Topic
Gibbs–Duhem equation
About: Gibbs–Duhem equation is a research topic. Over the lifetime, 393 publications have been published within this topic receiving 6248 citations. The topic is also known as: Gibbs-Duhem equation.
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TL;DR: In this paper, it is shown that the Gibbs energy may be a mathematical means for performing thermodynamic calculations, but it cannot be an energy source for producing work, i.e., irreversible (without work production) or reversible (with the obligatory production of work).
11 citations
TL;DR: In a multi-component homogeneous system, the relationship between partial molar and molar quantity (RPMQ) is proved to be an equivalent relation of the Gibbs-Duhem equation.
Abstract: In a multi-component homogeneous system, the relationship between partial molar and molar quantity (RPMQ) is proved to be an equivalent relation of the Gibbs-Duhem equation. The universal characteristics of a thermodynamic model to conform to the Gibbs-Duhem equation are inferred from the RPMQ. Based on the inference, an asymmetric regular solution model is suggested to deal with those systems that exhibit strong negative deviation, strong positive deviation, and both strong positive and negative deviation from ideality.
11 citations
TL;DR: In this article, an explicit examination of the concept of indistinguishability can clarify some of the implications of the quantum-mechanical resolution of the Gibbs paradox, which is not clear within the framework of classical thermodynamics how the identity of the particles effects the analysis.
Abstract: The Gibbs paradox concerns the entropy of mixing of ideal gases: although the entropy change of mixing samples of different gases is unequal to the entropy change of mixing samples of the same gas, it is not clear within the framework of classical thermodynamics how the identity of the particles effects the analysis. An explicit examination of the concept of indistinguishability can clarify some of the implications of the quantum-mechanical resolution of the Gibbs paradox.
11 citations
TL;DR: Various ways of building quasi-Newton matrix approximations that satisfy the special form of the Gibbs-Duhem equation are studied, and the method of iterated projections is used in order to develop thermodynamically consistent matrix approxIMations with good secant information.
Abstract: Various ways of building quasi-Newton matrix approximations that satisfy the special form of the Gibbs-Duhem equation are studied. Partition symmetry, the separability of the functions in γ and in ϕ, and the method of iterated projections are used in order to develop thermodynamically consistent matrix approximations with good secant information. Many examples are presented which show that exploiting the special form of the Gibbs-Duhem equation results in improved numerical performance. Ways of exploiting the Gibbs-Helmholtz equation in addition to the special form of Gibbs-Duhem equation, and thus the isobaric form of the Gibbs-Duhem equation, are also discussed.
11 citations
TL;DR: Gutman et al. as mentioned in this paper showed that the main problem in capillarity and electrocapillarity of solid surfaces is the lack of clarity in determining the surface stress and basic equations.
Abstract: In the previous paper (Gutman, JOSSEC 18:3217–3237, 2014), we have shown that the main problem in capillarity and electrocapillarity of solid surfaces is the lack of clarity in determining the surface stress and basic equations. Now, we continue the survey of efforts to solve this problem and show origins of erroneous results, accenting some important items: comparative analysis of Gibbs and Guggenheim approaches in surface thermodynamics (a geometrical dividing surface and finite-thickness surface layer, respectively), transformation of fundamental equations on per-unit-area basis to obtain Gibbs adsorption equation for finite-thickness surface layer, different attempts to derive the thermodynamic definition of “surface stress” in frames of Gibbs’ theory (including Shuttleworth’s approach), atomistic calculations of surface stress, surface stress in rational continuum mechanics, “modifications” of Gibbs–Duhem relations made for solid interface, and Maxwell relations in capillarity and electrocapillarity of solid interface. It is shown that the erroneous Shuttleworth’s approach is present in an explicit or implicit form in all efforts to introduce the surface stress in frames of Gibbsian theory (although Gibbs did not introduce surface stress). Therefore, “modernizations” or “generalizations” of the Gibbs–Duhem relation, the Gibbs adsorption equation, and the Lippmann equation to adopt them for a solid surface are unnatural and not necessary. Therefore, we recommend withdrawing the Shuttleworth equation and its consequences from circulation, including the IUPAC Recommendations.
11 citations