Entropy 2) Enthalpy 3) Internal energy 4) Activation energy
3. The rate of a chemical reaction tells us about
1) The reactants taking part in the reaction
2) The products formed in the reaction
3) How slow or fast the reaction is taking place
4) None of the above mentioned

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4. The rate constant of zero-order reactions has the unit

1) s–1 2) mol L–1 s–1 3) L2 mol–2s–1 4) L mol–1s–1
5. Which of the following is the right temperature coefficient (n) expression?
1) n = Rate constant at T + 100/Rate constant at T0
2) n = Rate constant at T + 200/Rate constant at T0
3) n = Rate constant at T + 300/Rate constant at T0
4) n = Rate constant at T + 400/Rate constant at T0
6. The rate constant of a reaction is k = 3.28 × 10–4 s–1. Find the order of the reaction
1) Zero order 2) First order 3) Second order 4) Third order
7. If K1 K2 are rate constants at temperatures T1 & T2 respetively, then the combined form of Arrhenius
equation is

 Ea 
 Hint:logk  log A  
 2.303 RT 

Ea  T1T2  K1 Ea
1) logK 2  log   2) log 
2.303R  T2  T1  K 2 2.303RT

K  Ea  T2  T1  K1  T  T1 
3) log  2     4) log  Ea  2 
 K 1  2.303R  T1T2  K2  T1T2 
8. What is the rate law for acid hydrolysis of an ester such as CH3COOC2H5 in aqueous solution?
1) k [CH3COOC2H5] 2) k [CH3COOC2H5] [H2O]
3) k [CH3COOC2H5]2 4) i
9. If a reaction’s rate is represented as rate = k [A]2[B], the reaction’s order will be
1) 2 2) 3 3) 1 4) 0
10. The number of molecules of the reactants involved in a single stage of the reaction indicates
1) The order of the reaction 2) The molecularity of the reaction
3) The rapid step of the reaction mechanism 4) The reaction half-life

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