臺灣博碩士論文加值系統

本研究主要目的在於探討鹽效應在混合溶劑三成份系統之液液平衡。在實驗方面，在298.15K下，乙酸正丁酯－正丁醇－水系統在飽和氯化鈉(氯化鉀或硫酸鉀)的濃度下，進行液液平衡實驗量測。由實驗結果可以觀察到液液平衡相圖中兩相之不互溶區明顯地變大。
為模擬鹽效應在混合溶劑系統之液液平衡，本研究利用TTK-Wilson活性係數模式來描述溶液中之非理想性。根據熱力學平衡準則，利用兩相中之每一成份活性必須相等，並配合質量均衡的觀念，來計算四成份電解質混合溶劑系統液液平衡組成。在所提出的計算方法中，不須要可調參數。在計算電解質混合溶劑系統之液液平衡時，可發現模擬結果與實驗數據相當吻合，其平均偏差小於0.7﹪。

The objective of this study is to investigate salt effects on liquid-liquid equilibria (LLE) of ternary mixed solvent systems. In the experimental part, the LLE measurements of n-butyl acetate－n-butanol－water systems saturated with sodium chloride (potassium chloride or potassium sulfate) were made at 298.15K. It was observed that the salt effect enlarges the area of the two-phase region in the LLE phase diagram.
To simulate the salt effects on LLE of ternary mixed solvent systems, a TTK-Wilson activity coefficient model was used to represent the non-idealities in the solution. Based on thermodynamic equilibrium criterion that the activity of each component must be the same in two phases and the concept of mass balance, we can reproduce the LLE data of quaternary mixed-solvent electrolyte systems. No adjustable parameter was needed in the proposed calculation method. It was found that the predicted results were in good agreement with experiment LLE data with a mean deviation less than 0.7﹪for each system.

摘要…………………………………………………………………… I
Abstract………………………………………………………………...II
誌謝…………………………………………………………………...III
目錄…………………………………………………………………...IV
圖表說明………………………………………………………………VI
第一章 緒論………………………………………………………….. 1
第二章 文獻回顧…………………………………………………….. 3
2.1 電解質溶液之分配平衡…………………………………….. 3
2.2 活性係數模式……………………………………………..….4
2.3 液液平衡計算……………………………………………..….7
第三章 電解質溶液之液液平衡實驗………………………….…… 12
3.1 前言…………………………….…………………………… 12
3.2 實驗裝置……………………………………………………. 12
3.3 儀器設備……………………………………………………. 12
3.4 實驗藥品………………………………………… 13
3.5 實驗方法………………………………………… 14
3.5.1二成份混合溶劑系統之液液平衡(不含電解質)..….14
3.5.2三成份混合溶劑系統之液液平衡(不含電解質)..….15
3.5.3 飽和電解質四成份混合溶劑之液液平衡………..…16
3.6 分析方法……………………………………………………..16
3.6.1液相中溶劑組成之分析……………………………….16
3.6.2檢量線的製作…………………………………………..17
3.6.2.1 二成份系統檢量分析…………………………….17
3.6.2.2 三成份系統檢量分析…………………………….19
3.6.3未知樣品分析………………………………………… 19
3.7結果與討論………………………………………………….. 20
第四章 理論模擬……………………………………………………. 38
4.1 TTK-Wilson活性係數模式………………………………… 38
4.2液液平衡計算方法…………………………………………...41
4.3結果與討論…………………………………………………...42
第五章 結論…………………………………………………………...54
參考文獻……………………………………………………….………56
符號說明……………………………………………………….………61
作者簡介……………………………………………………………….63
圖表說明
圖3-1 液液平衡實驗裝置示意圖……………………………………. 22
圖3-2 乙酸正丁酯(1)－水(3)系統之檢量線…...…………..………... 23
圖3-3 正丁醇(2)－水(3)系統之檢量線…..…………………..……… 24
圖3-4 在298.15K下，乙酸正丁酯(1)－正丁醇(2)－水(3)系統之液液平衡相圖……………………………………………..……..…..25
圖3-5 在298.15K下，飽和氯化鈉在乙酸正丁酯(1)－正丁醇(2)－水(3)系統之液液平衡相圖...……………………………………..26
圖3-6 在298.15K下，飽和氯化鉀在乙酸正丁酯(1)－正丁醇(2)－水(3)系統之液液平衡相圖...………………………….………… 27
圖3-7 在298.15K下，飽和硫酸鉀在乙酸正丁酯(1)－正丁醇(2)－水(3)系統之液液平衡相圖……………………………….……... 28
圖3-8 在298.15K下，飽和鹽效應於乙酸正丁酯(1)－正丁醇(2)－水 (3)系統之液液平衡比較……………………………………….29
圖4-1 在298.15K下，乙酸正丁酯(1)－正丁醇(2)－水(3)系統之液液平衡實驗數據與關聯結果之比較….…………………….….….. 43
圖4-2 在298.15K下，飽和氯化鈉在乙酸正丁酯(1)－正丁醇(2)－水(3)系統之液液平衡實驗數據與預估數據之比較………...…..44
圖4-3 在298.15K下，飽和氯化鉀在乙酸正丁酯(1)－正丁醇(2)－水(3)系統之液液平衡實驗數據與預估結果比較.……….…….….. 45
圖4-4 在298.15K下，飽和硫酸鉀在乙酸正丁酯(1)－正丁醇(2)－水(3)系統之液液平衡實驗數據與預估結果比較…….…….….. 40
表3-1 在298.15K下，正丁醇(1)－水(2)系統之液液平衡實驗數據與文獻值之比較……..……………………………………..……..30
表3-2 在298.15K下，乙酸正丁酯(1)－水(2)系統之液液平衡實驗數據與文獻值之比………………………………………………..31
表3-3 在298.15K下，飽和氯化鈉－正丁醇(1)－水(2)系統之液液平
衡實驗數據與文獻值之比較(salt free basis).………………….32
表3-4 在298.15K下，飽和氯化鉀－正丁醇(1)－水(2)系統之液液平衡實驗數據與文獻值之比較(salt free basis)…………………..33
表3-5 在298.15K下，乙酸正丁酯(1)－正丁醇(2)－水(3)系統之液液平衡實驗數據………………………….….……………………34
表3-6 在298.15K下，飽和氯化鈉－乙酸正丁酯(1)－正丁醇(2)－水(3)系統之液液平衡實驗數據與文獻值之比較……………….35
表3-7 在298.15K下，飽和氯化鉀－乙酸正丁酯(1)－正丁醇(2)－水(3)系統之液液平衡實驗數據與文獻值之比較……………….36
表3-8 在298.15K下，飽和硫酸鉀－乙酸正丁酯(1)－正丁醇(2)－水 (3)系統之液液平衡實驗數據與文獻值之………………….37
表4-1 Jaques-Furter方程式之參數值與TTK-Wilson模式中電解質(S)－水(3)之交互作用參數ΛS3之計算值…………………….…47
表4-2 在298.15K下，TK－Wilson模式中溶劑－溶劑交互作用參數Λij之值…………………..………………………………….…48
表4-3 在298.15K下，乙酸正丁酯(1)－正丁醇(2)－水(3)系統之液液平衡關聯數據…...………..…………………………………….49
表4-4 在298.15K下，飽和氯化鈉－乙酸正丁酯(1)－正丁醇(2)－水(3)系統之液液平衡預估數據………..………………..….....…50
表4-5 在298.15K下，飽和氯化鉀－乙酸正丁酯(1)－正丁醇(2)－水(3)系統之液液平衡預估數據………….……………..….....…51
表4-6 在298.15K下，飽和硫酸鉀－乙酸正丁酯(1)－正丁醇(2)－水(3)系統之液液平衡預估數據………………….……..….....…52
表4-7 在TTK-Wilson模式中計算所需莫耳體積之值……………..53

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