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In this work, we present two open literature databases, the VT-2005 Sigma Profile Database and the VT-2006 Solute Sigma Profile Database, that contain sigma profiles for 1,645 unique compounds. A sigma profile is a molecular-specific distribution of the surface-charge density, which enables the application of solvation-thermodynamic models to predict vapor-liquid and solid-liquid equilibria, and other properties. The VT-2005 Sigma Profile Database generally focuses on solvents and small molecules, while the VT-2006 Solute Sigma Profile Database primarily consists of larger, pharmaceutical-related solutes. We design both of these databases for use with the conductor-like screening model−segment activity coefficient (COSMO-SAC), a liquid-phase activity-coefficient model. The databases contain the necessary information to perform binary and multicomponent VLE and SLE predictions. We offer detailed tutorials and procedures for use with our programs so the reader may also use their own research on our research group website (www.design.che.vt.edu). We validate the VT-2005 Sigma Profile Database by pure component vapor pressure predictions and validate the VT-2006 Solute Sigma Profile Database by solid solubility predictions in pure solvents compared with literature data from multiple sources. Using both databases, we also explore the application of COSMO-SAC to solubility predictions in mixed solvents. This work also studies the effects of conformational isomerism on VLE and SLE property prediction. Finally, we compare COSMO-SAC solubility predictions to solubility predictions by the Non-Random Two-Liquid, Segment Activity Coefficient (NRTL-SAC) model. We find UNIFAC is a more accurate method for predicting VLE behavior than the COSMO-SAC model for many of the systems studied, and that COSMO-SAC predicts solute mole fraction in pure solvents with an average root-mean-squared error (log10(xsol)) of 0.74, excluding outliers, which is greater than the RMS error value of 0.43 using the NRTL-SAC model. / Master of Science

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第13789号 / 工博第2893号 / 新制||工||1427(附属図書館) / 26005 / UT51-2008-C705 / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 瀧川 敏算, 教授 木村 俊作, 教授 田中 文彦 / 学位規則第4条第1項該当

Les performances des modèles thermodynamiques actuels pour les solvants mixtes (en particulier avec alcools) électrolytiques sont limités. L’objectif de ce travail est d’étendre les capacités du modèle eGC-PPC-SAFT à ces systèmes. Ceci est fait en plusieurs étapes. Dans une première étape, le modèle PPC-SAFT existant est amélioré pour l’eau pure et les solvants usuels, par (1) introduisant une dépendance en température du diamètre sphère dure de l'eau et (2) adapter un minimum de paramètres ioniques sur les coefficients d’activité moyens et les densités des systèmes contenant des électrolytes forts ainsi que les sur les équilibres liquide vapeur des solvants mixtes d'électrolytes. Dans une troisième étape, le modèle final est utilisé pour représenter les équilibres liquide-liquide des solvants mixtes électrolytiques en étudiant les coefficients de partition de chacune des espèces dans le système. Pour cela, une stratégie de paramétrage des paramètres binaires ion-solvant a été développée, qui implique l’évaluation de l’impact de chacune des contributions individuelles du modèle ePPC-SAFT sur les coefficients de partition. Étant donné son importance dans le cadre de la modélisation thermodynamique de ces systèmes, une nouvelle règle de mélange pour le constant diélectrique est proposée. Au final, le modèle développé est capable de décrire les coefficients d’activité ainsi que les équilibres VLE et LLE des système électrolytiques avec solvants mixtes. / The capabilities of the current thermodynamic models are limited in dealing with mixed-solvent electrolyte systems, due to the complex interactions within these systems. The objective of this work is to extend eGC-PPC-SAFT model to these systems. This is done in several steps. First, a modification in the temperature dependent water diameter was proposed. Second, a minimum number of ion-water parameters are determined on mean ioninc activity coefficients and densities of strong electrolyte systems, as well as vapour-liquid equilibria (VLE) of mixed solvent electrolytes. In the third step, the model is used to study the liquid-liquid equilibrium (LLE) of the mixed-solvent electrolyte system. This was done by looking at the partition coefficients of the individual species in the systems. In doing so, a parameterization strategy was developed for ion-solvent binaries that involve assessing the impact of the individual ePPC-SAFT contribution on the partitioning of individual species. A new method for dealing with the condition of electroneutrality in liquid-liquid ionic systems was proposed that involves a direct correction on the fugacity coefficient. In view of the importance of this property, a new mixing rule for the dielectric constant of mixed solvent is proposed to provide the best description of LLE of mixed solvent electrolyte. The final model is capable of describing, the activity coefficient, VLE, and LLE of mixed-solvent electrolyte systems.

管径方向分配現象(Tube Radial Distribution Phenomenon: TRDP)を応用したクロマトグラフィー(TRDC)に関する研究と、TRDPの現象解明に関する研究を行った。TRDCに関する研究として、TRDCによる分離性能の改善と最適条件の検討、分析対象物の拡大を行い、併せてTRDCシステムの構築に貢献した。TRDPに関する研究として、TRDPの発生に必要な条件の検討、新たなTRDPを発生する溶液系の導入、及びTRDPの相形成の規則性について調べた。その結果、TRDPの全体的な原理の解明に貢献した。 / The author studied the development of capillary chromatography (TRDC) based on TRDP and the elucidation of TRDP. For study of TRDC, I studied the improvement of separation performance, the optical condition of TRDC and the expansion of analyte. As a result, the author contributed to the construction of TRDC system. For study of TRDP, The author studied the condition to generate TRDP, the introduction of the new solution system to generate TRDP, and the regularity of the phase formation of TRDP. As a result, the author contributed to the elucidation of the principle of TRDP. / 博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University

No / The electrophoretic mobilities of three beta-blocker drug practolol, timolol and propranolol, have been measured in electrolyte systems with mixed binary and ternary water-methanol-ethanol solvents with acetic acid/sodium acetate as buffer using capillary electrophoresis. The highest mobilities for the analytes studied have been observed in pure aqueous. the lowest values in ethanolic buffers The measured electrophoretic mobilities have been used to evaluate the accuracy of a mathematical model based on a mixture response surface method that expresses the mobility as a function of the solvent composition. Mean percentage error (MPE) has been computed considering experimental and calculated mobilities as an accuracy criterion. The obtained MPE for practolol, timolol and propranolol in the binary mixtures are between 0.9 and 2.6%, in the ternary water-methanol-ethanol solvent system the MPE was about 2.7%. The MPE values resulting from the proposed equation lie within the experimental relative standard deviation values and can he considered as an acceptable error.

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