臺灣博碩士論文加值系統

本研究利用熱示差掃描卡量計( Differential Scanning Calorimetry, DSC ) 量測苯甲酸 ( 1 ) + 3-甲基戊二酸 ( 2 )、苯甲酸 ( 1 ) + 2,3-二甲基丁二酸 ( 2 )、庚二酸 ( 1 ) + 2,3-二甲基丁二酸 ( 2 )、庚二酸 ( 1 ) + 2,2-二甲基丁二酸 ( 2 )、庚二酸 ( 1 ) + 3-甲基戊二酸 ( 2 )、2,2-二甲基丁二酸 ( 1 ) + 3-甲基戊二酸 ( 2 )、戊二酸 ( 1 ) + 2,2-二甲基丁二酸 ( 2 )、戊二酸 ( 1 ) + 3-甲基戊二酸 ( 2 )、戊二酸 ( 1 ) + 2,3-二甲基丁二酸 ( 2 )等九組兩成分混合物之固液相平衡數據。並利用DSC量測的實驗數據之資料，來計算 Wilson及 NRTL 方程式回歸，建構對應實驗數據之圖型，預測共熔溫度 ( eutectic temperatures )及液化溫度 ( liquidus temperatures )，以此固液相平衡數據提供於熱力學研究，並作為工業材料分離的基本資料。

Solid-liquid equilibria of the following nine systems have been measured using Differential Scanning Calorimetry ( DSC )：Benzoic acid ( 1 ) + 3-methylpentanedioic acid ( 2 )、Benzoic acid ( 1 ) + 2,3-dimethylbutanedioic acid ( 2 )、Heptanedioic acid ( 1 ) + 2,3-dimethylbutanedioic acid ( 2 )、Heptanedioic acid ( 1 ) + 2,2-dimethylbutanedioic acid ( 2 )、Heptanedioic acid ( 1 ) + 3-methylpentanedioic acid ( 2 )、2,2-dimethylbutanedioic acid ( 1 ) + 3-methylpentanedioic acid ( 2 )、Pentanedioic acid ( 1 ) + 2,2-dimethylbutanedioic acid ( 2 )、Pentanedioic acid ( 1 ) + 3-methylpentanedioic acid ( 2 )、Pentanedioic acid ( 1 ) + 2,3-dimethylbutanedioic acid ( 2 ). The experimental data were compared with the results calculated from the Wilson and the NRTL model. The study can supply the data of solid-liquid equilibrium for developing in thermodynamics thesis and providing basis reference data for industry segregation process.

目錄
誌謝 I
摘要 II
Abstract III
目錄 IV
表目錄 VII
圖目錄 X
第一章、 緒論 1
1.1 前言 1
1.2 研究背景與目的 1
1.3 固液相平衡之實驗方法 2
1.4 文獻回顧 3
第二章、 熱分析原理與實驗數據分析迴歸模式 5
2.1兩成份簡單共熔圖之介紹 5
2.1熱示差掃描卡量計 DSC 6
2.2.1熱流式DSC ( Heat Flux DSC ) 7
2.2.2補償式DSC ( Power compensation DSC ) 9
2.2.3 DSC之校正時機 10
2.3熱力學模式與相轉化曲線 12
2.3.1 熱力學模式 12
2.3.2 相轉化曲線 14
2.4熱力學模式 15
2.4.1 Wilson方程式 15
2.4.2 NRTL 方程式 17
第三章、 實驗 20
3.1實驗儀器 20
3.2 實驗藥品 21
3.2.1藥品來源 21
3.2.2藥品資料 21
3.2.3藥品結構式 23
3.4 藥品配置方法 24
3.5 實驗步驟 24
3.5.1 實驗前的準備 24
3.5.2 各兩成份系統之實驗步驟 25
3.6 數據處理 29
第四章、 結果與討論 31
4.1兩成分實驗系統 31
4.2 DSC曲線之圖形判斷 34
4.3 兩成份系統有機物相關之探討 36
4.4 影響實驗曲線之因素 46
4.4.1 試樣顆粒大小之均勻度 46
4.4.2 試樣填裝重量 46
4.4.3 運送氣體種類、純度及流量 47
4.4.4 使用之樣品盤( sample pan ) 47
4.4.5 加熱速率之影響 48
4.5 熱力學模式與Wilson方程式、NRTL方程式和共熔點比例法之對應結果 48
4.5.1 熱力學模式與共熔點比例法之對應結果 48
4.5.2 熱力學模式與Wilson、NRTL方程式之對應結果 58
第五章、 結論 71
參考文獻 72

參考文獻
[1]英‧中‧日化學大辭典, 高立圖書有限公司, 1993.
[2]黃定加, 物理化學, 高立圖書有限公司, 台北市, 1995, 242-262.
[3]Domanska, U.,Lachwa, J., (Solid + liquid) phase equilibria of binary mixtures containing N-methyl-2-pyrrolidinone and long-chain n-alkanols at atmospheric pressure. Fluid Phase Equilibria, 2002, 198, 1-14.
[4]許樹恩,吳泰伯., X光繞射原理與材料結構分析, 台北市, 1995, 293-297.
[5]Gray, A. P., Analytical Chemistry. Plenum Press, NY, 1986, 209-218.
[6]Flynn, J. H., in Status of Thermal Analysis, O. Menis, ed., NBS Special Publication. U.S. Gov’t. Printing Office, Washington, DC, Oct. 1970, 338, 119.
[7]Barrall, E. M., Precise Determination of Melting and Boiling Points by Differential Thermal Analysis and Differential Scanning Calorimetry ,Thermochim. Acta,1973,5,377-389.
[8]Matsuoka, M.; Ozawa, R. Determination of solid-liquid-phase equilibria of binary organic systems by differential scanning calorimetry. J. Cryst. Growth, 1989, 96, 596-604.
[9]Huang, C. C.; Chen, Y. P. Measurements and model prediction of the solid-liquid equilibria of organic binary mixtures. Chem. Eng. Sci. 2000, 55, 3175-3185.
[10]Flotter, E.; Hollander, B.; de Loos, T. W.; de Swaan Arons, J. Ternary System (n-Heptane + Docosane + Tetracosane): The Solubility of Mixtures of Docosane in Heptane and Data on Solid-Liquid and Solid-Solid Equilibria in the Binary System (Docosane + Tetracosane). J. Chem. Eng. Data 1997, 42, 562-565.
[11]Takiyama, H.; Suzuki, H.; Uchida, H.; Matsuoka, M. Determination of Solid–Liquid Phase Equilibria by Using Measured DSC Curves. Fluid Phase Equilib. 2002, 194–197, 1107–1117.
[12]Chen, Y. P.; Tang, M.; Kuo, J. C. Solid-liquid Equilibria for Binary Mixtures of N-Phenylacetamide with 4-Aminoacetopheneone, 3-Hydroxyacetophenone and 4-Hydorxyacetophenone, Fluid Phase Equilib. 2005, 232,182–188.
[13]Hammani, A.; Mehrotra, A. K. Nonisothermal Crystallization Kinetics of n-Paraffins with Chain Lengths Between Thirty and Fifty. Thermochimica 1992, 211, 137-153.
[14]Wang, T. C.; Lai, T. Y.; Chen, Y. P. Solid−Liquid Equilibria for Hexanedioic Acid + Benzoic Acid, Benzoic Acid + Pentanedioic Acid, and Hexanedioic Acid + Pentanedioic Acid. J. Chem. Eng. Data 2010, 55, 5797–5800.
[15]Gray, A. P., Analytical Chemistry. Plenum Press, NY, 1968, 209-218
[16]Wilson, G. M. Vapor-Liquid Equilibrium. XI: A New Expression for the Excess Free Energy of Mixing. J. Am. Chem. Soc. 1964, 86, 127-130.
[17]Renon, H.; Prausnitz, J. M., Local Compositions in Thermodynaic Excess Functions for Liquid Mixtures. AIChE J., 1968, 14, 135-144.
[18]Elbro, H. S.; Fredenslund, A.; Rasmussen, P. Group Contribution Method for the Prediction of Liquid Densities as a Function of Temperature for Solvents, Ind. Eng. Chem. Res. 1991, 30, 2576-2582.
[19]吳宇浩, 利用熱分析儀量測 N-Phenylacetamide +4-Aminoacetophenone、3-Hydroxyacetopenone、4-Hydroxyacetophenone 二成份有機混合物之固液相平衡, 國立台灣大學化學工程學研究所碩士論文, 2004.
[20]Poling P. E., Prausnitz J. M., O’Connell J. P., "The Properties of Gases and Liquids, fifth ed, McGraw-Hill, NY, 2001.