Chemical Equilibrium

Castro, Juan Carlos V.

Basic Concepts
- Chemical equilibrium exists when two opposing reactions occur simultaneously at
the same rate.
• A chemical equilibrium is a reversible reaction such that the forward reaction
rate is equal to the reverse reaction rate.

- Chemical equilibria are dynamic equilibria.

• Molecules are continually reacting, even though the overall composition of the
reaction mixture does not change.

- Graphically, this is a representation of the rates for the forward and reverse reactions
for this general reaction:
𝑎𝐴(𝑔) + 𝑏𝐵(𝑔) ↔ 𝑐𝐶(𝑔) + 𝑑𝐷(𝑔)

- One of the fundamental ideas of chemical equilibrium is that equilibrium can be

established from either the forward or reverse direction.

The Equilibrium Constant

- For a simple one-step mechanism reversible reaction such as:

𝐴(𝑔) + 𝐵(𝑔) ↔ 𝐶(𝑔) + 𝐷(𝑔)

 - The rates of the forward and reverse reactions can be represented as:

𝑅𝑎𝑡𝑒𝑓 = 𝑘𝑓 [𝐴][𝐵] → 𝑓𝑜𝑟𝑤𝑎𝑟𝑑 𝑟𝑎𝑡𝑒

𝑅𝑎𝑡𝑒𝑟 = 𝑘𝑟 [𝐶 ][𝐷 ] → 𝑓𝑜𝑟𝑤𝑎𝑟𝑑 𝑟𝑎𝑡𝑒

- Because the ratio of two constants is a constant, we can define a new constant as
follows:
𝑘𝑓 [𝐶 ][𝐷]
= 𝐾𝐶 → 𝐾𝐶 =
𝑘c [𝐴][𝐵]

- Similarly, for the general reaction:

𝐴(𝑔) + 𝐵(𝑔) ↔ 𝐶(𝑔) + 𝐷(𝑔)
We can define a constant:
[𝐶 ]𝑐 [𝐷 ]𝑑
𝐾𝑐 =
[𝐴]𝑎 [𝐵]𝑏
where Kc is the equilibrium constant.
Note: This expression is valid for all reactions.
- Kc is defined for a reversible reaction at a given temperature as the product of the
equilibrium concentrations (in M) of the products, each raised to a power equal to its
stoichiometric coefficient in the balanced equation, divided by the product of the
equilibrium concentrations (in M) of the reactants, each raised to a power equal to its
stoichiometric coefficient in the balanced equation.
Example 1: Write equilibrium constant expressions for the following reactions at 500°𝐶.
𝑃𝐶𝑙5 ↔ 𝑃𝐶𝑙3 + 𝐶𝑙2
[𝑃𝐶𝑙3 ][𝐶𝑙2 ]
𝐾c =
[𝑃𝐶𝑙5 ]
- Equilibrium constants are dimensionless because they involve a thermodynamic
quantity called activity.
• Activities are directly related to molarity.
Example 2: One liter of equilibrium mixture from the following system at a high
temperature was found to contain 0.172 mole of phosphorus trichloride, 0.086 mole of
chlorine, and 0.028 mole of phosphorus pentachloride. Calculate 𝐾𝑐 for the reaction.
𝑃𝐶𝑙5 ↔ 𝑃𝐶𝑙3 + 𝐶𝑙2
Given: PCl5 = 0.028 M; PCl3 = 0.172 M; Cl2 = 0.086 M
 [𝑃𝐶𝑙3 ][𝐶𝑙2 ]
𝐾𝑐 =
[𝑃𝐶𝑙5 ]
(0.172)(0.086)
𝐾𝑐 =
0.028
𝐾𝑐 = 0.53
Example 3: The decomposition of 𝑃𝐶𝑙5 was studied at another temperature. One mole of
𝑃𝐶𝑙5 was introduced into an evacuated 1.00-liter container. The system was allowed to
reach equilibrium at the new temperature. At equilibrium, 0.60 mole of 𝑃𝐶𝑙3 was present in
the container. Calculate the equilibrium constant at this temperature.
𝑃𝐶𝑙5 (𝑔) ↔ 𝑃𝐶𝑙3 (g) + 𝐶𝑙2 (𝑔)

𝑃𝐶𝑙5 (𝑔) 𝑃𝐶𝑙3 (g) 𝐶𝑙2 (𝑔)

Initial 1.00 M 0 0
Change -0.60 M +0.60 M +0.60 M
Equilibrium 0.40 M 0.60 M 0.60 M

(0.60)(0.60)
𝐾𝑐′ = = 0.90 𝑎𝑡 𝑎𝑛𝑜𝑡ℎ𝑒𝑟 𝑇
0.40
Example 4: At a given temperature, 0.80 mole of 𝑁2 and 0.90 mole of 𝐻2 were placed in an
evacuated 1.00-liter container. At equilibrium, 0.20 mole of 𝑁𝐻3 was present. Calculate 𝐾𝑐
for the reaction.
𝑁2 (𝑔) + 3𝐻2 (g) ↔ 2𝑁𝐻3 (𝑔)

𝑁2 (𝑔) 3𝐻2 (g) 2𝑁𝐻3 (𝑔)

Initial 0.80 M 0.90 M 0

Change -0.10 M -0.30 M +0.20 M
Equilibrium 0.40 M 0.60 M 0.60 M

[𝑁𝐻3 ]2 (0.20)2
𝐾𝑐 = = = 0.26
[𝑁2 ][𝐻2 ]3 (0.70)(0.60)3

Variation of K c with the Form of the Balanced

Equation
[𝑃𝐶𝑙5 ] (0.028)
𝐾𝑐′ = = = 1.9
[𝑃𝐶𝑙3 ][𝐶𝑙2 ] (0.172)(0.086)
 1 1
𝐾𝑐 = ′
𝑜𝑟 𝐾𝑐′ = = 1.9
𝐾𝑐 0.53
- Large equilibrium constants indicate that most of the reactants are converted to
products.
- Small equilibrium constants indicate that only small amounts of products are formed.

Kc for Non-elementary reaction

If a reaction can be expressed as the sum of two or more reactions, the equilibrium constant
for the overall reaction is given by the product of the equilibrium constants of the individual
reactions.
𝐴+𝐵 ↔𝐶+𝐷 𝐾𝐶′ [𝐶 ][𝐷]
𝐾𝐶′ =
[𝐴][𝐵]
𝐶+𝐷 ↔𝐸+𝐹 𝐾𝐶′′ [𝐸][𝐹]
𝐾𝐶′′ =
[𝐶 ][𝐷]
𝐴+𝐵 ↔𝐸+𝐹 𝐾𝐶 [𝐸][𝐹]
𝐾𝐶 =
[𝐴][𝐵]

𝐾𝐶 = 𝐾𝐶′ × 𝐾𝐶′′

The Reaction Quotient

- The mass action expression or reaction quotient has the symbol Q.
• Q has the same form as 𝐾𝑐 .
- The major difference between Q and 𝐾𝑐 is that the concentrations used in Q are not
necessarily equilibrium values.
Why do we need another “equilibrium constant” that does not use equilibrium
concentrations?
- Q will help use predict how the equilibrium will respond to an applied stress.
To make this prediction, we compare Q with 𝐾𝑐 ;
• If 𝑄𝑐 < 𝐾𝑐 , system proceeds from left to right to reach equilibrium.
• If 𝑄c = 𝐾𝑐 , the system is at equilibrium.
• If 𝑄𝑐 > 𝐾𝑐 , system proceeds from right to left to reach equilibrium.
Example 1: The equilibrium constant for the following reaction is 49 at 450°𝐶. If 0.22 mole
of 𝐼2 , 0.22 mole of 𝐻2 , and 0.66 mole of 𝐻𝐼 were put into an evacuated 1.00-liter container,
would the system be at equilibrium?
Note: The concentrations given in the problem are not necessarily equilibrium
concentrations.

We can calculate Q:
𝐻2 (𝑔) + 𝐼2 (𝑔) ↔ 2𝐻𝐼(𝑔)

𝐻2 (𝑔) 𝐼2 (g) 2𝐻𝐼(𝑔)

Concentrations 0.22 M 0.22 M 0.66

[𝐻𝐼 ]2 (0.66)2
𝑄= = = 9.0
[𝐻2 ][𝐼2 ] (0.22)(0.22)

𝑄 = 9.0, 𝑏𝑢𝑡 𝐾𝑐 = 49; 𝑄 < 𝐾𝑐

Uses of the Equilibrium Constant, K c

Example 2: The equilibrium constant, 𝐾𝑐 is 3.00 for the following reaction at a given
temperature. If 1.00 mole of 𝑆𝑂2 and 1.00 mole of 𝑁𝑂2 are put into an evacuated 2.00 L
container and allowed to reach equilibrium, what will be the concentration of each
compound at equilibrium?
𝑆𝑂2 (𝑔) + 𝑁𝑂2 (𝑔) ↔ 𝑆𝑂3 (𝑔) + 𝑁𝑂(𝑔)

𝑆𝑂2 (𝑔) 𝑁𝑂2 (𝑔) 𝑆𝑂3 (𝑔) 𝑁𝑂(𝑔)

Initial 0.500 M 0.500 M 0 0

Change -x M -x M +x M +x M
Equilibrium (0.500 − 𝑥)𝑀 (0.500 − 𝑥)𝑀 xM xM
[𝑆𝑂3 ][𝑁𝑂] (𝑥)(x)
𝐾𝑐 = → 3.00 =
[𝑆𝑂2 ][𝑁𝑂2 ] (0.500 − 𝑥)(0.500 − 𝑥)
Take the square root of both sides.
𝑥 0.865
1.73 = → 0.865 − 1.73𝑥 = 𝑥 → 0.865 = 2.73𝑥 → 𝑥 =
0.500 − 𝑥 2.73
𝑥 = 0.316 𝑀 = [𝑆𝑂3 ] = [𝑁𝑂]
(0.500 − 𝑥 )𝑀 = 0.184 𝑀 = [𝑆𝑂2 ] = [𝑁𝑂2 ]

Disturbing a System at Equilibrium: Predictions

Le Chatelier’s Principle
- If a change of conditions (stress) is applied to a system in equilibrium, the system
responds in the way that best tend to reduce the stress in reaching a new state of
equilibrium.
- Some possible stresses to a system at equilibrium are:
• Changes in concentration of reactants or products;
• Changes in pressure or volume (for gaseous reactions), and;
• Changes in temperature.
For convenience, we may express the amount of a gas in terms of its partial pressure
rather than its concentration. To derive this relationship, we must solve the ideal gas
equation:
𝑛
𝑃𝑉 = 𝑛𝑅𝑇 → 𝑃 = ( ) 𝑅𝑇
𝑉
𝑛
Because (𝑉) has the units mol/L;

𝑃 = []𝑅𝑇
Thus, at constant T, the partial pressure of a gas is directly proportional to its
concentration.

Le Chatelier’s Principle
Changes in Concentration
𝑎𝐴 + 𝑏𝐵 ↔ 𝑐𝐶 + 𝑑𝐷
Change Shifts the equilibrium to:
Increase concentration of product(s) left
Decrease concentration of product(s) right
Increase concentration of reactant(s) right
Decrease concentration of reactant(s) left

Changes in Volume and Pressure

𝐴(𝑔) + 𝐵(𝑔) ↔ 𝐶(𝑔)

Change Shifts the equilibrium to:

Increase pressure Side with fewest moles of gas
Decrease pressure Side with most moles of gas
Increase volume Side with most moles of gas
Decrease volume Side with fewest moles of gas

Changes in Temperature
 Change Endothermic Reaction Exothermic Reaction
Increase temperature K increases K decreases
Decrease temperature K decreases K increases

- Adding a Catalyst
• Does not change K.
• Does not shift the position of an equilibrium system.
• System will reach equilibrium sooner.

- Catalyst lowers 𝐸𝑎 for both forward and reverse reactions.

- Catalyst does not change equilibrium constant or shift equilibrium.

Partial Pressures and the Equilibrium Constant

- For gas phase reactions, the equilibrium constants can be expressed in partial pressures
rather than concentrations.
- For gases, the pressure is proportional to the concentration.
We can see this by looking at the ideal gas law:
𝑛𝑅𝑇
𝑃𝑉 = 𝑛𝑅𝑇 → 𝑃 =
𝑉
𝑛
Given 𝑉 = 𝑀:

𝑃
𝑃 = 𝑀𝑅𝑇; 𝑀 =
𝑅𝑇
Example: Consider this system at equilibrium at 500°𝐶.
2𝐶𝑙2 (𝑔) + 2𝐻2 𝑂(𝑔) ↔ 4𝐻𝐶𝑙(𝑔) + 𝑂2 (𝑔)
 [𝐻𝐶𝑙 ]4 [𝑂2 ] (𝑃𝐻𝐶𝑙 )4 (𝑃𝑂2 )
𝐾𝑐 = 𝑎𝑛𝑑 𝐾𝑝 = 2 2
[𝐶𝑙 ]2 [𝐻2 𝑂]2 (𝑃𝐶𝑙2 ) (𝑃𝐻2 𝑂 )

𝑃𝐻𝐶𝑙 4 𝑃𝑂2 1 5
( 𝑅𝑇 ) ( 𝑅𝑇 ) (𝑅𝑇)
4
(𝑃𝐻𝐶𝑙 ) (𝑃𝑂2 )
𝐾𝑐 = = ×
𝑃𝐶𝑙2 2 𝑃𝐻2𝑂 2 (𝑃𝐶𝑙 )2 (𝑃𝐻 𝑂 )2 1 4
(
( ) ( ) 𝑅𝑇)
2 2
𝑅𝑇 𝑅𝑇
𝐿∙atm
Where 𝑅 = 0.0821 𝑚𝑜𝑙∙K .

Also, we can see that the relationship between 𝐾𝑝 and 𝐾𝑐 is:

𝐾𝑝 = 𝐾𝑐 (𝑅𝑇) 𝛥𝑛 𝑜𝑟 𝐾𝑐 = 𝐾𝑝 (𝑅𝑇)−𝛥𝑛

𝛥𝑛 = (# 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑔𝑎𝑠𝑒𝑜𝑢𝑠 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − (# 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑔𝑎𝑠𝑒𝑜𝑢𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

Relationship Between ΔGorxn and the Equilibrium

Constant
- 𝛥𝐺°𝑟𝑥𝑛 is the standard free energy change.
• 𝛥𝐺°𝑟𝑥𝑛 is defined for the complete conversion of all reactants to all products.

- Δ𝐺 is the free energy change at nonstandard conditions.

• For example, concentrations other than 1 M or pressures other than 1 atm.
Δ𝐺is related to Δ𝐺° by the following relationship:
𝛥𝐺 = 𝛥𝐺° + 𝑅𝑇 𝑙𝑛 𝑄 𝑜𝑟 𝛥𝐺 = 𝛥𝐺° + 2.303𝑅𝑇 𝑙𝑜𝑔 𝑄
Where 𝑄 = 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑞𝑢𝑜𝑡𝑖𝑒nt
At equilibrium, Δ𝐺 = 0 and 𝑄 = 𝐾𝑐 . We can derive this relationship:
𝛥𝐺° = −𝑅𝑇 𝑙𝑛 𝐾 𝑜𝑟 𝛥𝐺° = −2.303 𝑅𝑇 𝑙𝑜𝑔 𝐾
For the following generalized reaction, the thermodynamic equilibrium constant is
defined as follows:
𝑎𝐴 + 𝑏𝐵 ↔ 𝑐𝐶 + 𝑑𝐷
(𝑎𝐶 )𝑐 (𝑎𝐷 )𝑑
𝐾=
(𝑎𝐴 )𝑎 (𝑎𝐵 )𝑏
Where 𝑎𝐴 𝑖𝑠 𝑡ℎ𝑒 𝑎𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑜𝑓 𝐴, 𝑠𝑎𝑚𝑒 𝑐𝑜𝑛𝑐𝑒𝑝𝑡 𝑔𝑜𝑒𝑠 𝑤𝑖𝑡ℎ 𝑡ℎ𝑒 𝑜𝑡ℎ𝑒𝑟𝑠

- The relationships among 𝛥𝐺°𝑟𝑥𝑛 , K, and the spontaneity of a reaction are:

 𝛥𝐺°𝑟𝑥𝑛 K Spontaneity at unit concentration
<0 >1 Forward reaction is spontaneous
=0 =1 System at equilibrium
>0 <1 Reverse reaction is spontaneous

- From the value of Δ𝐻° and K at one temperature, 𝑇1 , we can estimate the value of K at
another temperature, 𝑇2.
𝐾𝑇2 𝛥𝐻°(𝑇2 − 𝑇1 ) 𝐾𝑇 𝛥𝐻° 1 1
𝑙𝑛 = 𝑜𝑟 𝑙𝑛 2 = ( − )
𝐾𝑇1 𝑅(𝑇2 𝑇1 ) 𝐾𝑇1 𝑅 𝑇1 𝑇2

Formulas
Equilibrium Constant
For the general reaction:
𝐴(𝑔) + 𝐵(𝑔) ↔ 𝐶(𝑔) + 𝐷(𝑔)

[𝐶 ]𝑐 [𝐷 ]𝑑
𝐾𝐶 =
[𝐴]𝑎 [𝐵]𝑏
Non-elementary Reaction
𝐾𝐶 = 𝐾𝐶′ × 𝐾𝐶′′
Le Chatelier’s Principle
𝑛
𝑃𝑉 = 𝑛𝑅𝑇 → 𝑃 = ( ) 𝑅𝑇
𝑉
𝑛
Because (𝑉) has the units mol/L;

𝑃 = []𝑅𝑇
Changes in Concentration
𝑎𝐴 + 𝑏𝐵 ↔ 𝑐𝐶 + 𝑑𝐷
Change Shifts the equilibrium to:
Increase concentration of product(s) left
Decrease concentration of product(s) right
Increase concentration of reactant(s) right
Decrease concentration of reactant(s) left

Changes in Volume and Pressure

𝐴(𝑔) + 𝐵(𝑔) ↔ 𝐶(𝑔)
 Change Shifts the equilibrium to:
Increase pressure Side with fewest moles of gas
Decrease pressure Side with most moles of gas
Increase volume Side with most moles of gas
Decrease volume Side with fewest moles of gas

Changes in Temperature
Change Endothermic Reaction Exothermic Reaction
Increase temperature K increases K decreases
Decrease temperature K decreases K increases

- Adding a Catalyst
• Does not change K.
• Does not shift the position of an equilibrium system.
• System will reach equilibrium sooner.

- Catalyst lowers 𝐸𝑎 for both forward and reverse reactions.

Catalyst does not change equilibrium constant or shift equilibrium.
Partial Pressures and the Equilibrium Constant
𝑛𝑅𝑇
𝑃𝑉 = 𝑛𝑅𝑇 → 𝑃 =
𝑉
𝑛
Given 𝑉 = 𝑀:

𝑃
𝑃 = 𝑀𝑅𝑇; 𝑀 =
𝑅𝑇
𝐿∙atm
Where 𝑅 = 0.0821 𝑚𝑜𝑙∙K .
 Also, we can see that the relationship between 𝐾𝑝 and 𝐾𝑐 is:

𝐾𝑝 = 𝐾𝑐 (𝑅𝑇) 𝛥𝑛 𝑜𝑟 𝐾𝑐 = 𝐾𝑝 (𝑅𝑇)−𝛥𝑛

Relationship Between ΔGorxn and the Equilibrium Constant

Δ𝐺is related to Δ𝐺° by the following relationship:
𝛥𝐺 = 𝛥𝐺° + 𝑅𝑇 𝑙𝑛 𝑄 𝑜𝑟 𝛥𝐺 = 𝛥𝐺° + 2.303𝑅𝑇 𝑙𝑜𝑔 𝑄
Where 𝑄 = 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑞𝑢𝑜𝑡𝑖𝑒nt
At equilibrium, Δ𝐺 = 0 and 𝑄 = 𝐾𝑐 . We can derive this relationship:
𝛥𝐺° = −𝑅𝑇 𝑙𝑛 𝐾 𝑜𝑟 𝛥𝐺° = −2.303 𝑅𝑇 𝑙𝑜𝑔 𝐾
For the following generalized reaction, the thermodynamic equilibrium constant is
defined as follows:
𝑎𝐴 + 𝑏𝐵 ↔ 𝑐𝐶 + 𝑑𝐷
(𝑎𝐶 )𝑐 (𝑎𝐷 )𝑑
𝐾=
(𝑎𝐴 )𝑎 (𝑎𝐵 )𝑏
Where 𝑎𝐴 𝑖𝑠 𝑡ℎ𝑒 𝑎𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑜𝑓 𝐴, 𝑠𝑎𝑚𝑒 𝑐𝑜𝑛𝑐𝑒𝑝𝑡 𝑔𝑜𝑒𝑠 𝑤𝑖𝑡ℎ 𝑡ℎ𝑒 𝑜𝑡ℎ𝑒𝑟𝑠

- The relationships among 𝛥𝐺°𝑟𝑥𝑛 , K, and the spontaneity of a reaction are:

𝛥𝐺°𝑟𝑥𝑛 K Spontaneity at unit concentration
<0 >1 Forward reaction is spontaneous
=0 =1 System at equilibrium
>0 <1 Reverse reaction is spontaneous

- From the value of Δ𝐻° and K at one temperature, 𝑇1 , we can estimate the value of K at
another temperature, 𝑇2.
𝐾𝑇2 𝛥𝐻°(𝑇2 − 𝑇1 ) 𝐾𝑇 𝛥𝐻° 1 1
𝑙𝑛 = 𝑜𝑟 𝑙𝑛 2 = ( − )
𝐾𝑇1 𝑅(𝑇2 𝑇1 ) 𝐾𝑇1 𝑅 𝑇1 𝑇2