Maxwell Relations

Claimed by Ram Vempati (Fall 2024)

The Maxwell Relations are a set of partial derivative relations derived using Clairaut's Theorem that enable the expression of physical quantities such as Gibbs Free Energy and Enthalpy as infinitesimal changes in pressure (P), volume (V), temperature (T), and entropy (S). They are named after James Maxwell and build upon the work done by Ludwig Boltzmann in Thermodynamics and Statistical Mechanics

Derivations

Internal Energy

The first law of thermodynamics states that [math]\displaystyle{ {\Delta U = \Delta Q - \Delta W} }[/math] where [math]\displaystyle{ {\Delta Q} }[/math] is the heat added to the system and [math]\displaystyle{ {\Delta W} }[/math] is the work done by the system. We can re-express differentials Q and W with the state variables P,V,T,S using the substitutions [math]\displaystyle{ {dQ_{rev} = TdS} }[/math] (see Clausius Theorem) and [math]\displaystyle{ {dW = PdV} }[/math] (see Pressure-Volume Work). We thus arrive at the thermodynamic definition for internal energy: [math]\displaystyle{ {dU = T dS − P dV} }[/math].

The Maxwell Relation for Internal Energy can be found by applying Clairaut's Theorem to the system with the fundamental assumption that the variables can be expressed as Exact Differentials

Utility of Maxwell Relations

What are the mathematical equations that allow us to model this topic. For example [math]\displaystyle{ {\frac{d\vec{p}}{dt}}_{system} = \vec{F}_{net} }[/math] where p is the momentum of the system and F is the net force from the surroundings.

All Maxwell Relations

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Examples

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Connectedness

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History

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See also

• Temperature & Entropy
• Application of Statistics in Physics

Further reading

• Elements Of Classical Thermodynamics

References

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