11.

1 R E A C T I O N R AT E

C H E M I S T RY U N I T
SK027
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OBJECTIVES:

1. define rate laws, order of reaction and

rate constant
2. write the rate law / rate equation
3. calculate the order with respect to a
certain reactant and the overall order of
a reaction from experimental data.
4. calculate the value and determine the
units of rate constants, k.
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THE RATE LAW

The rate law for a chemical reaction relates the
rate of reaction to the concentrations of reactants.

At constant T & P, rate of chemical reaction
directly proportional to [reactants].
Rate ∝ [reactants]
Consider this equation, k = rate constant
aA + bB → cC m = reaction order with
respect to A
Rate ∝ [A]m [B]n
n = reaction order wrt B
Rate = k [A]m[B]n m + n= overall rxn order
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The exponents in a rate law / reaction order

must be determined by experiment.
They are not derived from the stoichiometric
coefficients in an overall chemical equation.
They are generally small, positive integers
(0,1,2…).

The rate constant, k and its value depends on

specific rxn, T & the presence of catalyst.
The larger k, the faster the reaction proceeds.
Units of k depend on the values of m, n, …

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Example 1:
Determining Reaction Order from Rate Laws
2NO(g) + O2(g) 2NO2(g)

rate = k [NO]2 [O2]

Solution:
The reaction order with respect to NO = 2
The reaction order with respect to O2 = 1
The overall reaction order = 3

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Example 2 :
S2O82- + 3I- 2SO42- + I3-
The above reaction is first order with respect to Iodide ion and
to thiosulphate ion.
a) Write the rate 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
= = M-1s-1
[S2O82-]1[I-]1 M2
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Determine rate law: Method Of Initial Rates

• The method of initial rates involves a series of
expt in which the initial [ ] of some reactants are
held constant and others are varied in order to
determine the rate law for that reaction.
• The effects of doubling one initial concentration:
– For zero-order reactions, no effect on rate.
– For first-order reactions, the rate doubles.
– For second-order reactions, the rate quadruples.
– For third-order reactions, the rate increases
eightfold.
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Method Of Initial Rates

Initial Rates of the Reaction:

2NO(g) + Cl2(g) → 2NOCl(g)

Exp. Initial [NO] Initial [Cl2] Initial rate, Ms-1

1 0.0125 0.0255 2.27 × 10-5
2 0.0125 0.0510 4.55 × 10-5
3 0.0250 0.0255 9.08 × 10-5

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Method Of Initial Rates (continue..)

2NO(g) + Cl2(g) → 2NOCl(g)
The rate law in general is; Rate = k [NO]m [Cl2]n
Compare 2 experiments, of [one reactant] varies and the
[ other reactant] constant.
m n
rate exp2 k[NO]exp2 [Cl 2 ]exp2
= m n
rate exp1 k[NO]exp1 [Cl 2 ]exp1
m n
4.55 ×10 -5 k(0.0125) (0.0510)
= m n
2.27 ×10 -5
k(0.0125) (0.0255)
2 = 2n Thus, n, order of rxn wrt Cl2 = 1
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Method Of Initial Rates (continue..)

m n
rate exp3 k[NO]exp3 [Cl 2 ]exp3
= m n
rate exp1 k[NO]exp1 [Cl 2 ]exp1

9.08 ×10 −5 k(0.0250) m (0.0255) n

−5
= m n
2.27 ×10 k(0.0125) (0.0255)
4 = 2m
Thus, m, order of rxn wrt NO = 2
Thus, rate law is Rate = k [NO]2 [Cl2]
Overall order of reaction = m + n = 2 + 1 = 3
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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]
Thus, this reaction is zero order with respect to A
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The order of reaction

A Products
Rate = k [A]x
ii) If x = 1 Rate = k [A]1
If the [A] is doubled, A 2A
Rate = k[2A]1
Rate = 2k[A]1
Double the [A] will double the rate of reaction.
Thus, this reaction is first order with respect to A
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The order of reaction

A Products
Rate = k [A]x
iii) If x = 2 Rate = k[A]2
If the [A] is doubled, A 2A
Rate = k[2A]2
Rate = 4k[A]2
Doubling the [A], the rate increase by a factor of 4.
Thus, the reaction is second order with respect to A
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Exercise: ClO2(aq) + 2OH- (aq) → products

The results of the kinetic studies are given below.
exp [ClO2] / M [OH-] / M Initial rate / Ms-1

1 0.0421 0.0185 8.21 ×10-3

2 0.0522 0.0185 1.26 ×10-2
3 0.0421 0.0285 1.26 ×10-2
a) Explain what is meant by the order of reaction
b) Referring to the data determine
(i) rate law /rate equation rate = k [ClO2]2[OH-]
(ii) rate constant, k k = 250 M-2s-1
(iii) the reaction rate if the concentration of both ClO2
and OH- = 0.05 M rate = 3.12 ×10-2 M/s
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Exercise:
Write rate law for this equation,
A + B → C
i) When [A] is double, rate also double. But double the
[B] has no effect on rate.
Rate = k[A]
ii) When [A] is increase 3x, rate increases 3x, and
increase of [B] 3x causes the rate to increase 9x.
Rate = k[A] [B]2
iii) Reduce [A] by half has no effect on the rate, but
reduce [B] by half causing the rate to be half of the
initial rate. Rate = k[B]

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Exercise: C + D → E
The results of the kinetic studies are given below.
exp Initial [ ] (M) Time The change in
interval concentration
[C] [D]
(Min) of C (M)
1 0.10 1.0 30 2.5 ×10-3
2 0.10 2.0 30 1.0 ×10-2
3 0.05 1.0 120 5.0 ×10-3
a) Calculate the rate of reaction for each experiment
8.33 ×10-5 ,3.33 × 10-4, 4.17×10-5 M min-1
a) Determine the order of reaction with respect to C
and D and write the rate law. rate = k [C] [D]2
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Exercise: C + D → E
The results of the kinetic studies are given below.
exp Initial [ ] (M) Time The change in
interval concentration
[C] [D]
(Min) of C (M)
1 0.10 1.0 30 2.5 ×10-3
2 0.10 2.0 30 1.0 ×10-2
3 0.05 1.0 120 5.0 ×10-3

c) State the effect on the reaction rate if the

concentration of D is doubled but the concentration
of C remains constant. rate increase by a factor of 4;
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