Centre for Foundation Studies, UTAR

Topic Scopes

TOPIC 6

Reaction Kinetics

Rate of reactions
Rate constant, half-life of a reaction
Zero,1st & 2nd order of reactions
Factors affecting rate of reactions:
concentration, temperature, catalyst and
surface area
Concept of activation energy
Arrhenius equation
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Reaction Rate

Reaction Kinetics

The change in the concentration of a

reactant or a product with time

Study of the rates of chemical reaction

______________ level (rates of reactions)
determination of a reaction rate
factors that influence rates
______________ level (chemical reaction)
reaction mechanism

Rate of reaction change in concentration

change in time

Methods for Expressing

Reaction Rates

D[A]
rate =
Dt

D[A] = change in concentration of

A over time period Dt

D[B]
Dt

D[B] = change in concentration of

B over time period Dt

rate =

[A] __creases with time, D[A] is negative

[B] __creases with time, D[B] is positive
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FHSC1114 Physical Chemistry

1) Initial rate
rate of the reaction when the reactants are
pure (precisely known)
2) Instantaneous rate (tangent rate)
rate of change in concentration at any
particular instant during a reaction
3) Average reaction rate
A measure of the change in concentration
over a defined period
The differences in concentrations of a reactant
between 2 points in time are divided by the
time elapsed
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Centre for Foundation Studies, UTAR

Reaction Rates and Stoichiometry

2A

Two moles of A disappear for each mole of B that

is formed.
rate = -

1 D[A]
2 Dt

rate =

aA + bB
Slope of
tangent

rate = -

D[B]
Dt

cC + dD

1 D[C]
1 D[D]
1 D[A]
1 D[B]
=
=
=d Dt
c Dt
a Dt
b Dt

Write the rate expression for the following

reaction:
N2 (g) + 3H2 (g)
2NH3 (g)
rate = -

D[N2]
Dt

=-

1 D[H2]
3 Dt

Extra Question
Decomposition of nitrogen pentaoxide is shown as below:
N2O5(s) ->NO2(g) + O2(g)

1 D[NH3]
Dt
2

(a) Balance the chemical equation for the decomposition of nitrogen

pentaoxide.
(b) Express the rate in terms of the change in concentration with time for
each substance.
(c) Determine the rate of disappearance of N2O5when the rate of
appearance of NO2 is 0.75 x 10-4 mol L-1 s-1 [Ans: 3.75 x 10-5 mol L-1s-1]

Rate Law
Expresses the relationship of the a reaction rate
to the rate constant and the concentrations of
the reactants raised to some powers.
aA + bB

cC + dD

Rate = k [A]x[B]y

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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.

The exponents x and y

are the reaction order
F2 (g) + 2ClO2 (g)

can be 0, 1, 2 or fraction
must be determined by experiment
total reaction order = (x + y)

FHSC1114 Physical Chemistry

2FClO2 (g)
1

rate = k [F2][ClO2]
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Interpreting Rate Law: Rate = k [A]x

Determining a Rate Equation

a) If x = 1, reaction is 1st order in A

Rate = k [A]1
If [A] doubles, then rate goes up by factor of
__
b) If x = 2, reaction is 2nd order in A.
Rate = k [A]2
Doubling [A] increases rate by __
c) If x = 0, reaction is zero order in A.
Rate = k [A]0
If [A] doubles, rate ________________

F2 (g) + 2 ClO2 (g)

2 FClO2 (g)

Rate = k[F2]x[ClO2]y
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No
change

x4

x4

14

No
change

x2

x2

Double [F2] with [ClO2] constant,

Quadruple [ClO2] with [F2] constant,

Rate doubles

Rate quadruples
Rate Experiment 2 k 0.10 M 0.040 M
4.8 10 Ms

Rate Experiment 1 k 0.10 Mx 0.010 My 1.2 10-3 Ms1

x

-3

-1

Rate Experiment 3 k 0.20 Mx 0.010 M y 2.4 10 -3 Ms-1

Rate Experiment1 k 0.10 Mx 0.010 M y 1.2 10 -3 Ms-1

Rate 3 0.20 2.4 10 3

Rate 1 0.10 1.2 10 3
x

Rate 2 0.040
4.8 10 3

Rate 1 0.010
1.2 10 3
y

2 = (2)x, x = ____

4 = (4)y, y = ______
The reaction is ______ order in [ClO2]

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Determining a Rate Constant, k

The reaction is ___ order in [F2]

x = ___ , y = ___
rate = ________

Zero-Order Reactions
A
D[A]
rate = - Dt

product
rate = k [A]0 = k

D[A]
Dt = k

[A] is the concentration of A at any time t

Rate = k [F2][ClO2]

[A] = [A]0 - kt

Using Exp. 1:
Rate = 1.2 x 10-3 M s-1 = k [0.10 M][0.010 M]
k = ______ M-1 s-1 = ______ L mol-1 s-1

[A]0 is the concentration of A at time t = 0

or
Using Exp. 2:
Rate = 4.8 x 10-3 M/s = k [0.10 M][0.040 M]
k = ______ M-1 s-1 = ______ L mol-1 s-1

FHSC1114 Physical Chemistry

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Centre for Foundation Studies, UTAR

First-Order Reactions
A
rate = -

D[A]
Dt

rate = k [A]

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

The reaction 2A
B is first order in A
with a rate constant of 2.8 x 10-2 s-1 at
800C. How long will it take for A to
decrease from 0.88 M to 0.14 M ?

product
-

D[A]
= k [A]
Dt

[A] is the concentration of A at any time t

[A]0 is the concentration of A at time t = 0

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Half-Life, t1/2
The time required
for a reactant to
decrease to half of
its initial
concentration /
amount

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Problem :
At a given temperature, hydrogen peroxide
(H2O2) decomposes to water and oxygen with
the rate law as below:
Rate = k[peroxide], k = 1.06 x 10-3 min-1

Half-Life & First-order Process

What amount of time is required for 15% of the

sample of to H2O2 decompose?
Fraction remaining = [A]t
[A]0
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Centre for Foundation Studies, UTAR

Solution:
After 15% of the H2O2 has decomposed,
85% remains.
fraction remaining is 0.85

ln(

Problem:
Radioactive decay is a first order process.
Tritium electron + helium
3H
0 e
3He
-1

[H 2 O 2 ]t
) kt
[H 2 O 2 ]o

85
) (1.06 10 3 min 1 )(t )
100
ln0.85 (1.06 10 3 min 1 )(t )
t

If you have 1.50 mg of tritium, how much is

ln(

left after 49.2 years? Given t1/2 = 12.3 years

min
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Solution:
ln [A]/[A]0 = -kt
[A] = ?
[A]0 = 1.50 mg,

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Second-Order Reactions
A

t = 49.2 years
rate = -

Need k, so we calc. k from:

k = 0.693 / t1/2 k = 0.0564 y-1

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

Now ln [A]/[A]0 = -kt = -(0.0564 y-1) (49.2 y)

= - 2.77
Take antilog: [A]/[A]0 = e-2.77 = 0.0627
0.0627 = fraction remaining
Because [A]0 = 1.50 mg, [A] = ______ mg

Summary of the Kinetics of Zero-Order,

First-Order and Second-Order For The
Reaction Type A Products

D[A]
= k [A]2
Dt

[A] is the concentration of A at any time t

[A]0 is the concentration of A at time t=0

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Factors Affecting Rates

- D[A]/Dt = k [A]1

rate = k [A]2

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- D[A]/Dt = k [A]0

D[A]
Dt

product

Concentrations
Temperature
Physical state of reactants
(surface area)
Catalysts

- D[A]/Dt = k [A]2
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FHSC1114 Physical Chemistry

Centre for Foundation Studies, UTAR

Temperature & Rates

Concentration & Rates

Mg(s) + 2 HCl(aq) MgCl2(aq) + H2(g)

Rate Temperature

Reactions generally
occur slower at lower
T.
Rate concentration
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Physical State of Reactants

(Surface Area)

If the reactants are in the same state, all

molecules can be fully exposed to 1
another
If the reactants are in different phases
(e.g. 1 is solid, 1 is gas), reaction rate is
inhibited by the inability of the molecules
to approach 1 another
Depend on the exposed surface area of
the reactants (the greater the surface
area, the faster the reaction)

Catalyst & Rates

A substance that increases the rate of a

chemical reaction without itself being
consumed.

Speed up reaction by altering the

mechanism to lower the activation energy
barrier

Ea (catalyzed) < Ea (uncatalyzed)

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Activation Energy, Ea

Catalysts: catalyzed decomposition of H2O2

2H2O2 2H2O + O2

The minimum amount of energy required

to initiate a chemical reaction.
A+ B
Exothermic Reaction

ratecatalyzed > rateuncatalyzed

FHSC1114 Physical Chemistry

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AB

+
+

C+D
Endothermic Reaction

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Centre for Foundation Studies, UTAR

Activation Energy, Ea

Collision Theory

Ea the energy required to surmount the

barrier

Reaction happens if the reacting molecules:

a) must collide with sufficient energy
b) must come together in the correct
orientation
affect the rate constant, k
determine the reaction rate

If the barrier is low, Ea is low, the energy

required is low, high proportion of the
reactant molecules may have sufficient
energy to react, the reaction will be fast

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Arrhenius Equation

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ln k = -

Ea 1
+ lnA
R T

k = A exp( -Ea / RT ) = Ae-Ea/RT

Plot ln k vs. 1/T

Slope = -Ea/ R

e-Ea/RT = fraction of molecules having the

minimum E required for reaction
k = rate constant
A = frequency factor (L mol-1 s-1)
R = 8.31 x 10-3 (kJ K-1 mol-1)
-Ea/ R

Ea = activation energy
T = temperature (K)

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Example:

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Solution:

The variation in the rate constant, k at two different temperatures

for the reaction is given in the following table.
2HI (g) H2 (g) +I2 (g)

Calculate the activation energy, Ea

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FHSC1114 Physical Chemistry

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Centre for Foundation Studies, UTAR

Catalysis

Learning Outcomes

Heterogeneous catalysis reactants and

catalysts are in different phases.
Haber synthesis of ammonia

Ostwald process production of nitric acid

Catalytic converters

Homogeneous catalysis reactants and

catalysts are dispersed in a single phase,
usually liquid.
Acid catalysis
Base catalysis
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FHSC1114 Physical Chemistry

Explain principles that govern properties of

chemical systems.
Discuss properties of gases, chemical bonds
and chemical kinetics.
Conduct and analyse experiments related to
physical chemistry.

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