Chemical Kinetics
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
[A]
rate = t
[A] = change in concentration of A over
time period t
[B]
rate =
t
[B] = change in concentration of B over
time period t
Because [A] decreases with time, [A] is negative.
2
[A]
rate = t
[B]
rate =
t
3
red-brown
Br2 (aq) + HCOOH (aq)
2Br- (aq) + 2H+ (aq) + CO2 (g)
time
t1 < t2 < t3
393 nm
light
Detector
[Br2] Absorption
Br2 (aq) + HCOOH (aq)
2Br- (aq) + 2H+ (aq) + CO2 (g)
slope of
tangent
slope of
tangent
slope of
tangent
[Br2]final [Br2]initial
[Br2]
average rate = =t
tfinal - tinitial
instantaneous rate = rate for specific instance in time
rate [Br2]
rate = k [Br2]
rate
= rate constant
k=
[Br2]
= 3.50 x 10-3 s-1
6
2H2O2 (aq)
2H2O (l) + O2 (g)
PV = nRT
n
P=
RT = [O2]RT
V
1
[O2] =
P
RT
[O2]
1 P
rate =
=
RT t
t
measure P over time
7
Reaction Rates and Stoichiometry
2A
Two moles of A disappear for each mole of B that is formed.
1 [A]
rate = 2 t
aA + bB
[B]
rate =
t
cC + dD
1 [A]
1 [B]
1 [C]
1 [D]
rate = ==
=
a t
b t
c t
d t
9
Write the rate expression for the following reaction:
CH4 (g) + 2O2 (g)
CO2 (g) + 2H2O (g)
[CH4]
[CO2]
1 [O2]
1 [H2O]
rate = =
==
t
t
t
2 t
2
10
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
11
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
12
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
13
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)
Experiment
[S2O82-]
[I-]
Initial Rate
(M/s)
0.08
0.034
2.2 x 10-4
0.08
0.017
1.1 x 10-4
0.16
0.017
2.2 x 10-4
rate = k [S2O82-]x[I-]y
y=1
x=1
rate = k [S2O82-][I-]
Double [I-], rate doubles (experiment 1 & 2)
Double [S2O82-], rate doubles (experiment 2 & 3)
2.2 x 10-4 M/s
rate
k=
=
= 0.08/Ms
2- [S2O8 ][I ]
(0.08 M)(0.034 M)
14
First-Order Reactions
A
k=
product
[A]
rate = t
rate
M/s
=
= 1/s or s-1
M
[A]
[A] = [A]0ekt
rate = k [A]
[A]
= k [A]
t
[A] is the concentration of A at any time t
[A]0 is the concentration of A at time t=0
ln[A] = ln[A]0 - kt
15
Graphical Determination of k
2N2O5
4NO2 (g) + O2 (g)
16
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]
ln[A]0 ln[A]
=
t=
k
ln
[A]0
[A]
k
ln
=
0.88 M
0.14 M
2.8 x 10 s
-2
-1
= 66 s
17
First-Order Reactions
The half-life, t, is the time required for the concentration of a
reactant to decrease to half of its initial concentration.
t = t when [A] = [A]0/2
ln
t =
[A]0
[A]0/2
k
ln 2
0.693
=
=
k
k
What is the half-life of N2O5 if it decomposes with a rate constant
of 5.7 x 10-4 s-1?
0.693
t = ln 2 =
= 1200 s = 20 minutes
-4 -1
5.7 x 10 s
k
How do you know decomposition is first order?
units of k (s-1)
18
First-order reaction
A
product
# of
half-lives [A] = [A]0/n
1
16
19
Second-Order Reactions
A
product
[A]
rate = t
rate
M/s
=
k=
2 = 1/Ms
2
M
[A]
1
1
=
+ kt
[A]
[A]0
rate = k [A]2
[A]
= k [A]2
t
[A] is the concentration of A at any time t
[A]0 is the concentration of A at time t=0
t = t when [A] = [A]0/2
t =
1
k[A]0
20
Zero-Order Reactions
A
product
[A]
rate = t
[A]
=k
t
rate
= M/s
k=
0
[A]
[A] = [A]0 - kt
rate = k [A]0 = k
[A] is the concentration of A at any time t
[A]0 is the concentration of A at time t = 0
t = t when [A] = [A]0/2
t =
[A]0
2k
21
Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions
Order
0
Concentration-Time
Equation
Rate Law
[A] = [A]0 - kt
rate = k
rate = k [A]
ln[A] = ln[A]0 - kt
rate = k [A]
1
1
=
+ kt
[A]
[A]0
Half-Life
t =
[A]0
2k
t = ln 2
k
1
t =
k[A]0
22
A+B
Exothermic Reaction
AB++
C+D
Endothermic Reaction
The activation energy (Ea ) is the minimum amount of
energy required to initiate a chemical reaction.
23
Temperature Dependence of the Rate Constant
k A e ( Ea / RT )
(Arrhenius equation)
Ea is the activation energy (J/mol)
R is the gas constant (8.314 J/Kmol)
T is the absolute temperature
A is the frequency factor
Alternate format:
Ea 1
ln k = + lnA
R T
24
Alternate Form of the Arrhenius Equation
At two temperatures, T1 and T2
or
25
Importance of Molecular Orientation
effective collision
ineffective collision
26
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.
2NO (g) + O2 (g)
2NO2 (g)
N2O2 is detected during the reaction!
Elementary step:
NO + NO
N 2 O2
+ Elementary step:
N2O2 + O2
2NO2
Overall reaction:
2NO + O2
2NO2
27
2NO (g) + O2 (g)
2NO2 (g)
Mechanism:
28
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
N 2 O2
+ 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.
Unimolecular reaction elementary step with 1 molecule
Bimolecular reaction elementary step with 2 molecules
Termolecular reaction elementary step with 3 molecules
29
Rate Laws and Elementary Steps
Unimolecular reaction
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-determining step should predict the same rate
law that is determined experimentally.
The rate-determining step is the slowest step in the
sequence of steps leading to product formation.
30
Sequence of Steps in Studying a Reaction Mechanism
31
The experimental rate law for the reaction between NO 2 and CO
to produce NO and CO2 is rate = k[NO2]2. The 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
32
Chemistry In Action: Femtochemistry
CH2
CH2
CH2
CH2
2 CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
2 CH2
CH2
CH2
33
A catalyst is a substance that increases the rate of a
chemical reaction without itself being consumed.
k A e ( Ea / RT )
Ea
Uncatalyzed
Catalyzed
ratecatalyzed > rateuncatalyzed
Ea < Ea
34
In heterogeneous catalysis, the reactants and the catalysts
are in different phases.
Haber synthesis of ammonia
Ostwald process for the production of nitric acid
Catalytic converters
In homogeneous catalysis, the reactants and the catalysts
are dispersed in a single phase, usually liquid.
Acid catalysis
Base catalysis
35
Haber Process
N2 (g) + 3H2 (g)
Fe/Al2O3/K2O
catalyst
2NH 3 (g)
36
Ostwald Process
4NH3 (g) + 5O2 (g)
Pt catalyst
2NO (g) + O2 (g)
2NO2 (g) + H2O (l)
4NO (g) + 6H2O (g)
2NO2 (g)
HNO2 (aq) + HNO3 (aq)
Pt-Rh catalysts used
in Ostwald process
37
Catalytic Converters
CO + Unburned Hydrocarbons +
2NO + 2NO2
catalytic
O2 converter
catalytic
converter
CO2 + H2O
2N2 + 3O2
38
Enzyme Catalysis
39
Binding of Glucose to Hexokinase
40
Enzyme Kinetics
[P]
rate =
t
rate = k [ES]
41
