• 한국응용과학기술학회지
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• 제27권4호
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• pp.452-460
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• 2010

Any theory of liquid should account for interactions between molecules, since molecules in a liquid are close to each other. For this matter statistical-mechanical methodology has been used and various models have been proposed on the basis of this methodology. Among them Kirkwood-Buff solution theory has attracted a lot of interest, because it is regarded as being the most powerful. In this article Kirkwood-Buff solution theory is revisited and its key equations are derived. On the way to these equations, the concepts of pair correlation function, radial distribution function, Kirkwood-Buff integration are explained and implemented. Since complexity of statical mechanics involved in this theory, the equations are applied to one-component systems and the results are compared to those obtained by classical thermodynamics. This may be a simple way for Kirkwood-Buff solution theory to be examined for its validity.

• 산업기술연구
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• 제19권
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• pp.253-260
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• 1999

Two thermodynamic models were used to predict the partial molar volumes of solutes in supercritical carbon dioxide at infinite dilution: (1) the Peng-Robinson equation of state with various mixing rules including those based on $EOS/G^E$ (2) the Kirkwood Buff fluctuation integral with the hard sphere expansion (HSE) method. The Kirkwood-Buff fluctuation integral method, in which an equation of state for pure component and molecular parameters are required, produced better results especially near the critical point than the Peng-Robinson equation of state with the several mixing rules based an $EOS/G^E$. When the $EOS/G^E$ mixing rules were used, poorer results were obtained compared with the classical mixing rule and Kirkwood-Buff model.