CHM101

FOUNDATION

CHEMISTRY
CHM101 M Kalulu
 Chemical Kinetics
 What we need to know
o Reactants
o Products
o Stoichiometry
 Rate of the reaction – How fast the reaction is.
o Some reactions are fast while others are slow.
 Definition: Chemical Kinetics is the study of rates of
reactions, rate laws, reaction mechanisms and
catalysis.

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Factors that affect rates of reactions

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 Reaction Rates

• Speed of a reaction is measured by the change in

concentration with time.
• For a reaction A  B

change in the number of moles of B

Average rate 
change in time
 moles of B 

t

• Suppose A reacts to form B. Let us begin with 1.00

mol A.
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 A B
[A] [A] = change in concentration of A over
rate = -
t time period t
[B] [B] = change in concentration of B over
rate =
t time period t

Because [A] decreases with time, [A] is negative.

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 A B

time

[A]
rate = -
t

[B]
rate =
t

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 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
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 rate a [Br2]
rate = k [Br2]
rate
k= = rate constant
[Br2]
= 3.50 x 10-3 s-1
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 Reaction Rates and Stoichiometry

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
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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

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 The 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.
aA + bB cC + dD

Rate = k [A]x[B]y

reaction is xth order in A

reaction is yth order in B
reaction is (x +y)th order overall

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

rate = k [F2]x[ClO2]y

Double [F2] with [ClO2] constant

Rate doubles x=1

Quadruple [ClO2] with [F2] constant rate = k [F2][ClO2]

Rate quadruples y = 1

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 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

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 Determine the rate law and calculate the rate constant for
the following reaction from the following data:
S2O82- (aq) + 3I- (aq) 2SO42- (aq) + I3- (aq)

Initial Rate
Experiment [S2O82-] [I-]
(M/s) rate = k [S2O82-]x[I-]y
1 0.08 0.034 2.2 x 10-4 y=1
2 0.08 0.017 1.1 x 10-4 x=1
3 0.16 0.017 2.2 x 10-4
rate = k [S2O82-][I-]

Double [I-], rate doubles (experiment 1 & 2)

Double [S2O82-], rate doubles (experiment 2 & 3)
rate 2.2 x 10-4 M/s
k= 2- -
= = 0.081/M•s
[S2O8 ][I ] (0.08 M)(0.034 M)

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 First-Order Reactions
[A]
A product rate = - rate = k [A]
t
[A]
- = k [A]
rate M/s t
k= = = 1/s or s-1 [A] is the concentration of A at any time t
[A] M
[A]0 is the concentration of A at time t=0
[A] = [A]0exp(-kt) ln[A] = ln[A]0 - kt

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 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 ?

[A]0 = 0.88 M
ln[A] = ln[A]0 - kt
[A] = 0.14 M
kt = ln[A]0 – ln[A]
[A]0 0.88 M
ln ln
ln[A]0 – ln[A] [A] 0.14 M
t= = = = 66 s
k k 2.8 x 10-2 s-1

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 First-Order Reactions
The half-life, t½, is the time required for the concentration of a
reactant to decrease to half of its initial concentration.

t½ = t when [A] = [A]0/2

[A]0
ln
[A]0/2 ln2 0.693
t½ = = =
k k k
What is the half-life of N2O5 if it decomposes with a rate
constant of 5.7 x 10-4 s-1?
t½ = ln2 = 0.693
= 1216 s = 20 minutes
k -4
5.7 x 10 s -1
units of k (s -1)
How do you know decomposition is first order?
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 Second-Order Reactions
[A]
A product rate = - rate = k [A]2
t

rate M/s [A]

k= = = 1/M•s - = k [A]2
[A] 2 M 2
t

1 1 [A] is the concentration of A at any time t

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

t½ = t when [A] = [A]0/2

1
t½ =
k[A]0

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 Zero-Order Reactions
[A]
A product rate = - rate = k [A]0 = k
t

rate [A]
k= = M/s - =k
[A] 0 t

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

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

t½ = t when [A] = [A]0/2

[A]0
t½ =
2k

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Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions

Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] = [A]0 - kt t½ =
2k

1 rate = k [A] ln[A] = ln[A]0 - kt t½ = ln2

k
1 1 1
2 rate = k [A]2 = + kt t½ =
[A] [A]0 k[A]0

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 A+B C+D

Exothermic Reaction Endothermic Reaction

The activation energy (Ea) is the minimum amount of

energy required to initiate a chemical reaction.
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Temperature Dependence of the Rate Constant

k = A • exp( -Ea/RT )
(Arrhenius equation)
Ea is the activation energy (J/mol)
R is the gas constant (8.314 J/K•mol)
T is the absolute temperature
A is the frequency factor

Ea 1
lnk = - + lnA
R T

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 Ea 1
lnk = - + lnA
R T

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 Determining the Energy of Activation

PROBLEM: The decomposition of hydrogen iodide,

2HI(g) H2(g) + I2(g)

has rate constants of 9.51x10-9L/mol*s at 500. K and 1.10x10-5

L/mol*s at 600. K. Find Ea.

PLAN: Use the modification of the Arrhenius equation to find Ea.

SOLUTION: -1
k2 Ea 1 1 k2 1 1
ln = - - Ea = - R ln -
k1 R T2 T1 k1 T2 T1

1.10x10-5L/mol*s 1 1
Ea = - (8.314J/mol*K) ln -
9.51x10-9L/mol*s 600K 500K

Ea = 1.76x105J/mol = 176kJ/mol

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Theories of reaction rates

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 Rateof reaction is related to the number of collisions.
 When molecules are moving, they do not move at the same
speed, because of collision.

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 For molecules to react, the bonds must be break, the net change
determines if the reaction is exothermic or endothermic.
 Bond breaking is endothermic while bond formation is exothermic.

When the new bonds between H and Cl are formed .The sufficient energy
is called Activation energy CHM101 M Kalulu 27
Transition State Theory

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 Catalysts
A catalyst is a substance that increases the rate of a
chemical reaction without itself being consumed.
k = A • exp( -Ea/RT ) Ea k

uncatalyzed catalyzed

ratecatalyzed > rateuncatalyzed

Ea‘ < Ea CHM101 M Kalulu
 Application of Kinetics
 In Industry
o Manufacturing
o Textile
 In Medicine
o Doses
o Shelf life (expiry date) of medicine, food, agricultural
products.

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