1

KINETICS
I. Introduction.
A. Need for kinetics.
1. Information not available from thermodynamics or the balanced chemical equation.
a. The speed of the reaction. Rate of the reaction.
1) Rate = time rate of change of the molar concentration of a reactant or product.
2) For the reaction 2NO(g) + 2H
2
(g) -----> N
2
(g) + 2H
2
O(g)

Rate =
![H
2
O]
!t
= -
![NO]
!t
= -
![H
2
]
!t
= 2
![N
2
]
!t

3) Dimensions = mol/ Ls or Ms
-1

4) Rate is always a positive number.
b. How the reaction takes place. That is, the sequence of bond breaking and bond
making by which reactants are converted into products.
1) Sequence of steps = Mechanism.
2) Written as a series of simple elementary (one step) reactions that sum to give the
balanced chemical equation.
2. Kinetics = Study of the rates and mechanisms of reactions.
--Rates are measured experimentally
-- Mechanisms are postulated to explain the experiments.
B. Instantaneous Rate.
1. For most reactions, plots of the concentrations of reactants or products versus time are
not straight lines. This means that the rate changes with time.
a. In most all cases the rate of a reaction will decrease as reactants are consumed and
products are formed.
b. Plot of concentration of a product vs. time for a reaction.
C
o
n
c
e
n
t
r
a
t
i
o
n
time
C
1
C
2
C
3
C
4
!t !t
!t !t
2
Rate
1
=
!t
C
1
- 0
; Rate
2
=
!t
C
2
- C
1
; Rate
3
=
!t
C
3
- C
2
; Rate
4
=
!t
C
4
- C
3


Rate
1
> Rate
2
> Rate
3
> Rate
4

2. Instantaneous rate = rate at a given instant in time = slope of the concentration vs. time
plot at that time.
If for the reaction 2NO(g) + 2H
2
(g) ------> N
2
(g) + 2H
2
O(g) the rate was
measured by following the appearance of H
2
O, then the instantaneous
rate at a particular time will be the slope of the [H
2
O] vs. time plot at that time.
!
L
!t"0
im

!t
![H
2
O]
=
dt
d[H
2
O]
Instantaneous Rate =
dt
d[H
2
O]

C. Variation of rate with concentration - Rate Law.
1. Rate Law = mathematical equation that gives the rate as a function of concentration.
Must be determined experimentally.
2. In many cases the rate law for a reaction such as aA + bB ------> dD + eE
is of the rather simple form
Rate = k[A]
x
[B]
y

a. x = the order of the reaction in A
y = the order of the reaction in B
x+y = overall order of the reaction.
b. x and y are usually small positive integers, they must be determined experimentally.
c. Example: Suppose the rate law was found to be of the form Rate = k[A]
2
[B]
x = 2 ! the reaction is said to be second order in A
y = 1 ! the reaction is said to be first order in B
x+y = 3 ! the reaction is overall third
This is a 3
rd
order reaction that is 2
nd
order in A and 1
st
order in B.
3. k = Specific rate constant = The proportionality constant between the rate and
concentrations.
a. Its value depends on the particular reaction.
3
b. It is independent of concentration.
c. It increases as the temperature increases.
1) The temperature dependence of k is given empirically by the Arrhenius
equation
k = Ae
-
RT
E
a
where
A = a temperature independent constant
E
a
= activation energy ( dimensions = J/mol; different for different
reactions)
R = gas constant = 8.314 J/mol K.
T = temperature in K.
e = natural log base.
2) The activation energy, E
a
, can be obtained experimentally by measuring k at
several temperatures and plotting lnk vs. 1/T.
lnk = -
RT
E
a
+ lnA


lnA
slope =
E
a
R
1/T
l
n
k
0

3) Activation energies give information regarding the mechanism of the reaction.
II. Determination of the Rate Law.
A. Initial Rate Method.
1. In general the rate law is of the form, Rate = k[A]
x
[B]
y
. x, y and k must be determined
experimentally. The approach to doing this using the initial rate method is as follows.
a. Mix reactants A and B so that you know their initial concentrations.
b. Experimentally measure the rate as soon after mixing as possible, this is the initial
rate.
1) The rate is measured so quickly that the concentrations of A and B are still at their
4
initial values.
2) Therefore, you have the rate at known reactant concentrations.
c. At the same temperature, repeat the experiment holding all but one reactant
concentration the same as in the first run.
d. Repeat this process varying one reactant concentration at a time. Will end up with
a series of rates at known reactant concentrations.
e. From the change in initial rate as an individual reactant concentration varies, one can
deduce the order with respect to the particular reactant.
2. Example: 2NO(g) + 2H
2
(g) -----> N
2
(g) + 2H
2
O(g)
a. At a particular temperature this reaction was studied using the initial rate method
and the following results were obtained.

Kinetic Initial Molarity Initial rate of formation
Run [H
2
] [NO] of H
2
O, M s
- 1
_____
1 0.0200 0.0300 0.112
2 0.0400 0.0300 0.224
3 0.0600 0.0300 0.336
4 0.0200 0.0600 0.448
5 0.0200 0.0900 1.008

The rate law is of the form, Rate = k[H
2
]
x
[NO]
y
.
b. Order in H
2
(value of x)
1) Use the results in Runs 1, 2, and 3. In these runs the concentration of NO
is constant, therefore the changes in the Initial Rate are due solely to changes
in the H
2
concentration.
2) Note that the reaction rate is directly proportional to [H
2
], that is, when the
[H
2
] was doubled the rate doubled and when the [H
2
] was tripled the rate
tripled.
3) The value of x = 1, the reaction is 1
st
order in H
2
.
c. The order in NO (value of y)
1) Use the results in Runs 1,4, and 5. ! Rate
!
"[NO]
y

2) When the [NO] was doubled ( Runs 1 and 4), the rate increased by a
factor of 4 = 2
2
and when the [NO] was tripled (Runs 1 and 5), the rate
increased by a factor of 9 = 3
2
.
Therefore, the reaction rate is proportional to the concentration of NO squared.
3) The value of y = 2, the reaction is 2
nd
order in NO.
d The rate law is then: Rate = k[H
2
][NO]
2
. That is it is a third order reaction, first
order in H
2
and second order in NO.
5
e. The value and the dimension of k.
1) Since the temperature in all the runs was the same, each run has the same
specific rate constant.
2) From Run 1 : Rate = 0.112 M s
- 1
= k[0.0200M][0.0300M]
2
! k =
[0. 0200M][0. 0300M]
2
0. 112 Ms
- 1
= 6. 2x10
- 3
M
- 2
s
- 1
3) Note that if the over-all order of a reaction is n, the specific rate constant has
the dimensions of M
-n+1
s
- 1
.
f. The complete rate law is: Rate = (6.2x10
- 3
M
- 2
s
- 1
)[H
2
][NO]
2

g. Many times it is not possible to increase the individual concentrations by simple
multiples. A more formal way of obtaining the orders is seen by taking the results
of Runs 4 and 5 to find the order in NO.
Rate
4
Rate
5
.
=
k [H
2
]
4
x
[NO]
4
y
k [H
2
]
5
x
[NO]
5
y
=
0. 448
1. 008
= 2. 25 =
k [0. 0200]
x
[0. 0600]
y
k [. 0200]
x
[0. 0900]
y
2. 25 =
0. 0600
0. 0900
y
= [1. 50]
y
! log(2. 25) = y log(1. 50) or y =
log(1. 50)
log(2. 25)
=
0. 176
0. 352
= 2

B. Use of integrated rate expressions.
1. The rate law is a differential expression in that it tells how the slope of the concentration
vs. time plot depends on the concentrations of the reaction species.
a. For simple reactions it is possible to use the rules of calculus and integrate the rate law
to give the specific concentration- time relationship (the integrated rate
expression).
b. Experimentally it is easy to measure the concentration of a reactant (or product) as
a function of time. It is possible to match the experimental concentration-time relation
with the correct integrated rate expression.
c. Will consider some simple examples.


2. A Zero Order Reaction.
a. Suppose the reaction A " Products is zero order in A.
6
Rate Law : Rate = -
dt
d[A]
= k[A]
0
= k or
dt
d[A]
= -k
b. This equation states that the slope of the [A] vs. time plot is constant ( = - k). This
means the plot of [A] vs. time is a straight line with a slope of -k, as shown below.


time, s
10 20 30 40 50 60
0.10
0.20
0.30
0.40
0.50
0.60
0.70
[
A
]
0.00
0

c. Only for a Zero order reaction will a plot of [A] vs. t yield a straight line.
3. A First Order Reaction.
a. Suppose the reaction A " Products is first order in A.
Rate Law : Rate = -
dt
d[A]
= k[A]
b. A plot of [A] vs. time is


0 10 20 30 40 50 60
-0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
time,s
[
A
]

The plot is not linear as found for the zero order reaction.
7
c. To find the correct concentration-time dependence, the rate equation can be
integrated. The variables can be separated and the resulting equation integrated.
Let [A]
0
= concentration of A at t = 0 and [A] = concentration of A at time t.
[A]
d[A]
= - k dt !

"
[A]
0
[A]

[A]
d[A]
= # k
"
0
t
dt or ln[A] - ln[A]
0
= - k t
! ln[A] = ln[A]
0
- k t
d. Therefore a plot of ln[A] vs. t will give a straight line whose slope is - k and an
intercept at t = 0 of ln[A]
0,
as shown below
.


10 20 30 40 50 60
- 4
- 3
- 2
- 1
time,s
l
n
[
A
]
0
0
ln(0.60)

Only for a first order reaction will a plot of ln[A] vs. t give a straight line.
4. A Second Order Reaction.
a. Suppose the reaction A " Products is second order in A.
Rate Law : Rate =
dt
d[A]
= - k[A]
2
b. A plot of [A] vs. time for this reaction is
8

20 40 60 80 100 120
0.1
0.2
0.3
0.4
0.5
0.6
0.7
time, s
[
A
]
0

This plot is different from both the zero and first order reactions.
c. The concentration-time dependence can be obtained by integration of the rate law.
Rearranging and integrating
!
[A]
0
[A]
-
[A]
2
d[A]
= k
!
0
t
dt or
[A]
1
-
[A]
0
1
= k t
!

[A]
1
=
[A]
0
1
+ k t
d. A plot of 1/[A] vs. time will give a straight line with a slope ok k, as shown below.


20 40 60 80 100 120
1.00
2.00
3.00
4.00
5.00
6.00
7.00
time, s
1
/
[
A
]
0

c. Only for a second order reaction will a plot of 1/[A] vs. t give a straight line.
5. Higher Order Reactions.
a. The general rate law would be
9
Rate = -
dt
d[A]
= k[A]
n
or
[A]
n
d[A]
= - k dt
This can be integrated to give, for n>1,
!
[A]
0
[A]

["]
n
d[A]
= - k
!
0
t
dt or
n-1
1
[A]
n-1
1
-
[A]
0
n-1
1
= k t
Therefore, a plot of 1/[A]
n-1
vs. t will yield a straight line.
b. Most reactions have rate laws involving several reactants of the form,
Rate = k [B]
y
[A]
x
. When more than one reactant is involved in the rate law, the
integrated rate expressions derived above can be used with the following procedures.
1) First run the reaction with the concentration of B much greater than that of A (at least
ten times the stoichiometric amount).
2) Under these conditions the concentration of B remains at its initial value, [B]
0
,
and k[B]
y
is a constant for the reaction (k[B]
0
y
). The rate law will be of the form
Rate = k
app
[A]
x
, where k
app
=k[B]
0
y
, and the order in A can be found as outlined
above. This is called running the reaction under pseudo x order conditions.
3) At the same temperature, the reaction can be rerun but now having A in large excess so
that k[A]
x
is a constant (run under pseudo y order conditions). The order in B can then
be found. Once the orders are found, k can be obtained from the k
app
's.
c. An alternate procedure would be to run the reaction under pseudo x order conditions
with a series of different B concentrations (all of which are much greater than the A
concentrations).
1) Will obtain a series of k
app
's all of the form k
app
= k[B]
y
.
2) A plot of ln(k
app
) vs. ln[B] will be a straight line whose slope is equal to y and
whose intercept at ln[B] = 0 is equal to lnk ( the equation being plotted is
ln(k
app
) = lnk + yln[B] ).
C. Half-life, t
1/2
.
1. Half-life = time required for the concentration of a reactant to decrease to one-half
its original value.
a. At t = t
1/2
, [A] = 1/2[A]
0

b. Each order will yield a different half-life expression. Therefore, half-life
measurements can be used to deduce the rate expression.
2. Orders and t
1/2
expressions.
a. Zero order reaction.
1) [A] = [A]
0
- kt ! 1/2[A]
0
= [A]
0
- kt
1/2

10
! t
1/2
=
2k
[A]
0
. Thus t
1/2
is directly proportional to [A]
0
.
2) Inspection of the following zero order plot shows this relationship.
.
time, s
10 20 30 40 50 60
0.10
0.20
0.30
0.40
0.50
0.60
0.70
[
A
]
0.00
0

Note that it takes 30 s for the concentration of A to fall from 0.60M to 0.30M
but only 15 s for the concentration of A to drop from 0.30M to 0.15M.
b. First order reaction.
1) ln[A] = ln[A]
0
- kt or
ln
[A]
[A]
0
= kt ! ln
1/2[A]
0
[A]
0
= ln 2 = kt
1/2
or t
1/2
=
k
ln 2
=
k
0. 693
2) Therefore for first order reactions the half-life is independent of concentration.
This can be seen in the following plot.

0 10 20 30 40 50 60
-0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
time,s
[
A
]

Note that the concentration drops by one-half every 10 s.
c. Second order reaction.
1) 1/[A] = 1/[A]
0
+ kt
11
! t
1/2
=
k[A]
0
1
. The half-life is inversely proportional to [A]
0
.
2) This inverse proportionality can be seen in the following data for a second
order reaction.

20 40 60 80 100 120
0.1
0.2
0.3
0.4
0.5
0.6
0.7
time, s
[
A
]
0
35 s 105 s

Note that it takes 35 s for [A] to drop from 0.60M to 0.30M while is takes 70 s
for it to decrease from 0.30M to 0.15M.
3. Half-life relationships in first order processes.
a. There are many processes in nature that are kinetically first order. Some examples
are : many chemical reactions; radioactive decay; and bacterial colony growth.
b. In all cases t
1/2
is a constant for a particular process at a particular temperature.
1) If t
1/2
is large, the process is slow.
2) If t
1/2
is small, the process is fast.
c. Consider some examples from radioactivity.
1) Nitrogen-13 (
13
N) is a radioactive isotope whose half-life is 10 min.
If one starts with 40.0 g of
13
N how will the amount change as time elapses ?

Elapsed time, Half-lives Fraction of
13
N Grams of
13
N
min. Elapsed Remaining Remaining

0.0 0.0 1.00 40.0
10.0 1.0 1/2 20.0
20.0 2.0 (1/2)
2
= 1/4 10.0
30.0 3.0 (1/2)
3
= 1/8 5.0
40.0 4.0 (1.2)
4
= 1/16 2.5
n(10.0) n (1/2)
n
(1/2)
n
(40.0)
1440 (1 day) 144 (1/2)
144
= 10
-53
4.0x10
-52
(all gone)
12

2) Carbon-14 (
14
C) has a half-life of 5740 years. If one starts with 2.0 g of

14
C, how much will remain after 6200 years ?
the number of half-lives elapsed, n = 6200/5740 = 1.08
the fraction of
14
C remaining = (1/2)
1.08
= 0.473
the amount remaining = (0.473)(2.0 g) = 0.95 g

d. Chemical Example. In dilute base at 20 C the reaction
2H
2
O
2
(aq) ----> 2H
2
O(l) + O
2
(g) is first order in H
2
O
2
with a specific rate
constant of 1.77x10
- 5
s
- 1
. If the initial H
2
O
2
concentration is 3.0M,
1) Calculate the initial rate of the reaction.
Rate = k[H
2
O
2
] = (1.77x10
- 5
s
- 1
)(3.0M) = 5.31x10
- 5
Ms
-1
.
2) Calculate the half-life of the reaction in seconds and in hours.
t
1/2
=
k
0. 693
=
1. 77x10
- 5
s
- 1
0. 693
= 3. 91x10
4
s.
t
1/2
(hr) =
3600 s/hr
3. 91x10
4
s
= 10. 9 hrs.
3) Calculate the concentration of H
2
O
2
after 12 hrs have elapsed.
Two ways
a) Use the integrated rate expression.
ln
[H
2
O
2
]
[H
2
O
2
]
0
= kt = (1. 77x10
- 5
s
- 1
)(12 hr)(3600 s/hr) = 0. 765
[H
2
O
2
]
[H
2
O
2
]
0
= e
0.765
= 2. 15 ! [H
2
O
2
] =
2. 15
[H
2
O
2
]
0
=
2. 15
3. 0
= 1. 4 M
b) Use the half-life equations.
The number of half-lives elapsed = n =
10. 9 hr
12 hr
= 1. 101
fraction remaining =
2
1
n
=
2
1
1.101
= 0. 466
concentration remainins = (0. 466)(3. 0M) = 1. 4M
4) Calculate the rate after 12 hours.
Rate = (1.77x10
- 5
s
- 1
)(1.4M) = 2.48x10
- 5
Ms
- 1
.

13
III. Collision Theory of Kinetics.
A. Introduction.
1. The Rate Law, which is experimentally determined, supplies information about
the mechanism of the reaction.
2. In order to use the information to postulate a mechanism, one must have the framework
of a theory. There are two theories that will be considered.
a. The Collision Theory. This is a classical theory based on the kinetic molecular theory.
It was first developed for gas phase reactions but can be generalized to solution
reactions.
b. The Absolute Reaction Rate Theory. This theory attempts to estimate the energy changes
that occur during each step in the reaction and relate these energy changes to the
reaction rates. Since the quantitative application of this theory requires the knowledge
of Quantum and Statistical Mechanics, only the basic ideas will be discussed here.
B. Postulates of the Collision Theory.
1. Reactions occur during the collision of reactant molecules.
a. The rate of a reaction should be proportional to the number of collisions per unit
volume per unit time between reactant molecules. From the Kinetic Molecular Theory
this can be given by the Collision Number, Z.
b. Consider a simple one step reaction involving the collision of an A and a B molecule
(a bimolecular reaction) of the type A + B ---> Products.
1)Rate # Z
AB

2) From the Kinetic Molecular Theory Z
AB
# [A] [B].
3) Therefore, Rate # [A] [B] or the rate law should be: Rate = k [A] [B].
The reaction should be first order in A and first order in B.
c. Consider a simple bimolecular reaction of the type 2A -----> Products.
1) Rate # Z
AA
# [A] [A].
2) The rate law should be of the form: Rate = k [A]
2
.
The reaction should be second order in A.
d. Consider a collision between three molecules, two A's and one B ( a termolecular
process).
1) Rate # Z
AAB
# [A]
2
[B]
2) Such a process would be second order in A and first order in B.
3) Compared to two-body collisions, three-body collisions are very rare. They are
so rare that such termolecular processes are not kinetically important.
e. Mechanisms will consist of either unimolecular (one molecule) or bimolecular (two
molecules) steps that sum to give the over-all balanced equation.
14
The unimolecular steps are first order and the bimolecular steps are second order.
2. Not all collisions are effective, that is, lead to reaction.
a. There are a large number of collisions per second for molecules in a gaseous
mixture. In a mixture of 1M A and 1M B at 0 C there is about 10
34
- 10
35

collisions per second per liter. If a reaction occurred at every collision, second
order rate constants of from 10
10
to 10
12
M
- 1
s
- 1
would be found. Very few
reactions are this fast. Therefore, only a small fraction of collisions are effective.
b. An effective collision must be a high energy collision. The high energy is needed to :
1) overcome electron-electron repulsion between reactant molecules.
2) start to break covalent bonds in the reactant molecules.
c. Only a small fraction of molecules have this much energy. Consider a typical
Boltzmann distribution of kinetic energies


F
r
a
c
t
i
o
n

o
f

m
o
l
e
c
u
l
e
s
h
a
v
i
n
g

a

p
a
r
t
i
c
u
l
a
r

K
E
KE
0
0
KE
minimum required
for reaction
E
a

1) Activation Energy, E
a
= energy above the average required for an effective
collision.
2) The fraction of molecules having an energy E
a
above the average is
e
-
RT
E
a

This then is the fraction of collisions that are effective.
3. Summary for a single step reaction : C + D ------> Products
a. Rate # (number of collisions per s per unit volume)(fraction that are effective)
! Rate " [C][D] e
-
RT
E
a
or Rate = Ae
-
RT
E
a
[C][D]

15
b. Note that this is of the form Rate = k [C][D] if
k = A e
-
RT
E
a

This is just the Arrhenius expression for k. Therefore, the collision theory
can account for the general form of the rate law and the temperature dependence
of k.
c. It is difficult, if not impossible, to calculate the pre-exponential factor A when
molecule orientation is important. That is, when the colliding molecules must
have a particular orientation in the collision complex. The inability of the
collision theory to account for this steric factor prevents its quantitative
application to most reactions. However, the ideas generated by the
theory are very useful when postulating mechanisms for reactions.
C. Variation of k with temperature. Activation energy calculations.
1. According to the Arrenhius equation, the rate constant increases exponentially
with temperature or ln k = - E
a
/RT + ln A. A plot of ln k vs 1/T will be
a straight line whose slope = - (E
a
/R).
2. This can be put in a convenient form for calculations using a two point method.
Let k
1
= the specific rate constant at T
1
.
Let k
2
= the specific rate constant at T
2
.
! ln k
2
= - (E
a
/R)(1/T
2
) + ln A

-{ln k
1
= - (E
a
/R)(1/T
1
) + ln A}
ln k
2
- ln k
1
= ln (k
2
/k
1
) = - E
a
/R [ 1/T
2
- 1/T
1
]
This equation relates five variables (k
1
, k
2
, T
1
, T
2
, and E
a
) ; if any four are
known the fifth can be calculated.
3. Example: A typical value of the activation energy is 70 kJ/mol. If a reaction
has a rate constant of 5.3x10
2
M
- 1
s
- 1
at 50.0 C, calculate k at 60.0 C.
Let k
1
= 5.3x10
2
M
- 1
s
- 1
; T
1
= 50.0 + 273.1 = 323.1 K
Let k
2
= ? T
2
= 60.0 + 273.1 = 333.1 K
ln
5. 3x10
2
k
2
= -
8. 314 J/mol K
70, 000 J/mol

333. 1 K
1
-
323. 1 K
1
= 0. 782
!
5. 3x10
2
k
2
= e
0.782
= 2. 19; ! 1. 2x10
3
M
- 1
s
- 1

Note that the rate constant about doubled. Thus for typical reactions the rate will
increase by a factor of from 2 to 3 for each 10 temperature rise.
16
IV. Mechanisms.
A. General.
1. Experimentally one can obtain the rate law and the stoichiometry of a reaction.
These two pieces of information can be used, along with the results of other
experiments, to postulate a mechanism for the reaction. Mechanisms can be single
step processes or can be composed of several steps.
a. If the reaction is a single step reaction,
1) the orders of the reactants must be the same as the coefficients in the balanced
chemical equation.
2) the over-all order should not be greater than second order.
b. The converse is not true. That is, all reactions in which the orders are the same
as the coefficients in the balanced equation are not necessarily single step
reactions.
2. Multi-step reactions.
a. Take place in several steps in which intermediate compounds (intermediates) are
formed in one step and consumed in another.
b. Each step proceeds at its own rate. The rate law can be written down using the collision
theory. Therefore, the steps will be either unimolecular or bimolecular.
1) Unimolecular : A ----> products
Rate = k [A] It will be first order in A.
2) Bimolecular : A + B ----> Products
Rate = k [A][B]
or
2 A ----> Products
Rate = k[A]
2

They will be second order.
c. The steps will sum to give the overall balanced equation. The overall rate law will
depend on the rate laws of the individual steps.
1) If all the steps proceed at about the same rate, the observed rate law will be
complex.
2) In many reactions one step will be much slower than all the rest. This slow
step is called the rate determining step.
3) The rate of the overall reaction is equal to the rate of this slow step.
4) The experimental rate law is obtained directly from the rate law of the rate
determining step.

17
B. Examples of Mechanisms Involving a Rate Determining Step..
1. Suppose a reaction proceeds by the following two step mechanism.
k
1

Step 1. A + B ------> C + D Slow

k
2

Step 2 C + B ------> E Fast

_________________________

Net A + 2B ------> D + E
a. C is an intermediate.
b. The rate Law for the reaction is the rate law for the slow step, Step 1.
! Rate = k
1
[A][B]. The reaction will be first order in A and first order in B.

2. Suppose the mechanism is
k
1

Step 1 2B B
2
Fast Equilibrium
k
- 1

k
2

Step 2 B
2
+ A -----> E + D Slow

_______________________

Net A + 2B -----> E + D
a. B
2
is an intermediate.
b. Rate Law for the reaction is the rate law for the slow step, Step 2, which is
Rate = k
2
[B
2
][A]. This can not be the experimental rate law. Since B
2
is an
intermediate, it can not appear in the experimental rate law.
c. Can use the equilibrium in Step 1 to obtain an expression for [B
2
] in terms of
reactant concentrations. Since it is a fast equilibrium, Rate Forward = Rate Reverse.
! k
1
[B]
2
= k
- 1
[B
2
] or [B
2
] =
k
1
k
-1
[B]
2

Substituting in the rate expression, one obtains
Rate = k
2 k
- 1
k
1
[B]
2
[A] or Rate = k
exp
[B]
2
[A]

The reaction will be first order in A and second order in B.
18

3. Consider the reaction 2NO(g) + 2H
2
(g) ------> N
2
(g) + 2H
2
O(g) .
The rate law was found to be Rate = k [NO]
2
[H
2
] .The reaction is thought to proceed
by the following three step mechanism.
k
1

Step 1 2NO N
2
O
2
fast equilibrium
k
- 1

k
2
Step 2 N
2
O
2
+ H
2
-------> N
2
O + H
2
O slow
k
3

Step 3 N
2
O + H
2
---------> N
2
+ H
2
O fast
Net: 2NO(g) + 2H
2
(g) ------> N
2
(g) + 2H
2
O(g)
a. N
2
O
2
and N
2
O are intermediates.
b. The rate of the reaction is the rate of step 2. The rate law is Rate = k[N
2
O
2
][H
2
]
The concentration of the intermediate, N
2
O
2
, can be expressed in terms of reactant
concentrations using the fast equilibrium in step 1. From step 1
[N
2
O
2
] = (k
1
/k
- 1
) [NO]
2
! Rate = k
2
(k
1
/k
- 1
)[NO]
2
[H
2
] = k
exp
[NO]
2
[H
2
]

C. Example of a mechanism where there is no uniquely slow step. Chain Reactions.
1. Consider the reaction H
2
(g) + Br
2
(g) ----> 2HBr(g) .
a. The experimental rate law was found to be
dt
d[HBr]
=
1 + k
B
[HBr] / [Br
2
]
k
A
[H
2
][Br
2
]
1/2

b. The mechanism is a chain reaction consisting of the following steps.
k
1

Step 1 Br
2
------> 2Br
k
2

Step 2 Br + H
2
------> HBr + H
k
3

Step 3 H + Br
2
-----> HBr + Br
k
4

Step 4 H + HBr -----> H
2
+ Br
k
5

Step 5 2Br -----> Br
2
c. H and Br are intermediates. They are characterized by the fact that they have unpaired
electrons. Such intermediates are called Free Radicals. All steps proceed at about the
19
same rate.
d. This reaction illustrates the general steps in a chain reaction mechanism.
1) Initiation Step. Step 1.
A stable molecule breaks down to give free radicals.
2) Chain Propagating Steps. Steps 2 and 3
A free radical reacts to form product and another free radical. In these steps the
number of free radicals is conserved.
3) Chain Inhibiting Steps. Step 4.
Product is removed but there is no net change in the number of free radicals.
4) Chain Terminating Step. Step 5.
Free radicals react to form stable substances. This decreases the number of free
radicals.
2. Some free radical reactions have Chain Branching Steps. In such steps more
radicals are formed than are consumed.
Consider the reaction 2H
2
+ O
2
----> 2H
2
O
a. Some steps are:
H
2
-----> 2H Initiation
H + O
2
-----> HO + O Chain Branching
O + H
2
-----> HO + H Chain Branching
HO + H
2
-----> H
2
O + H Chain Propagation
b. Because of the chain branching the reaction becomes faster and faster as time
goes on. If the reaction is exothermic, an explosion results.
V. Absolute Reaction Rate Theory.
A. Background.
1. Reactants and products are stable molecules and therefore reside in potential
energy minima. Separating these two minima is an energy barrier that represents
the activation energy; to get from one energy "valley" to the other, the activation
barrier must be traversed.
a. There are a number of pathways across the barrier, each representing a different
mechanism for the reaction. One will be uniquely low in energy and this determines the
actual reaction path.
b. A critical factor in determining the rate of the reaction is the energy of the highest energy
molecular configuration in the reaction scheme. This is called the transition state or
the activated complex. This high energy configuration has all the properties of a
normal molecule except that one vibration, that along the reaction coordinate will lead to
decomposition of the activated complex to form products (or reactants for the reverse
20
reaction).
Energy as a Function of Interatomic Distances in the
F + H-H F-H + H Reaction


c. Consider the simple displacement reaction F + H
2
-----> FH + H. The extent of this
reaction can be followed by monitoring the H$H and the H$F bond distances. The
reactants are characterized by a short H$H bond distance and a long H$F distance; the
products are characterized by the opposite bond distance pattern. The energy of the
system can be calculated by quantum mechanics as a function of these bond distances.
d. A contour diagram of the energy as a function of the H$H and H$F bond distances is
shown on the following page.
1) Point X represents the reactants and point Y the products. One could go from X to
Y in a number of ways. For example, the reaction path could be X " W " Y.
21
this would correspond to the mechanism:
H$H -----> 2H
H + F -----> H$F .
In this mechanism the H$H bond ruptures completely before the H$F bond
begins to form. Inspection of the diagram shows that this would be a very high
energy mechanism.
2) The lowest energy path is X " Z " Y. This represents a concerted displacement of
H in H
2
by F to give HF. In this pathway, the H$F bond forms as the H$H bond
breaks. This can be depicted as follows:
F + H$H ---> [ F---H---H]

---> F$H + H
X Z Y
The activated complex, [F--H--H]

, will immediately decompose to products during

a vibration in which the F and H move towards each other and the other H moves
away. A vibration in the opposite direction will lead to products.
3) The activation energy of the forward reaction is the difference in energy between
points Z (the activated complex) and X (reactants). The activation energy for the
reverse reaction is the energy difference between points Z and Y.
2. The energy changes are usually shown by plotting the energy along the reaction path
X " Z " Y. This path is called the Reaction Coordinate. It starts at the reactants and
goes through the transition state to products. Such a plot is shown below.


(Transition State or Activated Complex)
H-H + F
[F--H--H]

H-F + H
(Reactants)
(Products)
Reaction Coordinate
E
n
e
r
g
yE
af
ar
E
!"

22
a. E
af
= activation energy for the forward reaction.
E
ar
= activation energy for the reverse reaction.
b. At constant pressure, %H = E
af
$ E
ar
.
For an exothermic reaction, E
af
< E
ar
and for an endothermic reaction, E
af
> E
ar
.
3. A catalyst is a substance that increases the rate of a reaction, but is not consumed in the
reaction.
The introduction of a catalyst changes the mechanism leading to an activated complex of
lower energy. It does not change the energy of the reactants or the products. Thus a
catalyst will not change any of the thermodynamic parameters for the reaction. (see below)
4. For multistep reactions the Energy vs Reaction Coordinate diagram is a combination
of the diagrams for each step. For example for the two step mechanism
k
1

Step 1. A + B ------> C + D Slow
k
2

Step 2 C + B ------> E Fast

_________________________

Net A + 2B ------> D + E
the Energy vs Reaction Coordinate diagram is shown below.


A + B
T.S.(1)
C + D
T.S.(2)
E + D
!"
Reaction Coordinate
E
n
e
r
g
y
E
a1
E
a2

a. E
a1
= activation energy for Step 1.
23
E
a2
= activation energy for Step 2.
b. Since the first step is the slow step, E
a1
> E
a2
.
c. The reaction is written as endothermic.
B. Catalyst
1. Catalyst = Any substance that increases the rate of a chemical reaction but is not
consumed in the reaction.
a. Heterogeneous Catalysts = Phase of the catalyst is different from
that of the reaction. Most examples involve a solid state catalyst
increasing the rates of solution or gas phase reactions.

Pt(s)
CH
2
=CH
2
(g) + H
2
(g) ----------> CH
3
CH
3


MnO
2
(s)
2 H
2
O
2
(aq) -------> 2 H
2
O(l) + O
2
(g)

MnO
2
is the catalyst. The formula of the catalyst is written above the arrow.

b. Homogeneous Catalysts = Phase of the catalyst is the same as that of the reaction.
Example: The I

catalyzed decomposition of H
2
O
2

I

2 H
2
O
2
(aq) --------> 2 H
2
O(l) + O
2
(g)

2. Catalysts act by changing the mechanism allowing for lower energy transition states.
a. The catalyst concentration can appear in the rate law, but not in the balanced equation.
b. Example: I

catalyst of H
2
O
2
decomposition.
k
1

Step 1: H
2
O
2
+ I

--------> H
2
O + IO

Slow

k
2

Step 2: H
2
O
2
+ IO

--------> H
2
O + O
2
+ I

Fast

Net 2 H
2
O
2
-------> 2 H
2
O + O
2


Rate = Rate
1
= k
1
[H
2
O
2
][I

]

c. Note that a catalyst is not an intermediate. An intermediate is produced in one step and
consumed in a later one, while a catalyst may be consumed in one step and produced in a
later one.
24
3. A catalyst lowers the energy of the transition state, thereby increasing the rates of both the
forward and reverse reactions. It does not affect the equilibrium point, it decreases the time
required to reach equilibrium.

4. The following plot demonstrates the effect of a catalyst

With Catalyst
No Catalyst
[TS
1
]

[TS
2
]

REACTANTS
PRODUCTS
E
N
E
R
G
Y
REACTION COORDINATE
Effect of a Catalyst
25

Kinetics Problems

1. Define or write expressions for:
a) instantaneous rate f) activation energy
b) order g) activated complex (transition state)
c) mechanism h) bimolecular process
d) catalyst i) rate determining step
e) the Arrhenius equation
2. For the gaseous reaction A
2
(g) + B
2
(g) ---> C(g) the initial rate method gave the following
results at 25C.
Initial Concentration, M Initial Rate of Formation
Experiment A
2
B
2
of C in M/s_______
1 0.20 0.20 3.0x10
-6

2 0.20 0.40 6.0x10
-6

3 0.40 0.40 48.0x10
-6
a. What is the order in A
2
? What is the order in B
2
? What is the overall order?
b. Write the rate law for the reaction.
c. Calculate the value of the specific rate constant? Give its dimensions.
d. What would the rate of the reaction be if both A
2
and B
2
were 0.10M?
3. For the reaction 2X
2
(g) + Y
2
(g) ----> C(g) + E(g) the initial rate method gave the
following results at 25C.
Initial Concentration, M Initial Rate of Formation
Experiment X
2
Y
2
_ of C in Ms
-1
_________
1 2.0x10
-3
4.0x10
-3
3.00x10
-6

2 4.0x10
-3
4.0x10
-3
4.23x10
-6

3 2.0x10
-3
1.2x10
-2
15.6x10
-6

a. What is the order in X
2
? What is the order in Y
2
? What is the overall order of the reaction?
b. Write the rate law for the reaction.

4. For the gaseous reaction A(g) + B(g) C(g) the initial rate method yielded
the following data at 25C.
Initial concentration, M Initial rate of formation
Experiment A

B of C, M/min
1 0.10 0.10 1.0 x 10
-3

2

0.20

0.20 8.0 x 10
-3

3

0.10 0.20 4.0 x 10
-3
4
0.20

0.40 32 x 10
-3

26

a) Write the rate law for the reaction.
b) Calculate k, the specific rate constant, at 25 C.
c) Calculate what the initial rate would be if the initial concentration of A were
0.25 M and that of B 0.30 M.
5. Suppose that the reaction 2B ----> Products was studied by measuring the concentration of
B as a function of time and the following data was obtained.
time, min. [B] time, min. [B] time, min. [B]
0.00 0.0500 30.0 0.0286 50 0.0222
10.0 0.0400 40.0 0.0250 60 0.0200
20.0 0.0333 45.0 0.0235 80 0.0167
a. What is the order of the reaction in B ?
b. What is the value of the specific rate constant ? Give its dimensions.
6. Derive the expression for the half-life of a third order reaction of the form A ----> Products.
7. A sample of charcoal from a prehistoric site gave 3.2 counts per min. per g of carbon due to

14

C . Given that the half-life of
14

C is 5740 yr. and that fresh wood gives 15.2 counts per

min. per g of carbon, calculate the age of the charcoal.
8. A first-order reaction has a half-life of 10 minutes. What fraction of the starting reactant
concentration will remain at the end of 100 minutes? What is the specific rate constant of the
reaction?
9. Suppose that the first order reaction A ---> Products has a rate constant of 0.154 s
-1
at 25C
and one started with 0.24 M A,.
a. Calculate the half-life of the reaction.
b. Calculate the concentration of A after 10.0 s have elapsed.
c. If E
a
= 53.2 kJ/mol, calculate the rate constant at 65C.
10. A reaction has a specific rate constant equal to 2.0x10
6
Ms
-1
at 27C and 6.0x10
7
Ms
-1
at
77C, calculate the activation energy of the reaction.
11. Write the net reaction and the experimental rate expression predicted by each of the following
mechanisms. Identify any intermediates in the mechanism.
k
1

a. A + B AB fast equilibrium
k
-1

k
2

AB + B ----> D + E slow
k
1

27
b. C + A CA fast equilibrium
k
-1
k
2

CA ----> D + E slow

k
1

c. A
2
+ B
2
----> A
2
B + B slow
k
2

B + A
2
----> A
2
B fast
k
1

d. XY ----> X + Y slow
k
2

X + Z ----> XZ fast
e. k
1

Step 1 N
2
O
5
NO
2
+ NO
3
Fast equilibrium
k
2
k
3
Step 2 NO
3
+ H
2
NO
2
+ H
2
O Slow

12. The reaction A + 2B ----> C + D was run under conditions in which [B] = 100x[A] and
the plot of [A] vs time was


10 20 30 40 50 60
time, s
[
A
]
0
60
0
10
20
30
40
50

What is the order of the reaction in A?



28

13. In the course of studying the reaction 2AB ----> C + D at 25C the following plot was
obtained.

l
n
[
A
B
]
10 20 30 40 50 60
0.50
0.51
0.52
0.53
time,s
0
0
0.54


a. What is the initial concentration of AB?
b. What is the order of the reaction in AB?
c. Write the rate expression.
d. Calculate the value of the specific rate constant for the reaction.


14. Consider the following mechanism.
k
1

A
2
2A fast equilibrium
k
-1

k
2

A + B
2
-----> C + B slow
k
3

B + A ------> C fast
a. List the intermediates.
b. What is the experimental rate law predicted by the mechanism?
c. Sketch a plot of energy vs the Reaction Coordinate for this reaction. Assume that %H for
the reaction is negative.




29
15. Shown below is a plot of energy vs the Reaction Coordinate for a bimolecular reaction.


Reactants
Products
200
250
300
350
400
Reaction Coordinate
E
n
e
r
g
y
,

k
J

a. What is the activation energy for the forward reaction? 2) the activation energy
for the reverse reaction? What is the energy of the transition state of the reaction?
b. Is the reaction exothermic? What is the value of %H for the reaction?
c. Would the rate of the forward reaction show a greater percentage increase with temperature
than the rate of the reverse reaction?
d. On the sketch show qualitatively what the plot would look like if a catalyst were added.
30

16. Suppose that the reaction, A + 3B ---> D + 2E, was studied by measuring the concentration
of A as a function of time for several different B concentrations. The resulting data are
plotted below. Write the rate law for this reaction and evaluate the specific rate constant.

0
4
8
12
16
1
/
[
A
]
20
0 50 100 150 200 250
time,s
300
[B]
0
=20.0 M
[B]
0
=10.0 M

17. Suppose that the kinetics of the reaction 2A + 3B ----> D + 3E was studied by measuring
the concentration of A as a function of time at two different B concentrations. The results of
such a study are given in the plots shown below. What is the order in A, the order in B, and
the value of the specific rate constant for this reaction?

0
0.1
0.2
0.3
0.4
0.5
[
A
]
0.6
0.7
0.8
0 50 100 150 200
time,s
250 300
[B]
0
=8.0 M
[B]
0
=16.0 M

31


18. Shown below is a plot of Energy vs. the Reaction Coordinate (RC) for a reaction.

a. How many steps are in the reaction? b. Which step is the slow step? c. What is the
activation energy of this step? d. What is the energy of the transition state for this step? e.
What is !H for this reaction?
Reaction Coordinate
E
n
e
r
g
y
,

k
J
50
100
150
200
250
300
32
Kinetics Problems
(answers)

1. See Notes.
2. a. 3
rd
, 1
st
, 4
th
b. Rate = [A]
3
[B] c. 1.9x10
-3
M
-3
s
-1
d. 1.9x10
-7
Ms
-1
3. a. 1/2, 3/2, 2 b. Rate = k[X
2
]
1/2
[Y
2
]
3/2

4. a. Rate = k[A][B]
2
b. k = 1.0 M
-2
s
-1
c. Rate = 2.25x10
-2
Ms
-

5. a. second. b. 0.5 M
-1
s
-1

6. t
1/2
=
3
2k[A]
2
o

7. 12,900 yr.
8. 9.8x10
-4
, 6.93x10
-2
s
-1

9. a. 4.5 s. b. 0.05M c. 1.95 s
-1

10. 59.4 kJ/mol
11. Net Reaction Rate Law Intermediate(s)
A + 2B ---> D + E Rate =
k
1
k
-1
k
2
[B]
2
[A] AB
C + A ---> D + E Rate =
k
1
k
-1
k
2
[C][A] CA
2A
2
+ B
2
---> 2A
2
B Rate = k
1
[A
2
][B
2
] B
XY + Z ---> XZ +Y Rate = k
1
[XY] X
N
2
O
5
+ H
2
- 2 NO
2
+ H
2
O Rate = k
3
k
1
k
2
[N
2
O
5
][H
2
]
[NO
2
]
NO
3
12. first order, k = 0.046 s
-1
13. a. 1.66M b. First order c. Rate = k[AB] d. 7x10
-4
s
-1

14. a. A, B b. Rate = k
2
k
1
k
-1


[A
2
]
1/2
[B
2
]
15. a. 125 kJ, 50 kJ, 375 kJ b. No, 75 kJ c. Yes
16. Rate = k[A]
2
[B]
2
, where k = 1.7x10
-4
M
-3
s
-1

17. Rate = k[B]
2
[A], where k = 9x10
-5
M
-2
s
-1
18. a. 2; b. 1
st
; c. 250kJ/mol; d. 300 kJ/mol; e. +50 kJ/mol