Chemical Kinetics

Chapter 6
 Subtopics
 Definition of rate
 Rate Laws and Rate Constants
 Reaction Order
 The Determination of the Rate Law
 Integrated Rate Laws
 Half-Lives and Time Constants
 The Arrhenius Parameters
 Collision Theory
 Transition State Theory
Definition of Rate
 How do we describe the speed at which a reaction
occurs?

Rusting Iron Burning coal

 Chemical Kinetics
Thermodynamics – does a reaction take place?
Kinetics – how fast does a reaction proceed? How
reaction rates respond to changes in the
conditions or the presence of catalyst?
Identify the mechanism of a reaction.

Step in the investigation of the rate and mechanism of

a reaction:

- Determine the overall stoichiometry & any side

reactions.
- Determine how the concentrations of the reactants
and products change with time after reaction
has been initiated.
- Constant temperature
Reaction rate is the change in the concentration of a
reactant or a product with time (M/s).

 J 
Rate 
t
 J   Change in the molar concentration of species J.

∆t = time interval

* All rate are positive

 A B

time
[A]
rate = -
t
[B]
rate =
t
• For the reaction
aA  bB  cC  dD

1  A  1  B 1  C 1  D
rate  - -  
a t b t c t d t
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
 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 at specific time = slope of graph of its molar
concentration vs time.
 Self Test 1
The rate of formation of NH3 in the
reaction N2(g) + 3 H2(g) →2 NH3(g) was
reported as 1.2 mmol dm-3 s-1 under a
certain set of conditions. What is the rate
of consumption of H2?
Rate Laws and Rate
Constants
 Rate laws and rate constants
The rate of reactions is often found to be proportional to the
molar concentrations of the reactants raised to a simple
power.
Rate  k  A B 
k = Rate constant; independent of concentration but
depend on temperature

Rate law: an equation that expresses the rate of a reaction in

terms of the molar concentration (or partial
pressure) of the species in the overall reaction.

* Unit: mol dm-3 s-1

 Self Test 2
A reaction has a rate law of the form
k[A]2[B].
What are the units of the rate constant k if
the reaction rate was measured in mol dm-
3 s-1?

• Ans: dm6 mol-2 s-1

• Overall reaction order can be determined by the unit of k

Reaction Rate Law k unit

Order

Zero -rA=kA mol/dm3.s

One -rA=kACA s-1

Two -rA=kACA2 (dm)3/mol.s

Three -rA=kACA3 (dm3/mol)2.s-1

Rate law and rate constant of reaction:

- predict the rate of the reaction for any given

composition of the reaction mixture.

- predict the concentrations of the reactants

and products at any time after the start of reaction.

- mechanism of the reaction.

Reaction Order
 Reaction Order
Classification of reactions according to kinetics.

Exp: Rate  k  A B 

First order in A and first order in B

Overall order: the sum of the order of all the components.

• 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]
The Determination of the Rate
Law
Isolation method
Method of initial rates
 The determination of the rate law
• Isolation method
– All reactants except one are present in large
excess
– If reactant B in large excess, take it
concentration as constant throughout the
reaction.

Rate  k A  B
2

Rate  k  A  with k  k B
' ' 2
o
- The effective rate law is classified as pseudo
first-order and k’ is called effective rate
constant for a given, fixed concentration of B.
– If reactant A in large excess, the rate law is
simplified to
Rate  k ''  B with k ''  k A  o
2

– This called as pseudo second-order rate law.

 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= = = 0.08/M•s
[S2O8 ][I ]
2- -
(0.08 M)(0.034 M)
 The determination of the rate law

• Method of initial rates;

– the instantaneous rate is measured at the
beginning of the reaction for several different
initial concentrations of reactants.
Rate  k '  A
a

Rate  k '  A
a

0 o

log rate  log k ' a log A

0 0
 Integrated Rate Laws
An expression that gives the
concentration of a species as a
function of time.
 Zeroth-Order Reactions

 zeroth-order reaction is one whose rate is independent of concentration; its

differential rate law is rate = k. We refer to these reactions as zeroth order
because we could also write their rate in a form such that the exponent of the
reactant in the rate law is 0:
 Summary of the Kinetics of First-Order
and Second-Order Reactions

Concentration-Time
Order Rate Law Equation Half-Life

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
 First-Order Reactions
d[A]
A product rate = - rate = k [A]
dt
d[A]
rate M/s - = k [A]
k= = = 1/s or s-1 dt
[A] M
[A] is the concentration of A at any time t
[A]0 is the concentration of A at time t=0

[A] = [A]0exp(-kt) ln[A] = ln[A]0 - kt

If a plot of reactant concentration versus time is not linear but a plot of the
natural logarithm of reactant concentration versus time is linear, then the
reaction is first order.
 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 ?

ln[A] = ln[A]0 - kt [A]0 = 0.88 M

[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 s-2 -1
 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
The half life of a reactant is independent of its
concentration
= 1200 s = 20 minutes
 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
k 5.7 x 10-4 s-1
How do you know decomposition is first order?
units of k (s-1)
 Second-Order Reactions
d[A]
A product rate = - rate = k [A]2
dt

rate M/s d[A]

k= = 2 = 1/M•s
- = k [A]2
[A] 2 M dt

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

1
t½ = t when [A] = [A]0/2 t½ =
k[A]0
 Self Test 2
• Pb 10.9
• Pb 10.12
• Pb 10.21
The Arrhenius Parameters
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
 Ea 1
lnk = - + lnA
R T
 Figure 10.18
• High activation energy corresponds to a
reaction rate that is very sensitive to
temperature.
• Small activation energy shows a reaction
rate that varies only slightly with
temperature.
k1 E a  1 1 
ln    
k2 R  T2 T1 
Collision Theory
• Reaction occurs only if two molecules collide
with a certain minimum kinetic energy along
their line approach.
• The rate of collision (collision frequency) is
proportional to concentration of reactants.
Collision frequency  [A][B]

• However, not all collisions lead to reactions.

• Colliding molecules must have a total kinetic
energy equal to or greater than the activation
energy, Ea.
• The species temporarily formed by the reactant
molecules as a result of the collision before they
form the product is called the transition state or
activated complex.
• If the products more stable than reactant, then the
reaction will be accompanied by a release of heat.
• On the other hand if the products are less stable
than reactants.
 A+B C+D
Exothermic Reaction Endothermic Reaction

The activation energy (Ea) is the minimum amount of

energy required to initiate a chemical reaction.
Transition state theory
• The potential energy rises and reaches a
maximum.
• A cluster of atoms that is poised to pass
on to products or to collapse back into
reactants.