Method for Simplifying Thermodynamic Differentials

Zayan Akmal
November 2, 2024

1 Overview
This document outlines a consistent method for simplifying any well-defined thermodynamic differen-
tial consisting of the variables {U, H,
 A,G, S, P, V, T }, where N is assumed constant. The general form
∂I
of a thermodynamic differential is ; I, J, and K are variables from the set above and at most
∂J K
one of these is an energy variable {U, H, A, G}. Thus, the differential should be in this form prior
to using this method. While this method may not be the fastest way to simplify a given differential,
it is beneficial to have a consistent process that can be used in all cases.

Remember to use your best mathematical reasoning and intuition! (keep energy variables
at the top of differentials, use derivative rules to simplify to lowest terms, etc.).

2 The Method
This method is chronological: if the step’s conditions (→) apply, complete the step entirely be-
fore moving on to the next one. If the step’s conditions do not apply, move on to the next step.
 
∂I
Regardless of previous steps, the general differential form will always be referenced.
∂J K
The method will reduce differentials to single variables and CP , CV , αP , and κT . Make sure to
know your definitions of these!

2.1 Step 1
→ If an energy variable is held constant in the differential (K ∈ {U, H, A, G}), use the triple
product to rewrite in the following form:
∂K
       

∂I ∂J ∂K ∂I ∂J I
= −1 ⇒ = − ∂K

∂J K ∂K I ∂I J ∂J K ∂I J

If/once no energy variables are held constant in the differential, move on to Step 2.

2.2 Step 2
→ If an energy variable is inside the differential (I or J ∈ {U, H, A, G}), use the corresponding
energy equation to reduce the energy differential to single variables and differentials in S, P , V , and
T . The 4 main energy equations are given below:


 dU = T dS − P dV

dH = T dS + V dP


 dA = −SdT − P dV
dG = −SdT + V dP


If/once only single variables and differentials in S, P , V , T are left, move on to Step 3.

1
2.3 Step 3
→ If S is held constant in a differential (K = S), use the triple product to rewrite it.

→ If S is inside a differential with no T (I or J = S and I or J ̸= T ), use a Maxwell Rela-

tion to rewrite it.

If/once neither of the two conditions apply to your problem, move on to Step 4.

2.4 Step 4
→ If any differentials are left, use the dU and dH equations with definitions of CP , CV , αP , and
κT to rewrite them. As a rule of thumb:
 
∂S
is related to CP or CV



 ∂T
P or V



All other differentials are related to α or κ (use triple product as needed)
P T

Once only single variables and CP , CV , αP , and/or κT are left, you’re done!

2
 Deriving Classical Thermo Equations

October 10, 2024

Summary of Thermodynamic Equations

dU = T dS − P dV + µdN

H = U + PV

A = U − TS

G = H − TS = U + PV − TS

A(T, V, N ) = U − T S

G(T, P, N ) = H − T S = U + P V − T S

Thermodynamic Potentials
• Internal Energy (U): Represents the total energy of the system, typi-
cally written as:
dU = T dS − P dV + µdN
where T is temperature, S is entropy, P is pressure, V is volume, µ is the
chemical potential, and N is the number of particles.
• Enthalpy (H): Defined for processes at constant pressure:
H = U + PV

• Helmholtz Free Energy (A): This is the thermodynamic potential

when temperature and volume are constant:
A = U − TS

• Gibbs Free Energy (G): Defined for processes at constant temperature

and pressure:
G = H − TS = U + PV − TS

1
Legendre Transformation
Thermodynamic potentials can be related by Legendre transforms. The Helmholtz
free energy is obtained from internal energy by swapping entropy S for temper-
ature T :
A(T, V, N ) = U − T S
Similarly, the Gibbs free energy is obtained by further swapping volume V for
pressure P :
G(T, P, N ) = H − T S = U + P V − T S

Maximization and Minimization Principles

In thermodynamics, the following conditions hold:
• At constant entropy and volume: Internal energy U is minimized at
equilibrium.

• At constant temperature and volume: Helmholtz free energy A is

minimized at equilibrium.
• At constant temperature and pressure: Gibbs free energy G is min-
imized at equilibrium.

Experimentally Measurable Thermodynamic Quan-

tities
Some key experimentally measurable quantities include:
• T – Temperature
• P – Pressure

• V – Volume
• N – Number of particles
• ∆hlatent – Latent heat of phase change

• CV – Heat capacity at constant volume

• CP – Heat capacity at constant pressure
• κT – Isothermal compressibility
• αP – Thermal expansion coefficient