Temperature dependence

O
change in ∆rG
= -(change in T) x ∆rS
O
O
∆rS < 0
T↑↑:
•exothermic reaction O
shifts towards reactants ∆rS ≈ 0
•endothermic reaction
shifts towards products
O
∆rS > 0

Effect on K:
∆rG
O
∆r H
O
∆r S
O ∆r H O ∆r S O
ln K = − =− + ln K ' = − +
RT RT R RT ' R
K ' ∆r H O  1 1  van’t Hoff
⇒ ln K '− ln K = ln =  −  equation
K  Walter: Chem 260
R  T T 'Nils
 The effect of compression
Le Chatelier:
When a system at equilibrium is compressed,
the composition of a gas-phase equilibrium adjusts
so as to reduce the number of molecules in the gas phase
O
BUT: ∆rG is measured at 1 bar and
DOES NOT CHANGE WITH PRESSURE
⇒ K IS INDEPENDENT OF PRESSURE

Example: N2(g) + 3 H2(g) → 2 NH3(g)

2
p NH 3 (2 p NH 3 ) 2 1
K= 3
pressure doubled K'= 3
= K
p N 2 pH 2 (2 p N 2 )(2 pH 2 ) 4

BUT: K and K’ must be identical ⇒ partial

pressures must adjust ⇒ more NH3 formed
(Haber-Bosch process) Nils Walter: Chem 260
 Consequences of equilibrium
Atkins, Chapter 8
aC × aD
c d
reaction aA + bB → cC + dD ⇒ K =
a A × aB
a b

K is truly a constant (@ constant T): retains its value even

if individual activities change ⇒ adjustment

E.g., proton transfer equilibria following Brønsted-Lowry theory:

a A− × a H O +
HA(aq) + H2O(aq) A-(aq) + H3O+(aq) ⇒ K = 3

acid conjugate base a HA × a H 2O

aBH + × aOH −
B(aq) + H2O(aq) BH+(aq) + OH-(aq) ⇒ K =
base conjugate acid a B × a H 2O

Proton transfer equilibria are fast, highly

reversible, and important in biology Nils Walter: Chem 260
 Brønsted-Lowry theory
Definition: pH = − log a +
H 3O
acidicity constant:
a A− × a H O + a A− × a H O +
K= 3
Ka = 3

a HA × a H 2O aH2O = constant aHA

pK a = − log K a
a
basicity constant:
aBH + × aOH − aBH + × aOH − ≈
K= Kb = []
a B × a H 2O aH2O = constant aB
pK b = − log K b
autoprotolysis
Autoprotolysis equilibrium of water: constant:
2 H2O(aq) OH-(aq) + H3O+(aq) ⇒ K w = a H + × aOH −
3O
pK w = − log K w
K w = 10 −14 (@ 25! C ) ⇒ pK w = 14 = pHNils
+ Walter:
pOH Chem 260
 Acid and base strength
a A− × a H O +
K a × Kb = 3

aHA
aHA × aOH −
×
a A−
conjugate base
= aH O + × aOH − = K w
3

⇒ pKa + pKb = pKw

As the strength of an acid

decreases, the strength of
its conjugate base increases
and vice versa
Ka > 1, pKa < 0: strong acid (HCl, HNO3)
Kb > 1, pKb < 0: strong base (O2-) Nils Walter: Chem 260