2

1. The Rate of a Reaction

2. The Rate Law
3. The Relation Between Reactant Concentration
and Time
4. Reaction Mechanisms
 [Link] Rate of a Reaction 3
Chemical Kinetics is the area of chemistry concerned with the speeds,
or rates, at which a chemical reaction occurs.
“Kinetic” suggests movement or change. Kinetics also refers to the rate
of a reaction or reaction rate.
Reaction rate is the change in the concentration of a reactant or
product with time *(M/s)

•E
Knowledge of reaction rates is important is processes such as: 4
[Link] steps in vision
[Link]
1,2,3 take place on a timescale
[Link] chain reactions
as short as 10−12 to 10−6

4. Curing of cement and conversion of graphite to diamond takes

years to complete
5. Useful in drug design, pollution control and in food processing
 Reactants products 5

• During the course of a reaction, reactants are consumed while

products are formed
• As a result we can follow the progress of a reaction by monitoring
either the decrease in concentration of the reactants or the increase in
concentration of the products
 6

Rates of reactions can be determined by monitoring the

change in concentration of either reactants or products
as a function of time t.
[A] = concentration of reactant A
• For the reaction A  B there are two ways of measuring rate: 7

(1) the speed at which the reactants disappear

(2) the speed at which the products appear
• Reactions are reversible, so as products accumulate they can begin to
turn back into reactants.
• Early on the rate will depend on only the amount of reactants
present. We want to measure the reactants as soon as they are
mixed.
• The most useful (and general) way of measuring the rate of the
reaction is in terms of change in concentration per unit time…
•
Most Common Units… Rate = M/s
Where Molarity (M) = moles/Liter
 Chemical Kinetics

Thermodynamics – does a reaction take place?

Kinetics – how fast does a reaction proceed?
A B

D[A]
rate = - D[A] = change in concentration of A over
Dt time period Dt

D[B] D[B] = change in concentration of B over

rate = time period Dt
Dt
Because [A] decreases with time, D[A] is negative.

8
Eng. Dorothy Maina Kenyatta University
The rate of a reaction is a positive quantity, so a minus sign is 9
needed in the rate expression to make the rate positive.
On the other hand, the rate of product formation does not
require a minus sign because the ∆[B] is a positive quantity (the
concentration of B increases with time)
 Reaction rates and stoichiometry
Consider the reaction:
2𝐴 → 𝐵
2 moles of A disappear for each mole of B that forms−that is,
the rate of disappearance of A is twice as fast as the rate of
appearance of B

1∆ 𝐴 ∆𝐵
𝑟𝑎𝑡𝑒 = − 𝑜𝑟 𝑟𝑎𝑡𝑒 =
2 ∆𝑡 ∆𝑡

10
In general, for the reaction

𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷

The rate is given by

1∆ 𝐴 1∆ 𝐵 1∆ 𝐶 1∆ 𝐷
𝑟𝑎𝑡𝑒 = − =− = =
𝑎 ∆𝑡 𝑏 ∆𝑡 𝑐 ∆𝑡 𝑑 ∆𝑡

11
Example
Write the rate expressions for the following reactions in
terms of the disappearance of the reactants and
appearance of the products

a)𝐼 −
𝑎𝑞 + 𝑂𝐶𝑙 −
𝑎𝑞 → 𝐶𝑙 −
𝑎𝑞 + 𝑂𝐼 −
𝑎𝑞

b)3𝑂2 𝑔 → 2𝑂3 𝑔

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(a) Because Stoichiometric coefficients equals 1

13
Example
4𝑁𝑂2 𝑔 + 𝑂2 𝑔 → 2𝑁2 𝑂5 𝑔

Suppose that, at a particular moment during the above reaction,

molecular oxygen is reacting at the rate of 0.024M/𝑠 .
a)At what rate is 2𝑁2 𝑂5 𝑔 being formed?
b)At what rate is 𝑁𝑂2 𝑔 reacting?

Strategy
We need to express the rate of reaction in terms of the
stoichiometric coefficients

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15
The Rate Law
 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..
• The overall concentration dependence of reaction rate is given in a rate law or rate
expression.
• Here’s what a general rate law for a reaction will look like…

𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷

Rate = k [A]m [B]n

- [A] & [B] represent the reactants.
- The exponents m and n are called “reaction orders”.
- The proportionality constant k is called the rate constant.
- The overall reaction order is the sum of the reaction orders:
m+n
• Reaction order is defined as the sum of the powers to
which all reactant concentrations appearing in the rate law
are raised.

• Alternatively we say that

Rate = k [A]m[B]n
reaction is mth order in A

reaction is nth order in B

reaction is (m+n)th order overall

 Rate Laws

• Rate laws are always determined experimentally.

• Reaction order is always defined in terms of reactant

(not product) concentrations.

• The order of a reactant is not related to the

stoichiometric coefficient of the reactant in the balanced
chemical equation.

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

rate = k [F2][ClO2] 1
 how to determine Rate law of a reaction
• Consider reaction between fluorine and chlorine dioxide
𝐹2(𝑔) + 2𝐶𝑙𝑂2(𝑔) → 2𝐹𝐶𝑙𝑂2(𝑔)
Determine how the initial rate depends on the starting
concentrations
WHY initial rate?
1. As the reaction proceeds, the concentrations of the reactants
decrease and accuracy in measurement would reduce
[Link] may be a reverse reaction of the type which would
introduce an error in rate measurement
Products reactants
Both 1 and 2 complications are absent during the early stages of
the reaction
• Looking at entries 1 and 3, we see that as we double
[𝐹2 ] 𝑤ℎ𝑖𝑙𝑒 ℎ𝑜𝑙𝑑𝑖𝑛𝑔 [𝐶𝑙𝑂2 ] constant, the reaction rate doubles
• Thus the rate is directly proportional to [𝐹2 ]
• Data in entries 1 & 2 show that as we quadruple [𝐶𝑙𝑂2 ] at constant
[𝐹2 ] , the rate increases by four times, so that the rate is also directly
proportional to [𝐶𝑙𝑂2 ]
• The rate law is summarized as:
𝑟𝑎𝑡𝑒 = 𝑘 𝐹2 [𝐶𝑙𝑂2 ]
Because both 𝐹2 𝑎𝑛𝑑 [𝐶𝑙𝑂2 ] are raised to the first power, the reaction is
first order in 𝐹2 , first order in 𝐶𝑙𝑂2 and (1+1) or second order overall.
Note that [𝐶𝑙𝑂2 ] is raised to the power of 1 whereas its stoichiometric
coefficient in the overall equation is 2.
The equality of reaction order (1st) and stoichiometric coeff, (1) for 𝐹2
is coincidental in this case.
We can calculate the rate constant form the reactant concentrations
and initial rate
𝑟𝑎𝑡𝑒 1.2𝑥10−3 𝑀/𝑠
𝑘= = =1.2/M.s
𝐹2 [𝐶𝑙𝑂2 ] (0.10𝑀)(0.010𝑀)
• Suppose for the general equation
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
We have m=1 and n=2. The rate law for the reaction is:
𝑟𝑎𝑡𝑒 = 𝑘 𝐴 [𝐵]2
• This reaction is first order in A, second order in B, and third overall (1+2=3)
• Let us assume that initially [A]=1.0M and [B]=1.0M
• Therate law tells that if we double the conc. of A from 1.0M to 2.0M at
constant [B], we also double the reaction rate:
For [A]=1.0M 𝑟𝑎𝑡𝑒1 = 𝑘(1.0𝑀)(1.0𝑀)2
=k(1.0𝑀3 )
Hence rat𝑒2 = 2(𝑟𝑎𝑡𝑒1 )

For [A]=2.0M 𝑟𝑎𝑡𝑒1 = 𝑘(2.0𝑀)(1.0𝑀)2

=k(2.0𝑀3 )
Example
The reaction of nitric oxide with hydrogen at 1280°C is
2𝑁𝑂(𝑔) + 2𝐻2 (𝑔) → 𝑁2 (𝑔) + 2𝐻2 𝑂(𝑔)

From the following data:

Experiment [NO] (M) [𝑯𝟐 ] (M) Initial Rate (M/s)
1 5.0 x10 3 2.0 x10 3 1.3 x10 5
2 10.0 x103 2.0 x10 3
5.0 x10 5
3
3 4.0 x10 10.0 x105
Determine:
a) The rate law
b) The rate constant
c) the rate of the reaction when [NO]=12.0x10−3 𝑀 𝑎𝑛𝑑 𝐻2 = 6.0𝑥10−3 𝑀
Hint:
• We assume the rate law takes the form Rate = k [NO]x [𝐻2 ]y
• Once the orders of the reactants are known, we can calculate k from
any set of rate and concentrations
• Finallythe rate law enables us to calculate the rate at any
concentrations of NO and 𝐻2
Solution
a) Experiments 1 & 2 show that when we double the concentration of
NO at constant 𝐻2 , the rate quadruples.

Experiment [NO] (M) [𝑯𝟐 ] (M) Initial Rate (M/s)

1 5.0 x10 3
2.0 x10 3
1.3 x10 5
2 10.0 x103 2.0 x10 3 10.0 x105
• Taking the ratio of the rates from these 2 experiments:
b)The rate constant k can be calculated using the data from any one of the
experiments. Rearranging the rate law, we get
rate
k
[ NO]2 [ H 2 ]
The relationship between Reactant Concentration and Time
Half-Life
• Half-life is defined
as the time required
for one-half of a
reactant to react.
• Because [A] at t1/2 is
one-half of the
original [A],
[A]t = 0.5 [A]0.

Chemical
Kinetics
 Half-Life
For a first-order process, set [A]t=0.5 [A]0 in
integrated rate equation:

NOTE: For a first-order

process, the half-life
Chemical
does not depend on [A]0. Kinetics
 Half-Life- 2nd order
For a second-order process, set
[A]t=0.5 [A]0 in 2nd order equation.

Chemical
Kinetics
• Examples of first order reactions
1. Decomposition of ethane: C2 H 6  2CH 3
2. Decomposition of ethane:
Example N 2O5 ( g )  4 NO2 ( g )  O2 ( g )

The conversation of cyclopropane to propene in the gas phase is a first

order reaction with a rate of 6.7𝑥10−4 𝑠 −1 at 500°C

a) If the initial concentration of cyclopropane was 0.25M, what is the

concentration after 8.8min?

b) How long in minutes will it take for the concentration of cyclopropane

to decrease from 0.25M to 0.15M?
Solution
a) We are given =0.25 and asked for . In applying equation
(1.2), since k is given per sec, first we convert 8.8min to seconds:
b) We are asked to calculate the time it takes to for cyclopropane to
decrease in concentration from 0.25M to 0.15M