9/27/2017

Thermodynamics of Reaction

Reaction in General
Reaction:
𝑎𝐴 + 𝑏𝐵 ↔ 𝑐𝐶 + 𝑑𝐷
The ratio products and reactants:
𝑐 𝑑
𝐶 𝐷
𝑄= 𝑎 𝑏
𝐴 𝐵
At equilibrium the ratio (Q) equal to equilibrium constant (K)

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Free Energy of Reaction

Total Gibbs free energy:

𝐺𝑇 = 𝐺𝐴 + 𝐺𝐵 + 𝐺𝐶 + 𝐺𝐷
Total Gibbs free energy is a function of reaction
conversion ( )
At equilibrium, total free energy is minimum (at
constant P and T)
dGT
0
d

The change of GT
For a certain chemical reaction,

∆𝐺 = ∆𝐺𝑇 = 𝜗𝑖 𝐺𝑖 𝑝𝑟𝑜𝑑 − 𝜗𝑖 𝐺𝑖 𝑟𝑒𝑎𝑐𝑡

i = stoichiometric reaction
Gi = free energy / mole

At constant pressure and temperature,

G  H  T S
• G < 0 ; GT decreases as reaction proceeds  reaction is spontaneous
• G = 0; GT minimum  equilibrium
• G > 0; GT increases as reaction proceeds  reaction is not spontaneous

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The change of GT
Free energy of component i at T can be calculated,
Gi  G of ,i  RT ln ai

Free energy formation Chemical activity of component i

at standard conditions

Therefore,  i vi 
  ai 
 products
G  G  RT ln i
o

 vi 
  ai 
 reactants
G o   (i Gio ) prod   (i Gio ) react
Gio  free energy change per mole of i at standard condition

Chemical Activity (ai)

• For ions and molecules in solution:
ai   i [i ]
i : activity coefficient; for dilute system   1

• For pure solids or liquids at equilibrium: ai  1

• For gases in equilibrium with a solution:

ai   i Pi
At low pressure (atmospheric) i  1
Pi : partial pressure
• For mixtures of liquids: ai  X i

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Example: Calcination of Calcite


CaCO3(s)   CaO(s) + CO 2(g)

aCaO  aCO2
G  G o  RT ln
aCaCO3
The reaction is heterogeneous in which CaCO3 and
CaO are separated pure entity.
aCaO  1 ; aCaCO3  1
If total pressure is relatively low,
aCO2  PCO2

Example #2
G  G o  RT ln PCO2

• At equilibrium G = 0
G o   RT ln PCO2
• If G < 0, the reaction will proceed spontaneously.
• If G > 0, the reaction will NOT proceed spontaneously.

Question:
At which temperature the reaction is favorable?

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Relation G with H and T

Basic thermodynamics equation:
dG   SdT  VdP
At constant pressure,
 dG 
dG   SdT    S
 dT  p
For a finite change in state,
 d G 
   S
 dT p

Relation #2

G  H  T S
 d G 
G  H  T  
 dT  p
Divided all terms by T2

Gibbs-Helmholtz equation

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Relation #2
At equilibrium,
G o   RT ln K

Since Ho and Go are not function of P,