Lecture 3

• Significance of Thermodynamic Potentials

• Open systems and chemical potential
• Omega/Grand Potential
• Applications of Maxwell’s relations
 Thermodynamic Potentials

Enthalpy H = U + PV
Helmholtz Free Energy F = U − TS
Gibbs Free Energy G = U + PV − TS

Maxwell’s Relations
𝜕𝑇 𝜕𝑃
=−
𝜕𝑉 𝑆
𝜕𝑆 𝑉

𝜕𝑇 𝜕𝑉
=
𝜕𝑃 𝑆
𝜕𝑆 𝑃

𝜕𝑃 𝜕𝑆
=
𝜕𝑇 𝑉
𝜕𝑉 𝑇

𝜕𝑉 𝜕𝑆
=−
𝜕𝑇 𝑃
𝜕𝑃 𝑇
Utility of TD potentials
Once you have calculated any one TD potential, all other thermodynamic properties follow
from it. For example, once Helmholtz free energy is known, you can get

𝜕𝑆 𝜕2𝐹
𝜕𝐹 Specific 𝐶𝑉 = 𝑇 = −𝑇
Entropy 𝑆=− 𝜕𝑇 𝜕𝑇 2
𝜕𝑇 𝑉
Heat 𝑉 𝑉

𝜕𝐹 2
𝜕(𝐹/𝑇)
Internal Energy 𝑈 = 𝐹 + 𝑇𝑆 = 𝐹 − 𝑇 = −𝑇
𝜕𝑇 𝑉
𝜕𝑇 𝑉

𝜕𝐹
Equation of state 𝑃=−
𝜕𝑉 𝑇

𝜕(𝐺/𝑇)
Small Exercise for you: Show that 𝐻 = −𝑇 2
𝜕𝑇 𝑃
Relevance of TD potentials
Entropy of an isolated system can never decrease. The equilibrium state of an isolated system is a state of
maximum entropy. However, an isolated system is of little experimental interest.

What about systems in contact with heat bath ?: Here, the system entropy is allowed to decrease as long as the
total entropy of composite system + bath increases. Want to identify property of the system alone and not the
composite that is maximized or minimized when equilibrium is established.

Δ𝑆 + Δ𝑆𝑟 ≥ 0 Δ𝑆𝑟 is the entropy change of the Tr Δ𝑆 + 𝑇𝑟 Δ𝑆𝑟 ≥ 0

reservoir
Tr Δ𝑆 − Δ𝑈 − 𝑃𝑟 Δ𝑉 ≥ 0
𝑇𝑟 Δ𝑆𝑟 = Δ𝑈𝑟 + 𝑃𝑟 Δ𝑉𝑟 Reservoir is at constant temperature 𝑇𝑟
and Pressure 𝑃𝑟 always by definition Δ𝑈 + 𝑃𝑟 Δ𝑉 − Tr Δ𝑆 ≤ 0

Conservation of energy and volume implies, Define Availability A ≡ U + Pr V − Tr S

Δ𝑈𝑟 = −Δ𝑈 Δ𝑉𝑟 = −ΔV Δ𝐴 ≤ 0
The equilibrium state of the system is characterized
by changes that minimize the availability.
 A ≡ U + Pr V − Tr S
Δ𝐴 ≤ 0 Δ𝑈 + 𝑃𝑟 Δ𝑉 − Tr Δ𝑆 ≤ 0

(1) Isolated system: No coupling between reservoir and system. Δ𝑈 = 0 and Δ𝑉 = 0. Then you get back the
expected result, Δ𝑆 ≥ 0. 𝑆(𝑈, 𝑉) is a maximum at equilibrium.

(2) Volume and temperature of the system are held fixed.

That is, 𝑇𝑟 = 𝑇 and Δ𝑉 = 0
Then, Δ𝑈 − TΔ𝑆 ≤ 0
Or, Δ𝐹 ≤ 0 Helmholtz free energy 𝐹(𝑇, 𝑉) is minimum at equilibrium when constraint of
constant internal energy is removed

(3) Temperature and pressure of the system are held fixed

That is, 𝑇𝑟 = 𝑇 and 𝑃 = 𝑃𝑟
Then, Δ𝑈 + 𝑃Δ𝑉 − 𝑇Δ𝑆 ≤ 0
Or, Δ𝐺 ≤ 0 Gibbs free energy G(𝑇, 𝑃) is minimum at equilibrium when both constraints of
constant internal energy and volume are removed.
Open systems: Exchange of particles and chemical potential
Differences in chemical potential drives flow of particles from one place to another in the same way as
differences in temperature cause flow of heat.
Chemical potential is relevant for chemical reactions because they involve in changes in number of particles
as reaction proceeds.
Chemical potential is also related to conservation laws as would be evident when we discuss quantum
statistical mechanics
Chemical potential is the change in internal energy that takes place when you add a particle to the system while
keeping its entropy and volume fixed/unchanged.

𝜕𝑈 Has further implications because you are wanting to keep entropy constant
𝜇= while adding particles given that entropy is an extensive quantity
𝜕𝑁 𝑆,𝑉

𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉 − 𝜇 𝑑𝑁 For a multicomponent system such as a mixture of different

gases described by numbers of particles Ni; one has to replace
𝜇𝑑𝑁 by σ𝑖 𝜇𝑖 𝑑𝑁𝑖
 𝑑𝐹 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇 + 𝜇𝑑𝑁

𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃 + 𝜇𝑑𝑁

𝜕𝐹 𝜕𝐺 Constraints here are more easily accessible to experiments

𝜇= 𝜇=
𝜕𝑁 𝜕𝑁 𝑃,𝑇
𝑉,𝑇

Consider 2 systems that are isolated from the surroundings but can
𝑇1 , 𝑁1 , 𝜇1 𝑑𝑁 exchange particles with each other and are at same temperature
𝑇2 , 𝑁2 , 𝜇2
𝑇1 ≡ 𝑇2

Say, system 1 gains particle by an amount dN. Then system 2 must have lost particles by an amount -dN
Net change in entropy 𝑑𝑆 = −𝜇1 𝑑𝑁 − 𝜇2 (−𝑑𝑁)
dS = 𝜇2 − 𝜇1 𝑑𝑁 ≥ 0 This implies, 𝜇2 > 𝜇1

Equilibrium is achieved when 𝜇1 = 𝜇2

Chemical potential as Gibbs free energy per particle
Extensive nature of entropy implies 𝑆 𝜆𝑈, 𝜆𝑉, 𝜆𝑁 = 𝜆𝑆(𝑈, 𝑉, 𝑁)
Differentiate both sides with 𝜆 and then set 𝜆 = 1 to get
Go to whiteboard

𝑈 𝑃𝑉 𝜇𝑁
𝑆= + −
𝑇 𝑇 𝑇
𝜇𝑁 = 𝑈 + 𝑃𝑉 − 𝑇𝑆 ≡ 𝐺
𝐺
𝜇= Gibbs free energy per particle
𝑁
𝑑𝐺 = 𝜇𝑑𝑁 + 𝑁𝑑𝜇 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃 + 𝜇𝑑𝑁
𝑁𝑑𝜇 + 𝑆𝑑𝑇 − 𝑉𝑑𝑃 = 0 Gibbs Dunhem equation
How chemical potential of a phase depends on pressure and temperature.
Hugely important in phase transitions (Gibbs Phase rule and Clausius Clapeyron equation)
Grand potential/Omega potential
Ω = −𝑃𝑉 = 𝐹 − 𝐺 Where F and G involve chemical potential

dΩ = −𝑃𝑑𝑉 − 𝑉𝑑𝑃 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇 − 𝑁𝑑𝜇

𝜕Ω 𝜕Ω Ω 𝜕Ω
𝑆=− 𝑃=− =− 𝑁=−
𝜕𝑇 𝑉,𝜇
𝜕𝑉 𝑇,𝜇
𝑉 𝜕𝜇 𝑇,𝑉

𝜕Ω
𝐺 = 𝜇𝑁 = −𝜇
𝜕𝜇 𝑇,𝑉
Applying Maxwell’s relations: Overview
1) Write down a TD potential relevant to the problem.

2) Obtain Maxwell’s relation

3) Invert the Maxwell’s relation using reciprocal theorem:

𝜕𝑥 1
=
𝜕𝑧 𝑦 𝜕𝑧
𝜕𝑥 𝑦
4) Combine partial differentials using reciprocity theorem:

𝜕𝑥 𝜕𝑦 𝜕𝑧
= −1
𝜕𝑦 𝑧 𝜕𝑧 𝑥 𝜕𝑥 𝑦

𝜕𝑥 𝜕𝑧 𝜕𝑥
Combining (3) and (4), =−
𝜕𝑦 𝑧 𝜕𝑦 𝑥 𝜕𝑧 𝑦
Excercise

• Find the ratio of isothermal and adiabatic compressibilities in terms of

experimentally determinable quantities.
Excercise
2
𝑉𝑇𝛽𝑃
By considering S(T, V), show that 𝐶𝑃 − 𝐶𝑉 =
𝜅𝑇
Volume dependence of the internal energy
𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉
𝜕𝑈 𝜕𝑆
=𝑇 −𝑃
𝜕𝑉 𝑇
𝜕𝑉 𝑇
𝜕𝑃
=𝑇 −𝑃 Useful relationship for analysing expansion of gases
𝜕𝑇 𝑉

𝜕𝑃 𝑃
For an ideal gas, 𝑃𝑉 = 𝑁𝑘𝐵 𝑇 and =
𝜕𝑇 𝑉 𝑇

𝜕𝑈
= 𝑃 − 𝑃 = 0 The internal energy U of an ideal gas is a function only of T
𝜕𝑉 𝑇
alone
 Entropy of the ideal gas
𝜕𝑆 𝜕𝑆
𝑑𝑆 = 𝑑𝑇 + 𝑑𝑉
𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝐶𝑉 𝜕𝑃
= 𝑑𝑇 + 𝑑𝑉
𝑇 𝜕𝑇 𝑉

For an ideal gas 𝜕𝑃 𝑁𝑘𝐵 𝑛𝑅 𝑛 is no of moles of gas

= =
𝜕𝑇 𝑉
𝑉 𝑉
𝐶𝑉 𝑛𝑅
𝑑𝑆 = 𝑑𝑇 + 𝑑𝑉
𝑇 𝑉

Entropy of ideal 𝑆 = 𝐶𝑉 ln 𝑇 + 𝑛𝑅𝑙𝑛𝑉 + 𝑆0 S0 is an arbitrary constant

gas
 Entropy of the ideal gas
𝜕𝑆 𝜕𝑆
𝑑𝑆 = 𝑑𝑇 + 𝑑𝑃
𝜕𝑇 𝑃
𝜕𝑃 𝑇
𝐶𝑃 𝜕𝑉
= 𝑑𝑇 − 𝑑𝑃
𝑇 𝜕𝑇 𝑃

For an ideal gas 𝜕𝑉 𝑁𝑘𝐵 𝑛𝑅 𝑛 is no of moles of gas

= =
𝜕𝑇 𝑃
𝑃 𝑃
𝐶𝑃 𝑛𝑅
𝑑𝑆 = 𝑑𝑇 − 𝑑𝑃
𝑇 𝑃

Entropy of ideal 𝑆 = 𝐶𝑃 ln 𝑇 − 𝑛𝑅𝑙𝑛𝑃 + 𝑠0 s0 is an arbitrary constant

gas
 Joule Expansion

Real gases cool down in this process

A gas is kept in the left half of a box by a partition. The right half is evacuated.
The partition is removed and the gas expands irreversibly to fill the entire box.
The gas expands into a vacuum while the entire system is thermally isolated

𝛿𝑄 = 0 𝛿𝑊 = 0 𝑑𝑈(𝑇, 𝑉) = 0

𝜕𝑇 𝜕𝑈 𝜕𝑇
Define Joule Coefficient, Γ𝐽 = =−
𝜕𝑉 𝜕𝑉 𝑇
𝜕𝑈 𝑉
𝑈
𝜕𝑈 1 −1 𝜕𝑃
=− = 𝑇 −𝑃
𝜕𝑉 𝐶 𝐶𝑉 𝜕𝑇
𝑇 𝑉 𝑉
= 0 for an ideal gas