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 B
D[A] D[A] = change in concentration of A over
rate = -
Dt time period Dt
D[B] D[B] = change in concentration of B over
rate =
Dt time period Dt

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

Because [B] increases with time, D[B] is positive.
 A B

time

D[A]
rate = -
Dt

D[B]
rate =
Dt
 Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

time

393 nm Detector
light
D[Br2] a DAbsorption
 Br2 (aq) + HCOOH (aq) 2Br– (aq) + 2H+ (aq) + CO2 (g)

slope of
tangent
slope of
tangent slope of
tangent

D[Br2] [Br2]final – [Br2]initial

average rate = – =–
Dt tfinal - tinitial
instantaneous rate = rate for specific instance in time
 rate a [Br2]
rate = k [Br2]
rate
k= = rate constant
[Br2]
= 3.50 x 10–3 s–1
 Reaction Rates and Stoichiometry

2A B

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

1 D[A] D[B]
rate = – rate =
2 Dt Dt

aA + bB cC + dD

1 D[A] 1 D[B] 1 D[C] 1 D[D]

rate = – =– = =
a Dt b Dt c Dt d Dt
Write the rate expression for the following reaction:

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g)

D[CH4] 1 D[O2] D[CO2] 1 D[H2O]

rate = – =– = =
Dt 2 Dt Dt 2 Dt
 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
 F2 (g) + 2ClO2 (g) 2FClO2 (g)

Determine x and y in the rate law Rate = k [F2]x[ClO2]y

Double [F2] with [ClO2] held constant:

The rate doubles
Therefore, x = 1

Quadruple [ClO2] with [F2] held constant:

The rate quadruples
Therefore, y = 1 The rate law is
Rate = k [F2]1[ClO2]1
 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
 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 ] (0.08 M)(0.034 M)
2– –
 Integrated Rate Laws
Consider a simple 1st order rxn: A ® B

Differential form:

How much A is left after time t ? Integrate:

Chemical
Kinetics
 Integrated Rate Laws
The integrated form of first order rate law:

Can be rearranged to give:

[A]0 is the initial concentration of A (t =0).

[A]t is the concentration of A at some time, t,
during the course of the reaction. Chemical
Kinetics
 Integrated Rate Laws
Manipulating this equation produces…

…which is in the form y = mx + b

Chemical
Kinetics
 First-Order Reactions

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

13.3
 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]t = ln[A]0 – kt
[A]t = 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

13.3
 Half-Life of 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 5.7 x 10 s
–4 –1

How do you know decomposition is first order?

units of k (s-1) 13.3
 Half-Life of a First-Order Reaction

The half-life of a first-order reaction stays the same.

Comparison of Graphs for a First-Order Reaction

A straight line is obtained from a graph of ln[A] vs. time,

characteristic of a first-order reaction.
 activation energy (Ea )
+
+
A+B AB C+D
Exothermic Reaction Endothermic Reaction

The activation energy (Ea ) is the minimum amount of

energy required to initiate a chemical reaction.
 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

For Two Temperatures: ln(k1/k2) = Ea/R(1/T2 – 1/T1) 13.4

 Ea 1
lnk = - + lnA
R T

Y-Intercept = lnA

Slope = –Ea/R

13.4
Importance of Orientation

13.4
K + CH3I KI + •CH3
 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 N2O2

+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
2NO (g) + O2 (g) 2NO2 (g)
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.
• Unimolecular reaction – elementary step with 1 molecule
• Bimolecular reaction – elementary step with 2 molecules
• Termolecular reaction – elementary step with 3 molecules
 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-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.
 The experimental rate law for the reaction between NO2
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
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
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
• Zeolites
• Enzymes

In homogeneous catalysis, the reactants and the catalysts

are dispersed in a single phase, usually liquid.

• Acid catalysis
• Base catalysis
 Haber Process

Fe/Al2O3/K2O
N2 (g) + 3H2 (g) 2NH3 (g)
catalyst
 Catalytic Converters

catalytic
CO + Unburned Hydrocarbons + O2 converter CO2 + H2O

catalytic
2NO + 2NO2 converter 2N2 + 3O2
Enzyme Catalysis