Chapter 13

Contents and Concepts
Chapter 13
Rates of Reaction Rates
Reactions 1. Definition of Reaction Rate
2. Experimental Determination of Rate
3. Dependence of Rate on Concentration
4. Change of Concentration with Time
5. Temperature and Rate; Collision and
Transition-State Theories
6. Arrhenius Equation
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Learning Objectives
Reaction Rates
1. Definition of a Reaction Rate
Reaction Mechanisms
a. Define reaction rate.
7. Elementary Reactions
b. Explain instantaneous rate and average
8. The Rate Law and the Mechanism
rate of a reaction.
9. Catalysis
c. Explain how the different ways of
expressing reaction rates are related.
d. Calculate average reaction rate.
Copyright © Cengage Learning. All rights reserved. 13 | 3 Copyright © Cengage Learning. All rights reserved. 13 | 4
2. Experimental Determination of Rate 4. Change of Concentration with Time

a. Describe how reaction rates may be a. Learn the integrated rate laws for first-
experimentally determined. order, second-order, and zero-order
reactions.
b. Use an integrated rate law.
3. Dependence of Rate on Concentration
c. Define half-life of a reaction.
a. Define and provide examples of a rate law,
d. Learn the half-life equations for first-order,
rate constant, and reaction order. second-order, and zero-order reactions.
b. Determine the order of reaction from the e. Relate the half-life of a reaction to the rate
rate law. constant.
c. Determine the rate law from initial rates. f. Plot kinetic data to determine the order of a
reaction.
1
6. Arrhenius Equation
5. Temperature and Rate; Collision and a. Use the Arrhenius equation.
Transition-State Theories
Reaction Mechanisms
a. State the postulates of collision theory.
7. Elementary Reactions
b. Explain activation energy (Ea). a. Define elementary reaction, reaction mechanism,
c. Describe how temperature, activation and reaction intermediate. Determine the rate law
from initial rates.
energy, and molecular orientation influence
b. Write the overall chemical equation from a
reaction rates. mechanism.
d. State the transition-state theory. c. Define molecularity.
e. Define activated complex. d. Give examples of unimolecular, bimolecular, and
termolecular reactions.
f. Describe and interpret potential-energy e. Determine the molecularity of an elementary
curves for endothermic and exothermic reaction.
reactions. f. Write the rate equation for an elementary reaction.
8. The Rate Law and the Mechanism

a. Explain the rate-determining step of a mechanism.
b. Determine the rate law from a mechanism with an
initial slow step.
c. Determine the rate law from a mechanism with an Chemical kinetics is the study of reaction rates,
initial fast, equilibrium step. including how reaction rates change with varying
conditions and which molecular events occur
9. Catalysis
a. Describe how a catalyst influences the rate of a during the overall reaction.
reaction.
b. Indicate how a catalyst changes the potential-
energy curve of a reaction.
c. Define homogeneous catalysis and
heterogeneous catalysis.
d. Explain enzyme catalysis.
The following questions are explored in this Which conditions will affect the rate of a reaction?
chapter:
Four variables affect the rate of reaction:

• How is the rate of a reaction measured?
1. The concentrations of the reactants
• Which conditions will affect the rate of a
reaction? 2. The concentration of the catalyst
• How do you express the relationship of rate to 3. The temperature at which the reaction
the variables affecting the rate? occurs
• What happens on a molecular level during a 4. The surface area of the solid reactant or
chemical reaction? catalyst
2
Concentrations of Reactants
Often the rate of reaction increases when the
concentration of a reactant is increased. In some
reactions, however, the rate is unaffected by the
concentration of a particular reactant, as long as Concentration of Catalyst
it is present at some concentration. Hydrogen peroxide, H2O2, decomposes rapidly in
the presence of HBr, giving oxygen and water.
Some of the HBr is oxidized to give the orange
Br2, as can be seen above.
Each test tube contains

potassium permanganate,
KMnO4, and oxalic acid,
H2C2O4, at the same
concentrations. Permanganate
Temperature at Which Reaction Occurs ion oxidizes oxalic acid to
Usually reactions speed up when the temperature CO2 and H2O.
increases. It takes less time to boil an egg at sea Top: One test tube was placed
level than on a mountaintop, where water boils in a beaker of warm water
at a lower temperature. Reactions during (40°C); the other was kept at
cooking go faster at higher temperature. room temperature (20°C).
Bottom: After 10 minutes, the
test tube at 40°C showed a
noticeable reaction, whereas
Copyright © Cengage Learning. All rights reserved. 13 | 15 Copyright © Cengage Learning. All rights reserved.
the other did not. 13 | 16
Surface Area of a Solid Reactant Reaction rate is the increase in molar

or Catalyst concentration of product of a reaction per unit
If a reaction involves a solid with a time or the decrease in molar concentration of
gas or liquid, then the surface area reactant per unit time. The unit is usually mol/(L
of the solid affects the reaction • s) or M/s.
rate. Because the reaction occurs
at the surface of the solid, the rate
increases with increasing surface
area. For example, a wood fire
burns faster if the logs are
chopped into smaller pieces.
Similarly, the surface area of a
solid catalyst is important to the
rate of reaction.
Right: The photo shows a powder
igniting.
3
2N2O5(g) 4NO2(g) + O2(g)
We can express these changes in concentration

as follows. Square brackets mean molarity.
The rate of this reaction can be found by ∆[O 2 ]
measuring the concentration of O2 at various Rate of formation of O2 =
∆t
times. Alternatively, the concentration of NO2
could be measured. Both of these ∆[NO 2 ]
Rate of formation of NO2 =
concentrations increase with time. The rate ∆t
could also be determined by measuring the ∆[N 2 O 5 ]
concentration of N2O5, which would decrease Rate of decomposition of N2O5 = −
∆t
over time.
These equations give the average rate over the

time interval ∆t. As ∆t decreases and
approaches zero, the equations give the
instantaneous rate.
We can relate these expressions by taking into The next slides illustrate this relationship
account the reaction stoichiometry. graphically for the increase in concentration of
O2.
∆[O 2 ] 1 ∆[NO 2 ] 1 ∆[N 2 O 5 ]
= =−
∆t 4 ∆t 2 ∆t
The average rate

is the slope of
the hypotenuse
of the triangle As ∆t gets smaller and
formed. approaches zero, the
hypotenuse becomes
a tangent line at that
point.
The slope of the

tangent line equals
the rate at that point.
4
Peroxydisulfate ion oxidizes iodide ion Calculate the average rate of formation
? to triiodide ion, I3-. The reaction is

S2O82-(aq) + 3I-(aq)
2SO42-(aq) + I3-(aq)
? of O2 in the following reaction during
the time interval from 1200 s to 1800 s.
At 1200 s, [O2] = 0.0036 M; at 1800 s,
[O2] = 0.0048 M.
How is the rate of reaction that is
expressed as the rate of formation of I3- ∆[O 2 ] (0.0048 - 0.0036 ) M
=
related to the rate of reaction of I-? ∆t (1800 - 1200 ) s
0.0012 M
∆[I 3 - ] 1 ∆[I - ] =
=− 600 s
∆t 3 ∆t
= 2.0 × 10 -6 M/s
Rates are determined experimentally in a variety of

ways.
For example, samples can be taken and analyzed

from the reaction at several different intervals.
Continuously following the reaction is more

a. The slope at point A is greater than the slope at
convenient. This can be done by measuring
point B, so the instantaneous rate at point A is
pressure, as shown on the next slide, or by
greater than the instantaneous rate at point B.
measuring light absorbance when a color
b. No. If it were, the graph would be linear. change is part of the reaction.
The reaction rate usually depends on the

concentration of one or more reactant. This
relationship must be determined by experiment.
This information is captured in the rate law, an

equation that relates the rate of a reaction to the
concentration of a reactant (and catalyst) raised
to various powers. The proportionality constant,
k, is the rate constant.
5
The reaction order with respect to a specific
For the generic reaction reactant is the exponent of that species in the
aA + bB +cC dD + eE experimentally determined rate law.
the rate law is The overall order of a reaction is the sum of the
Rate = k[A]m[B]n[C]p orders of the reactant species from the
experimentally determined rate law.
For the reaction Hydrogen peroxide oxidizes iodide ion
? in acidic solution:
H2O2(aq) + 3I-(aq) + 2H+(aq)
I3-(aq) + 2H2O(l)
The rate law for the reaction is
the rate law is Rate = k[H2O2][I-]
Rate = k[NO2][F2]
In this case, the exponent for both NO2 and F2 is 1 (which

does not need to be written). a.What is the order of reaction with
respect to each reactant species?
We say the reaction is first order in each. The reaction is
second order overall. b.What is the overall order?
H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq) + 2H2O(l)
Given: Rate = k[H2O2][I-]
a. The reaction is first order in H2O2.

The reaction is first order in I-.
The reaction is zero order in H+.
a. The concentration of Q does not affect the
rate. The rate will depend only on [R].
b. The reaction is second order overall.
b. Rate = k[R]2
6
Returning to the decomposition of N2O5, we have
the following data:
The rate law for a reaction must be determined
experimentally. 2N2O5(g) 2N2(g) + 5O2(g)
Initial N2O5 Initial Rate of

We will study the initial rates method of Concentration Disappearance of N2O5
determining the rate law. This method measures
Experiment 1 1.0 × 10-2 M 4.8 × 10-6 M/s
the initial rate of reaction using various starting
concentrations, all measured at the same Experiment 2 2.0 × 10-2 M 9.6 × 10-6 M/s
temperature.
Note that when the concentration doubles from

experiment 1 to 2, the rate doubles.
Examining the effect of doubling the initial 2NO(g) + O2(g) 2NO2(g)

concentration gives us the order in that reactant.
When rate is multiplied by m is

? Obtain the rate law and the rate
constant using the following data for
the initial rates of disappearance of NO:
½ -1
Initial Rate of
1 0 Reaction of NO, M/s
Exp. [NO]0, M [O2]0, M
2 1 1 0.0125 0.0253 0.0281
4 2
2 0.0250 0.0253 0.112
In this case, when the concentration doubles, the 3 0.0125 0.0506 0.0561
rate doubles, so m = 1.
[O2] remains constant in experiments 1 and 2.

To find the order in NO, we will first identify two
experiments in which the concentration of O2 remains The generic rate law is rate = k[NO]m[O2]n. We will
constant. Then, we will divide the rate laws for those two put the result from experiment 2 in the numerator
experiments. Finally, we will solve the equation to find the because its rate is larger than that of experiment 1.
order in NO.
M
s = (0.0250 M ) (0.0253 M )
0.112 m n
To find the order in O2, we will repeat this procedure, this
time choosing experiments in which the concentration of M (0.0125 M ) (0.0253 M )n
m
NO remains constant.
0.0281
s
4 = 2m
Once the order in NO and the order in O2 are known, data
from any experiment can be substituted into the rate law. m=2
The rate law can then be solved for the rate constant k.
The reaction is second order in NO.
7
[NO] remains constant in experiments 1 and 3. It is also possible to find the order by examining
The generic rate law is rate = k[NO]m[O2]n. We will the data qualitatively.
put the result from experiment 3 in the numerator
because its rate is larger than that of experiment 1. Again choosing experiments 1 and 2, we note
that the concentration of NO is doubled and the
M
s = (0.0125 M ) (0.0506 M )
0.0.0561 m n rate is quadrupled. That means the reaction is
second order in NO.
0.0281
M (0.0125 M ) (0.0253 M )n
m
s
Choosing experiments 1 and 3, we note that the
2 = 2n concentration of O2 is doubled and the rate is
n =1 doubled. That means the reaction is first order in
The reaction is first order in O 2 . O 2.
The rate law is rate = k[NO]2[O2]. Iron(II) is oxidized to iron(III) by chlorine

Solving for k, we obtain
k=
rate
[NO] [O 2 ]
2
? in an acidic solution:
2Fe2+(aq) + Cl2(aq)
2Fe3+ (aq) + 2Cl-(aq)
Using data from experiment 1:
M
0.0281
7.11× 103
What is the reaction order with respect
k= s = to Fe2+, Cl2, and H+? What is the rate
(0.0125 M ) (0.0253 M ) M 2 • s
2
law and the relative rate constant?

Using data from experiment 2: k = 7.08 × 103/M2 s
Using data from experiment 3: k = 7.10 × 103/M2 s
These values are the same to 2 significant figures.
The generic rate law is

The following data were collected. The rates Rate = k[Fe2+]m[Cl2]n[H+]p
given are relative, not actual.
To find the order in Fe2+, we choose two
Exp. [Fe2+], M [Cl2], M [H+], M Rate, M/s experiments in which both [Cl2] and [H+] remain
constant: 1 and 2, or 3 and 4.
1 0.0020 0.0020 1.0 1.0 × 10-5 Exp [Fe2+] [Cl2] [H+] Initial Rate
2 0.0040 0.0020 1.0 2.0 × 10-5 1 0.0020 0.0020 1.0 1.0 × 10-5
2 0.0040 0.0020 1.0 2.0 × 10-5
3 0.0020 0.0040 1.0 2.0 × 10-5
3 0.0020 0.0040 1.0 2.0 × 10-5
4 0.0040 0.0040 1.0 4.0 × 10-5 4 0.0040 0.0040 1.0 4.0 × 10-5
5 0.0020 0.0020 0.5 2.0 × 10-5 In each case, the concentration of Fe2+ doubles
and the rate doubles.
6 0.0020 0.0020 0.1 1.0 × 10-4
The reaction is first order in Fe2+; m = 1.
8
To find the order in Cl2, we choose two To find the order in H+, we choose two
experiments in which both [Fe2+] and [H+] remain experiments in which both [Fe2+] and [Cl2]
constant: 1 and 3, or 2 and 4. remain constant: 1 and 5, 1 and 6, or 5 and 6.
Exp [Fe2+] [Cl2] [H+] Initial Rate
1 0.0020 0.0020 1.0 1.0 × 10-5 1 0.0020 0.0020 1.0 1.0 × 10-5
3 0.0020 0.0040 1.0 2.0 × 10-5 5 0.0020 0.0020 0.5 2.0 × 10-5
2 0.0040 0.0020 1.0 2.0 × 10-5 From experiment 5 to experiment 1, the
concentration doubles while the rate is halved.
4 0.0040 0.0040 1.0 4.0 × 10-5
1 0.0020 0.0020 1.0 1.0 × 10-5
In each case, the concentration of Cl2 doubles and 6 0.0020 0.0020 0.1 1.0 × 10-4
the rate doubles.
From experiment 6 to experiment 1, the
concentration is increased 10 times, the rate is
The reaction is first order in Cl2; n = 1. cut to one-tenth of the original rate.
The rate law is rate = k[Fe2+][Cl2][H+]-1 .

Another way to express this is
5 0.0020 0.0020 0.5 2.0 × 10-5
Rate =
[ ]
k Fe 2+ [Cl2 ]
6 0.0020 0.0020 0.1 1.0 × 10-4 H+ [ ]
From experiment 6 to experiment 5, the
concentration is increased 5 times; the rate is Using data from experiment 1:
cut to one-fifth of the original rate.
1.0 × 10 −5 (1.0 M )
M
rate [H] s 2.50
k= = =
Each of these describes the order in H+ as p = -1. [ ]
Fe 2+ [Cl2 ] (0.002 M )(0.002 M ) M • s
The same value for k is obtained using each

experiment.
Note that the units on the rate constant are specific

to the overall order of the reaction.
• For a zero-order reaction, the unit is M/s or

mol/(L s).
• For a first-order reaction, the unit is 1/s or s-1.
• For a second-order reaction, the unit is
1/(M s) or L/(mol s).
If you know the rate constant, you can deduce the

overall rate of reaction.
9
a. These factors might include things such as
genetics, diet, exercise, weight, and stress.
The rate law tells us the relationship between the
rate and the concentrations of reactants and
b. You would need to run controlled studies catalysts.
quantifying each of the factors and measures of
aging.
To find concentrations at various times, we need to
use the integrated rate law. The form used
c. When smoking doubles, aging increases depends on the order of reaction in that reactant.
fourfold. That is a second-order reaction, so
m = 2.
Cyclopropane is used as an anesthetic.

The isomerization of cyclopropane to
? propene is a first-order reaction with a

rate constant of 9.2/s. If an initial
sample of cyclopropane has a
concentration of 6.00 M, what will the
cyclopropane concentration be after
1.00 s?
The rate law is

Rate = k[cyclopropane]
ln
[A ]t =-
9.2
• 1.00 s = - 9.2
k = 9.2/s
[A]0 = 6.00 M
[A ]0 s
t = 1.00 s [A ]t = e −9.2 = 1.01 × 10 −4
[A]t = ?
[A ]0
The reaction is first order, so the integrated rate law [A ]t = 1.01 ×10 −4 (6.00 M )
is [A ]
ln t
= - kt
[A ]0 [A ]t = 6.1×10 −4 M
10
The half-life of a reaction, t½, is the time it takes for
the reactant concentration to decrease to one-
half of its initial value.
By substituting ½[A] 0 for [A]t, we solve the

integrated rate law for the special case of t = t½.
Ammonium nitrite is unstable because
? ammonium ion reacts with nitrite ion to

produce nitrogen:
The rate is first order in nitrite, NO2-:
k = 3.0 × 10-3/s
NH4+(aq) + NO2-(aq) N2(g) + 2H2O(l) For first-order reactions:

kt½ = 0.693
In a solution that is 10.0 M in NH4+, the 0.693 0.693
t1/2 = =
reaction is first order in nitrite ion (at low k 3.0 × 10 -3
concentrations), and the rate constant at s
25°C is 3.0 × 103/s.
t½ = 2.3 × 102 s = 3.9 min
What is the half-life of the reaction?
Let’s look again at the integrated rate laws:

Zero Order : [A]t = - kt + [A] 0
For a zero-order reaction, a plot of [A]t versus t is
linear. The y-intercept is [A]0.
y = mx + b
First Order : ln [A]t = - kt + ln [A] 0
y = mx + b For a first-order reaction, a plot of ln[A]t versus t is
linear. The graph crosses the origin (b = 0).
y = mx + b
1 1
= kt +
Second Order :
[A]t [A]0
In each case, the rate law is in the form of y = mx + For a second-order reaction, a plot of 1/[A]t versus t
b, allowing us to use the slope and intercept to find is linear. The y-intercept is 1/[A]0.
the values.
11
Graphs of concentration and time can also be
used to determine the order of reaction in that
reactant.
• For zero-order reactions, [A] versus t is

linear.
• For first-order reactions, ln[A] versus t is
linear.
• For second order reactions, 1/[A] versus t is
linear. Left: The plot of ln[NO2] versus t is not linear, so
the reaction is not first order.
This is illustrated on the next slide for the Right: The plot of 1/[NO2] versus t is linear, so the
decomposition of NO2. reaction is second order in NO2.
Rate Constant and Temperature

The rate constant depends strongly on
temperature. How can we explain this
relationship?
[A]0 The initial concentration
Zero Order : t1/2 = decreases in each time
2k
interval. The only Collision theory assumes that reactant molecules
0.693
First Order : t1/2 = equation that results in a must collide with an energy greater than some
k larger value for t½ is the minimum value and with the proper orientation.
1 second-order equation.
Second Order : t1/2 =
k [A]t The minimum energy is called the activation
The reaction is second
order. energy, Ea.
We will now explore the effect of a temperature

increase on each of the three requirements for a
reaction to occur.
Certainly, Z will increase with temperature, as the
The rate constant can be given by the equation average velocity of the molecules increases with
temperature.
k = Zfp
However, this factor alone cannot explain the
where
dramatic effect of temperature changes.
Z = collision frequency
f = fraction of collisions with the minimum energy
p = orientation factor
12
The fraction of molecular collisions having the
minimum energy required is given by f:
Ea
− 1
f =e RT
= Ea The reaction rate also depends on p, the proper
e RT orientation for the collision. This factor is
independent of temperature.
Now we can explain the dramatic impact of
temperature. The fraction of collisions having the
minimum energy increases exponentially with
temperature.
Importance of Molecular Orientation in

the Reaction of NO and Cl2
Transition-state theory explains the reaction

resulting from the collision of two molecules in
terms of an activated complex (transition state),
(A) NO approaches with its N atom toward Cl2, an unstable grouping of atoms that can break up
and an NOCl bond forms. Also, the angle of to form products.
approach is close to that in the product NOCl.
(B) NO approaches with its O atom toward Cl2. No

NOCl bond can form, so NO and Cl2 collide and
then fly apart.
The potential energy diagram for a reaction

visually illustrates the changes in energy that
occur.
The next slide shows the diagram for the reaction
NO + Cl2 NOCl2‡ NOCl + Cl
where NOCl2‡ indicates the activated complex.
13
The reaction of NO with Cl2 is an endothermic
reaction.
The next slide shows the curve for a generic

exothermic reaction.
Sketch a potential energy diagram for E
?
n
the decomposition of nitrous oxide. e
N2O(g) N2(g) + O(g) r Ea(reverse)
g Ea= 251 kJ = 84 kJ
y
N2 + O
The activation energy for the forward Products
p
reaction is 251 kJ; ∆Ho = +167 kJ. e
Label your diagram appropriately. r ∆H = 167 kJ
What is the reverse activation energy? m N2O

o
Reactants
l
Progress of reaction
Rate constants for most chemical reactions closely

follow an equation in the form
A more useful form of the Arrhenius equation is
E
− a
k = Ae RT
2
k  Ea  1 1
ln   =  − 
This is called the Arrhenius equation. A is the  k1  R T
 1 T 2 
frequency factor, a constant.
14
In a series of experiments on the
? decomposition of dinitrogen pentoxide,

N2O5, rate constants were determined
at two different temperatures: This is actually two problems.
• At 35°C, the rate constant was

First, we will use the Arrhenius equation to find Ea.
1.4 × 10-4/s.
• At 45°C, the rate constant was
Then, we will use the Arrhenius equation with Ea to
5.0 × 10-4/s. find the rate constant at a new temperature.
What is the activation energy?
What is the value of the rate constant
at 55°C?
 5.0 × 10 /s   1 1 
-4
Ea
ln  =  − 
 1.4 × 10 /s  8.315 J  308 K 318 K 
-4
mol • K
We will solve the left side and rearrange the right side.
T1 = 35°C = 308 K T2 = 45°C = 318 K  
 
k1 = 1.4 × 10-4/s k2 = 5.0 × 10-4/s  10 K 
1.273 = Ea
 J  
  8.315 (318 K)(308 K) 
 mol • K  
2
k  Ea  1 1
ln   =  −   J 
 k1  R  T1 T2  1.273 8.315 (318 K)(308 K)
 mol • K 
Ea =
10 K
Ea = 1.0 4 × 10 5 J/mol
J
1.04 × 10 5
 k2  mol  1 1 
ln  =  − 
 1.4 × 10 /s  8.315 J  308 K 328 K 
-4
mol • K
T1 = 35°C = 308 K T2 = 55°C = 328 K J
1.04 × 10 5
k1 = 1.4 × 10-4/s k2 = ?  k2  mol  20 K 
ln  =  
Ea = 1.04 × 105 J/mol  1.4 × 10 -4
/s  8.315 J  308 K • 328 K 
mol • K
 
2
k  Ea  1 1 k2
ln   =  −  ln   = 2.476
 1.4 × 10 /s 
-4
 k1  R T
 1 T 2 
k2
= 11.90
1.4 × 10 - 4 /s
k 2 = 1.7 × 10 -3 /s
15
Reaction Mechanism Each step in the reaction mechanism is called an
A balanced chemical equation is a description of elementary reaction and is a single molecular
the overall result of a chemical reaction. However, event.
what actually happens on a molecular level may
be more involved than what is represented by this
single equation. For example, the reaction may The set of elementary reactions, which when
take place in several steps. That set of steps is added give the balanced chemical equation, is
called the reaction mechanism. called the reaction mechanism.
Because an elementary reaction is an actual

The slowest step in the reaction mechanism is
molecular event, the rate of an elementary reaction
called the rate-determining step (RDS). The rate
is proportional to the concentration of each
law for the RDS is the rate law for the overall
reactant molecule. This means we can write the
reaction.
rate law directly from an elementary reaction.
For example, the reaction of NO2 with F2 is

Rate Law and Reaction Mechanism believed to occur in the following elementary
steps:
A reaction mechanism cannot be directly observed.
NO2 + F2 NO2F + F (slow step)
F + NO2 NO2F (fast step)
We can, however, determine the rate law by
experiment and decide if the reaction mechanism The overall reaction is
is consistent with that rate law. 2NO2 + F2 2NO2F
The rate of a reaction is determined completely by What is the rate law for this mechanism?
the slowest step, the rate-determining step.
Rate = k[NO2][F2]
16
For example, we look again at the mechanism for
the reaction of NO2 with F2:
NO2 + F2 NO2F + F (Slow step)

A reaction intermediate is a species produced F + NO2 NO2F (Fast step)
during a reaction that does not appear in the net
equation because it reacts in a subsequent step in The overall reaction is
the mechanism. 2NO2 + F2 2NO2F
F does not appear in the overall reaction equation.

It is produced in the first step and used in the
second step. Thus F is a reaction intermediate.
A catalyst is not consumed in a reaction. Rather, it

is present in the beginning, is used in one step,
and is produced again in a subsequent step. As a
result, the catalyst does not appear in the overall
Catalysis reaction equation.
Catalysis is an increase in the rate of reaction that
results from the addition of a catalyst. A catalyst increases the reaction rate by providing
an alternative reaction path with a lower activation
energy. When Ea is reduced, k increases
Enzymes are biological catalysts. exponentially.
This relationship is illustrated on the potential

energy diagram for the decomposition of ozone.
Consider the following reaction:

NO2(g) + CO(g) NO(g) + CO2(g)
At 500 K, the reaction mechanism is believed to

involve two elementary reactions:
NO2(g) + NO2(g) NO3(g) + NO(g) (Slow step)
NO3(g) + CO(g) NO2(g) + CO2(g)
The overall reaction equation is
NO2(g) + CO(g) NO(g) + CO2(g)
NO3 is a reaction intermediate: It is produced in

the first step and used in the second step. There is
no catalyst.
Rate = k[NO2][NO2] = k[NO2]2
17
Write the rate law for the first step in Chlorofluorocarbons, such as CCl2F2,
? the mechanism for the decomposition

of ozone. ? decompose in the stratosphere as a
result of their irradiation with the short-
wavelength ultraviolet light present at
Cl(g) + O3(g) ClO(g) + O2(g) those altitudes. The decomposition
yields chlorine atoms that catalyze the
ClO(g) + O(g) Cl(g) + O2(g) decomposition of ozone in the
presence of oxygen atoms (present in
Rate = k[Cl][O3] the stratosphere) to give oxygen
molecules.
The mechanism of the decomposition is

The decomposition of hydrogen
?
Cl(g) + O3(g) ClO(g) + O2(g) (Slow step)
peroxide is catalyzed by iodide ion. The
ClO(g) + O(g) Cl(g) + O2(g)
reaction mechanism is thought to be
What is the overall reaction equation?
H2O2(aq) + I-(aq) H2O(l) + IO-(aq)
O3(g) + O(g) 2O2(g)
IO (aq) + H2O2(aq) H2O(l) + O2(g) + I-(aq)
-
Is there a reaction intermediate? If so, what is it?

At 25°C, the first step is slow relative to the
Yes. ClO.
Is there a catalyst? If so, what is it?
second step. What is the rate law predicted
Yes. Cl. by the reaction mechanism? Is there a
What is the rate law for the overall reaction? reaction intermediate?
Rate = k[Cl][O3]
H2O2(aq) + I-(aq) H2O(l) + IO-(aq)

IO (aq) + H2O2(aq) H2O(l) + O2(g) + I-(aq)
-
Overall reaction equation:

2H2O2(aq) 2H2O(l) + O2(g)
I- was present in the beginning, used in the first

step, and produced in the second step. It is a
catalyst.
IO- was produced in the first step and used in the
second step. It is an intermediate.
Rate = k[H2O2][I-] IO- is the intermediate.

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Contents and Concepts

Copyright © Cengage Learning. All rights reserved. 13 | 2

2. Experimental Determination of Rate 4. Change of Concentration with Time

8. The Rate Law and the Mechanism

Four variables affect the rate of reaction:

Each test tube contains

Surface Area of a Solid Reactant Reaction rate is the increase in molar

We can express these changes in concentration

These equations give the average rate over the

The average rate

The slope of the

? to triiodide ion, I3-. The reaction is

Rates are determined experimentally in a variety of

For example, samples can be taken and analyzed

Continuously following the reaction is more

The reaction rate usually depends on the

This information is captured in the rate law, an

For the reaction Hydrogen peroxide oxidizes iodide ion

In this case, the exponent for both NO2 and F2 is 1 (which

H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq) + 2H2O(l)

Given: Rate = k[H2O2][I-]

a. The reaction is first order in H2O2.

Initial N2O5 Initial Rate of

Note that when the concentration doubles from

Examining the effect of doubling the initial 2NO(g) + O2(g) 2NO2(g)

When rate is multiplied by m is

[O2] remains constant in experiments 1 and 2.

The rate law is rate = k[NO]2[O2]. Iron(II) is oxidized to iron(III) by chlorine

law and the relative rate constant?

The generic rate law is

The rate law is rate = k[Fe2+][Cl2][H+]-1 .

The same value for k is obtained using each

Note that the units on the rate constant are specific

• For a zero-order reaction, the unit is M/s or

If you know the rate constant, you can deduce the

Cyclopropane is used as an anesthetic.

? propene is a first-order reaction with a

The rate law is

By substituting ½[A] 0 for [A]t, we solve the

Ammonium nitrite is unstable because

? ammonium ion reacts with nitrite ion to

NH4+(aq) + NO2-(aq) N2(g) + 2H2O(l) For first-order reactions:

Let’s look again at the integrated rate laws:

• For zero-order reactions, [A] versus t is

Rate Constant and Temperature

We will now explore the effect of a temperature

Importance of Molecular Orientation in

Transition-state theory explains the reaction

(B) NO approaches with its O atom toward Cl2. No

The potential energy diagram for a reaction

The next slide shows the diagram for the reaction

NO + Cl2 NOCl2‡ NOCl + Cl

where NOCl2‡ indicates the activated complex.

The next slide shows the curve for a generic

Sketch a potential energy diagram for E

What is the reverse activation energy? m N2O

Rate constants for most chemical reactions closely

frequency factor, a constant.