A system comes to equilibrium when it

reaches its minimum Gibbs energy

At constant temperature and pressure

Equilibrium at minimum Gibbs energy

Approached from either direction
Dynamic

Equilibrium composition
At constant T and p, a reaction mixture tends to
adjust its composition until its Gibbs energy is a
minimum.

(a) Does not go

(b) equal reactants and products
(c) goes almost to completion

Chemical potential of mixtures

Mixture of reactants & products at equilibria
partial molar properties

G = nAGA + nBGB
Chemical potential,
G = nAA + nBB
is a measure of the ability of the substance to
bring about physical and chemical change

DrG
DrG is the difference in of reactants and products
at the composition of the reaction mixture.

aA + b B c C + d D
DrG = (cC + dD) (aA + bB)

DrG
Slope of graph of G against change in composition

DrG = 0 equilibrium at constant T and p

Variation of DrG with composition

= J + RT lnaJ
Thermodynamic activity, a
effective concentration
p
ideal gases: a
p 1 bar
p
[ A]
solutions: a
[ A] 1 mol dm3
[ A]
pure l or s: a(pure solid) a(pure liquid) 1

aC aD
Dr G Dr G RT ln a b
aA aB
c

Reaction quotient & equilibria

To simplify the expression
Reaction quotient, Q (dimensionless)
aC aD
Q a b
a A aB
Dr G Dr G RT ln Q
c

Equilibrium composition
aCc aDd
K a b
aA aB equilibrium
0 Dr G RT ln K
Dr G RT ln K

Q&K

Product- or Reactant Favoured

Product-favored
K>1

Reactant-favored
K<1

Thermodynamically feasible DrG < 0, K > 1

Exergonic

Not thermodynamically feasible DrG > 0, K <1

endergonic

T when a reaction will go

When DrG changes from +ive to ive
switch from K < 1 to K > 1
Dr H
T
Dr S

Endothermic reaction
goes at higher T

Exothermic goes at lower T

Changes in conditions
Le Chateliers principal
When a system at equilibrium is subjected to a
disturbance, the composition of the system adjusts so
as to tend to minimize the effect of the disturbance.
General rule of thumb

Catalyst
Temperature
Pressure

Catalyst
rxnGo = fGo (products) fGo (reactants)
Independent of pathway
K is unchanged
Equilibrium may be reached more quickly, but a
catalyst does not change the equililibrium
constant (or composition) of a reaction.

Effect of temperature
When T is raised, the equilibrium composition of
an exothermic reaction will tend to shift towards
reactants; the equilibrium composition of an
endothermic reaction will tend to shift towards
products.

Effect of temperature
Change in DrG = (change in T) DrS
Gas formation dominates the sign of DrS

Effect of temperature
K changes with T
vant Hoff equation

Effect of temperature
vant Hoff equation

Dr H 1 1
ln K ' ln K

R T T'

If T'> T, then DrH is ive (endothermic) and K' > K

Equilibrium constant for an endothermic reaction
increases with T
Equilibrium constant for an exothermic reaction
decreases with T

Change in pressure
When a system is compressed, the composition of
a gas-phase equilibrium adjusts so as to reduce
the number of molecules in the gas phase.

DrG is standard state, 1 bar, so doesnt change

regardless of pressure
K is independent of the pressure at which the
reaction is carried out.

Change in pressure
K does not change in varying p, but composition
might
H2(g) + I2(s) 2 HI(g)

Half volume (double ptotal)

pHI
2pHI
K
to K '
2K
pH2
2pH2
K would change, so composition must change to
re-obtain K
2

Shift to reactants side.

Use the data below to calculate the standard Gibbs

energy change and the equilibrium constant, K, at
298 K for the reaction
CO (g) + H2O (g) CO2 (g) + H2 (g)

CO (g)
H2O (g)
CO2 (g)
H2 (g)

fHo298 / kJ mol1
110.5
241.8
393.5
0

So298 / J K1 mol1
197.7
188.8
213.7
130.7

H2(g) + I2(g) 2 HI(g)

Place 1.00 mol each of H2 and I2 in a 1.00 L flask.
Calculate equilibrium concentrations.
2

HI
Kc
55.3
H2 I2

Set up ICE table to define EQUILIBRIUM

concentrations.
[H2]
[I2]
Initial
1.00
1.00
Change
x
x
Equilib
(1.00 x)
(1.00 x)

[HI]
0
+2x
2x

Kc

2x

1.00 x 1.00 x
2
2x
55.3
2
1.00 x

55.3

2x

55.3
1.00 x
2x
55.3 7.436
1.00 x
2

x 0.79

[H2] = [I2] = 1.00 - x = 0.21 M

[HI] = 2x = 1.58 M