Chapter 14

Chemical
Kinetics
 14.1 Reaction Rates
• Kinetics: the study of how fast
reactions take place
• Some reactions are fast
(photosynthesis)
• Some reactions are slow (conversion of
diamond to graphite)

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 Importance of Studying
Reaction Rates
• Speed up desirable reactions
• Minimize damage by undesirable
reactions
• Useful in drug design, pollution control,
and food processing

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 Rate of Reaction
• Expressed as either:
– Rate of disappearance of reactants
(decrease or negative)
OR
– Rate of appearance of products (increase
or positive)

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Average Reaction Rate

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 Average Reaction Rate
• Equation A B

• rate =   [A] or  [B]

t t

• Why the negative on [A]?

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 Average Reaction Rate
Br2(aq) + HCOOH(aq)2Br(aq) + 2H+(aq) + CO2(g)
Note: Br2 disappears over time

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 Average Reaction Rate
Br2(aq) + HCOOH(aq) 2Br(aq) + 2H+(aq) + CO2(g)

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 Calculate Average Rate
• Avg. rate = [Br2 ]  [Br2 ]
final initial
t  t
final initial

• Avg. rate = 0.0101 M  0.0120 M

50 s  0 s
= 3.80 M /s

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 Average Rate
• Average rate depends on time interval
• Plot of [Br2] vs time = curve
• Plot of Rate vs [Br2] = straight line

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 Instantaneous Rate
• Instantaneous: rate at a specific
instance in time (slope of a tangent to
the curve)

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 Rate Constant
• Using data from Table 14.1 - what can
you conclude?

Time (s) [Br2] Rate (M/s)

50 0.0101 3.52 x 105
250 0.00596 1.75 x 105

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 Rate Constant
Answer:
• When the [Br2] is halved; the rate is
halved
• Rate is directly proportional to [Br2]
• rate = k [Br2]
• k = proportionality constant and is
constant as long as temp remains
constant
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 Rate Constant
• Calculate the value of the rate constant for
any set of data and get basically the same
answer!
• k = rate / [Br2]

3.52 x 105 M/s

k   3.5 x 103 /s
0.0101 M

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 Stoichiometry and Reaction
Rate
• When stoichiometric ratios are not 1:1
rate of reaction is expressed as follows
General equation:
aA + bB  cC + dD

1  [A] 1  [B] 1  [C] 1  [D]


rate = a t    
b t c t d t

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 Stoichiometry and Reaction
Rate
• Write the rate expression for the
following reaction
2NO(g) + O2(g)  2NO2(g)

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 Stoichiometry and Reaction
Rate
4PH3(g)  P4(g) + 6H2(g)
If molecular hydrogen is formed at a rate of
0.168 M/s, at what rate is P4 being
produced?

1  [PH3] 1  [P4] 1  [H2]

  
4 t 1 t 6 t

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Stoichiometry and Reaction
Rate
4PH3(g)  P4(g) + 6H2(g)

1  [H2] 1
 (0.168 M /s)  0.028 M /s
6 t 6

1  [P4]
 0.028 M /s
1 t

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14.2 Dependence of Reaction
Rate on Reactant
Concentration
• Rate law expression
For the general equation:
aA + bB  cC + dD
rate law = k[A]x[B]y
k = proportionality constant
x and y = the order of the reaction with
respect to each reactant
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 Order
• Exponents represent order
• Only determined via experimental data
– 1st order - rate directly proportional to
concentration
– 2nd order - exponential relationship
– 0 order - no relationship
• Sum of exponents (order) indicates
overall reaction order

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Experimental Determination of
Rate Law
• Method of initial rates - examine
instantaneous rate data at beginning of
reaction

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 rate = k[F2]x [ClO2]y
Find order (exponents) by comparing data
Exp. 1 and 3: [ClO2] is held constant

[F2] [rate] 3 M /s
3  0.20 M 3  2.4 10
2 2
[F2] 0.10 M [rate] 1.2  103 M /s
1
1
1st order with respect to [F2] (rate and M directly related)
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 rate = k[F2]1[ClO2]y
Find order (exponents) by comparing data
Exp. 1 and 2: [F2] is held constant

[ClO2] [rate] 3 M /s
2  0.040 M  4 2  4.8 10
4
[ClO2] 0.010 M [rate] 1.2  103 M /s
1 1
1st order with respect to [ClO2] (rate and M directly related)
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 rate = k[F2]1[ClO2]1 overall order = 2
Find k (use any set of data)

[rate] 2.1  104 M /s

k   9.3 M 2  s1
[A] [B]2 (0.10 M ) (0.015 M ) 2

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 Determining Rate Law
Exp. [A] (M) [B] (M) Initial
Rate
(M/s)
1 0.10 0.015 2.1 x 104

2 0.20 0.015 4.2 x 104

3 0.10 0.030 8.4 x 102

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 What is Different?
• In experiment 1 and 2; [B] is constant;
[A] doubles and rate doubles - the
reaction is 1st order with respect to [A]
• In experiment 1 and 3; [A] is constant;
[B] doubles but the rate quadruples!
This means that the reaction is 2nd
order with respect to [B]

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 Calculate the Rate Constant
• Rate = k[A] [B]2
• The rxn is 1st order w/ respect to [A]
• The rxn is 2nd order w/ respect to [B]
• The rxn is 3rd order overall (1 + 2)

[rate] 2.1  104 M /s

k   9.3 M 2  s1
[A] [B]2 (0.10 M) (0.015 M )2

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14.3 Dependence of Reactant
Concentration on Time
• First-Order reactions may be
expressed in several ways
• Example: A  products
rate = k[A]

 [ A]
rate  
t

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 Integrated Rate Law
(First order)
When the two expressions are set equal to
each other,we get an expression that can be
rearranged in the form of a straight line.

ln  A   kt  ln  A 0

y = mx + b

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 Graphical Methods
• Given concentration and time data,
graphing can determine order

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 Integrated Rate Law
(First order)
• For a 1st order reaction, a plot of ln [A]
vs time yields a straight line
• The slope = k (the rate constant)

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 Try Graphing
Time (s) P (mmHg)
0 284
100 220
150 193
200 170
250 150
300 132
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 Graphing
• Plot ln [Pressure] on y-axis and time on
x-axis
• If the plot is a straight line, then the
integrated rate law equation can be
used to find the rate constant, k, or the
slope of the line can be calculated for
the rate constant.

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 Integrated Rate Law
• The rate constant for the reaction
2A  B is 7.5 x 103 s1 at 110C. The
reaction is 1st order in A. How long (in
seconds) will it take for [A] to decrease
from 1.25 M to 0.71 M?

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• Another form of the integrated rate law
[A]
ln t   kt
[A]
0

  7.5  103 s1 (t)

(0.71 M)
ln
(1.25 M)

t  75 s

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 Your Turn!
• Consider the same first order reaction
2A  B, for which k = 7.5 x 103 s1 at
110C. With a starting concentration of
[A] = 2.25 M, what will [A] be after 2.0
minutes?

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 Half-Life (1st order)
• Half-life: the time
that it takes for the
reactant
concentration to
drop to half of its
original value.

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 Calculating First Order
Half-life
• Half-life is the time that it takes for the
reactant concentration to drop to half of
its original value.
• The expression for half-life is simplified
as
0.693
t1/ 2 =
k

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 Half-Life
• The decomposition of ethane (C2H6) to
methyl radicals (CH3) is a first order
reaction with a rate constant of
5.36 x 104 s1 at 700 C.
C2H6  2CH3

Calculate the half-life in minutes.

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 Half-Life
0.693
t1/2  4 1
 1293 s
5.36  10 s

1 min
1293 s   21.5 min
60 s

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 Dependence of Reactant
Concentration on Time
Second-order reactions may be expressed in
several ways
• Example: A  product
rate = k[A]2
 [A]
rate  
t

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 Integrated Rate Law for
Second Order Reactions
Again, the relationships can be combined to
yield the following relationship in the form of a
straight line

1 1
 kt 
 A  A 0

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 Integrated Rate Law for
Second Order Reactions
• For a 2nd order reaction, a plot of 1/[A]
vs time yields a straight line
• The slope = k (the rate constant)

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 Calculating Second-Order
Half-life
The expression for half-life is simplified as
1
t1/2 
k [A]0
Note: half-life for 2nd order is inversely
proportional to the initial reaction
concentration

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 Calculating Second Order
Half-life
I(g) + I(g)  I2(g)
The reaction is second order and has a rate
constant of 7.0 x 109 M1 s1 at 23C.
a) If the initial [I] is 0.086 M, calculate the
concentration after 2.0 min.
b) Calculate the half-life of the reaction
when the initial [I] is 0.60 M and when the
[I] is 0.42 M.
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a) Use integrated rate equation for 2nd
order

1 1 1 1
 (7.0  10 M s ) 120s 
9

 A  0.086 M 
1
 8.4  10 M
11

1 12
[A]  1
 1.2  10 M
8.4  10 M
11

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b) Use the half-life formula for 2nd order
(note: half-life does not remain constant for a
2nd-order reaction!)

1 10
t1/2  1 1
 2.4  10 s
(7.0  10 M
9
s ) (0.60 M )
1 10
t1/2  1 1
 3.4  10 s
(7.0  10 M
9
s ) (0.42 M )

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 Zero Order
Zero Order reactions may exist but are
relatively rare
• Example: A  product
rate = k[A]0 = k
• Thus, a plot of [A] vs time yields a
straight line.

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Summary of Orders

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14.4 Dependence of Reaction
Rate on Temperature
• Most reactions occur faster at a higher
temperature.
• How does temperature alter rate?

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 Collision Theory
• Particles must collide in order to react
• The greater frequency of collisions, the
higher the reaction rate
• Only two particles may react at one time
• Many factors must be met:
– Orientation
– Energy needed to break bonds (activation
energy)
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Collision Theory

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 Collision Theory
• Though it seems simple, not all
collisions are effective collisions
• Effective collisions: a collision that
does result in a reaction
• An activated complex (transition state)
forms in an effective collision

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Activation Energy

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 The Arrhenius Equation
• The dependence of the rate constant of a
reaction on temperature can be expressed

k  Ae Ea / RT
Ea = activation energy
R = universal gas constant
A = frequency factor T = Kelvin temp

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 Arrhenius Equation

Ea 1
ln  k       ln  A 
R t 
In the form of a straight line…what plot will give a straight line?

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 Arrhenius Equation
• A plot of ln k vs 1/T will give a straight
line
• The slope of line will equal Ea/R
• The activation energy may be found by
multiplying the slope by “R”

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 Graphing with Arrhenius
• Rate constants for the reaction
CO(g) + NO2(g)  CO2(g) + NO(g)
Were measured at four different
temperatures. Plot the data to
determine activation energy in kJ/mol.

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 Graphing
k (M1 s1) T (Kelvin)

0.0521 288

0.101 298

0.184 308

0.332 318

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 Graphing
Steps:
• Make a column of ln k data
• Make a column of inverse temp (1/T)
• Plot ln k vs 1/T
• Calculate the slope
• Multiply slope by R

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 Arrhenius Another Way!
• Another useful arrangement of the
Arrhenius equation enables calculation
of: 1) Ea (with k at two different temps)
2) the rate constant at a different
temperature (with Ea, k and temps)
k1 Ea  1 1 
ln  
k2 R  T 2 T 1 


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 Arrhenius Another Way!
• Use the data to calculate activation
energy of the reaction mathematically
T (Kelvin) k (s1)
400 2.9 x 103
450 6.1 x 102
500 7.0 x 101

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 Arrhenius
 k1 
 ln 
Ea  R  k2
1 1 
  
 T2 T1 
 2.9  103 
 ln 
 6.1  102 
Ea  8.3145J/Kmol  
1 1
  
 450 400 
 
 91 kJ/mol

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 14.5 Reaction Mechanisms
• Most reactions occur in a series of steps
• The balanced equation does not tell us
how the reaction occurs!
• There are often a series of steps which
add together to give the overall reaction
• The series of steps is the reaction
mechanism

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 Reaction Mechanisms
• Most chemical reactions occur in a
series of steps
• Energy of activation must be overcome
to form intermediates

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 Reaction Mechanism
Consider:
2NO(g) + O2(g)  2NO2(g)
The reaction cannot occur in a single
step.
One proposed mechanism:
Step 1: NO + NO  N2O2
Step 2: N2O2 + O2  2NO2
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 Reaction Mechanism
N2O2 is an intermediate in the reaction
mechanism
Intermediate: a substance that is
produced in an early step and
consumed in a later step
Elementary reaction: one that occurs in
a single collision of the reactant
molecules
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 Reaction Mechanism
• Molecularity: the number of reactant
molecules involved in the collision
• Unimolecular: one reactant molecule
• Bimolecular: two reactant molecules
• Termolecular: three reactant molecules
(fairly rare)

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 Rate Determining Step
• If the elementary reactions are known,
the order can be written from the
stoichiometric coefficients of the rate-
determining step
• Rate-determining step: the slowest
step in the mechanism

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 Rate-Determining Step
• Steps of a mechanism must satisfy two
requirements
– Sum of elementary steps must equal the
overall balanced equation
– The rate law must have same rate law as
determined from experimental data

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• The decomposition of hydrogen
peroxide (2H2O2  2H2O + O2 )
may occur in the following two steps
Step 1: H2O2 + I ¾ ¾® H2O + IO
k 1

Step 2: H2O2 + IO ¾ k2¾® H O + O + I

2 2

If step 1 is the rate-determining step, then

the rate law is
rate = k1[H2O2] [I]

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• I does not appear in the overall
balanced equation
• I serves as a catalyst in the reaction -
it is present at the start of the reaction
and is present at the end
• IO is an intermediate

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Potential Energy Diagram

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 Reaction Mechanism
• Given overall equation:
H2(g) + I2(g)  2HI(g)
Step 1: I2 ¬¾ ¾k¾¾® 2I (fast)
1 k

-1

Step 2: H2 + 2I ¾ k2¾® 2HI (slow)

rate = k2[H2] [I]2
This rate expression does not meet the
requirement..I is an intermediate and
should not appear in the rate expression

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• Consider the first equilibrium step: the
forward rate is equal to the reverse rate
k1[I2] = k-1 [I]2 k1/k-1 [I2] = [I]2

If we substitute for [I]2 , the rate law becomes

rate = k[H2] [I2]

This now matches the overall balanced
equation!

(When step 2 is rate-determining this

substitution is always possible)
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 14.6 Catalysis
• Catalyst - a substance that increases
the rate of a chemical reaction without
being used up itself
• Provides a set of elementary steps with
more favorable kinetics than those that
exist in its absence
• Many times a catalyst lowers the
activation energy
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Reaction Pathway with
Catalyst

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 Types of Catalysts
• Heterogeneous catalysts - reactants
and catalyst are in different phases
• Homogeneous catalysts - reactants
and catalysts are dispersed in single
phase
• Enzyme catalysts - biological catalysts

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 Heterogeneous Catalysts
• Most important in industrial chemistry
• Used in catalytic converters in
automobiles
– Efficient catalytic converter serves two
purposes; oxidizes CO and unburned
hydrocarbons into CO2 and H2O; converts
NO and NO2 into N2 and O2

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Catalytic Converter

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 Homogeneous Catalysts
• Usually dispersed in liquid phase
• Acid and base catalyses are the most
important types of homogeneous
catalysis in liquid solution
• Advantages of homogeneous catalysts
– Reactions performed at room conditions
– Less expensive
– Can be designed to function selectively

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 Biological Catalysts
• Enzymes: large protein molecule that
contains one or more active sites where
interactions with substrates occur
• Enzymes are highly specific (lock and
key)

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Reaction Pathway without and
with Enzyme-Substrate

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Enzyme-Substrate Complex

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Biological Molecules
(binding of glucose to
hexokinase)

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 Key Points
• Rate of reaction can be determined in
several ways
– Instantaneous rate
– Average rate
– Graphing using integrated rate laws
– Mechanisms

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 Key Points
• Write rate law expressions
• Calculate rate constant with proper units
• Distinguish orders: 1st, 2nd, 0 order
• Calculate half-life
• Collision theory and relationship to
Arrhenius equation

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 Key Points
• Calculate activation energy graphically
and mathematically
• Reaction mechanisms
– Elementary reactions
– Molecularity
– Rate law from slow step
– Intermediates and catalysts

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 Key Points
• Catalysis
– Heterogeneous
– Homogeneous
– Enzymes

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