CHAPTER 14

1. Chemical Equilibrium

2. The Equilibrium Constant

3. How to Interpret Kc

4. Le Châtelier’s Principle

5. Calculating Equilibrium Concentrations

Learning Outcomes
Chapter 14 Outcomes
I (can)…
 Understand the dynamic nature of chemical
equilibrium and how equilibria respond to various
perturbations.

 Correctly use mathematical models and methods to

describe equilibria, kinetics, heat transfers, and the
behavior of gases, and use these models to make
predictions.
Chemical Equilibrium
 What is Going On?

A ⇌ B

Why don’t the concentration

[A]0 appear to change after a
Concentration

certain point?
No more energy can be
released.
Internal energy is
changing instead.
The forward and reverse
rates are equal.

[B]0 ∆H is zero.
Time (min)
Dynamic Equilibrium

CO(g) + 3H2(g) → CH4(g) + H2O(g)

CH4(g) + H2O(g) → CO(g) + 3H2(g)

 Reactions are dynamic – going in both directions.

CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g)

Chemical Equilibrium
 Chemical equilibrium is the state reached by a
reaction mixture when the rates of forward and
reverse reactions have become equal.

A ⇌ B

𝑹𝒂𝒕𝒆𝒇𝒐𝒓𝒘𝒂𝒓𝒅 = 𝑹𝒂𝒕𝒆𝒓𝒆𝒗𝒆𝒓𝒔𝒆
Reaching Equilibrium
CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g)

Does the reaction go to

100% completion?
Yes
No
I cannot tell

Note that the reaction does not go 100% to products.

At equilibrium there is a mixture of reactants and products.
Reaching Equilibrium
CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g)

Which rate was initially

faster?
Forward rate
Reverse rate
I cannot tell

Rates are equal!

Reaching Equilibrium

Why does the rate of the reverse reaction increase with time?
The forward rate of the reaction is decreasing.
The rate of the chemical reaction is increasing.
The concentrations of the reactants are decreasing.
The concentrations of the products are increasing.
Determining Equilibrium Concentrations

 We can determine the equilibrium concentrations

using the initial concentrations and the equilibrium
concentration of one product or reactant.
CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g)
 Determining Equilibrium Concentrations

 For the methanation

reaction, determine
the equilibrium
composition given
the following
information:

CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g)

Starting: 1.000 mol 3.000 mol 0 mol 0 mol
Equilibrium: -- -- -- 0.387 mol
The Equilibrium Constant
 Concentration vs. Time
2HI(g) ⇌ H2(g) + I2(g)

dynamic
equilibrium
region equilibrium
concentrations

non-equilibrium
kinetic region
(Ch. 13)
Describing Equilibrium
 Decomposition of dinitrogen tetroxide:

N2O4(g) ⇌ 2NO2(g)

Colorless
Gas
Describing Equilibrium
 All three of the test
N2O4(g) ⇌ 2NO2(g)
tubes are at equilibrium.
 Why is the composition
(color) different?

 What experimental
variable(s) might be
different?
Describing Equilibrium
 Decomposition of dinitrogen tetroxide is a single
elementary step.
kf
N2O4(g) ⇌ 2NO2(g)
kr

Rate = kf[N2O4] = kr[NO2]2

𝒌𝒇 [𝑵𝑶𝟐 ]𝟐
= = 𝑲𝒄
𝒌𝒓 [𝑵𝟐 𝑶𝟒 ]
 Ozone Decomposition
2O3(g) → 3O2(g)
 The rate law can be explained by a two-step
mechanism:
k1
Step 1: O3(g) ⇌ O2(g) + O∙(g) (fast, equilibrium)
k-1
k2
Step 2: O3(g) + O∙(g) → 2O2(g) (slow)

Rate = k[O3]2/[O2] (determined by experiment)

 Law of Mass Action
 The law of mass action is a relation that states that the values
of the equilibrium-constant expression (Kc) are constant for a
particular reaction at a given temperature, whatever
equilibrium concentrations are substituted.
 “active mass” used to be an old term for concentration

aA + bB ⇌ dD + eE
Products
Equilibrium
reactions are treated [𝑫]𝒅 [𝑬]𝒆 equilibrium
as if they were 𝑲𝒄 = concentrations are
elementary [𝑨]𝒂 [𝑩]𝒃 in mol/L (M)
reactions
Reactants
Example of the Law of Mass Action

Conclusion: [H2][I2]/[HI]2 = constant (Kc)

Equilibrium-Constant Experessions
 Write the equilibrium-constant expression for the
following reaction in terms of concentration (Kc).

2CH4(g) + 3O2(g) ⇌ 2CO2(g) + 4H2O(g)

What is the value of Kc at this temperature?
𝐶𝐻4 [𝑂2 ]
𝐾𝑐 = 𝐶𝑂2 [𝐻2 𝑂]

𝐶𝑂2 [𝐻2 𝑂]
𝐾𝑐 = 𝐶𝐻4 [𝑂2 ]

𝐶𝐻4 2 [𝑂2 ]3
𝐾𝑐 = 𝐶𝑂2 2 [𝐻2 𝑂]4

𝐶𝑂2 2 [𝐻2 𝑂]4

𝐾𝑐 = 𝐶𝐻4 2 [𝑂2 ]3
Equilibrium-Constant Experessions
 Write the equilibrium-constant expression for the
following reaction in terms of concentration (Kc).

2CO2(g) + 4H2O(g) ⇌ 2CH4(g) + 3CO2(g)

What is the value of Kc at this temperature?
𝐶𝐻4 [𝑂2 ]
𝐾𝑐 = 𝐶𝑂2 [𝐻2 𝑂]

𝐶𝑂2 [𝐻2 𝑂]
𝐾𝑐 = 𝐶𝐻4 [𝑂2 ]

𝐶𝐻4 2 [𝑂2 ]3
𝐾𝑐 = 𝐶𝑂2 2 [𝐻2 𝑂]4

𝐶𝑂2 2 [𝐻2 𝑂]4

𝐾𝑐 = 𝐶𝐻4 2 [𝑂2 ]3
Obtaining Equilibrium Constants
 Carbon dioxide decomposes at elevated temperatures to
carbon monoxide and oxygen:

2CO2(g) ⇌ 2CO(g) + O2(g)

 At 3000 K, 2.00 mol CO2 is placed into a 1.000-L container
and allowed to come to equilibrium. At equilibrium, 0.90 mol
CO2 remains.

What is the value of Kc at this temperature?

0.60
0.82
1.2
1.7
Heterogeneous Equilibrium
 Heterogeneous equilibrium is an equilibrium involving
reactants or products in more than one phase.

How does the concentration of a How does the concentration of a

pure solid change with volume?
It increases as volume increases.
It decreases as volume increases.
It doesn’t change.
I have no idea.
pure liquid change with volume?
It increases as volume increases.
It decreases as volume increases.
It doesn’t change.
I have no idea.
Writing Kc for Pure Solids / Liquids
 When water in the form of
steam is passed over hot
coke (carbon), a mixture
of hydrogen and carbon
monoxide called water
gas is formed. This mixture
can be used as a fuel.
H2O(g) + C(s) ⇌ CO(g) + H2(g)
 Write the equilibrium-
constant expression (Kc) Pure solids and liquids are treated
for this process differently since their concentrations do
not change over the course of the
reaction (until they disappear).
Equilibrium for Gaseous Reactions (Kp)

 When all of our reactants and products are gases:

𝒏 𝑷
𝑷𝑽 = 𝒏𝑹𝑻 =
𝑽 𝑹𝑻

 We can re-write our equilibrium constant as Kp

aA(g) + bB(g) ⇌ dD(g) + eE(g)

𝑷𝑫 𝒅 𝑷𝑬 𝒆
𝑲𝒑 = 𝒂 𝒃
𝑷𝑨 𝑷𝑩
Relationship between Kc and Kp
 By plugging in the molar concentration of gases (n/V = P/RT)
into the Kc expression, you can derive:

Where ∆n = coefficients of
𝑲𝒑 = 𝑲𝒄 (𝑹𝑻)∆𝒏 gaseous products – coefficients
of gaseous reactants

 What is the Kp for the following reaction at 1200K?

CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g) Kc = 3.92

Kp = 3.92 × (0.0821 × 1200)-2 = 4.04 × 10-4

 Note: We don’t often use units in the values of Kc and Kp (they

don’t have any real meaning). But you must matchup the
pressures to the value of R that you use.
Kc for the Sum of Reactions

 If a given chemical equation can be obtained by taking the

sum of other equations, the equilibrium constant for the given
equation equals the product of the equilibrium constants for the
added equations.

CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g) K1 = 3.92

CH4(g) + 2H2S(g) ⇌ CS2(g) + 4H2(g) K2 = 3.3 × 104

CO(g) + 2H2S(g) ⇌ CS2(g) + H2(g) + H2O(g)

K1K2 = 1.3 × 105

How to Interpret Kc
The Equilibrium Constant
 Kc is the value obtained for the equilibrium-constant expression
when equilibrium concentrations are substituted.

[𝑫]𝒅 [𝑬]𝒆
aA + bB ⇌ dD + eE 𝑲𝒄 =
[𝑨]𝒂 [𝑩]𝒃

A large Kc indicates relatively _________ concentrations of reactants

and relatively __________ concentrations of products at equilibrium.
high, low
high, high
low, low
low, high
The Equilibrium Constant
 Kc is the value obtained for the equilibrium-constant expression
when equilibrium concentrations are substituted.

[𝑫]𝒅 [𝑬]𝒆
aA + bB ⇌ dD + eE 𝑲𝒄 =
[𝑨]𝒂 [𝑩]𝒃

A small Kc indicates relatively _________ concentrations of reactants

and relatively __________ concentrations of products at equilibrium.
high, low
high, high
low, low
low, high
What does the Magnitude of Kc Mean?

 A very large value of Kc (or Kp) means that the reaction goes
to “completion.”

[products] >> [reactants] when Kc >> 1

 A very small value of Kc (or Kp) means that very little product is
present.

[products] << [reactants] when Kc << 1

 When Kc has an intermediate value (0.01 to 100), both

products and reactants have significant concentrations.

[products] ≈ [reactants] when Kc ≈ 1

Magnitude of Kc (or Kp)
 Which of the following reactions…
 favor products?
 favor reactants?
Magnitude of Kp

2H2(g) + O2(g) ⇌ 2H2O(g) Kp = 1.4 × 1083

 140,000,000,000,000,000,000,000,000,000,000,0
00,000,000,000,000,000,000,000,000,000,000,00
0,000,000,000,000,000

 What do you know about this reaction?

https://www.youtube.com/watch?v=qOTgeeTB_kA
Reaction Rate and Kc
 If a reaction is extremely slow, will equilibrium be
established?
 A reaction can be thermodynamically favored (i.e. K >> 1),
but it may be kinetically controlled.
 If the reaction is slow, it may not reach equilibrium for a
very long time.

 If the reaction is very fast, what does this tell us about

the size of Kc?
The rate of a reaction tells us nothing
about Kc and vice versa!!!
Effect of a Catalyst on Kc
 A catalyst has no effect on the value of Kc.

A catalyst allows a reaction to reach equilibrium

faster, but does not affect the value of Kc
The Reaction Quotient (Qc)
 The reaction quotient (Qc), is an expression that has
the same form as the equilibrium-constant expression
but whose concentration values are not necessarily at
equilibrium.
 We can use Qc to assess a reaction at instantaneous, non-
equilibrium conditions.

aA + bB ⇌ dD + eE

[𝑫]𝒅 [𝑬]𝒆
𝑸𝒄 =
[𝑨]𝒂 [𝑩]𝒃
The Reaction Quotient (Qc)
 Qc has the same form as the equilibrium-constant expression
but concentrations are not necessarily at equilibrium.

[𝑫]𝒅 [𝑬]𝒆
aA + bB ⇌ dD + eE 𝑸𝒄 =
[𝑨]𝒂 [𝑩]𝒃

If your calculation for Qc is larger than the actual value of Kc, what
does that mean about the reaction?
There must be more products than there would be at equilibrium.
There must be more reactants than there would be at equilibrium.
The reaction is too slow.
The reaction is too fast.
The Reaction Quotient (Qc)
 Qc has the same form as the equilibrium-constant expression
but concentrations are not necessarily at equilibrium.

[𝑫]𝒅 [𝑬]𝒆
aA + bB ⇌ dD + eE 𝑸𝒄 =
[𝑨]𝒂 [𝑩]𝒃

If your calculation for Qc is smaller than the actual value of Kc, what
does that mean about the reaction?
There must be more products than there would be at equilibrium.
There must be more reactants than there would be at equilibrium.
The reaction is too slow.
The reaction is too fast.
Reaction Quotient
 We can use Qc to assess a reaction at instantaneous, non-
equilibrium conditions.

Not enough Too much

products products
Practice Problem

N2(g) + 3H2(g) ⇌ 2NH3(g)

Kc = 0.500 at 400 °C

 1.00 mol N2, 3.00 mol H2, and 0.0500 mol NH3 are added to
a 5.00-L reaction vessel.

In which direction with the system shift in

order to establish equilibrium at 400 °C?
Towards the products (to the right).
Towards the reactants (to the left).
No shift, the reaction is at equilibrium.
Le Châtelier’s Principle
Le Châtelier’s Principle
 What happens to a reaction system when you:
 Change the concentrations of reactants or products?
 Change the partial pressure of gaseous reactants and products by
changing the volume?
 Change the temperature?

 Le Châtelier’s principle states that when a system in chemical

equilibrium is disturbed by a change in temperature, pressure,
or a concentration, the system shifts in composition in a way
that tends to counteract this change.
 Changing the Concentration
 You run the following reaction using 1.000 mol CO and 3.000
mol H2 in a 10.00-L flask. At equilibrium, the following is true:

CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g)

0.613 mol 1.839 mol 0.387 mol 0.387 mol

 What would happen if we condensed the water and removed

it from the flask?

⇌ CH44(g) + H22O(g)
CO(g) + 3H22(g) →
Initial: 0.613 mol 1.839 mol 0.387 mol 0 mol

Equilibrium: 0.419 mol 1.473 mol 0.509 mol 0.122 mol

Changing the Concentration
 Consider the following reaction:

N2(g) + 3H2(g) ⇌ 2NH3(g)

 You want to maximize the production of ammonia.

 NH3 has a normal boiling point of −33.34 °C.
 N2 is a relatively cheap gas ($0.60/kg) that is purified from
air.
 H2 is a more expensive gas ($10/kg ).
Changing the Concentration
 If you add more reactant, or remove some product, the
reaction will shift to the “right” (the forward direction) and the
product concentrations will increase.

↑ ↑ ↓ ↓
If: aA + bB ⇌ dD + eE

Then: aA + bB → dD + eE
Changing the Concentration
 If you remove some reactant, or add more product, the
reaction will shift to the “left” (the reverse direction) and the
reactant concentrations will increase.

↓ ↓ ↑ ↑
If: aA + bB ⇌ dD + eE

Then: aA + bB ← dD + eE
Changing the Pressure
CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g)

In which direction with the system shift in order to establish

equilibrium if the volume is decreased?
Towards the products (to the right).
Towards the reactants (to the left).
No shift, the reaction stays at equilibrium.
Changing the Pressure
 Another way to think about it:

CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g)

4 moles of gas 2 moles of gas

 What happens if you increase the pressure (by changing the

volume)?
 According to Le Châtelier’s principle, the system responds to the change
by trying to reduce the pressure.

 Reaction should shift to the right where there are less moles of
gas.
 Changing the Temperature
CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g); ∆H° = −206.2 kJ
In which direction with the system shift in order to establish
equilibrium if the reaction temperature is increased?
Towards the products (to the right).
Towards the reactants (to the left).
No shift, the reaction stays at equilibrium.

Key: Consider energy as

either a reactant or a
product of the reaction.
Changing the Temperature
 For an endothermic reaction (∆H° is positive), the
amount of products are increased at equilibrium by
an increase in temperature.
 Kc is larger at higher T

 For an exothermic reaction (∆H° is negative), the

amount of products are increased at equilibrium by
an decrease in temperature.
 Kc is larger at lower T
 Changing the Temperature

CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g); ∆H° = −206.2 kJ

Under what conditions would you expect the production of
methane to be maximized according to Le Châtelier’s principle?
High pressure, low temperature
High pressure, high temperature
Low pressure, low temperature
Low pressure, high temperature

 What other things might you do to increase your yield

of methane?