KINETICS

(CHAPTER 5)

CHM 271
 2

Lesson Outcomes
• Determine the rate of reactions with correct units
• Explain the factor affecting rate of reaction
• Determine the order of reaction
• Calculate activation energy by Arrhenius equation
 3

RATES OF REACTION
 4

Introduction
• Chemical Kinetics: Study of chemical reactions and the
interactions of the moving molecules
• Reaction rate is the change in the concentration of a reactant
or a product with time
Rate of Reaction = change in concentration of A
change in time

(conc A2 - conc A1)

= -  (conc A)
t2-t1 t
• The unit for reaction rates mol dm-3 s-1 or mol L-1 s-1 or M s-1
 5

The decrease in the number of A molecules (reactant are

consumed) and the increase in the number of molecules B
(products are formed)

A B
∆[A] D[A] = change in concentration of A over
rate = -
∆t time period, ∆t
∆[B] D[B] = change in concentration of B over
rate =
∆t time interval, ∆t

Because [A] decreases with time, ∆[A]

is negative
 6

A B

∆[A]
rate = -
∆t

∆[B]
rate =
∆t
 7

Example
red-brown Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

time

t1< t2 < t3

393 nm Detector
light
∆[Br2] a ∆ Absorption 7
 8

Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

slope of
tangent
slope of
tangent slope of
tangent

∆[Br2] [Br2]final – [Br2]initial

average rate = - =-
∆t tfinal - tinitial
instantaneous rate = rate for specific instance in time
 9

rate = k [Br2]
rate
k= = rate constant
[Br2]
= 3.50 x 10-3 s-1
 10

Rates and Coefficients

2A B

Two moles of A disappear for each mole of B that is formed.

1 ∆[A] ∆[B]
rate = - rate =
2 ∆t ∆t

aA + bB cC + dD

1 ∆[A] 1 ∆[B] 1 ∆[C] 1 ∆[D]

rate = - =- = =
a ∆t b ∆t c ∆t d ∆t
 11

Write the rate expression for the following reaction:

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g)

∆[CH4] 1 ∆[O2] ∆[CO2] 1 ∆[H2O]

rate = - =- = =
∆t 2 ∆t ∆t 2 ∆t
 12

Expressing Reaction Rates

• For a chemical reaction, there are many ways to express the
reaction rate. The relationships among expressions depend
on the equation
• Note: the expression and reasons for their relations for the
reaction
2 NO + O2 (g) → 2 NO2 (g)
[O2] 1 [NO] 1 [NO2]
Reaction rate = – =– =
t 2 t 2 t
• Make sure you can write expressions for any reaction and
figure out the relationships. For example, give the reaction
rate expressions for
2 N2O5 → 4 NO2 + O2
 13

Example
The concentrations of N2O5 are 1.24×10-2 and 0.93×10-2 M at 600
and 1200 s after the reactants are mixed at the appropriate
temperature. Evaluate the reaction rates for
2 N2O5 →4 NO2 + O2
Solution:
 14

RATE LAW & ORDER OF

RECTION
 15

Rate Equation
• 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
• For a general reaction;

rate = k [A]m [B]n

*Where :
k is a rate constant
m is reaction order with respect to A
n is reaction order with respect to B,
m + n is the overall reaction order
 16

Rate Constant
1. The rate constant is independent of the concentrations of
the chemical species involved in the reaction.
2. However, it depends on other factors such as temperature or
ionic strength.
3. The units of the rate constant depend on the overall reaction
order.
4. In general, the form of the rate law is NOT determined by the
reaction stoichiometry, but is determined by the reaction
mechanism.
5. If the value of k is high, the reaction rate is high.

k=rate/([A]m[B]n)
=(mol L-1)1-(m+n) s-1
 17

• The unit of rate constant depends on the order from the rate
law.
• Example:
2nd order rate law

Rate = k [A][B]
d[A]/dt = k [A][B]

molL-1/s = k [molL-1][molL-1]
k = L/mol.s
OR k = 1/M.s
k = M-1.s-1
 18

Reaction Orders
2NO + O2 2NO2

Usually the rate of a reaction is a function of the

concentrations of reactants.

rate = k [NO]2 [O2]1

The orders of 1 and 2 for [O2] and [NO] respectively has been
determined by experiment, NOT from the chemical equation.

So, this reaction is 3rd order overall

 19

Reaction Orders and The Rate Law

Determine the reaction order with respect to the given rate law.
(a) 2NO(g) + O2(g) → 2NO2(g); rate = k[NO]2[O2]
(b) CH3CHO(g) → CH4(g) + CO(g); rate = k[CH3CHO]3/2
(c) H2O2(aq) + 3I-(aq) + 2H+(aq) → I3-(aq) + 2H2O(l); rate = k[H2O2][I-]
*Look at the rate law and NOT at the stoichiometry of the
chemical reaction
(a) The reaction is 2nd order in NO, 1st order in O2, and 3rd
order overall.
(b) The reaction is 3/2 order in CH3CHO and 3/2 order overall
(c) The reaction is 1st order in H2O2, 1st order in I- and zero
order in H+, while being 2nd order overall.
 20

Units of Rate Constant

The rate equation Order Unit of rate
constant
R=k[A]0[B]0 0 mol/L.s (Ms-1)
=k
R=k[A]1 1 1/s (s-1)
R=k[b]1
R=k[A]1[B]1 2 L /mol.s (M-1s-1)
R=k[A]2
R=k[B]2
R=k[A]2[B]1 3 L2/mol2.s (M-2s-1)
(or any other possible
combinations)
 21

METHODS TO DETERMINE
ORDER OF REACTION
 22

How to determine the Reaction Orders

1. Initial Rate Method
(using experimental data)
2. Integrated Rate Law Method
(by manipulating the data and plotting the appropriate graph)
3. Half Life Method
(using formula and plotting a graph)
4. The Differential Method

*Focus on 1, 2 and 3 only

 23

1. Initial Rate Method

In a general reaction,

aA + bB cC + dD

rate = k [A]m [B]n

If concentrations of B is kept constant, we can measure the

reaction rate of A at various concentrations.
 24

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

Initial Reactant
Initial Rate
Concentrations (mol/L)
Experiment (mol/L*s)
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
 25

2NO(g) + O2(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 [O2]1m m
k [O2]2m[NO]2n [O2]2
= = =
rate1 k [O2]1m[NO]1n [O2]2m [O2]1

6.40x10-3mol/L*s 2.20x10-2mol/L m
=
3.21x10-3mol/L*s 1.10x10-2mol/L
2 = 2m Do a similar calculation for
m=1 the other reactant(s).
 26

Example
Many gaseous reactions occur in a car engine and exhaust system

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.
Initial Initial [NO2] Initial [CO]
Experiment (mol/L) (mol/L)
Rate(mol/L*s)
1 0.005 0.10 0.10
2 0.080 0.40 0.10
3 0.005 0.10 0.20
 27

2. Integrated Rate Law

[A]
rate = - = k [A] first order rate equation
t
[A]t
ln = - kt ln [A]t = -kt + ln [A]o
[A]o
[A]
rate = - = k [A]2 second order rate equation
t
1 1 1 1
- = kt = kt +
[A]t [A]0 [A]t [A]0
[A]
rate = - = k [A]0 zero order rate equation
t
[A]t = - kt + [A]0
 28

First Order

Y = mX + C

Slope,m = -k
Y-intercept, C = ln [A]o

ln[A]t = -kt + ln[A]0

 29

Second Order

Y = mX + C

Slope,m = k
Y-intercept, C = 1/[A]o

1/[A]t = kt + 1/[A]0
 30

Zeroth Order

Y = mX + C

Slope,m = -k
Y-intercept, C = [A]o

[A]t = -kt + [A]0

 31

Example

Determination of the reaction order for

the decomposition of N2O5.
 32

3. Half Life Method

The half-life (t½) of a reaction is the time required to reduce the
reactant to half of its original value.
OR
time it takes for the reactant concentration to decrease one-
half of its initial concentration.

1.00 M 0.50 M 0.25 M 0.125 M

1min 1min 1min
 33

First Order Reaction

• Half life and depends on the Rate Constant but NOT the
concentration.

Thus, 1st t½ = 2nd t½ = 3rd t½

• The half life of the first order is always constant (only 1
value).
t1/2 = ln 2 = 0.693
k k
1.00 M 0.50 M 0.25 M 0.125 M
5 min 5 min 5 min
 34

A plot of [N2O5] vs time for three half-lives.

for a first-order process

ln 2 0.693
t1/2 = =
k k
 35

Second Order Reaction

• Half life and depends on the initial concentration and Rate
Constant.

Thus, 3rd t½= 2(2nd t½) and 2nd t½ = 2(1st t½)

• The half life of the second order is always DOUBLE the
preceding one.
t1/2 = 1
k[A]o
1.00 M 0.50 M 0.25 M 0.125 M
5 min 10 min 20 min
 36

Zeroth Order Reaction

• Half life and depends on the initial concentration and Rate
Constant.
t1/2 = [A]o
2k
You will get a horizontal line, because rate = k [A]0

Rate = k (a horizontal line)

rate
k Independent to [Reactant]

[A]
 37

Example
Cyclopropane is the smallest cyclic hydrocarbon. Because its 60 °
bond angles allow poor orbital overlap, its bonds are weak. As a
result, it is thermally unstable and rearranges to propene at
1000°C via the first-order reaction. If the rate constant is 9.2 s -1
a)What is the half-life of the reaction?
b)How long does it take for the concentration of cyclopropane to
reach one-quarter of the initial value?
 38

Use the half-life equation, t1/2 = 0.693 , to find the half-life.

k
One-quarter of the initial value means two half-lives have
passed.

SOLUTION:
 39

Summary
Zero Order First Order Second Order

Rate law rate = k rate = k [A] rate = k [A]2

Units for k mol/L*s 1/s L/mol*s

Integrated rate law in [A]t = -k t + [A]0 ln[A]t = -k t + ln[A]0 1/[A]t = k t + 1/[A]0

straight-line form

Plot for straight line [A]t vs. t ln[A]t vs. t 1/[A]t = t

Slope, y-intercept -k, [A]0 -k, ln[A]0 k, 1/[A]0

Half-life [A]0/2k ln 2/k 1/k [A]0

 40

FACTORS AFFECTING
RATES OF REACTION
 41

Factors Affecting Rates of Reaction

1. Chemical nature of the reactants
2. Ability of the reactants to come in contact with each other
3. Concentrations of the reactants
4. Temperature
5. Availability of rate-accelerating agents called catalysts
 42

Collision Theory
• The basis of the collision theory is that gas molecules must
collide before a reaction can happen
• According to this theory, not all collisions between the
molecules result in the formation of products
• Effective collisions between molecules, which result in the
formation of products, only can occur when these 2 conditions
are fulfilled:
a) The colliding molecules posses a minimum energy,
termed the activation energy
b) The reactant molecules collide at the correct orientation
 43

a) The colliding molecules posses a minimum energy,

termed the activation energy:
- The activation energy (Ea) is the energy to break down
the chemical bonds between atoms of the reactant
molecules to enable these atoms to form new bonds
in the product molecules.

b) The reactant molecules collide at the correct orientation:

- The colliding reactant molecules only react when the
orientation of collision favors the formation of products
(steric factor).
 44

• For example,
2CO(g) + 2NO(g) → 2CO2(g) + N2(g)
The effective collision occurs when the molecules having the
activation energy collides with the following orientation:

O≡C O=N O=C=O + ½ N≡N (effective collision)

One ineffective collision is shown below:

O≡C O=N No products (ineffective collision)

• It is important that effective collision only results when 2

reactants molecules having the activation energy collide at the
correct orientation
• Chemical reaction does not occur if only one of these
conditions is fulfilled
 45

• The height of the activation barrier influences the rate:

1. If Ea is large, then few molecules possess enough energy to
get over the barrier. A few products are formed and the
rate is slow.
2. If Ea is small, then many molecules possess enough energy
to get over the barrier. More products are formed and the
rate is faster.
• The activated complex is a species intermediate between
reactants and products with the maximum potential energy.
 46

RELATION BETWEEN RATE

AND TEMPERATURE
 47

Effect of Temperature
• The rate of reaction increases with increasing temperature
since molecules move faster and therefore, increase the
number of collisions between molecules (collision frequency).
• Therefore at higher temperature,
- the molecules collide more frequently.
- each collision is more energetic.
• As the collision frequency increases, the number of molecules
having kinetic energy higher than Ea increases. Therefore more
reaction take place
48
 49

Effect of Ea and T on the Fraction of

Collisions
Ea (kJ/mol) f (at T = 298 K)

50 1.70x10-9

75 7.03x10-14

100 2.90x10-18

T f (at Ea = 50 kJ/mol)

250C(298K) 1.70x10-9

350C(308K) 3.29x10-9

450C(318K) 6.12x10-9
 50

Effect of Temperature on Collision

Energies
 51

The Arrhenius Equation

The relationship between the rate constant and temperature is
given by Arrhenius equation:

k  Ae Ea Where,
RT - k is the rate constant at T

- Ea is the activation energy

ln k = ln A - Ea/RT - R is 8.314 J/mol.K (energy gas
constant
-1 - T is the Kelvin temperature
k2 1 1 - A is the collision frequency
Ea = R ln -
k1 T1 T2 factor
 52

Determination of the Activation Energy

ln k = -Ea/R (1/T) + ln A
 53

Example
The decomposition of hydrogen iodide, has rate constants of
9.51x10-9L /mol∙s at 500 K and 1.10x10-5 L/mol∙s at 600 K. Find Ea.
2HI(g) H2(g) + I2(g)

Solution:
-1
k2 Ea 1 1 k2 1 1
ln = - - Ea = R ln -
k1 R T2 T1 k1 T1 T2
 54

Example
At a certain temperature, ethanal decomposed according to
the following equation:
CH3CHO → CH4 + CO
Calculate the activation energy for the decomposition of
ethanal from the data given in the table below,

T (K) 700 730 760 790 810

k (mol-1 s-1) 0.011 0.035 0.105 0.343 0.789
 55

Solution:

1/T (K-1) 700 730 760 790 810

ln k 0.011 0.035 0.105 0.343 0.789

1/T (K-1)

Slope = -2.1×104 k=-Ea/R

ln k Ea=2.1×104×8.314 Jmol-1
=1.8×102 kJmol-1
 56

Exercise:
Question 1:
The reaction 2NOCl(g)→2NO(g) + Cl 2(g) has an Ea of 1.00×102
kJ/mol and a rate constant of 0.286 L/mol∙s at 500 K. What is the rate
constant at 490 K?
Answer:
k1= 0.175 L/mol∙s

Question 2:
The decomposition 2NO2(g)→2NO(g) + O2(g) has an Ea of 1.14×105
kJ/mol and a rate constant of 7.02×10-3 L/mol∙s at 500 K. At what
temperature will the rate be twice as fast?

Answer:
T2= 513 K
 57

REACTION MECHANISM
 58

Reaction Mechanism
What is Reaction Mechanism?

• A reaction mechanism is a collection OR series of elementary

reactions or steps (also called elementary steps) that explains
how the overall reaction proceeds.
• Elementary reaction is a single molecular reaction such as a
collision of molecules resulting in a chemical reaction.
• Reaction mechanism is used to predict the RATE LAW.
 59

Reaction mechanisms of Ozone depletion

O2 2O
2O + 2O3 4O2 (ozone breakdown)
 60

Elementary reaction is classified base on the number of

reactant molecules involve in a reaction.

Elementary reaction Molecularity Rate Law

A product Unimolecular Rate = k [A]

2A product Bimolecular Rate = k [A]2

A+ B product Bimolecular Rate = k [A][B]

2A + B product Termolecular Rate = k [A]2[B]

 61

Reaction Intermediate
• Reaction intermediate always formed (appear) in an early
elementary step BUT not in the overall balance equation.
• Exist in very low concentration.
• Eg:
Hydrogen gas reacts with iodine gas to form hydrogen iodide.
I2 + H2 → 2HI (overall equation)
The reaction may proceed by the following mechanisms:
Elementary step 1: I2 ↔ 2I
Elementary step 2: 2I + H2 → 2HI

→Reaction intermediate is iodine atom, I.

 62

Rate Determining Step

• The SLOWEST STEP in elementary reaction is the
• Rate-determining step of the overall reaction
• Rate law of rate-determining steps DETERMINE the overall
reaction rate law
• Eg: Consider a three-step reaction
step 1 : A→B (fast)
step 2 : B→C (slow)
step 3 : C→D (fast)
overall reaction: A→D

→ Rate determining step is Step 2.

 63

Correlating The Mechanism With Rate

Law
A valid mechanism must meet 3 criteria:
a) The elementary steps must be add up to the overall
balanced equation
b) The elementary steps must be reasonable. They should
generally involve one reactant particle (unimolecular) or
two (bimolecular)
c) The mechanism must correlate with the rate law
 64

Example
Hydrogen gas reacts with nitrogen monoxide to form nitrogen
and water.
2NO + 2H2 → N2 + 2H2O (overall)
The reaction may proceed by the following mechanisms
Step 1: 2NO ↔ N2O2 (fast)
Step 2: N2O2 + H2 → N2O + H2O (slow)
Step 3: N2O + H2 → N2 + H2O (fast)
• Reaction intermediate is N2O2
• Rate-determining step is N2O2 + H2 → N2O + H2O
• Rate = k[NO]2[H2]
Note: Only for elementary step, the equation coefficient can be used
as the reaction orders in the rate law
 65

CATALYTIC KINETICS
 66

Catalyst
• Catalyst: A substance that increases the rate of reaction by
reducing the activation energy of the reaction so that the
reaction proceeds faster
• In general, a catalyst lowers the energy of activation. Lowering
the Ea increases the rate constant, k, and thereby increases
the rate of the reaction.
• A catalyst increase the rate of the forward and the reverse
reactions.
• A catalyzed reaction yields the products more quickly but does
not yield more product than the uncatalyzed reaction.
• A catalyst lowers Ea by providing a different mechanism, for the
reaction through a new, lower energy pathway.
 67

Energy Diagram of a Catalyzed and

Uncatalyzed Reaction
 68

Homogenous vs. heterogeneous

catalysts
• A catalyst in the same phase (gases and solutions) as the
reactants is a homogeneous catalyst. It effective, but recovery
is difficult.
• When the catalyst is in a different phase than reactants (and
products), the process involve heterogeneous catalysis.
Chemisorption, absorption, and adsorption cause reactions to
take place via different pathways.
• Platinum is often used to catalyze hydrogenation.
 69

Heterogeneous catalysis in chemical industry

Chemical reaction Catalyst Industrial

product
N2 + 3H2 → 2NH3 Fe, Al2O3, K2O NH3
2SO2 + O2 → 2SO3 Pt or V2O5 H2SO4
-CH=CH- + H2 → -CH2- Ni or Pt or Pd Saturated fat
CH2-
4NH3 + 5O2 → 4NO + Pt and Rh HNO3
6H2O
CO + 2H2 → CH3OH ZnO and Cr2O3 CH3OH