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Chemistry

The Molecular Nature of

Matter and Change

Sixth Edition

Martin S. Silberberg

16-1 Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Chapter 16

Chemical Reactions

16-2

Kinetics: Rates and Mechanisms of Chemical Reactions

Product

16-3

Figure 16.1 A faster reaction (top) and a slower reaction (bottom).

16-4

Figure 16.2 The wide range of reaction rates.

16-5

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.

16-6

Figure 16.3 The effect of surface area on reaction rate.

A hot steel nail glows feebly The same mass of steel wool

when placed in O2. bursts into flame.

16-7

Figure 16.4 Sufficient collision energy is required for a

reaction to occur.

16-8

Expressing the Reaction Rate

concentrations of reactants or products per unit time.

concentration of A at t1 and at t2:

change in concentration of A conc A2 - conc A1 A]

Rate = =- =-

change in time t2 - t1 t

is decreasing. This gives the rate a positive value.

16-9

Table 16.1 Concentration of O3 at Various Times in its

Reaction with C2H4 at 303 K

Concentration of O3

Time (s) (mol/L)

0.0 3.20x10-5 [C2H4]

10.0 rate = -

2.42x10-5 t

20.0 1.95x10-5 [O3]

=-

30.0 1.63x10-5 t

40.0 1.40x10-5

50.0 1.23x10-5

60.0 1.10x10-5

16-10

Figure 16.5 Three types of reaction rates for the reaction of O 3

and C2H4.

16-11

Figure 16.6A Plots of [reactant] and [product] vs. time.

C2H4 + O3 C2H4O + O2

[C2H4] decreases.

[C2H4] [O3]

Rate = - =-

t t

[C2H4O] [O2]

= =

t t

16-12

Figure 16.6B Plots of [reactant] and [product] vs. time.

H2 + I2 2HI

[HI] increases twice as

fast as [H2] decreases.

Rate = - =- =

t t 2 t

Rate = = -2 = -2

t t t

and its numerical value depend on which

substance serves as the reference.

16-13

In general, for the reaction

aA + bB cC + dD

equation, the rate is expressed as:

rate = -

1

=- = 1 [D]

a t b t c t d t

16-14

Sample Problem 16.1 Expressing Rate in Terms of Changes in

Concentration with Time

PROBLEM: Hydrogen gas has a nonpolluting combustion product

(water vapor). It is used as a fuel abord the space shuttle

and in earthbound cars with prototype engines:

2H2(g) + O2(g) 2H2O(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/Ls, at what rate is

[H2O] increasing?

PLAN: We choose O2 as the reference because its coefficient is 1. For

every molecule of O2 that disappears, two molecules of H2

disappear, so the rate of [O2] decrease is the rate of [H2]

decrease. Similarly, the rate at which [O2] decreases is the rate

at which [H2O] increases.

16-15

Sample Problem 16.1

SOLUTION:

[O2] 1 [H2] 1 [H2O]

(a) Rate = - =- =

t 2 t 2 t

1 [H2O] [O2]

=- = -(-0.23 mol/Ls)

2 t t

[H2O]

= 2(0.23 mol/Ls) = 0.46 mol/Ls

t

16-16

The Rate Law

aA + bB cC + dD

Rate = k[A]m[B]n

given reaction at a given temperature.

determined by experiment.

The values of m and n are not necessarily related in any way to

the coefficients a and b.

16-17

Reaction Orders

A reaction has an individual order with respect to or in

each reactant.

For the simple reaction A products:

[A]1 and the reaction is first order with respect to A.

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.

16-18

Figure 16.7 Plots of reactant concentration, [A], vs. time for

first-, second-, and zero-order reactions.

16-19

Figure 16.8 Plots of rate vs. reactant concentration, [A], for

first-, second-, and zero-order reactions.

16-20

Individual and Overall Reaction Orders

For the reaction 2NO(g) + 2H2(g) N2(g) + 2H2O(g):

The rate law is rate = k[NO]2[H2]

The reaction is second order with respect to NO, first

order with respect to H2 and third order overall.

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.

16-21

Sample Problem 16.2 Determining Reaction Orders from Rate

Laws

PROBLEM: For each of the following reactions, use the give rate law

to determine the reaction order with respect to each

reactant and the overall order.

(a) 2NO(g) + O2(g) 2NO2(g); rate = k[NO]2[O2]

(b) CH3CHO(g) CH4(g) + CO(g); rate = k[CH3CHO]3/2

(c) H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq) + 2H2O(l); rate = k[H2O2][I-]

PLAN: We inspect the exponents in the rate law, not the coefficients

of the balanced equation, to find the individual orders. We add

the individual orders to get the overall reaction order.

SOLUTION:

(a) The exponent of [NO] is 2 and the exponent of [O2] is 1, so the

reaction is second order with respect to NO, first order

with respect to O2 and third order overall.

16-22

Sample Problem 16.2

2 2

(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 with respect to H+.

16-23

Determining Reaction Orders

the rate law will have the form

Rate = k[A]m[B]n

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.

16-24

Table 16.2 Initial Rates for the Reaction between A and B

Experiment (mol/Ls) (mol/L) (mol/L)

1 1.75x10-3 2.50x10-2 3.00x10-2

2 3.50x10-3 5.00x10-2 3.00x10-2

3 3.50x10-3 2.50x10-2 6.00x10-2

4 7.00x10-3 5.00x10-2 6.00x10-2

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

16-25

Finding m, the order with respect to A:

We compare experiments 1 and 2, where [B] is kept

constant but [A] doubles:

[A] 2 [A]2 m

2 2 = =

= m n m

Rate 1 k[A] 1 [B] 1 [A]1

[A]1

m

3.50x10-3 mol/Ls 5.00x10-2 mol/L

=

1.75x10 mol/Ls

-3

2.50x10-2 mol/L

16-26

Finding n, the order with respect to B:

We compare experiments 3 and 1, where [A] is kept

constant but [B] doubles:

[B] 3 [B]3 n

3 3 = =

= m n n

Rate 1 k[A] 1 [B] 1 [B]1

[B]1

m

3.50x10-3 mol/Ls 6.00x10-2 mol/L

=

1.75x10 mol/Ls

-3

3.00x10-2 mol/L

16-27

Table 16.3 Initial Rates for the Reaction between O2 and NO

Initial Reactant

Concentrations (mol/L)

Initial Rate

Experiment (mol/Ls) [O2] [NO]

1 3.21x10-3 1.10x10-2 1.30x10-2

2 6.40x10-3 2.20x10-2 1.30x10-2

3 12.48x10-3 1.10x10-2 2.60x10-2

4 9.60x10-3 3.30x10-2 1.30x10-2

5 28.8x10-3 1.10x10-2 3.90x10-2

16-28

Finding m, the order with respect to O2:

We compare experiments 1 and 2, where [NO] is kept

constant but [O2] doubles:

Rate 2 k[O2] m [NO] n [O2] m [O2]2 m

= 2 2 2 =

m n = m

Rate 1 k[O2] 1 [NO] 1 [O2] 1 [O2]1

m

6.40x10-3 mol/Ls 2.20x10-2 mol/L

=

3.21x10-3mol/Ls 1.10x10-2 mol/L

16-29

Sometimes the exponent is not easy to find by inspection.

In those cases, we solve for m with an equation of the form

a = bm:

log a log 1.99

m= = = 0.993

log b log 2.00

fractions.

16-30

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 n

= 12.8x10-3 mol/Ls 2.60x10-2 mol/L

=

Rate 1 [NO]1 3.21x10-3mol/Ls 1.30x10-2 mol/L

log a log 3.99

Alternatively: n= = = 2.00

log b log 2.00

16-31

Sample Problem 16.3 Determining Reaction Orders from Rate Data

system. One of these is

NO2(g) + CO(g) NO(g) + CO2(g) rate = k[NO2]m[CO]n

Use the following data to determine the individual and

overall reaction orders:

Experiment (mol/Ls) (mol/L) [CO]

(mol/L)

1 0.0050 0.10 0.10

2 0.080 0.40 0.10

3 0.0050 0.10 0.20

16-32

Sample Problem 16.3

PLAN: We need to solve the general rate law for m and for n and

then add those orders to get the overall order. We proceed by

taking the ratio of the rate laws for two experiments in which

only the reactant in question changes concentration.

SOLUTION:

To calculate m, the order with respect to NO2, we compare

experiments 1 and 2:

m m

rate 2 k [NO2]m2[CO]n2 [NO2] 2 0.080 0.40

= = =

rate 1 k [NO ] [CO]

m

2 1

n

1 [NO2] 1 0.0050 0.10

16 = (4.0)m so m = 2

16-33

Sample Problem 16.3

1 and 3:

n n

rate 3 k [NO2]m3[CO]n3 [CO] 3 0.0050 0.20

= = =

rate 1 k [NO ] [CO]

m

2 1

n

1 [CO] 1 0.0050 0.10

1.0 = (2.0)n so n = 0

16-34

Sample Problem 16.4 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:

Expt no: 1 2 3 4

Initial rate (mol/Ls) 0.50x10-4 1.0x10-4 2.0x10-4 ?

(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 experiment 4.

PLAN: We find the individual reaction orders by seeing how a change

in each reactant changes the rate. Instead of using

concentrations we count the number of particles.

16-35

Sample Problem 16.4

SOLUTION:

(a) For reactant A (red):

Experiments 1 and 2 have the same number of particles of B, but

the number of particles of A doubles. The rate doubles. Thus the

order with respect to A is 1.

For reactant B (blue):

Experiments 1 and 3 show that when the number of particles of B

doubles (while A remains constant), the rate quadruples. The

order with respect to B is 2.

The overall order is 1 + 2 = 3.

doubles while the number of particles of B does not change. The

rate should double, so rate = 2 x 2.0x10-4 = 4.0x10-4mol/Ls

16-36

Table 16.4 Units of the Rate Constant k for Several Overall

Reaction Orders

Overall

Reaction Units of k

General formula:

Order (t in seconds)

L order-1

0 mol/Ls

(or mol L-1s-1) mol

Units of k =

1 1/s (or s )

-1

unit of t

2 L/mols

(or L mol-1s-1)

3 L2/mol2s

(or L2 mol-2s-1)

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

16-37

Figure 16.9 Information sequence to determine the kinetic

parameters of a reaction.

Series of plots of

concentration vs.

time

each plot.

Initial rates

Compare initial rates when [A] changes and

[B] is held constant (and vice versa).

Reaction

orders Substitute initial rates, orders, and

concentrations into rate = k[A]m[B]n, and

solve for k.

Rate constant (k)

and actual rate law

16-38

Integrated Rate Laws

First-order rate equation:

rate = - [A] = k [A] ln

[A]0

= - kt

t [A]t

Second-order rate equation:

1 1

rate = - [A] = k [A]2 - = kt

t [A]t [A]0

Zero-order rate equation:

t

16-39

Sample Problem 16.5 Determining the Reactant Concentration

after a Given Time

PROBLEM: At 1000oC, 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) If the initial C4H8 concentration is 2.00 M, what is the

concentration after 0.010 s?

(b) What fraction of C4H8 has decomposed in this time?

The problem tells us the reaction is first-order, so we use the

integrated first-order rate law:

[C4H8 ]0

ln = - kt

[C4H8 ]t

16-40

Sample Problem 16.5

SOLUTION:

[C4H8 ]0 2.00 mol/L

(a) ln = - kt ln = (87 s-1)(0.010 s) = 0.87

[C4H8 ]t [C4H8 ]t

2.00 mol/L

= e0.87 = 2.4

[C4H8 ]t

2.4

[C4H8]0 - [C4H8]t 2.00 M - 0.87 M

= = 0.58

[C4H8]0 2.00 M

16-41

Figure 16.10A Graphical method for finding the reaction order

from the integrated rate law.

First-order reaction

ln [A]0 = - 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.

16-42

Figure 16.10B Graphical method for finding the reaction order

from the integrated rate law.

Second-order reaction

integrated rate law

1 1

- = kt

[A]t [A]0

straight-line form

1 1

= kt +

[A]t [A]0

1

A plot of vs. time gives a straight line for a second-order reaction.

[A]

16-43

Figure 16.10C Graphical method for finding the reaction order

from the integrated rate law.

Zero-order reaction

[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 first-order reaction.

16-44

Figure 16.11 Graphical determination of the reaction order for the

decomposition of N2O5.

construct three different plots. Since the

plot of ln [N2O5] vs. time gives a straight

line, the reaction is first order.

16-45

Reaction Half-life

The half-life (t1/2) 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.

t1/2 = ln 2 = 0.693

k k

Radioactive decay is a first-order process. The half-life for a

radioactive nucleus is a useful indicator of its stability.

16-46

Figure 16.12 A plot of [N2O5] vs. time for three reaction half-lives.

ln 2 0.693

t1/2 = =

k k

16-47

Sample Problem 16.6 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:

s.

(b) Find the rate constant of 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)?

16-48

Sample Problem 16.6

SOLUTION:

(a) After 30.0 s, the number of particles of A has decreased from 8

to 4; since [A] has halved in this time, 30.0 s is the half-life of

the reaction. After 60.0 s another half-life will have passed, and

the number of A particles will have halved again. Each A

particle forms one B and one C particle.

t = 60.0 s

16-49

Sample Problem 16.6

(b) The rate constant k is determined using the formula for t1/2 of a

first-order reaction:

0.693 0.693 0.693

t1/2 = so k= = = 2.31 x 10-2 s-1

k t1/2 30.0 s

(c) After 90.0 s, three half-lives will have passed. The number of A

particles will have halved once again, and each A will produced one

B and one C. There will be 1 A, 7 B and 7 C particles.

7

mole fraction of B, XB = = 0.467

1+7+7

16-50

Sample Problem 16.7 Determining the Half-Life of a First-Order

Reaction

PROBLEM: Cyclopropane is the smallest cyclic hydrocarbon.

Because its 60 bond angles allow poor orbital overlap, its

bonds are weak. As a result, it is thermally unstable and

rearranges to propene at 1000C 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?

PLAN: The reaction is first order, so we find t1/2 using the half-life

equation for a first order reaction. Once we know t1/2 we can

calculate the time taken for the concentration to drop to 0.25 of

its initial value.

16-51

Sample Problem 16.7

SOLUTION:

0.693 0.693

(a) t1/2 = = = 0.075 s

k 9.2 s-1

requires 2 half-lives to pass.

16-52

Half-life Equations

concentration.

For a second-order reaction, t1/2 is inversely proportional

to the initial concentration:

1

t1/2 = (second order process; rate = k[A]2)

k[A]0

the initial concentration:

[A]0

t1/2 = (zero order process; rate = k)

2k0

16-53

Table 16.5 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/Ls 1/s L/mols

Half-life [A]0 ln 2 1

2k k k[A]0

Integrated rate law [A]t = -kt + [A]0 ln[A]t = -kt + ln[A]0 1 1

= kt +

in straight-line form [A]t [A]0

1

Plot for straight line [A]t vs. t ln[A]t vs. t vs. t

[A]t

Slope, y intercept -k, [A]0 -k, ln[A]0 k, 1

[A]0

16-54

Collision Theory and Concentration

must collide in order to react.

a larger number of collisions, hence increasing reaction

rate.

the numbers of reactant particles, not their sum.

Concentrations are multiplied in the rate law, not added.

16-55

Figure 16.13 The number of possible collisions is the product,

not the sum, of reactant concentrations.

add another

6 collisions

4 collisions

add another

9 collisions

16-56

Temperature and the Rate Constant

For many reactions, an increase of 10C will double or triple the rate.

as T increases. This is expressed in the Arrhenius

equation:

k = rate constant

k = Ae-Ea/RT A = frequency factor

Ea = activation energy

16-57

Figure 16.14 Increase of the rate constant with temperature for

the hydrolysis of an ester.

(mol/Ls) (L/mols)

1 0.100 0.200 288 1.04x10-3 0.0521

2 0.100 0.200 298 2.20x10-3 0101

3 0.100 0.200 308 3.68x10-3 0.184

4 0.100 0.200 318 6.64x10-3 0.332

16-58

Activation Energy

must exceed a certain energy threshold.

activated state. The energy difference between the

reactants and the activated state is the activation

energy (Ea) for the reaction.

16-59

Figure 16.15 Energy-level diagram for a reaction.

sufficient energy to reach an and is exothermic in the forward

activated state. direction.

16-60

Temperature and Collision Energy

kinetic energy of the particles. This leads to more

frequent collisions and reaction rate increases.

sufficient energy equal to or greater than Ea increases.

Reaction rate therefore increases.

16-61

Figure 16.16 The effect of temperature on the distribution of

collision energies.

16-62

Table 16.6 The Effect of Ea and T on the Fraction (f) of

Collisions with Sufficient Energy to Allow Reaction

50 1.70x10-9

75 7.03x10-14

100 2.90x10-18

T f (at Ea = 50 kJ/mol)

16-63

Calculating Activation Energy

-Ea/RT Ea 1

k = Ae so ln k = ln A -

R T

straight-line form

k2 Ea 1 1

ln =-

k1 R T2 T1

16-64

Figure 16.17 Graphical determination of the activation energy.

Ea 1

ln k = ln A -

R T

16-65

Sample Problem 16.8 Determining the Energy of Activation

2HI(g) H2(g) + I2(g), has rate constants of 9.51x10-9

L/mols at 500. K and 1.10x10-5 L/mols at 600. K.

Find Ea.

PLAN: We are given two rate constants and two temperatures, so we

can use the Arrhenius equation to solve for Ea.

SOLUTION:

-1

k E 1 1 k 1 1

ln 2 = - a so Ea = -R ln 2

k1 R T2 T1 k1 T2 T1

-1

ln 1.10x10-5 L/mols 1 1

Ea = -(8.314 J/molK)

9.51x10-9 L/mols 600.K 500. K

16-66

Molecular Structure and Reaction Rate

have both sufficient energy and the appropriate relative

orientation between the reacting particles.

factor for the reaction.

k = Ae -Ea/RT A = pZ p = orientation probability factor

Z = collision frequency

to the structural complexity of the reactants.

16-67

Figure 16.18 The importance of molecular orientation to an

effective collision.

orientation of these two

molecules that leads to an

effective collision.

16-68

Transition State Theory

formation of a transition state or activated complex.

partial bonds. It is a transitional species partway

between reactants and products.

Transition states cannot be isolated.

potential energy.

The energy required to form the transition state is the activation

energy.

16-69

Figure 16.19 The transition state of the reaction between BrCH3

and OH-.

BrCH3 + OH- Br- + CH3OH

Br and between C and O. It has a trigonal bypyramidal shape.

16-70

Figure 16.20 Depicting the reaction between BrCH3 and OH-.

16-71

Figure 16.21 Reaction energy diagrams and possible transition

states for two reactions.

16-72

Sample Problem 16.9 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 Hrxn for the reaction as written

is -392 kJ. Draw a reaction energy diagram, predict a

structure for the transition state, and calculate Ea(rev).

products are much lower in energy than the reactants. The

small Ea(fwd) (19 kJ) means that the energy of the reactants

lies only slightly below that of the transition state. We

calculate the value of Ea(rev) from the value of H and Ea(fwd).

To predict the transition state structure, we note that one O-O

bond of O3 breaks and a new O-O bond forms.

16-73

Sample Problem 16.9

SOLUTION:

Hrxn = Ea(fwd) Ea(rev)

Ea= 19 kJ

Potential Energy

Hrxn = -392 kJ 411kJ

2O2

Reaction progress

16-74

Reaction Mechanisms

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 reaction stoichiometry reaction order equals

molecularity for an elementary step only.

16-75

Table 16.7 Rate Laws for General Elementary Steps

16-76

Sample Problem 16.10 Determining Molecularity and Rate Laws

for Elementary Steps

PROBLEM: The following elementary steps are proposed for a

reaction mechanism:

(1) NO2Cl(g) NO2(g) + Cl(g)

(2) NO2Cl(g) + Cl(g) NO2(g) + Cl2(g)

(a) Write the overall balanced equation.

(b) Determine the molecularity of each step.

(c) Write the rate law for each step.

PLAN: We find the overall equation from the sum of 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 molecularities as reaction orders.

16-77

Sample Problem 16.10

SOLUTION:

(a) Writing the overall balanced equation:

(2) NO2Cl(g) + Cl(g) NO2(g) + Cl2(g)

2NO2Cl(g) 2NO2(g) + Cl2(g)

Step(2) is bimolecular.

rate2 = k2[NO2Cl][Cl]

16-78

The Rate-Determining Step of a Reaction

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) NO2(g) + NO2(g) NO3(g) + NO(g) [slow; rate-determining]

(2) NO2(g) + CO(g) NO2(g) + CO2(g) [fast]

the rate law for the overall reaction.

16-79

Correlating Mechanism with the Rate Law

The elementary steps must add up to the overall balanced equation.

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.

16-80

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) NO2(g) + F2(g) NO2F(g) + F(g) [slow; rate determining]

(2) NO2(g) + F(g) NO2F(g) [fast]

2NO2(g) + F2(g) 2NO2F(g)

rate2 = k2[NO2][F] correlates with the observed rate law.

16-81

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) + O2(g) NO3(g) [fast]

(2) NO3(g) + NO(g) 2NO2(g) [slow; rate determining]

2NO (g) + O2(g) 2NO2(g)

rate1(rev) = k-1[NO3] rate1(fwd) = rate1(rev)

rate2 = k2[NO3][NO] k1[NO][O2] = k-1[NO3]

16-82

k1

[NO3] = [NO][O2]

k-1

k-1

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.

including the slow (rate-determining) step appear in the

overall rate law.

16-83

Figure 16.22 Reaction energy diagram for the two-step reaction of

(A) NO2 and F2 and of (B) NO and O2.

which occurs at the energy maximum for that step.

16-84

Catalysis: Speeding up a Reaction

without itself being consumed in the reaction.

pathway that has a lower total activation energy than the

uncatalyzed reaction.

reactions.

reaction.

16-85

Figure 16.23 Reaction energy diagram for a catalyzed (green) and

uncatalyzed (red) process.

16-86

Figure 16.24 The catalyzed decomposition of H2O2.

A homogeneous catalyst is in the same phase as the reaction mixture.

added to a solution of H2O2. catalyzes the H2O2 decomposition; the

intermediate Br2 turns the solution orange.

16-87

Figure 16.25 The metal-catalyzed hydrogenation of ethene.

16-88

Figure 16.26A Two models of enzyme action.

having a fixed shape. This shape matches the shape of its

substrate(s). The active site is therefore specific to its substrate.

16-89

Figure 16.26B Two models of enzyme action.

changing shape in order to bind its substrate(s) more

effectively. The active site is still selective towards certain

substrates.

16-90

Chemical Connections

Figure B16.1 Satellite images of the increasing size of the

Antarctic ozone hole (purple).

16-91

Chemical Connections

Figure B16.2 Reaction energy diagram for breakdown of O2

by Cl atoms. (Not drawn to scale.)

16-92

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