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Aditya vardhan
Chemical kinetics 1 adichemadi @ gmail.com
CHEMICAL KINETICS
Chemical kinetics deals with
1) Study of rates of reactions
2) Factors affecting rate of reaction
3) Study of mechanisms of reactions
Rate of reaction : The rate of reaction is defined as the change in molar concentration of either
reactants or products in unit time.
change in concentration
rate r =
time interval
Let ‘dc’ is the decrease in concentration of reactants in a small interval of time ‘dt’ then
dc
r=- ( negative sign indicates decrease in concentration )
dt
If ‘dx’ is the increase in concentration of products in a small interval of time ‘dt’ then
N
HA
dx
r= ( positive sign indicates increase in concentration )
dt
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E.g., For a reaction, A
B RD
EG
by
d A d B
rate r
LL
ed
dt dt
VA
AL O
ar
G C
In general for a reaction, pP + qQ rR + sS
ep
AN IOR
the relations between rates of reaction with respect to P,Q,R and S can be written as
Pr
YA
1 d P 1 d Q 1 d R 1 d S
AR N
- =- =+ =+
W U
p dt q dt r dt s dt
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AG T
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d N2 1 d H2 1 d NH 3
- -
dt 3 dt 2 dt
VA
V.
concentration of reactants
N
HA
E
RDTime
EG
by
LL
ed
3) Temperature : The average kinetic energy and hence the number of collisions increase with abso-
VA
AL O
ar
Usually the rate of a reaction is doubled when the temperature is increased by 10oC.
AN IOR
Pr
Temperature Coefficient : The ratio of rate constants of a reaction at two different temperatures
YA
k t +10o C
AG T
VI
k t oC
DE
AD
The relation between rate constant and temperature can be shown by Arrhenius equation.
k = A.e-Ea/RT
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V.
log A
Ea
slope = -
2.303 R
log k
1
T
Relation between two rate constants at two different temperatures can be given as
k2 Ea 1 1
log = -
k1 2.303R T1 T2
N
k2 E a T2 -T1
HA
or log =
k1 2.303R T1T2
E
RD
EG
4) Catalyst: Catalyst is a substance which alters the rate of reaction without being consumed or without
by
A catalyst increases the rate of reaction by providing a new path with lower activation energy for the
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AL O
ar
reaction. In case of reversible reactions, catalyst lowers the activation energies of both forward and
G C
ep
backward reaction to the same extent and helps in attaining the equilibrium quickly.
AN IOR
Pr
YA
AR N
W U
without catalyst
Potential energy
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AG T
VI
in presence of catalyst
I
DE
AD
VA
V.
Reaction coordinate
Problems :
1) Write the relations between the rates with respect to reactants & products in the following reaction.
2N2O 2N2 + O2
Rate Equation or Rate Expression or Rate Law: Equation that describes mathematical dependance
of rate of reaction on the concentration terms of the reactants is called Rate Equation.
Order of reaction :Sum of the powers of the concentration terms in the rate equation is called order
of reaction.
For a general reaction, xA + yB + zC products.
Prepared by V. Aditya vardhan
Chemical kinetics 4 adichemadi @ gmail.com
x y z
if the rate expression is r = k A B C
Then the order of this reaction is equal to x + y + z
Note: Order of a reaction is to be determined experimentally. It may have positive or negative or zero
or a fractional values.
In case of simple reactions, the order of reaction and hence the rate equation can be written
according to stoichiometric equation. But the actual rate law should be written by conducting experi-
ments.
Depending on the order of reaction, chemical reactions can be divided into zero, first, second &
third order reactions as follows.
N
r = k[N2]0[H2]0
HA
First order reaction: Total order of the reaction is one.
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Examples: RD
EG
by
r = k[N2O5]
G C
ep
SO2Cl2 SO2+Cl2
YA
AR N
r = k [ SO2Cl2]
W U J
r = k[H2O2]
4) All radioactive disintegrations
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V.
Rate constant (k): The rate of a reaction at the unit concentrations of all the reactants of the reaction is
called specific rate (or) rate constant.
rate = k when [reactants] = 1
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k= x
dt A n
HA
mole / litre 1
Units of k = x n
sec mole / litre
E
RD
EG
by
1-n
mole / litre
LL
ed
=
VA
AL O
ar
sec
G C
ep
= Ln-1 .mole
- n-1
.sec-1
AN IOR
Pr
YA
-1 -1
For zero order reaction mole .L sec
Molecularity
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Elementary reactions: The chemical reactions which occur in one single step are called elementary
reactions.
But most of the reactions occur in more than one step. The sequence of elementary steps that occur
during a reaction is referred to as mechanism of that reaction.
Rate determining step: The elementary step or reaction with slowest rate is called rate determining step
or rate limiting step. The rate of overall reaction depends on this step.
Molecularity: Total number of atoms or molecules or ions taking part in an elementary reaction is called
molecularity of that elementary reaction (or step).
It is only possible to define the molecularity of an elementary step. But the molecularity of the overall
reaction which involves more than one step cannot be defined.
Molecularity is an integer. It cannot be zero or fractional. The maximum value observed is 3. It can be
deduced theoretically from the proposed mechanism
Prepared by V. Aditya vardhan
Chemical kinetics 6 adichemadi @ gmail.com
Differences between Order and Molecularity
Order Molecularity
1) Sum of the powers of concentration terms 1) Total number of atoms or molecules or
in rate expression is called order. ions taking part in an elementary reaction is
called molecularity
2) It may have zero or positive or negative or 2) It can only have integral values (1,2 or 3).
integer or fractional values. Its value cannot be zero or fractional.
3) It is determined experimentally 3) It is deduced theoretically from the
mechanism of the reaction.
N
dc dx
HA
- = =kco
dt dt
dx
E
o
or =k a-x k RD
EG
by
dt
LL
ed
or dx = k dt
VA
AL O
ar
G C
or x = kt
ep
AN IOR
Pr
x
YA
or k=
t
AR N
W U
N
Where a = initial concentration of reactant
HA
x = concentration reacted in an interval of time 't'
(a-x) = concentration of reactant after time 't'
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RD
EG
by
Half life (t1/2) of a reaction :The time required for initial concentration of reactants to become half is
LL
ed
G C
ep
a
a-x = a-
W U
Then = a/2
2
J
AG T
VI
2.303 a 2.303
log2 = 2.303 x 0.3010 ( log2 = 03010)
I
DE
k= log t
AD
0.693
V.
or t1/2
k
N
HA
x
E
RD t
EG
by
LL
ed
a
VA
For a first order reaction, the graph of log
AL O
versus 't' should be a straight line with positive slope
ar
a-x
G C
ep
a
AG T
VI
log
a-x
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AD
t
VA
V.
x
For a second order reaction, the graph of a a-x vs 't' must be a straight line passing through the
x OR b(a-x)
a(a-x) log
a(b-x)
t t
is inversely proportional to a
Half life t 1
2
n-1
Prepared by V. Aditya vardhan
Chemical kinetics 9 adichemadi @ gmail.com
1
t1
2 a n -1
where a = initial concentration
n = order
The order 'n' of a reaction can be calculated by comparing two half lives - t 1 & t 1 with initial
2 2
N
dt dt
HA
For two initial concentrations c1,c2, we have
dc1 dc 2
- =kc1n ; - =kc n2
E
dt dt RD
EG
by
dc
LL
log - 1 log k + nlogc1
ed
dt
VA
AL O
ar
G C
ep
dc
AN IOR
dt
YA
AR N
W U
dc dc
log - 1 - log - 2 n log c1 nlogc 2 n log c1 logc 2
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or
AG T
dt dt
VI
I
DE
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dc dc
log - 1 - log - 2
n dt dt
VA
log c1 logc2
V.
For two different initial concentrations c1 and c2, the rates are determined at any given time from c-t graph.
These are substituted in the above equation and 'n' is calculated.
concentration of reactants
concentration of reactants
c1
c2
N
6) The collisions taking place between activated molecules are called activated collisions. The reaction
occurs only during the activated collisions.
HA
Activated molecules constitute a small fraction of total molecules. Similarly activated collisions consti-
tute small fraction of total collisions. Hence all the chemical reactions do not occur in fraction of second.
E
RD
EG
A+A A* + A
by
A* + A* products
LL
ed
VA
AL O
ar
G C
AN IOR
A* = Activated molecule
Pr
YA
8 kT
J
2
Z AB .n A .n B
AG T
VI
I
DE
AD
8) The relation between specific rate (k), temperature (T) and activation energy Ea can be given as follows
k = A.e -Ea /RT
or
k = p.Z.e-Ea /RT
where p = probability factor
The concept of activation energies of both forward and backward reactions (Ea and Ea') can be
shown graphically as follows.
Prepared by V. Aditya vardhan
Chemical kinetics 11 adichemadi @ gmail.com
Energy barrier
ET
Ea E1a
ET
ER
H
Ep
N
H = Enthalpy of reaction
HA
Problems :
1) The rate constant of a first order reaction is 1.386 sec-1. What is it's half life.
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RD
2) The initial concentration of A is 0.5 moles/litre. If the concentration becomes 0.25 mole/litre in 5 sec.
EG
by
AN IOR
Pr
1) The rate of a reaction increases with time as the concentration of reactants decreases.
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AG T
3) The units of rate constants for the following reaction are (L / mol /sec).
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AD
5) The rate of consumption of hydrogen gas is thrice of formation of Ammonia in the following reaction.
V.