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Chemical Kinetics-II
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Order of Reaction
The rate of a given chemical reaction at constant temperature depends on the product of
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the concentration terms of the reactants. The equation representing the rate of reaction is
called rate law. The sum of the powers of the concentration terms in the rate equation is
called order of the reaction.
For a general reaction, aA + bB products, if the rate equation is given as, Rate = k [A]x
[B]y.
The order with respect to reactant A is x, with respect to reactant B is y and the
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overall order of the reaction is (x+y). Here the stoichiometric coefficients of the reactants
a and b mayor may not be equal to x and y.
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Order of the reaction may be zero, a finite number or fractional. Accordingly reactions
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are classified as zero, first, second, third, etc., or in general nth order reaction.
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Zero order: Reaction in which rate of the reaction is independent of the concentration of
the reaction substances is called zero order reaction. Starting from an initial concentration
of reactant is [R]0 = a, if x is the concentration transformed in a time interval of t,
the concentration of the reactant after time t is [R] t = (a x).
Rate
dC d (a x )
k ( a x) 0 k
dt
dt
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Half life t1/2=a/2k
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E.g 1. H 2 g Cl2 g
2HCI g
M0
2NH3 g
N2 g 3H2 g
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2.
Au
2HI
H 2 I2
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3.
rate =
rate constant
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slope = k
(a-x)
Rate
Time
Time
First order: Reaction in which rate of the reaction is directly proportional to the single
concentration term of the reacting substance is called first order reaction.
1
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A Products, r k1 A
dx
k1 a x
dt
2.
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1.
2.303
a
log
t
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sec-1
4.
5.
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3.
0.693
k1
A g B g C g
Pi be the initial pressure of A and Pt the total pressure of the reaction mixture at
time t then
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k
pi
2.303
log
t
2pi p t
Examples
1
N2 O5 g N 2 O4 g O2 g
2
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H
CH 3COOH C2 H 5OH
CH 3COOC2 H 5 H 2 O
ln a
ln
(a-x)
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slope = k
ks
ln (a-x)
Time
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a
Time
slope = k
#In a First order reaction both Rate constant & half life are independent of initial
concentration of reactants.
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# The time taken for completion of given fraction of first order reaction is always
constant.
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iv. 99% of 1st order =20/3 t1/2
v. 99.9% of 1st order =10 t1/2
Second Order Reactions
2A products
2
or r k2 A B
1.
2.
lit. mole-1.sec-1
1
k2 a
Examples
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r k 2 A
A + B products
or
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3.
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4) 2HI H 2 I 2
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r = K3[A]2[B]1
(or)
A+B+C products
r = K3[A]1[B]1[C]1
1
a2
Examples
1.
2 NO O2 2 NO2
2.
2 NO Cl2 2 NOCl
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3.
H2 Br2 2HBr
K O3 O 2
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Rate =
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The reactions with molecularity greater than or equal to 2 but order is one are called
Pseudo unimolecular or Pseudo first order reactions.
E.g.: 1. Hydrolysis of ethyl acetate in acid medium
2. Inversion of cane sugar
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molecularity
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1. The number of atoms or molecules or ions participating in the slowest step is called
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mechanism.
5. The slowest elementary step of the reaction is called rate determining step or rate
limiting step.
6. The probability that more than three molecules can collide and react
simultaneously is very small. Hence, the molecularity greater than three is not
observed.
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Eg: 1.
2.
4.
5.
2NO O2 2NO 2
with order 2.
H
CH 3COOH C2 H 5OH , Bimolecular with order 1.
CH 3COOC2 H 5 H 2 O
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3.
2HI H2 I 2 , Bimolecular
order 1.
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It is also called trial and error method. The kinetic data is substituted in one of the
integrated rate laws and the specific rates are calculated. If the same value of k is
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obtained from the data of a reaction, the trail of choosing the rate law is successful and
the corresponding order is obtained.
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Order of reaction
Zero order
dC/dt =K
First order
- dC/dt =K[a-x]
Second order
- dC/dt =K[a-x]2
x
t
2.303
a
log
t
ax
1
x
t a (a x)
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Alternately, the order can also be ascertained graphically interpreting the results in terms
of integrated rate law.
x vs time is a straight line parallel to time axis denotes zero order.
ii.
log [a/(a x)] vs time is a straight line with a positive slope passing through
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[x/a (a x)]vs time is a straight line with a positive slope passing through origin
Zero order
log
Time
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Time
second order
second order
first order
x
a a x
log
Time
ba x
a b x
Time
2. Half-time method: The time required for the initial concentration (a) of the reactant to
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become one-half of its value (a/2) during the progress of the reaction is called half-time
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Products, t1/2
1
a
n 1
(or ) t1/2 a1 n
nA
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a
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Say a given reaction is started separately with two initial concentrations a 1, and
a2. The half - time values (t1/2)1 and (t1/2)2 are determined experimentally and the
order is established from the equation.
(t1/2 )1
a
2
(t1/2 ) 2 a1
n 1
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3. Differential method: The rate of a reaction of order n is given for two initial
concentrations, C1 and C2 as
dC1
dC
kC1n and 2 kC2n
dt
dt
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dC
dC
log 1 log 2
dt
dt
n
log C1 log C2
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4. Ostwalds isolation method: The isolation method is useful for the determination of
order with respect to each of the reactant separately.
X + Y Products
By applying Ostwalds method, the order nx with respect to the reactant X and ny
with respect to reactant Y are separately determined.
For the purpose of determining orders, two experiments are conducted. In one
experiment, concentration of Y is taken in large excess compared to that of X. Order, n x
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above.
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#) Concentration Vs time:
X-axis
Y-axis
i) Zero
time
ii) 1st
time
log C
iii) nth
time
1/C
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Order
Nature of graph
origin
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#)
X-axis
Y-axis
Nature of graph
t1/2
ii) 1st
t1/2
iii) 2nd
t1/2
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i) Zero
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