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11.

1
RATE LAW
Objectives:

At the end of the lesson the students should be able


to:
1. define rate law and write the rate equation
2. define the order of reaction and the rate constant
3. calculate the order with respect to a certain reactant
from experimental data
4. determine the overall order of a reaction from
experimental data
5. calculate the value and determine the units of
rate constants
The Rate Law
The rate law expresses the relationship of the rate of a
reaction to the rate constant and the concentrations of
the reactants raised to some powers.
aA + bB cC + dD

Rate α [reactant]
Rate = k [A]x[B]y
reaction order is x with respect to A
reaction order is y with respect to B
Overall reaction order is (x + y)
The exponents x, y, … can be integers,
fractions or decimal or negative values.

k is called rate constant


Rate Law
• The values of x and y can only be determined
experimentally.
• Reaction order is usually defined in terms of
reactant concentrations.
• The order of a reactant is not related to the stoichiometric
coefficients of the reactants in the balanced chemical
equation.

F2 (g) + 2ClO2 (g) 2FClO2 (g)

rate = k [F2][ClO2] 1
The units of rate
constant, k
A Products

Rate, r = k [A]x

i) The reaction is zero order

Rate = k [A]0

Rate = k

unit k =unit rate


= mol L-1 s-1 or M s-1
ii) First order rate
Rate = k [A]1 k=
[A]

M s-1
Unit k =
M

= s-1
iii) Second order
Rate = k [A]2
rate
k=
[A]2
M s-1
Unit k = = M-1 s-1
M2
Example :
S2O82- + 3I- 2SO42- + I3-

The above reaction is first order with respect to iodide ions


to thiosulphate ions.
a) Write the rate of equation for the reaction.
b) What is the unit of rate constant, k?
Solution :
a) Rate = k [S2O82- ]1[I-]1

b) Rate = k [S2O82- ]1[I-]1


k= rate Ms-1
Unit k = = M-1 s-1
[S2O82- ]1[I-]1 M2
The order of
reaction
For reaction

A Products

Rate = k [A]x
i) If x = 0
Rate = k [A]0

Rate = k
Rate is not dependent on [A]

Therefore this reaction is zero order with respect to A


ii) If x= 1
Rate = k [A]1
Assume [A]i = 1.0M

Rate = k (1.0M)

If the [A] is doubled from 1.0M to 2.0M,

Rate = k (2.0M)

= 2k(1.0M)
hence
Rate = 2k[A]
Doubling the [A] will double the rate of reaction.

Therefore this reaction is first order with respect to A


iii) If x = 2
Rate = k[A]2

Assume [A]i = 1.0 M

Rate = k (1.0 M)2

If the [A] is doubled from 1.0 M to 2.0 M,


Rate = k (2.0 M)2

= 4k(1.0 M)
hence
Rate = 4k[A]
Doubling [A], the rate will increase by a factor of 4.
Therefore the reaction is second order with respect to
Example

Determining Reaction Order from Rate Law

For each of the following reactions, determine the


reaction order with respect to each reactant and the
overall order from the given rate law.

(a) 2NO(g) + O2(g) 2NO2(g); rate = k[NO]2[O2]

The reaction order respect to NO : 2


The reaction order respect to O2 : 1
overall reaction order = 3
(b) CH3CHO (g) CH4(g) + CO(g);
rate = k[CH3CHO]3/2
Solution:
The reaction order with respect to CH3CHO : 3/2
The reaction order (overall) : 3/2
(c) H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq) + 2H2O(l);
rate = k[H2O2][I-]
Solution:
The reaction of order with respect to H2O2 : 1
The reaction of order with respect to I- : 1
and zero order in H+, while overall order is 2.
Determination of the orders of reaction rate;

O2(g) + 2NO(g) 2NO2(g)

Initial Reactant
Concentrations (molL-1 ) Initial Rate
Experiment (M s-1 )
O2 NO

1 1.10x10-2 1.30x10-2 3.21x10-3

2 2.20x10-2 1.30x10-2 6.40x10-3

3 1.10x10-2 2.60x10-2 12.8x10-3

4 3.30x10-2 1.30x10-2 9.60x10-3

5 1.10x10-2 3.90x10-2 28.8x10-3


Solution:
O2(g) + 2NO(g) 2NO2(g)

rate = k [O2]m[NO]n

Compare 2 experiments in which the concentration of one


reactant varies and the concentration of the other
reactant(s) remains constant.
rate2 k [O2]2m[NO]2n [O2]2m m
[O2]2
rate1 = = =
k [O2]1m[NO]1n [O2]1m [O2]1

6.40x10-3 Ms-1 2.20x10-2 mol/L m


=
3.21x10-3 Ms-1 1.10x10-2 mol/L
;
2 = 2m ,m=1
The reaction is first order with respect to O2
Do a similar calculation for the other reactant(s).
To find the order with respect to NO, we
compare experiment 3 and 1, in which [O2] is
held constant and [NO] is doubled:
n
Rate 3 k [O ]
2 3
m
[NO] 3
n
[NO] 3
= =
Rate 1 k [O2]1m [NO]1n [NO]1
n
12.8 x 10 Ms-3 -1
2.60 x 10-2 mol/L
=
3.21 x 10 Ms-3 -1
1.30 x 10-2 mol/L
4 = 2n ; n = 2

The reaction is second order with respect to NO


Thus the rate law is :

Rate = k[O2][NO]2
Exercise:
ClO2(aq) + 2OH- (aq) → products
The results of the kinetic studies are given below.
exp [ClO2] [OH-] Initial rate,
M M Ms-1
1 0.0421 0.0185 8.21 × 1 0-3
2 0.0522 0.0185 1.26 × 1 0-2
3 0.0421 0.0285 1.26 × 1 0-2

a) Explain what is meant by the order of reaction.


b) Reffering to the data determine
(i) rate law /rate equation
(ii) rate constant, k
(iii) the reaction rate if the concentration of both ClO2
and OH- = 0.05 M
Exercise:
Write rate law for this equation,
A + B → C
i) When [A] is doubled, rate also doubles. But
doubling the [B] has no effect on rate.
ii) When [A] is increased 3x, rate increases 3x,
and increasing of [B] 3x causes the rate to
increase 9x.
iii) Reducing [A] by half has no effect on the rate,
but reducing [B] by half causes the rate to be
half the value of the initial rate.
Exercise:
Many gaseous reactions occur in a car engine and exhaust
system. One of the gas reaction is given below.
NO2(g) + CO(g) NO(g) + CO2(g)
Rate = k [NO2]m[CO]n
Use the following data to determine the individual and overall reaction orders:

Experiment Initial Rate(Ms-1 ) Initial [NO2](M) Initial [CO](M)

0.0050 0.10 0.10


1

2 0.080 0.40 0.10

3 0.0050 0.10 0.20