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Residual Entropy, the Third Law and Latent Heat
Department of Chemistry, University of North Dakota, Grand Forks, ND 58202, USA
Department of Chemistry, Occidental College, Los Angeles, CA 90041, USA
* Author to whom correspondence should be addressed.
Received: 24 July 2008; in revised form: 10 September 2008 / Accepted: 15 September 2008 / Published: 20 September 2008
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
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Kozliak, E.; Lambert, F.L. Residual Entropy, the Third Law and Latent Heat. Entropy 2008, 10, 274-284.
Kozliak E, Lambert FL. Residual Entropy, the Third Law and Latent Heat. Entropy. 2008; 10(3):274-284.
Kozliak, Evguenii; Lambert, Frank L. 2008. "Residual Entropy, the Third Law and Latent Heat." Entropy 10, no. 3: 274-284.