Showing papers on "Gibbs–Duhem equation published in 2020"
TL;DR: In this article, a new formulation of poromechanics extended to adsorption which does not assume Gibbs-Duhem equation is proposed. But the authors do not consider the nonvalidity of Gibbs Duhem equation in general for adsorbed fluid.
13 citations
TL;DR: In this article, the area test based on the generalized Gibbs-Duhem equations was applied and the Peng and Robinson/Stryjek and Vera equation of state with Panagiotopoulos-Reid combining rule (PRSV/PR EoS) was employed to correlate the isothermal P-T-x data.
Abstract: The thermodynamic consistency analysis of ten mixtures of CO2/associating solvents with total of 160 isothermal data sets was investigated. For this purpose, the area test based on the generalized Gibbs–Duhem equations was applied and the Peng and Robinson/Stryjek and Vera equation of state with Panagiotopoulos–Reid combining rule (PRSV/PR EoS) was employed to correlate the isothermal P–T–x data. The binary adjustable constants in PRSV/PR EoS were figured out by optimization of errors on pressure and defined area simultaneously as an objective function in bubble pressure algorithm. The results turn out that among 160 isotherms meaningfully investigated, 29 data sets were found to be thermodynamically consistent, 72 data sets were found to be not fully consistent, 55 data sets were found to be thermodynamically inconsistent, and 4 data sets were found to be tried with other models.
12 citations
TL;DR: In this paper, an attempt is made to demonstrate (once again) some of the problems with the derivation of the generalized Lippmann equation considered to be valid by many researchers for solid electrodes and to address the problems in the framework of the Gibbs model of the interface by using only the basic principles of thermodynamics.
Abstract: In the present communication, an attempt is made to demonstrate (once again) some of the problems with the derivation of the “generalized Lippmann equation” considered to be valid by many researchers for solid electrodes and to address the problems in the framework of the Gibbs model of the interface by using only the basic principles of thermodynamics. By surveying the relevant literature, it has been shown that during the derivation of the equation, it was completely ignored that the Gibbs-Duhem equation (i.e., the electrocapillary equation) is a mathematical consequence which follows directly from the homogeneous degree one property of the corresponding thermodynamic potential function; consequently, the resulting expression cannot be correct. Some alternative approaches have also been considered. The adequacy of the open system and the partly closed system approach has been critically discussed, together with the possibility of introducing new thermodynamic potential functions.
4 citations
01 Jan 2020
TL;DR: In this article, the authors reviewed the contradictory discussions made so far in the electrochemistry community for the thermodynamics associated with surface stress and surface tension of a solid electrode have been reviewed.
Abstract: The contradictory discussions made so far in the electrochemistry community for the thermodynamics associated with surface stress and surface tension of a solid electrode have been reviewed. The reviewed subjects include the controversial arguments for the validity of the Gibbs–Duhem equation derived from the excess internal energy for a solid electrode and for the incompatibility of the Shuttleworth equation with Hermann’s mathematical structure of thermodynamics. In addition, the review is concerned with the thermodynamic issues for the application of the Shuttleworth equation to a solid electrode and for the surface stress measurement by a cantilever bending method.