CH 1 Chemical Kinetics

Copyright 2011 Pearson Education, Inc.
Chapter 1
Chemical Kinetics
Kinetics: Rates and Mechanisms of Chemical Reactions
1.1 Expressing Reaction Rate: Differential rate law
Graphical representation of reaction rate
1.2 The Rate Law : Order of reaction, Initial rate method
Integrated rate law, rate constant, half -life
1.3 Collision Theory: Activation energy, effective collisions
1.6 Arrhenius Equation: Determination of rate constant and
activation energy
1.7 Reaction Mechanism: Intermediates, molecularity,
rate determining step
1.4 Factors affecting reaction rate: Concentration, temperature, catalyst,
nature of reactants
1.5 Transition State Theory: Activated complex
Chemical Kinetics
The speed of a chemical reaction is called its
reaction rate
The rate of a reaction is a measure of how fast
the reaction makes products, or how fast the
reactants are consumed.
Chemical kinetics is the study of the factors
that affect the rates of chemical reactions
Such as temperature, reactant concentrations

3 Tro: Chemistry: A Molecular Approach, 2/e
Defining Reaction Rate
The rate of a chemical reaction is generally
measured in terms of how much the concentration
of a reactant decreases in a given period of time
or product concentration increases
For reactants, a negative sign is placed in front of
the definition
| | | | | | ( )
( )
( )
( )
0625 0
0 6 1
8 7
Rate
t t
X X
t
X
Rate
1 2
1 2
. =
=
A
A
=
| | | | | | ( )
( )
( )
( )
25 0
0 6 1
8 4
Rate
t t
A A
t
A
Rate
1 2
1 2
. =
=
A
A
=
at t = 0
[A] = 8
[B] = 8
[C] = 0
at t = 0
[X] = 8
[Y] = 8
[Z] = 0
at t = 16
[A] = 4
[B] = 4
[C] = 4
at t = 16
[X] = 7
[Y] = 7
[Z] = 1
| | | | | | ( )
( )
( )
( )
25 0
0 6 1
0 4
Rate
t t
C C
t
C
Rate
1 2
1 2
. =
=
A
A
=
| | | | | | ( )
( )
( )
( )
0625 0
0 6 1
0 1
Rate
t t
Z Z
t
Z
Rate
1 2
1 2
. =
=
A
A
=
Reaction Rate Changes Over Time
As time goes on, the rate of a reaction generally
slows down
because the concentration of the reactants
decreases
At some time the reaction stops, either because
the reactants run out or because the system has
reached equilibrium
Average Rate
The average rate is the change in measured
concentrations in any particular time period
linear approximation of a curve

Reaction Rate and Stoichiometry
In most reactions, the coefficients of the balanced
equation are not all the same
H
2 (g)
+ I
2 (g)
2 HI
(g)
For these reactions, the change in the number of
molecules of one substance is a multiple of the
change in the number of molecules of another
for the above reaction, for every 1 mole of H
2
used, 1
mole of I
2
will also be used and 2 moles of HI made
therefore the rate of change will be different
To be consistent, the change in the concentration of
each substance is multiplied by 1/coefficient
H
2
I
2

HI
Stoichiometry tells us that for
every 1 mole/L of H
2
used,
2 moles/L of HI are made.
Assuming a 1 L container, at
10 s, we used 0.181 moles of
H
2
. Therefore the amount of
HI made is 2(0.181 moles) =
0.362 moles.
At 60 s, we used 0.699 moles
of H
2
. Therefore the amount
of HI made is 2(0.699 moles)
= 1.398 moles.
The average rate is
the change in the
concentration in a
given time period
In the first 10 s, the
A[H
2
] is 0.181 M,
so the rate is
average rate in a given
time period = slope of
the line connecting the
[H
2
] points; and +slope
of the line for [HI]
the average rate for the
first 10 s is 0.0181 M/s
Instantaneous Rate
The instantaneous rate is the change in
concentration at any one particular time
Determined by taking the slope of a line tangent to the
concentartion vs time curve at any particular point.
The initial rate is the reaction rate at the
beginning of a reaction
slope of a line tangent to the curve at time t = 0
No product formed yet, reversed rate = 0
H
2 (g)
+ I
2 (g)
2 HI
(g)

Using [H
2
], the
instantaneous
rate at 50 s is
Using [HI], the
instantaneous
rate at 50 s is
Problem 1.1: For the reaction given, the [I
] changes from1.000 M to 0.868 M

in the first 10 s. Calculate the average rate in the first 10 s, and A[H
+
]/At.
H
2
O
2

(aq)
+ 3 I
(aq)
+ 2 H
+
(aq)
I
3
(aq)
+ 2 H
2
O
(l)

13
solve the rate
equation for the rate
(in terms of the
change in
concentration of the
given quantity)
solve the rate
equation (in terms of
the change in the
concentration for the
quantity to find) for
the unknown value
Tro: Chemistry: A Molecular Approach, 2/e
Practice :
If 2.4 x 10
2
g of NOBr (MM 109.91 g) decomposes in a 2.0 x
10
2
mL flask in 5.0 minutes, find the average rate of Br
2

production in M/s.

2 NOBr(g) 2 NO(g) + Br
2
(l)
2 mol NOBr:1 mol Br
2
, 1 mol = 109.91g, 1 mL=0.001 L
Solve:
Conceptual
Plan:

Relationships:
240.0 g NOBr, 200.0 mL, 5.0 min.
A[Br
2
]/At, M/s
Given:
Find:
Practice If 2.4 x 10
2
g of NOBr decomposes in a 2.0 x 10
2
mL
flask in 5.0 minutes, find the average rate of Br
2
production
2 NOBr(g) 2 NO(g) + Br
2
(l)
15
A M
A mole Br
2

Rate
A min
A s
}
5.45 M Br
2
, 3.0 x 10
2
s
A[Br
2
]/At, M/s
240.0 g NOBr, 0.2000 L, 5.0 min.
A[Br
2
]/At, M/s
Practice: Consider the reaction:
8A(g) + 5B(g) 8C(g) + 6D(g)
If [C] is increasing at the rate of 4.0 mol L
1
s
1
, at what rate is
[B] changing?
A. -0.40 mol L
1
s
1

B. -2.5 mol L
1
s
1

C. -4.0 mol L
1
s
1

D. -6.4 mol L
1
s
1

E. None of these choices is correct, since its rate of
change must be positive.

Tro: Chemistry: A Molecular Approach 16
In general, the differential rate law for the reaction
aA + bB cC + dD
rate =
1
a
- = -
A[A]
At
1
b
A[B]
At
1
c
A[C]
At
= +
1
d
A[D]
At
= +
The numerical value of the rate depends upon the substance that
serves as the reference. The rest is relative to the balanced
chemical equation.
SOLUTION:
Expressing Rate in Terms of Changes in Concentration with Time
PROBLEM 1.2:
Because it has a nonpolluting product (water vapor), hydrogen
gas is used for fuel aboard the space shuttle and may be used
by earthbound engines in the near future.
2H
2
(g) + O
2
(g) 2H
2
O(g)
(a) Express the rate in terms of changes in [H
2
], [O
2
], and [H
2
O] with time.
(b) When [O
2
] is decreasing at 0.23 mol/L*s, at what rate is [H
2
O] increasing?
-
1
2
A[H
2
]
At
= -
A[O
2
]
At
= +
A[H
2
O]
At
1
2
0.23 mol/L*s = +
A[H
2
O]
At
1
2
= 0.46 mol/L*s
A[H
2
O]
At
rate = (a)
A[O
2
]
At
- = - (b)
The Rate Law
The rate law of a reaction is the mathematical
relationship between the rate of the reaction and the
concentrations of the reactants
and homogeneous catalysts as well
The rate law must be determined experimentally!!
The rate of a reaction is directly proportional to the
concentration of each reactant raised to a power
For the reaction aA + bB products the rate
law would have the form given below
n and m are called the orders for each reactant
k is called the rate constant
Reaction Order
The exponent on each reactant in the rate law
is called the order with respect to that reactant
The sum of the exponents on the reactants is
called the overall order of the reaction
The rate law for the reaction given:
2 NO(g) + O
2
(g) 2 NO
2
(g)
is: Rate = k[NO]
2
[O
2
]
The reaction is:
second order with respect to [NO],
first order with respect to [O
2
],
and third order overall.
SOLUTION:
Determining Reaction Order from Rate Laws
PROBLEM 1.3:
For each of the following reactions, determine the
reaction order with respect to each reactant and the
overall order from the given rate law.
(a) 2NO(g) + O
2
(g) 2NO
2
(g) rate = k[NO]
2
[O
2
]
(b) H
2
O
2
(aq) + 3I
-
(aq) + 2H
+
(aq) I
3
-
(aq) + 2H
2
O(l) rate = k[H
2
O
2
][I
-
]
PLAN:
Look at the rate law and not the coefficients of the chemical reaction.
(a) The reaction is 2nd order in NO, 1st order in O
2
, and 3rd order overall.
(b) The reaction is 1st order in H
2
O
2
, 1st order in I
-
and zero order in H
+
,
while being 2nd order overall.
Rate = k[NO][O
3
]
Solve:
Conceptual
Plan:
Relationships:
[NO] = 1.00 x 10
6
M, [O
3
] = 3.00 x 10
6
M,
Rate = 6.60 x 10
6
M/s
k, M
1
-s
1
Given:
Find:
Example: The rate equation for the reaction of NO with ozone is
Rate = k[NO][O
3
]. If the rate is 6.60 x 10
5
M/sec when [NO] = 1.00 x 10
6
M
and [O
3
] = 3.00 x 10
6
M, calculate the rate constant k
Rate, [NO], [O
3
] k
Practice:
The rate law for the decomposition of acetaldehyde,
CH3CHO, is Rate = k[CH3CHO]
2
.
What is the rate of the reaction when the [CH3CHO]
= 1.75 x 10
3
M and the rate constant is 6.73 x 10
6

M
1
s
1
?
Rate = k[acetaldehyde]
2

Solve:
Conceptual
Plan:
Relationships:
[CH3CHO] = 1.75 x 10
3
M, k= 6.73 x 10
6
M
1
s
1

Rate, M/s
Given:
Find:
Practice What is the rate of the reaction when the
[CH3CHO] = 1.75 x 10
3
M and the rate constant is 6.73 x
10
6
M
1
s
1
?
k, [acetaldehyde] Rate
Finding the Rate Law:
the Initial Rate Method
The rate law must be determined experimentally
The rate law shows how the rate of a reaction
depends on the concentration of the reactants
Changing the initial concentration of a reactant will
therefore affect the initial rate of the reaction
25
if for the reaction
A Products

Rate = k[A]
n

then doubling the
initial concentration
of A doubles the
initial reaction rate
then doubling the
of A does not
change the initial
reaction rate. Thus,
n = 0 (Zero Order)
Rate = k

then doubling the
of A quadruples the
initial reaction rate
Proposed rate law: Rate = k[A]
n

If a reaction is Zero Order, the rate of the reaction
is always the same
doubling [A] will have no effect on the reaction rate
If a reaction is First Order, the rate is directly
proportional to the reactant concentration
doubling [A] will double the rate of the reaction
If a reaction is Second Order, the rate is directly
proportional to the square of the reactant
concentration
doubling [A] will quadruple the rate of the reaction
Determining the Rate Law when there are Multiple
Reactants
Changing each reactant will effect the overall rate
of the reaction
By changing the initial concentration of one
reactant at a time, the effect of each reactants
concentration on the rate can be determined
In examining results, we compare differences in
rate for reactions that only differ in the
concentration of one reactant
Example 13.2: Determine the rate law and rate constant for the
reaction NO
2(g)
+ CO
(g)
NO
(g)
+ CO
2(g)

given the data below
Comparing Expt #1 and Expt #2,
the [NO
2
] changes but the [CO]
does not
Example 13.2: Determine the rate law and rate constant
for the reaction NO
2(g)
+ CO
(g)
NO
(g)
+ CO
2(g)

for the reaction NO
2(g)
+ CO
(g)
NO
(g)
+ CO
2(g)

for the reaction NO
2(g)
+ CO
(g)
NO
(g)
+ CO
2(g)

reaction NO
2(g)
+ CO
(g)
NO
(g)
+ CO
2(g)

n = 2, m = 0
reaction NO
2(g)
+ CO
(g)
NO
(g)
+ CO
2(g)

Substitute the
concentrations
and rate for
any experiment
into the rate
law and solve
for k
Expt.
Number
Initial
[NO
2
], (M)
Initial
[CO], (M)
Initial Rate
(M/s)
1. 0.10 0.10 0.0021
2. 0.20 0.10 0.0082
3. 0.20 0.20 0.0083
4. 0.40 0.10 0.033

Rate = k[NO
2
]
2
for expt 1
0.0021
M
s
= k 0.10 M
( )
2
k =
0.0021
M
s
0.01 M
2
= 0.21 M
1
- s
1
Practice Determine the rate law and rate constant for the
reaction NH
4
+
+ NO
2
N
2
+ 2 H
2
O
Practice Determine the rate law and rate constant for the
reaction NH
4
+
+ NO
2
N
2
+ 2 H
2
O
Rate = k[NH
4
+
]
n
[NO
2
]
m

Integrated Rate Laws
For the reaction A Products, the rate law
depends on the concentration of A
Applying calculus to integrate the rate law gives
another equation showing the relationship
between the concentration of A and the time of the
reaction this is called the Integrated Rate Law
First Order Reactions
Rate = k[A]
1
= k[A]
ln[A] = kt + ln[A]
initial

Graph ln[A] vs. time gives straight line with
slope = k and yintercept = ln[A]
initial

used to determine the rate constant
t
= 0.693/k. The half-life of a first order

reaction is constant
When Rate = M/sec, k = s
1
ln[A]
initial

ln[A]
time
Half-Life
The half-life, t
1/2
, of a reaction is the
time it takes for the concentration of the
reactant to fall to its initial value
The half-life of the reaction depends on
the order of the reaction
The Half-Life of a First-Order Reaction Is Constant
Rate Data for: C
4
H
9
Cl + H
2
O C
4
H
9
OH + HCl
C
4
H
9
Cl + H
2
O C
4
H
9
OH + 2 HCl
C
4
H
9
Cl + H
2
O C
4
H
9
OH + 2 HCl
C
4
H
9
Cl + H
2
O C
4
H
9
OH + 2 HCl
slope =
2.01 x 10
3

k =
2.01 x 10
3
s
-1
Zero Order Reactions
Rate = k[A]
0
= k
Integrated rate law: [A] = kt + [A]
initial

Graph of [A] vs. time is straight line with
slope = k and yintercept = [A]
initial

t

= [A
initial
]/2k = [A0]/2k
When Rate = M/sec, k = M/sec
[A]
initial

[A]
time
Second Order Reactions
Rate = k[A]
2

1/[A] = kt + 1/[A]
initial

Graph 1/[A] vs. time gives straight line with
slope = k and yintercept = 1/[A]
initial
used to determine the rate constant
t
= 1/(k[A
0
])
When Rate = M/sec, k = M
1
-s
1
1/[A]
initial

1/[A]
time
PLAN:
SOLUTION:
Determining the Half-Life of a First-Order Reaction
PROBLEM 1.3:
Cyclopropane is the smallest cyclic hydrocarbon. It is
thermally unstable and rearranges to propene at 1000
o
C
via the following first-order reaction:
CH
2
H
2
C CH
2
(g)
A
H
3
C CH CH
2
(g)
The rate constant is 9.2 s
-1
, (a) What is the half-life of the reaction?
(b) How long does it take for the concentration of cyclopropane to
reach one-quarter of the initial value?
Use the half-life equation, t
1/2
=
0.693
k

One-quarter of the initial value means two half-lives have passed.
t
1/2
= 0.693/9.2 s
-1
= 0.075 s (a) 2 t
1/2
= 2(0.075 s) = 0.150 s
(b)
Copyright 2011 Pearson Education, Inc. 49 Tro: Chemistry: A Molecular Approach, 2/e
Table 1 Units of the Rate Constant k
Overall Reaction Order Units of k (t in seconds)
0 mol/L*s (or mol L
-1
s
-1
)
1 1/s (or s
-1
)
2 L/mol*s (or L mol
-1
s
-1
)
3 L
2
/ mol
2
*s (or L
2
mol
-2
s
-1
)
Example 13.4: The reaction SO
2
Cl
2(g)
SO
2(g)
+ Cl
2(g)
is first order
with a rate constant of 2.90 x 10
4
s
1
at a given set of conditions.
Find the [SO
2
Cl
2
] at 865 s when [SO
2
Cl
2
]
initial
= 0.0225 M
51
the new concentration is less than the original,
as expected
[SO
2
Cl
2
]
init
= 0.0225 M, t = 865, k = 2.90 x 10
-4
s
1

[SO
2
Cl
2
]

Check:
Solution:
Conceptual
Plan:
Relationships:
Given:
Find:
[SO
2
Cl
2
] [SO
2
Cl
2
]
init
, t, k
Practice
The reaction Q 2 R is second order in Q. If the
initial [Q] = 0.010 M and after 5.0 x 10
2
seconds the
[Q] = 0.0010 M, find the rate constant.
Practice The reaction Q 2 R is second order in Q. If the
initial [Q] = 0.010 M and after 5.0 x 10
2
seconds the [Q] =
0.0010 M, find the rate constant
53
[Q]
init
= 0.010 M, t = 5.0 x 10
2
s, [Q]
t
= 0.0010 M
k

Solution:
Conceptual
Plan:

Relationships:
Given:
Find:
k [Q]
init
, t, [Q]
t

Graphical Determination of
the Rate Law for A Product
Plots of [A] vs. time, ln[A] vs. time, and 1/[A] vs.
time allow determination of whether a reaction is
zero, first, or second order
Whichever plot gives a straight line determines the
order with respect to [A]
if linear is [A] vs. time, Rate = k[A]
0
if linear is ln[A] vs. time, Rate = k[A]
1

if linear is 1/[A] vs. time, Rate = k[A]
2

Practice Complete the Table and Determine the
Rate Equation for the Reaction A 2 Product
55
What will the rate be when the [A] = 0.010 M?
Practice Complete the Table and Determine the
Rate Equation for the Reaction A 2 Product
Conclusion for the determination of the rate
equation for the reaction A 2 Product
Because the graph 1/[A] vs. time is linear,
the reaction is second order,
60
Rate = k[A]
2

k = slope of the line = 0.10 M
1
- s
1
Relationship Between
Order and Half-Life
For a zero order reaction, the half-life is directly
proportional to the initial concentration. The lower
the initial concentration of the reactants, the
shorter the half-life
t
1/2

= [A]
init
/2k
For a first order reaction, the half-life is
independent of the concentration. (t
1/2
= constant)
t
1/2
= ln(2)/k
For a second order reaction, the half-life is
inversely proportional to the initial concentration
increasing the initial concentration shortens the
half-life
t
1/2
= 1/(k[A]
init
)
Example 13.6: Molecular iodine dissociates at 625 K with a first-
order rate constant of 0.271 s
1
. What is the half-life of this
reaction?
62
the new concentration is less than the original,
as expected
k = 0.271 s
1

t
1/2
Check:
Solution:
Conceptual
Plan:

Relationships:
Given:
Find:
t
1/2
k
Practice
The reaction Q 2 R is second order in Q. If the
initial [Q] = 0.010 M and the rate constant is 1.8
M
1
s
1
find the length of time for [Q] = [Q]
init
Practice : The reaction Q 2 R is second order in Q. If the
initial [Q] = 0.010 M and the rate constant is 1.8 M
1
s
1
find
the length of time for [Q] = [Q]
init

64
[Q]
init
= 0.010 M, k = 1.8 M
1
-s
1

t
1/2
, s
Solution:
Conceptual
Plan:

Relationships:
Given:
Find:
t
1/2
[Q]
init
, k
Collision Theory
For most reactions, for a reaction to take place, the
reacting molecules must collide with each other
on average about 10
9
collisions per second
Once molecules collide they may react together or
they may not, depending on two factors
1. whether the collision has enough energy to "break
the bonds holding reactant molecules together";
and
2. whether the reacting molecules collide in the
proper orientation for new bonds to form
Activation Energy
Molecules must possess a certain minimum kinetic
energy called the activation energy for a reaction
to occur
energy needed to break the bonds of the reacting
molecules
Reaction with low activation energy is easier to take
place, and is faster
Effective Collisions
Kinetic Energy Factor
For a collision to be
effective, the reacting
molecules must have
sufficient kinetic
energy to overcome
the energy barrier.
Orientation Factor
The proper orientation results when the atoms
are aligned in such a way that the old bonds can
break and the new bonds can form
The more complex the reactant molecules, the
less frequently they will collide with the proper
orientation
Orientation Effect
Collision Frequency
The collision frequency is the number of collisions
that happen per unit time
The more collisions per second there are, the
more collisions can be effective and lead to
product formation
Collisions in which these two conditions are met
(and therefore lead to reaction) are called
effective collisions
The higher the frequency of effective collisions,
the faster the reaction rate
Any factor that can increase the frequency of
effective collisions would increase the rate of a
reaction
Factors Affecting Reaction Rate

Under specific conditions, every reaction has its own
characteristic rate, which may be controlled by four
factors:

1. Concentrations of reactants
2. Chemical nature of reactants
3. Temperature
4. The use of a catalyst
Factors Affecting Reaction Rate:
Reactant Concentration
Generally, the larger the concentration of
reactant molecules, the faster the reaction
increases the frequency of effective collisions
between reactant molecules
concentration of gases depends on the partial
pressure of the gas
higher pressure = higher concentration
Concentrations of solutions depend on the
solute-to-solution ratio (molarity)
Factors Affecting Rate Temperature

Increasing the temperature raises the average
kinetic energy of the reactant molecules
Increasing the temperature increases the number of
molecules with sufficient kinetic energy to overcome
the activation energy, leads to increase in frequancy
of effective collisions. Hence, increasing the rate of
reaction
The distribution of kinetic energy is shown by the
Boltzmann distribution curves
Factors Affecting Rate Catalyst
Catalysts are substances that affect the rate of a
reaction without being consumed
Catalysts generally speed up a reaction
They give the reactant molecules a different path
to follow with a lower activation energy
Catalysts
Homogeneous catalysts are in the same phase
as the reactant particles
Cl
(g)
in the destruction of O
3(g)

Heterogeneous catalysts are in a different
phase than the reactant particles
solid catalytic converter in a cars exhaust system
Types of Catalysts
Factors Affecting Reaction Rate:
Nature of the Reactants
Nature of the reactants means what kind of reactant
molecules and what physical conditions they are in
small molecules tend to react faster than large molecules
gases tend to react faster than liquids, which react faster
than solids
powdered solids are more reactive than blocks
more surface area for contact with other reactants
certain types of chemicals are more reactive than others
e.g. potassium metal is more reactive than sodium
ions react faster than molecules
no bonds need to be broken
The Transition State Theory
There is an energy barrier to almost all reactions
There exists an intermediate stage when reactant
molecules change into products.
The activated complex or transition state is a
chemical species with partially broken and partially
formed bonds
an intermediate formed between reactant and
product molecules
has highest energy and extremely unstable
Figure 2
Reaction energy diagrams and possible transition states.
Energy Profile of a Catalyzed Reaction
polar stratospheric
clouds contain ice
crystals that catalyze
reactions that release
Cl from atmospheric
chemicals
Reaction progress
P
o
t
e
n
t
i
a
l

E
n
e
r
g
y SOLUTION:
Drawing Reaction Energy Diagrams and Transition States
PROBLEM 1.5: A key reaction in the upper atmosphere is
O
3
(g) + O(g) 2O
2
(g)
The E
a(fwd)
is 19 kJ, and the AH
rxn
for the reaction is -392 kJ. Draw a
reaction energy diagram for this reaction, postulate a transition state, and
calculate E
a(rev)
.
PLAN:
Exothermic reaction. The reactants are at a higher energy level than the
products and the transition state is slightly higher than the reactants.
O
3
+O
2O
2
E
a
= 19 kJ
AH
rxn
= -392 kJ
E
a(rev)
= (392 + 19) kJ =
411kJ
O
O
O
O
breaking
bond
forming
bond
transition state
Changing the temperature changes the rate constant,
k, of the rate law
The Arrhenius Equation shows the relationship
between absolute temperature, T, and rate constant,
k :
R is the gas constant in energy units, 8.314 J/(molK)
where T is the temperature in kelvins
A is called the Arrhenius constant (which includes the
frequency factor and the orientation factor)
E
a
is the activation energy, the minimum energy
needed for the molecules to react
The Arrhenius Equation
The Arrhenius Equation:
The Exponential Factor
The exponential factor in the Arrhenius equation is a
number between 0 and 1
The larger the activation energy, Ea, the fewer molecules
that have sufficient energy to overcome the energy barrier,
the smaller the rate constant k.
Increase in temperature, T, will gives a larger k value
therefore increasing the temperature will increase the reaction rate
Arrhenius Plots
The Arrhenius Equation: The integrated form
this equation is in the linear form y = mx + b
where y = ln(k) and x = (1/T)
A graph of ln(k) vs. (1/T) is a straight line
(R)(slope of the line) = E
a
(in Joules), R = 8.314 J/(molK)
e
yintercept
= A (unit is the same as k)
Example 13.7: Determine the activation energy and
frequency factor for the reaction O
3(g)
O
2(g)
+ O
(g)

given the following data:
Example 13.7: Determine the activation energy and
frequency factor for the reaction O
3(g)
O
2(g)
+ O
(g)

Example 13.7: Determine the Ea and the Arrhenius
constant, A, for the reaction O
3(g)
O
2(g)
+ O
(g)

90
slope, m = 1.12 x 10
4
K
yintercept, b = 26.8
Arrhenius Equation:
Two-Point Form
If you only have two (T,k) data points, the following
forms of the Arrhenius Equation can be used:
Example 13.8: The reaction NO
2(g)
+ CO
(g)
CO
2(g)
+ NO
(g)

has a rate constant of 2.57 M
1
s
1
at 701 K and 567 M
1
s
1

at 895 K. Find the activation energy in kJ/mol
92
most activation energies are tens to hundreds
of kJ/mol so the answer is reasonable
T
1
= 701 K, k
1
= 2.57 M
1
s
1
, T
2
= 895 K, k
2
= 567 M
1
s
1

E
a
, kJ/mol
Check:
Solution:
Conceptual
Plan:

Relationships:
Given:
Find:
E
a
T
1
, k
1
, T
2
, k
2
Practice: It is often said that the rate of a reaction doubles for
every 10 C rise in temperature. Calculate the activation
energy for such a reaction.
93
Hint:
make T
1
= 300 K, T
2
= 310 K
and k
2
= 2k
1

Practice Find the activation energy in kJ/mol for
increasing the temperature 10
C doubling the rate

94
most activation energies are tens to hundreds
of kJ/mol so the answer is reasonable
T
1
= 300 K, T
1
= 310 K, k
2
= 2 k
1

E
a
, kJ/mol
Check:
Solution:
Conceptual
Plan:

Relationships:
Given:
Find:
E
a
T
1
, k
1
, T
2
, k
2
Reaction Mechanisms
We generally describe chemical reactions with an
equation listing all the reactant molecules and product
molecules
But the probability of more than 3 molecules colliding
at the same instant with the proper orientation and
sufficient energy to overcome the energy barrier is
negligible
Most reactions occur in a series of small reactions
involving 1, 2, or at most 3 molecules
Describing the series of reactions that occurs to
produce the overall observed reaction is called a
reaction mechanism
Knowing the rate law of the reaction helps us
understand the sequence of reactions in the
mechanism
An Example of a Reaction Mechanism
Overall reaction:
H
2(g)
+ 2 ICl
(g)
2 HCl
(g)
+ I
2(g)

Mechanism:
Step 1: H
2(g)
+ ICl
(g)
HCl
(g)
+ HI
(g)

Step 2: HI
(g)
+ ICl
(g)
HCl
(g)
+ I
2(g)

The reactions (1) and (2) in this mechanism are called
the elementary steps, meaning that they cannot be
broken down into simpler steps, and that the
molecules actually interact directly in this manner
without any other steps
Overall: H
2
(g) + 2 ICl(g) 2 HCl(g) + I
2
(g)
Step (1): H
2
(g) + ICl(g) HCl(g) + HI(g)
Step (2): HI(g) + ICl(g) HCl(g) + I
2
(g)
Intermediates
Notice that the HI is a product in Step 1, but then a
reactant in Step 2
Because HI is made but then consumed, HI does
not show up in the overall reaction
Materials that are products in an early mechanism
step, but then a reactant in a later step, are called
intermediates
Adding equations (1) and (2), removing HI, will give
the overall equation.

Molecularity
The number of reactant particles in an elementary step
is called its molecularity
A unimolecular step involves one particle
A bimolecular step involves two particles
though they may be the same kind of particle
A termolecular step involves three particles
though these are exceedingly rare in elementary
steps
Rate Laws for Elementary Steps
Each step in the mechanism is like its own little
reaction with its own activation energy and own
rate law
The rate law for an overall reaction must be
determined experimentally
But the rate law of an elementary step can be
deduced directly from the equation of the step
H
2
(g) + 2 ICl(g) 2 HCl(g) + I
2
(g)
1) H
2
(g) + ICl(g) HCl(g) + HI(g) Rate = k
1
[H
2
][ICl]
2) HI(g) + ICl(g) HCl(g) + I
2
(g) Rate = k
2
[HI][ICl]
Rate Laws of Elementary Steps
Rate Determining Step
In most mechanisms, one step occurs slower than the
other steps
The result is that product formation cannot occur any
faster than the slowest step the step determines the
rate of the overall reaction
We call the slowest step in the mechanism the rate
determining step
the slowest step has the largest activation energy
The rate law of the rate determining step determines the
rate law of the overall reaction
Another Reaction Mechanism
The first step in this
mechanism is the rate
determining step.
The first step is slower than the
second step because its
activation energy is larger.
The rate law of the first step is
the same as the rate law of the
overall reaction.
102
NO
2(g)
+ CO
(g)
NO
(g)
+ CO
2(g)
Rate
obs
= k[NO
2
]
2

1. NO
2(g)
+ NO
2(g)
NO
3(g)
+ NO
(g)
Rate = k
1
[NO
2
]
2
Slow
2. NO
3(g)
+ CO
(g)
NO
2(g)
+ CO
2(g)
Rate = k
2
[NO
3
][CO] Fast
Validating a Mechanism
To validate (not prove) a mechanism, two
conditions must be met:
1. The elementary steps must sum to the overall
reaction
2. The rate law predicted by the mechanism must
be consistent with the experimentally observed
rate law
Mechanisms with a Fast
Initial Step
When a mechanism contains a fast initial step, the rate
limiting step may contain intermediates
When a previous step is rapid and reaches equilibrium,
the forward and reverse reaction rates are equal so
the concentrations of reactants and products of the
step are related
and the product is an intermediate
Substituting into the rate law of the RDS will produce a
rate law in terms of just reactants
An Example
1. 2 NO
(g)
N
2
O
2(g)
Fast
2. H
2(g)
+ N
2
O
2(g)
H
2
O
(g)
+ N
2
O
(g)
Slow Rate = k
2
[H
2
][N
2
O
2
]
3. H
2(g)
+ N
2
O
(g)
H
2
O
(g)
+ N
2(g)
Fast

k
1

k
1

2 H
2(g)
+ 2 NO
(g)
2 H
2
O
(g)
+ N
2(g)
Rate
obs
= k [H
2
][NO]
2

Example 13.9: Show that the proposed mechanism for the
reaction 2 O
3(g)
3 O
2(g)
matches the observed rate law
Rate = k[O
3
]
2
[O
2
]
1

1. O
3(g)
O
2(g)
+ O
(g)
Fast

2. O
3(g)
+ O
(g)
2 O
2(g)
Slow Rate = k
2
[O
3
][O]
k
1

k
1

Practice Mechanism
Determine the overall reaction, the rate determining
step, the rate law, and identify all
intermediates of the following mechanism
1. A + B
2
AB + B Slow
2. A + B AB Fast
Practice Mechanism
Determine the overall reaction, the rate determining
step, the rate law, and identify all intermediates of
the following mechanism
1. A + B
2
AB + B Slow
2. A + B AB Fast

reaction 2 A + B
2
2 AB
B is an intermediate
The first step is the rate determining step
Rate = k[A][B
2
], same as RDS

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] changes from1.000 M to 0.868 M

= 0.693/k. The half-life of a first order

C doubling the rate

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