Reaction Rates and Equilibrium

18.
3 Reversible Reactions and Equilibrium >
Chapter 18
Reaction Rates and Equilibrium
18.1 Rates of Reaction
18.2 The Progress of Chemical
Reactions
18.3 Reversible Reactions

and Equilibrium
18.4 Solubility Equilibrium

18.5 Free Energy and Entropy
1 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

18.3 Reversible Reactions and Equilibrium > CHEMISTRY & YOU
How did chemists help farmers

produce more food?
Fertilizers can increase
the amount of a crop per
unit of land. Most
fertilizers contain
ammonia or nitrogen
compounds made from
ammonia.

Reversible
18.3 Reversible Reactions and Equilibrium > Reactions
Reversible Reactions
What happens at the molecular
level in a chemical system at
equilibrium?

Reversible
• You may have inferred that chemical

reactions always progress in one direction.
• This inference is not true. Some reactions are
reversible.
• A reversible reaction is one in which the
conversion of reactants to products and the
conversion of products to reactants occur
at the same time.

Reversible
Here is an example of a reversible

reaction.
2SO2(g) + O2(g)  2SO3(g)
2SO2(g) + O2(g)  2SO3(g)
• The first reaction is called the forward

reaction.
• The second reaction is called the reverse
reaction.

Reversible
2SO2(g) + O2(g)  2SO3(g)

2SO2(g) + O2(g)  2SO3(g)
The two equations can be combined into one
using a double arrow.
2SO2(g) + O2(g) 2SO3(g)
The double arrow tells you that the reaction is

reversible.

Reversible
Molecules of SO2 and O2 react to give

SO3. Molecules of SO3 decompose to give
SO2 and O2.
Reversible
Establishing Equilibrium
When the rates of the forward and
reverse reactions are equal, the reaction
has reached a state of balance called
chemical equilibrium.

18.3 Reversible Reactions and Equilibrium > Interpret Graphs
This graph shows the This graph shows the

progress of a reaction progress of the reaction that
that starts with begins with an initial
concentrations of SO2 concentration of SO3, and
and O2, but with zero zero concentrations for SO2
SO3. and O2.
Notice that after a certain time, the concentrations remain

constant.
Reversible
Conditions at Equilibrium
Chemical equilibrium is a dynamic state.
When the store Equilibrium is

opens, only the reached when
forward the rate at
reaction which
occurs as shoppers move
shoppers from the first
head to the floor to the
second floor. second is equal to the rate at
which shoppers move from the
second floor to the first.
Reversible
Conditions at Equilibrium
At chemical equilibrium, both the

forward and reverse reactions
continue, but because their rates
are equal, no net change occurs in
the concentrations of the reaction
components.

Reversible
Concentrations at Equilibrium
Although the rates of the forward and
reverse reactions are equal at equilibrium,
the concentrations of the components
usually are not.
• The relative concentrations of the reactants
and products at equilibrium mark the
equilibrium position of a reaction.

Reversible
The equilibrium position tells you whether
the forward or reverse reaction is more
likely to happen.
• Suppose a single reactant, A, forms a single
product, B.
• If the equilibrium mixture contains 1% A and
99% B, then the formation of B is said to be
favored. A B
1% 99%
Reversible
In principle, almost all reactions are reversible
to some extent under the right conditions.
• In practice, one set of components is often so favored
at equilibrium that the other set cannot be detected.
• When no reactants can be detected, you can say that
the reaction has gone to completion, or is irreversible.
• When no products can be detected, you can say that
no reaction has taken place.

18.3 Reversible Reactions and Equilibrium >
Why is equilibrium considered to be a

dynamic state?

Why is equilibrium considered to be a

dynamic state?
Both the forward and reverse reactions

are constantly taking place, but their
rates are equal, so no net change occurs
in the concentrations of the products or
reactants.

18.3 Reversible Reactions and Equilibrium > Factors Affecting
Equilibrium: Equilibrium:
Le Châtelier’s Principle
Factors Affecting Equilibrium:

What three stresses can cause a
change in the equilibrium position
of a chemical system?

Factors Affecting Factors Affecting
18.3 Reversible Reactions and Equilibrium > Equilibrium:
The French chemist Henri Le Châtelier

(1850–1936) proposed what has come to
be called Le Châtelier’s principle: If a
stress is applied to a system in dynamic
equilibrium, the system changes in a way
that relieves the stress.

Stresses that upset the equilibrium

of a chemical system include
changes in the concentration of
reactants or products, changes in
temperature, and changes in
pressure.

Concentration
Changing the amount, or concentration, of
any reactant or product in a system at
equilibrium disturbs the equilibrium.
• The system will adjust to minimize the effects
of the change.

Concentration
Consider the decomposition of carbonic
acid (H2CO3) in aqueous solution.
H2CO3(aq) CO2(aq) + H2O(l)

< 1% > 99%
• The system has reached equilibrium.

• The amount of carbonic acid is less
than 1%.
Suppose carbon dioxide is added to the

system. Add CO 2
Direction of shift
• This increase in the concentration of CO2 causes

the rate of the reverse reaction to increase.
• Adding a product to a reaction at equilibrium
pushes a reversible reaction in the direction of the
reactants.
Suppose carbon dioxide is removed.

Add CO2
Direction of shift
Remove CO2
Direction of shift
• This decrease in the concentration of CO2 causes

the rate of the reverse reaction to decrease.
• Removing a product always pulls a reversible
reaction in the direction of the products.

Factors Affecting
An equilibrium between
carbonic acid, carbon
dioxide, and water exists
in your blood.
• During exercise, the concentration of CO 2 in the blood
increases. This shifts the equilibrium in the direction of
carbonic acid.
• The increase in the level of CO2 also triggers an increase in
the rate of breathing. With more breaths per minute, more
CO2 is removed through the lungs.
• The removal of CO2 causes the equilibrium to shift toward
the products, which reduces the amount of H 2CO3.
Factors Affecting
Temperature
Increasing the temperature causes the

equilibrium position of a reaction to shift
in the direction that absorbs heat.
• In other words, it will shift in the direction
that reduces the stress.

Temperature
Add heat
Direction of shift
N2(g) + 3H2(g) 2NH3(g) + heat
Remove heat (cool)
Direction of shift
Heat can be considered to be a product, just

like NH3.
• Heating the reaction mixture at equilibrium pushes
the equilibrium position to the left, which favors the
reactants.
• Cooling, or removing heat, pulls the equilibrium
position to the right, and the product yield increases.
Pressure
Equilibrium systems in which some

reactants and products are gases can
be affected by a change in pressure.
• A shift will occur only if there are an
unequal number of moles of gas on each
side of the equation.

Pressure
When the plunger is pushed down, the volume
decreases and the pressure increases.
Initial equilibrium Equilibrium is A new equilibrium

disturbed by an position is
increase in established with
pressure. fewer molecules.
Pressure
You can predict which way the equilibrium
position will shift by comparing the number of
molecules of reactants and products.
Add pressure
Direction of shift
N2(g) + 3H2(g) 2NH3(g)
Reduce pressure
Direction of shift
• When two molecules of ammonia form, four molecules

of reactants are used up.
• A shift toward ammonia (the product) will reduce the
number of molecules.
Fritz Haber and Karl Bosch figured out how to

increase the yield of ammonia when nitrogen
and hydrogen react. Their success came from
controlling the temperature and pressure. In
which direction did they adjust each factor
and why?

Fritz Haber and Karl Bosch figured out how

to increase the yield of ammonia when
nitrogen and hydrogen react. Their success
came from controlling the temperature and
pressure. In which direction did they adjust
each factor and why?
An increase in pressure and a decrease in
temperature would increase the yield of
ammonia by shifting the equilibrium toward the
production of ammonia.

Catalysts and Equilibrium

Catalysts decrease the time it takes to
establish equilibrium.
• However, they do not affect the amounts of
reactants and products present at
equilibrium.

18.3 Reversible Reactions and Equilibrium > Sample Problem 18.2
Applying Le Châtelier’s Principle

What effect will each of the following
changes have on the equilibrium position
for this reversible reaction?
PCl5(g) + heat PCl3(g) + Cl2(g)
a. Cl2 is added.
b. Pressure is increased.
c. Heat is removed.
d. PCl3 is removed as it forms.
1 Analyze Identify the relevant concepts.

According to Le Châtelier’s principle, the
equilibrium position will shift in a direction that
minimizes the imposed stress.

2 Solve Apply the concepts to this problem.

Start with the addition of Cl2.
• Cl2 is a product.
• Increasing the concentration of a product
shifts the equilibrium to the left.
Add Cl2
Direction of shift


Analyze the effect of an increase in pressure.
• Reducing the number of For a change in
molecules that are gases pressure, compare the
decreases the pressure. number of molecules of
gas molecules on both
• The equilibrium shifts to sides of the equation.
the left.
Increase pressure
Direction of shift


Analyze the effect of removing heat.
• The reverse reaction produces heat.
• The removal of heat causes the
equilibrium to shift to the left.
Remove heat
Direction of shift


Analyze the effect of removing PCl3.
• PCl3 is a product.
• Removal of a product as it forms causes
the equilibrium to shift to the right.

Remove PCl3
Direction of shift
In the following equilibrium reaction, in which

direction would the equilibrium position shift
with an increase in pressure?
4HCl(g) + O2(g) 2Cl2(g) +2H2O(g)

In the following equilibrium reaction, in which

direction would the equilibrium position shift
with an increase in pressure?
4HCl(g) + O2(g) 2Cl2(g) +2H2O(g)
Reducing the number of molecules that

are gases decreases the pressure. The
equilibrium will shift to the right.
18.3 Reversible Reactions and Equilibrium > Equilibrium
Constants
Equilibrium Constants
What does the size of an equilibrium
constant indicate about a system at
equilibrium?

Constants
Chemists express the equilibrium position as a

numerical value.
• This value relates the amounts of reactants
to products at equilibrium.
aA + bB cC + dD
• In this general reaction, the coefficients a,

b, c, and d represent the number of moles.

Constants
The equilibrium constant (Keq) is the ratio of

product concentrations to reactant concentrations
at equilibrium.
aA + bB cC + dD
• From the general equation, each concentration
is raised to a power equal to the number of
moles of that substance in the balanced
chemical equation.
[C]c x [D]d
Keq =
[A]a x [B]b
Constants
The value of Keq depends on the temperature

of the reaction.
• The flask on the left is in a dish of hot water.
• The flask on the right is in ice.
Dinitrogen tetroxide is a
colorless gas. Nitrogen
dioxide is a brown gas.
N2O4(g) 2NO2(g)

Constants
The size of the equilibrium constant

indicates whether reactants or products
are more common at equilibrium.

Constants
The size of the equilibrium constant

indicates whether reactants or products
are more common at equilibrium.
• When Keq has a large value, such as 3.1 x 1011, the

reaction mixture at equilibrium will consist mainly of
product.
• When Keq has a small value, such as 3.1 x 10–11, the
mixture at equilibrium will consist mainly of reactant.
• When Keq has an intermediate value, such as 0.15 or
50, the mixture will have significant amounts of both
46
reactant and product. Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.
Expressing and Calculating Keq

The colorless gas dinitrogen tetroxide (N2O4)
and the brown gas nitrogen dioxide (NO2)
exist in equilibrium with each other.
N2O4(g) 2NO2(g)
A liter of the gas mixture at equilibrium
contains 0.0045 mol of N2O4 and 0.030 mol of
NO2 at 10oC. Write the expression for the
equilibrium constant (Keq) and calculate the
value of the constant for the reaction.
1 Analyze List the knowns and the unknowns.

Modify the general expression for the
equilibrium constant and substitute the known
concentrations to calculate Keq.
KNOWNS UNKNOWN
[N2O4] = 0.0045 mol/L Keq (algebraic expression) = ?
[NO2] = 0.030 mol/L Keq (numerical value) = ?

2 Calculate Solve for the unknowns.

• Start with the general expression for
the equilibrium constant. Place the concentration of
[C]c x [D]d the product in the
Keq = [A]a x [B]b numerator and the
concentration of the
reactant in the
denominator. Raise each
• Write the equilibrium constant concentration to the power
equal to its coefficient in
expression for this reaction. the chemical equation.
[NO2]2
Keq = [N O ]
2 2


Substitute the concentrations that are known
and calculate Keq.
(0.030 mol/L)2 (0.030 mol/L x 0.030 mol/L)

Keq = (0.0045 mol/L) = (0.0045 mol/L)
Keq = 0.20 mol/L = 0.20

You can ignore the unit
mol/L; chemists report
equilibrium constants
without a stated unit.
3 Evaluate Does the result make sense?

• Each concentration is raised to the correct
power.
• The numerical value of the constant is
correctly expressed to two significant figures.
• The value for Keq is appropriate for an
equilibrium mixture that contains significant
amounts of both gases.

Finding the Equilibrium Constant

One mole of colorless hydrogen gas
and one mole of violet iodine vapor
are sealed in a 1-L flask and
allowed to react at 450oC. At
equilibrium, 1.56 mol of colorless
hydrogen iodide is present, together
with some of the reactant gases.
Calculate Keq for the reaction.
H2(g) + I2(g) 2HI(g)

1 Analyze List the knowns and the unknown.

Find the concentrations of the reactants at
equilibrium. Then substitute the equilibrium
concentrations in the expression for the
equilibrium constant for this reaction.
KNOWNS UNKNOWN
[H2] (initial) = 1.00 mol/L Keq = ?
[I2] (initial) = 1.00 mol/L
[HI] (equilibrium) = 1.56 mol/L

2 Calculate Solve for the unknown.

First find out how much H2 and I2 are consumed in
the reaction.
x + x = 1.56 mol
Let mol H2 used = mol I2 used = x.
2x = 1.56 mol
The number of mol H2 and mol I2
x = 0.780 mol used must equal the number of mol
HI formed (1.56 mol).


• Calculate how much H2 and I2 remain in the
flask at equilibrium.
mol H2 = mol I2 = (1.00 mol – 0.780 mol) = 0.22 mol
• Write the expression Use the general

expression for Keq as a
for Keq. guide:
[C]c x [D]d
[HI] 2
Keq =
[A]a x [B]b
Keq = [H ] x [I ]
2 2


Substitute the equilibrium concentrations of
the reactants and products into the equation
and solve for Keq.
(1.56 mol/L)2
Keq = 0.22 mol/L x 0.22 mol/L
1.56 mol/L x 1.56 mol/L
Keq = 0.22 mol/L x 0.22 mol/L
Keq = 5.0 x 101


• Each concentration is raised to the correct
power.
• The value of the constant reflects the
presence of significant amounts of the
reactions and product in the equilibrium
mixture.

Finding Concentrations at Equilibrium

Bromine chloride (BrCl) decomposes to form
bromine and chlorine.
2BrCl(g) Br2(g) + Cl2(g)
At a certain temperature, the equilibrium
constant for the reaction is 11.1. A sample
of pure BrCl is placed in a 1-L container
and allowed to decompose. At equilibrium,
the reaction mixture contains 4.00 mol Cl2.
What are the equilibrium concentrations of
Br2 and BrCl?
1 Analyze List the knowns and the unknowns.

Use the balanced equation, the equilibrium constant,
and the equilibrium constant expression to find the
unknown concentrations. According to the balanced
equation, when BrCl decomposes, equal numbers of
moles of Br2 and Cl2 are formed.
KNOWNS UNKNOWN
[Cl2] (equilibrium) = 4.00 mol/L [Br2] (equilibrium) = ? mol/L
Keq = 11.1 [BrCl] (equilibrium) = ? mol/L


• The volume of the container is 1 L, so
calculate [Br2] at equilibrium.
4.00 mol
[Br2] = 1L = 4.00 mol/L
• Write the equilibrium expression for the reaction.

[Br2] x [Cl2]
Keq = [BrCl]2


• Rearrange the equation to solve for [BrCl]2.
[Br2] x [Cl2]
[BrCl]2 = Keq
• Substitute the known values for Keq, [Br2], and
[Cl2].
4.00 mol/L x 4.00 mol/L
[BrCl]2 = 11.1
= 1.44 mol2/L2
• Calculate the square root.
[BrCl] = 1.44 mol2/L2 = 1.20 mol/L
Use your
calculator to find
the square root.


It makes sense that the equilibrium
concentration of the reactant and the
products are both present in significant
amounts because Keq has an intermediate
value.

HCl is formed when H2 and Cl2 react at

high temperatures.
H2(g) + Cl2(g) 2HCl(g)
At equilibrium, [HCl] = 1.76 x 10–2 mol/L,
and [H2] = [Cl2] = 1.60 x 10–3 mol/L. What
is the value of the equilibrium constant?

HCl is formed when H2 and Cl2 react at

high temperatures.
H2(g) + Cl2(g) 2HCl(g)
At equilibrium, [HCl] = 1.76 x 10–2 mol/L,
and [H2] = [Cl2] = 1.60 x 10–3 mol/L. What
is the value of the equilibrium constant?
[HCl]2 (1.76 x 10–2 mol/L)2
Keq = =
[H2] x [Cl2] (1.60 x 10–3 mol/L) x (1.60 x 10–3 mol/L)
Keq = 121
18.3 Reversible Reactions and Equilibrium > Key Concepts
At chemical equilibrium, both the forward and

reverse reactions continue, but because their
rates are equal, no net change occurs in the
concentrations of the reactant components.
Stresses that upset the equilibrium of a

chemical system include changes in
concentration of reactants or products,
changes in temperature, and changes in
pressure.

18.3 Reversible Reactions and Equilibrium > Key Concept and
Key Equation
The size of the equilibrium constant indicates

whether reactants or products are more
common at equilibrium.
[C]c x [D]d
Keq =
[A]a x [B]b

18.3 Reversible Reactions and Equilibrium > Glossary Terms
• reversible reaction: a reaction in which the

conversion of reactants into products and the
conversion of products into reactants occur
simultaneously
• chemical equilibrium: a state of balance in
which the rates of the forward and reverse
reactions are equal; no net change in the
amount of reactants and products occurs in
the chemical system

• equilibrium position: the relative

concentrations of reactants and products of a
reaction that has reached equilibrium;
indicates whether the reactants or products
are favored in the reversible reaction
• Le Châtelier’s principle: when a stress is
applied to a system in dynamic equilibrium, the
system changes in a way that relieves the
stress

• equilibrium constant: the ratio of product

concentrations to reactant concentrations at
equilibrium, with each concentration raised to
a power equal to the number of moles of that
substance in the balanced chemical equation

END OF 18.3

Reaction Rates and Equilibrium

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18.

3 Reversible Reactions and Equilibrium >

18.3 Reversible Reactions

18.4 Solubility Equilibrium

1 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

How did chemists help farmers

2 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

3 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

• You may have inferred that chemical

4 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

Here is an example of a reversible

• The first reaction is called the forward

5 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

2SO2(g) + O2(g)  2SO3(g)

The double arrow tells you that the reaction is

6 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

Molecules of SO2 and O2 react to give

8 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

This graph shows the This graph shows the

Notice that after a certain time, the concentrations remain

When the store Equilibrium is

At chemical equilibrium, both the

11 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

12 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

14 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

Why is equilibrium considered to be a

15 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

Why is equilibrium considered to be a

Both the forward and reverse reactions

16 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

Factors Affecting Equilibrium:

17 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

The French chemist Henri Le Châtelier

18 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

Stresses that upset the equilibrium

19 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

20 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

H2CO3(aq) CO2(aq) + H2O(l)

• The system has reached equilibrium.

Suppose carbon dioxide is added to the

• This increase in the concentration of CO2 causes

Suppose carbon dioxide is removed.

• This decrease in the concentration of CO2 causes

23 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

Increasing the temperature causes the

25 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

Heat can be considered to be a product, just

Equilibrium systems in which some

27 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

Initial equilibrium Equilibrium is A new equilibrium

• When two molecules of ammonia form, four molecules

Fritz Haber and Karl Bosch figured out how to

30 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

Fritz Haber and Karl Bosch figured out how

31 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

Catalysts and Equilibrium

32 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

Applying Le Châtelier’s Principle

1 Analyze Identify the relevant concepts.

34 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

2 Solve Apply the concepts to this problem.

35 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.

2 Solve Apply the concepts to this problem.