residual entropy, the third law and latent heat剩余熵,第三定律和潜热.pdfVIP

Entropy 2008, 10, 274-284; DOI: 10.3390/ OPEN ACCESS entropy ISSN 1099-4300 /entropy Article Residual Entropy, the Third Law and Latent Heat 1, 2 Evguenii Kozliak * and Frank L. Lambert 1 Department of Chemistry, University of North Dakota, Grand Forks, ND 58202, USA 2 Department of Chemistry, Occidental College, Los Angeles, CA 90041, USA. E-mail: flambert@ * Author to whom correspondence should be addressed. E-mail: ekozliak@ Received: 24 June 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.