Coupled reactions can overcome an

unfavorable ∆rG
aC × aD
c d
∆rG = − RT ln K K= a
O
@ equilibrium:
a A × aB
b

exergonic:
∆ r G < 0 ⇒ K > 1 ⇒ aC × a D > a A × a B ⇒ products will
O c d a b

endergonic: dominate in equilibrium

∆ r G > 0 ⇒ K < 1 ⇒ aC × a D < a A × a B ⇒ reactants will
O c d a b

dominate in equilibrium
enzymes
BUT: If an endergonic reaction use ATP:
∆rG > 0) is coupled with a
O
(∆
strongly exergonic one (∆∆rGO ‘ < 0):
∆rG O + ∆rG O ‘ < 0
Nils Walter: Chem 260
 Sample problem 1:

Estimate the composition of a solution

in which G6P and F6P are in
equilibrium at 25oC, and draw a
graph to show how the spontaneity of
the reaction varies with composition;
∆rG = + 1.7 kJ mol-1
O

Nils Walter: Chem 260

 Sample problem 2:

In an industrial process N2 at 1 bar is

mixed with H2 at 3 bar and the two
gases are allowed to reach equilibrium
with the product ammonia in a reactor
of constant volume. At the
temperature of the reaction, K = 977.
What are the equilibrium partial
pressures of the three gases?

Nils Walter: Chem 260

 Le Chatelier’s principle
When a system at equilibrium is subjected to a
disturbance, its composition adjusts so as to tend to
minimize the effect of the disturbance

⇒ When a system at equilibrium is heated,

a) the equilibrium composition of an
exothermic reaction will shift towards reactants,
b) while the equilibrium composition of an Why?
endothermic reaction will shift towards products
O O O ⇒ qualitatively:
∆rG = ∆rH - T∆
∆rS change in ∆rG = -(change in T) x ∆rS
O O

and neither reaction enthalpy

nor entropy shall vary with T Nils Walter: Chem 260