CHM 111- Chemical Kinetics

Prof. Soriyan O.O.

COURSE OUTLINE
Module 4: Chemical Kinetics

◼ Week 10 - Chemical Kinetics: rate of reaction

◼ Week 11 - Rate of equation and temperature, reaction mechanisms
and rate equation for simple reactions.

Text Books
◼ Bahl A, Bahl B.S and Tuli G.D – Essentials of Physical Chemistry
(Chapter 20)
◼ Martin S, Silberberg - Chemistry 5th Edition – (Chapter 16) pages
684 - 728
◼ Catherine E Housecraft and Edwin C Constable - Chemistry 4th
Edition (Chapter 15)
 REACTION KINETICS
▪ Why do we put food in fridge?
o to make it last longer
o But how does this work?

▪ Why do we have to boil an egg to make it hard?

o Why not just wait until it does itself?

These questions can be answered by knowing about

Reaction kinetics.
▪ The boiling of an egg and the way in which food “goes
off” has to do with making chemical reactions to go
faster or slower.
 REACTION KINETICS
Reaction kinetics is a study of
the rates of chemical
reactions, the factors which
affect them and the
mechanism by which the
chemical reaction occurs.
RATES OF REACTION OR REACTION RATES

To introduce the concept of rate of reaction, let us consider the

decomposition of nitrogen dioxide:
𝑁𝑂2 𝑔 → 2𝑁𝑂 𝑔 + 𝑂2 (𝑔)
◼ Suppose in a particular experiment, we start with a flask of NO2 at
300oC and we measure the concentrations of NO2, NO and O2.
◼ The result is as follows:
Concentrati
on (mol dm-
3)

Time [NO2] [NO] [O2]

(s)
0 0.0100 0 0
50 0.0079 0.0021 0.0011
100 0.0065 0.0035 0.0018
150 0.0055 0.0045 0.0023
200 0.0048 0.0052 0.0026
250 0.0043 0.0057 0.0029
300 0.0038 0.0062 0.0031
350 0.0034 0.0066 0.0033
400 0.0031 0.0069 0.0035
CONCLUSION OF THE EXPERIMENT

From this result:

◼ Concentration of the reactant (NO2) decreases with time

◼ Concentrations of the products (NO and O2) increases with

time.
◼ Reaction kinetics deals with the speed at which these changes
occur.
◼ For a chemical reaction, the quantity that changes is the

amount or the concentration of reactant or product.

Hence:
◼ Rate of reaction or reaction rate of a chemical reaction is
the change in concentration of reactant or product per unit
time.
 RATE OF REACTION
𝒄𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒐𝒇 𝑨 𝒂𝒕 𝒕𝒊𝒎𝒆 𝒕𝟐 −𝒄𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒐𝒇 𝑨 𝒂𝒕 𝒕𝒊𝒎𝒆 𝒕𝟏
◼ 𝑹𝒂𝒕𝒆 𝒐𝒇 𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 =
𝒕𝟐 −𝒕𝟏

[𝐴]𝑡2 −[𝐴]𝑡1
=
𝑡2 −𝑡1
∆[𝐴]
=
∆𝑡
◼ where A = a specific reactant or product
◼ [ ] - indicate concentration
◼ Δ – a change in a given quantity

◼ Let calculate the average rate at which the concentration of NO2

changes over the first 50 secs of the reaction, using the above data.
 RATE OF REACTION
∆[𝑁𝑂2 ]
𝑅𝑎𝑡𝑒 =
∆𝑡
∆[𝑁𝑂2 ]𝑡=50𝑠 −[𝑁𝑂2 ]𝑡=0
=
50𝑠−0𝑠
0.0079𝑚𝑜𝑙 𝑑𝑚−3 −0.01𝑚𝑜𝑙 𝑑𝑚−3
=
50𝑠
= −4.2 × 10−5 𝑚𝑜𝑙 𝑑𝑚−3 𝑠 −1
◼ Since the concentration of NO2 decreases with time
∆ 𝑁𝑂2 = −𝑣𝑒 (𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒)
◼ It is customary to work with positive reaction in Chemistry.
Therefore, we define the rate of this particular reaction as:
∆[𝑁𝑂2 ]
𝑅𝑎𝑡𝑒 = −
∆𝑡
Hence for the above problem,
𝑅𝑎𝑡𝑒 = −(−4.2 × 10−5 𝑚𝑜𝑙 𝑑𝑚−3 𝑠 −1 )
= 4.2 × 10−5 𝑚𝑜𝑙 𝑑𝑚−3 𝑠 −1
time period ( s)

UNITS OF RATE OF REACTION

Units of rate of reaction = concentration/unit time = mol dm-3s-1
The average rate for this reaction during several other time intervals
are as follows:

∆[𝑵𝑶𝟐 ] Time period (s)

∆𝒕

4.2 x 10-5 0 - 50
2.8 x 10-5 50 - 100
2.0 x 10-5 100 – 150
1.4 x 10-5 150 - 200
1.0 x 10-5 200 - 250
CONCENTRATION – TIME GRAPH
12_291
0.0100

NO 2

0.0075
Concentrations (mol/L)

0.0026 [NO 2 ]
0.0006

t 70s
0.005
110 s

NO

0.0003
0.0025 70s

O2

50 100 150 200 250 300 350 400

Time (s)
The rate can also be defined in terms of products.
◼ In doing this, we must take into account the coefficients
in the balanced equation for the reaction
◼ This is because the stoichiometry determines the

relative rates of the consumption of the reactants and

the generation of the products
◼ e.g 2𝑁𝑂2 𝑔 → 2𝑁𝑂 𝑔 + 𝑂2 (𝑔)

◼ Both NO2 and NO have a coefficient of 2

◼ Therefore, NO is produced at the same rate as NO2 is

consumed.
◼ In contrast, O2 has a coefficient of 1 which means it is produced
half as fast as NO, which has a coefficient of 2.
◼ Therefore, the rate of NO produce is twice the rate of O2

produced
◼ Slope of NO2 = 2 × Slope of O2

Rate after 250 s:

8.6 × 10−5 𝑚𝑜𝑙 𝑑𝑚−3 𝑠 −1 𝑓𝑜𝑟 𝑁𝑂
4.3 × 10−5 𝑚𝑜𝑙 𝑑𝑚−3 𝑠 −1 𝑓𝑜𝑟 𝑂2
In general,
aA + bB → cC + dD
1 ∆𝐴 1 ∆𝐵 1 ∆𝐶 1 ∆𝐷
𝑅𝑎𝑡𝑒 = − =− = =
𝑎 ∆𝑡 𝑏 ∆𝑡 𝑐 ∆𝑡 𝑑 ∆𝑡

For a reaction,
BrO3- (aq) + 5Br- (aq) +6H+ → 3Br2 (aq) + 3H2O (l)

∆[𝐵𝑟𝑂3− ] 1 ∆[𝐵𝑟 − ] 1 ∆[𝐵𝑟2 ]

𝑅𝑎𝑡𝑒 = − = − = and so on
∆𝑡 5 ∆𝑡 3 ∆𝑡
Example 1: Thiosulphate ion is oxidized by iodine according to the following reaction:
2𝑆2 𝑂32− 𝑎𝑞 + 𝐼2 𝑎𝑞 → 𝑆4 𝑂62− 𝑎𝑞 + 2𝐼 − (𝑎𝑞)
If 0.0080 mole of S2O32- is consumed in 1.0 liter of solution per sec, what is the rate of
consumption of I2? At what rate are S4O62- and I- produced?

Solution: Rate of consumption of S2O32- = 0.008 mol l-1s-1.

From the stoichiometry:
1 ∆[S2 O2−
3 ] 1 ∆[I2 ] ∆[S4 O2−
6 ] 1 ∆[I− ]
Rate = = = =
2 ∆t 1 ∆t ∆t 2 ∆t
∆ S2 O2−
3 ∆ 𝐼2
=2
∆t ∆t
or
∆ I2 1 ∆ S2 O2−
3
=
∆t 2 ∆t
1
= 0.008 𝑚𝑜𝑙 𝑙 −1 𝑠 −1 = 0.004 𝑚𝑜𝑙 𝑙 −1 𝑠 −1
2

∆ S4 O2−
6
= 0.004 𝑚𝑜𝑙 𝑙 −1 𝑠 −1
∆t
∆ 𝐼−
= 0.008𝑚𝑜𝑙 𝑙 −1 𝑠 −1
∆t
FACTORS AFFECTING THE RATE OF REACTION

A number of factors can be changed to alter the rate of a chemical

reaction. These are:
1. Physical State of reactants
2. Concentration of reactants
3. Temperature of reaction
4. Surface area and size of reactants
5. The presence of a catalyst
6. The pressure of gaseous reaction
7. The presence of light

Note: 6 and 7 are for selected reaction

 RATE EQUATION (LAW)
The rate equation or law is an experimentally determined
equation that shows how the rate of reaction is dependent on
the concentration of the reactants raised to appropriate powers.

Let consider the general reaction: 𝒂𝑨 + 𝒃𝑩 → 𝒄𝑪 + 𝒅𝑫

The rate depends on concentrations of A and B
The relationship is as follows:
𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑅𝑎𝑡𝑒 𝛼 𝐴 𝑚 𝐵 𝑛
If the proportionality constant is k.
Therefore,
𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑅𝑎𝑡𝑒 = 𝑘 𝐴 𝑚 𝐵 𝑛
This equation is known as the rate law or rate equation.
◼ 𝐴 and 𝐵 represent the molar concentration of the reactants A and
B.
◼ The letter m and n represent the exponents of 𝐴 and 𝐵 in the rate
law.
 RATE EQUATION (LAW)
◼ It is the power to which each concentration must
be raised to give the correct dependence of the
rate on concentration.
◼ These exponents must be determined by actual
experiment – they CANNOT be found by theory.
◼ There is no connection between these exponents and
the coefficients of A and B in the balanced equation for
the overall reaction.
◼ The exponents are usually simple whole number

such as 0, 1 or 2 but they can be a fraction.

◼ k is the proportionality constant.
 RATE CONSTANT (k)
◼ The rate constant, k, is the proportionality constant
in the rate equation which relates the rate of the
reaction to the concentration of the reactants.
◼ The rate constant, k

◼ is experimentally determined and has no fixed unit.

◼ is dependent on the particular reaction, temperature

and the presence of a catalyst (if any).

◼ k increases with temperature and catalyst

◼ determines how fast the reaction can proceed.

In general, the larger the k value, the faster the

reaction.
 RATE CONSTANT (k)
Since,
𝑅𝑎𝑡𝑒 = 𝑘 𝐴 𝑚 𝐵 𝑛

When the reactants are present at unit concentration

𝑅𝑎𝑡𝑒 = 𝑘

The rate constant is the rate of reaction when concentrations

of the reactants are unity.

◼ The rate constant for any reaction can be determined.

◼ either by measuring the rate at unit concentration of reactants

◼ by knowing the rate at any concentration of reactant using the

relation
 RATE CONSTANT (k)
𝑅𝑎𝑡𝑒
𝑅𝑎𝑡𝑒 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡, 𝑘 =
𝐴𝑚 𝐵 𝑛

𝑚𝑜𝑙 𝑑𝑚−3 𝑠𝑒𝑐 −1

Unit of Rate constant =
(𝑚𝑜𝑙𝑑𝑚−3 )𝑧

where 𝑧 = 𝑚 + 𝑛

Note: Time may also be minutes, hours or years

 ORDER OF REACTION
◼ The order of a reaction is the sum of the powers to which
the concentration of the reactants is raised to in the rate
equation.
Consider the rate equation: 𝑅𝑎𝑡𝑒 = 𝑘 𝐴 𝑚 𝐵 𝑛
◼ The reaction is of order m with respect to A and of order n with
respect to B
◼ The overall order of the above reaction is m + n
◼ If the exponent m = 1, the reaction is first order in reactant A

◼ If the exponent m = 2, the reaction is second order in

reactant A
◼ If the exponent m = 3, the reaction is third order in reactant

A
◼ It is possible for exponent m = 0, i.e that the rate of the reaction is
independent of the concentration of the component A
◼ Hence it zero order in A
 ORDER OF REACTION
If the rate law of a particular reaction is
𝑅𝑎𝑡𝑒 = 𝑘 𝐴 𝐵 2
◼ The reaction is first order in A and second order in B

◼ The overall order of the reaction = 1 + 2 = 3: Third

order.

◼ The order of reaction can ONLY be determined

experimentally and they usually zero, positive whole
number (0,1,2) or fractions
 Example
Example 2: For a reaction: A + B product, the rate equation is
𝑅𝑎𝑡𝑒 = 𝑘 𝐴 𝑚 𝐵 𝑛 , If m = 1 and n = 2.
i. If [A] doubles while keeping [B] constant, what will happen to the rate of the
reaction?
ii. How will the rate of reaction change, if [B] increases by 3 times while keeping
[A]?
iii. If [B] is halved while keeping [A] constant, how will the rate change?
Solution:
i. If [A] doubles while keeping [B] constant i.e 𝑅𝑎𝑡𝑒 𝛼 𝐴 , the rate will
be doubled
ii. If [B] increases by 3 times while keeping [A] constant i.e 𝑅𝑎𝑡𝑒 𝛼 𝐵 2 ,
the rate of the reaction will increase 9 times
iii. If [B] is halved while keeping [A] constant, the rate will decrease 4
times.
 EXAMPLE
Example 5: The following results were obtained for a reaction
between A and B.

Mol dm-3 Mol dm-3 Mol dm-3s-1

Run [A] [B] Rate
1 0.50 1.0 2.0
2 0.50 2.0 8.0
3 0.50 3.0 15.0
4 1.0 3.0 36.0
5 2.0 3.0 72.0

a) What is the order of reaction with respect to A and with respect

to B?
b) What is the rate law for the reaction?
c) Calculate the rate constant.
 Solution
i. Let the rate law be 𝑅𝑎𝑡𝑒 = 𝑘 𝐴 𝑚 𝐵 𝑛
Compare run (4) and (5) in which [B] is constant
𝑅𝑢𝑛5 𝑅𝑎𝑡𝑒5 2.0 𝑚 3.0 𝑛
= =
𝑅𝑢𝑛4 𝑅𝑎𝑡𝑒4 1.0 3.0
2𝑚 = 2
𝑚=1
Compare run 2 and 1 in which [A] is constant
𝑛
𝑅𝑢𝑛2 𝑅𝑎𝑡𝑒2 2.0 8
= = =
𝑅𝑢𝑛1 𝑅𝑎𝑡𝑒1 1.0 2
2𝑛 = 4 = 22
𝑛 = 2The reaction is first order with respect to A and second order
with respect to B.
ii. The rate law is 𝑅𝑎𝑡𝑒 = 𝑘 𝐴 𝐵 2
 MOLECULARITY OF A REACTION
Molecularity is the sum of stoichiometric coefficients of
reactants involved in the stoichiometric equation of the
reaction.
e.g. 2𝐴 + 3𝐵 → 3𝐶 + 2𝐷
Stoichiometric coefficient of A and B are 2 and 3
Molecularity = 2 +3 = 5
There is no simple relationship between order and
molecularity.
 ZERO ORDER REACTION
When no concentration terms affect the rate of reaction or
when the rate of reaction remain same throughout the
reaction. The reaction is ZERO order
Let us consider a reaction
𝐴 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑡=0 𝑎 -
𝑡 =𝑡 𝑎−𝑥 𝑥
Since the rate remain the same
𝑑𝑥
=𝑘
𝑑𝑡
Integrating
න 𝑑𝑥 = 𝑘 න 𝑑𝑡

𝑥 = 𝑘𝑡 + 𝑧 (𝑖𝑛𝑡𝑒𝑔𝑟𝑎𝑡𝑖𝑜𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡)
 ZERO ORDER REACTION
Value if integration constant z is obtained
by taking the conditions x = 0 when t = 0
𝑧=0
Therefore, rate equation is
𝑥
𝑥 = 𝑘𝑡 or 𝑘=
𝑡
Unit of rate constant of zero order
= 𝒎𝒐𝒍 𝒅𝒎−𝟑 𝒔−𝟏 or 𝒄𝒐𝒏𝒄. 𝒕𝒊𝒎𝒆 −𝟏
HALF-LIFE OF A REACTION
The half life or half life period is the time required for the
concentration of reactant to decrease to half of its initial
value.
It is represented by 𝑡1Τ2
𝐶𝑜
And it is calculated by taking 𝑡 = 𝑡1Τ2 when 𝑐 = in the integrated
2
rate equation of its order.
Half-life period 𝑡1Τ2 of a zero order
𝑎
𝑡 = 𝑡1Τ2 when 𝑥 =
2
𝑎
𝑡1Τ2 =
2𝑘
Half life of a zero order is directly proportional to the initial
concentration.
 HALF-LIFE OF A REACTION
From equation zero order equation the plot of 𝑥 or 𝑎 − 𝑥 versus time
give the slope of rate constant, 𝑘.
FIRST ORDER REACTIONS
Consider a first order reaction,
𝐴 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑡=0 𝑎 -
𝑡 =𝑡 𝑎−𝑥 𝑥
Since the rate remain the same
𝑑𝑥 𝑑𝑥
𝑅𝑎𝑡𝑒 = = 𝑘 𝑎 − 𝑥 or = 𝑘𝑑𝑡
𝑑𝑡 𝑎−𝑥
Integrating
𝑑𝑥
‫׬‬ = 𝑘 ‫𝑡𝑑 ׬‬
𝑎−𝑥
𝑙𝑛 𝑎 − 𝑥 = 𝑘𝑡 + 𝑧
At 𝑡 = 0 and 𝑥 = 0
𝑧 = ln 𝑎
𝑎
𝑙𝑛 = 𝑘𝑡
𝑎−𝑥
1 𝑎 2.303 𝑎
Hence, 𝑘 = 𝑙𝑛 or 𝑘 = 𝑙𝑜𝑔
𝑡 𝑎−𝑥 𝑡 𝑎−𝑥
HALF-LIFE FOR FIRST ORDER
Units of rate constant for first order = (time)-1 i.e. sec-1,
min-1 or hour-1
Half-life for first order
𝑎
Obtained by substituting 𝑡 = 𝑡1Τ2 when 𝑥 =
2

2.303 𝑎
𝑘= 𝑙𝑜𝑔
𝑡1ൗ 𝑎 − 𝑎ൗ2
2

2.303 ln 2
𝑡1Τ2 = 𝑙𝑜𝑔 2 or 𝑡1Τ2 =
𝑘 𝑘

Half-life of first order of independent of initial concentration

of reactant
Rearrange the above equation
𝑘
𝑙𝑜𝑔 𝑎 − 𝑥 = − 𝑡 + log 𝑎
2.303
 CONCLUSION

Thanks for listening

I
wish you
the best in your
examination