Standard Free energy and

equilibrium constant

Osama Aadil Saadi

160301029
MS&E-09
Content:
• Relation between ΔG and K
• Effect of temperature on K (Le Chateliers
principle)
• variation in K in case of gases, solutions
and solids
 Equilibrium constant:

It is the ratio of activities of products to the activities

of reactants. It is written as
𝞹 𝑎𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
K=
𝞹 𝑎𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

K= equilibrium constant
a= activity
 Relation between ΔG° and K

Consider the reaction

A + B 2C
Constant pressure and temperature
No net change in composition.

At equilibrium, free energy of reactants is equal to

products.
 𝐺𝐴 + 𝐺𝐵 = 2𝐺𝐶

(𝐺𝐴0 +𝑅𝑇 ln 𝑎𝐴 ) + (𝐺𝐵0 + 𝑅𝑇 ln 𝑎𝐵 ) = 2 (𝐺𝐶0 + 𝑅𝑇 ln 𝑎𝐶 )

Rearranging the equation
2
𝑎 𝐶
2𝐺𝐶0 − 𝐺𝐴0 + 𝐺𝐵0 = −𝑅𝑇 ln
𝑎𝐴 . 𝑎𝐵
2
𝑎𝐶
∆𝐺 0 = −𝑅𝑇 ln
𝑎𝐴 . 𝑎𝐵
∆𝐺 0 is the standard free energy change
 2
𝑎𝐶
K=
𝑎𝐴 .𝑎𝐵

∆𝐺 0 = −𝑅𝑇 ln 𝐾
 Effect of temperature on K

∆𝐺 0 = ∆𝐻 0 − 𝑇∆𝑆 0

∆𝐺 0 ∆𝐻 0
= − ∆𝑆 0
𝑇 𝑇
−𝑅𝑇 ln 𝑘𝑝 ∆𝐻 0
= − ∆𝑆 0
𝑇 𝑇
∆𝐻 0 ∆𝑆 0
ln 𝑘𝑝 = − +
𝑅𝑇 𝑅
Partial differentiating
𝜕 ln 𝑘𝑝 ∆𝐻 0
=
𝜕𝑇 𝑅𝑇 2
The equation is one of mathematical expressions for Le Chatelier’s
Principle

If ∆𝐻 > 0, 𝑘𝑝 increases as temperature increases (endothermic).

If ∆𝐻 < 0, 𝑘𝑝 decreases as temperature increases (exothermic).
 K in case of gases, solutions and
solids
In general case
𝞹 𝑎𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
K=
𝞹 𝑎𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
For gases
𝑝𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
𝑘=
𝑝𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
For ideal solution
𝑎𝐴 = 𝑋𝐴
For non-ideal solution
𝑎𝐴 = 𝛾𝐴 𝑋 𝐴
For pure solid
𝑎𝐴 = 1

EXAMPLE:
Calculate Kp for the reaction of H2 with N2 to give NH3 at 25°C.
ΔG° for this reaction is −32.7 kJ/mol of N2.
∆𝐺 0 = −𝑅𝑇 ln 𝐾
∆𝐺 0
= ln K
−𝑅𝑇
(−32.7)(1000)
ln K= =13.2
(8.314)(298)

K = 5.4 ×10