Chapter 5

Kinetics: Rates and Mechanisms of

Chemical Reactions

16-1
 Kinetics: Rates and Mechanisms of Chemical Reactions

5.1 Focusing on Reaction Rate

5.2 Expressing the Reaction Rate

5.3 The Rate Law and Its Components

5.4 Integrated Rate Laws: Concentration Changes over Time

5.5 Collision Theory and Concentration

5.6 Reaction Mechanisms: The Steps from Reactant to

Product

5.7 Catalysis: Speeding Up a Reaction

16-2
 So far chemical changes tell us???

1- reactant and product form (type and amount)

2- a balanced equation to calculate yield
•BUT DID NOT EXPLAIN 3 DYNAMIC
ASPECT.
– How fast is the reaction proceeding
– How far will the reaction proceed toward
completion
– Will the reaction proceed by releasing energy or by
requiring it
16-3
 This chapter answer Question 1

• Chemical kinetics; study of reaction rate

• Change of concentration of reactant or product
as a function of time.
• Different reactions have different rates.
• Knowing reaction rate is important
– Medicine acts can save life
– Faster polymer form can make more profit

16-4
 Figure 16.1 A faster reaction (top) and a slower reaction (bottom).

16-5
 5.1 FOCUSING ON 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 16.4 Sufficient collision energy is required for a
reaction to occur.

16-7
 5.2 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 A2 – conc A1 A]
Rate = =– =–
change in time t2 – t1 t

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.

16-8
 Figure 16.6A Plots of [reactant] and [product] vs. time.
C2H4 + O3 → C2H4O + O2

[O2] increases just as fast as

[C2H4] decreases.

[C2H4] [O3]
Rate = – = –
t t
[C2H4O] [O2]
= =
t t

16-9
 Figure 16.6B Plots of [reactant] and [product] vs. time.
H2 + I2 → 2HI
[HI] increases twice as
fast as [H2] decreases.

[H2] [I2] 1 [HI]

Rate = – =– =
t t 2 t

[HI] [H2] [I2]

Rate = = –2 = –2
t t t

The expression for the rate of a reaction

and its numerical value depend on which
substance serves as the reference.

16-10
 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 [A] 1 [B] = 1 [C] = 1 [D]

rate = – =–
a t b t c t d t

16-11
 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 aboard 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/L·s, 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 ½ the rate of [H2]
decrease. Similarly, the rate at which [O2] decreases is ½ the rate
at which [H2O] increases.

16-12
 Sample Problem 16.1

SOLUTION:
[O2] 1 [H2] 1 [H2O]
(a) Rate = – =– =
t 2 t 2 t

(b) Calculating the rate of change of [H2O]:

1 [H2O] [O2]
=– = – (– 0.23 mol/L·s)
2 t t

[H2O]
= 2(0.23 mol/L·s) = 0.46 mol/L·s
t

16-13
 5.3 The Rate Law

For any general reaction occurring at a fixed temperature

aA + bB → cC + dD

Rate = k[A]m[B]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.

16-14
 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.
Rate = k[A]1 = k[A]
If the rate quadruples when [A] doubles, the rate depends
on [A]2 and the reaction is second order with respect to [A].
Rate = k[A]2
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.
Rate = k[A]0 = k(1) = k
16-15
 Plots of reactant concentration, Plots of rate vs. reactant
[A], vs. time for first-, second-, concentration, [A], for first-,
and zero-order reactions. second-, and zero-order reactions.

16-16
 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.

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.

16-17
 Determining Reaction Orders

For the general reaction A + 2B → C + D,

the rate law will have the form
Rate = k[A]m[B]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.

16-18
 Sample Problem 16.3 Determining Reaction Orders from Rate Data

PROBLEM: Many gaseous reactions occur in a car engine and exhaust

systems. 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:

Initial Rate Initial [NO2] Initial

Experiment (mol/L·s) (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

16-19
 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

The reaction is second order in NO2.

16-20
 Sample Problem 16.3

To calculate n, the order with respect to CO, we compare experiments

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

The reaction is zero order in CO.

rate = k[NO2]2[CO]0 or rate = k[NO2]2

16-21
 Table 16.3 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/L·s
(or mol L-1s-1) mol
Units of k =
1 1/s (or s )
-1 unit of t

2 L/mol·s
(or L mol-1s-1)
3 L2/mol2·s
(or L2 mol-2s-1)

The value of k is easily determined from experimental rate

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

16-22
 5.4 Integrated Rate Laws
An integrated rate law includes time as a variable.
First-order rate equation:
rate = – [A] = k [A] ln
[A]0
= kt
t [A]t
Second-order rate equation:
[A] 1 1
rate = – = k [A]2 – = kt
t [A]t [A]0
Zero-order rate equation:
[A] [A]t – [A]0 = –kt
rate = – = k [A]0
t

16-23
 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?

PLAN: We must find the concentration of cyclobutane at time t, [C4H8]t.

The problem tells us the reaction is first-order, so we use the
integrated first-order rate law:
[C4H8 ]0
ln = kt
[C4H8 ]t

16-24
 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

[C4H8]t = 2.00 mol/L = 0.83 mol/L

2.4

(b) Finding the fraction that has decomposed after 0.010 s:

[C4H8]0 - [C4H8]t 2.00 M – 0.83 M
= = 0.58
[C4H8]0 2.00 M

16-25
 Graphical method for finding the reaction order from the
integrated rate law.
First-order reaction Second-order reaction Zero-order reaction

integrated rate law

integrated rate law integrated rate law
[A]0 1 1
ln = kt – = kt [A]t - [A]0 = –kt
[A]t [A]t [A]0
straight-line form
straight-line form straight-line form
1 1 [A]t = –kt + [A]0
ln[A]t = –kt + ln[A]0 = kt +
[A]t [A]0
16-26
 Figure 16.11 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.

16-27
 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
t½= =
k k

The half-life for a first-order reaction is a constant.

16-28
 Figure 16.12 A plot of [N2O5] vs. time for three reaction half-lives.

for a first-order process

ln 2 0.693
t1/2 = =
k k

16-29
 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 1000ºC via the following first-
order reaction:
H2
C

H2C CH2 (g) CH3 CH CH2 (g)
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 t½using the half-life
equation for a first order reaction. Once we know t½ we can
calculate the time taken for the concentration to drop to 0.25 of
its initial value.

16-30
 Sample Problem 16.7

SOLUTION:
0.693 0.693
(a) t½ = = = 0.075 s
k 9.2 s–1

(b) For the initial concentration to drop to one-quarter of its value

requires 2 half-lives to pass.

Time = 2(0.075 s) = 0.15 s

16-31
 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:
1
t1/2 = (second order process; rate = k[A]2)
k[A]0

For a zero-order reaction, t1/2 is directly proportional to

the initial concentration:
[A]0
t1/2 = (zero order process; rate = k)
2k

16-32
 Table 16.4 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]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

16-33
 5.5 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.

16-34
 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 = rate constant
-Ea/RT A = frequency factor
k = Ae
Ea = activation energy

Higher T larger k increased rate

16-35
 Figure 16.14 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.

16-36
 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.

16-37
 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.

Smaller Ea larger f larger k increased rate

*f = fraction of collisions

16-38
 Calculating Activation Energy
Ea can be calculated from the Arrhenius equation:
Ea/RT
– Ea 1
k = Ae so ln k = ln A –
R T
straight-line form

If data is available at two different temperatures:

k2 Ea 1 1
ln =– –
k1 R T2 T1

16-39
 Figure 16.17 Graphical determination of the activation energy.

Ea 1
ln k = ln A –
R T

16-40
 Sample Problem 16.8 Determining the Energy of Activation

PROBLEM: The decomposition of hydrogen iodide,

2HI(g) → H2(g) + I2(g), has rate constants of 9.51x10-9
L/mol·s at 500. K and 1.10x10-5 L/mol·s 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/mol·s 1 1
Ea = – (8.314 J/mol·K) –
9.51x10-9 L/mol·s 600.K 500. K

= 1.76x105 J/mol = 1.76x102 kJ/mol

16-41
 5.6 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.

16-42
 Table 16.6 Rate Laws for General Elementary Steps

Elementary Step Molecularity Rate Law

A product Unimolecular Rate = [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]

16-43
 Sample Problem 16.10 Determining Molecularity 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 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.

16-44
 Sample Problem 16.10
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) + CCl4(g)
Cl2(g) + CHCl3(g) → HCl(g) + CCl4(g)
(b) Determining the molecularity of each step: The first step has one reactant, Cl 2,
so it is unimolecular. The second and third steps have two reactants (Cl and
CHCl3; Cl(g) + CCl3), so they are bimolecular.
(c) Writing rate laws for the elementary steps:
(1) Rate1 = k1[Cl2]
(2) Rate2 = k2[Cl][CHCl3]
(3) Rate3 = k3[Cl][CCl3]

16-45
 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) NO2(g) + NO2(g) → NO3(g) + NO(g) [slow; rate-determining]
(2) NO3(g) + CO(g) → NO2(g) + CO2(g) [fast]

Observed rate law: rate = k[NO2]2

The rate law for the rate-determining step becomes

the rate law for the overall reaction.

16-46
 5.7 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 H or the overall yield for

a reaction.

16-47
 Figure 16.23 Reaction energy diagram for a catalyzed (green) and
uncatalyzed (red) process.

16-48