13 Lecture

Chemistry: A Molecular Approach, 2nd Ed.
Nivaldo Tro
Chapter 13
Chemical
Kinetics
Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
Copyright ! 2011 Pearson Education, Inc.
Ectotherms
Lizards, and other cold-blooded creatures, are
ectotherms animals whose body temperature
matches their environments temperature
When a lizards body temperature drops, the
chemical reactions that occur in its body slow
down
as do all chemical reactions when cooled
This causes the lizard to become lethargic and to
slow down
Chemical kinetics is the study of the factors that
affect the rates of chemical reactions
Such as temperature
Tro: Chemistry: A Molecular Approach, 2/e 2 Copyright ! 2011 Pearson Education, Inc.
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 uses reactants
The ability to control the speed of a chemical
reaction is important
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
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
at t = 0 at t = 0
[A] = 8 [X] = 8
[B] = 8 [Y] = 8
[C] = 0 [Z] = 0
at t = 16 at t = 16
[A] = 4 [X] = 7
[B] = 4 [Y] = 7
[C] = 4 [Z] = 1
[C[]A ] ([C](2[A]2[C]1[)A ]1) [Z[X] ] ([Z(][2X]2[Z ][1X) ]1)

Rate = == Rate ==
Rate ==
tt (t 2 (t 2t1) t1) t t (t 2 (t 2t1)t1)
(4(4 0 )8 ) ((
1708) )
Rate = = =0.025.25 Rate ==
Rate ==00.0625
.0625
(1(616 0)0) (1(16600))
at t = 16 at t = 16
[A] = 4 [X] = 7
[B] = 4 [Y] = 7
[C] = 4 [Z] = 1
at t = 32 at t = 32
[A] = 2 [X] = 6
[B] = 2 [Y] = 6
[C] = 6 [Z] = 2
[C[]A ] ([C]2([A[]C 1)[A ]1)

] Z[]X]([Z]2([X[]Z2 ]
[ )[X]1)
Rate = = = 2 Rate == = =
Rate 1
tt (t 2 (t12) t1) tt (t 2 (t12) t1)
(6(2 4)4 )
=
(2(6 1)7)= 0.0625
Rate = = 0=.125
0.125 Rate =
Rate = 0.0625
(32(32 161)6 ) (32(32
161)6 )
at t = 32 at t = 32
[A] = 2 [X] = 6
[B] = 2 [Y] = 6
[C] = 6 [Z] = 2
at t = 48 at t = 48
[A] = 0 [X] = 5
[B] = 0 [Y] = 5
[C] = 8 [Z] = 3
[C[]A ] ([C](2[A][2C]1[)A ]1) Z[]X] ([Z]2([

[ X][2Z ] [
)X]1)
Rate = == Rate ==
Rate == 1
tt (t 2 (tt21) t1) tt (t 2 (tt21) t1)
(8(0 6 )2) ( 3(
52 )6 )
Rate = = =0.0125
.125 Rate ==
Rate =0=.00625
.0625
(48 323)2)
(48 (48(48 32
3)2)
Hypothetical Reaction
Red ! Blue
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
over time
Red ! Blue
Red ! Blue
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
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
To be consistent, the change in the concentration of
each substance is multiplied by 1/coefficient
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
Hypothetical Reaction Red ! Blue
H2 I2
HI
StoichiometryThe
tellsaverage
us that rate
for is
every 1 mole/L
theofchange
H2 used,
in the
2 moles/L of concentration
HI are made. in a
Assuming a 1given time period

L container, at
10 s, we used 0.181 moles of
Inthe
H2. Therefore theamount
first 10 s,
of the
D[H2] ismoles)
HI made is 2(0.181 0.181=M,
0.362 moles.so the rate is
At 60 s, we used 0.699 moles

of H2. Therefore the amount
of HI made is 2(0.699 moles)
= 1.398 moles.
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 s is 0.0108 M/s
the average rate for the
the average rate for the

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
H2 (g) + I2 (g) ! 2 HI (g)
Using [H2], the
instantaneous
rate at 50 s is
Using [HI], the

instantaneous
rate at 50 s is
Example 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 D[H+].
H2O2 (aq) + 3 I!(aq) + 2 H+(aq) ! I3!(aq) + 2 H2O(l)
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
Practice If 2.4 x 102 g of NOBr (MM 109.91 g)
decomposes in a 2.0 x 102 mL flask in 5.0 minutes,
find the average rate of Br2 production in M/s
2 NOBr(g) ! 2 NO(g) + Br2(l)
Practice If 2.4 x 102 g of NOBr decomposes in a 2.0 x 102 mL
flask in 5.0 minutes, find the average rate of Br2 production
2 NOBr(g) ! 2 NO(g) + Br2(l)
Given: 240.0
5.45 MgBr
NOBr,
2, 3.00.2000
200.0
x 102 mL,
sL, 5.0
5.0min.
min.
Find: D[Br2]/Dt, M/s
Conceptual
D mole Br2 DM
Ds }
Plan: Rate
D min
Relationships: 2 mol NOBr:1 mol Br2, 1 mol = 109.91g, 1 mL=0.001 L
Solve:
Measuring Reaction Rate
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
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
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 complementary color
Total pressure the total pressure of a gas
mixture is stoichiometrically related to partial
pressures of the gases in the reaction
Sampling the Reaction Mixture at
Specific Times
At specific times during the reaction, drawing off
aliquots, (samples from the reaction mixture), and
doing quantitative analysis
titration for one of the components
gravimetric analysis
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
Methods for Determining Concentrations
in a Mixture
in a Mixture
in a Mixture
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. potassium metal is more reactive than sodium
ions react faster than molecules
no bonds need to be broken
Temperature
Increasing temperature increases reaction rate
chemists rule of thumbfor each 10 C 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
Catalysts
Catalysts are substances that 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
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
Concentrations of solutions depend on the
solute-to-solution ratio (molarity)
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 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
Sample Rate Laws
The bottom reaction is autocatalytic because a product affects the rate.

Hg2+ is a negative catalyst; increasing its concentration slows the reaction.
Example: The rate equation for the reaction of NO with ozone is
Rate = k[NO][O3]. If the rate is 6.60 x 105 M/sec when [NO] =
1.00 x 106 M and [O3] = 3.00 x 106 M, calculate the rate constant
Given: [NO] = 1.00 x 106 M, [O3] = 3.00 x 106 M,
Rate = 6.60 x 106 M/s
Find: k, M1!s1
Conceptual Rate, [NO], [O3] k
Plan:
Relationships: Rate = k[NO][O3]
Solve:
Practice The rate law for the decomposition of
acetaldehyde is Rate = k[acetaldehyde]2.
What is the rate of the reaction when the
[acetaldehyde] = 1.75 x 103 M and the rate constant
is 6.73 x 106 M1s1?
Practice What is the rate of the reaction when the
[acetaldehyde] = 1.75 x 103 M and the rate constant is
6.73 x 106 M1s1?
Given: [acetaldehyde] = 1.75 x 103 M, k= 6.73 x 106 M1s1
Find: Rate, M/s
Conceptual k, [acetaldehyde] Rate
Plan:
Relationships: Rate = k[acetaldehyde]2
Solve:
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
then doubling the

if for the reaction initial concentration
A Products of A quadruples
doubles
does notthe the
change
initial reaction
the initial
rate
reaction rate
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 NO2(g) + CO(g) ! NO(g) + CO2(g)
given the data below
Comparing Expt #1 and Expt #2,

the [NO2] changes but the [CO]
does not
n = 2, m = 0
Substitute the Expt. Initial Initial Initial Rate
concentrations Number [NO2], (M) [CO], (M) (M/s)
and rate for
1. 0.10 0.10 0.0021
any experiment
into the rate 2. 0.20 0.10 0.0082
law and solve 3. 0.20 0.20 0.0083
for k 4. 0.40 0.10 0.033
Rate = k[NO2 ]2
for expt 1
( )
2
0.0021 M
s = k 0.10 M
0.0021 Ms 1 1
k= = 0.21 M s
0.01 M2
Practice Determine the rate law and rate constant for
the reaction NH4+ + NO2 N2 + 2 H2O
Practice Determine the rate law and rate constant for
the reaction NH4+ + NO2 N2 + 2 H2O
Rate = k[NH4+]n[NO2!]m
Finding the Rate Law:
Graphical Methods
The rate law must be determined experimentally
A graph of concentration of reactant vs. time can
be used to determine the effect of concentration
on the rate of a reaction
This involves using calculus to determine the
area under a curve which is beyond the scope
of this course
Later we will examine the results of this analysis
so we can use graphs to determine rate laws for
several simple cases
Reactant Concentration vs. Time
A ! Products
insert figure 13.6
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
Half-Life
The half-life, t1/2, of a
reaction is the length
of 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
Zero Order Reactions
Rate = k[A]0 = k
constant rate reactions
[A] = kt + [A]initial
Graph of [A] vs. time is straight line with
slope = k and yintercept = [A]initial
t = [Ainitial]/2k
When Rate = M/sec, k = M/sec
[A]initial
[A]
time
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 = s1
ln[A]initial
ln[A]
time
The Half-Life of a First-Order Reaction
Is Constant
Rate Data for
C4H9Cl + H2O C4H9OH + HCl
C4H9Cl + H2O ! C4H9OH + 2 HCl
slope =
2.01 x 103
k=
2.01 x 103 s-1
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[A0])
When Rate = M/sec, k = M1!s1
1/[A]
1/[A]initial
time
Rate Data For
2 NO2 2 NO + O2
Rate Data For
2 NO2 2 NO + O2
Rate Data Graphs for
2 NO2 2 NO + O2
2 NO2 2 NO + O2
ln(P NO2) vs. Time
4.8
4.6
4.4
4.2
3.8
3.6
3.4
3.2
2.8
2.6
2.4
0 50 100 150 200 250
Time (hr)
2 NO2 2 NO + O2
Example 13.4: The reaction SO2Cl2(g) ! SO2(g) + Cl2(g) is first
order with a rate constant of 2.90 x 104 s1 at a given set of
conditions. Find the [SO2Cl2] at 865 s when [SO2Cl2]initial = 0.0225
M
Given: [SO2Cl2]init = 0.0225 M, t = 865, k = 2.90 x 10-4 s1
Find: [SO2Cl2]
Conceptual
Plan: [SO2Cl2]init, t, k [SO2Cl2]
Relationships:
Solution:
Check: the new concentration is less than the original,

as expected
Practice The reaction Q ! 2 R is second order in Q.
If the initial [Q] = 0.010 M and after 5.0 x 102 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 102 seconds
the [Q] = 0.0010 M, find the rate constant
Given: [Q]init = 0.010 M, t = 5.0 x 102 s, [Q]t = 0.0010 M
Find: k
Conceptual
Plan: [Q]init, t, [Q]t k
Relationships:
Solution:
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
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
Practice Complete the table and
determine the rate equation for the
reaction A 2 Product
Because the graph 1/[A] vs. time is
linear, the reaction is second order,
Rate ! k[A]2
k ! slope of the line ! 0.10 M1!
s 1
Relationship Between
Order and Half-Life
For a zero order reaction, the lower the initial
concentration of the reactants, the shorter the
half-life
t1/2 = [A]init/2k
For a first order reaction, the half-life is
independent of the concentration
t1/2 = 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
t1/2 = 1/(k[A]init)
Example 13.6: Molecular iodine dissociates at 625 K with a first-
order rate constant of 0.271 s1. What is the half-life of this
reaction?
Given: k = 0.271 s1
Find: t1/2
Conceptual
Plan: k t1/2
Relationships:
Solution:
Check: the new concentration is less than the original,

as expected
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 M1s1 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 M1s1 find the length of time for [Q] = [Q]init
Given: [Q]init = 0.010 M, k = 1.8 M1!s1
Find: t1/2, s
Conceptual
Plan: [Q]init, k t1/2
Relationships:
Solution:
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:
where T is the temperature in kelvins

R is the gas constant in energy units, 8.314 J/(molK)
A is called the frequency factor, the rate the reactant
energy approaches the activation energy
Ea is the activation energy, the extra energy needed
to start the molecules reacting
Activation Energy and the
Activated Complex
There is an energy barrier to almost all
reactions
The activation energy is the 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 of its partial
bonds
Isomerization of Methyl Isonitrile
methyl isonitrile rearranges to acetonitrile
for the reaction to occur, the

H3CN bond must break, and a
new H3CC bond form
Energy Profile for the
Isomerization of Methyl Isonitrile
As the reaction
begins, the
the activated
frequency
activation is CN
energy
the
the bond
number
is
complex weakens
difference
ofismolecules
a in
enough
that begin
energy
chemical between
speciesfor the
to form the
the
with C!N
activated
reactants
partial group
complex
and the to
bonds in
a givenstart
activated to rotate
period
complex of time
The Arrhenius Equation:
The Exponential Factor
The exponential factor in the Arrhenius equation is a
number between 0 and 1
Tt 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
Arrhenius Plots
The Arrhenius Equation can be algebraically
solved to give the following form:
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)
eyintercept = A (unit is the same as k)
Example 13.7: Determine the activation energy and
frequency factor for the reaction O3(g) ! O2(g) + O(g)
given the following data:
slope, m = 1.12 x 104 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 NO2(g) + CO(g) ! CO2(g) + NO(g)
has a rate constant of 2.57 M1s1 at 701 K and 567 M1s1
at 895 K. Find the activation energy in kJ/mol
Given: T1 = 701 K, k1 = 2.57 M1s1, T2 = 895 K, k2 = 567 M1s1
Find: Ea, kJ/mol
Conceptual
Plan: T1, k1, T2, k2 Ea
Relationships:
Solution:
Check: most activation energies are tens to hundreds

of kJ/mol so the answer is reasonable
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.
Hint:
make T1 = 300 K, T2 = 310 K
and k2 = 2k1
Practice Find the activation energy in kJ/mol for
increasing the temperature 10 C doubling the rate
Given: T1 = 300 K, T1 = 310 K, k2 = 2 k1

Find: Ea, kJ/mol
Conceptual
Plan: T1, k1, T2, k2 Ea
Relationships:
Solution:
Check: most activation energies are tens to hundreds

of kJ/mol so the answer is reasonable
Collision Theory of Kinetics
For most reactions, for a reaction to take place,
the reacting molecules must collide with each
other
on average about 109 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
Effective Collisions
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 the
activated complex can
form
Orientation Effect
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 the
activated complex
Collision Theory and the Frequency
Factor of the Arrhenius Equation
The Arrhenius Equation includes a term, A,
called the Frequency Factor
The Frequency Factor can be broken into two
terms that relate to the two factors that
determine whether a collision will be effective
Collision Frequency
The collision frequency is the number of

collisions that happen per second
The more collisions per second there are, the
more collisions can be effective and lead to
product formation
Orientation Factor
The orientation factor, p, is a statistical term
relating the frequency factor to the collision
frequency
For most reactions, p < 1
Generally, the more complex the reactant
molecules, the smaller the value of p
For reactions involving atoms colliding, p 1
because of the spherical nature of the atoms
Some reactions actually can have a p > 1
generally involve electron transfer
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 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
Molecular Interpretation of
Factors Affecting Rate Reactant Nature
Reactions generally occur faster in solution than in pure
substances
mixing gives more particle contact
particles separated, allowing more effective collisions per second
forming some solutions breaks bonds that need to be broken
Some materials undergo similar reactions at different rates
either because they have a (1) higher initial potential energy
and are therefore closer in energy to the activated complex, or
(2) because their reaction has a lower activation energy
CH4 + Cl2 ! CH3Cl + HCl is about 12x faster than CD4 + Cl2 !
CD3Cl + DCl because the CH bond is weaker and less stable than
the CD bond
CH4 + X2 ! CH3X + HX occurs about 100x faster with F2 than with Cl2
because the activation energy for F2 is 5 kJ/mol but for Cl2 is 17 kJ/mol
Factors Affecting Rate Temperature
Increasing the temperature raises the
average kinetic energy of the reactant
molecules
There is a minimum amount of kinetic energy
needed for the collision to be converted into
enough potential energy to form the activated
complex
Increasing the temperature increases the
number of molecules with sufficient kinetic
energy to overcome the activation energy
Factors Affecting Rate Concentration
Reaction rate generally increases as the
concentration or partial pressure of reactant
molecules increases
except for zero order reactions
More molecules leads to more molecules with
sufficient kinetic energy for effective collision
distribution the same, just bigger curve
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:
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 reactions 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
Elements of a Mechanism
Intermediates
H2(g) + 2 ICl(g) ! 2 HCl(g) + I2(g)
1) H2(g) + ICl(g) ! HCl(g) + HI(g)
2) HI(g) + ICl(g) ! HCl(g) + I2(g)
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
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 from the equation of the step
H2(g) + 2 ICl(g) ! 2 HCl(g) + I2(g)
1) H2(g) + ICl(g) ! HCl(g) + HI(g) Rate = k1[H2][ICl]
2) HI(g) + ICl(g) ! HCl(g) + I2(g) Rate = k2[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 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
Another Reaction Mechanism
NO2(g) + CO(g) ! NO(g) + CO2(g) Rateobs = k[NO2]2
1. NO2(g) + NO2(g) ! NO3(g) + NO(g) Rate = k1[NO2]2 Slow
2. NO3(g) + CO(g) ! NO2(g) + CO2(g) 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.
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
k1
1. 2 NO(g) ! N2O2(g) Fast
k1
2. H2(g) + N2O2(g) ! H2O(g) + N2O(g) Slow Rate = k2[H2][N2O2]
3. 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
Example 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
1.O3(g) ! O2(g) + O(g) Fast
k1
2.O3(g) + O(g) ! 2 O2(g) Slow Rate = k2[O3][O]
Practice Mechanism
Determine the overall reaction, the rate
determining step, the rate law, and identify all
intermediates of the following mechanism
1. A + B2 AB + B Slow
2. A + B AB Fast
Practice Mechanism
intermediates of the following mechanism
1. A + B2 AB + B Slow
2. A + B AB Fast
reaction 2 A + B2 2 AB
B is an intermediate
The first step is the rate determining step
Rate = k[A][B2], same as RDS
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) V. Slow Cl(g) + O3(g) ! O2(g) + ClO(g) Fast
ClO(g) + O(g) ! O2(g) + Cl(g) Slow
Ozone Depletion over the Antarctic
Factors Affecting Rate Catalysts
Catalysts generally speed a reaction
They give the reactant molecules a different
path to follow with a lower activation energy
heterogeneous catalysts hold one reactant
molecule in proper orientation for reaction to occur
when the collision takes place
and sometimes also help to start breaking bonds
homogeneous catalysts react with one of the
reactant molecules to form a more stable activated
complex with a lower activation energy
Energy Profile of a Catalyzed Reaction
polar stratospheric
clouds contain ice
crystals that catalyze
reactions that release
Cl from atmospheric
chemicals
Practice Mechanism
catalysts and intermediates of the following
mechanism
1. HQ2R2 + R Q2R2 + HR Fast
2. Q2R2 Q2R + R Slow
Practice Mechanism
catalysts and intermediates of the following
mechanism
1. HQ2R2 + R Q2R2 + HR Fast
2. Q2R2 Q2R + R Slow
reaction HQ2R2 Q2R + HR
R is a catalyst
Q2R2 is an intermediate
The second step is the rate determining step
Rate = k[Q2R2] = k[HQ2R2][R]
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
Types of Catalysts
Catalytic Hydrogenation
H2C=CH2 + H2 CH3CH3
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 the
substrate for reaction
1) Enzyme + Substrate ! EnzymeSubstrate Fast
2) EnzymeSubstrate Enzyme + Product Slow
EnzymeSubstrate Binding:
the Lock and Key Mechanism
Enzymatic Hydrolysis of Sucrose

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Chemistry: A Molecular Approach, 2nd Ed.

The rate of a chemical reaction is generally

[C[]A ] ([C](2[A]2[C]1[)A ]1) [Z[X] ] ([Z(][2X]2[Z ][1X) ]1)

[C[]A ] ([C]2([A[]C 1)[A ]1)

[C[]A ] ([C](2[A][2C]1[)A ]1) Z[]X] ([Z]2([

The number of molecules

The rate of the reaction can

As time goes on, the rate of a reaction

The average rate is the change in measured

Assuming a 1given time period

At 60 s, we used 0.699 moles

the average rate for the

The instantaneous rate is the change in

Using [HI], the

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

then doubling the

Comparing Expt #1 and Expt #2,

insert figure 13.6

For the reaction A ! Products, the rate law

Check: the new concentration is less than the original,

What will the rate be when the [A] = 0.010 M?

Check: the new concentration is less than the original,

where T is the temperature in kelvins

methyl isonitrile rearranges to acetonitrile

for the reaction to occur, the

this equation is in the form y = mx + b

Check: most activation energies are tens to hundreds

Given: T1 = 300 K, T1 = 310 K, k2 = 2 k1

Check: most activation energies are tens to hundreds

For a collision to lead

The collision frequency is the number of

The first step is slower than the

To validate (not prove) a mechanism, two

3. 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

mechanism without catalyst mechanism with catalyst

ClO(g) + O(g) ! O2(g) + Cl(g) Slow

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