Chapter 13

Chemical Kinetics

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further distribution permitted without the prior written consent of McGraw-Hill Education.
 Chemical Kinetics (1 of 2)
Thermodynamics – does a reaction take place?
Kinetics – how fast does a reaction proceed?
Reaction rate is the change in the concentration of a
reactant or a product with time (M/s).

A→B
Δ [ A ] Δ [ A ] = change in concentration of A over
rate = −
Δt time period Δ t
Δ [ B] Δ [ B] = change in concentration of Bover
rate =
Δt time period Δ t
Because [ A ] decreases with time, Δ [ A ] is negative.

© McGraw-Hill Education. 13-2

 Chemical Kinetics (2 of 2)
A→B

Δ [A]
rate = −
Δt
Δ [B]
rate =
Δt

© McGraw-Hill Education. 13-3

 Reaction Rates and Stoichiometry
2A → B
Two moles of A disappear for each mole of B that is
formed.

1 Δ [A] Δ [ B]
rate =
− rate =
2 Δt Δt

aA + bB → c C + d D
1 Δ [A] 1 Δ [ B] 1 Δ [ C ] 1 Δ [ D ]
rate =
− =
− ==
a Δt b Δt c Δt d Δt

© McGraw-Hill Education. 13-4

 Example 13.1 (1 of 2)

Write the rate expressions for the following reactions in

terms of the disappearance of the reactants and the
appearance of the products:
( a ) I− ( aq ) + OCl− ( aq ) → Cl− ( aq ) + OI− ( aq )
( b ) 4NH3 ( g ) + 5O2 ( g ) → 4NO ( g ) + 6H 2 O ( g )

© McGraw-Hill Education. 13-5

 Example 13.1 (2 of 2)
Strategy
To express the rate of the reaction in terms of the change in concentration
of a reactant or product with time, we need to use the proper sign (minus
or plus) and the reciprocal of the stoichiometric coefficient.

Solution
(a) Because each of the stoichiometric coefficients equals 1,
Δ  I −  Δ OCl−  Δ Cl−  Δ OI − 
rate =
− =
− = =
Δt Δt Δt Δt

(b) Here the coefficients are 4, 5, 4, and 6, so

1 Δ [ NH 3 ] 1 Δ [ O 2 ] 1 Δ [ NO ] 1 Δ [ H 2 O ]
rate =
− =
− = =
4 Δt 5 Δt 4 Δt 6 Δt

© McGraw-Hill Education. 13-6

 Example 13.2 (1 of 4)
Consider the reaction

4NO 2 ( g ) + O 2 ( g ) → 2N 2 O5 ( g )

Suppose that, at a particular moment during the reaction,

molecular oxygen is reacting at the rate of 0.024 M/s.

a) At what rate is N2O5 being formed?

b) At what rate is NO2 reacting?

© McGraw-Hill Education. 13-7

 Example 13.2 (2 of 4)
Strategy
To calculate the rate of formation of N2O5 and disappearance of
NO2, we need to express the rate of the reaction in terms of the
stoichiometric coefficients as in Example 13.1:

1 Δ [ No 2 ] Δ [ O 2 ] 1 Δ [ N 2 O5 ]
rate =
− =
− =
4 Δt Δt 2 Δt
We are given

Δ [O2 ]
= − 0.024 M s
Δt

where the minus sign shows that the concentration of O2 is

decreasing with time.
© McGraw-Hill Education. 13-8
 Example 13.2 (3 of 4)

Solution
a) From the preceding rate expression we have

Δ [O2 ] 1 Δ [ N 2 O5 ]
− =
Δt 2 Δt

Therefore

Δ [ N 2 O5 ]
− 2 ( − 0.024 M s ) =
= 0.048 M s
Δt

© McGraw-Hill Education. 13-9

 Example 13.2 (4 of 4)
b) Here we have

1 Δ [ NO 2 ] Δ [O2 ]
− =
−
4 Δt Δt

So
Δ [ NO 2 ]
4 ( −0.024 M s ) =
= − 0.096 M s
Δt

© McGraw-Hill Education. 13-10

 The Rate Law (1 of 2)
The rate law expresses the relationship of the rate of a
reaction to the rate constant and the concentrations of the
reactants raised to some powers.

aA + bB → cC + dD

Rate = k [ A ] [ B]
x y

Reaction is xth order in A

Reaction is yth order in B
Reaction is (x+y)th order overall

© McGraw-Hill Education. 13-11

 The Rate Law (2 of 2)
F2 ( g ) + 2ClO 2 ( g ) → 2FClO 2 ( g )
Table 13.2 Rate data for reaction between
rate = k [ F2 ] [ClO2 ] F2 and ClO2
x y

[F2 ] ( M ) [ClO 2 ] ( M ) Initial Rates ( M s )

1.010 0.010 1.2×10−3
Double [ F2 ] with [ ClO 2 ] constant 2.010 0.040 4.8×10−3
Rate Doubles 3.020 0.010 2.4×10−3
x=1

Quadruple [ ClO 2 ] with [ F2 ] contant rate = k [ F2 ][ ClO 2 ]

Rate Quadruples
y=1

© McGraw-Hill Education. 13-12

 Rate Laws
Rate laws are always determined experimentally.

Reaction order is always defined in terms of reactant (not product)

concentrations.

The order of a reactant is not related to the stoichiometric

coefficient of the reactant in the balanced chemical equation.

F2 ( g ) + 2ClO 2 ( g ) → 2FClO 2 ( g )

rate = k [ F2 ][ ClO 2 ]
−1

© McGraw-Hill Education. 13-13

 Example 13.3 (1 of 6)
The reaction of nitric oxide with hydrogen at 1280°C is
2NO ( g ) + 2H 2 ( g ) → N 2 ( g ) + 2H 2 O ( g )

From the following data collected at this temperature, determine

a) the rate law
b) the rate constant
c) the rate of the reaction when [ NO
= ] 12.0 × 10−3 M and
[ H2=] 6.0 ×10−3 M
Experiment [ NO] ( M ) [H2 ]( M ) Initial Rates ( M s )
1 5.0 ×10−3 2.0 ×10−3 1.3 ×10−5
2 10.0 ×10−3 2.0 ×10−3 5.0 ×10−5
3 10.0 ×10−3 4.0 ×10−3 10.0 ×10−5

© McGraw-Hill Education. 13-14

 Example 13.3 (2 of 6)
Strategy
We are given a set of concentration and reaction rate data and asked to
determine the rate law and the rate constant.

We assume that the rate law takes the form

rate = k [ NO ] [ H 2 ]
x y

How do we use the data to determine x and y?

Once the orders of the reactants are known, we can calculate k from any
set of rate and concentrations.

Finally, the rate law enables us to calculate the rate at any concentrations
of NO and H2.
© McGraw-Hill Education. 13-15
 Example 13.3 (3 of 6)
Solution
(a) Experiments 1 and 2 show that when we double the concentration of
NO at constant concentration of H2, the rate quadruples.Taking the ratio
of the rates from these two experiments

k (10.0 × 10 M ) ( 2.0 × 10 M)
−3 x −3 y
rate 2 5.0 × 10 M s
−5
= = ≈ 4
rate1 1.3 × 10−5 M s k ( 5.0 × 10−3 M ) ( 2.0 × 10 M)
x −3 y

Therefore,

(10.0 × 10 M )=
−3 x

2=
x
4
( 5.0 × 10 M )
−3 x

or x = 2, that is, the reaction is second order in NO.

© McGraw-Hill Education. 13-16
 Example 13.3 (4 of 6)
Experiments 2 and 3 indicate that doubling [H2] at constant [NO]
doubles the rate. Here we write the ratio as
k (10.0 × 10 M ) ( 4.0 × 10 M )
−3 x −3 y
rate3 10.0 × 10 M s
−5
= = 2=
rate 2 5.0 × 10−5 M s k (10.0 × 10−3 M ) ( 2.0 × 10−3 M )
x y

Therefore,

( 4.0 × 10−3 M )= 2=y 2

y

( 2.0 × 10 M )
−3 y

or y = 1, that is, the reaction is first order in H2. Hence the rate
law is given by
rate = k [ NO ] [ H 2 ]
2

which shows that it is a (2 + 1) or third-order reaction overall.

© McGraw-Hill Education. 13-17
 Example 13.3 (5 of 6)
b) The rate of constant k can be calculated using the data
from any one of the experiments. Rearranging the rate
law, we get
rate
k=
[ NO] [ H 2 ]
2

The data from experiment 2 give us

5.0 × 10−5 M s
k=
(10.0 × 10 M ) ( 2.0 × 10−3 M )
−3 2

= 2.5 × 102 M 2 .s

© McGraw-Hill Education. 13-18

 Example 13.3 (6 of 6)
c) Using the known rate constant and concentrations of NO and
H2, we write

( 2.5 × 10 M .s ) (1 2.0 × 10 M ) ( 6.0 × 10−3 M )

2 2 −3 2
rate =
= 2.2 × 10−4 M s

Comment
Note that the reaction is first order in H2, whereas the
stoichiometric coefficient for H2 in the balanced equation is 2.
The order of a reactant is not related to the stoichiometric
coefficient of the reactant in the overall balanced equation.
© McGraw-Hill Education. 13-19
 Chapter 14

Chemical Equilibrium

© 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.
21

14.1 The Concept of Equilibrium and the Equilibrium

Constant

Few chemical reactions proceed in only one direction. Most are

reversible, at least to some extent. At the start of a reversible
process, the reaction proceeds toward the formation of
products. As soon as some product molecules are formed, the
reverse process begins to take place and reactant molecules
are formed from product molecules.

Chemical equilibrium is achieved when the rates of the forward

and reverse reactions are equal and the concentrations of the
reactants and products remain constant.
 N2O4 ⇋ 2NO2
Figure 14.1 A reversible reaction between N2O4 and NO2 molecules.

• As a system approaches
equilibrium, both the
forward and reverse
reactions are occurring.
• At equilibrium, the
forward and reverse
reactions are proceeding
at the same rate.
 The Equilibrium Constant
• Forward reaction:
N2O4 (g) → 2 NO2 (g)
• Rate law:
Rate = kf [N2O4]

• Reverse reaction:
2 NO2 (g) → N2O4 (g)
• Rate law:
Rate = kr [NO2]2
 The Equilibrium Constant
• Therefore, at equilibrium
Ratef = Rater
kf [N2O4] = kr [NO2]2
• Rewriting this, it becomes kf [NO2]2
=
kr [N2O4]
The ratio of the rate constants is a constant
at that temperature, and the expression
becomes
kf [NO2] 2
where K is
K= =
the equilibrium
constant. kr [N2O4]
25
26

Table 14.1 shows some experimental data for the reaction just described at
25°C. The gas concentrations are expressed in molarity, which can be
calculated from the number of moles of gases present initially and at
equilibrium and the volume of the flask in liters.
Note that the equilibrium concentrations of NO2 and N2O4 vary, depending
on the starting concentrations. We can look for relationships between [NO2]
and [N2O4] present at equilibrium by comparing the ratio of their
concentrations. The simplest ratio, that is, [NO2]/[N2O4], gives scattered
values.
But if we examine other possible mathematical relationships, we find that
the ratio [NO2]2/[N2O4] at equilibrium gives a nearly constant value that
averages 4.63 × 10−3, regardless of the initial concentrations present:

where K is a constant. Note that the exponent 2 for [NO2] in this

expression is the same as the stoichiometric coefficient for
NO2 in the reversible reaction.
What Does the Value of K Mean?

• If K >> 1, the reaction

is product-favored;
product predominates
at equilibrium.
What Does the Value of K Mean?

• If K >> 1, the reaction

is product-favored;
product predominates
at equilibrium.

• If K << 1, the reaction is

reactant-favored;
reactant predominates
at equilibrium.
29

14.2 Writing Equilibrium Constant Expressions

Homogeneous Equilibria
The term homogeneous equilibrium applies to reactions in
which all reacting species are in the same phase. An example
of homogeneous gas-phase equilibrium is the dissociation of
N2O4. The equilibrium constant, as given in

N2O4 (g) 2 NO2 (g)

[NO2]2
Kc = [N O ]
2 4
Note that the subscript in Kc indicates that the concentrations of
the reacting species are expressed in molarity or moles per liter.
The Equilibrium Constant for Homogeneous
Equilibria

• To generalize this expression, consider the

reaction

aA + bB cC + dD
• The equilibrium expression for this
reaction would be
[C]c[D]d
Kc =
[A]a[B]b
What Are the Equilibrium Expressions for These
Homogeneous Equilibria?
32
33
34

Heterogeneous Equilibria
As you might expect, a heterogeneous equilibrium results
from a reversible reaction involving reactants and products that
are in different phases. For example, when calcium carbonate is
heated in a closed vessel, the following equilibrium is attained:
The Concentrations of Solids and Liquids are
Essentially Constant
Both can be obtained by dividing the density of
the substance by its molar mass—and both of
these are constants at constant temperature.

• C(s) + H2O(g)→ CO(g) + H2(g)

C(s) final
C(s) initial
same CONCENTRATION of C(s)
The Concentrations of Solids and Liquids
Are Essentially Constant

Therefore, the concentrations of solids and

liquids do not appear in the equilibrium
expression

PbCl2 (s) Pb2+ (aq) + 2 Cl−(aq)

Kc = [Pb2+] [Cl−]2
C(s) + H2O(g) → CO(g) + H2(g)

[CO(g)] [H2(g)]
Kc = X
[C(s)] [H2O(g)]

[CO(g)] [H2(g)]
Kc =
[H2O(g)]
SAMPLE EXERCISE Writing Equilibrium-Constant Expressions
for Heterogeneous Reactions
Write the equilibrium-constant expression for Kc for each of the following reactions:

Solution
(a) The equilibrium-constant expression is

Because H2O appears in the reaction as a pure liquid, its concentration does not appear in the
equilibrium-constant expression.

(b) The equilibrium-constant expression is

Because SnO2 and Sn are both pure solids, their concentrations do not appear in the equilibrium-
constant expression.

PRACTICE EXERCISE
Write the following equilibrium-constant expressions:
39
 Manipulating Equilibrium Constants
The equilibrium constant of a reaction in the
reverse reaction is the reciprocal of the
equilibrium constant of the forward reaction.

[NO2]2
N2O4 (g) 2 NO2 (g) Kc = [N O ] = 0.212 at 100°C
2 4
[N2O4] 1
2 NO2 (g) N2O4 (g) cK =
[NO2]2
=
0.212
= 4.72 at 100°C
 Manipulating Equilibrium Constants
The equilibrium constant of a reaction that has been
multiplied by a number is the equilibrium constant raised to
a power that is equal to that number.

[NO2]2
N2O4 (g) 2 NO2 (g) Kc = [N O ] = 0.212 at 100°C
2 4

[NO2]4
2 N2O4 (g) 4 NO2(g) Kc = [N O ]2 = (0.212)2 at 100°C
2 4
42