Thermodynamic process

Abstract: Thermodynamic data for the condensed phases of 78 elements as currently used by SGTE (Scientific Group Thermodata Europe) are tabulated. SGTE is a consortium of seven organisations in Western Europe engaged in the compilation of a comprehensive, self consistent and authoritative thermochemical database for inorganic and metallurgical systems. The data are being published here in the hope that they will become widely adopted within the international community as a sound basis for the critical assessment of thermodynamic data, thereby, perhaps, limiting unnecessary duplication of effort. The data for each phase of each element considered aie presented as expressions showing, as a function of temperature, the variation of (a) G-HSER, the Gibbs energy relative to the enthalpy of the “Standard Element Reference” ie the reference phase for the element at 298.15 K and (b) the difference in Gibbs energy between each phase and this reference phase (ie lattice stability). The variation of the heat capacity of the various phases and the Gibbs energy difference between phases are also shown graphically. For certain elements the thermodynamic data have been assessed as a function of pressure as well as temperature. Where appropriate a temperature— pressure phase diagram is also shown. Throughout this paper the thermodynamic data are expressed in terms of J mol−1. The temperatures of transition between phases have been assessed to be consistent with the 1990 International Temperature Scale (ITS90).

Abstract: Although thermodynamic fluctuation theory originated from statistical mechanics, it may be put on a completely thermodynamic basis, in no essential need of any microscopic foundation. This review views the theory from the macroscopic perspective, emphasizing, in particular, notions of covariance and consistency, expressed naturally using the language of Riemannian geometry. Coupled with these concepts is an extension of the basic structure of thermodynamic fluctuation theory beyond the classical one of a subsystem in contact with an infinite uniform reservoir. Used here is a hierarchy of concentric subsystems, each of which samples only the thermodynamic state of the subsystem immediately larger than it. The result is a covariant thermodynamic fluctuation theory which is plausible beyond the standard second-order entropy expansion. It includes the conservation laws and is mathematically consistent when applied to fluctuations inside subsystems. Tests on known models show improvements. Perhaps most significantly, the covariant theory offers a qualitatively new tool for the study of fluctuation phenomena: the Riemannian thermodynamic curvature. The thermodynamic curvature gives, for any given thermodynamic state, a lower bound for the length scale where the classical thermodynamic fluctuation theory based on a uniform environment could conceivably hold. Straightforward computation near the critical point reveals that the curvature equals the correlation volume, a physically appealing finding. The combination of the interpretation of curvature with a well-known proportionality between the free energy and the inverse of the correlation volume yields a purely thermodynamic theory of the critical point. The scaled equation of state follows from the values of the critical exponents. The thermodynamic Riemannian metric may be put into the broader context of information theory.