Reading Assignments:

Chapter 13 in
R. Chang, Chemistry, 8th Ed., McGraw-Hill,
2005

Or Related topics in other textbooks.

Chemical Kinetics Consultation outside lecture room:

Office Hours:
Chapter 13 Tuesday & Thursday 10 am -12 pm
Wednesday 1-4 pm
@Room 313-3 or by appointment

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Chemical Kinetics A B

Thermodynamics –
Kinetics –

Reaction rate is the change in the concentration of a

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

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

slope of
time tangent
slope of
tangent
slope of
Br2 (aq) tangent

393 nm
∆[Br2]
393 nm Detector average rate = -
light ∆t
∆[Br2] α ∆Absorption
instantaneous rate = rate for specific instance in time
13.1 13.1

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

PV = nRT
n
P= RT = [O2]RT
V
1
[O2] = P
RT
rate α [Br2]
rate = k [Br2]

measure ∆P over time

13.1 13.1
 2H2O2 (aq) 2H2O (l) + O2 (g) 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]
rate = -
a ∆t

13.1 13.1

The Rate Law

Write the rate expression for the following reaction:
The rate law expresses the relationship of the rate of a reaction
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g) to the rate constant and the concentrations of the reactants
raised to some powers.
aA + bB cC + dD

reaction is xth order in A

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

13.1 13.2
 F2 (g) + 2ClO2 (g) 2FClO2 (g) Rate Laws
• Rate laws are always determined experimentally.

rate = k [F2]x[ClO2]y • Reaction order is always defined in terms of reactant

(not product) concentrations.

• The order of a reactant is not related to the

Double [F2] with [ClO2] constant stoichiometric coefficient of the reactant in the balanced
chemical equation.
Rate doubles
x=1 F2 (g) + 2ClO2 (g) 2FClO2 (g)
Quadruple [ClO2] with [F2] constant
Rate quadruples
y=1
13.2 13.2

First-Order Reactions
Determine the rate law and calculate the rate constant for
the following reaction from the following data: ∆[A]
S2O82- (aq) + 3I- (aq) 2SO42- (aq) + I3- (aq) A product rate = - rate = k [A]
∆t
Initial Rate ∆[A]
Experiment [S2O82-] [I-] rate M/s - = k [A]
(M/s) rate = k [S2O82-]x[I-]y k=
[A]
=
M
= 1/s or s-1 ∆t
1 0.08 0.034 2.2 x 10-4 y=1 [A] is the concentration of A at any time t
[A]0 is the concentration of A at time t=0
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-] [A] = [A]0exp(-kt) ln[A] = ln[A]0 - kt

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

Double [S2O82-], rate doubles (experiment 2 & 3)

13.2 13.3
 First-Order Reactions
The reaction 2A B is first order in A with a rate
constant of 2.8 x 10 s-1 at 800C. How long will it take for
-2
The half-life, t½, is the time required for the concentration of a
A to decrease from 0.88 M to 0.14 M ? reactant to decrease to half of its initial concentration.

[A]0 = 0.88 M t½ = t when [A] = [A]0/2

ln[A] = ln[A]0 - kt
[A] = 0.14 M
[A]0
kt = ln[A]0 – ln[A] 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?

How do you know decomposition is first order?

13.3 13.3

Second-Order Reactions
First-order reaction
∆[A]
A product A product rate = - rate = k [A]2
∆t
# of ∆[A]
rate M/s
half-lives [A] = [A]0/n k= = = 1/M•s - = k [A]2
[A]2 M2 ∆t
1 2
1 1 [A] is the concentration of A at any time t
2 4 = + kt
[A] [A]0 [A]0 is the concentration of A at time t=0

3 8

4 16

13.3 13.3
 Zero-Order Reactions
Summary of the Kinetics of Zero-Order, First-Order
∆[A] and Second-Order Reactions
A product rate = - rate = k [A]0 = k
∆t

rate ∆[A] Concentration-Time

k= = M/s - =k
[A]0 ∆t Order Rate Law Equation Half-Life
[A]0
[A] is the concentration of A at any time t 0 [A] = [A]0 - kt t½ =
[A] = [A]0 - kt 2k
[A]0 is the concentration of A at time t=0

1 rate = k [A] t½ = ln2

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

13.3 13.3