Kinetika Kimia

Chemical Kinetics
Chapter 13
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.
13.1
time
[A]
rate = t
[B]
rate =
t
13.1
Br2 (aq) + HCOOH (aq)
2Br- (aq) + 2H+ (aq) + CO2 (g)
time
393 nm
light
Detector
393 nm
Br2 (aq)
[Br2] Absorption
13.1
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
13.1
rate [Br2]
rate = k [Br2]
rate
= rate constant
k=
[Br2]
= 3.50 x 10-3 s-1
13.1
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

13.1
2H2O2 (aq)
2H2O (l) + O2 (g)
13.1
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
13.1
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
13.1
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
13.2
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
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.
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)
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)
13.2
First-Order Reactions
A
k=
product
[A]
rate = t
rate
M/s
=
= 1/s or s-1
M
[A]
[A] = [A]0exp(-kt)
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
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] = 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
13.3
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
ln2
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 = ln2 =
= 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)
13.3
First-order reaction
A
product
# of
half-lives
[A] = [A]0/n
16
13.3
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

t = t when [A] = [A]0/2

t =
1
k[A]0
13.3
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

t = t when [A] = [A]0/2

t =
[A]0
2k
13.3
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 = ln2
k
1
t =
k[A]0
13.3
A+B
Exothermic Reaction
C+D
Endothermic Reaction
The activation energy (Ea) is the minimum amount of

energy required to initiate a chemical reaction.
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/Kmol)
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
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
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
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

13.5
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.
13.5
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
13.5
A catalyst is a substance that increases the rate of a

chemical reaction without itself being consumed.
k = A exp( -Ea/RT )
Ea
uncatalyzed
catalyzed
ratecatalyzed > rateuncatalyzed

Ea < Ea
13.6
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
13.6
Haber Process
N2 (g) + 3H2 (g)
Fe/Al2O3/K2O
catalyst
2NH 3 (g)
13.6
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
Hot Pt wire
over NH3 solution
13.6
Catalytic Converters
CO + Unburned Hydrocarbons + O2
2NO + 2NO2
catalytic
converter
catalytic
converter
CO2 + H2O
2N2 + 3O2
13.6
Enzyme Catalysis
13.6
uncatalyzed
enzyme
catalyzed
13.6

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Chemical Kinetics

[A] = change in concentration of A over

[B] = change in concentration of B over

Br2 (aq) + HCOOH (aq)

2Br- (aq) + 2H+ (aq) + CO2 (g)

Br2 (aq) + HCOOH (aq)

2Br- (aq) + 2H+ (aq) + CO2 (g)

2H2O (l) + O2 (g)

measure P over time

2H2O (l) + O2 (g)

Reaction Rates and Stoichiometry

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

Write the rate expression for the following reaction:

CO2 (g) + 2H2O (g)

The Rate Law

reaction is xth order in A

F2 (g) + 2ClO2 (g)

Double [F2] with [ClO2] constant

Rate laws are always determined experimentally.

Reaction order is always defined in terms of reactant

The order of a reactant is not related to the

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

[A] is the concentration of A at any time t

What is the half-life of N2O5 if it decomposes with a rate

[A] is the concentration of A at any time t

t = t when [A] = [A]0/2

[A] is the concentration of A at any time t

t = t when [A] = [A]0/2

Summary of the Kinetics of Zero-Order, First-Order

The activation energy (Ea) is the minimum amount of

Temperature Dependence of the Rate Constant

N2O2 is detected during the reaction!

Intermediates are species that appear in a reaction

The molecularity of a reaction is the number of molecules

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

Writing plausible reaction mechanisms:

The sum of the elementary steps must give the overall

The rate-determining step should predict the same rate

The rate-determining step is the slowest step in the

The experimental rate law for the reaction between NO 2

What is the equation for the overall reaction?

What is the intermediate?

A catalyst is a substance that increases the rate of a

ratecatalyzed > rateuncatalyzed

In heterogeneous catalysis, the reactants and the catalysts

Haber synthesis of ammonia

Ostwald process for the production of nitric acid

In homogeneous catalysis, the reactants and the catalysts

N2 (g) + 3H2 (g)

2NO (g) + O2 (g)

4NO (g) + 6H2O (g)

Pt-Rh catalysts used

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