Chapter 2- Chemical

Reaction Kinetics
 SCOPE
• Factors affecting Reaction Rate
• Reaction Rate Expression
• The Rate Law and Its Component
• Integrated Rate Laws: - First and Second
Order Reactions
• The Effect of Temperature on Reaction
Rate
• Catalysis
 LEARNING OUTCOME

• Able to determine simple reaction orders.

• Able to apply the Arrhenius equation and
rate law in calculations.
• Able to identify reaction mechanism and
rate determine step for a given reaction.
• Able to understand basic concepts in
catalysis.
 2.1 Reaction rates
• Chemical kinetics is the study of the rate
of a reaction
• The reaction rate is the speed with which
reactants disappear and products form
• Reaction rates are always reported as
positive values
• The unit is mol L–1 s–1
 Average, Instantaneous and Initial Rates
• Instantaneous rate:
slope of a line tangent to the
curve at a particular point
(e)

• Initial rate:
the instantaneous rate at the
moment reactants are mixed
(a)

• Average rate:
slope of line joining any two
points (b, c, d)
 Reaction Rate Expressions
• Rate of reaction: the change in concentrations of reactants or
products per unit time
• Average rate = Δ 
Δt
• = delta = (final - initial) concentration of reactant/product
• use [ ] to express concentration in moles/liter

• Consider this reaction A → B

• Average rate = -
ΔA 
=
ΔB
Δt Δt
• The unit of rate is: mol/L.s or M/s
2.1 Reaction rates
Consider the reaction A →B
 2.1 Reaction rates
• The concentration of the reactant, A,
decreases with time
conc of A at time t2 – conc of A at time t1 -Δ[A]
rate (A) = =
t2 – t1 Δt

• The concentration of the product, B,

increases with time
conc of B at time t2 – conc of B at time t1 Δ[B]
rate (B) = =
t2 – t1 Δt
 2.1 Reaction rates
• Calculate the average rate at which [A]
changes in the first 50 seconds
-Δ[A]
rate (A) =
Δt
-([A]t=50 – [A]t=0)
=
50 s – 0 s
-(0.0629 mol L-1 – 0.0750 mol L-1)
=
50 s
= -(-2.4 × 10-4 mol L-1 s-1)

= 2.4 × 10-4 mol L-1 s-1

 2.1 Reaction rates
• The rate at a particular time is called the
instantaneous rate
• This can be determined from the slope of
a tangent to the curve
• For example, at t = 50 s
-d[A]
rate = -(slope of tangent line) =
dt
= 0.017mol L-1 / 74.4 s
= 2.3 × 10-4 mol L-1 s-1
 2.1 Reaction rates
Example 1: A→ B
Supposed the rxn begins with 1.00 mol A.
At t =0 there is 1.00 mol A, no B present.
At t =10 min, there is 0.74 mol A and 0.26 mol B
At t =40 min, there is 0.30 mol A and 0.70 mol B.
Calculate average rate from t = 0 to t = 10 min.
Δ(moles B)
=
average rate Δt
(mol B at t = 10 min) - (mol B at t = 0)
=
10 min − 0 min
0.26 mol - 0 mol
= = 0.026 mol/min
10 min - 0 min
 2.1 Reaction rates
Consider :

C4H9Cl(aq)+H2O(l) → C4H9OH(aq)+HCl (aq)

Butyl chloride Butyl alcohol

We can calculate the average rate in

terms of the disappearance of C4H9Cl.
 2.1 Reaction rates
C4H9Cl(aq)+H2O(l) → C4H9OH(aq)+HCl (aq)

Time (s) [ C4H9Cl ] (M)

0.0 0.1000
50.0 0.0905
100.0 0.0820
150.0 0.0741
200.0 0.0671
300.0 0.0549
400.0 0.0448
500.0 0.0360
800.0 0.0200

Plot [ C4H9Cl ] versus time

 0.12 [C4H9Cl] vs time

0.1

0.08
[C4H9Cl]

0.06

0.04

0.02

0
0 100 200 300 400 500 600 700 800 900
time
• Average rate of disappearance of C4H9Cl
Δ (C4H9 Cl)
=−
Δt
 C4H9 Clfinal time − C4H9 Clinitial time 
= − 
 (final time ) − (initial time ) 
Time (s) [ C4H9Cl ] (M) Ave.rate (M/s)
0.0 0.1000
1.9 x 10-4
50.0 0.0905
1.7 x 10-4
100.0 0.0820
1.6 x10-4
150.0 0.0741
1.4x10-4
200.0 0.0671
1.22x10-4
300.0 0.0549
1.01 x10-4
400.0 0.0448
0.80x10-4
500.0 0.0360 0.56x10-4
800.0 0.0200
 Reaction Rates and Stoichiometry
Reaction : relationship one-to-one
C4H9Cl (aq) + H2O (l) C4H9OH (aq) + HCl (aq)

1 mole of C4H9OH is produced for each mole of C4H9Cl

consumed. H2O is consumed and HCl is produced.

ΔH2 O ΔHCl
− =
Rate = Δt Δt
ΔC4H9 Cl ΔC4H9 OH
− =
Δt Δt
 Reaction Rates and Stoichiometry
Reaction : relationship is not one-to one
2HI (g) H2 (g) + I2(g)
The rate of disappearance of HI is twice the rate of
appearance of H2 and I2 .

1 ΔHI ΔH2  ΔI2 

rate = − = =
2 Δt Δt Δt

In general for: aA + bB → cC + dD

1 ΔA  1 ΔB 1 ΔC 1 ΔD

rate = − =− = =
a Δt b Δt c Δt d Δt
Reaction Rates and Stoichiometry
Example 2:

Write the rate expressions for the following

reactions in terms of the disappearance of
the reactants and the appearance of the
products.
4NH3 (g) + 5O2 (g) 4NO (g) + 6H2O (g)

19
 Reaction Rates and Stoichiometry

Answer:

1 ΔNH 3  1 ΔO 2  1 ΔNO

rate = − =− =
4 Δt 5 Δt 4 Δt
1 ΔH 2 O
=
6 Δt

20
 Reaction Rates and Stoichiometry
Example 3:
2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O(g)
– If the butane concentration is decreasing at a
rate of 0.20 mol L–1 s–1, at what rate is the
oxygen concentration decreasing?
– Solution:
0.20 mol C4H10 13 mol O2 1.3 mol O2
rate (O2) = x =
Ls 2 mol C4H10 Ls

– Oxygen reacts at a rate of 1.3 mol L–1 s–1

 2.2 Factors affecting
reaction rate
• Principal factors influence reaction rates:
1. Chemical nature of the reactants
2. Ability of the reactants to come in contact
with each others
3. Concentrations of the reactants
4. Temperature
5. Availability of rate-accelerating agents
called catalysts
 2.2 Factors affecting
reaction rate
• Chemical nature of the reactants
– During reactions, bonds break and new
bonds form
– Some reactions are fast by nature and
others are slow
 2.2 Factors affecting
reaction rate
• Ability of the reactants to meet
– Most reactions involve two or more reactants
whose particles (atoms, ions or molecules)
must collide for the reaction to occur
– In a homogeneous reaction, all of the reactants
are in the same phase
– In a heterogeneous reaction, the reactants are
present in different phases
Surface area  , Rate 
 2.2 Factors affecting
reaction rate
– The area of contact between the phases
determines the reaction rate
A: nail (low surface area) B: Steel wool (high surface area)
 2.2 Factors affecting
reaction rate
• Concentrations of the reactants
– The rates of both homogeneous and
heterogeneous reactions are affected by the
concentrations of the reactants
• For example, red-hot steel wool bursts into flame
when thrust into pure oxygen

Rate  collision frequency  concentration

Concn  , Rate 
 2.2 Factors affecting
reaction rate
• Temperature of the system
– Almost all chemical reactions
occur faster at higher
temperatures
Rate  collision energy  temperature

Temperature  , rate 

a: energetic collision - lead to product

b,c,d: molecules just bounce off!!
2.2 Factors affecting
reaction rate
• Presence of catalysts
– Catalysts are substances that increase
the rate of chemical reactions without
being used up
– For example, enzymes that direct our
body chemistry are all catalysts
 2.3 Rate laws
• A rate law is an equation in which the
rate is given as a function of reactant
concentrations
– for example, rate = k[HI]n

• k is the rate constant of the reaction

• n is the order of the reactant
• Both rate constant and order must be
experimentally determined
 2.3 Rate laws
• The value of the rate constant depends
on the particular reaction being studied
and the temperature at which the reaction
occurs
• The order can be positive or negative, an
integer or a fraction
• The order cannot be deduced from the
balanced equation
 2.3 Rate laws
• Types of rate laws:
– A differential rate law expresses the rate as a
function of concentration
– An integrated rate law expresses the
concentration as a function of time
– Rate laws help to identify the steps by which a
chemical reaction occurs
– The sum of the individual reaction steps is
called the reaction mechanism
 2.3 Rate laws
• Consider the hypothetical reaction:
A + B → products
– The rate law for the reaction is:
rate = k[A]n[B]m
– The values of n and m can be discovered by
looking for patterns in the rate data
– order cannot be deduced from the balanced
equation
• Consider the following reaction:

H 2 SeO3 + 6 I − + 4 H + → Se + 2 I 3− + 3H 2O

• From experiment, the rate law (determined

from initial rates) is
rate = k[ H 2 SeO3 ]1[ I − ]3[ H + ]2
 2.3 Rate laws
– Suppose that the data in the table below has
been obtained in a series of five experiments:
 2.3 Rate laws
– For experiments 1, 2 and 3 [B] is held
constant. Any changes in the rate must be due
to the change in [A]
– The rate law says that at constant [B] the rate
must be proportional to [A]n
n
rateexp 2 [A]exp 2 rateexp 2 0.40 mol L-1 s-1
= = =2
rateexp 1 [A]exp 1 rateexp 1 0.20 mol L-1 s-1

and
[A]exp 2 0.20 mol L-1
= =2
[A]exp 1 0.10 mol L-1
 2.3 Rate laws
– So doubling [A] from experiment 1 to
experiment 2 doubles the rate
– The relationship reduces to:
2.0 = 2.0n
– The only value of n that makes this equation
true is n = 1
– The reaction must be first order with respect
to A
 2.3 Rate laws
– In the final three experiments, the
concentration of B changes while the
concentration of A is held constant
– This time it is [B] that affects the rate
m
rateexp 4 [B]exp 4
=
rateexp 3 [B]exp 3

– For experiments 3 and 4, we have:

4.0 = 2.0m
– Therefore, m must equal 2
 2.3 Rate laws
– We now know that the rate law for the
reaction must be:

rate = k[A]1[B]2

– The overall order is the sum of the orders for

each reactant in the rate law = 3

– What is the value of k?

 LESSON OUTCOME
At the end of the lesson, students should be
able to:
1. Write expression for integrated rate laws
2. Determine half life

41
 2.3 Rate laws
• The integrated rate law
– Integrated rate laws express concentration as a
function of time
– Consider the hypothetical reaction:
A → products
– The (differential) rate law has the form:
d[A]
rate = – = k[A]
dt
42
 2.3 Rate laws
Assume A → products is first order
The differential rate law has the form:
d[A]
rate = – = k[A]
dt
– The integrated rate law would be:
[ A]0 − kt
ln = kt or [ A]t = [ A]0 e
[ A]t

[A]0 is [A] at t (time) = 0

[A]t is [A] at t = t
e = base of natural logarithms = 2.71828…
 2.3 Rate laws
d[A]
rate = – = k[A]
dt
A = − k t dt
A t d
A  A
0
0
ln A t − ln A 0 = − k t
ln A t = − k t + ln A 0
[A]0
ln = kt or [A]t = [A]0e-kt
[A]t
 2.3 Rate laws
– For first order reactions a plot of the natural
logarithm of concentration versus reaction
time always gives a straight line

45
 Example 4 (Workbook)
The specific rate constant for the first-order
decomposition of N2O5 in CCl4 at 45oC is 6.32
 10-4 s-1
2N2O5 4NO2 + O2

a. What is the concentration of N2O5 remaining

after 2.00 hr if the initial concentration of N2O5
was 0.500 M ?

b. How much time required for 90% of N2O5 to

decompose ?
46
 ln  At = − k t + ln  A0
a)

ln[A]t = -6.32 x 10-4x 7200s + ln 0.5

= -45504 x 10-4 + (-0.693)

= -4.55-0.693
[A]t = ln (-5.24)

[A]t = 1.65 M
b) ln At = − k t + ln A0
ln 0.05= -6.32 x 10-4x t + ln 0.5

t = - ln0.05-ln 0.5
6.32 x 10-4
t = - (-2.99-0.693)
6.32 x 10-4
t = 3.68x 104

t = 5820s= 1.61hrs
 2.3 Rate laws
• Second-order rate laws
– Assume B → products is second order
– The differential rate law is:
d[B]
rate = = k[B]2
– dt
– The integrated rate law would be:
1 1
= kt +
[B]t [B]0
49
  A 
Rate = − = k A 2
t
 A  A t dA  t
= − k  t , −  = k  dt
A2 A 0 A 2 0

1 1 1 1
− = kt , = kt +
At A0 At A0
 2.3 Rate laws
– When a reaction is second order, a plot of
1/[B]t versus t should yield a straight line with
a slope k

51
 2.3 Rate laws
• Zero-order rate laws
– The differential rate law is:
rate = k[C]0 = k(1) = k
– The integrated rate law is:
[C]t = – kt + [C]0
– A plot of [C] versus time gives a straight
line of slope –k

52
2.3 Rate laws

53
 Graphical determination of reaction order
Plot of ln[N2O5] vs. time gives straight line, indicating
first order reaction.

54
 Half life
The amount of time required for half of a
reactant to disappear is called the half-life,
t1/2
– The half-life of a first-order reaction is not
affected by the initial concentration
[ A]0
First - order rate law : ln = kt
[ A]t
1
at t = t1/ 2 , [ A]t = [ A]0 , substituting
2
[ A]0 ln 2
ln 1 = kt1/ 2 or t1/ 2 =
2
[ A]0 k 55
First-order radioactive decay of iodine-131. The
initial concentration is represented by [I]0.

56
– The half-life of a second-order reactions
DOES depend on the initial concentration

1 1
Second - order rate law : − = kt
[ B]t [ B]0
1
at t = t1/ 2 , [ B]t = [ B]0 , substituting
2
1 1
1
− = kt1/ 2
2
[ B]0 [ B]0
1 l
= kt1/ 2 or t1/ 2 =
[ B]0 k[ B]0

57
SUMMARY

58
 Example (Workbook)

Carbon-14 (14C) is a radioactive isotope with a

half-life of 5.73 x 103 years. It decays following
the first order reaction. The amount of 14C
present in an object can be used to determined
its age. Calculate the rate constant for decay of
14C and determine how long is required for 90%

of the 14C in a sample to decompose.

 LESSON OUTCOME
At the end of the lesson, students should be
able to:
1. Explain Collision Theory and Transition
State theory
2. Apply Arrhenius equation to calculate rate
constant or activation energy.
3. Express rate law based on elementary
reactions
4. Derive rate law using rate-determining
step 60
 2.4 Theory of chemical
kinetics
• Collision theory
– One of the simplest models to explain
reaction rates is collision theory
– Collision theory says that the rate of a
reaction is proportional to the number of
effective collisions per second among the
reactant molecules
– An effective collision is one that actually
gives product molecules
 2.4 Theory of chemical
kinetics
– Concentration can influence the number of
effective collisions per second
– As reactant concentrations increase, the
number of effective collisions increases
– Not every collision between reactant
molecules actually results in a chemical
change
– Only a very small fraction of all the collisions
can really lead to a net change
– Why is this so?
 2.4 Theory of chemical
kinetics
• Molecular orientation
– When two reactant molecules collide they must
be oriented correctly for a reaction to occur
(see next slide)
2.4 Theory of chemical kinetics
 2.4 Theory of chemical
kinetics
• Activation energy
– The activation energy (Ea) is the minimum
energy required for a reaction to occur
– The activation energy determines the rate of
a reaction
– At a given temperature, only a certain fraction
of the collisions possess enough energy to be
effective and form products
2.4 Theory of chemical
kinetics
 2.4 Theory of chemical
kinetics
– The arrangement found on the top of the
potential energy ‘hill’ is called the activated
complex or transition state
– Once the transition state is reached, the
reaction proceeds to give products, with the
release of energy
– A reaction intermediate corresponds to an
energy minimum between two transition
states
 Transition State Theory
The activated complex is unstable species and what exists
is neither reactant nor product but a transitional species
with partial bonds. Consider reaction between:
CH3Br + OH- CH3OH + Br-
 2.4 Theory of chemical
kinetics
• Temperature effects
– The rate of a reaction increases with
increasing temperature
 2.4 Theory of chemical
kinetics
– The activation energy is related to the rate
constant by the Arrhenius equation
k = Ae-Ea/RT
k = rate constant
Ea = activation energy
R = universal gas constant
T = temperature (in Kelvin)
A = pre-exponential or frequency factor
 2.4 Theory of chemical
kinetics
– The activation energy can also be obtained
from two rate components measured at
different temperatures
– Most reactions obey the Arrhenius equation
to a good approximation

k2 –Ea 1 1
ln = –
k1 R T2 T1
 Example 5 (Workbook)
An alteration in the structure of a certain virus follows
first-order kinetics with Ea = 587 kJ/mol .The half-life at
29.6oC is 1.62  104 s ( 1 yr = 3.154  107 s ).
What are the rate constants at 29.6oC and the half-life at
32oC for the alteration of the virus ?
 Example 5 (Workbook)
An alteration in the structure of a certain virus follows first-
order kinetics with Ea = 587 kJ/mol .The half-life at 29.6oC is
1.62  104 s ( 1 yr = 3.154  107 s ).
What are the rate constants at 29.6oC and the half-life at 32oC
for the alteration of the virus ?

Solution:
For a first order rxn: k1 = 0.693 / t1/2

Rate constant at 29.6oC = 0.693 / 1.62  104 s

= 4.28  10-5 s-1
 Solution
Ea is given, so k2 can be calculated using the Arrhenius
equation.The t 1/2 at 32.0oC can be obtained from k2.

k1 E  1 1 
ln =− a  − 
k2 R  T1 T2 
 4.28  10 -5 s -1  (587 kJ/mol)(1000 J/kJ)
ln  =
 k2  8.314 J/mol.K
 
 1 1 
 − 
 305.0 K 302.6 K 
k 2 = 2.68  10 - 4 s -1
 Solution

thus the half - life at 32o C:

t 1/2 = 0.693 / k 2
0.693
=
2.68  10 − 4 s-1
= 2.58  103 s
2.5 Reaction mechanisms
• Most reactions do not occur in a single
step
• The net overall reaction is the result of a
series of simple reactions
• Each of these is called an elementary
process
• The entire set of elementary processes is
the reaction mechanism
 2.5 Reaction mechanisms
• The rate law of an elementary process can
be written from its chemical equation
• This rule only applies to elementary
processes
• The overall rate law derived from the
mechanism must agree with the
observed rate law for the overall
reaction
 Example 6
The following two reactions are proposed as elementary steps in the
mechanism for an overall reaction:

(1) NO2Cl (g) NO2 (g) + Cl (g)

(2) NO2Cl(g) + Cl (g) NO2(g) + Cl2(g)

Overall reaction: (1) + (2)

Overall rxn: 2NO2Cl(g) 2NO2 (g) + Cl2

Reaction intermediate is a substance that is formed and used up in

the overall reaction, does not appear in the overall reaction: Cl (g)

Rxn(1) : Unimolecular, Rate = k1[NO2Cl]

Rxn(2): Bimolecular, Rate = k2[NO2Cl][Cl]
2.5 Reaction mechanisms
• The rate-determining step
– Consider the gaseous reaction:
2NO2Cl → 2NO2 + Cl2

– The actual mechanism of the reaction is the

following two-step sequence of elementary
processes:
NO2Cl → NO2 + Cl• (slow)
NO2Cl + Cl• → NO2 + Cl2 (fast)

– The Cl radical formed is an intermediate

 2.5 Reaction mechanisms
• In any multistep mechanism, one step is
usually much slower than the others
• The slow step in a mechanism is called the
rate-determining step
• The rate law for the rate-determining step
is directly related to the rate law for the
overall reaction
Rate laws for elementary steps
• The rate limiting step will dominate the expression
of rate laws.

• Eg:
Step 1: NO (g) + Br2 (g) → NOBr2 (fast)
Step 2: NOBr2 (g) + NO (g) → 2NOBr (g) (slow)

 Rate law : Rate=k[NOBr2] [NO]

 Example 7
• NO catalyzes the decomposition of N2O possibly through the
following mechanism:
NO(g) + N2O(g) → N2(g) + NO2(g)
2NO2(g) → 2NO(g) + O2(g)

What is the overall reaction?

(1)  2 → 2NO (g) + 2N2O (g) → 2N2 (g) + 2NO2 (g)
(2) → 2NO2(g) → 2NO(g) + O2(g)
_________________________________
2N2O (g) → 2N2 (g) +O2(g)

NO = catalyst;
NO2=intermediate
The End