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Paul Ehrenfest
Paul Ehrenfest was a student in Ludwig Boltzmann's classes on kinetic theory of gases at the University of Vienna. When Boltzmann committed suicide in 1906, Ehrenfest was chosen by the editors of the Enzyklopädie der mathematischen Wissenschaften to prepare an article on the statistical mechanics of gases that Boltzmann had promised to write for them.
It took Ehrenfest, working with his wife Tatiana, five years to prepare the article, which later appeared as their book, The Conceptual Foundations of the Statistical Approach in Mechanics.
The Ehrenfests reviewed Boltzmann's attempts to prove his H-Theorem, with emphasis on his Stosszahlansatz (Collision Number Assumption) and the idea of "Molecular Chaos." Where other authors had sometimes identified these two assumptions, the Ehrenfests saw these as different assumptions.
The Ehrenfests greatly simplified the demonstration that particles would approach an equilibrium distribution. Where Boltzmann derived his result in the full generality of three dimensions with several pages of equations, the Ehrenfests produced a simple two-dimensional example.
They imagined an infinite plane with two kinds of “molecules.” P-molecules are infinitesimal points moving with constant speeds in four possible directions, right, up, left, and down, with corresponding distributions f1, f2, f3, f4. The equilibrium distribution corresponding to Maxwell-Boltzmann equilibrium would be
f1 = f2 = f3 = f4 = N/4,
where N is the total number of P-molecules. The Q-molecules are fixed immovable squares on a diagonal as shown in the figure.
Ehrenfest’s 2-dimensional collisions.
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