Chemical Kinetics 455

Chapter

11
Chemical Kinetics

The branch of physical chemistry which deals with (3) Very slow reactions : These reactions are
the rate at which the chemical reactions occur, the extremely slow and take months together to show any
mechanism by which the chemical reactions take place measurable change.
and the influence of various factors such as
concentration, temperature, pressure, catalyst etc., on Examples
the reaction rates is called the chemical kinetics. (i) Rusting of iron :
Types of chemical reactions
On the basis of reaction rates, the chemical
reactions have been classified into the following three (ii)
types,
(1) Very fast or instantaneous reactions : Rate of a reaction
These reactions occur at a very fast rate generally these The rate (speed or velocity) of a reaction is the
reactions involve ionic species and known as ionic change in concentration in per unit time.
reactions. It is almost impossible to determine the rates
Conc. (mole/lit.)

of these reactions. or
Examples
where or dx is the concentration change, i.e.,
(i) in the time interval or dt, i.e., .
Conc. of product
(Precipitation reaction) Concentration is generally expressed in active mass,
i.e., mole L–1
(ii) (Neutralization  The rate measured over a long time interval is
called average rate and the rate measured for an
reaction) infinitesimally small time interval is called
(2) Moderate reaction : These reactions proceed instantaneous rate and
with a measurable rates at normal temperature and it is Instantaneous rate Conc. of reactant

these reactions are studied in chemical kinetics. Mostly  For the reaction Time (Sec)
these reactions are molecular in nature. Rate of disappearance of a reactant isChange
negative
of
Examples concentration with
Rate of disappearance of A
increase in time
(i) Decomposition of :

Rate of disappearance of B

(ii) Decomposition of : Rate of formation of a product is positive

 456 Chemical Kinetics
concentration of the reactants means rate of reaction
Rate of formation of C decreases with decrease in concentration.
(4) Presence of catalyst : The function of a
Rate of formation of D catalyst is to lower down the activation energy. The
greater the decrease in the activation energy caused by
 In terms of stoichiometric coefficient rate may be the catalyst, higher will be the reaction rate.
Reaction
expressed as path
Without
catalyst
Ea

Potential
Energy
Ea Reaction
path
with
 The rate of reaction is always positive. catalyst
 The rate of chemical reaction decreases as the Reactants
Energy of Reaction
reaction proceeds.
Products
 Unit of rate of a reaction = =mole
A catalyst changes the reaction
path
–1
L time –1 (5) Effect of sunlight : There are many chemical
reactions whose rate are influenced by radiations
In term of gaseous reaction the unit is atm time-1
particularly by ultraviolet and visible light. Such
and
reactions are called photochemical reactions. For
Rate in atm time-1= Rate in mole example, Photosynthesis, Photography, Blue printing,
Factors affecting rate of a reaction Photochemical synthesis of compounds etc.
The radiant energy initiates the chemical reaction
The rate of a chemical reaction depends on the by supplying the necessary activation energy required
following things for the reaction.
(1) Nature of reactants
Law of mass action and Rate constant
(i) Physical state of reactants : This has
The rate at which a substance reacts is directly
considerable effect over rate of reaction.
proportional to its active mass and the rate at which a
reaction proceeds is proportional to the product of the
active masses of the reacting substances.
(ii) Physical size of the reactants : Among the  For a reaction, product
solids, rate increases with decrease in particle size of
the solid. Rate ;
(iii) Chemical nature of the reactants
(a) Reactions involving polar and ionic substances Where k is called rate constant or velocity
including the proton transfer reactions are usually very constant.
fast. On the other hand, the reaction in which bonds is
When , then
rearranged, or electrons transferred are slow.
(b) Oxidation-reduction reactions, which Thus, rate constant k is also called specific
involve transfer of electrons, are also slow as reaction rate.
compared to the ionic substance.  The value of rate constant depends on, nature
(c) Substitution reactions are relatively much of reactant, temperature and catalyst. It is independent
slower. of concentration of the reactants.
(2) Effect of temperature : The rate of chemical
reaction generally increases on increasing the  Unit of rate constant
temperature. The rate of a reaction becomes almost
double or tripled for every rise in temperature.
Temperature coefficient of a reaction is defined as
the ratio of rate constants at two temperatures differing Where order of reaction.
by (generally 25°C and 35°C) 10°C.
Rate law : Molecularity and Order of a reaction
Molecularity is the sum of the number of
molecules of reactants involved in the balanced
chemical equation. Molecularity of a complete reaction
has no significance and overall kinetics of the reaction
(3) Concentration of reactants : The rate of a depends upon the rate determining step. Slowest step is
chemical reaction is directly proportional to the the rate-determining step. This was proposed by Van't
Hoff.
 Chemical Kinetics 457
Example :
(Unimolecular)

(Rate determining step)

(Bimolecular)
(Trimolecular)
(Here, the overall order of reaction is equal to
The total number of molecules or atoms whose
two.)
concentration determine the rate of reaction is known as
 Molecularity of a reaction is derived from the
order of reaction.
mechanism of the given reaction. Molecularity can not be
Order of reaction = Sum of exponents of the conc. terms
greater than three because more than three molecules may
in rate law
not mutually collide with each other.
For the reaction  Molecularity of a reaction can't be zero,
The rate law is negative or fractional. order of a reaction may be zero,
negative, positive or in fraction and greater than three.
Then the overall order of reaction.
Infinite and imaginary values are not possible.
where x and y are the orders with respect to  When one of the reactants is present in the large
individual reactants. excess, the second order reaction conforms to the first
 If reaction is in the form of reaction mechanism order and is known as pesudo unimolecular reaction.
then the order is determined by the slowest step of (Table 11.1)
mechanism.
Table : 11.1 Order and molecularity of some reaction
S. Chemical equation Molecularit Rate law Order w.r.t.
No y First Second Overal
. reacta reactant l
nt
1. product a+b a b a+b

2. product a+b 2 zero, if B is in 2

excess

3. 2 1* ----- 1
(Bimolecular
)
4. 2 1* Zero, if H2O is 1
(Bimolecular in excess
)
5. 2 1* Zero, if H2O is 1
(Bimolecular in excess
)

6. 2 1* Zero, if OH– 1
(Bimolecular does not take
) part in slow
step
7. 2 1 1 2
(Bimolecular
)
8. 1 1 ---- 1
(Unimolecul
ar)
9. 1 1.5 ---- 1.5
(Unimolecul
ar)
10. 5 1 1 2
(H+is medium)
 458 Chemical Kinetics
11. 2 1 -1 with respect 1
(Bimolecular to O2
)
*Pseudo-unimolecular reactions.
Table : 11.2 Rate constant and other parameters of different order reactions
Orde Rate constant Unit of rate Effect on rate by (Half-life
r constant changing conc. to m period) T50=
times
0 conc. time–1 No change
(mol L–1 s–1)

1 time–1 (s–1) m times

,

2 conc–1 time–1 m2 times

(for the (mol L–1) s–1
L mol–1 s–1
case when each reactant has equal
concentration)

(for the

case when both reactants have different

concentration)
3 conc–2 time–1 m3 times
(mol L–1)–2 s–1
L2 mol–2 s–1
n conc(1–n) time–1 mn times
; (mol L–1)(1–n) s–1
L(n–1) mol(1–n) s–1

Methods for determination of order of a reaction (2) Half-life method : This method is employed
only when the rate law involved only one concentration
(1) Integration method (Hit and Trial method)
term.
(i) The method can be used with various sets of
and with integrated rate equations. ; ;

(ii) The value of is determined and checked for

all sets of and . A plotted graph of vs log a gives a straight
(iii) If the value of is constant, the used equation line with slope , determining the slope we can
gives the order of reaction. find the order n. If half-life at different concentration is
(iv) If all the reactants are at the same molar given then,
concentration, the kinetic equations are :

(For first order

reactions)

(For second order

reactions)
This relation can be used to determine order of
(For third order reaction ‘n’
Plots of half-lives Vs concentrations (t 1/2  a1–
n
reactions) )
 Chemical Kinetics 459

t1/2 
t1/2 

t1/2 

t1/2 
Zero 1st order 2nd 3rd
order order order

Conc. Conc. 1/a 1/a2 …..(iii)

(3) Graphical method : A graphical method
based on the respective rate laws, can also be used. and are determined from
(i) If the plot of Vs is a straight line,
concentration Vs time graphs and the value of can
the reaction follows first order.
be determined.
(ii) If the plot of Vs is a straight line, the (5) Ostwald's isolation method (Initial rate
method)
reaction follows second order. This method can be used irrespective of the
number of reactants involved e.g., consider the
(iii) If the plot of Vs is a straight line,
reaction, .
the reaction follows third order. This method consists in finding the initial rate of
(iv) In general, for a reaction of nth order, a graph the reaction taking known concentrations of the
different reactants (A, B, C).
of Vs must be a straight line.
Suppose it is observed as follows,
Conc. [A]

log. [A] 

(i) Keeping the concentrations of B and C constant,

Plots from integrated rate equations


if concentration of A is doubled, the rate of reaction

Zero order 1st order 2nd order 3rd order
becomes four times. This means that, Rate i.e.,
1 1 order with respect to A is 2
[A] [A]2 (ii) Keeping the concentrations of A and C
t t t t constant, if concentration of B is doubled, the rate of
reaction is also doubled. This means that, Rate  [B]
Rate 

Plots of rate Vs concentrations [Rate = i.e., order with respect to B is 1

Rate 

Rate 
Rate 

k(conc.)n ] (iii) Keeping the concentrations of A and B

constant, if concentration of C is doubled, the rate of
Zero order 1st 2nd 3rd
order order order reaction remains unaffected. This means that rate is
independent of the concentration of C i.e., order with
respect to C is zero. Hence the overall rate law
expression will be, Rate = k[A]2 [B] [C]0
Conc. Conc. (Conc.) (Conc.)
2
3  Overall order of reaction = 2 + 1 + 0 = 3.
(4) Van't Haff differential method : The rate of Theories of reaction rate
reaction varies as the nth power of the concentration
Where is the order of the reaction. Thus for two (1) Collision theory
(i) The basic requirement for a reaction to occur is
different initial concentrations and equation, can
that the reacting species must collide with one another.
be written in the form,
This is the basis of collision theory for reactions.
and (ii) The number of collisions that takes place per
second per unit volume of the reaction mixture is known
as collision frequency (Z). The value of collision
Taking logarithms,
frequency is very high of the order of in
case of binary collisions.
(iii) Every collision does not bring a chemical
…..(i) change. The collisions that actually produce the product
are effective collisions. The effective collisions, which
and bring chemical change, are few in comparison to the
total number of collisions. The collisions that do not
…..(ii) form a product are ineffective elastic collisions, i.e.,
molecules just collide and disperse in different
Subtracting equation (ii) from (i),
directions with different velocities.
Fraction of
molecules

Fraction of
molecules
capable of
bringing
effective collisions

Energy E
Distribution of energies at a
definite temperature
 460 Chemical Kinetics
(b) The fraction of effective collisions (Properly
oriented and possessing sufficient energy), f i.e.,

Where f is fraction of effective collision and Z is

the collision frequency.
(iv) For a collision to be effective, the following two (vii) The physical meaning of the activation energy
barriers are to be cleared, is that it is the minimum relative kinetic energy which
(a) Energy barrier : “The minimum amount of the reactant molecules must possess for changing into
energy which the colliding molecules must possess as to the products molecules during their collision. This
make the chemical reaction to occur, is known as means that the fraction of successful collision is equal
threshold energy”.
 In the graph 'E' corresponds to minimum or to called Boltzmann factor.
threshold energy for effective collision.
(viii) It may be noted that besides the requirement
 There is an energy barrier for each reaction. The of sufficient energy, the molecules must be properly
reacting species must be provided with sufficient energy to oriented in space also for a collision to be successful.
cross the energy barrier.
Thus, if is the collision frequency, P is the
(b) Orientation barrier : The colliding molecules
should also have proper orientation so that the old orientation factor (Steric factor) then,
bonds may break and new bonds are formed. For . If we compare this equation with
example, During this
Arrhenius equation.
reaction, the products are formed only when the
colliding molecules have proper orientation at the time
We know that pre-exponential form 'A' in
of collisions. These are called effective collisions.
Arrhenius equation is, .
Collisions not properly oriented
Concept of activation energy
O O O
Molecule Molecule O The excess energy (Over and above the average
N O N N O N N
s
approach s
Separate N energy of the reactants) which must be supplied to the
O O O O O reactants to undergo chemical reactions is called
NO2 + NO2
O
Collision NO2 NO2 activation energy ,
No product
Properly oriented collisions form products

O O O O O O
Molecule Bond Activation energy = Threshold energy –
N N N N N N
s
approach Formatio Average kinetic energy of the reacting molecules.
O O O O n O O
NO2 + NO2 Product (a) Zero activation energy = Fraction of effective
Collision N2O4
collision (f) will be very large = Very fast reaction
Fig. 11.1
(v) Thus, the main points of collision theory are (Instantaneous reaction).
as follows, (b) Low activation energies = Fraction of effective
(a) For a reaction to occur, there must be collisions collision (f) will be large = Fast reactions.
between the reacting species. (c) High activation energies = Fraction of effective
(b) Only a certain fraction of the total number of collision (f) will be small = Slow reaction.
collisions is effective in forming the products. The activation energy depends upon the
(c) For effective collisions, the molecules should nature of chemical bonds undergoing rupture and is
possess sufficient energy as well as orientation. independent of enthalpies of reactants and products.
(vi) The fraction of effective collisions, under According to the concept of activation energy, the
ordinary conditions may vary from nearly zero to about reactants do not change directly into the products. The
one for ordinary reactions. Thus, the rate of reaction is reactant first absorb energy equal to activation energy
proportional to : and form activated complex. At this state, the molecules
must have energy at least equal to the threshold energy.
(a) The number of collisions per unit volume per
This means that the reaction involves some energy
second (Collision frequency, Z) between the reacting
barrier which must be overcome before products are
species
formed. The energy barrier is known as activation
energy barrier.
 Chemical Kinetics 461
Threshold Activated When log k plotted against , we get a straight
energy complex line. The intercept of this line is equal to log A and slope
Et (Et)
Energy barrier
Ea (activation equal to .
energy)

Therefore .
Er Reactants Energy of
E the
(Er) reaction
Ep

log k
Products (Ep)

Progress of reaction
(2) Transition state theory
(i) According to transition state theory the Slope

activated complex is supposed to be in equilibrium with

1/T reaction at two different
Rate constants for the
the reactant molecules.
(ii) Once the transition state is formed it can either temperatures and ,
return to the initial reactants or proceeds to form the
products.
(iii) Assuming that once formed the transition state
proceeds to products we can say that rate is …..(iii)
proportional to concentration of transition state. where and are rate constant at temperatures
Mathematically, Rate Transition state and respectively .
Rate= Constant × Transition state
(iv) The activation energy for the forward reaction,
Mechanism of the reaction
(1) Reaction involving first order consecutive
and the activation energy for the reverse reaction
reactions
are related to the enthalpy of the reaction (i) In such reactions, the reactions form a stable
intermediate compound before they are finally
by the equation .
converted into the products.
(a) For endothermic reactions, so that (ii) For example, reactants (R) are first converted to
intermediate (I) which is then converted to product (P) as

(b) For exothermic reaction, so that

Therefore, the reaction takes place in two steps,
. both of which are first order i.e.,
Arrhenius equation Step I : ; Step II :
Arrhenius proposed a quantitative relationship This means that I is produced by step I and consumed
between rate constant and temperature as, by step II. In these reactions, each stage will have its
…..(i) own rate and rate constant the reactant concentration
Concentration

will always decrease and product concentration will

The equation is called Arrhenius equation. always increase as shown in fig.
In which constant A is known as frequency factor.
This factor is related to number of binary molecular P
collision per second per litre.
is the activation energy. I
T is the absolute temperature and
R
R is the gas constant
Time
Both A and are collectively known as
Concentration profile of reactants (R),
Arrhenius parameters. intermediate (I) and products (P) as a
Taking logarithm equation (i) may be written as, function of time
(2) Reaction involving slow step : When a
reaction occurs by a sequence of steps and one of the
step is slow, then the rate determining step is the slow
…..(ii) step. For example in the reaction
The value of activation energy increases, the ; , if then I is converted into
value of k decreases and therefore, the reaction rate products as soon as it is formed, we can say that
decreases.
 462 Chemical Kinetics
(3) Parallel reactions : In such type of reactions in UV light may not occur on exposure to yellow light
the reactants are more reactive, which may have (lower and lesser E/Photon)
different orders of the reactions taking place (iv) The rate of photochemical reactions depend
simultaneously. For example, in a system containing upon the intensity of radiation’s absorbed.
and is consumed in the following two (v) The values for light initiated reactions may
reactions, ; or may not be negative.
(vi) The temperature does not have marked effect
The rate of disappearance of will be sum of
on the rate of light initiated reactions.
the rates of the two reactions i.e.,
(2) Mechanism of some photochemical
reactions
(i) Photochemical combination of H2 and Cl2 :
A mixture of and on exposure to light give rise
Photochemical reaction
to the formation of HCl, showing a chain reaction and
Absorption of radiant energy by reactant
molecules brings in photophysical as well as thereby producing molecules of per
photochemical changes. According to Einstein's law of photon absorbed.
photochemical equivalence, the basic principle of photo
processes, each reactant molecule is capable of
The mechanism leading to very high yield of HCl
absorbing only one photon of radiant energy. The
as a result of chemical change can be as follows.
absorption of photon by a reactant molecule may lead
Chlorine molecules absorb radiant energy to form an
to any of the photo process.
excited molecule which decomposes to chlorine free
Reactant molecule radicals (Cl) to give chain initiation step.
Absorption of
Light absorption step : ........(i)
photon (As per
Einstein law) Chain initiation step :
Excitation of Knock out the electron
electronic level from the reactant
........(ii)
species The chlorine free radical then combines with
Excited molecule Photoelectric effect
molecule to form HCl and free radical. The free
radical so formed again combines with another

Photophysical Photochemical molecule to give HCl and free radical back resulting
process process into chain propagation step.
(i) Oxidation
(i) Fluorescence (ii) Reduction Chain propagation step :
(ii) Phosphorescence (iii) Dissociation
........(iii)
The chemical reactions, (iv) which
Double are initiated as a
result of absorption ofdecompositionlight, are known as
(v) Isomeric
photochemical reactions. Intransformation
such cases, the absorbed The combination of two free radicals leads to
energy is sufficient to activate
(vi)the reactant molecules to
Photosensitization chain terminating step.
cross the energy barrier existing between the reactants
Chain terminating step : ........(iv)
and products or in other words, energy associated with
each photon supplies activation energy to reactant (ii) Photochemical combination of H2 and Br2 :
molecule required for the change. The combination of and to form HBr in
(1) Characteristics of photochemical presence of light is also an example of chain reaction
reactions like photochemical combination of and . Here
(i) Each molecule taking part in a photo process
absorbs only one photon of radiant energy thereby two molecules absorb photon, however, inspite of
chain reaction only one molecule of HBr is formed for
increasing its energy level by
each 100 photon absorbed by 100 molecules of .
(ii) Photochemical reactions do not occur in dark.
(iii) Each photochemical reaction requires a Mechanism
definite amount of energy which is characteristic of a
Light absorption step :
particular wavelength of photon. For example, reactions
needing more energy are carried out in presence of UV ........(i)
light (lower , more E/Photon). A reaction-taking place Chain initiation step :
........(ii)
 Chemical Kinetics 463
Chain propagation step : is endothermic.
........(iii)
.
 Drapper’s effect : , Such
.......(iv)
reactions are accompanied by the increase in the
Chain termination step : ........(v)
volume. This is called Drapper’s effect. The reason is
The lower values of HBr formation per photon of that the reaction is exothermic and heat released
light absorbed has been attributed to the fact that step raises the temperature and gas expands resulting in
(III) is highly endothermic and thus before step (III) can the increase in volume.
take place most of the bromine free radicals recombine  Actinometer : A device which is used to
as per step (V) to give molecule and thus providing measure the intensity of radiation is konwn as
less feasibility for step (IV) i.e. steps regenerating free actimometer. e.g., Uranyl oxalate actinometer.
radicals. Also the decomposition of HBr increases with  Amount of the substance left after ‘n’ half lives
increase in temperature.
(3) Quantum yield (or quantum efficiency) : The .
quantum efficiency or yield of a photochemical
reaction may be expressed as,  Free energy change for thermochemical
reactions is always negative but remember, for
photochemical reaction may not always be negative.
(4) Application of photochemistry : It may be +ve also because a part of the light energy
Photochemistry has significant role in our daily life. absorbed is converted into the free energy of the
Some of the photochemical reactions commonly known products.
as cited below,  Negative catalysts or inhibitors are those
(i) Photosynthesis in plants substances which decrease the rate of a reaction.
(ii) Photography
 Example of fourth order reaction, ⇌
(iii) The formation and destruction of ozone layer
(iv) Photoetching in electronic industry
(v) Many polymerization reactions.  Grothus-Draper law : When light falls on a
(vi) Modern printing technology substance, a part of light is absorbed, a part is
(vii) Free radical combinations to obtain many reflected and a part is transmitted. only that part of
compounds. light which is absorbed causes a particular reaction to
occur.
 Stark’s Einstein law of photochemical
equivalence According to this law, every atom or
molecule taking part in photochemical reaction absorbs
only one quantum of radiaton.
 Kinetics of fast reactions can be studied by (i)
 Different reactions have different rates because Relaxation method (ii) Flash photolysis technique etc.
their activation energies are different. Lesser the
activation energy faster is the reaction.  Enzyme catalysed reactions are faster than metal
catalysed reactions, the former has lower activation
 The reaction, , exhibits a small

negative temperature coefficient and the rate of

reaction decreases with increase of temperature.
 Fuels in contact with oxygen do not burn by
themselves. This is because they need activation
energy (provided by the flame) to initiate the reaction. Rate of a reaction
Thus, fuels are thermodynamically unstable ( is –ve) 1. The rate of a chemical reaction
but kinetically stable. [MP PMT 1973; CPMT 1982]
 Quantum efficiency of the photochemical (a) Increases as the reaction proceeds
reaction, is very high while that of (b) Decreases as the reaction proceeds
(c) May increase or decrease during the reaction
, is very low. This is because after
(d) Remains constant as the reaction proceeds
the chain initiating step
 464 Chemical Kinetics
(a) Pressure (b) Temperature
(c) Concentration (d) Catalyst
3. The rate at which a substance reacts depends on
its
[MP PMT 1987; BHU 1999; KCET 2005]
(a) Atomic weight (b) Equivalent weight
(c) Molecular weight (d) Active mass
4. The rate law for the reaction
is given by
Rate . The rate of the reaction will be
[IIT 1988]
(a) Doubled on doubling the concentration of
sodium hydroxide
(b) Halved on reducing the concentration of alkyl
halide to one half
(c) Decreased on increasing the temperature of
the reaction
(d) Unaffected by increasing the temperature of
the reaction
5. If doubling the concentration of a reactant `A'
increases the rate 4 times and tripling the
concentration of `A' increases the rate 9 times,
the rate is proportional to [AIIMS 1991]
(a) Concentration of `A'
(b) Square of concentration of `A'
(c) Under root of the concentration of `A'
(d) Cube of concentration of `A'
6. The rate of chemical reaction at constant
temperature is proportional to
(a) The amount of products formed
(b) The product of masses of the reactants
(c) The product of the molar concentration of the
reactants
(d) The mean free path of the reaction
7. The concentration of a reactant decreases from
0.2 M to 0.1 M in 10 minutes. The rate of the
reaction is
(a) 0.01 M (b)
(c) 0.01 mol (d) 1 mol

8. When a reaction is progressing

(a) The rate of the reaction goes on increasing
(b) The concentration of the products goes on
decreasing
(c) The concentration of the reactants goes on
decreasing
(d) The reaction rate always remains constant