臺灣博碩士論文加值系統

本研究利用示差掃描熱量分析儀 ( Differential Scanning Calorimetry, DSC ) 量測丙二酸 ( 1 ) + 戊二酸 ( 2 ) 、丙二酸 ( 1 ) + 辛二酸 ( 2 ) 、丙二酸 ( 1 ) + 壬二酸 ( 2 ) 、丙二酸 ( 1 ) + 癸二酸 ( 2 ) 、丙二酸 ( 1 ) + 3-甲基戊二酸 ( 2 ) 、丙二酸 ( 1 ) + 2,2-二甲基丁二酸 ( 2 ) 、丙二酸( 1 ) + 2,3-二甲基丁二酸 ( 2 ) 等七組兩成分混合物之固液相平衡數據，其相平衡圖皆為簡單共熔型 ( simple eutectic ) 之圖形。將此七組所量測的數據結果，以數學理論模型Clarke-Glew方程式迴歸表示量測結果，再依照半經驗Wilson與NRTL方程式來對應驗證，即可建構出各組實驗數據相對應之圖形，進而預測出共熔點 ( eutectic point, X1 ) 及共熔溫度 ( eutectic temperatures, TE ) 。
在本研究中，丙二酸 ( 1 ) + 戊二酸 ( 2 ) 兩成分混合物的Wilson、NRTL及Clarke-Glew方程式之迴歸計算出X1分別為0.359、0.375及0.368，所計算出TE分別為343.09 K、338.48 K及347.54 K，半經驗式Wilson以及NRTL平均絕對偏差均在0.29 %以下；丙二酸 ( 1 ) + 辛二酸 ( 2 ) 兩成分混合物的Wilson、NRTL及Clarke-Glew方程式之迴歸計算出X1分別為0.593、0.592及0.595，所計算出TE分別為382.55 K、382.59 K及383.74 K，半經驗式Wilson以及NRTL平均絕對偏差均在0.10 %以下；丙二酸 ( 1 ) + 壬二酸 ( 2 ) 兩成分混合物的Wilson、NRTL及Clarke-Glew方程式之迴歸計算出X1分別為0.402、0.398及0.385，所計算出TE分別為366.36 K、366.51 K及366.69 K，半經驗式Wilson以及NRTL平均絕對偏差均在0.10 %以下；丙二酸 ( 1 ) + 癸二酸 ( 2 ) 兩成分混合物的Wilson、NRTL及Clarke-Glew方程式之迴歸計算出X1分別為0.600、0.586及0.613，所計算出TE分別為381.98 K、382.11 K及386.02 K，半經驗式Wilson以及NRTL平均絕對偏差均在0.13 %以下；丙二酸 ( 1 ) + 3-甲基戊二酸 ( 2 ) 兩成分混合物的Wilson、NRTL及Clarke-Glew方程式之迴歸計算出X1分別為0.291、0.286及0.255，所計算出TE分別為346.69 K、348.08 K及350.26 K，半經驗式Wilson以及NRTL平均絕對偏差均在0.27 %以下；丙二酸 ( 1 ) + 2,2-二甲基丁二酸 ( 2 ) 兩成分混合物的Wilson、NRTL及Clarke-Glew方程式之迴歸計算出X1分別為0.596、0.563及0.571，所計算出TE分別為375.46 K、367.38 K及377.63 K，半經驗式Wilson以及NRTL平均絕對偏差均在0.55 %以下；丙二酸 ( 1 ) + 2,3-二甲基丁二酸 ( 2 ) 兩成分混合物的Wilson、NRTL及Clarke-Glew方程式之迴歸計算出X1分別為0.410、0.409及0.509，所計算出TE分別為364.61 K、365.01 K及371.09 K，半經驗式Wilson以及NRTL平均絕對偏差均在0.46 %以下。
在以上這七組有機酸兩成分系統所得數據資料，不但可以提供給業界作為材料分離的基本依據，也可以補充熱力學理論研究時所需的固液相平衡數據。

In this research, the writer using Differential Scanning Calorimetry ( DSC ) of the solid-liquid equilibria for seven organic binary mixtures ― malonic acid ( 1 ) + glutaric acid ( 2 ), malonic acid ( 1 ) + suberic acid ( 2 ), malonic acid ( 1 ) + azelaic acid ( 2 ), malonic acid ( 1 ) + sebacic acid ( 2 ), malonic acid ( 1 ) + 3-methylglutaric acid ( 2 ), malonic acid ( 1 ) + 2,2-dimethylsuccinic acid ( 2 ), malonic acid ( 1 ) + 2,3-dimethylsuccinic acid ( 2 ). Simple eutectic phase diagrams for these systems are observed. Simple eutectic phase diagrams for these systems were observed. The experimental results were correlated by the Clarke-Glew ( CG ) activity coefficient models. The experimental data were well correlated by both the Wilson and the non-random two-liquid ( NRTL ) activity coefficient models. Finally, we used the data to describe the presentation that predicted the eutectic point ( X1 ) and eutectic temperatures ( TE ).
Solid-liquid equilibria for seven organic binary mixtures were calculated by the Wilson, NRTL and CG models ― malonic acid ( 1 ) + glutaric acid ( 2 ) (X1=0.359, 0.375 and 0.368, TE=343.09 K, 338.48 K and 347.54 K, AADT less than 0.29 % ) ; malonic acid ( 1 ) + suberic acid ( 2 ) (X1=0.593, 0.592 and 0.595, TE=382.55 K, 382.59 K and 383.74 K, AADT less than 0.10 % ) ; malonic acid ( 1 ) + azelaic acid ( 2 ) (X1=0.402, 0.398 and 0.385, TE=366.36 K, 366.51 K and 366.69 K, AADT less than 0.10 % ) ; malonic acid ( 1 ) + sebacic acid ( 2 ) (X1=0.600, 0.586 and 0.613, TE=381.98 K, 382.11 K and 386.02 K, AADT less than 0.13 % ) ; malonic acid ( 1 ) + 3-methylglutaric acid ( 2 ) (X1=0.291, 0.286 and 0.255, TE=346.69 K, 348.08 K and 350.26 K, AADT less than 0.27 % ) ; malonic acid ( 1 ) + 2,2-dimethylsuccinic acid ( 2 ) (X1=0.596, 0.563 and 0.571, TE=375.46 K, 367.38 K and 377.63 K, AADT less than 0.55 % ) ; malonic acid ( 1 ) + 2,3-dimethylsuccinic acid ( 2 ) (X1=0.410, 0.409 and 0.509, TE=364.61 K, 365.01 K and 371.09 K, AADT less than 0.46 % ).
This study not only supply the data of solid-liquid equilibrium for doing research and developing about thermodynamics but also provide basis reference data for industry segregation process.

致謝 I
中文摘要 II
Abstract IV
目錄 VI
表目錄 IX
圖目錄 XI
附錄 1
第一章 緒論 3
1.1 研究背景與目的 3
1.2 固液相平衡之實驗方法 4
1.2.1 目視量測法 4
1.2.2 x-光繞射分析法 5
1.2.3 熱分析法 5
1.3 文獻回顧 6
第二章 熱分析原理與實驗數據分析迴歸模式 9
2.1 兩成分簡單共熔圖之介紹 9
2.2 示差掃描熱量分析儀DSC 11
2.2.1 熱流式DSC ( Heat Flux DSC ) 11
2.2.2 補償式DSC ( Power compensation DSC ) 13
2.2.3 DSC之校正 14
2.3 熱力學模式與相轉化曲線 16
2.3.1 熱力學模式 16
2.3.2 相轉化曲線 18
2.4 熱力學模式之理論模型 19
2.4.1 Wilson Model 20
2.4.2 NRTL Model 24
2.4.3 Clarke-Glew Equation 25
第三章 實驗 26
3.1 實驗儀器 26
3.1.1 示差掃描熱量分析儀 ( DSC ) 26
3.1.2 示差掃描熱量分析儀之冷卻機 27
3.1.3 熱重分析儀 ( TGA ) 28
3.1.4 電子天平 29
3.1.5 其他儀器設備 30
3.2 實驗藥品 31
3.2.1 藥品來源 31
3.2.2 藥品資料 32
3.2.3 藥品結構式 34
3.3 藥品配製 35
3.4 實驗步驟 35
3.4.1 實驗前置作業 35
3.4.2 各組兩成份混合物之實驗步驟 37
3.5 數據處理 39
3.5.1 繪製兩成分混合物的固-液相平衡圖 40
3.5.2 繪製共熔點相轉化的比例並比對實驗量測數據的圖形 40
3.5.3 輸入實驗數據建構其Wilson model與NRTL model相對應的理論模型圖 40
第四章 結果與討論 41
4.1 兩成分實驗系統 41
4.2 DSC曲線之圖形判別 44
4.3 兩成分系統有機物相關之探討 46
4.4 影響實驗曲線之因素 61
4.4.1 藥品顆粒大小之均勻度 61
4.4.2 試樣填裝與配製 61
4.4.3 使用之樣品盤 ( sample pan ) 62
4.4.4 藥品的裂解性質 62
4.4.5 氣體介質種類、純度及流量 63
4.4.6 加熱速率之影響 63
4.5 熱力學模式與Wilson、NRTL及Clarke-Glew方程式之對應結果 64
第五章 結論 74
參考文獻 76

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