Physical Chemistry II

(CHE21M5)

Lecture #5:
2nd Law of Thermodynamics
“Gibbs Free Energy”
Elements Of Physical Chemistry, Peter Atkins & Julio de Paula, 5th
Ed, p98 - 104
Recap: Entropy, ∆S
• Entropy: The measure of dispersion of energy or disorder
• ∆Suniv = ∆Ssystem + ∆Ssurrounding ≥ 0 (spontaneous)
• ∆S  +ve, more molecules on the product side than the reactant side
• ∆S  -ve, more molecules on the reactants side than the product side

Predicting the ∆S sign

• 2 SO2 (g) + O2 (g)  2 SO3 (g) -ve
• CaCO3 (s)  CaO (s) + CO2 (g) +ve
• N2 (g) + 3 H2 (g)  2 NH3 (g) -ve
• H2O (s)  H2O (l) +ve

• 2H2 (g) + O2 (g)  2H2O (l) –ve

NB: According to ∆S, the reaction is non spontaneous,

but we know its spontaneous because its an explosive
reaction and does not need energy to happen. Why is this?
The Spontaneity of chemical reactions

Total entropy of the overall isolated system (2nd Law):

∆Suniv = ∆Ssystem + ∆Ssurrounding ≥ 0 (spontaneous)
Gibbs Free Energy, ∆G
∆Ssurr
• JJ. W. Gibbs discovered how to combine the two calculations ??
into one (∆Ssystem , ∆Ssurrounding)
• The Gibbs “free energy” is the energy available to do
maximum work. ∆Suniv = ∆Ssystem + ∆Ssurr
• A good measure to determine if a process is ∆𝐻
∆Ssurr = - (at const. T and P)
thermodynamically favourable or spontaneous. This requires 𝑇
H and S. Reactions are favourable when they result in a ∆𝐻
∆Suniv = ∆Ssystem -
decrease in H and an increase in S of the system 𝑇
-T∆Suniv = -T∆Ssystem + ∆H (x –T)
• If G decreases as the reaction proceeds, then the reaction
has a spontaneous tendency to convert the reactants into -T∆Suniv = ∆H -T∆Ssystem
products. If G increases, the reverse reaction is ∆G = -T∆Suniv
spontaneous. [ A + B <--> C]
• Because H, T, and S are state functions, G is a state function ∆G = ∆H -T∆Ssystem
• For a spontaneous reaction at constant temperature and
pressure, the Gibbs energy decreases (opposite to entropy)
If ∆H -T∆Ssystem < 0, process is
• Standard Gibbs free energy of formation spontaneous (negative)
ΔGof = σ n Δ𝐆o(products) - σ n Δ𝑮o(reactants) If ∆H -T∆Ssystem > 0, process is not
spontaneous (positive)
The Spontaneity of chemical reactions

∆Suniv = ∆Ssystem + ∆Ssurrounding ≥ 0

Gibbs Free Energy, ∆G Ice to water: The system (the water) will decrease in entropy first
because its temperature will go down and second because it will
go from a liquid to a solid. The entropy of the surroundings will
∆G = ∆H -T∆S increase since energy (heat) is flowing into the surroundings from
the system. H2O (s)  H2O (l)
∆H < 0 ∆H > 0 What happens to Spontaneous at
ice at 0 ºC? T> 0
∆S > 0 spontaneous
Spontaneous ∆H > 0; ∆S > 0
only at high T

Spontaneous Not ∆H < 0; ∆S < 0

∆S < 0 only at low T spontaneous
Spontaneous at
T< 0

Important!!!! While ΔH and ΔG values are

generally reported in units of kJ/mol, ΔS is
often reported in J/K•mol. Before using this
equation, the value for ΔS must be converted
to kJ/K•mol so that the units work out correctly.
Properties: Gibbs Free Energy, ∆G

∆H T ∆S ∆G = ∆H -T∆S
So at equilibrium: ΔG⁰ = 0
For standard conditions: 0 = ΔH⁰- TΔS⁰
Gibbs Free Energy Rearrange and solve for the temperature T:
TΔS⁰ =ΔH⁰
ΔHo
T= o
∆G < 0 ∆G = 0 ∆G > 0
ΔS

Thermodynamic equilibrium: when there is

Equilibrium no tendency for the state of a system to
change spontaneously i.e boiling liquid
spontaneous Not spontaneous
Maximum
non-expansion work

Exansion work  Pressure volume work by/on gas

Non-expansion  electrical, motional, friction
Properties: Gibbs Free Energy, ∆G

𝒅𝒒
dS = 𝑻
dq = TdS
Gibbs Free Energy, ∆G: Examples
• Calculate the standard reaction Gibbs energy for the formation of CO2

Exercise: Calculate the standard reaction Gibbs energy for

N2(g) + 3 H2(g) → 2 NH3(g) at 25°C. [16,5 kJ/mol]
Gibbs Free Energy, ∆G: Examples
1. At what temperatures is the following reaction spontaneous?
Br2 (l)  Br2(g) (where ∆H = 30,91 kJ/mol, ∆S = 93,2 J/K)

For a equilibrium reaction: ΔG = 0

∆G = ∆H -T∆S
0 = 30,91x103 – 93,2T
30,91x103 = 93,2T
T = 331,7K
For spontaneity ΔG < 0 (negative), Therefore T > 331,7K
Also check T < 331,7K to confirm

2. At 25°C (298 K), the reduction of copper(I) oxide, ΔH = 58.1 kJ, ΔS=165 J/K is
nonspontaneous, ΔG = 8.9 kJ
Calculate the temperature at which the reaction becomes spontaneous. [T < 352 K]
Gibbs Free Energy, ∆G: Examples
Example: Using the appendix table of standard thermodynamic quantities,
determine the temperature at which the following process is at equilibrium.
CHCl3 (ℓ) ⇌ CHCl3 (g)

Solution: We need H and S to determine T