07 Chapter 15 Equilibrium

GENERAL CHEMISTRY
PRINCIPLES AND MODERN APPLICATIONS

ELEVENTH EDITION
PETRUCCI HERRING MADURA BISSONNETTE
Principles of Chemical
Equilibrium 15
PHILIP DUTTON
UNIVERSITY OF WINDSOR
DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY
Slide 15 - 1 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

CONTENTS
Solutions and their
Physical Properties 15-1 The Nature of the Equilibrium
State
15-2 The Equilibrium Constant
Expression
15-3 Relationships Involving
Equilibrium Constants
15-4 The Magnitude of an Equilibrium

Constant
15-5 Predicting the Direction of Net
Chemical Change
15-6 Altering Equilibrium Conditions:

Le Châtelier’s Principle
15-7 Equilibrium Calculations: Some
Illustrative Examples

Relation Between Rate Constants And Equilibrium
Constants For Elementary Reactions
k1
k1 [NO]2 = k-1 [N2O2]
2 NO(g) k-1
N2O2(g)
Reaction slows down k1 [N2O2]

Rate = k1 [NO] 2 K= =
as NO is consumed k-1 [NO]2
Reaction speeds up as
Rate = k-1 [N2O2] N2O2 is produced
For multistep reactions:
No matter how different the rate k1 k2 k3
constants are, there is a time where K= x x …
both reactions occur at the same rate. k-1 k-2 k-3
Slide 3 of 32 General Chemistry: Chapter 15 05/07/23Copyright © 2011 Pearson Canada Inc.

Simple Reaction Profiles
H = Eaf  Ear
no reaction at RT no reaction at RT k = A eEa/RT
(kinetic control), K>>1 (kinetic control), K<<1
K = kf / kr
Potential Energy
Potential Energy
exothermic
Potential Energy
Fast equilibrium, K >1
slow
Eaf Ear
H
Reaction Progress Reaction Progress Reaction Progress

fast, endothermic,
fast, exothermic, no reaction, K<<1 Fast equilibrium, K <1
Potential Energy
Potential Energy
Potential Energy
reaction goes to (thermodynamic

completion, K>>1 control)

15-1 The Nature of the Equilibrium State
In a closed reaction vessel at constant temperature, a reaction proceeds

spontaneously toward equilibrium. At equilibrium, the reaction quotient Q
attains the same constant value, K, irrespective of the starting amounts of
reactants and products.
2 Cu2+(aq) + Sn2+(aq) 2 Cu+(aq) + Sn4+(aq) (15.1)

k1
2 Cu2+(aq) + Sn2+(aq) 2 Cu+(aq) + Sn4+(aq)
k-1
• This is a multistep reaction because an elementary process

would be termolecular.
• The equilibrium constant includes the rate constants of the
individual steps.
k1 k2 k3 [Cu+]2[Sn4+]
K= x x … =
k-1 k-2 k-3 [Cu2+]2[Sn2+]
• The equilibrium constant expression contains the stoichiometric

factors as exponents because the equilibrium concentrations are
of interest not concentrations at a given time.
• K must be the same for all experiments.

1. The reaction quotient Q has the same value at equilibrium
no matter what the starting concentrations are.
2. The equilibrium value of Q is represented by the symbol
K and is called the equilibrium constant

incorrect
FIGURE 15-1
Three approaches to equilibrium in the reaction
correct
FIGURE 15-3
Three approaches to equilibrium in the reaction
Slide 10 of 32 General Chemistry: Chapter 15 Copyright © 2011 Pearson Canada Inc.

Activity
Accounts for non-ideal behaviour in solutions and gases.

An effective concentration.
Thermodynamic concept introduced by Lewis.
Dimensionless ratio referred to a chosen reference state.
B[B]
aB = 0 = B[B]
cB0 is a standard reference state
cB
= 1 mol L-1 (ideal conditions)

Activity
A similar expression applies to gases
BPB
aB = 0 = BPB
PB0 is a standard reference state
PB
= 1 bar (ideal conditions)

(15.2)
2
(15.3)

The Dynamic Nature of the Equilibrium
Condition
The equilibrium condition is dynamic, with the forward and reverse
reactions occurring not only indefinitely but also at exactly the same rate.
AgI(s) Ag+(aq) + I−(aq)

FIGURE 15-2
Dynamic equilibrium illustrated

aA + bB + … cC + dD + … (15.4)
(15.5)
(15.6)
(15.7)
in 15.7, equilibrium values of a are implied

Equilibria Involving Gases
(15.8)
∆ν = (c + d +…) − (a + b +…)
The sum of coefficients The sum of coefficients

for the products for the reactants
(15.9)
(15.10)

Equilibria in Aqueous Solution
(15.11)
(15.12)
(15.13)

Equilibria Involving Pure Liquids and Solids
2 Al(s) + 6 H+(aq) 2 Al3+(aq) + 3 H2(g)
Pure solids and liquids are not included in equilibrium constant expressions
Recall from Chapter 13

C(s) + H2O(g) CO(g) + H2(g)

CaCO3(s) CaO(s) + CO2(g)

Adding additional
CaCO3 or CaO has
no effect on the
equilibrium
FIGURE 15-3
Equilibrium in the reaction CaCO3(s) CaO(s) + CO2(g)

15-3 Relationships Involving the
Equilibrium Constant
Relationship of K to the Balanced Chemical Equation
• When we reverse an equation, we invert the value of K.

• When we multiply the coefficients in a balanced equation
by a common factor we raise the equilibrium constant to
the corresponding power.
• When we divide the coefficients in a balanced equation by
a common factor we take the corresponding root of the
equilibrium constant.

Copyright © 2017 Pearson Canada
Slide 25 of 16
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Combining Equilibrium Constant Expressions
N2O(g) + ½O2(g) 2 NO(g) Kc= ?
N2(g) + ½O2(g) N2O(g) K(a)= 5.4×10−19 (15.15)
N2(g) + O2(g) 2 NO(g) K(b)= 4.6×10−31 (15.16)

N2(g) + ½O2(g) N2O(g) K(a)= 5.410−19 (15.15)
(a) N2O(g) N2(g) + ½O2(g) K’(a)= 1/5.410−19 = 1.9 1018
(b) N2(g) + O2(g) 2 NO(g) K(b)= 4.610−31 (15.16)
Overall: N2O(g) + ½O2(g) 2 NO(g) Koverall= ?
= 1.9×1018 × 4.6×10−31 = 8.5×10−13

N2(g) + ½O2(g) N2O(g) K(a)= 5.410−19 (15.15)
(a) N2O(g) N2(g) + ½O2(g) K’(a)= 1/5.410−19 = 1.9 1018
(b) N2(g) + O2(g) 2 NO(g) K(b)= 4.610−31 (15.16)
= 1.9×1018 × 4.6×10−31 = 8.5×10−13

N2(g) + ½O2(g) N2O(g) K(a)= 5.410−19 (15.15)
(a) N2O(g) N2(g) + ½O2(g) K’(a)= 1/5.410−19 = 1.9 1018
(b) N2(g) + O2(g) 2 NO(g) K(b)= 4.610−31 (15.16)
= 1.9×1018 × 4.6×10−31 = 8.5×10−13

N2(g) + ½O2(g) N2O(g) K(a)= 5.410−19 (15.15)
(a) N2O(g) N2(g) + ½O2(g) K’(a)= 1/5.410−19 = 1.9 1018
(b) N2(g) + O2(g) 2 NO(g) K(b)= 4.610−31 (15.16)
= 1.9×1018 × 4.6×10−31 = 8.5×10−13

N2(g) + ½O2(g) N2O(g) K(a)= 5.410−19 (15.15)
(a) N2O(g) N2(g) + ½O2(g) K’(a)= 1/5.410−19 = 1.9 1018
(b) N2(g) + O2(g) 2 NO(g) K(b)= 4.610−31 (15.16)
= 1.9×1018 × 4.6×10−31 = 8.5×10−13

Relationship Between KP and Kc for Reactions
Involving Gases
(15.17)

15-4 The Magnitude of the Equilibrium
Constant.
A very large value of K signifies that the reaction, as written, exhibits a
strong tendency to go to completion. An equilibrium mixture contains
about as much product as can be formed from the given initial amounts
of reactants.
A very small value of K signifies that the reaction, as written, exhibits very
little tendency to occur. An equilibrium mixture contains reactants, in
essentially their initial amounts, and very small amounts of products.

H = Eaf  Ear
K = kf / kr
Potential Energy
Potential Energy
exothermic
Potential Energy
slow
Eaf Ear
H

fast, exothermic, fast, endothermic, Fast equilibrium, K <1
Potential Energy
Potential Energy
Potential Energy
reaction goes to no reaction, K<<1

completion, K>>1

H = Eaf  Ear
K = kf / kr
Potential Energy
Potential Energy
exothermic
Potential Energy
slow
Eaf Ear
H

Potential Energy
Potential Energy
Potential Energy

completion, K>>1

2 H2(g) + O2(g) 2 H2O(l) K = 1.4×1083
A reaction goes essentially to completion if K =1010 and not at all if K =10−10.

15-5 Predicting the Direction of Net Change.
K = 1.48
[Cu2+]2
FIGURE 15-4
Predicting the direction of net change

15-6 Altering Equilibrium Conditions:
Le Châtelier’s Principle
When an equilibrium system is subjected to a change in temperature, pressure, or

concentration of a reacting species, the system responds by attaining a new
equilibrium that partially offsets the impact of the change.

Effect of Changing the Amounts of Reacting
Species on Equilibrium

FIGURE 15-5
Changing equilibrium conditions by changing the amount of a reacting species
2 SO2(g) + O2(g) 2 SO3(g), Kc= 2.8102 at 1000 K
Original equilibrium Immediately following disturbance
[SO3]2
Q= = Kc Q > Kc
[SO2] [O2]
2
k1
2 SO2(g) + O2(g) 2 SO3(g)
k−1

Effect of Changes in Pressure or Volume
on Equilibrium
1. Add or remove a gaseous reactant or product.
Changes Pgas.
2. Adding an inert gas to the constant volume reaction

mixture.
Relative partial pressures are unchanged.
3. Change the pressure by changing the volume of the

system.

2 SO2(g) + O2(g) 2 SO3(g) Kc = 2.8102 at 1000 K
nSO3 2
[SO3]2 V nSO32
Kc = = = V
[SO2]2[O2] n 2 nO 2 nSO22 nO2
SO2
V V
nSO32
If V is reduced by a factor of 10, then must
increase by a factor of 10 nSO22 nO2

FIGURE 15-6
Effect of a pressure change on equilibrium in the reaction
2 SO2(g) + O2(g) 2 SO3(g)
When the volume of an equilibrium mixture of gases is reduced, a net change
occurs in the direction that produces fewer moles of gas. When the volume is
increased, a net change occurs in the direction that produces more moles of gas.

Effect of Temperature on Equilibrium
Raising the temperature of an equilibrium mixture shifts the equilibrium

condition in the direction of the endothermic reaction. Lowering the
temperature causes a shift in the direction of the exothermic reaction.
For endothermic reactions, K increases as temperature increases. For

exothermic reactions, K decreases as temperature increases.

H = Eaf  Ear
K = kf / kr
Potential Energy
Potential Energy
exothermic
Potential Energy
slow
Eaf Ear
H

Potential Energy
Potential Energy
Potential Energy

completion, K>>1

Consider a slow and a fast reaction
slower Does the rate of a slow

reaction or the rate of
-Ea the fast reaction
faster R increase more when T
is increasing?
Slow reactions
have high Ea.
Fast reactions
have low Ea
FIGURE 14-12
Temperature dependence of the rate constant k for a reaction

H = Eaf  Ear
K = kf / kr
Potential Energy
Potential Energy
exothermic
Potential Energy
slow
Eaf Ear
H

Potential Energy
Potential Energy
Potential Energy

completion, K>>1

Effect of a Catalyst on Equilibrium
A catalyst has no effect on the condition of equilibrium in a reversible
reaction.
Sulfuric acid is produced from SO3

SO3(g) + H2O(l) H2SO4(aq)

15-7 Equilibrium Calculations:
Some Illustrative Examples.
Five numerical examples are given in the text that
illustrate ideas that have been presented in this chapter.
Refer to the “comments” which describe the
methodology. These will help in subsequent chapters.
Exercise your understanding by working through the
examples with a pencil and paper.

Calculating Equilibrium Quantities from
Kc and Kp Values
• When starting with initial reactants and no products and
with the known value of the equilibrium constant, these
data are used to calculate the amount of substances present
at equilibrium.
• Typically, an ICE table is constructed, and the symbol x is
used to identify one of the changes in concentration that
occurs in establishing equilibrium.
• Then, all the other concentration changes are related to x,
the appropriate terms are substituted into the equilibrium
constant expression, and the equation solved for x.
M

End of Chapter

Example 14.11
In a 10.0-L vessel at 1000 K, 0.250 mol SO2
and 0.200 mol O2 react to form 0.162 mol
SO3 at equilibrium. What is Kc, at 1000 K,
for the reaction that is shown here?
2 SO2(g) + O2(g) 2 SO3(g)
Example 14.12
Consider the reaction
H2(g) + I2(g) 2 HI(g) Kc = 54.3 at 698 K
If we start with 0.500 mol I2(g) and 0.500 mol H2(g) in a 5.25-L
vessel at 698 K, how many moles of each gas will be present at
equilibrium?
Example 14.13
Suppose that in the reaction of Example 14.12, the initial amounts
are 0.800 mol H2 and 0.500 mol I2. What will be the amounts of
reactants and products when equilibrium is attained?
Example 14.14
Carbon monoxide and chlorine react to form phosgene, COCl2,
which is used in the manufacture of pesticides, herbicides, and
plastics:
CO(g) + Cl2(g) COCl2(g) Kc = 1.2 x 103 at 668 K
How much of each substance, in moles, will there be at
equilibrium in a reaction mixture that initially has 0.0100 mol
CO, 0.0100 mol Cl2, and 0.100 mol COCl2 in a 10.0-L flask?
Example 14.15
A sample of phosgene, COCl2(g), is introduced into a
constant-volume vessel at 395 ºC and observed to exert an
initial pressure of 0.351 atm. When equilibrium is
established for the reaction
CO(g) + Cl2(g) COCl2(g) Kp = 22.5
what will be the partial pressure of each gas and the total
gas pressure?

07 Chapter 15 Equilibrium

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GENERAL CHEMISTRY

PRINCIPLES AND MODERN APPLICATIONS

PETRUCCI HERRING MADURA BISSONNETTE

Slide 15 - 1 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

15-4 The Magnitude of an Equilibrium

15-6 Altering Equilibrium Conditions:

Slide 15 - 2 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

Reaction slows down k1 [N2O2]

Slide 3 of 32 General Chemistry: Chapter 15 05/07/23Copyright © 2011 Pearson Canada Inc.

Reaction Progress Reaction Progress Reaction Progress

reaction goes to (thermodynamic

Reaction Progress Reaction Progress Reaction Progress

Slide 4 of 32 General Chemistry: Chapter 15 05/07/23Copyright © 2011 Pearson Canada Inc.

In a closed reaction vessel at constant temperature, a reaction proceeds

2 Cu2+(aq) + Sn2+(aq) 2 Cu+(aq) + Sn4+(aq) (15.1)

Slide 15 - 5 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

• This is a multistep reaction because an elementary process

• The equilibrium constant expression contains the stoichiometric

Slide 6 of 32 General Chemistry: Chapter 15 05/07/23Copyright © 2011 Pearson Canada Inc.

Slide 15 - 8 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

Slide 10 of 32 General Chemistry: Chapter 15 Copyright © 2011 Pearson Canada Inc.

Accounts for non-ideal behaviour in solutions and gases.

Slide 11 of 32 General Chemistry: Chapter 15 Copyright © 2011 Pearson Canada Inc.

Slide 12 of 32 General Chemistry: Chapter 15 Copyright © 2011 Pearson Canada Inc.

Slide 15 - 14 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

AgI(s) Ag+(aq) + I−(aq)

Slide 15 - 15 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

Slide 15 - 16 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

in 15.7, equilibrium values of a are implied

The sum of coefficients The sum of coefficients

Slide 15 - 18 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

Slide 15 - 19 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

2 Al(s) + 6 H+(aq) 2 Al3+(aq) + 3 H2(g)

Recall from Chapter 13

Slide 15 - 20 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

Slide 15 - 21 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

Slide 15 - 22 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

Slide 15 - 23 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

• When we reverse an equation, we invert the value of K.

Slide 15 - 24 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

N2O(g) + ½O2(g) 2 NO(g) Kc= ?

N2(g) + ½O2(g) N2O(g) K(a)= 5.4×10−19 (15.15)

N2(g) + O2(g) 2 NO(g) K(b)= 4.6×10−31 (15.16)

Slide 15 - 29 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

(a) N2O(g) N2(g) + ½O2(g) K’(a)= 1/5.410−19 = 1.9 1018

(b) N2(g) + O2(g) 2 NO(g) K(b)= 4.610−31 (15.16)

Overall: N2O(g) + ½O2(g) 2 NO(g) Koverall= ?

= 1.9×1018 × 4.6×10−31 = 8.5×10−13

(a) N2O(g) N2(g) + ½O2(g) K’(a)= 1/5.410−19 = 1.9 1018

(b) N2(g) + O2(g) 2 NO(g) K(b)= 4.610−31 (15.16)

Overall: N2O(g) + ½O2(g) 2 NO(g) Koverall= ?

= 1.9×1018 × 4.6×10−31 = 8.5×10−13

(a) N2O(g) N2(g) + ½O2(g) K’(a)= 1/5.410−19 = 1.9 1018

(b) N2(g) + O2(g) 2 NO(g) K(b)= 4.610−31 (15.16)

Overall: N2O(g) + ½O2(g) 2 NO(g) Koverall= ?

= 1.9×1018 × 4.6×10−31 = 8.5×10−13

(a) N2O(g) N2(g) + ½O2(g) K’(a)= 1/5.410−19 = 1.9 1018

(b) N2(g) + O2(g) 2 NO(g) K(b)= 4.610−31 (15.16)

Overall: N2O(g) + ½O2(g) 2 NO(g) Koverall= ?

= 1.9×1018 × 4.6×10−31 = 8.5×10−13

(a) N2O(g) N2(g) + ½O2(g) K’(a)= 1/5.410−19 = 1.9 1018

(b) N2(g) + O2(g) 2 NO(g) K(b)= 4.610−31 (15.16)

Overall: N2O(g) + ½O2(g) 2 NO(g) Koverall= ?

= 1.9×1018 × 4.6×10−31 = 8.5×10−13