Introductory Chemistry, 3rd Edition

Nivaldo Tro

Chapter 15
Chemical
Equilibrium

Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
2009, Prentice Hall
 Equilibrium vs. Disequilibrium
• When systems are at equilibrium with their
surroundings, their conditions are the same as the
surroundings and they stay that way.
• When systems are in disequilibrium with their
surroundings, their conditions are not the same as the
surroundings.
• Systems that are in disequilibrium tend to change
until they reach equilibrium with their surroundings.
• Living things are in controlled disequilibrium with
their environment—they are not at the same
conditions as the environment and do not tend to
change toward those conditions.
Tro's Introductory Chemistry, 2
Chapter 15
 Reaction Rates
• Some chemical reactions proceed rapidly.
 Like the precipitation reactions studied in Chapter 7
where the products form practically the instant the two
solutions are mixed.
• Other reactions proceed slowly.
 Like the decomposition of dye molecules of a sofa
placed in front of a window.
• The rate of a reaction is measured in the amount of
reactant that changes into product in a given
period of time.
 Generally moles of reactant used per second.
 Like miles per hour.
• Chemists study ways of controlling reaction rates.
Tro's Introductory Chemistry, 3
Chapter 15
 Collision Theory
• In order for a reaction to take place, the reacting
molecules must collide with each other.
• Once molecules collide they may react together
or they may not, depending on two factors:
1. Whether the collision has enough energy to “start to
break the bonds holding reactant molecules
together."
2. Whether the reacting molecules collide in the proper
orientation for new bonds to form.

Tro's Introductory Chemistry, 7

Chapter 15
 Effective Collisions
• Collisions in which these two conditions are
met (and therefore the reaction occurs) are
called effective collisions.
• The higher the frequency of effective
collisions, the faster the reaction rate.
• There is a minimum energy needed for a
collision to be effective. We call this the
activation energy.
The lower the activation energy, the faster the
reaction will be.
Tro's Introductory Chemistry, 8
Chapter 15
 Effective Collisions:
Kinetic Energy Factor

For a collision to
lead to overcoming
the energy barrier,
the reacting
molecules must have
sufficient kinetic
energy so that when
they collide, it can
form the activated
complex.
Tro's Introductory Chemistry, 9
Chapter 15
Effective Collisions:
Orientation Effect

Tro's Introductory Chemistry, 10

Chapter 15
Reaction Energy Diagram

Tro's Introductory Chemistry, 11

Chapter 15
 Factors Effecting Reaction Rate:
Reactant Concentration
• The higher the concentration of reactant
molecules, this increases the frequency of
reactant molecule collisions the faster the
reaction will generally go.
• Since reactants are consumed as the reaction
proceeds, the speed of a reaction generally
slows over time.

Tro's Introductory Chemistry, 12

Chapter 15
Effect of Concentration on Rate

Low concentrations of reactant

molecules leads to fewer effective
collisions, therefore a slower
reaction rate.

High concentrations of reactant

molecules lead to more effective
collisions, therefore a faster
reaction rate.
Tro's Introductory Chemistry, 13
Chapter 15
 Factors Effecting Reaction Rate:
Temperature
• Increasing the temperature increases the energy so
that their collisions can overcome the activation
energy.
• And, increasing the temperature also increases the
frequency of collisions.
• Both these mean that increasing temperature
increases the reaction rate.

Tro's Introductory Chemistry, 14

Chapter 15
Effect of Temperature on Rate

Low temperatures lead to fewer

molecules with enough energy to
overcome the activation energy,
and less frequent reactant
collisions, therefore a slower
reaction rate
High temperatures lead to more
molecules with enough energy to
overcome the activation energy,
and more frequent reactant
collisions, therefore, a faster
reaction rate.
 Chemical Equilibrium
• When a reaction reaches equilibrium, the
production of both reactants and products is
constant.
• The forward and reverse reactions still
continue.
• Because they go at the same rate, the amounts
of materials does not appear to change.

Tro's Introductory Chemistry, 18

Chapter 15
 Equilibrium

As the reaction proceeds, the forward reaction

Initially, we only have reactant molecules in the slows down as the reactants get used up. At the
mixture. The reaction can only proceed in the same time, the reverse reaction speeds up as
forward direction, making products. product concentration increases.

Once equilibrium is established, the

Eventually, the forward and reverse rates are equal. concentrations of the reactants and products in
At this time equilibrium is established. the final mixture do not change, (unless
conditions are changed).
 Equilibrium ≠ Equal
• The rates of the forward and reverse reactions are
equal at equilibrium.
• But that does not mean the concentrations of
reactants and products are equal.

Tro's Introductory Chemistry, 23

Chapter 15
 Equilibrium, Continued
As Initially,
Because
Once
Eventually, theonly
theequilibrium
forward theisforward
reactant
the reactionestablished,
concentration
reaction proceeds
proceeds
in reaction
itthe
decreases,
makes
forward
the takes
products
the
reverse and place.
forward
reverse
and uses
direction reaction
asreactions
reactants.
fast asslows.
As
proceed
it the products
proceedsat in
thethe
same
accumulate,
rate, so
forward the
direction.
reverse
concentrations
At reaction
this time of
speeds
all materials
equilibrium up.
is established.
stay constant.
Rate

Rate forward
Rate reverse

Time
Tro's Introductory Chemistry, 24
Chapter 15
• What occurs in a reaction at
equilibrium.
• When the number of people
moving up is the same as the
number of people moving
down, the number of people
on each floor remains
constant, and the two
populations are in
equilibrium.
• Equilibrium occurs when the
forward and reverse reactions
are the same.
25Chapter Seven
 An Analogy: Population Changes

When Narnians feel However, as time passes,

overcrowded, some will
emigrate to Middle Earth.
emigration will occur in both
directions at the same rate, leading
to populations in Narnia and
Middle Earth that are constant,
though not necessarily equal.

Tro's Introductory Chemistry, 26

Chapter 15
 Equilibrium Constant
• Even though the concentrations of reactants
and products are not equal at equilibrium,
there is a relationship between them.
• For the reaction H2(g) + I2(g) ⇔ 2HI(g) at
equilibrium, the ratio of the concentrations
raised to the power of their coefficients is
constant.
[ HI]2
K eq =
[ H 2 ] × [ I2 ]
Tro's Introductory Chemistry, 27
Chapter 15
 Equilibrium Constant, Continued
• For the general equation aA + bB ⇔ cC + dD,
the relationship is given below:
The lowercase letters represent the coefficients of
the balanced chemical equation.
Always products over reactants.
• The constant is called the equilibrium
constant, Keq. c
[ C] × [ D ]
d
K eq =
[ A ] × [ B]
a b

Tro's Introductory Chemistry, 28

Chapter 15
 Writing Equilibrium Constant
Expressions
• For aA + bB ⇔ cC + dD,
the equilibrium constant K eq =
[ ] c
C × D [ ] d

expression is: [ A ] a × [ B] b
• So for the reaction
2 N2O5 ⇔ 4 NO2 + O2, the K = [ NO 2 × [ O2 ]
] 4

[ ]
eq 2
equilibrium constant N O
2 5
expression is:

Tro's Introductory Chemistry, 29

Chapter 15
 Equilibrium Constants for
Heterogeneous Equilibria
• Pure substances in the solid and liquid state have
constant concentrations.
 Adding or removing some does not change the
concentration because they do not expand to fill the
container or spread throughout a solution.
• Therefore, these substances are not included in the
equilibrium constant expression.
For the reaction CaCO3(s) + 2 HCl(aq) ⇔ CaCl2(aq) + CO2(g) + H2O(l):

K eq =
[ CaCl 2 ] × [ CO 2 ]
[ HCl] 2
Tro's Introductory Chemistry, 30
Chapter 15
 Write the Equilibrium Constant
Expressions, Keq, for Each of the Following:

• 2 CO2(g) ⇔ 2 CO(g) + O2(g)

• BaSO4(s) ⇔ Ba+2(aq) + SO4-2(aq)

• CH4(g) + 2 O2(g) ⇔ CO2(g) + 2 H2O(l)

Tro's Introductory Chemistry, 31
Chapter 15
 Write the Equilibrium Constant
Expressions, Keq, for Each of the Following,
Continued:
• 2 CO2(g) ⇔ 2 CO(g) + O2(g)
[CO]2•[O2]
Keq =
[CO2]2

• BaSO4(s) ⇔ Ba+2(aq) + SO4-2(aq)

Keq = [Ba+2]•[SO4-2]

• CH4(g) + 2 O2(g) ⇔ CO2(g) + 2 H2O(l)

[CO2]
Keq = [CH4]•[O2]2 32
What Does the Value of Keq Imply?
• When the value of Keq > > 1, we know that when the
reaction reaches equilibrium, there will be many more
product molecules present than reactant molecules.
 The position of equilibrium favors products.
• When the value of Keq < < 1, we know that when the
reaction reaches equilibrium, there will be many more
reactant molecules present than product molecules.
 The position of equilibrium favors reactants.

Tro's Introductory Chemistry, 33

Chapter 15
A Large Equilibrium Constant

Tro's Introductory Chemistry, 34

Chapter 15
A Small Equilibrium Constant

Tro's Introductory Chemistry, 35

Chapter 15
 Write the Equilibrium Constant
Expressions, Keq, and Predict the Position of
Equilibrium for Each of the Following:
• 2 HF(g) ⇔ H2(g) + F2(g) Keq = 1 x 10-95

• 2 SO2(g) + O2(g) ⇔ 2 SO3(g) Keq = 8 x 1025

• N2(g) + 2 O2(g) ⇔ 2 NO2(g) Keq = 3 x 10-17

Tro's Introductory Chemistry, 36
Chapter 15
 Write the Equilibrium Constant Expressions,
Keq, and Predict the Position of Equilibrium for
Each of the Following, Continued:
• 2 HF(g) ⇔ H2(g) + F2(g) Keq = 1 x 10-95
[ H 2 ] × [ F2 ]
K eq = Favors reactants.
[ HF] 2

• 2 SO2(g) + O2(g) ⇔ 2 SO3(g) Keq = 8 x 1025

[ SO3 ] 2
K eq = Favors products.
[ SO 2 ] 2 × [ O 2 ]
• N2(g) + 2 O2(g) ⇔ 22NO2(g) Keq = 3 x 10-17
[ NO2 ]
K eq = Favors reactants.
[ N 2 ] × [ O2 ] 2
 Calculating Keq
• The value of the equilibrium constant may be
determined by measuring the concentrations of all
the reactants and products in the mixture after the
reaction reaches equilibrium, then substituting in
the expression for Keq.
• Although you may have different amounts of
reactants and products in the equilibrium mixture,
the value of Keq will always be the same.
 The value of Keq depends only on the temperature.
 The value of Keq does not depend on the amounts of
reactants or products with which you start.
Tro's Introductory Chemistry, 38
Chapter 15
Initial and Equilibrium Concentrations for
H2(g) + I2(g) ⇔ 2HI(g)
Initia Equili Equilibrium
l brium Constant
[HI] 2

[H2] [I2] [HI] [H2] [I2] [HI] K =

[H ][I ]
eq

2 2

[0.78]2
0.50 0.50 0.0 0.11 0.11 0.78 = 50
[0.11][0.11]
[0.39]2
0.0 0.0 0.50 0.055 0.055 0.39 = 50
[0.055][0.055]
[1.17]2
0.50 0.50 0.50 0.165 0.165 1.17 = 50
[0.165][0.165]
[0.934]2
1.0 0.5 0.0 0.53 0.033 0.934 = 50
[0.53][0.033]
Tro's Introductory Chemistry, 39
Chapter 15
 Example 15.3—Find the Value of Keq for the Reaction
from the Given Concentrations:
2 CH4(g) ⇔ C2H2(g) + 3 H2(g).
Given: [CH4] = 0.0203 M, [C2H2] = 0.0451 M, [H2] = 0.112 M
Find:
Keq
Solution Map: [CH ], [C H ], [H ] Keq
4 2 2 2
[C2H 2 ] × [H 2 ]3
K eq =
Relationships: [CH 4 ]2

Solve:
[C2 H 2 ] × [H 2 ]3 ( 0.0451)( 0.112 ) 3
K eq = = = 0.154
[CH 4 ]2 ( 0.0203) 2

Check: Keq is unitless.

Tro's Introductory Chemistry, 40
Chapter 15
 Practice—Calculate Keq for the Reaction
2 NO2(g) ⇔ N2O4(g)
at 100 °C if the Equilibrium Concentrations Are
[NO2] = 0.0172 M and [N2O4] = 0.0014 M.

Tro's Introductory Chemistry, 47

Chapter 15
Practice—Find the Value of Keq for the Reaction from the
Given Concentrations:
2 NO2(g) ⇔ N2O4(g).
Given: [NO2] = 0.0172 M, [N2O4] = 0.0014 M
Find:
Keq
Solution Map: [NO2], [N2O4] Keq
[N 2O 4 ]
K eq =
Relationships: [NO2 ]2
Solve:
[N 2O 4 ] ( 0.0014 )
K eq = = = 4 .7
[NO2 ] 2
( 0.0172) 2

Check: Keq is unitless.

Example 15.4—Find the Value of [HI] for the Reaction at
Equilibrium from the Given Concentrations and Keq:
H2(g) + I2(g) ⇔ 2HI(g)
Given: [I2] = 0.020 M, [H2] = 0.020 M, Keq = 69
Find: [HI]
Solution Map: [I2], [H2], Keq [HI]
[HI]2
K eq =
Relationships: [H 2 ] × [I2 ]
Solve:
[HI]
[HI]22
K eq2 ]×K
K eq × [H ×[H
[I
eq22=
]]=× [I 2 ] = [HI]×2[H × [I
=2[]HI ] 2]
[H[H22]]×× [I22]]

69 × ( 0.020 ) × ( 0.020 ) = [HI] = 0.17 M

Tro's Introductory Chemistry, 49
Chapter 15
 Disturbing and Re-Establishing
Equilibrium
• Once a reaction is at equilibrium, the
concentrations of all the reactants and products
remain the same.
• However, if the conditions are changed, the
concentrations of all the chemicals will change
until equilibrium is re-established.
• The new concentrations will be different, but the
equilibrium constant will be the same.
 Unless you change the temperature.

Tro's Introductory Chemistry, 58

Chapter 15
 Le Châtelier’s Principle
• Le Châtelier’s principle guides us in
predicting the effect on the position of
equilibrium when conditions change.
• “When a chemical system at equilibrium is
disturbed, the system shifts in a direction
that will minimize the disturbance.”

Tro's Introductory Chemistry, 59

Chapter 15
 An Analogy: Population
Changes, due to a Gold Rush!

When the populations of Narnia and

When an influx of population enters Middle Earth are in equilibrium, the
Middle Earth from somewhere outside emigration rates between the two
Narnia, it disturbs the equilibrium states are equal so the populations
established between Narnia and stay constant.
Middle Earth.
The result will be people moving from Middle
Earth into Narnia faster than people moving
from Narnia into Middle Earth. This will
continue until a new equilibrium between the
populations is established, However, the new
populations will have different numbers of
people than the old ones. 60
 The Effect of Concentration
Changes on Equilibrium
• Adding a reactant will decrease the amounts of the other
reactants and increase the amount of the products until a
new position of equilibrium is found.
That has the same Keq.
• Removing a product will increase the amounts of the
other products and decrease the amounts of the reactants.
You can use to this to drive a reaction to completion!
• Remember: Adding more of a solid or liquid does not
change its concentration and, therefore, has no effect on
the equilibrium.

Tro's Introductory Chemistry, 61

Chapter 15
The Effect of Concentration Changes
on Equilibrium, Continued

When NO2
is added,
some of it
combines
to make
more N2O4.

Tro's Introductory Chemistry, 62

Chapter 15
The Effect of Concentration Changes
on Equilibrium, Continued

When N2O4
is added,
some of it
decomposes
to make
more NO2.

Tro's Introductory Chemistry, 63

Chapter 15
Practice—Predict the Effect on the Equilibrium
When the Underlined Substance Is Added to
the Following Systems:
• 2 CO2(g) ⇔ 2 CO(g) + O2(g)

• BaSO4(s) ⇔ Ba2+(aq) + SO42-(aq)

• CH4(g) + 2 O2(g) ⇔ CO2(g) + 2 H2O(l)

Tro's Introductory Chemistry, 64
Chapter 15
Practice—Predict the Effect on the Equilibrium
When the Underlined Substance Is Added to
the Following Systems, Continued:
• 2 CO2(g) ⇔ 2 CO(g) + O2(g)
Shift right, removing some of the added CO2 and
increasing the concentrations of CO and O2.

• BaSO4(s) ⇔ Ba2+(aq) + SO42-(aq)

Shift left, removing some of the added Ba2+ and
reducing the concentration of SO42-.

• CH4(g) + 2 O2(g) ⇔ CO2(g) + 2 H2O(l)

Shift right, removing some of the added CO2 and decreasing the O2,
while increasing the concentration of CO2. 65
 Effect of Volume Change
on Equilibrium
• For solids, liquids, or solutions, changing
the size of the container has no effect on the
concentration.
• Changing the volume of a container
changes the concentration of a gas.
Same number of moles, but different number of
liters, resulting in a different molarity.

Tro's Introductory Chemistry, 66

Chapter 15
 Effect of Volume Change
on Equilibrium, Continued
• Decreasing the size of the container increases the
concentration of all the gases in the container.
 This increases their partial pressures.
• If their partial pressures increase, then the total
pressure in the container will increase.
• According to Le Châtelier’s principle, the
equilibrium should shift to remove that pressure.
• The way to reduce the pressure is to reduce the
number of molecules in the container.
• When the volume decreases, the equilibrium shifts
to the side with fewer molecules.
Tro's Introductory Chemistry, 67
Chapter 15
The Effect of Volume Change on Equilibrium,
Continued

When
Sincethe
there
pressure
are more
is decreased
gas
molecules
by increasing
on the reactants
volume, the
side
position
of theof
reaction,
equilibrium
whenshifts
the
toward
pressure
the is
side
increased
with thethe
greater
position
number of of
equilibrium
molecules—the
shifts
towardreactant
the products.
side.

Tro's Introductory Chemistry, 68

Chapter 15
 The Effect of Temperature
Changes on Equilibrium
• Exothermic reactions release energy and
endothermic reactions absorb energy.
• If we write heat as a product in an
exothermic reaction or as a reactant in an
endothermic reaction, it will help us use Le
Châtelier’s principle to predict the effect of
temperature changes.
However, heat is not matter and not written in a
proper equation.
Tro's Introductory Chemistry, 71
Chapter 15
The Effect of Temperature Changes on
Equilibrium for Exothermic Reactions
• For an exothermic reaction, heat is a product.
• Increasing the temperature is like adding heat.
• According to Le Châtelier’s principle, the equilibrium
will shift away from the added heat.
• The concentrations of C and D will decrease and the
concentrations of A and B will increase.
• The value of Keq will decrease.
• How will decreasing the temperature effect the
system? [ C] × [ D ]
c d
aA + bB ⇔ cC + dD + heat K eq =
[ A ] a × [ B] b
Tro's Introductory Chemistry, 72
Chapter 15
The Effect of Temperature Changes on
Equilibrium for Endothermic Reactions
• For an endothermic reaction, heat is a reactant.
• Increasing the temperature is like adding heat.
• According to Le Châtelier’s principle, the equilibrium
will shift away from the added heat.
• The concentrations of C and D will increase and the
concentrations of A and B will decrease.
• The value of Keq will increase.
• How will decreasing the temperature effect the
system? [ C] c × [ D ] d
Heat + aA + bB ⇔ cC + dD K eq =
[ A ] a × [ B] b
Tro's Introductory Chemistry, 73
Chapter 15
The Effect of Temperature
Changes on Equilibrium

Tro's Introductory Chemistry, 74

Chapter 15
Practice—Predict the Effect on the Equilibrium
When the Temperature Is Reduced.
• Heat + 2 CO2(g) ⇔ 2 CO(g) + O2(g)

• BaSO4(s) ⇔ Ba2+(aq) + SO42-(aq) (endothermic)

• CH4(g) + 2 O2(g) ⇔ CO2(g) + 2 H2O(l) (exothermic)

Tro's Introductory Chemistry, 75
Chapter 15
Practice—Predict the Effect on the Equilibrium
When the Temperature Is Reduced, Continued.

• Heat + 2 CO2(g) ⇔ 2 CO(g) + O2(g)

Shift left, reducing the value of Keq.

• Heat + BaSO4(s) ⇔ Ba2+(aq) + SO42-(aq)

Shift left, reducing the value of Keq.

• CH4(g) + 2 O2(g) ⇔ CO2(g) + 2 H2O(l) + Heat

Shift right, increasing the value of Keq. 76
 Solubility and Solubility Product
• Even “insoluble” salts dissolve somewhat in water.
 Insoluble = less than 0.1 g per 100 g H2O.
• The solubility of insoluble salts is described in terms
of equilibrium between undissolved solid and
aqueous ions produced.
AnYm(s) ⇔ n A+(aq) + m Y-(aq)
• Equilibrium constant for this process is called the
solubility product constant, Ksp.
Ksp = [A+]n[Y-]m
• If there is undissolved solid in equilibrium with the
solution, the solution is saturated.
• Larger Ksp = more soluble.
 For salts that produce the same number of ions.
Tro's Introductory Chemistry, 77
Chapter 15
Example—Determine the Ksp of PbBr2 if its
Solubility Is 1.44 x 10-2 M.
PbBr2(s) ⇔ Pb2+(aq) + 2 Br–(aq)
init -- 0 0
equil -- 0.0144 0.0288

Ksp = [Pb2+][Br–]2 = (0.0144)(0.0288)2 = 1.19 x 10-5

Tro's Introductory Chemistry, 78

Chapter 15
 Example 15.9—
Calculating Molar Solubility
from Ksp

Tro's Introductory Chemistry, 79

Chapter 15
Example 15.9:
• Calculate the molar solubility of BaSO4.
Ksp = 1.07 x 10-10 at 25 °C

Tro's Introductory Chemistry, 80

Chapter 15
Example:
Calculate the molar solubility
of BaSO4.
Ksp = 1.07 x 10-10 at 25 °C
Information:
Given: Ksp = 1.07 x 10-10
Find: [BaSO4], M = [Ba2+] = [SO42-]
Equation: Ksp = [Ba2+][SO42-]
Solution Map: Ksp → [Ba2+]

• Apply the solution map:

K sp = [ Ba 2 + ] × [SO 4 2−
]
=[ ] ×[
] =[ ]2
1.07 × 10-10 Ba 2 + Ba 2 + Ba 2 +

1.07 × 10−10 = [ Ba 2 + ]
1.03 × 10-5 = [ Ba 2 + ]
Tro's Introductory Chemistry, 85
Chapter 15
 Activation Energy
• The energy barrier that prevents any
collision between molecules from being an
effective collision is called the activation
energy.
• The larger the activation energy of a
reaction, the slower it will be.
At a given temperature.

Tro's Introductory Chemistry, 87

Chapter 15
 Exothermic Reaction
Activation
energy,
large
Relative potential energy

Activation
energy,
Reactants small

∆Hreaction Products

Progress of reaction

Tro's Introductory Chemistry, 88

Chapter 15
 Endothermic Reaction

Activation
Relative potential energy

energy

Products

Reactants ∆Hreaction

Progress of reaction

Tro's Introductory Chemistry, 89

Chapter 15
 Catalysts
• A catalyst is a substance that increases the
rate of a reaction, but is not consumed in the
reaction.
• Catalysts lower the activation energy of a
reaction.
• Catalysts work by providing an easier
pathway for the reaction.

Tro's Introductory Chemistry, 90

Chapter 15
Catalyst Effect on Activation
Energy

Tro's Introductory Chemistry, 91

Chapter 15
 Catalyst Effect on
Activation Energy, Continued

Tro's Introductory Chemistry, 92

Chapter 15
 Enzymes
• Enzymes are protein molecules produced by
living organisms that catalyze chemical reactions.
• The enzyme molecules have an active site to
which organic molecules bind.
• When the organic molecule is bound to the active
site, certain bonds are weakened.
• This allows a particular chemical change to occur
with greater ease and speed.
 i.e., the activation energy is lowered.

Tro's Introductory Chemistry, 93

Chapter 15
 Sucrase

Tro's Introductory Chemistry, 94

Chapter 15