Chemistry

The Molecular Nature of Matter and Change Eighth

Edition

Martin S. Silberberg and Patricia G. Amateis

©McGraw-Hill Education. All rights reserved. Authorized only for instructor use in the classroom.  No reproduction or further distribution permitted without the prior written consent of McGraw-Hill Education.
 Kinetics: Rates and Mechanisms of Chemical
Reactions
• 16.1 Focusing on Reaction Rate
• 16.2 Expressing the Reaction Rate
• 16.3 The Rate Law and Its Components
• 16.4 Integrated Rate Laws: Concentration Changes Over
Time
• 16.5 Theories of Chemical Kinetics
• 16.6 Reaction Mechanisms: The Steps from Reactant to
Product
• 16.7 Catalysis: Speeding Up a Reaction

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 A Faster Reaction and a Slower Reaction

Figure 16.1
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 The Wide Range of Reaction Rates

Figure 16.2
©McGraw-Hill Education. Source: (explosion): © Crown Copyright/Health & Safety Lab./Science Source; (fruit and
 Factors That Influence Reaction Rate
• Particles must collide in order to react.
• The higher the concentration of reactants, the greater
the reaction rate.
– A higher concentration of reactant particles allows a greater
number of collisions.
• The physical state of the reactants influences reaction
rate.
– Substances must mix in order for particles to collide.

• The higher the temperature, the greater the reaction

rate.
– At higher temperatures particles have more energy and
therefore collide more often and more effectively.

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 The Effect of Surface Area on Reaction Rate

• A hot steel nail glows feebly when

placed in O2.

• The same mass of steel wool

bursts into flame.

Figure 16.3
©McGraw-Hill Education. Source: © McGraw-Hill Education/Stephen Frisch, photographer
 Sufficient Collision Energy Is Required for a
Reaction to Occur

Figure 16.4
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 Expressing the Reaction Rate
• Reaction rate is measured in terms of the changes in
concentrations of reactants or products per unit time.
• For the general reaction A → B, we measure the
concentration of A at t1 and at t2:
change in concentration of A conc A 2  conc A1 Δ A 
Rate   
change in time t2  t1 Δt
• Square brackets indicate a concentration in moles per liter.
• The negative sign is used because the concentration of A is
decreasing. This gives the rate a positive value.

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 Three Types of Reaction Rates for the Reaction
of O3 and C2H4
C 2 H 4  g   O3  g   C2 H 4 O  g   O 2  g 

Time (s) Concentration of O3

(mol/L)
0.0 3.20x10-5
10.0 2.42x10-5
20.0 1.95x10-5
30.0 1.63x10-5
40.0 1.40x10-5
50.0 1.23x10-5
60.0 1.10x10-5

Figure 16.5
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 Plots of [Reactant] and [Product] vs. Time
• [O2] increases just as fast as [C2H4] decreases.
Δ C2 H 4  Δ  O3 
Rate   
Δt Δt
Δ C 2 H 4 O  Δ O 2 
Rate  
Δt Δt

Figure 16.6A
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 Plots of [Reactant] and [Product] vs. Time:
H2 + I 2
• [HI] increases twice as fast as [H2] decreases.
Δ H 2  Δ I2 
1 Δ HI 
Rate    
Δt Δt 2 Δt
Δ HI Δ H 2  Δ I2 
Rate    2  2
Δt Δt Δt

Figure 16.6B
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 General Form of Reaction Rates
• In general, for the reaction
aA + bB  cC + dD
• where a, b, c, and d are the coefficients for the balanced
equation, the rate is expressed as:
1 Δ A  1 Δ  B 1 Δ C  1 Δ  D 
Rate     
a Δt b Δt c Δt d Δt

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 Sample Problem 16.1 – Problem
Expressing Rate in Terms of Changes in Concentration with
Time
• PROBLEM: Hydrogen gas has a nonpolluting combustion
product (water vapor). This gas is used as a fuel aboard the
space shuttle and in earthbound cars with prototype engines:
2H 2  g   O 2  g   2H 2 O  g 

(a) Express the rate in terms of changes in [H2], [O2], and [H2O]
with time.

(b) When [O2] is decreasing at 0.23 mol/L⋅s, at what rate is

[H2O] increasing?
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 Sample Problem 16.1 – Plan
• PLAN: (a) Of the three substances in the equation, let’s
choose O2 as the reference because its coefficient is 1. For
every molecule of O2 that disappears, two molecules of H2
disappear. Thus, the rate of [O2] decrease is one-half the rate
of [H2] decrease. By similar reasoning, the rate of [O2]
decrease is one-half the rate of [H2O] increase.
(b) Because [O2] is decreasing, the change in its concentration
must be negative. We substitute the given rate as a negative
value (−0.23 mol/L⋅s) into the expression and solve for
Δ[H2O]/Δt.

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 Sample Problem 16.1 - Solution
• SOLUTION: (a) Expressing the rate in terms of each
component:
Δ O 2  1 Δ H 2  1 Δ H 2 O
Rate    
Δt 2 Δt 2 Δt
(b) Calculating the rate of change of [H2O]:
1 Δ H 2O Δ O2   mol 
    0.23 
2 Δt Δt  Ls
Δ  H 2O  mol  mol
 2  0.23   0.46
Δt  Ls L s

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 The Rate Law
• For any general reaction occurring at a fixed temperature:
aA + bB  cC + dD
Rate = k  A  B 
m n

• The term k is the rate constant, which is specific for a given

reaction at a given temperature.
• The exponents m and n are reaction orders and are
determined by experiment.
– The values of m and n are not necessarily related in any way to the
coefficients a and b.

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 Reaction Orders
• A reaction has an individual order “with respect to” or “in”
each reactant.
• For the simple reaction A → products:
• If the rate doubles when [A] doubles, the rate depends on [A]1
and the reaction is first order with respect to A.
• If the rate quadruples when [A] doubles, the rate depends on
[A]2 and the reaction is second order with respect to [A].
• If the rate does not change when [A] doubles, the rate does
not depend on [A], and the reaction is zero order with respect
to A.

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 Plots of Reactant Concentration, [A], vs. Time
for First-, Second-, and Zero-Order Reactions

Figure 16.7
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 Plots of Rate vs. Reactant Concentration, [A],
for First-, Second-, and Zero-Order Reactions

Figure 16.8
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 Individual and Overall Reaction Orders
• For the reaction 2NO  g   2H 2  g   N 2  g   2H 2 O  g 

rate  k  NO  H 2 
2
• The rate law is
• The reaction is second order with respect to NO, first order
with respect to H2 and third order overall.
• Note that the reaction is first order with respect to H2 even
though the coefficient for H2 in the balanced equation is 2.
• Reaction orders must be determined from experimental data
and cannot be deduced from the balanced equation.

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 Sample Problem 16.2 – Problem
Determining Reaction Orders from Rate Laws
• PROBLEM: For each of the following reactions, use the given
rate law to determine the reaction order with respect to each
reactant and the overall order; for the reaction in (a),
determine the factor by which the rate changes if [NO] is
tripled and [O2] is doubled.
(a) 2NO  g   O 2  g   2NO 2  g  ; rate  k  NO  O2 
2

(b) CH 3CHO  g   CH 4  g   CO  g  ; rate  k CH3CHO 

3/2

(c) H 2 O 2  aq   3I   aq   2H +  aq   I3  aq   2H 2 O  l  ;
rate  k  H 2 O 2   I  

©McGraw-Hill Education.
 Sample Problem 16.2 – Plan
• PLAN: We inspect the exponents in the rate law, not the
coefficients of the balanced equation, to find the individual
orders, and then take their sum to find the overall reaction
order. To find the change in rate for the reaction in (a), we
substitute 3 for [NO] in the rate law (since that concentration
changes by a factor of 3) and 2 for [O2] (since that
concentration changes by a factor of 2), and solve for the rate.

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 Sample Problem 16.2 - Solution
• SOLUTION: (a) The exponent of [NO] is 2, so the reaction is
second order with respect to NO, first order with respect to
O2, and third order overall. Finding the change in rate:
Rate  k  NO 2  O 2   k 3  2   k 18  18k
2 2

The rate increases by a factor of 18.

(b) The reaction is 3 2 order in CH3CHO and 3 2 order overall.
(c) The reaction is first order in H2O2, first order in I−, and
second order overall.
The reactant H+ does not appear in the rate law, so the
reaction is zero order in H+.

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 Determining Reaction Orders
• For the general reaction A + 2B → C + D, the rate law will have
the form:
Rate  k A  B
m n

• To determine the values of m and n, we run a series of

experiments in which one reactant concentration changes
while the other is kept constant, and we measure the effect
on the initial rate in each case.

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 Initial Rates for the Reaction between A and B

Experiment Initial Rate Initial [A] (mol/L) Initial [B] (mol/L)

(mol/L·s)

1 1.75×10−3 2.50×10−2 3.00×10−2

2 3.50×10−3 5.00×10−2 3.00×10−2

3 3.50×10−3 2.50×10−2 6.00×10−2

4 7.00×10−3 5.00×10−2 6.00×10−2

• [B] is kept constant for experiments 1 and 2, while [A] is

doubled. Then [A] is kept constant while [B] is doubled.

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 Calculating the Order of A
• Finding m, the order with respect to A:
• We compare experiments 1 and 2, where [B] is kept constant
but [A] doubles:
m
Rate 2 k A 2 B2 A 2  A 2 
m n m

   
Rate 1 k A  B A 1  A 1 

m n m
1 1

3 2 n
3.50  10 mol/L  s  5.00  10 mol/L 

1.75  10 mol/L  s  2.50  102 mol/L 
3

• Dividing, we get 2.00 = (2.00)m so m = 1

©McGraw-Hill Education.
 Calculating the Order of B
• Finding n, the order with respect to B:
• We compare experiments 3 and 1, where [A] is kept constant
but [B] doubles:
n
Rate 3 k  A 3  B3  B3   B3 
m n n

  
Rate 1 k  A 1  B1  B1   B1 
m n n

n
3.50  10 mol/L  s  6.00  10 mol/L 
3 2

3
 2 
1.75  10 mol/L  s  3.00 10 mol/L 
• Dividing, we get 2.00 = (2.00)n so n = 1

©McGraw-Hill Education.
 Initial Rates for the Reaction Between O2 and NO
O 2  g   2NO  g   2NO 2  g 
Rate  k O 2   NO 
m n

Initial Rate
Experiment (mol/L·s) Initial [A] (mol/L) Initial [B] (mol/L)

1 1.75×10−3 2.50×10−2 3.00×10−2

2 3.50×10−3 5.00×10−2 3.00×10−2

3 3.50×10−3 2.50×10−2 6.00×10−2

4 7.00×10−3 5.00×10−2 6.00×10−2

©McGraw-Hill Education.
 Calculating the Order with Respect to O2
• Finding m, the order with respect to O2:
• We compare experiments 1 and 2, where [NO] is kept
constant but [O2] doubles:
m
Rate 2 k O 2 2  NO 2 O 2 2  O2 2 
m n m

   
Rate 1 k O 2   NO  O2 1   2 1 
m n m
O
1 1

m
6.40  10 mol/L  s  2.20  10 mol/L 
3 2

3.21  10 mol/L  s  1.10  102 mol/L 
3

• Dividing, we get 1.99 = (2.00)m or 2 = 2m, so m = 1

• The reaction is first order with respect to O2.

©McGraw-Hill Education.
 Using Logarithms to Solve for Reaction Order
• Sometimes the exponent is not easy to find by inspection. In
those cases, we solve for m with an equation of the form a =
b m:
log a log 1.99
m   0.993
log b log 2.00
• This confirms that the reaction is first order with respect to
O2.
• Reaction orders may be positive integers, zero, negative
integers, or fractions.

©McGraw-Hill Education.
 Using Logarithms for the Order of NO
• Finding n, the order with respect to NO:
• We compare experiments 1 and 3, where [O2] is kept constant
but [NO] doubles:
n
Rate 3   NO 3  12.8  10 3 mol/L  s  2.60  10 2 mol/L 
n

  ; 
Rate 1   NO 1  3.21  10 mol/L  s  1.30  10 2 mol/L 
3

• Dividing, we get 3.99 = (2.00)n or 4 = 2n, so n = 2.

log a log 3.99
• Alternatively: n    2.00
log b log 2.00
• The reaction is second order with respect to NO.
• The rate law is given by: rate  k O 2  NO 
2

©McGraw-Hill Education.
 Units of the Rate Constant k for Several Overall
Reaction Orders
Overall Reaction Order Units of k (t in seconds)
0 mol/L·s (or mol L−1 s−1)
1 1/s (or s−1)
2 L/mol·s (or L mol−1 s−1)
3 L2/mol2·s (or L2 mol−2 s−1)

General formula:

• The value of k is easily determined from experimental rate

data. The units of k depend on the overall reaction order.

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 Information Sequence to Determine the
Kinetic Parameters of a Reaction

Figure 16.9
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 Sample Problem 16.3 – Problem
Determining Reaction Orders and Rate Constants from Rate
Data
• PROBLEM: Many gaseous reactions occur in car engines and
exhaust systems. One of these is
NO 2  g   CO  g   NO  g   CO2  g  rate  k  NO2  CO
m n

(a) Use the following data to determine the individual and

overall reaction orders.
(b) Calculate k using the data from experiment 1
Initial Rate Initial [NO2]
Experiment Initial [CO] (mol/L)
(mol/L·s) (mol/L)
1 0.0050 0.10 0.10
2 0.080   0.40 0.10
3 0.0050 0.10 0.20

©McGraw-Hill Education.
 Sample Problem 16.3 – Plan
• PLAN: (a) We need to solve the general rate law for m and for
n and then add those orders to get the overall order. To solve
for each exponent, we proceed as in the text, taking the ratio
of the rate laws for two experiments in which only the
reactant in question changes. (b) We substitute the values for
the rate and the reactant concentrations from experiment 1
into the rate law and solve for k.

©McGraw-Hill Education.
 Sample Problem 16.3 – Solution (a), Part 1
• SOLUTION: (a) Calculating m in [NO2]m: We take the ratio of
the rate laws for experiments 1 and 2, in which [NO2] varies
but [CO] is constant:
m
Rate 2 k  NO 2 2 CO 2   NO 2 2  0.080 mol/L  s  0.40 mol/L  m
m n

   ;  
Rate 1 k  NO 2 m CO n
1 1
  NO 
2 1 0.0050 mol/L  s  0.10 mol/L

This gives 16 = (4.0)m, so we have m = log 16/log 4.0 = 2.0.

The reaction is second order in NO2.

©McGraw-Hill Education.
 Sample Problem 16.3 – Solution (a), Part 2
• SOLUTION: (a) Calculating n in [CO]n: We take the ratio of the
rate laws for experiments 1 and 3, in which [CO] varies but
[NO2] is constant:
n
Rate 3  CO 3  0.0050 mol/L  s  0.20 mol/L 
n

  ;  
Rate 1  CO 1  0.0050 mol/L  s  0.10 mol/L 


We have 1.0 = (2.0)n, so n = 0. The rate does not change when

[CO] varies, so the reaction is zero order in CO.
Therefore, the rate law is:

Rate  k  NO 2  CO   k  NO 2 
2 0 2

The reaction is second order overall.

©McGraw-Hill Education.
 Sample Problem 16.3 – Solution (b)
• SOLUTION: (b) From experiment 1, rate = 0.0050 mol/L·s and
[NO2] = 0.10 mol/L. Calculating k:
Rate  k  NO 2 
2

Rate 0.0050 mol/  L  s

k 
 NO 
2
2
 0.10 mol/L 2

k  0.50 L/mol  s

©McGraw-Hill Education.
 Sample Problem 16.4 – Problem
Determining Reaction Orders from Molecular Scenes
• PROBLEM: At a particular temperature and volume, two
gases, A (red) and B (blue), react. The following molecular
scenes represent starting mixtures for four experiments:

(a) What is the reaction order with respect to A? With respect

to B? The overall order?
(b) Write the rate law for the reaction.
(c) Predict the initial rate of Expt 4.

©McGraw-Hill Education.
 Sample Problem 16.4 – Plan
• PLAN: (a) As before, we find the individual reaction orders by
seeing how a change in each reactant changes the rate. In this
case, however, instead of using concentration data, we count
numbers of particles. The sum of the individual orders is the
overall order. (b) To write the rate law, we use the orders from
part (a) as exponents in the general rate law. (c) Using the
results from Expts 1 through 3 and the rate law from part (b),
we find the unknown initial rate of Expt 4.

©McGraw-Hill Education.
 Sample Problem 16.4 – Solution (a)
• SOLUTION: (a) The rate law is rate = k[A]m[B]n.  For reactant A
(red) in Expts 1 and 2 (k and number of  B particles are
constant):
m
k A 2 B2  A 2  1.0 10 4 mol/L  s
m n m
Rate 2  4 particles 
  ; 
Rate 1 k A m Bn  A   0.50 10 4 mol/L  s  2 particles 
1 1  1 

• Thus, 2 = (2)m so the order with respect to A is 1. For reactant

B in Expts 1 and 3 (k and number of A particles are constant):
n
k A 3 B3  B3  2.0 104 mol/L  s  4 particles 
m n n
Rate 3
  ; 
Rate 1 k A m Bn  B  0.50 104 mol/L  s  2 particles 
1 1  1 

• Thus, 4 = (2)n so the order with respect to B is 2. The overall

order is 1 + 2 = 3.

©McGraw-Hill Education.
 Sample Problem 16.4 – Solution (b) and (c)
• SOLUTION: (b) Writing the rate law: The general rate law is
rate = k[A] [B] , so we have: Rate  k  A B 
2
m n

(c) Finding the initial rate of Expt 4: There are several

possibilities, but let’s compare Expts 3 and 4, in which the
number of particles of A doubles (from 2 to 4) and the
number of particles of B doesn’t change. Since the rate law
shows that the reaction is first order in A, the initial rate in
Expt 4 should be double the initial rate in Expt 3, or 4.0×10−4
mol/L·s.

©McGraw-Hill Education.
 Integrated Rate Laws
• An integrated rate law includes time as a variable.
• First-order rate equation:
Δ A  A 0
Rate    k  A ; ln  kt
Δt A t
• Second-order rate equation:
Δ A  1 1
 k A  ;
2
Rate     kt
Δt A t A 0
• Zero-order rate equation:
Δ A 
 k A  ; A t  A 0  kt
0
Rate  
Δt

©McGraw-Hill Education.
 Sample Problem 16.5 – Problem
Determining the Reactant Concentration After a Given Time
• PROBLEM: At 1000°C, cyclobutane (C4H8) decomposes in a
first-order reaction, with the very high rate constant of 87 s−1,
to two molecules of ethylene (C2H4).
(a) The initial C4H8 concentration is 2.00 M. What is the
concentration after 0.010 s?
(b) How long will it take for 70.0% of the C4H8 to decompose?

©McGraw-Hill Education.
 Sample Problem 16.5 – Plan
• PLAN: (a) We must find the concentration of cyclobutane at
time t, [C4H8]t. We are told that this is a first-order reaction, so
we use the integrated first-order rate law:
C4 H8 0
ln  kt
C4 H8 t
We know k (87 s−1), t (0.010 s), and [C4H8]0 (2.00 M), so we can
solve for [C4H8]t.
(b) If 70.0% of the C4H8 has decomposed, 30.0% of it remains
([C4H8]t). We know k (87 s−1), [C4H8]0 (2.00 M), and [C4H8]t
(0.300 × 2.00 M = 0.600 M), so we can solve for t.

©McGraw-Hill Education.
 Sample Problem 16.5 - Solution
• SOLUTION: (a) Substituting the data into the integrated rate law:
2.00 mol/L
ln  87 s 1   0.010 s   0.87
C4 H8 t
Taking the antilog of both sides and solving for [C4H8]t:

2.00 mol/L 2.00 mol/L

 e0.87  2.4; C4 H8 t   0.83 mol / L
C4 H8 t 2.4

(b) Substituting the data into the integrated rate law:

2.00 mol/L
ln  87 s 1  t 
0.600 mol/L
t  0.014 s

©McGraw-Hill Education.
 Graphical Method for Finding the Reaction Order
from the Integrated Rate Law: First Order Reactions

• Integrated rate law:

A 0
ln  kt
A  t
• Straight-line form:
ln A t  kt  ln A 0

• A plot of ln[A] vs. time gives a

straight line for a first-order
reaction.

©McGraw-Hill Education.
 Graphical Method for Finding the Reaction Order
from the Integrated Rate Law: Second Order
Reactions
• Integrated rate law:
1 1
  kt
A t A 0
• Straight-line form:
1 1
 kt 
A t A 0
• A plot of vs. time gives a
straight line for a second-order
reaction.

©McGraw-Hill Education.
 Graphical Method for Finding the Reaction Order
from the Integrated Rate Law: Zero Order Reactions

• Integrated rate law:

A t  A 0  kt
• Straight-line form:
A t  kt  A 0
• A plot of [A] vs. time gives a
straight line for a zero-order
reaction.

©McGraw-Hill Education.
 Graphical Determination of the Reaction Order for the
Decomposition of N2O5: Data Table

Time (min) [N2O5] ln[N2O5] 1/[N2O5]

0 0.0165 -4.104 60.6
10 0.0124 -4.390 80.6
20 0.0093 -4.68 110
30 0.0071 -4.95 140
40 0.0053 -5.24 190
50 0.0039 -5.55 260
60 0.0029 -5.84 340

©McGraw-Hill Education.
 Graphical Determination of the Reaction Order
for the Decomposition of N2O5
• The concentration data is used to construct three different
plots.

• Since the plot of ln [N2O5] vs. time gives a straight line, the
reaction is first order.
Figure 16.11
©McGraw-Hill Education.
 Reaction Half-Life
• The half-life (t½ ) for a reaction is the time taken for the
concentration of a reactant to drop to half its initial value.
• For a first-order reaction, t1/2 does not depend on the starting
concentration.
ln 2 0.693
t1/2  
k k
• The half-life for a first-order reaction is a constant.
– Radioactive decay is a first-order process. The half-life for a radioactive
nucleus is a useful indicator of its stability.

©McGraw-Hill Education.
 A Plot of [N2O5] vs. Time for Three Reaction
Half-Lives

Figure 16.12
©McGraw-Hill Education.
 Sample Problem 16.6 – Problem
Using Molecular Scenes to Find Quantities at Various Times
• PROBLEM: Substance A (green) decomposes to two other
substances, B (blue) and C (yellow), in a first-order gaseous
reaction. The molecular scenes below show a portion of the
reaction mixture at two different times:

(a) Draw a similar molecular scene of the reaction mixture at t = 60.0 s.

(b) Find the rate constant for the reaction.
(c) If the total pressure (Ptotal) of the mixture is 5.00 atm at 90.0 s, what is
the partial pressure of substance B (PB)?

©McGraw-Hill Education.
 Sample Problem 16.6 – Plan
• PLAN: We are shown molecular scenes of a reaction at two times, with
various numbers of reactant and product particles, and have to predict
quantities at two later times.
(a) We count the number of A particles and see that A has decreased by
half after 30.0 s; thus, the half-life is 30.0 s. The time t = 60.0 s represents
two half-lives, so the number of A will decrease by half again, and each A
forms one B and one C.
(b) We substitute the value of the half-life to find k.
(c) First, we find the numbers of particles at t = 90.0 s, which represents
three half-lives. To find PB, we multiply the mole fraction of B, XB, by Ptotal
(5.00 atm) . To find XB, we know that the number of particles is equivalent
to the number of moles, so we divide the number of B particles by the
total number of particles.

©McGraw-Hill Education.
 Sample Problem 16.6 - Solution
• SOLUTION: (a) The number of A particles decreased from 8 to 4 in one
half-life (30.0 s), so after two half-lives (60.0 s), the number of A particles
will be 2 (1/2 of 4). Each A decomposes to 1 B and 1 C, so 6 (8−2) particles
of A form 6 of B and 6 of C.
(b) Finding the rate constant, k:
0.693 0.693 0.693
t1/2  ; k   2.31  102 s 1
k t1/2 30.0 s
(c) Finding the number of particles after 90.0 s: After a third half-life, there
will be 1 A, 7 B, and 7 C particles.
Finding the mole fraction of B, XB:
7 B particles 7
XB    0.467
1  7  7 total particles 15
Finding the partial pressure of B, PB:
PB  X B  Ptotal  0.467  5.00 atm  2.33 atm
©McGraw-Hill Education.
 Sample Problem 16.7 – Problem
Determining the Half-Life of a First-Order Reaction
• PROBLEM: Cyclopropane is the smallest cyclic hydrocarbon.
Because its 60° bond angles reduce orbital overlap, its bonds
are weak. As a result, it is thermally unstable and rearranges
to propene at 1000°C via the following first-order reaction:

The rate constant is 9.2 s−1.

(a) What is the half-life of the reaction?
(b) How long does it take for the concentration of
cyclopropane to reach one-quarter of the initial value?

©McGraw-Hill Education.
 Sample Problem 16.7 – Plan
• PLAN: (a) The cyclopropane rearrangement is first order, so to
find t1/2 we use Equation 16.7 and substitute for k (9.2 s−1).
(b) Each half-life decreases the concentration to one-half of its
initial value, so two half-lives decrease it to one-quarter of its
initial value.

©McGraw-Hill Education.
 Sample Problem 16.7 - Solution
• SOLUTION: (a) Solving for t1/2:
ln 2 0.693
t1/2   1
 0.075 s
k 9.2 s
It takes 0.075 s for half the cyclopropane to form propene at
this temperature.
(b) Finding the time to reach one-quarter of the initial
concentration:
Time  2 t1/2   2  0.075 s  0.15 s

©McGraw-Hill Education.
 Half-Life Equations
• For a first-order reaction, t1/2 does not depend on the initial
concentration.
• For a second-order reaction, t1/2 is inversely proportional to
the initial concentration:
t1/2 
1
k A0

second-order process; rate  k  A 
2

• For a zero-order reaction, t1/2 is directly proportional to the
initial concentration:
 A 0
t1/2   zero-order process; rate  k 
2k

©McGraw-Hill Education.
 An Overview of Zero-Order, First-Order, and
Simple Second-Order Reactions
Zero Order First Order Second Order
Rate law rate = k rate = k[A] rate = k[A]2
Units for k mol/L·s 1/s L/mol·s
Half-life [A]02k ln   2 k 1k[A]0
Integrated rate law ln [A]t = ‒kt + ln
in straight-line [A]t = ‒kt + [A]0 1/[A]t = kt +1/[A]0
[A]0
form
Plot for straight [A]t vs. t ln [A]t vs. t 1/[A]t vs. t
line
Slope, y-intercept ‒k, [A]0 ‒k, ln [A]0 k, 1/[A]0

Graph

©McGraw-Hill Education.
 Collision Theory and Concentration
• The basic principle of collision theory is that particles must
collide in order to react.
• An increase in the concentration of a reactant leads to a larger
number of collisions, hence increasing reaction rate.
• The number of collisions depends on the product of the
numbers of reactant particles, not their sum.
– Concentrations are multiplied in the rate law, not added.

©McGraw-Hill Education.
The Number of Possible Collisions is the Product, Not
the Sum, of Reactant Concentrations

Figure 16.3
©McGraw-Hill Education.
 Temperature and the Rate Constant
• Temperature has a dramatic effect on reaction rate.
– For many reactions, an increase of 10°C will double or triple the rate.

• Experimental data shows that k increases exponentially as T

increases. This is expressed in the Arrhenius equation:
k  Ae  Ea / RT
– k = rate constant
– A = frequency factor
– Ea = activation energy

Higher T  larger k  increased rate

©McGraw-Hill Education.
 Increase of the Rate Constant with
Temperature for the Hydrolysis of an Ester

Expt [Ester] [H2O] T (K) Rate k

(mol/L·s) (L/mol·s)
1 0.100 0.200 288 1.04x10-3 0.0521
2 0.100 0.200 298 2.20x10-3 0.101
3 0.100 0.200 308 3.68x10-3 0.184
4 0.100 0.200 318 6.64x10-3 0.332

• Reaction rate and k increase exponentially as T increases.

Figure 16.14
©McGraw-Hill Education.
 Activation Energy
• In order to be effective, collisions between particles must
exceed a certain energy threshold.
• When particles collide effectively, they reach an activated
state. The energy difference between the reactants and the
activated state is the activation energy (Ea) for the reaction.
• The lower the activation energy, the faster the reaction.

Smaller Ea  larger f  larger k  increased rate

©McGraw-Hill Education.
 Energy-level Diagram for a Reaction

• Collisions must occur with sufficient energy to reach an

activated state.
• This particular reaction is reversible and is exothermic in the
forward direction.
Figure 16.15
©McGraw-Hill Education. Source: © Sipa via AP Images
 Temperature and Collision Energy
• An increase in temperature causes an increase in the kinetic
energy of the particles. This leads to more frequent collisions
and reaction rate increases.
• At a higher temperature, the fraction of collisions with
sufficient energy equal to or greater than Ea increases.
Reaction rate therefore increases.

©McGraw-Hill Education.
 The Effect of Temperature on the Distribution
of Collision Energies

Figure 16.16
©McGraw-Hill Education.
 The Effect of Ea and T on the Fraction (f) of
Collisions with Sufficient Energy to Allow
Reaction
Ea (kJ/mol) f (at T = 298 K)
  50 1.70 × 10 − 9
  75  7.03 × 10 − 14
100  2.90 × 10 − 18
T f (at Ea = 50 kJ/mol)
25°C (298 K) 1.70 × 10 − 9
35°C (308 K) 3.29 × 10 − 9
45°C (318 K) 6.12 × 10 − 9

©McGraw-Hill Education.
 Calculating Activation Energy
• Ea can be calculated from the Arrhenius equation:
k  Ae  Ea / RT ;
Ea  1
Straight line from: ln k  ln A   
R T
• If data is available at two different temperatures:
k2 Ea 1 1
ln     
k1 R  T2 T1 

©McGraw-Hill Education.
 Graphical Determination of the Activation
Energy

Ea  1
ln k  ln A   
R T

Figure 16.17
©McGraw-Hill Education.
 Sample Problem 16.8 – Problem and Plan
Determining the Energy of Activation
• PROBLEM: The decomposition of hydrogen iodide, 2HI(g) ⟶
H2(g) + I2(g), has rate constants of 9.51×10−9 L/mol·s at 500. K
and 1.10×10−5 L/mol·s at 600. K. Find Ea.
• PLAN: We are given the rate constants, k1 and k2, at two
temperatures, T1 and T2 . We solve for Ea.

©McGraw-Hill Education.
 Sample Problem 16.8 - Solution
• SOLUTION:

k2 Ea  1 1 
ln     
k1 R  T2 T1 
1
 k2   1 1 
Ea  R  ln    
 k1   T1 T2 
 L 
1.10  105 1
 J  mol  s   1 1 
  8.314  ln   
 mol  K   9.51  109 L   500  K 600  K 
 
mol  s
 1.76  105 kJ / mol

©McGraw-Hill Education.
 Molecular Structure and Reaction Rate
• For a collision between particles to be effective, it must have
both sufficient energy and the appropriate relative
orientation between the reacting particles.
• The term A in the Arrhenius equation is the frequency factor
for the reaction.
k  Ae  Ea / RT
A  pZ
– p = orientation probability factor
– Z = collision frequency

• The term p is specific for each reaction and is related to the

structural complexity of the reactants.

©McGraw-Hill Education.
The Importance of Molecular Orientation to An
Effective Collision
• NO  g   NO 3  g   2NO 2  g 
• There is only one relative
orientation of these two
molecules that leads to an
effective collision.

Figure 16.18

©McGraw-Hill Education.
 Transition State Theory
• An effective collision between particles leads to the formation
of a transition state or activated complex.
• The transition state is an unstable species that contains
partial bonds. It is a transitional species partway between
reactants and products.
– Transition states cannot be isolated.

• The transition state exists at the point of maximum potential

energy.
– The energy required to form the transition state is the activation
energy.

©McGraw-Hill Education.
 The Transition State of the Reaction Between
BrCH3 and OH-
BrCH 3  OH   Br   CH 3OH

• The transition state contains partial bonds (dashed) between

C and Br and between C and O. It has a trigonal bypyramidal
shape.
Figure 16.19
©McGraw-Hill Education.
 Depicting the Reaction Between BrCH3 and OH–

Figure 16.20
©McGraw-Hill Education.
 Reaction Energy Diagrams and Possible
Transition States for Two Reactions

Figure 16.21
©McGraw-Hill Education.
 Sample Problem 16.9 – Problem and Plan
Drawing Reaction Energy Diagrams and Transition States
• PROBLEM: A key reaction in the upper atmosphere is O3(g) +
O(g) → 2O2(g). The Ea(fwd) is 19 kJ, and the ΔHrxn for the
reaction as written is −392 kJ. Draw a reaction energy
diagram, predict a structure for the transition state, and
calculate Ea(rev).
• PLAN: The reaction is highly exothermic (ΔHrxn = −392 kJ), so
the products are much lower in energy than the reactants.
The small Ea(fwd) (19 kJ) means that the energy of the reactants
lies slightly below that of the transition state. We calculate
Ea(rev). To predict the transition state, we sketch the species
and note that one of the bonds in O3 weakens, and this
partially bonded O begins forming a bond to the separate O
atom.
©McGraw-Hill Education.
 Sample Problem 16.9 - Solution
• SOLUTION:
ΔH rxn  Ea fwd   Ea rev 

Ea rev    Ea fwd   ΔH rxn  19 kJ   392 kJ   411 kJ

The reaction energy diagram (not drawn to scale), with

transition state, is shown below.

©McGraw-Hill Education.
 Reaction Mechanisms
• The mechanism of a reaction is the sequence of single
reaction steps that make up the overall equation.
• The individual steps of the reaction mechanism are called
elementary steps because each one describes a single
molecular event.
• Each elementary step is characterized by its molecularity, the
number of particles involved in the reaction.
• The rate law for an elementary step can be deduced from the
reaction stoichiometry – reaction order equals molecularity
for an elementary step only.

©McGraw-Hill Education.
 Rate Laws for General Elementary Steps

Elementary Step Molecularity Rate Law

A ⟶ product Unimolecular Rate = k[A]

2A ⟶ product Bimolecular Rate = k[A]2

A + B ⟶ product Bimolecular Rate = k[A][B]

2A + B ⟶ product Termolecular Rate = k[A]2[B]

©McGraw-Hill Education.
 Sample Problem 16.10 – Problem
Determining Molecularities and Rate Laws for Elementary Steps
• PROBLEM: The following elementary steps are proposed for
a reaction mechanism:
1. Cl2  g   2Cl  g 
2. Cl  g   CHCl3  g   HCl  g   CCl3  g 
3. Cl  g   CCl3  g   CCl4  g 
(a) Write the balanced equation for the overall reaction.
(b) Determine the molecularity of each step.
(c) Write the rate law for each step

©McGraw-Hill Education.
 Sample Problem 16.10 – Plan
• PLAN: We find the overall equation by adding the elementary
steps. The molecularity of each step equals the total number
of reactant particles. We write the rate law for each step using
the equation coefficients as reaction orders.

©McGraw-Hill Education.
 Sample Problem 16.10 – Solution (a) and (b)
• SOLUTION: (a) Writing the overall balanced equation:
(1) Cl2  g   2Cl  g 
(2) Cl  g   CHCl3  g   HCl  g   CCl3  g 
(3) Cl  g   CCl3  g   CCl4  g 
Cl2  g   Cl  g   CHCl3  g   Cl  g   CCl3  g  
2Cl  g   HCl  g   CCl3  g   CCl 4  g 

Cl 2  g  + CHCl 3  g   HCl  g  + CCl 4  g 

(b) Determining the molecularity of each step: The first step has
one reactant, Cl2, so it is unimolecular. The second and third
steps have two reactants (Cl and CHCl3; Cl(g) + CCl3), so they are
bimolecular.

©McGraw-Hill Education.
 Sample Problem 16.10 – Solution (c)
• SOLUTION: (c) Writing rate laws for the elementary steps:
(1) Rate1  k1 Cl2 
(2) Rate 2  k2 ClCHCl3 
(3) Rate3  k3 ClCCl3 

©McGraw-Hill Education.
 The Rate-Determining Step of a Reaction
• The slowest step in a reaction is the rate-determining or rate-
limiting step.
The reaction NO2  g   CO  g   NO  g   CO2  g 
• has been proposed to occur by a two-step mechanism:
(1) NO 2  g  +NO 2  g   NO 3  g   NO  g  slow; rate-determining 
(2) NO3  g   CO  g   NO 2  g   CO 2  g  fast 

• Observed rate law: rate  k  NO 2 

2

• The rate law for the rate-determining step becomes the rate
law for the overall reaction.

©McGraw-Hill Education.
 Correlating Mechanism with the Rate Law
• A valid mechanism must meet three criteria:
– The elementary steps must add up to the overall balanced equation.
– The elementary steps must be reasonable.
– The mechanism must correlate with the observed rate law.

• A mechanism is a hypothesis –we cannot prove it is correct,

but if it is consistent with the data, and can be used to predict
results accurately, it is a useful model for the reaction.

©McGraw-Hill Education.
 Mechanisms with a Slow Initial Step
• The overall reaction 2NO2(g) + F2(g) →2NO2F(g) has an
experimental rate law Rate = k[NO2][F2].
• The accepted mechanism is
1. NO 2  g   F2  g   NO 2 F  g   F  g  slow; rate determining 
2. NO 2  g   F  g   NO 2F  g  fast 
2NO 2  g   F2  g   2NO2 F  g 
• The elementary steps sum to the overall balanced equation.
• Both steps are bimolecular and are therefore reasonable.
rate1  k1  NO2 F2 ; rate2  k2  NO2 F

• Step 1 is the slow step, and rate1 correlates with the observed
rate law.
• The mechanism is therefore reasonable.
©McGraw-Hill Education.
 Mechanisms with a Fast Initial Step
• The overall reaction 2NO (g) + O2(g) →2NO2(g) has an
experimental rate law Rate = k[NO]2[O2]. A proposed
mechanism is:
1. NO  g   O 2  g   NO3  g  fast, reversible 
2. NO3  g   NO  g   2NO 2  g  slow; rate determining 
2NO  g   O 2  g   2NO 2  g 
• The elementary steps sum to the overall balanced equation.
Both steps are bimolecular and are therefore reasonable.
rate1fwd  k1  NO O 2  ; rate1rev  k1  NO3 ; rate 2  k2  NO3  NO 
• When equilibrium (1) has been established
rate1fwd   rate1rev 
k1  NO O2   k1  NO3 
©McGraw-Hill Education.
 Mechanisms with a Fast Initial Step, Cont’d
k1
 NO3    NOO2 
k1
 k1 
rate 2  k2  NO3  NO   k2   NO O2    NO 
 k2 
• The ratio of rate constants is itself a constant, equal to the
overall rate constant for the reaction, so
• rate2 = k[NO]2[O2] which is consistent with the observed rate
law.
• For any mechanism, only reactants involved up to and
including the slow (rate-determining) step appear in the
overall rate law.

©McGraw-Hill Education.
 Sample Problem 16.11 – Problem and Plan
• PROBLEM: Consider the reaction mechanism in Sample Problem 16.10.
(a) Identify the intermediates in the mechanism.
(b) Assuming that step 2 is the slow (rate-determining) step, show that the
mechanism is consistent with the observed rate law: Rate = k[Cl2]1/2[CHCl3].
• PLAN: (a)  We write each elementary step and sum to get the overall
reaction. Intermediates are substances that are produced in one
elementary step and consumed as reactants in a subsequent elementary
step. (b)  We use the reactants in the slow step to write its rate law; if an
intermediate is present in the rate law, we eliminate it by expressing it in
terms of reactants.

©McGraw-Hill Education.
 Sample Problem 16.11 – Solution (a)
• SOLUTION: (a) Determining the intermediates:

1. Cl2  g   2Cl  g  fast 

2. Cl  g   CHCl3  g   HCl  g   CCl3  g  slow 
3. Cl  g   CCl3  g   CCl4  g  fast 
Cl2  g   Cl  g   CHCl3  g   Cl  g   CCl3  g   2Cl  g   HCl  g  
CCl3  g   CCl 4  g 

The species Cl is formed in step 1 and consumed in

subsequent steps 2 and 3.
Likewise, CCl3 is formed in step 2 and used up in step 3. Both
Cl and CCl3 are referred to as intermediates.

©McGraw-Hill Education.
 Sample Problem 16.11 – Solution (b)
•SOLUTION: (b) Correlating the reaction mechanism and the rate law:
Step 2 is the rate-determining step:
Cl  g   CHCl3  g   HCl  g   CCl3  g  slow 
The rate law can be written using the slow, elementary step in the
proposed mechanism: Rate  k2 Cl CHCl3 
The species Cl is an intermediate; hence, [Cl] must be expressed in terms
of reactant concentrations. For the equilibrium in step 1:
Rate1fwd  Rate1rev ; or k1 Cl 2   k1 Cl 
2

k1
Cl  Cl2 
k1
Substituting for [Cl] in the rate law for the slow step:
k1
Rate  k2 Cl CHCl 3   k2   CHCl 3 
1/ 2
Cl
k1
k1
With k  k2 , this rate law is consistent with the observed rate law.
k1
©McGraw-Hill Education.
 Reaction Energy Diagram for the Two-Step
Reaction of (A) NO2 and F2 and of (B) NO and O2

• Each step in a multi-step reaction has its own transition state,

which occurs at the energy maximum for that step.
Figure 16.22
©McGraw-Hill Education.
 Catalysis: Speeding up a Reaction
• A catalyst is a substance that increases the reaction rate
without itself being consumed in the reaction.
• In general, a catalyst provides an alternative reaction pathway
that has a lower total activation energy than the uncatalyzed
reaction.
• A catalyst will speed up both the forward and the reverse
reactions.
• A catalyst does not affect either DH or the overall yield for a
reaction.

©McGraw-Hill Education.
 Reaction Energy Diagram for a Catalyzed
(Green) and Uncatalyzed (Red) Process

Figure 16.23
©McGraw-Hill Education.
 The Catalyzed Decomposition of H2O2

• A small amount of NaBr is added

to a solution of H2O2.
• Oxygen gas forms quickly as Br-
(aq) catalyzes the H2O2
decomposition; the
intermediate Br2 turns the
solution orange.
• The solution becomes colorless
when the Br2 is consumed in the
final step of the mechanism.

©McGraw-Hill Education.
Figure 16.26 Source: © McGraw-Hill Education/Charles Winters/Timeframe Photography, Inc.
 The Metal-catalyzed Hydrogenation of Ethene

• A heterogeneous catalyst is in a different phase than the

reaction mixture.
Figure 16.25
©McGraw-Hill Education.
 Lock-and-Key Model of Enzyme Action

• The lock-and-key model visualizes the enzyme active site

having a fixed shape. This shape matches the shape of its
substrate(s). The active site is therefore specific to its
substrate.
Figure 16.26A
©McGraw-Hill Education.
 Induced-Fit Model of Enzyme Action

• The induced-fit model visualizes the enzyme active site

changing shape in order to bind its substrate(s) more
effectively. The active site is still selective toward certain
substrates.
Figure 16.26B
©McGraw-Hill Education.
 Satellite Images of the Increasing Size of the
Antarctic Ozone Hole (Purple)

Figure B16.1
©McGraw-Hill Education. Source: NASA image courtesy Ozone Hole Watch
 Reaction Energy Diagram for Breakdown of O2
by Cl Atoms

Figure B16.2
©McGraw-Hill Education.