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Ludwig BoltzmannThe Man Who Trusted Atoms$
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Carlo Cercignani

Print publication date: 2006

Print ISBN-13: 9780198570646

Published to Oxford Scholarship Online: January 2010

DOI: 10.1093/acprof:oso/9780198570646.001.0001

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The problem of polyatomic molecules

The problem of polyatomic molecules

(p.153) 8 The problem of polyatomic molecules
Ludwig Boltzmann


Oxford University Press

Polyatomic molecules created difficulties in kinetic theory from the start, with the problem of thermal capacities or specific heats. If the problem of specific heats was initially solved with the discovery of noble gases, the reconsideration of the old experiments on mercury vapour for monatomic gases, and Ludwig Boltzmann's suggestion to consider diatomic molecules as having five degrees of freedom, for more complex molecules the problem was bound to resurface later and to show up as one of the unsolved problems of classical mechanics. Before taking up this subject again, another difficulty which kinetic theory had to meet very soon is discussed. When Boltzmann wrote his equation, he included the case of polyatomic gases. He also made a remark on the importance of the extension of the H-theorem to this case. As a matter of fact, although the Boltzmann equation is correct, his original proof of the H-theorem for this case is not completely general, as pointed out for the first time by H.A. Lorentz in 1887.

Keywords:   thermal capacities, polyatomic molecules, H-theorem, specific heats, Boltzmann equation, H.A. Lorentz, kinetic theory, classical mechanics

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