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Entropy 2008, 10(3), 274-284; doi:10.3390/e10030274
Article

Residual Entropy, the Third Law and Latent Heat

1,*  and 2
1 Department of Chemistry, University of North Dakota, Grand Forks, ND 58202, USA 2 Department of Chemistry, Occidental College, Los Angeles, CA 90041, USA
* Author to whom correspondence should be addressed.
Received: 24 July 2008 / Revised: 10 September 2008 / Accepted: 15 September 2008 / Published: 20 September 2008
(This article belongs to the Special Issue Configurational Entropy)
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Abstract

A novel thermodynamic treatment of residual entropy in crystals, involving the configurational partition function, is suggested, which is consistent with both classical and statistical thermodynamics. It relates residual entropy to the inherent latent heat which would be released upon cooling if the reversible path were available. The nature of this heat is that if the crystal possessing residual entropy freezes above its Boltzmann’s characteristic temperature of molecular alignment, the difference in energy between different molecular arrangements is overcome by the kT heat bath to form a nearly-ideal solution. However, upon cooling below this characteristic temperature, they would separate with a concomitant release of the corresponding energy, provided the reversible path were available.
Keywords: Configurational entropy; residual entropy; entropy of mixing; thermodynamics Configurational entropy; residual entropy; entropy of mixing; thermodynamics
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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Kozliak, E.; Lambert, F.L. Residual Entropy, the Third Law and Latent Heat. Entropy 2008, 10, 274-284.

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