Chem Chapter 13 LEC

Chemistry: A Molecular Approach, 1st Ed.
Nivaldo Tro
Chapter 13
Chemical
Kinetics
Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
2008, Prentice Hall
Kinetics
kinetics is the study of the factors that affect
the speed of a reaction and the mechanism
by which a reaction proceeds.
experimentally it is shown that there are 4
factors that influence the speed of a
reaction:
nature of the reactants,
temperature,
catalysts,
concentration
Tro, Chemistry: A Molecular Approach
Defining Rate
rate is how much a quantity changes in a given
period of time
the speed you drive your car is a rate the distance
your car travels (miles) in a given period of time (1
hour)
so the rate of your car has units of mi/hr
distance
Speed
time
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
concentration
Rate
time
[product]
[reactant]
Rate
time
time
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.
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
2C1 A 1
C A C 2 A
Rate
t 2 tt21 t1
tt
4 4 08 0.025.25
Rate
1616 00
1 X 1
ZX Z 2 X
2
Rate
t 2 t 21 t1
tt
17 0 8 0.00625
Rate
.0625
1616 00
at t = 16
[A] = 4
[B] = 4
[C] = 4
at t = 16
[X] = 7
[Y] = 7
[Z] = 1
at t = 32
[A] = 2
[B] = 2
[C] = 6
at t = 32
[X] = 6
[Y] = 6
[Z] = 2
2C1 A 1
C A C 2 A
Rate
t 2 tt21 t1
tt
6 2 44 0.0125
Rate
.125
1616 00
1 X 1
ZX Z 2 X
2
Rate
t 2 t 21 t1
tt
2 617 0.00625
.0625
Rate
1616 00
at t = 32
[A] = 2
[B] = 2
[C] = 6
at t = 32
[X] = 6
[Y] = 6
[Z] = 2
at t = 48
[A] = 0
[B] = 0
[C] = 8
at t = 48
[X] = 5
[Y] = 5
[Z] = 3
2C1 A 1
C A C 2 A
Rate
t 2 tt21 t1
tt
8 0 62 0.0125
.125
Rate
1616 00
1 X 1
ZX Z 2 X
2
Rate
t 2 t 21 t1
tt
35 26 0.00625
.0625
Rate
1616 00
Hypothetical Reaction
Red Blue
Time
(sec)
Number Number
Red
Blue
0
100
84
16
10
71
29
15
59
41
20
50
50
25
42
58
30
35
65
35
30
70
40
25
75
45
21
79
50
18
82
in this reaction,
one molecule of Red turns
into one molecule of Blue
the number of molecules
will always total 100
the rate of the reaction can
be measured as the speed of
loss of Red molecules
over time, or the speed of
gain of Blue molecules
9
over time
Red Blue
10
Red Blue
11
Reaction Rate and Stoichiometry

in most reactions, the coefficients of the balanced equation
are not all the same
H2 (g) + I2 (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 H2 used, 1 mole of I2
will also be used and 2 moles of HI made
therefore the rate of change will be different
in order to be consistent, the change in the concentration

of each substance is multiplied by 1/coefficient
[H 2 ]
[I 2 ]
1 [HI]
Rate

t
t
2 t
12
Average Rate
the average rate is the change in measured
concentrations in any particular time period
linear approximation of a curve
the larger the time interval, the more the average

rate deviates from the instantaneous rate
13
Hypothetical Reaction Red Blue

Avg. Rate Avg. Rate Avg. Rate
(5 sec
Number Number
intervals)
Red
Blue
Time
(sec)
0
100
84
16
3.2
10
71
29
2.6
15
59
41
2.4
20
50
50
1.8
25
42
58
1.6
30
35
65
1.4
35
30
70
40
25
75
45
21
79
0.8
50
18
82
0.6
(10 sec
intervals)
(25 sec
intervals)
2.9
2.1
2.3
1.5
1
0.7
14
H2
Time (s) [H2], M
0.000 1.000
10.000 0.819
20.000 0.670
30.000 0.549
40.000 0.449
50.000 0.368
60.000 0.301
70.000 0.247
80.000 0.202
90.000 0.165
100.000 0.135
I2
HI
Avg. Rate, M/s Avg. Rate, M/s

-[H2]/t
[HI], M
1/2 [HI]/t
0.000
StoichiometryThe
tells
us thatrate
for is
average
every
1 mole/L
H0.0181
0.362
0.0181
theofchange
2 used,
in the
2 moles/L
HI are 0.0149
made. in a
0.660
0.0149of concentration
given time period.
Assuming
0.902
0.0121a 1 L container,
0.0121at
10 s, we used 0.181 moles of
In the first
10 s, the
1.102
0.0100
H2. 0.0100
Therefore the amount
of
[H2] is0.0081
-0.181 M,
1.264
0.0081
HI made is 2(0.181 moles) =
so the rate is
1.398
0.0067
0.0067
0.362
moles
0.181 M
0.699 moles
At 60
s, we used
1.506
0.0054
0.0054
10.000
s
of H0.0045
the0.0045
amount
M
2. Therefore
0.0181
1.596
s
of HI made is 2(0.699 moles)
1.670
0.0037
0.0037
= 1.398 moles
15
1.730
0.0030
0.0030
average rate in a given

time period = slope of
the line connecting the
[H2] points; and +slope
of the line for [HI]
the average rate for the
first 80
10 s is 0.0108
40
0.0181 M/s
0.0150
16
Instantaneous Rate
the instantaneous rate is the change in
concentration at any one particular time
slope at one point of a curve
determined by taking the slope of a line tangent

to the curve at that particular point
first derivative of the function
for you calculus fans
17
H2 (g) + I2 (g) 2 HI (g)
Using [H2], the

instantaneous rate at
50 s is:
Rate
0.28 M
40 s
Rate 0.0070
M
s
Using [HI], the

instantaneous rate at
50 s is:
1 0.56 M
2
40 s
Rate
Rate 0.0070
M
s
18
Ex 13.1 - For the reaction given, the [I] changes from

1.000 M to 0.868 M in the first 10 s. Calculate the
average rate in the first 10 s and the [H+].
H2O2 (aq) + 3 I(aq) + 2 H+(aq) I3(aq) + 2 H2O(l)
Solve the equation
for the Rate (in
terms of the change
in concentration of
the Given quantity)
Solve the equation
of the Rate (in terms
of the change in the
concentration for the
quantity to Find) for
the unknown value
1 [I ]
1 0.868 M 1.000 M
Rate

10 s
3 t
3
Rate 4.40 10-3
M
s
1 [H ]
Rate
2 t
[H ]
2 Rate
t
[H ]
M
M
2 4.40 10-3
8.80 10-3
s
s
t
Measuring Reaction Rate

in order to measure the reaction rate you need to be
able to measure the concentration of at least one

component in the mixture at many points in time
there are two ways of approaching this problem (1) for
reactions that are complete in less than 1 hour, it is best
to use continuous monitoring of the concentration, or
(2) for reactions that happen over a very long time,
sampling of the mixture at various times can be used
when sampling is used, often the reaction in the sample is
stopped by a quenching technique
20
Continuous Monitoring
polarimetry measuring the change in the degree of
rotation of plane-polarized light caused by one of the

components over time
spectrophotometry measuring the amount of light of
a particular wavelength absorbed by one component
over time
the component absorbs its complimentary color
total pressure the total pressure of a gas mixture is

stoichiometrically related to partial pressures of the
gases in the reaction
21
Sampling
gas chromatography can measure the concentrations
of various components in a mixture
for samples that have volatile components
separates mixture by adherence to a surface
drawing off periodic aliquots from the mixture and

doing quantitative analysis
titration for one of the components
gravimetric analysis
22
Factors Affecting Reaction Rate

Nature of the Reactants
nature of the reactants means what kind of reactant
molecules and what physical condition 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., the activity series of metals
ions react faster than molecules

no bonds need to be broken
23

Temperature
increasing temperature increases reaction rate
chemists rule of thumb - for each 10C rise in
temperature, the speed of the reaction doubles
for many reactions
there is a mathematical relationship between

the absolute temperature and the speed of a
reaction discovered by Svante Arrhenius
which will be examined later
24

Catalysts
catalysts are substances which affect the speed of
a reaction without being consumed.
most catalysts are used to speed up a reaction,
these are called positive catalysts
catalysts used to slow a reaction are called negative
catalysts.
homogeneous = present in same phase

heterogeneous = present in different phase
how catalysts work will be examined later
25

Reactant Concentration
generally, the larger the concentration of
reactant molecules, the faster the reaction
increases the frequency of reactant
molecule contact
concentration of gases depends on the partial
pressure of the gas
higher pressure = higher concentration
concentration of solutions depends on the

solute to solution ratio (molarity)
26
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 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
Rate k[A] [B]

27
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 order of the reaction
The rate law for the reaction:
2 NO(g) + O2(g) 2 NO2(g)
is Rate = k[NO]2[O2]
The reaction is
second order with respect to [NO],
first order with respect to [O2],
and third order overall
28
Sample Rate Laws
The reaction is autocatalytic, because a product affects the rate.

Hg2+ is a negative catalyst, increasing its concentration slows the reaction.
29
Reactant Concentration vs. Time

A Products
30
Half-Life
the half-life, t1/2, of a
reaction is the length

of time it takes for the
concentration of the
reactants to fall to
its initial value
the half-life of the
reaction depends on
the order of the
reaction
31
Zero Order Reactions
Rate = k[A]0 = k
constant rate reactions

[A] = -kt + [A]0
graph of [A] vs. time is straight line with
slope = -k and y-intercept = [A]0
t = [A0]/2k
when Rate = M/sec, k = M/sec
[A]0
[A]
slo
p
time
e=
-k
32
First Order Reactions

Rate = k[A]
ln[A] = -kt + ln[A]0
graph ln[A] vs. time gives straight line with
slope = -k and y-intercept = ln[A]0
used to determine the rate constant
t = 0.693/k
the half-life of a first order reaction is
constant
the when Rate = M/sec, k = sec-1
33
ln[A]0
slo
p
ln[A]
e=
time
34
Half-Life of a First-Order Reaction

Is Constant
35
Rate Data for

C4H9Cl + H2O C4H9OH + HCl
Time (sec)
[C4H9Cl], M
0.0
0.1000
50.0
0.0905
100.0
0.0820
150.0
0.0741
200.0
0.0671
300.0
0.0549
400.0
0.0448
500.0
0.0368
800.0
0.0200
10000.0
0.0000
36
C4H9Cl + H2O C4H9OH + 2 HCl
37
38

slope =
-2.01 x 10-3
k=
2.01 x 10-3 s-1
t1
2
0.693
k
0.693
2.0110 3 s -1
345 s
39
Second Order Reactions

Rate = k[A]2
1/[A] = kt + 1/[A]0
graph 1/[A] vs. time gives straight line with
slope = k and y-intercept = 1/[A]0
used to determine the rate constant
t = 1/(k[A0])
when Rate = M/sec, k = M-1sec-1
40
p
o
l
s
1/[A]
k
=
e
l/[A]0
time
41
Rate Data For

2 NO2 2 NO + O2
Partial
Pressure
Time (hrs.) NO2, mmHg
ln(PNO2)
1/(PNO2)
100.0
4.605
0.01000
30
62.5
4.135
0.01600
60
45.5
3.817
0.02200
90
35.7
3.576
0.02800
120
29.4
3.381
0.03400
150
25.0
3.219
0.04000
180
21.7
3.079
0.04600
210
19.2
2.957
0.05200
240
17.2
2.847
0.05800
42
Rate Data Graphs For

2 NO2 2 NO + O2
43

2 NO2 2 NO + O2
44

2 NO2 2 NO + O2
45
Determining the Rate Law

can only be determined experimentally
graphically
rate = slope of curve [A] vs. time
if graph [A] vs time is straight line, then exponent on A in rate
law is 0, rate constant = -slope
if graph ln[A] vs time is straight line, then exponent on A in rate
law is 1, rate constant = -slope
if graph 1/[A] vs time is straight line, exponent on A in rate law
is 2, rate constant = slope
initial rates
by comparing effect on the rate of changing the initial
concentration of reactants one at a time
46
47
Practice - Complete the Table and

Determine the Rate Equation for the
Reaction A 2 Prod
[A], (M) [Prod], (M) Time (sec)
0.100
1/[A]
0.067
50
0.050
100
0.040
150
0.033
200
0.029
250
ln([A])
48
Practice - Complete the Table and

Determine the Rate Equation for the
Reaction A 2 Prod
[A], (M) [Prod], (M) Time (sec)
ln([A])
1/[A]
0.100
-2.3
10
0.067
0.066
50
-2.7
15
0.050
0.100
100
-3.0
20
0.040
0.120
150
-3.2
25
0.033
0.134
200
-3.4
30
0.029
0.142
250
-3.5
35
49
50
51
52
Practice - Complete the Table and Determine

the Rate Equation for the Reaction A 2
Prod
the reaction is second order,
-[A]
Rate =
= 0.1 [A]2
t
53
Ex. 13.4 The reaction SO2Cl2(g) SO2(g) + Cl2(g) is first order

with a rate constant of 2.90 x 10-4 s-1 at a given set of conditions.
Find the [SO2Cl2] at 865 s when [SO2Cl2]0 = 0.0225 M
Given:
[SO2Cl2]0 = 0.0225 M, t = 865, k = 2.90 x 10-4 s-1
Find:
Concept Plan:
[SO2Cl2]
Relationships:
for a 1st order process : ln[A] kt ln[A]0
Solution:
[SO2Cl2]0, t, k
[SO2Cl2]
ln[SO 2Cl 2 ] kt ln[SO 2Cl 2 ]0
ln[SO 2Cl 2 ] 2.90 10- 4 s -1 865 s ln 0.0225

ln[SO 2Cl 2 ] 0.251 3.79 4.04
[SO 2Cl 2 ] e (-4.04) 0.0175 M
Check: the new concentration is less than the original, as

expected
Initial Rate Method

another method for determining the order of a
reactant is to see the effect on the initial rate of the

reaction when the initial concentration of that
reactant is changed
for multiple reactants, keep initial concentration of all
reactants constant except one
zero order = changing the concentration has no effect on
the rate
first order = the rate changes by the same factor as the
concentration
doubling the initial concentration will double the rate
second order = the rate changes by the square of the factor

the concentration changes
doubling the initial concentration will quadruple the rate
55
Ex 13.2 Determine the rate law and rate constant for the
reaction NO2(g) + CO(g) NO(g) + CO2(g)
given the data below.
Write a general
rate law
including all
reactants
Examine the
data and find
two experiments
in which the
concentration of
one reactant
changes, but the
other
concentrations
are the same
Expt.
Initial
Initial
Initial
Expt.
Initial
Initial Rate
Rate
Initial
Number
(M/s)
[NO22],
], (M)
(M) [CO],
Number [NO
[CO], (M)
(M)
(M/s)
1.
0.10
0.10
0.0021
2.
0.20
0.10
0.0082
3.
4.
0.20
0.40
0.20
0.10
0.0083
0.033
Rate k[NO 2 ] [CO]
Comparing Expt #1 and Expt #2, the

[NO2] changes but the [CO] does not
56
Determine by
what factor the
concentrations
and rates change
in these two
experiments.
[NO 2 ]expt 2
[NO 2 ]expt 1
Expt.
Initial
Initial Rate
Initial
Number [NO2], (M) [CO], (M)
(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
0.20 M
2
0.10 M
Rate expt 2
Rate expt 1
0.0082 M s
4
M
0.0021 s
57
Determine to
what power the
concentration
factor must be
raised to equal
the rate factor.
[NO 2 ]expt 2
[NO 2 ]expt 1
Expt.
Initial
Initial Rate
Initial
(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
0.20 M
n
M
Rate
0
.
0082
expt
2
2
s
[NO 2 ]expt 2
Rate expt 2
4
0.10 M

M
Rate expt 1 0.0021 s
[NO 2 ]expt 1
2n 4
n2
Rate expt 1
58
Repeat for the
other reactants
[CO]expt 3
[CO]expt 2
Expt.
Initial
Initial Rate
Initial
(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
0[CO]
expt 3
.20 M
Rate
Rateexpt
expt3 3
[CO] 2 Rate
expt 2
Rateexpt
0.10 M
expt2 2
2m 1
m0
0.0083 M s
1
0.0082 M s
59
Substitute the
exponents into
the general rate
law to get the
rate law for the
reaction
Expt.
Initial
Initial Rate
Initial
(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
n0
m
2
n = 2, mRate
= 0 Rate
2k][NO
k[NO
[CO]
2 ] [CO]
2
Rate k[NO 2 ]
60
Substitute the
concentrations
and rate for any
experiment into
the rate law and
solve for k
Expt.
Initial
Initial Rate
Initial
(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
0.0021 M s
-1
-1
k
0
.
21
M
s
0.01 M 2
61
Practice - Determine the rate law and rate constant for the
reaction NH4+1 + NO2-1
Expt. Initial
Initial
Initial Rate,
[NH4+], M [NO2-], M (x 10-7), M/s
No.
1
0.0200
0.200
10.8
0.0600
0.200
32.3
0.200
0.0202
10.8
0.200
0.0404
21.6
62
Practice - Determine the rate law and rate constant for the
reaction NH4+1 + NO2-1
Expt.
No.
Initial
[NH4+], M
Initial
[NO2-], M
Initial Rate,
(x 10-7), M/s
0.0200
0.200
10.8
0.0600
0.200
32.3
0.200
0.0202
10.8
0.200
0.0404
21.6
Expt 2 0.0600
For [NH 4 ],
3
Expt 1 0.0200
Expt 2 32.3 10 7
Rate,
7
Expt 1 10.8 10
Rate Factor [NH 4 ]n 3 3n
n 1, first order
Rate = k[NH4+]n[NO2]m
Rate k[NH 4 ][NO 2 ]

for expt 1
10.8 10-7 M s k 0.0200 M 0.200 M
10.8 10-7 M s
k
2.70 10 4 M -1 s -1
4.00 10-3 M 2
Expt 4 0.0404
For [NO 2 ],
2
Expt 3 0.0202
Expt 4 21.6 10 7
Rate,
7
Expt 3 10.8 10
Rate Factor [NO 2 ]m 2 2 m
m 1, first order
63
The Effect of Temperature on Rate
changing the temperature changes the rate
constant of the rate law

Svante Arrhenius investigated this relationship
and showed that:
Ea
k A e RT
where T is the temperature in kelvins

R is the gas constant in energy units, 8.314 J/(molK)
A is a factor called the frequency factor
Ea is the activation energy, the extra energy needed to start
the molecules reacting
64
65
Activation Energy and the

Activated Complex
energy barrier to the reaction
amount of energy needed to convert reactants
into the activated complex
aka transition state
the activated complex is a chemical species with

partially broken and partially formed bonds
always very high in energy because partial bonds
66
Isomerization of Methyl Isonitrile
methyl isonitrile rearranges to acetonitrile

in order for the reaction to occur,
the H3C-N bond must break; and
a new H3C-C bond form
67
Energy Profile for the

Isomerization of Methyl Isonitrile
As the reaction
the activated
collision
activation
frequency
complex
energy
begins, the
C-N
is athe
chemical
number
difference
species
of in
bond
weakens
molecules
energy
with
partial
between
that
bonds
the
enough
for the
approach
reactants
the
peak
theto in a
CN and
group
givenstart
activated
period
complex
of time
to
rotate
68
The Arrhenius Equation:

The Exponential Factor
the exponential factor in the Arrhenius equation is a number
between 0 and 1
it represents the fraction of reactant molecules with sufficient
energy so they can make it over the energy barrier
the higher the energy barrier (larger activation energy), the fewer
molecules that have sufficient energy to overcome it
that extra energy comes from converting the kinetic energy of
motion to potential energy in the molecule when the molecules

collide
increasing the temperature increases the average kinetic energy of the
molecules
therefore, increasing the temperature will increase the number of
molecules with sufficient energy to overcome the energy barrier
therefore increasing the temperature will increase the reaction rate
69
70
Arrhenius Plots
the Arrhenius Equation can be algebraically
solved to give the following form:
Ea 1
ln(k )
ln A
R T
this equation is in the form y = mx + b
where y = ln(k) and x = (1/T)
a graph of ln(k) vs. (1/T) is a straight line
(-8.314 J/molK)(slope of the line) = Ea, (in Joules)
ey-intercept = A, (unit is the same as k)
71
Ex. 13.7 Determine the activation energy and frequency

factor for the reaction O3(g) O2(g) + O(g) given the
following data:
Temp, K
k, M-1s-1
Temp, K
k, M-1s-1
600
3.37 x 103
1300
7.83 x 107
700
4.83 x 104
1400
1.45 x 108
800
3.58 x 105
1500
2.46 x 108
900
1.70 x 106
1600
3.93 x 108
1000
5.90 x 106
1700
5.93 x 108
1100
1.63 x 107
1800
8.55 x 108
1200
3.81 x 107
1900
1.19 x 109
72

following data:
use a
spreadsheet
to graph
ln(k) vs.
(1/T)
73

following data:
Ea = m(-R)
solve for Ea
A = ey-intercept
solve for A
9.3110 4
Ea 1.12 10 4 K 8.314
mol K
mol
kJ
Ea 93.1
J
mol
A e 26.8 4.36 1011
A 4.36 1011 M -1 s 1
74
Arrhenius Equation:
Two-Point Form
if you only have two (T,k) data points, the
following forms of the Arrhenius Equation can

be used:
k
E 1
1
a

R T1 T2
k1
ln
Rx
Ea
1
T2
k1
k1
ln
R x ln
k2
k2
1
T1 T2
T1
T1 T2
k1
R T1 T2 x ln
k2
T1 T2
75
Ex. 13.8 The reaction NO2(g) + CO(g) CO2(g) + NO(g) has a rate
constant of 2.57 M-1s-1 at 701 K and 567 M-1s-1 at 895 K. Find the
activation energy in kJ/mol
Given:
Find:
Concept Plan:
T1 = 701 K, k1 = 2.57 M-1s-1, T2 = 895 K, k2 = 567 M-1s-1
Ea, kJ/mol
T1, k1, T2, k2
Ea
k2
E 1
1
a

R T1 T2
k1
ln
Relationships:
-1
-1
Ea
1
567 M s
1
ln
Solution: 2.57M -1 s -1 8.314 molJK 701 K 895 K
5.3965
1.45 105
Ea
4
-1
3
.
0
9
2
10
K
J
1
8.314 mol K
J
mol
kJ
145 mol
Ea
Check: most activation energies are tens to hundreds of

kJ/mol so the answer is reasonable
Collision Theory of Kinetics

for most reactions, in order for a reaction to take
place, the reacting molecules must collide into
each other.
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";
2. whether the reacting molecules collide in the
proper orientation for new bonds to form.
77
Effective Collisions
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
when two molecules have an effective
collision, a temporary, high energy (unstable)
chemical species is formed - called an
activated complex or transition state
78
Kinetic Energy Factor
for a collision to lead
to overcoming the
energy barrier, the
reacting molecules
must have sufficient
kinetic energy so that
when they collide it
can form the
activated complex
79
Orientation Effect
80
Collision Theory and

the Arrhenius Equation
A is the factor called the frequency factor and
is the number of molecules that can approach
overcoming the energy barrier
there are two factors that make up the frequency
factor the orientation factor (p) and the
collision frequency factor (z)
RTEa
k A e
pze
Ea
RT
81
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
reactions between atoms generally have p = 1
reactions where symmetry results in multiple orientations
leading to reaction have p slightly less than 1
for most reactions, the orientation factor is less than 1

for many, p << 1
there are some reactions that have p > 1 in which an electron
is transferred without direct collision
82
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 steps that occur to produce the
overall observed reaction is called a reaction
mechanism
knowing the rate law of the reaction helps us understand
the sequence of steps in the mechanism
83
An Example of a Reaction Mechanism

Overall reaction:
H2(g) + 2 ICl(g) 2 HCl(g) + I2(g)
Mechanism:
1) H2(g) + ICl(g) HCl(g) + HI(g)
2) HI(g) + ICl(g) HCl(g) + I2(g)
the steps in this mechanism are 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
84
Elements of a Mechanism
Intermediates
H2(g) + 2 ICl(g) 2 HCl(g) + I2(g)

notice that the HI is a product in Step 1, but then a
reactant in Step 2
since HI is made but then consumed, HI does not
show up in the overall reaction
materials that are products in an early step, but then a
reactant in a later step are called intermediates
85
Molecularity
the number of reactant particles in an elementary
step is called its molecularity
a unimolecular step involves 1 reactant particle
a bimolecular step involves 2 reactant particles
though they may be the same kind of particle
a termolecular step involves 3 reactant particles

though these are exceedingly rare in elementary steps
86
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 from the equation of the step
H2(g) + 2 ICl(g) 2 HCl(g) + I2(g)

Rate = k1[H2][ICl]
Rate = k2[HI][ICl]
87
Rate Laws of Elementary Steps
88
Rate Determining Step

in most mechanisms, one step occurs slower than the
other steps
the result is that product production 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
89
Another Reaction Mechanism

NO2(g) + CO(g) NO(g) + CO2(g)
1) NO2(g) + NO2(g) NO3(g) + NO(g)
2) NO3(g) + CO(g) NO2(g) + CO2(g)
Rateobs = k[NO2]2
Rate = k1[NO2]2 slow
Rate = k2[NO3][CO] fast
The first step is slower than the

second step because its
activation energy is larger.
The first step in this mechanism
is the rate determining step.
The rate law of the first step is
the same as the rate law of the
overall reaction.
90
Validating a Mechanism
in order 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
91
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
92
An Example
k1
2 NO(g) N2O2(g)
k-1
H2(g) + N2O2(g) H2O(g) + N2O(g)
Fast
Slow Rate = k2[H2][N2O2]
H2(g) + N2O(g) H2O(g) + N2(g)
Fast
2 H2(g) + 2 NO(g) 2 H2O(g) + N2(g) Rateobs = k [H2][NO]2

for Step 1 Rateforward = Ratereverse
k1[NO]2 k1[N 2O 2 ]
k1
[N 2O 2 ]
[NO]2
k1
Rate k2 [H 2 ][N 2O 2 ]
k1
Rate k2 [H 2 ] [NO2 ]2
k1
k2k1
Rate
[H 2 ][NO2 ]2
k1
93
Ex 13.9 Show that the proposed mechanism for the

reaction 2 O3(g) 3 O2(g) matches the observed rate law
Rate = k[O3]2[O2]-1
k1
O3(g) O2(g) + O(g)

k-1
O3(g) + O(g) 2 O2(g) Slow

for Step 1 Rateforward = Ratereverse
k1[O3 ] k1[O 2 ][O]

k1
[O]
[O3 ][O2 ]1
k1
Fast
Rate = k2[O3][O]
Rate k2[O3 ][O]

k1
Rate k2[O3 ] [O3 ][O2 ]-1
k1
k2 k1
Rate
[O3 ]2 [O 2 ]-1
k1
94
Catalysts
catalysts are substances that affect the rate of a reaction
without being consumed

catalysts work by providing an alternative mechanism
for the reaction
with a lower activation energy
catalysts are consumed in an early mechanism step,

then made in a later step
mechanism without catalyst
mechanism with catalyst
O3(g) + O(g) 2 O2(g)
Cl(g) + O3(g) O2(g) + ClO(g)
Fast
ClO(g) + O(g) O2(g) + Cl(g)
Slow
V. Slow
95
Ozone Depletion over the Antarctic
96
Energy Profile of Catalyzed Reaction
polar stratospheric clouds

contain ice crystals that
catalyze reactions that
release Cl from
atmospheric chemicals
97
Catalysts
homogeneous catalysts are in the same phase as
the reactant particles
Cl(g) in the destruction of O3(g)
heterogeneous catalysts are in a different phase

than the reactant particles
solid catalytic converter in a cars exhaust system
98
Types of Catalysts
99
Catalytic Hydrogenation
H2C=CH2 + H2 CH3CH3
100
Enzymes
because many of the molecules are large and
complex, most biological reactions require a
catalyst to proceed at a reasonable rate
protein molecules that catalyze biological
reactions are called enzymes
enzymes work by adsorbing the substrate
reactant onto an active site that orients it for
reaction
101
Enzyme-Substrate Binding
Lock and Key Mechanism
102
Enzymatic Hydrolysis of Sucrose
103

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Chemistry: A Molecular Approach, 1st Ed.

Defining Reaction Rate

for reactants, a negative sign is placed in front of the

Tro, Chemistry: A Molecular Approach

Reaction Rate Changes Over Time

at some time the reaction stops, either because the

Tro, Chemistry: A Molecular Approach

Tro, Chemistry: A Molecular Approach

Reaction Rate and Stoichiometry

in order to be consistent, the change in the concentration

Tro, Chemistry: A Molecular Approach

the larger the time interval, the more the average

Tro, Chemistry: A Molecular Approach

Hypothetical Reaction Red Blue

Avg. Rate, M/s Avg. Rate, M/s

average rate in a given

Tro, Chemistry: A Molecular Approach

determined by taking the slope of a line tangent

H2 (g) + I2 (g) 2 HI (g)

Using [H2], the

Using [HI], the

Ex 13.1 - For the reaction given, the [I] changes from

Rate 4.40 10-3

Measuring Reaction Rate

able to measure the concentration of at least one

Tro, Chemistry: A Molecular Approach

rotation of plane-polarized light caused by one of the

total pressure the total pressure of a gas mixture is

Tro, Chemistry: A Molecular Approach

drawing off periodic aliquots from the mixture and

Tro, Chemistry: A Molecular Approach

Factors Affecting Reaction Rate

small molecules tend to react faster than large molecules;

certain types of chemicals are more reactive than others

ions react faster than molecules

Factors Affecting Reaction Rate

there is a mathematical relationship between

Factors Affecting Reaction Rate

homogeneous = present in same phase

Factors Affecting Reaction Rate

concentration of solutions depends on the

The Rate Law

the rate of a reaction is directly proportional to the

for the reaction aA + bB products the rate law

n and m are called the orders for each reactant

Rate k[A] [B]

Sample Rate Laws

The reaction is autocatalytic, because a product affects the rate.

Reactant Concentration vs. Time

Tro, Chemistry: A Molecular Approach

the half-life, t1/2, of a

reaction is the length

Zero Order Reactions

constant rate reactions

Tro, Chemistry: A Molecular Approach

First Order Reactions

Half-Life of a First-Order Reaction

Tro, Chemistry: A Molecular Approach

Rate Data for

Tro, Chemistry: A Molecular Approach

C4H9Cl + H2O C4H9OH + 2 HCl

Tro, Chemistry: A Molecular Approach

C4H9Cl + H2O C4H9OH + 2 HCl