臺灣博碩士論文加值系統

本論文分為二部分，第一部份為高壓下藥物溶解度關聯，收集近年文獻中15種藥物，於超臨界二氧化碳中溶解度數據，利用一溶液模式，即規則溶液模式(regular solution model)配合Flory-Huggins equation，在不同溫度及壓力下，描述藥物溶質的無限稀薄活性係數，進行藥物溶解度計算。藉由模式中，溶質莫耳體積視為可調參數與超臨界二氧化碳密度關聯，並將關係式模式進行無因次化修正，利用其來進行溶解度數據迴歸計算，最後將參數進行簡化與關聯，並使用MST、Chrastil兩個半經驗式比較結果。研究觀察使用規則溶液模式(regular solution model)配合Flory-Huggins equation計算15種藥物於超臨界二氧化碳中溶解度數據，總共412個實驗數據點，所得到之結果令人相當滿意。此外，進一步考慮模式中唯一參數，提出藥物分子與二氧化碳分子量比值有相關聯，使該模式更溶易應用於溶解度預測行為。

第二部分為酒精汽油溶解度之量測，酒精汽油為未來不可或缺的產品，酒精因有容易吸收大氣中水氣，而可能造成酒精汽油中儲存於汽車油箱或地下儲槽，而產分相，建立相關液液相平衡數據亦是當重要，研究中以戊烷、己烷和環己烷之混合物為汽油替代組成，液-液平衡實驗系統包括，三組三成分系統：乙醇-水-戊烷、乙醇-水-己烷及乙醇-水-環己烷;三組四成份系統：乙醇-水-戊烷-己烷、乙醇-水-戊烷-環己烷及乙醇-水-己烷-環己烷;一組五成份系統：乙醇-水-戊烷-己烷-環己烷分別在293.15 K、303.15 K及308.15 K三個溫度下進行實驗，並與文獻數據進行比較，最後以UNIQUAC液相模式迴歸每個系統兩成份參數，運用在五成份系統擬合結果，實驗值與計算值誤差均小於RMSD小於0.02以下。

This thesis is divided into two parts. The first part is the solid solubility data of 15 pharmaceutical compounds in supercritical carbon dioxide Under different temperatures and pressures, the infinite dilution activity coefficient for pharmaceutical compound is described by regular solution model associated with the
Flory-Huggins equation.While correlating the data, the molarvolume of the solid solute is considered as a variable consisting of two parameters for the model. This volume is then transformed into a reduced form by introducing the critical density of carbon dioxide and even simplified to be with only one parameter involved. Comparing the correlation results obtained from the commonly used semi-empirical models of Mendez-Santigo-Teja and Chrastil. It is observed that regular solution model calculated with the Flory-Huggins equation of 15 pharmaceutical compounds in supercritical carbon dioxide solubility data, a total of 412 data points and obtained quite satisfactory results. In addition, a further consideration that the only parameter included in the present model could be expressed in terms of the ratio of the molecular weight of compound to that of CO2, and makes the model become a more
general and could be applied for prediction.

The second part of the solubility measurements of gasohol, the liquid-liquid equilibria of the mixtures consisted of ethanol, water, and the main components of gasoline fuel: pentane, hexane, and cyclohexane were experimentally determined. This study is related to the phase behavior when water in atmosphere is absorbed into ethanol + gasoline fuel (gasohol) and then possibly separates into two liquid phases in an automobile fuel tank or an underground storage tank. The liquid-liquid equilibria in this study include three ternary systems: ethanol + water + pentane, ethanol + water + hexane, and ethanol + water + cyclohexane; three quaternary systems: ethanol + water + pentane + hexane, ethanol + water + pentane + cyclohexane, and ethanol + water +hexane + cyclohexane; one quinary system: ethanol + water + pentane + hexane + cyclohexane. The present experiments were conducted at 293.15, 303.15, and 308.15 K, and the experimental data were collected and some were compared to that available in literature, and finally all data were correlated with the UNIQUAC
activity coefficient model.

中文摘要 I
英文摘要 II
表目錄 V
圖目錄 VII
符號說明(Ⅰ) IX
符號說明(Ⅱ) XI
第一章 緒論
1-1超臨界流體特性及應用 1
1-2 應用熱力學性質於固體溶解度重要性 3
第二章 固體藥物於超臨界二氧化碳中之溶解度關聯
2-1研究背景與動機 6
2-2數學模式 6
2-3 藥物溶解度計算結果與討論 11
第三章 結論 15
第四章 緒論
4-1前言 30
4-2 酒精汽油國際發展現況 30
4-3 研究動機與目的 31
第五章 酒精汽油之溶解度量測
5-1 液液相平衡理論 32
5-2 液液平行之形成 33
5-3 活性係數模式 35
第六章 實驗部分
6-1 實驗系統選擇 38
6-2 實驗藥品 38
6-3 實驗設備 38
6-4 樣品分析之條件 39
6-5 檢量線之配置 39
6-6 實驗步驟 39
6-7 實驗數據處理 40
第七章 溶解度量測結果與討論 44
第八章 結論 46

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