The Geometry of Thermodynamics (Part 2)

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.

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James Clerk Maxwell and the geometrical figure with which he proved his famous thermodynamic relations

Historical background

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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The Liquefaction of Gases – Part II

The CarnotCycle blog has a continuation of last month’s The Liquefaction of Gases, as you might expect, named The Liquefaction of Gases, Part II, and it’s another intriguing piece. The story here is about how the theory of cooling, and of phase changes — under what conditions gases will turn into liquids — was developed. There’s a fair bit of mathematics involved, although most of the important work is in in polynomials. If you remember in algebra (or in pre-algebra) drawing curves for functions that had x³ in them, and in finding how they sometimes had one and sometimes had three real roots, then you’re well on your way to understanding the work which earned Johannes van der Waals the 1910 Nobel Prize in Physics.

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Future Nobel Prize winners both. Kamerlingh Onnes and Johannes van der Waals in 1908.

On Friday 10 July 1908, at Leiden in the Netherlands, Kamerlingh Onnes succeeded in liquefying the one remaining gas previously thought to be non-condensable – helium – using a sequential Joule-Thomson cooling technique to drive the temperature down to just 4 degrees above absolute zero. The event brought to a conclusion the race to liquefy the so-called permanent gases, following the revelation that all gases have a critical temperature below which they must be cooled before liquefaction is possible.

This crucial fact was established by Dr. Thomas Andrews, professor of chemistry at Queen’s College Belfast, in his groundbreaking study of the liquefaction of carbon dioxide, “On the Continuity of the Gaseous and Liquid States of Matter”, published in the Philosophical Transactions of the Royal Society of London in 1869.

As described in Part I of…

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