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dc.contributor.advisorLaird, Brian B
dc.contributor.authorKern, Jesse
dc.date.accessioned2015-12-11T22:35:32Z
dc.date.available2015-12-11T22:35:32Z
dc.date.issued2015-08-31
dc.date.submitted2015
dc.identifier.otherhttp://dissertations.umi.com/ku:14156
dc.identifier.urihttp://hdl.handle.net/1808/19173
dc.description.abstractThe properties of a diverse range of mixture systems at interfaces are investigated using a variety of computational techniques. Molecular simulation is used to examine the thermodynamic, structural, and transport properties of heterogeneous systems of theoretical and practical importance. The study of binary hard-sphere mixtures at a hard wall demonstrates the high accuracy of recently developed classical-density functionals. The study of aluminum–gallium solid–liquid heterogeneous interfaces predicts a significant amount of prefreezing of the liquid by adopting the structure of the solid surface. The study of ethylene-expanded methanol within model silica mesopores shows the effect of confinement and surface functionalzation on the mixture composition and transport inside of the pores. From our molecular-dynamics study of binary hard-sphere fluid mixtures at a hard wall, we obtained high-precision calculations of the wall-fluid interfacial free energies, γ. We have considered mixtures of varying diameter ratio, α = 0.7,0.8,0.9; mole fraction, x1 = 0.25,0.50,0.75; and packing fraction, η < 0.50. Using Gibbs-Cahn Integration, γ is calculated from the system pressure, chemical potentials, and density profiles. Recent classical density-functional theory predictions agree very well with our results. Structural, thermodynamic, and transport properties of the aluminum–gallium solid–liquid interface at 368 K are obtained for the (100), (110), and (111) orientations using molecular dynamics. Density, potential energy, stress, and diffusion iii profiles perpendicular to the interface are calculated. The layers of Ga that form on the Al surface are strongly adsorbed and take the in-plane structure of the underlying crystal layers for all orientations, which results in significant compressive stress on the Ga atoms. Bulk methanol–ethylene mixtures under vapor-liquid equilibrium conditions have been characterized using Monte Carlo and molecular dynamics. The simulated vapor-liquid coexistence curves for the pure-component and binary mixtures agree well with experiment, as do the mixture volumetric expansion results. Using chemical potentials obtained from the bulk simulations, the filling of a number of model silica mesopores with ethylene and methanol is simulated. We report the compositions of the confined fluid mixtures over a range of pressures and for three degrees of nominal pore hydrophobicity.
dc.format.extent186 pages
dc.language.isoen
dc.publisherUniversity of Kansas
dc.rightsCopyright held by the author.
dc.subjectChemistry
dc.subjectMaterials Science
dc.subjectAdsorption
dc.subjectCatalysis
dc.subjectHeterogeneous interfaces
dc.subjectMaterials science
dc.subjectMolecular simulation
dc.subjectSurface chemistry
dc.titleMolecular simulation of fluid mixtures in bulk and at solid-liquid interfaces
dc.typeDissertation
dc.contributor.cmtememberThompson, Ward H
dc.contributor.cmtememberCaricato, Marco
dc.contributor.cmtememberJohnson, Carey K
dc.contributor.cmtememberBravo-Suarez, Juan
dc.thesis.degreeDisciplineChemistry
dc.thesis.degreeLevelPh.D.
dc.rights.accessrightsopenAccess


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