Chemical

Thermodynamics
• The Second Law of Thermodynamics
• Gibbs Free Energy and Chemical
Equilibrium
• Standard Free Energy of Formation
The Second Law of Thermodynamics
• States that the total entropy of the universe is
continually increasing.
• Natural process proceed in the direction that
increases the total entropy.
• In spontaneous process, the overall entropy
increases.
• In reversible process, the total entropy remains
constant.
The Second Law of Thermodynamics
• ΔS universe = ΔS system + ΔS surroundings
• Under standard condition,
ΔS° universe = ΔS° system + ΔS° surroundings
ΔS° universe > 0 (zero) for spontaneous process
• Sample Problem: Show quantitatively, that the
process for dissolving NaCl in water at 25°C, has a
positive entropy change value
NaCl (s) → NaCl (aq)
Gibbs Free Energy, G
•The balance between enthalpy and entropy.
•Named after William Gibbs.
•For a reaction that takes place at STP, the
sign of the free energy change serves as basis
for predicting spontaneity.
•G = H – TS
•ΔG° = ΔH° - TΔS°
Gibbs Free Energy, G
•ΔG < 0, reaction is spontaneous in
forward direction
•ΔG > 0, nonspontaneous in forward
direction, work is needed for reaction to
happen
•ΔG = 0, reaction is at equilibrium
Gibbs Free Energy, G
•Sample Problem: A drying agent has the
chemical composition CaSO4. Calculate
ΔG° at 25°C, for the following reaction,
which has a ΔS° value of -139.7 J/K and
ΔH° is -18.0 kJ.
CaSO4(s) → Ca+2 (aq) + SO4-2 (aq)
ΔH ΔS ΔG Characteristics of Reaction
- + Always - Spontaneous at all temperatures
Nonspontaneous at all
+ - Always +
temperatures
+ + - at high T Spontaneous at high temperature
Nonspontaneous at low
+ + + at low T
temperature
- - - at low T Spontaneous at low temperature
Nonspontaneous at high
- - + at high T
temperature
 Activity
Given the ΔH° and ΔS°, calculate the ΔG° values for the following
reactions and indicate whether the reaction is spontaneous at
STP. If a reaction is not spontaneous, state what may be done to
make the reaction spontaneous.

Chemical Reaction ΔH° (kJ) ΔS° (J/K)

a.C(graphite) + 2H2(g) → CH4 (g) -74.9 +186.3
b.CH3CH3(g) → H2(g) + C2H4(g) +137 +121
c. N2 (g) + 2H2 (g) → N2H4 (l) +50.6 -331
Standard Free Energy of Formation, ΔG f°
•Defined as the free energy change when
one mole of a compound is formed from
the constituent elements in their stable
states at 1 atm pressure.
•ΔG f° = Σn ΔG f° products - Σn ΔG f° reactants
Where: n = number of moles
•Calculated ΔG f° is only valid at 25°C.
Standard Free Energy of Formation, ΔG f°
Sample Problem: Calculate the ΔG° for
the following reaction at 25°C
CaSO (s) → Ca (aq) + SO4 (aq)
4 2+ -2