Chemical Kinetics

Ch t 13
Chapter

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 Chemical Kinetics

Thermodynamics – does a reaction take place?

Kinetics – how fast does a reaction proceed?

Reaction rate is the change in the concentration of a

reactant or a product with time (M/s).

A B
∆[A] ∆[A] = change in concentration of A over
rate = -
∆t time period ∆t
∆[B]
[B] ∆[B] = change in concentration of B over
rate =
∆t time period ∆t
Because [A] decreases with time, ∆[A] is negative.

13.1
 A B

time

∆[A]
rate = -
∆t

∆[B]
rate =
∆t

13.1
 Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

time

393 nm Detector
light
∆[Br2] α ∆Absorption
13.1
 Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

slope of
tangent
slope of
t
tangentt
slope of
tangent

∆[Br2] [Br2]final – [Br2]initial

average rate = - =-
∆t tfinal
fi l - tinitial
i iti l

instantaneous rate = rate for specific instance in time

13.1
 t α [Br
rate [B 2]
rate = k [Br2]
rate
t
k= = rate constant
[Br2]
3 50 x 10-33 s-11
= 3.50

13.1
 2H2O2 (aq)
( ) 2H2O (l) + O2 (g)
( )

PV = nRT
n
P= RT = [O2]RT
V
1
[O2] = P
RT

∆[O2] 1 ∆P
rate = =
∆t RT ∆t

measure ∆P over time

13.1
13.1
 Reaction Rates and Stoichiometry

2A B

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

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

13.1
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

13.1
 The Rate Law
The rate law
Th l expresses the
h relationship
l i hi off the
h rate off a reaction
i
to the rate constant and the concentrations of the reactants
raised to some powers.
p
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

13.2
 F2 (g) + 2ClO2 (g) 2FClO2 (g)

rate = k [F2]x[ClO2]y

Double [F2] with [ClO2] constant

Rate doubles
x=1
rate = k [F2][ClO2]
Quadruple [ClO2] with [F2] constant
Rate q
quadruples
p
y=1
13.2
 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.
q

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

rate = k [F2][ClO2] 1

13.2
 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- -
= = 0.08/M
0 08/M•s
[S2O8 ][I ] (0.08 M)(0.034 M)
13.2
 First-Order Reactions
∆[A]
A product rate = - rate = k [A]
∆t
∆[A]
rate M/s - = k [A]
k=
[A]
=
M
= 1/s or s-1 ∆t
[A] is the concentration of A at any time t
[A]0 is the concentration of A at time t=0

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

13.3
2N2O5 4NO2 (g) + O2 (g)

13.3
 The reaction 2A B is first order in A with a rate
constant off 2 8 x 10-22 s-11 at 800C.
2.8 C HHow llong will
ill iit take
k ffor 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
0.14
t= = = = 66 s
k k 2.8 x 10-2 s-1

13.3
 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
= 1200 s = 20 minutes
k -4
5.7 x 10 s -1

How do you know decomposition is first order?

units of k (s-1) 13.3
First-order reaction
A product

# of
half-lives [A] = [A]0/n
1 2

2 4

3 8

4 16

13.3
 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

13.3
 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

13.3
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

13.3
 +
+
A+B AB C+D
Exothermic Reaction Endothermic Reaction

The activation energy (Ea ) is the minimum amount of

energy required
i d tto iinitiate
iti t a chemical
h i l reaction.
ti

13.4
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

13.4
 Ea 1
lnk = - + lnA
R T

13.4
13.4
 Reaction Mechanisms

The overall progress of a chemical reaction can be represented

at the molecular level by a series of simple elementary steps
or elementary reactions.

The sequence of elementary steps that leads to product

formation is the reaction mechanism
mechanism.

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

N2O2 is detected during the reaction!

Elementary step: NO + NO N2O2

+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
13.5
2NO (g) + O2 (g) 2NO2 (g)

13.5
Intermediates are species that appear in a reaction
mechanism but not in the overall balanced equation.
An intermediate is always formed in an early elementary step
and consumed in a later elementary step.

Elementary step: NO + NO N2O2

+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2

The molecularity of a reaction is the number of molecules

reacting in an elementary step.
• U i l
Unimolecular
l reaction
ti – elementary
l t step
t with
ith 1 molecule
l l
• Bimolecular reaction – elementary step with 2 molecules
• Termolecular reaction – elementary step with 3 molecules
13.5
 Rate Laws and Elementary Steps

Unimolecular reaction A products rate = k [A]

Bimolecular reaction A+B products rate = k [A][B]

Bimolecular reaction A+A products rate = k [A]2

Writing plausible reaction mechanisms:

• The sum of the elementary steps must give the overall
balanced equation for the reaction.
• The rate
rate-determining
determining step should predict the same rate
law that is determined experimentally.
The rate
rate-determining
determining step is the slowest step in the
sequence of steps leading to product formation.
13.5
Sequence of Steps in Studying
y g a Reaction Mechanism

13.5
 The experimental rate law for the reaction between NO2
and
d CO tto produce
d NO andd CO2 is t = k[NO2]2. The
i rate Th
reaction is believed to occur via two steps:
Step 1: NO2 + NO2 NO + NO3
Step 2: NO3 + CO NO2 + CO2
What is the equation for the overall reaction?
NO2+ CO NO + CO2

What is the intermediate?

NO3

What can you say about the relative rates of steps 1 and 2?
rate = k[NO2]2 is the rate law for step 1 so
step 1 must be slower than step 2
13.5