How Gibbs derived the Phase Rule

I knew I’d been forgetting something about the end of summer. I’m embarrassed again it was Peter Mander’s Carnot Cycle blog resuming its discussions of thermodynamics.

The September article is about Gibbs’s phase rule. Gibbs here is Josiah Willard Gibbs, who established much of the mathematical vocabulary of thermodynamics. The phase rule here talks about the change of a substance from one phase to another. The classic example is water changing from liquid to solid, or solid to gas, or gas to liquid. Everything does that for some combinations of pressure and temperature and available volume. It’s just a good example because we can see those phase transitions happen whenever we want.

The question that feels natural to mathematicians, and physicists, is about degrees of freedom. Suppose that we’re able take a substance and change its temperature or its volume or its pressure. How many of those things can we change at once without making the material different? And the phase rule is a way to calculate that. It’s not always the same number because at some combinations of pressure and temperature and volume the substance can be equally well either liquid or gas, or be gas or solid, or be solid or liquid. These represent phase transitions, melting or solidifying or evaporating. There’s even one combination — the triple point — where the material can be solid, liquid, or gas simultaneously.

Carnot Cycle presents the way that Gibbs originally derived his phase rule. And it’s remarkably neat and clean and accessible. The meat of it is really a matter of counting, keeping track of how much information we have and how much we want and looking at the difference between the things. I recommend reading it even if you are somehow not familiar with differential forms. Simply trust that a “d” followed by some other letter (or a letter with a subscript) is some quantity whose value we might be interested in, and you should follow the reasoning well.

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The Phase Rule formula was first stated by the American mathematical physicist Josiah Willard Gibbs in his monumental masterwork On the Equilibrium of Heterogeneous Substances (1875-1878), in which he almost single-handedly laid the theoretical foundations of chemical thermodynamics.

In a paragraph under the heading “On Coexistent Phases of Matter”, Gibbs gives the derivation of his famous formula in just 77 words. Of all the many Phase Rule proofs in the thermodynamic literature, it is one of the simplest and shortest. And yet textbooks of physical science have consistently overlooked it in favor of more complicated, less lucid derivations.

To redress this long-standing discourtesy to Gibbs, CarnotCycle here presents Gibbs’ original derivation of the Phase Rule in an up-to-date form. His purely prose description has been supplemented with clarifying mathematical content, and the outmoded symbols used in the single equation to which he refers have been replaced with their…

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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 Geometry of Thermodynamics (Part 1)

I should mention that Peter Mander’s Carnot Cycle blog has a fine entry, “The Geometry of Thermodynamics (Part I)” which admittedly opens with a diagram that looks like the sort of thing you create when you want to present a horrifying science diagram. That’s a bit of flavor.

Mander writes about part of what made J Willard Gibbs probably the greatest theoretical physicist that the United States has yet produced: Gibbs put much of thermodynamics into a logically neat system, the kind we still basically use today, and all the better saw represent it and understand it as a matter of surface geometries. This is an abstract kind of surface — looking at the curve traced out by, say, mapping the energy of a gas against its volume, or its temperature versus its entropy — but if you can accept the idea that we can draw curves representing these quantities then you get to use your understanding how how solid objects (and Gibbs even got made solid objects — James Clerk Maxwell, of Maxwell’s Equations fame, even sculpted some) look and feel.

This is a reblogging of only part one, although as Mander’s on summer holiday you haven’t missed part two.

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Volume One of the Scientific Papers of J. Willard Gibbs, published posthumously in 1906, is devoted to Thermodynamics. Chief among its content is the hugely long and desperately difficult “On the equilibrium of heterogeneous substances (1876, 1878)”, with which Gibbs single-handedly laid the theoretical foundations of chemical thermodynamics.

In contrast to James Clerk Maxwell’s textbook Theory of Heat (1871), which uses no calculus at all and hardly any algebra, preferring geometry as the means of demonstrating relationships between quantities, Gibbs’ magnum opus is stuffed with differential equations. Turning the pages of this calculus-laden work, one could easily be drawn to the conclusion that the writer was not a visual thinker.

But in Gibbs’ case, this is far from the truth.

The first two papers on thermodynamics that Gibbs published, in 1873, were in fact visually-led. Paper I deals with indicator diagrams and their comparative properties, while Paper II

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Reblog: Mixed-Up Views Of Entropy

The blog CarnotCycle, which tries to explain thermodynamics — a noble goal, since thermodynamics is a really big, really important, and criminally unpopularized part of science and mathematics — here starts from an “Unpublished Fragment” by the great Josiah Willard Gibbs to talk about entropy.

Gibbs — a strong candidate for the greatest scientist the United States ever produced, complete with fascinating biographical quirks to make him seem accessibly peculiar — gave to statistical mechanics much of the mathematical form and power that it now has. Gibbs had planned to write something about “On entropy as mixed-up-ness”, which certainly puts in one word what people think of entropy as being. The concept is more powerful and more subtle than that, though, and CarnotCycle talks about some of the subtleties.

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Tucked away at the back of Volume One of The Scientific Papers of J. Willard Gibbs, is a brief chapter headed ‘Unpublished Fragments’. It contains a list of nine subject headings for a supplement that Professor Gibbs was planning to write to his famous paper “On the Equilibrium of Heterogeneous Substances”. Sadly, he completed his notes for only two subjects before his death in April 1903, so we will never know what he had in mind to write about the sixth subject in the list: On entropy as mixed-up-ness.

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