Chemical Kinetics

Chemical Kinetics
y Study of rate of reactions and factors affecting
it like temperature, pressure, catalyst and Concept Ladder
radiations is called chemical kinetics.
y On the basis of rate, reactions can be of slow, Chemical Kinetics basically
moderate and very fast type. tells us about how fast
y Very fast reactions take 10–14 to 10–16 seconds or slow a reaction is.
for their completion, for example, ionic Reactions with moderate
reactions, such as the one shown below: speed are studied using
NaCl + AgNO3 
→ AgCl + NaNO3 chemical kinetics.

y Fast reactions are not studied under kinetics.

These are studied by flash-photolysis and
spectrographic methods.
y Blackening of white lead,Rusting of iron,
formation of water at room temperature
burning of coal and are not studied under Rack your Brain
kinetics.
y Reactions with moderate speed, like molecular Can we study the rate of
reactions, are studied under kinetics. For e.g., neutralisation reaction of a
hydrolysis of ester or sugar. strong acid and base using
chemical kinetics?
Rate of Reaction
Rate of reaction is defined as the rate of
change of concentration of a reactant or a
product per unit time.

[C2 ] − [C1 ] Previous Year’s Questions

Rate of reaction =
t2 − t 1
y Rate of reaction decreases with time because For the reaction, N2  3H2  2 NH3
concentration of the reactant also decreases.
, if d [NH3 ]  2  104 mol L1s1 , the
This can be observed from the following
dt
reaction. −d [H2 ]
value of would be
2NO2 + F2 
→ 2NO2F dt
Here, rate of reaction is measured by the  [AIPMT]
decrease in concentration of F2. (1) 4 × 10-4 mol L-1 s-1
Chemical Kinetics

y Unit for rate of reaction is mol L–1 time–1 or (2) 6 × 10-4 mol L-1 s-1
atm time–1 (gaseous substance). (3) 1 × 10-4 mol L-1 s-1
(4) 3 × 10-4 mol L-1 s-1

1.
 Average Rate of Reaction
As rate varies greatly with time so we use Concept Ladder
average reaction rate. By dividing the total change
in concentration of reactant or product by a time Average rate of reaction
interval, we actually get the average rate of the is termed as the rate of
reaction. reaction measured over
the long time interval.
[x] [R] [P]
Avg. rate  
t t t

Previous Year’s Questions

For the chemical reaction,

N2 (g) + 3 H2 (g)  2 NH3 (g)
the correct option is
 [NEET-2019]
(1) 3 d [H2 ] = 2 d [NH3 ]
dt dt
(2)  1 d [H ] 1 d [NH3 ]
2

3 dt 2 dt
(3)  d [N ] d [NH ]
2
2 3

dt dt
(4) d [N ] 1 d [NH ]
 2
 3

dt 2 dt

Definition

Instantaneous Rate of Reaction The instantaneous rate of reaction

Instantaneous rate of reaction is equal to
i.e., rate of reaction at any instant
very small change in concentration (d[x]) during a
of time is the rate of change of
d[x]
Chemical Kinetics

very small interval of time (dt). It is given as concentration of any one of the
dt
reactants or products at that
instant of time.

2.
 dx
y = tan θ = −slope
dt
y It is written for any of the reactant or the
product in terms of stoichiometric coefficients
VJ as follows:

dx 1 d(J)
=
dt VJ dt
pA + qB → rC + sD Concept Ladder
−1 d[A] −1 d[B] 1 d[C] 1 d[D]
= = = The average rate of the
p dt q dt r dt s dt
reaction is the average
of the all instantaneous


Taking N2 + 3H2 
 2NH3 as an example, the reaction rates over a period
instantaneous rate of reaction is calculated as of time during the reaction.
follows:

d[x] −d[N2 ]
For N2 , =
dt dt
−d[x] −d[H2 ]
For H2 , =
dt dt
d[x] d[NH3 ]
For NH3 , =
dt dt
Rack your Brain
5Br − + BrO3− + 6H+ → 3Br2 + 3H2O
aq. aq. aq. 'l '
aq.

−1 d[Br ] −
−d[BrO3− ] What is the slope of the
Rate
= =
5 dt dt tangents for reactants and
−1 d[H+ ] 1 d[Br2 ] 1 d[H2O] products respectively in the
Chemical Kinetics

= = plot of concentration vs time?

6 dt 3 dt 3 dt

3.
 y For reactants, negative sign indicates decrease
in concentration. Definition
y For a reversible reaction at dynamic
equilibrium, the net reaction rate is zero. According to the law of mass
action, it states that the rate of
Features of Rate of Reaction chemical equation is directly
y Rate of reaction is always a positive quantity. proportional to the product of the
y It is proportional to the active masses of the
active mass of the reactants, with
reactant.
y It is measured by measuring active mass or each active mass term raised to
molar concentration of a reactant or a product the power equal to its respective
with respect to time. stoichiometric coefficient in
y It varies with time, therefore it is better to a balanced equation with a
use average reaction rate. constant temperature which was
later discarded.
Specific Reaction Rate or Velocity Constant
Consider,
nA   Product
dx
  [A]n
dt
dx Rack your Brain
or   k[A]n
dt
Find out the units of rate
Rate law equation constant for a 3rd order reaction.
If [A]n = 1 then

dx
− k (At a particular temperature)
=
dt
k = Rate constant or specific reaction rate
y At concentration value of unity, rate of
reaction is equal to the value of rate constant. Concept Ladder
y Rate constant, k ∝ Temperature (rate
constant always Increases with increase in The rate of reaction is
temperature). directly proportional to the
y Rate constant does not depend upon presence product of concentration
of reactant and each
of a catalyst or on nature of reactant.
concentration is raised
y Rate constant does not depend upon
to some power which
Chemical Kinetics

pressure, volume or concentration.

may or may not be equal
y Unit of rate constant is represented as (mole/
to stereochemistry
litre)1–n time–1 (Here n = Order of reaction).
experimentally.

4.
Factors Affecting Rate of Reaction
Physical state of reactants Concept Ladder

Gaseous state > liquid state > solid state


Decrea sing order of rate of reaction
→ Concentration of reactant,
surface area, temperature,
Temperature
nature of reactant are
For every rise of 10°C in temperature, rate or
some basic factors which
dx/ dt increases by two to three times or rate
affects the rate of reaction.
increases with temperature as the number of
effective collisions increases.
k t  C  10C
Temperature coefficient 
k t C
The value of temperature coefficient lies in
between 2 to 3.

Increase in Rate of Reaction with Rise of Rack your Brain

Temperature
We know that all the molecules of the
reactants do not have the same energy. According
to Maxwell distribution curve for energies, if
energies of the reacting molecules are plotted
against the corresponding fractions (ΔN/N) at
a particular temperature T, a curve of the type
shown in figure given below is obtained. Suppose
the threshold energy is attained at the point Et .
Here and beyond this point Et , all collisions will
be effective and hence, a chemical reaction can
take place. The shaded area under the curve AB
gives the fraction of molecules having energies
equal to or greater than the threshold energy. (F)
If the temperature is raised from T K to (T +
10) K, the distribution curve shifts towards right,
as shown, but the magnitude of the threshold
energy will remain the same. Now, the shaded
Why are reactions of higher order
less in number?
Previous Year’s Questions
The decomposition of phosphine
(PH3) on tungsten at low pressrue
is a first-order reaction. It is
because the
 [NEET-2016]
(1) rate is proportional to the
surface coverage
(2) rate is inversely proportional to
the surface coverage
(3) rate is independent of the
Chemical Kinetics

area beyond Et becomes almost double (in surface coverage

some cases triple also) and the fraction of the (4) rate of decomposition is very
molecules having energy equal to or greater than slow.

5.
 threshold energy also becomes double or triple
and hence, the reaction at (T + 10) K, becomes
much higher, (accordingly doubles or triples) than
at T K.

y A negative temperature coefficient is observed Previous Year’s Questions


only in the case of 2NO + O2 
 2NO2
Which one of the following
statements for the order of a
reaction is incorrect?
 [AIPMT-2011]
(1) Order can be determined only
experimentally
(2) Order is not influenced by
stoichiometric coefficient of the
reactants
(3) Order of a reaction is sum of
power to the concentration terms
of reactants to express the rate of
Chemical Kinetics

reaction.
(4) Order of reaction is always
whole number.

6.
Concentration
Rate of reaction (dx/dt) ∝ Concentration. Concept Ladder

Pressure The rate of a reaction can be

For gaseous reactants increased by increasing the
dx temperature, concentration,
∝ Pressure (as P ∝ C)
dt surface area, pressure,
intensity of radiation or by
adding a catalyst.
Surface area
In the case of heterogenous reactions, greater
is the surface area, faster is the rate of reaction
due to presence of more number of active sites.
dx
∝ Surface area
dt Rack your Brain
Example
(1) Coal dust burns fast than large coal piece Why boiling of an egg in an open
(2) Wood shavings burn fast than a log of Wood vessel takes more time in a hill
station?
Nature of reactant and product
For ionic reactants, rate of reaction is fast,
as activation energy is zero for these. Molecules
have a slower reaction rate as they require higher
activation energy.
Previous Year’s Questions
Radiation
For a photochemical reaction For the reaction, A + B → Products,
dx it is observed that
∝ Intensity of radiation
dt (i) on doubling the initial
concentration of A only, the rate
Rate of reaction for photochemical reactions of reaction is also doubled and
depends upon the intensity of light radiations
(ii) on doubling the initial
and it increases by absorption of photons.
concentration of both A and B,
Positive catalyst there is a change by a factor of 8
Positive catalyst increases rate of a reaction in the rate of the reaction.
by providing an alternative path which requires a The rate of this reaction is
lesser activation energy.  [AIPMT]
y A negative catalyst decreases the rate of (1) rate = k[A][B]2
Chemical Kinetics

reaction.
(2) rate = k[A]2[B]2
y Catalysts are more effective in ‘solid powdered
form’, which provides a greater surface area, (3) rate = k[A][B]
that is, more number of active sites. (4) rate = k[A]2[B]

7.
Chemical Kinetics

8.
Collision Theory
y A reaction takes place when the reacting
molecules undergo collisions with each other.
In other words, any chemical reaction is the
result of effective collisions.
y For effective collisions
(a) Colliding molecules must have sufficient
kinetic energy. Concept Ladder
(b) Collision should be properly oriented.
The rate of reaction
increases with increase in
temperature because of
the increase in the effective
number of collisions.

Rack your Brain

A reaction has enough number

y The minimum amount of energy needed to of collisions having energy
Chemical Kinetics

convert a reactant into product is known greater than threshold energy,

as threshold energy. This is the minimum
still the reaction is very slow.
amount of energy possessed by the reacting
molecules, in order to have effective collisions Why?
for the formation of product.

9.
Chemical Kinetics

10.
y According to this theory, rate of reaction is
given as
Previous Year’s Question
Rate = f Z
where, f = Fraction of molecules with potential
An increase in the concentration of
energy greater than threshhold energy.
the reactants of a reaction leads to
−Ea /RT
f=e
change in [NEET-2014]
P = Orientation factor
Z = Collision frequency (1) heat of reaction
y Activated state or transition state theory (2) threshold energy
or absolute rate theory was given by Henry (3) collision frequency
Erying. (4) activation energy
C
A + B → ABC 
Activated complex
→ AB + C
Pr oduct

Activation Energy Concept Ladder

It is the minimum amount of additional
external energy needed to change a reactant A catalyst speeds up the
into product, or to make potential energy of the reaction by lowering the
reactants equal to the threshold energy. It is potential energy barrier
denoted by Ea. and thus by decreasing the
Ea = Threshold energy – Potential energy of activation energy.
reactants or Average kinetic energy of reactants
1
Rate of Reaction ∝
Ea

Hence, lower the value of activation energy, faster

will be the reaction.

Q1 The rate of a particular reaction quadruples when the temperature changes

from 293 K to 313 K. Calculate activation energy.

Sol. K2/K1 = 4, T1 = 293 K, T2 = 313 K

K2 Ea  1 1
log    
Chemical Kinetics

K1 2.303 R  T2 T1 
Thus, on calculating and substituting values, we get
Ea = 52.86 KJ mol-1

11.
 Rack your Brain

Coal is a good fuel but it doesn’t

react with oxygen until a flame
is applied. Why?

Concept Ladder

The Arrhenius equation

is often used to compare
the rate of constants
Arrhenius Equation
measured at two different
Arrhenius equation is used to evaluate
temperatures.
energy of activation and to show the effect of
temperature on rate constant as follows:
−Ea /RT
k = Ae
or alternatively,
Ea
log
= 10
k log 10 A −
2.303 RT
Here A is the Arrhenius or pre-exponential
Previous Year’s Question
factor or frequency factor.
−Ea
Here e RT is known as Boltzmann factor. The rate constants k1 and k2 for two
y When Ea is zero or temperature is infinite (∞) different reaction are 1016e–2000/T
k = Ae° = A and 1015e–1000/T, respectively. The
‘A’ signifies frequency of binary collisions or temperature at which k1 = k2 is
total number of collisions per unit volume per
unit time. [NEET]
y At two different temperatures T1 and T2.
(1) 1000 K
2.303 R T 1T2 k2
Ea = log 10 (2) 2000/2.303 K
( T2 − T1 ) k1
Chemical Kinetics

(3) 2000K
 a  Ea (T2 − T1 ) (4) 1000/2.303K
log 10  =
 a − x  2.303 R T1 T2

12.
Graph Between log10 k and 1/T
When a graph is plotted between log10 k and 1/T,
a straight line with a negative slope is obtained.
Here, slope is equal to –Ea /2.303R, that is,
Εa = –2.303 R. Here, intercept is equal to log10 A.
In Exothermic Reactions
Potential energy of reactant > potential energy
of product Ea of backward reaction > Ea of forward
reaction.
Previous Year’s Questions
The rate of reaction between two
reactants A and B decreases by a
factor of 4 if the concentration of
reactant B is doubled. The order
of this reaction with respect to
reactant B is
 [AIPMT]
(1) 2 (2) –2
(3) 1 (4) –1

Elementary and Complex Reactions

It is interesting to know that a balanced
chemical equation never shows us a true picture
of how the reaction is taking place as very rarely Rack your Brain
a reaction gets completed in only one step.
y The reaction which occurs in one step is
Can activation energy have zero
known as an elementary reaction and when
or negative values? If not, why?
a sequence of such reactions (mechanism)
Chemical Kinetics

provides us with the desired products then

these reactions are termed as complex
reactions.

13.
 y Such reactions may be consecutive, reverse or
side reactions. For example, in the complete Concept Ladder
combustion of an alkane the final products
are always carbon dioxide and water. However, Reactions of higher order
during this reaction a series of elementary are very rare as the chances
reactions take place during which alcohols, for the molecules to
aldehydes and acids are formed. come together in a proper
Molecularity orientation to undergo
y Molecularity is the number of particles (atoms, effective collisions are very
ions or molecules) that must collide with one less.
another simultaneously,which results in a
chemical reaction.
y It is a theoretical value.
y It is always a whole number.
y It never determines the rate of reaction.
y It never depends upon external factors like
temperature and pressure.
y Molecularity cannot be more than three as
there is nearly no chance for more than three Rack your Brain
molecules to undergo an effective collision at
a time. The specific reaction rate is
y In a multistep reaction, molecularity is equal to the rate of reaction.
determined separately in each step. Reaction is of which order?
y In case of complex reactions, (reactions taking
place in a number of steps), the slowest step
is called the rate determining step or rate
limiting step.
y The overall molecularity of a complex reaction
is equal to the molecularity of the slowest
step.
y If molecularity of a reaction is 1 the reaction
is called unimolecular as in the following
reaction: Concept Ladder
PCl5 
→ PCl 3 + CI2
y If molecularity is 2, the reaction is called
bimolecular. Molecularity of a reaction is
mostly between 1 to 3, but
C12H22O11 + H2O 
→ C6H12O6 + C6H12O6
never zero. It is rare that
Chemical Kinetics

Glucose Fructose
molecularity exceeds 3.
y If molecularity is 3, the reaction is called
termolecular
2FeCI3 + SnCI2 
→ 2FeCI2 + SnCI4

14.
Order of Reaction
Order of reaction is defined as number of Concept Ladder
reactants which determine rate of reaction,
or alternatively, it is the number of reactants,
whose molar concentration changes during the In rate law of expression
chemical reaction. It can also be defined as the the sum of powers to which
sum of exponents, raised on active masses of the concentration terms are
reactants in a rate law equation. raised is known to be order
Look at the example ahead, of reaction.
mA + nB 
→ Pr oducts
For this, the rate law equation is
Rate k = [A]m [B]n
Hence, order = m + n
y It is an experimental value.
y It may be zero, negative or a fraction.
y It determines the rate of reaction.
y Order of reaction depends upon temperature,
pressure and concentration. (external factors)
y Anything present in excess, is not counted in
order of reaction, for example, in hydrolysis
of ester and sugar, water is in excess, so it is
neglected for order.
y Order of any reaction is determined by the Previous Year’s Question
slowest step of a reaction.
y High order reactions are rare due to less Which one of the following
chance of effective collisions between statement for the order of a reaction
molecules.
is incorrect? [NEET]
Mechanism:
(1) Order is not influenced by


O3 
 O2 + O2 [fast] (1)
stochiometric coefficient of


O3 + [O] 
 2 O2 [Slow] (2) the reactants
Rate = K[O3 ][O] (2) Order of reaction is sum of
[O3 ] power to the concentration
As [O] = K from eq(i) terms of reactants to express
[O2 ]
the rate of reaction
So
(3) Order of reaction is always the
R a te = K 1[O3 ]2 [O2 ]−1
Chemical Kinetics

whole number
Hence, it is a first order reaction. (4) Order can be determined by
experiments only

15.
 Zero-order Reaction
In zero-order reactio. concentration of the Concept Ladder
reactants.
dx In the plot concentration
− ∝ [Concentration]0 vs time for a zero order
dt
A →P reaction, the slope gives the
dx value of rate constant and
(A)° k
= k= intercept gives the initial
dt
concentration.
On integrating it, we get
x = k.t + c
If c = 0 then
x = k.t
x
k=
t
Rack your Brain
y Unit of is mol L–1 time–1

Examples of a zero-order reaction What will be the plot of the rate

y Photochemical reactions of reaction vs time for a zero
order reaction?
hν
H2 + CI2  → 2HCI
(studied over watch surface)
1
N2 O  → N2 + O2
2
(studied over platinum surface)
Previous Year’s Question
2NH3 
→ N2 + 3H2
CH3COCH3 + I2 
→ CH3COCH2I + HI In a zero order reaction, for every
2HI  → H2 + I2
10°C rise of temperature, the rate
(studied over gold surface)
is doubled. If the temperature is
y Iodination of acetone. increased from 10°C to 100°C, the
y Enzyme catalysed reactions.
Features of a zero-order reaction rate of the reaction will become.
y The concentration of the reactant decreases
linearly with time [NEET]
[A]t = [A]0 – kt
(1) 256 times
y Rate = k (at all concentrations)
Chemical Kinetics

(2) 212 times

y t1/2 ∝ a0 (initial concentration)
(3) 64 times
y Here rate and concentration of reactants do
(4) 128 times
not vary with time.

16.
First-order Reaction
Here the reaction rate is determined by one Concept Ladder
concentration variable term only.
Here, t = Time period If a ∝ P0
k = Rate constant
Ar or a or N0 = Initial amount (a − x) ∝ 2P0 − Pt
A or a – x or N = Amount left after time t 2.303 P0
k= log 10
t 2P0 − Pt
Examples of a first-order reaction

∆ 1
H2O2 → H2O + O
2 2
∆
NH4NO2 → N2 + 2H2O
∆
2N2O5 → 4NO2 + O2
∆
SO2CI2 → SO2 + CI2
C=H N NCl + H2O 
6 5
→ C6H5OH + N2 + HCl
All radioactive disintegration processes are
examples of Ist order.

Features of a first-order reaction Rack your Brain

y Unit of k is time–1
y k does not depend upon concentration units How the plot of [A] vs. t for a
or change in concentration. first order reaction looks like?
y t1/2 does not depend upon initial concentration
(a). It depends only upon rate constant.
0.693
t 1/2 =
k

Concept Ladder

If the amount of substance

left after one half life is
Chemical Kinetics

[A0]/2, then the amount of

substance left after n- half
lives is [A0]/2n.

17.
Chemical Kinetics

18.
Second-order Reaction
Examples of a second-order reaction Concept Ladder



2 O3 
 3 O2 The integrated rate equation
CH3COOC2H5 + NaOH 
→ CH3COONa + C2H5OH for nth order is given by
2 Cl 2O 
→ 2 Cl 2 + O2 1  1 1 
=K  n− 1 − 
2NO2 
→ 2NO + O2 t (n − 1)  [C] [C0 ]n− 1 

Features of a second-order reaction Where n = 2,3….

y Unit of k is L mol–1 time–1
1
t 1/2 ∝
a
y When concentrations are same
1 x
k=
t a(a − x)
Previous Year’s Questions
y When concentrations are different
2.303 b(a − x)
k= log 10 The given reaction,
t(a − b) a(b− x)
2FeCl3 + SnCl2 → 2FeCl3 + SnCl4
y The change in the unit of concentration, is an example of
changes the value of k here.
 [AIPMT]
(1) third order reaction
Third-order Reaction
(2) first order reaction
(3) second order reaction
dx
− ∝ [A]3 or [A]1 [B]1 [C]1 (4) none of these
dt

Examples of a third-order reaction

2NO + O2 
→ 2NO2
2NO + Cl 2 
→ 2NOCl
2FeCl 3 + SnCl 2 
→ SnCl 4 + 2FeCl 2

Q2 What is the order of reaction whose rate constant has the same units as the
rate of reaction?
Chemical Kinetics

Sol. Zero order

19.
 Features of a third-order reaction
Rack your Brain
1  1 1 
=k  − 2 The half life of a reaction is
2t  (a − x)2
a 
inversely proportional to the
1
t 1/2 ∝ square of initial Concentration,
a2
what is the order of reaction ?
y The change in the unit of concentration
changes the value of A here.
y Unit of k is L2 mol–2 time–1

Pseudo First-order Reactions

Pseudo first-order reactions are the reactions
which are not truly of the first order but under
certain conditions become reactions of the first
order.
Here molecularity is more than 1, but order of Concept Ladder
reaction is always one. Few example of pseudo
first-order reactions are as follows: If one of the reactants
is present in excess, its
Hydrolysis of ethyl acetate concentration does not
change much with time
CH3COOC2H5 + H2O 
→ CH3COOH + C2H5OH through out the reaction,
Rate cons tan t (k) is given as hence the reaction is
2.303 V − V0 considered as a pseudo first
k= log 10 ∞
t V∞ − Vt order reaction.
Here V∞ = Volume at inf inite
V0 = Initial volume
Vt = Volume at time t

Hydrolysis of sugar

C12H22O11 + H2O 

→ C6H12O6 + C6H12O6
Glucose Fructose

Rate constant in this case is given as

2.303 r −r Rack your Brain
k= log 10 0 ∞
t rt − r∞
Chemical Kinetics

Hydrolysis of ethyl acetate with

Here r0 = Initial optical rotation
HCl is a first order reaction,
r∞ = Rotation at infinite dilution
why?
rt = Rotation at t time

20.
Methods for determining order of reaction
Order of a reaction is determined mainly by: Concept Ladder
1. Initial concentration method
2. Integration method The ozone layer that is found
3. Graphical method: When a graph is plotted in the earth’s stratosphere is
between 1/(a – x)n–t and time t, a straight line formed by the photochemical
is formed. dissociation of molecular
4. Half-life method oxygen into oxygen atoms
and these atoms react with
n− 1 molecules of oxygen to form
(t 1/2 )1 a 
=  2 ozone.
(t 1/2 )2  a 1 
or
log (t 1/2 )1 − log(t 1/2 )2
n= 1 +
log a2  − log a 1 
Rack your Brain
Here n is the order of reaction
5. Van’t Hoff differential method
 − d C     What would accelerate a
log   1   − log  − d C2   photochemical reaction more
 dt   dt  effectively : a catalyst or high
n=    
log C1  − log C2  intensity of light?

Photochemical reactions
Those reactions which take place only in
the presence of light are called photochemical
reactions, for example, photosynthesis and
formation of HCl. They proceed by chain reaction
mechanism using atoms or free radicles.
y For such reactions ∆G0 (standard Gibbs free
energy change) can be positive. For example,
synthesis of carbohydrate and HCl formation.
y Red light has lowest energy. Some
photochemical reactions can be initiated by
red light.
y Such reactions are not affected by
temperature, however, they are affected by
intensity of light radiations.
Previous Year’s Questions
When initial concentration of a
reactant is doubled in a reaction,
its half-life period is not affected.
The order of the reaction is
 [AIPMT]
(1) second
(2) more than zero but less than
first
Chemical Kinetics

y The retina in the eye undergoes geometrical (3) zero

isomerization by absorbing photons of light (4) first
to enable sight.

21.
 Photosensitizer
It is a substance which when added Concept Ladder
to a reaction mixture, helps to start the
photochemical reaction, but it does not undergo To begin a photochemical
any chemical change, for example, chlorophyll in process, an atom or
photosynthesis and Hg vapours in dissociation of molecule must absorb a
H2. quantum of light energy
from a photon. When this
By photosensitizer
Non − photoactive → Photoactive occurs, the energy of the
atom or molecule increases
Luminiscence above its normal level.
It is the emission of light unaccompanied by
heat.
Chemiluminiscence
It is the conversion of chemical energy in to
cold-light energy, for example, in fire flies the light
emitted is due to oxidation of luciferin protein by
the enzyme luciferase (bioluminiscence).
Definition
Fluorescence
Here emission of light stops instantaneously
Quantum Efficiency is a measure of
when radiation being projected on a fluorescent
the number of product molecules
substance, is cut off, for example CaF2 .
formed by the quantum of energy
absorbed from each photon.
Phosphorescence
Here emission of light occurs for some time
even after light radiation being projected on
a phosphorescence substance, is cut off. For
example, ZnS.

Quantum efficiency (φ)

Number of molecules reacting in a given time

φ= Rack your Brain
Number of quanta absorbed at the same time

y For HCl, φ is high (as both steps are exothermic). How quantum efficiency can be
y For HBr, φ is low (as second step is measured in terms of energy
endothermic). adsorbed by photons?
Chemical Kinetics

22.
 Rate law equation for reactions involving parallel
and side reactions: Definition
Here reactant reacts or decomposes in more
than one way. The reaction in which a substance
reacts or decomposes in more
than one way are called parallel
or side reactions.

Rate = (k1 + k2 ) [A]

Previous Year’s Questions
y Fraction yield of A = k1 /k1 + k2
y Fraction yield of B = k2 /k1 + k2
k1 k2 Activation energy (Ea) and
y Successive reaction: A  → B  →C
rate constants (k1 and k2) of a
Here, rate of disappearance of A = k1 + k2 [A]
chemical reaction at two different
−k 1T
[A]t = [A]0 e temperatures (T1 and T2) are
related by
k 1[A]0 −k 1T −k2T
=[B]t [A]0 (e −e )  [AIPMT]
k2 − k 1 k E  
(1) ln 2   a  1  1 
k1 R  T1 T2 
Modified Arrhenius Equation
d In k E (2) ln k 2   Ea  1  1 
= k1 R  T2 T1 
dT RT2
y The exponential form of the expression for a (3) ln k 2   Ea  1  1 
k1 R  T2 T1 
first order reaction is
k E  
[A] = [A]0 e−kT (4) ln 2  a  1  1 
k1 R  T1 T2 
It is called Wilhelmy’s equation.

Q3 The rate constant of a reaction at 700 K and 760 K are 0.011 M-1 s-1 and 0.105
M-1 s-1 respectively. Calculate the value of Arrhenius parameters.
Chemical Kinetics

Sol. 2.824 × 1010

23.
 Some Important Graphs
Rate Versus Concentration

Integrated Rate Equation

Chemical Kinetics

24.
  1 
Half-lives Versus Concentration  t 1/2 vs n− 1 
 a 

Chemical Kinetics

25.
 Q4 For the reaction R → P, the concentration of a reactant changes from 0.03 M
to 0.02 M in 25 min. Calculate the average rate of reaction using units of time
both in minutes and seconds.

Sol. Average rate  

[R]

[R]2  [R]1

0.02 M  0.03 M

0.01M
t t2  t 1 25 min 25 min

0.01 M
 4  104 mol. L1 min1   6.66  106 mol L1 sec1
25  60 s

Q5 For the reaction 3H2 + N2 → 2NH3, how are the rate of reaction expression
d [H2 ] d [NH3 ]
− and inter-related?
dt dt

Sol. 
1 d [H2 ] 1 d [NH3 ]

3 dt 2 dt

Q6 If the time required to decompose SO2Cl2 to half of its initial amount is 60

minutes and the decomposition is a first-order reaction, then calculate the
rate constant of the reaction.

Sol. For a first-order reaction. k =

0.693
t 1/2

0.693 0.693 0.693

   1.925  104 s1
t 1/2 60 min 60  60 sec

Q7
Chemical Kinetics

For the reaction : 2Fe2+ + H2O2 → 2Fe3+ + 2OH–

the rate of formation of Fe3+ is given by : rate = K[Fe2+][H2O2].
Suggest possible mechanism for the reaction.

26.
Sol. Fe2+ + H2O2 → Fe3+ + OH– + OH (slow)
Fe2+ + OH → Fe3+ + OH– (fast)

Q8 The rate constant for a reaction of zero order A is 0.0030 mol L-1 s-1. How long
will it take for the initial conc. of A to fall from 0.10M to 0.075M?

Sol. For a zero order reaction

K  0.0030 mol L1 s1

[A]0  0.10 M [A]  0.075 M
[A]0  [A]
K
t
0.10  0.075
t  8.33 s
0.0030

Q9 A first order reaction is 75% complete in 60 min. Find the half-life of this
reaction.

Sol. k
2.303
log
a
t a  x 
2.303 100
 log
t 100  75
2.303
 log 4
t
2.303
  0.6
6020  0.0231
60
0.693 0.693
t 1/2    30 min
k 0.0231

Q10 Calculate the factor by which the rate of reaction is increased for a temperature
Chemical Kinetics

rise of 10°C from 25°C to 35°C. The energy of activation is 35 kcal mol-1.

27.
 Sol. Given, Ea = 35 × 103 cal mol-1, R = 1.987 cal, T2 = 308 K, T1 = 298 K

k 2 35  103  308  298 

 2.303 log 10   
k1 1.987  308  298 
k 
or  2   6.812
 k1 
or k 2  6.812  k 1
 r1 k 2 
 r2  6.812  r1   
 r2 k 1 

Q11 For the reaction : C12H22O11  H2O 

H
 C6H12O6  C6H12O6


Write :
(a) Rate of reaction expression
(b) Molecularity

Sol. (a) Rate  

d [C12 H22O11 ]
 
d H2O
dt dt
d [C12 H22O11 ] d [C6 H12O6 ]
 
dt dt
(b) Molecularity = 2

Q12 For the reaction, A → B, the rate of reaction becomes 27 times when the
concentration of A is increased 3 times. What is the order of the reaction?

Sol. r  k A 
n

n
27 r  k 3A 
n
27 r k 3A 
 
r k A 
n
Chemical Kinetics

or 33  3n
 Order off the reaction  3

28.
 Q13 The rate constant for first order reaction is 60/s. How much time will it take to
reduce the concentration of the reaction to 1/10 of its initial value?

Sol. 2.303 R0 

t log
K R 
2.303 R0 
t log  
1 R 
10
2.303
t log 10
60
2.303
t
60
 3.38  102 s1

Q14 The rate constant of a reaction is 1.5 × 10 s-1 at 50°C and 4.5 × 107 sec-1 at
7

100°C. Evaluate the Arrhenius parameter and Ea.

Sol. k 2 Ea  T2  T1 
2.303 log   
k1 R  T1T2 
4.5  107 Ea  373  323 
 2.303 log   
1.5  107
8.314  373  323 
 Ea  2.2  104 J mol 1

Ea /RT
Now, k  A  e
2.2 104
 4.5  10  A  e
7 8.314373

A  5.42  1010 sec1

Q15 For a reaction, Cl   Cl   Cl 2 , the pre-exponential factor is 2 × 1013 sec-1 at

298 K. Calcualte the value of rate constant for the reaction.
Chemical Kinetics

Sol. Ea for free radical combination is zero. Thus,

K  Ae
Ea /RT
if E a
 0
 K  A  2  1013 sec1

29.
 Summary

C1  − C2 
1. Rate of reaction =
t2 − t 1
2. Instantaneous reaction rate is given as

dx 1 d J
=
dt Vj dt
aA + bB  → cC + dD
Rate of reaction
1 d[A] 1 d[B] 1 1 d[D]
= − =− = =
a dt b dt c d dt
3. Activation energy Ea = Threshold energy – Potential energy of reactants
4. Arrehenius equation
−Ea /RT
k = Ae
or
Ea
log
= 10
k log 10 A −
2.303 RT

5. At two different temperatures T1 and T2

2.303 R T1 T2 k2
Ea = log 10
T2 − T1 k1
k2 Ea (T2 − T1 )
log 10 =
k1 2.303 R T1 T2

6. Order of reaction
Rate = k [A]m [B]n
Order = m + n

First-order reaction

dx
− ∝ [A]1
dt
N
Chemical Kinetics

2.303 a
t= log 10 or 0
k a−x N

30.
 2.303 a − x 1 
k= log 10
t2 − t 1 a − x2 
2.303 r −r
t= log 0 ∞
t2 t 1
− rt − r∞

Second-order reaction
When concentrations are different
2.303 b (a − x)
k= log 10
t (a − b) a (b− x)

Half-life method
n− 1
(t 1/2 )1 a 
=  2
(t 1/2 )2  a 1 
log (t 1/2 )1 − log (t 1/2 )2
n= 1 +
log a2  − log a 1 

Van’t Hoff differential method

 − d C    
log   1   − log  − d C2  
 dt   dt 
n=    
log C1  − log C2 

Pseudo-unimolecular reactions
2.303 V − V0
k= log ∞
t V∞ − Vt

Here V∞ = Volume at infinity

V0 = Initial volume
Vt = Volume at t time
7. Modified arrhenius equation
d In k E
=
dT RT2
8. Quantum efficiency
Number of molecules in a given time
Chemical Kinetics

φ=
Number of quanta absorbed at the same time

31.