Chem 3 Chemical Equilibrium Lecture Notes Part 3 c!

e-γoT 2010
LE CHATELIER’S PRINCIPLE & GIBB’S FREE ENERGY (17.6)
Demo: Chromate-Dichromate Equilibrium (ADOBCY)
2CrO42- (aq) +2H+ (aq)  Cr2O72- (aq) + H2O (l)
2CrO42- (aq) + H2O (aq)  Cr2O72- (aq) + 2OH- (aq)
Stress: Acidity/Basicity
Observation: Color Change

Le Chatelier’s Principle: When a system at equilibrium is subjected to a stress, the system will adjust so as to relieve the
stress
These stresses or factors affecting chemical equilibrium could be:
 Change in concentration of the species
 Change in pressure
 Change in volume
 Change in temperature
 Effect of catalysis
 Effect of inert gas

Example: Consider the hypothetical reaction: 2A(g) + B(g)  C(g) + D(g) + heat
1. Adding more A - direction: →, ↑ [A], ↓ [B], ↑[C], ↑ [D], KEQ: no change
2. Removal of B – direction: ←, ↑ [A], ↓ [B], ↓ [C], ↓ [D], KEQ: no change
3. Heating the reaction vessel: direction: ←, ↑ [A], ↑ [B], ↓ [C], ↓ [D], KEQ: ↓
4. What will be the effect of a + catalyst, - catalyst? No effect
5. Increasing the pressure: direction: →, ↓ [A], ↓ [B], ↑[C], ↑ [D], KEQ: no change
6. Increasing the volume of the reaction vessel: direction: ←, ↑ [A], ↑ [B], ↓ [C], ↓ [D], KEQ: no change
7. Adding inert species X into the vessel will cause which effect on the equilibrium system? ↑ Ptotal, ↓ Χ

∆G = ∆H - T∆S ∆Go = -RTlnKEQ

Case 1: Keq > 1, ∆G <0 therefore spontaneous
Case 2: Keq < 1, ∆G >0 therefore nonspontaneous
Case 3: Keq = 1, ∆G =0 therefore equilibrium