Lecture21Ch161April15

Lecture21Ch161April15 - Summary of last lecture Mayer...

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Summary of last lecture Mayer functions, cluster expansion, virial coefficients The Van der Waals equation
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Chemistry 161: Statistical Chemistry 161: Statistical Thermodynamics Thermodynamics Lecture 21 Lecture 21 Thermodynamic Perturbation theory Thermodynamic Perturbation theory (TPT), correlation functions (TPT), correlation functions Key Concepts and Lessons: a) High T expansion b) Correlation functions c) Relation of pair corr to TD functions d) Alternative - and better- derivation of the WdW eq Reading: McQuarrie Ch13.1-3
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The Van der Waals equation: We get therefore: p + a ± 2 = ± kT 1 + b ± ( ) ² 1 1 ³ b ± Or in the canonical from: p + a ± 2 ( ) 1 ± ² b ³ ´ µ · ¸ = kT This is famous van der Waals equation which was obtained here in a non-rigorous form as an extrapolation Of virial expansion from low densities to high densities.
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