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 has been shown by the method of statistical mechanics that the existing first approximation to the regular solutions is incorrect and the correct approximation has been obtained by finding the distribution function for a given number of bonds between the unlike molecules in solution.
Abstract: It has been shown by the method of statistical mechanics that the existing first approximation to the regular solutions is incorrect. The correct approximation has been obtained by finding the distribution function for a given number of bonds between the unlike molecules in solution. Equations have been derived to represent the excess Gibbs energy (Gibbs free energy), enthalpy, and entropy of mixing of binary systems. Calculated and experimental results are compared to show the usefulness of derived equations.
10 citations
TL;DR: In this article, the kinetic and thermodynamic behavior of a chemical system undergoing coupled competitive reactions is analyzed and illustrated by considering the hydrogenation reaction of a Vaska type complex, and the meaning of kinetic/thermodynamic controls and of kinetic stability is thoroughly revisited.
Abstract: The kinetic and thermodynamic behavior of a chemical system undergoing coupled competitive reactions is analyzed It is illustrated by considering the hydrogenation reaction of a Vaska type complex In a first part, the meaning of kinetic/thermodynamic controls and of kinetic stability is thoroughly revisited The different regimes are defined by reference to the characteristic times emerging from equations describing the evolution In a second part, it is shown how the Gibbs free energy of the reacting system varies when successively submitted to kinetic and thermodynamic controls
10 citations
TL;DR: In this article, a thermodynamic inconsistency in the Pelton-Flengas analytical solution of the Gibbs-Duhem equation for ternary systems has been identified and a new analytical solution is presented and a reasonable calculation procedure is suggested.
Abstract: A thermodynamic inconsistency in the Pelton–Flengas analytical solution of the Gibbs–Duhem equation for ternary systems has been identified. A new analytical solution is presented and a reasonable calculation procedure is suggested. A sample calculation has been carried out for the Zn–In–Cd system, using a Fortran 77 computer program designed for the purpose. The results are in good agreement with those obtained graphically. The whole calculation only requires ca. 1 min computer time.
10 citations
TL;DR: In this paper, an extension of the Gibbs-Duhem integration method that permits direct evaluation of vapour-liquid equilibria of mixtures by molecular dynamics is presented, where the coexistence pressure is adjusted to satisfy the Clapeyron-type equation.
Abstract: We present an extension of the Gibbs-Duhem integration method that permits direct evaluation of vapour-liquid equilibria of mixtures by molecular dynamics. The Gibbs-Duhem integration combines the best elements of the Gibbs ensemble Monte Carlo technique and thermodynamic integration. Given conditions of coexistence of pure substances, simultaneous but independent molecular dynamics simulations of each phase at constant number of particles, constant pressure, constant temperature and constant fugacity fraction of species 2 are carried out in succession along coexistence lines. In each simulation, the coexistence pressure is adjusted to satisfy the Clapeyron- type equation. The Clapeyron-type equation is a first-order nonlinear differential equation that prescribes how the pressure must change with the fugacity fraction of species 2 to maintain coexistence at constant temperature. The Clapeyron- type equation is solved by the predictor-corrector method. Running averages of mole fraction and compressibility factor for the two phases are used to evaluate the right-hand side of the Clapeyron-type equation. The Gibbs-Duhem integration method is applied to three prototypes of binary mixtures of the two-centre Lennard- Jones fluid having various elongations. The starting points on the coexistence curve were taken from published data.
9 citations
TL;DR: In this article, the Gibbs energy of Cu 3 P formation was determined by means of triple Knudsen cell mass spectrometry and the calculated vapor pressure of phosphorus and phase diagram of the Cu-P system were excellently consistent with the literature data.
Abstract: Thermodynamic evaluation of Cu–Cu 3 P system has been conducted by applying subregular solution model with Gibbs energy of Cu 3 P formation that was newly determined by means of triple Knudsen cell mass spectrometry. Both the calculated vapor pressure of phosphorus and phase diagram of Cu–P system are excellently consistent with the literature data in the composition range of Cu–Cu 3 P, indicating that there is no significant thermodynamic inconsistency between the present work based on the Gibbs energy of Cu 3 P formation determined and the literature data.
9 citations