Chemical Equilibria

CHEMICAL EQUILIBRIA
Outline
The equilibrium Constant, Kc
The Law of Mass Action
Gas Phase Equilibrium Constant, Kp
TOPICAL OBJECTIVES
At the end of this topic, students should be able to:
i. To define the state of dynamic equilibrium
ii. State the characteristics and requirements for dynamic
equilibrium
iii. State what the equilibrium constant, K represent
iv. To quantitatively determine the composition of a reaction
mixture when it is at a state of dynamic equilibrium?
v. Predict and explain how specific changes made to a system at
equilibrium affects the equilibrium position
We mostly describe chemical reactions as going to completion:
AgNO3 (aq) + NaCl (aq)  AgCl (s) + NaNO3 (aq)
 Identify limiting reactant
 Calculate theoretical & percent yields
◆ For many chemical reactions, this discussion is not appropriate
because they do not go to completion.
◆ For these reactions we want to talk about: when they reach dynamic
equilibrium
 [reactants] & [products] present at equilibrium

Reddish-brown gas colorless gas
 Put NO (g) in a sealed container at 25°C
 see decrease in intensity of brown color as

NO2 is converted to N2O4
 Contents of container never go completely

colorless
∴ the reaction does not go to completion
 At some point the intensity of brown color

stops changing
∴the [NO2] is constant NO2 N2O4
 The system has reached a state of dynamic

equilibrium
For a system at equilibrium:
◆ both forward and reverse reactions are occurring simultaneously
◆ rate of forward reaction must equal rate of reverse reaction
OR
Rate of forward = Rate of reverse
◆ concentrations of reactants and products remain constant with
time
Changes in Rate and Concentration as a System
Approaches Equilibrium:
CO (g) + 3 H2 (g) ⇄ CH4 (g) + H2O (g)
CO (g) + 3 H2 (g) ⇄Occurs

This has not formed ye
CH4 (g) + H2O (g)
KC Values for Related Reactions
How does KC change if the chemical reaction is/ has:
i. Written in reverse?
ii. The stoichiometric coefficients are changed i.e.

multiplied by n
iii. The sum of 2 or more chemical reactions

I. REVERSE REACTION
For a reversed chemical equation, Kc is

the reciprocal of the original equilibrium
constant.
II. Reaction multiplied by a Factor “n”
If the stoichiometric coefficients are multiplied by

some factor, n, Kc must be raised to the nth power.
III. SUM OF REACTIONS
For the sum of 2 or more chemical reactions
For the sum of 2 or equations, Kc for the

overall reaction is the product of the Kcs
for the component reactions.
Summary of K’s for Related Equations:
Gas Phase Equilibrium Constant, KP
Partial pressures of reactants and products present at equilibrium
Relationship between KC and KP: At a given temperature is:
KP = KC(RT)∆n
∆n = mol gas phase product – mol gas phase reactant
KP = KC when ∆n = 0
Heterogeneous Equilibria
• Reactants and products are present in different phases
Examples:
H2O (l) ⇄ H2O (g)
CO2 (g) + C (s) ⇄ 2 CO (g)
• Concentrations of pure liquids and pure solids are

constant and do not change
• Solids and liquids are not included in the equilibrium

expression
• two very important examples for upcoming chapters
• Heterogeneous equilibria involving weak acids and/or
weak bases:
• HNO2 (aq) + H2O (l) ⇄ H3O+ (aq) + NO2– (aq)
Kc = –––––––––––––
Heterogeneous equilibria involving the solubility of ionic
compounds:
Ca(IO3)2 (s) ⇄ Ca2+ (aq) + 2 IO3– (aq)
Kc = [Ca2+][IO3–]2
Predicting the Direction of Change:
Q vs K
How do you decide if:
i. a system is/ is not at equilibrium
ii. It proceed in the forward or reverse direction to reach
equilibrium?
We use “arbitrary initial concentrations” to calculate
• the reaction quotient, Qc
• for the reaction:
aA+bB ⇄cC+dD
c d
[C] [D]
Qc  a b
[A] [B]
Problem Set: Class Example
Determination of Equilibriun Concentrations
Process for Solving Equilibrium Problems:
• Using an Equilibrium (or ICE) Table
 Start with balanced chemical equation
 Create 3 rows for each gas or sol’n phase species:
• I = Initial concentration or pressure
• C = Change (∆) in concentration or

• Pressure as system moves to equilibrium
• E = Equilibrium concentration or pressure

Process for Solving Equilibrium Problems:
Using an Equilibrium (or ICE) Table
Reaction:
2 A (g) + B (g) ⇄ 3 C (g)

ICE Table:
What we don’t know:

 How much A and B will be consumed (and how much C will form) to get the
system to equilibrium?
OR
 We don’t know how [A], [B], and [C] will change as system approaches
equilibrium
∴ define our unknown “x”
Solution To The Eample
Determine the equilibrium composition of a
reaction using pressure data and KP
CO (g) + H2O (g) ⇄ CO2 (g) + H2 (g); KP = 4.24
A vessel is filled with 12.0 atm CO (g) and 12.0 atm

H2O (g) at 800 K, and the reaction progresses until
equilibrium is established.
Determine the pressure (in atm) of each species

present in the reaction mixture at equilibrium.
Equilibrium Calculations
To calculate value of KC or KP from the given initial
concentrations or pressures, and one equilibrium concentration
or pressure consider the following example:
H2 (g) + I2 (g) ⇄ 2 HI (g)
If 0.750 M H2 and 0.990 M I2 are combined and allowed to

react. When equilibrium is established, the concentration of I2
is found to be 0.330 M.
Determine KC for this reaction.
Solution: We apply the ICE method
Strategy:
• Use given equilibrium [I2] and [I2]
• Defined (in table) equilibrium to solve for x
• Use x to determine equilibrium [H2] and [HI]
• Plug those concentrations in to solve for KC
Problem Set: Take home
Determine the equilibrium composition of a reaction given
arbitrary initial data
N2O4 (g) ⇄ 2 NO2 (g); KC = 4.64 x 10–3
At some point after the initiation of the reaction, the mixture

is found to contain 0.0200 M N2O4 and 0.0300 M NO2.
• Determine the concentration of N2O4 and NO2 present in
this system at equilibrium.
Le Chatelier’s Principle
Stresses include:
 Changes in concentration or pressure of reactants or
products by the addition or removal
 Changes in pressure as a result of changes in volume of
container
 Changes in temperature (value of K will change) addition
of a catalyst
Changes in Concentration or Pressure
If the concentration or pressure of a substance is increased
by the addition of more reactant or product . . .
 The equilibrium position will shift in the direction that

consumes the added substance
OR
 The equilibrium position will shift away from the

increased concentration
If the concentration or pressure of a substance is decreased
by the removal of a reactant or product . . .
The equilibrium shifts in the direction that replenishes the

removed substance
OR
The equilibrium position will shift toward the decreased

concentration
Effect of Changing Pressure on
Equilibrium Position
There are 3 ways to change the pressure of a chemical
reaction system:
1. Add or remove a gas phase reactant or product
• The Preactant or Pproduct are related (through PV=nRT) to
molar concentration
• The result of adding or removing gas phase reactant or

product can be predicted according to the guidelines
stated above for effect of changing concentration.
2. Add an inert gas
 The addition of an inert gas to a system changes the total
pressure of the system, but not the partial pressures (i.e.
changing concentrations) of gas phase reactants or
products
 The result is no change in equilibrium position
3. Change the volume of the container
P and V are inversely proportional
If the equilibrium is disturbed by changing the volume of
the container, Le Chatelier’s Principle predicts:
An ↑P resulting from ↓V will bring about net reaction in the

direction that ↓s # moles of gas phase species
(i.e. ↓V chemical system ↓s).
A ↓n P resulting from ↑V will bring about net reaction in the

direction that ↑# moles of gas phase species
(i.e. ↑V chemical system ↑s).
Effect of Changing Temperature on
Equilibrium Position & K
The temperature (T) dependence of the equilibrium position
and the value of the equilibrium constant is dependent on
the sign of ∆H of the reaction.
1. Exothermic reaction will Kc ↓ as T ↑;

 Equilibrium shift to the left as temperature increases
2. Endothermic reaction Kc ↑ as T↓;

 Equilibrium is to the right as temperature increases
Effect of a Catalyst on the Equilibrium Position
• The addition of a catalyst does not effect the equilibrium
position of a reaction :
• only the rate at which the system reaches equilibrium.

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CHEMICAL EQUILIBRIA

AgNO3 (aq) + NaCl (aq)  AgCl (s) + NaNO3 (aq)

 Identify limiting reactant

 Calculate theoretical & percent yields

◆ For many chemical reactions, this discussion is not appropriate

because they do not go to completion.

 [reactants] & [products] present at equilibrium

 see decrease in intensity of brown color as

 Contents of container never go completely

∴ the reaction does not go to completion

 At some point the intensity of brown color

∴the [NO2] is constant NO2 N2O4

 The system has reached a state of dynamic

◆ rate of forward reaction must equal rate of reverse reaction

CO (g) + 3 H2 (g) ⇄Occurs

ii. The stoichiometric coefficients are changed i.e.

iii. The sum of 2 or more chemical reactions

For a reversed chemical equation, Kc is

If the stoichiometric coefficients are multiplied by

For the sum of 2 or equations, Kc for the

Relationship between KC and KP: At a given temperature is:

H2O (l) ⇄ H2O (g)

CO2 (g) + C (s) ⇄ 2 CO (g)

• Concentrations of pure liquids and pure solids are

• Solids and liquids are not included in the equilibrium

• HNO2 (aq) + H2O (l) ⇄ H3O+ (aq) + NO2– (aq)

• I = Initial concentration or pressure

• C = Change (∆) in concentration or

• E = Equilibrium concentration or pressure

2 A (g) + B (g) ⇄ 3 C (g)

What we don’t know:

CO (g) + H2O (g) ⇄ CO2 (g) + H2 (g); KP = 4.24

A vessel is filled with 12.0 atm CO (g) and 12.0 atm

Determine the pressure (in atm) of each species

H2 (g) + I2 (g) ⇄ 2 HI (g)

If 0.750 M H2 and 0.990 M I2 are combined and allowed to

At some point after the initiation of the reaction, the mixture

 The equilibrium position will shift in the direction that

 The equilibrium position will shift away from the

The equilibrium shifts in the direction that replenishes the

The equilibrium position will shift toward the decreased

• The result of adding or removing gas phase reactant or

An ↑P resulting from ↓V will bring about net reaction in the

A ↓n P resulting from ↑V will bring about net reaction in the

1. Exothermic reaction will Kc ↓ as T ↑;

2. Endothermic reaction Kc ↑ as T↓;

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