I should mention — I should have mentioned earlier, but it has been a busy week — that CarnotCycle has published the second part of “The Geometry of Thermodynamics”. This is a bit of a tougher read than the first part, admittedly, but it’s still worth reading. The essay reviews how James Clerk Maxwell — yes, that Maxwell — developed the thermodynamic relationships that would have made him famous in physics if it weren’t for his work in electromagnetism that ultimately overthrew the Newtonian paradigm of space and time.
The ingenious thing is that the best part of this work is done on geometric grounds, on thinking of the spatial relationships between quantities that describe how a system moves heat around. “Spatial” may seem a strange word to describe this since we’re talking about things that don’t have any direct physical presence, like “temperature” and “entropy”. But if you draw pictures of how these quantities relate to one another, you have curves and parallelograms and figures that follow the same rules of how things fit together that you’re used to from ordinary everyday objects.
A wonderful side point is a touch of human fallibility from a great mind: in working out his relations, Maxwell misunderstood just what was meant by “entropy”, and needed correction by the at-least-as-great Josiah Willard Gibbs. Many people don’t quite know what to make of entropy even today, and Maxwell was working when the word was barely a generation away from being coined, so it’s quite reasonable he might not understand a term that was relatively new and still getting its precise definition. It’s surprising nevertheless to see.
Every student of thermodynamics sooner or later encounters the Maxwell relations – an extremely useful set of statements of equality among partial derivatives, principally involving the state variables P, V, T and S. They are general thermodynamic relations valid for all systems.
The four relations originally stated by Maxwell are easily derived from the (exact) differential relations of the thermodynamic potentials:
dU = TdS – PdV ⇒ (∂T/∂V)S = –(∂P/∂S)V
dH = TdS + VdP ⇒ (∂T/∂P)S = (∂V/∂S)P
dG = –SdT + VdP ⇒ –(∂S/∂P)T = (∂V/∂T)P
dA = –SdT – PdV ⇒ (∂S/∂V)T = (∂P/∂T)V
This is how we obtain these Maxwell relations today, but it disguises the history of their discovery. The thermodynamic state functions H, G and A were yet to…
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