New Chemical Affinity with Reference to Equilibrium and Reaction Trajectories of Interphase Mass Transfer.

概要

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A highly simple and effective new methodology has been proposed to analyze the reaction kinetics of non-equilibrium mass transport. Interphase mass transfer in an evidently non-ideal liquid system has been described as trajectories on a reaction plane by introducing a logarithmic driving force LG which equals to A+/RT, where A+ is newly defined chemical affinity of a solute. The affinity A+ is referenced not only to the reaction state but to the equilibrium state, and is different from the De Donder's affinity defined solely by a reaction state. The affinity A+ is always smaller than the conventional one. It has also been concluded that extractive transfer might occur in a region A+>0. This description of transfer phenomena enables us to treat the reactions directly without the knowledge of rigorous activities of solutes, and is independent to the selection of concentration scale as well as the reference systems for chemical potentials. The affinity A+, i.e. the upper limit of the reaction trajectories, and the rate of the decrease in the logarithmic driving force have been represented by A+ ?? -RT ln ξ and -dLG/dξ=1/ξ using the degree of advancement ξ. Consequently, the thermodynamic analysis of reaction trajectories gave insights about the reaction kinetics and its characteristics for two phase systems containing multi-solutes.
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