臺灣博碩士論文加值系統

本論文主要目的在於提出Setschenow方程式之修正，並應用於描述電解質混合溶劑三成份系統之液液平衡。
在實驗方面，完成正丁醇－水、異丁醇－水及第二丁醇－水二成份系統及正丁醇－水－氯化鈉三成份系統之液液平衡數據，並與文獻比較以驗證實驗之可信度，接著進行298.15K時正丁醇－水－氯化鉀、異丁醇－水－氯化鉀和第二丁醇－水－氯化鉀之液液平衡數據。在理論方面，利用本文所提之Extended Setschenow方程式來計算水相中電解質之莫耳分率，並以TTK-Wilson模式來計算電解質混合溶液中溶劑之活性係數。根據相平衡之物質均衡觀念來計算兩液相之組成，本計算方法中僅須兩個可調參數，在計算12組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。其平均偏差介於0.004至0.015之間。

The objective of this study is to modified Setschenow equation to describe the salt effects on liquid-liquid equilibria (LLE) of mixed solvent systems.
In experimental part, the experiments of LLE for binary systems of n-butanol- water, iso-butanol- water and sec-butanol- water and that for ternary system of n-butanol- water- NaCl were made and checked with literature data (De Santis, 1976). The LLE data for ternary systems of n-butanol- water- KCl, iso-butanol- water- KCl and sec-butanol- water- KCl were measured at a single temperature of 298.15K. In the theoretical simulation, the Setscheonw equation was modified and used to calculate the mole fraction of electrolyte in the aqueous phase. The activity coefficients of solvents in mixed solvent-electrolyte systems were calculated by the TTK-Wilson model. Based on the material balance in phase equilibria, the mole fractions in both phases were calculated by using two adjustable parameters. It was found that the theoretical simulations for the twelve systems reported in this study were in good agreement with experimental data. The mean deviation range from 0.004 to 0.015.

摘要………………………………………………………… I
Abstract……………………………………….……………...II
誌謝………………………………………………………...III
目錄………………………………………………………...IV
圖表說明…………………………………………………..VII
第一章 緒論…………………………………………….. 1
第二章 電解質溶液之熱力學基本性質……………….. 4
2.1濃度單位…………………………….……...………….. 4
2.1.1重量莫耳濃度…………………………………………4
2.1.2莫耳分率…….………………………………………...4
2.2 熱力學基本性質…………………………….. 5
2.2.1逸壓……………………………………………………5
2.2.2活性與活性係數………………………………………5
2.2.3相平衡觀念……………………………………………6
第三章 文獻回顧……………………………………….. 8
3.1 前言…………………………………………………….. 8
3.2 電解質效應的定性描述……………………………….. 8
3.3 Setschenow方程式…………………………………………9
3.4 活性係數模式………………………………………..…11
3.5 相平衡計算…………………………………………..…15
第四章 電解質溶液之液液平衡實驗…………….…… 18
4.1 前言…………………………….……………………… 18
4.2 實驗裝置………………………………………………. 18
4.3 儀器設備………………………………………………. 19
4.4 實驗藥品…………………………………….............…. 20
4.5 實驗方法……………………………….............………. 21
4.5.1非電解質水溶液之液液平衡實驗.........................…….21
4.5.2電解質水溶液之液液平衡實驗……….21
4.6 分析方法……………………………............…………. 22
4.6.1液相中溶劑組成之分析……………… 22
4.6.2檢量線的製作………………………… 23
4.6.3未知樣品分析………………………… 24
4.6.4液相中電解質成份之分析……………… 24
4.7結果與討論……………………………………….. 26
第五章 理論計算……………………………………………………. 52
5.1 前言…………………………………………………………. 52
5.2 Setschenow方程式…………………..………………….……52
5.2.1 Setschenow方程式…………………………………….. 53
5.2.2 Extended Setschenow方程式………………………..….54
5.2.3 Modified Setschenow方程式………………………..….54
5.3 TK-Wilson活性係數模式……………………………………55
5.4 TTK-Wilson活性係數模式………………………………… 56
5.5 TTK-Wilson活性係數模式參數…………………………….57
5.5.1 與 ……………………………………………… 57
5.5.2 與 ………………………………………………57
5.6 液液平衡計算方法…………………………………………..59
5.6.1 由進料組成計算兩相組成……………………………59
5.6.2由有機相組成計算水相組成………………………….60
5.7 結果與討論…………………………………………………..60
第六章 結論…………………………………………………………108
參考文獻……………………………………………………….…….110
符號說明……………………………………………………….…….114
作者簡介……………………………………………………………..116
圖表說明
圖4-1 液液平衡實驗裝置示意圖……………………………………. 29
圖4-2 NBA (1)－H2O (2)系統之GC檢量線………………..………... 30
圖4-3 IBA (1)－H2O (2)系統之GC檢量線…………………..……… 31
圖4-4 SBA (1)－H2O (2)系統之GC檢量線…………………..……... 32
圖4-5 NBA(1)－Water(2)系統在常壓下液液平衡數據與文獻比較...33
圖 4-6 在常壓、298.15K下NBA (1)－Water(2)－NaCl(S)系統實驗值與文獻值[25]之比較………….……. 34
圖4-7 在常壓、288.15K下NBA(1)－Water(2)－NaCl(S)系統之液液平衡相圖…………………….……... 35
圖4-8 在常壓、298.15K下NBA(1)－Water(2)－NaCl(S)系統之液液平衡相圖………………….…….….. 36
圖4-9在常壓、308.15K下NBA(1)－Water(2)－NaCl(S)系統之液液平衡相圖………………………….….. 37
圖4-10在常壓、298.15K下NBA(1)－Water(2)－KCl(S)系統之液液平衡相圖………………………….….. 38
圖4-11在常壓、298.15K下IBA(1)－Water(2)－KCl(S)系統之液液平衡相圖………………………….….. 39
圖4-12在常壓、298.15K下SBA(1)－Water(2)－KCl(S)系統之液液平衡相圖………………………….….. 40
圖4-13 NBA (1)－Water(2)－NaCl (S)在常壓下、298.15K之相圖，以重量百分比表示之……………… 41
圖4-14 溫度效應對NBA於水相及有機相之分佈曲線圖…………42
圖4-15 KCl於丁醇－水系統液液平衡之電解質效應圖…………....43
圖5-1 NBA (1)－Water (2)－NaCl (S)系統在288.15K時 與之關係圖…………………………………….…63
圖5-2 NBA (1)－Water (2)－NaCl (S)系統在293.15K時 與之關係圖…………………………………………64
圖5-3 NBA (1)－Water (2)－NaCl (S)系統在298.15K時 與之關係圖………………….……………………66
圖5-4 NBA (1)－Water (2)－NaCl (S)系統在288.15K時 與之關係圖…………………………………….…66
圖5-5 NBA (1)－Water (2)－NaCl (S)系統在308.15K時 與之關係圖…………………………………………67
圖5-6 NBA (1)－Water (2)－NaCl (S)系統在313.15K時 與之關係圖………………….……………………68
圖5-7 NBA (1)－Water (2)－KCl (S)系統在298.15K時 與之關係圖…………………………………………69
圖5-8 SBA (1)－Water (2)－NaCl (S)系統在298.15K時 與之關係圖…………………………………………70
圖5-9 SBA (1)－Water (2)－KCl (S)系統在298.15K時 與之關係圖…………………………………………71
圖5-10 IBA (1)－Water (2)－NaCl (S)系統在298.15K時 與之關係圖…………………………………………72
圖5-11 IBA (1)－Water (2)－KCl (S)系統在298.15K時 與之關係圖…………………………………….……73
圖5-12 298.15K時NBA(1)-Water(2)-KCl(S)系統以本文所提出之Modified Setschenow方程式中與之關係圖…….74
圖5-13 298.15K時NBA(1)-Water(2)-KCl(S)系統以原始之Setschenow方程式中與之關係圖……………..75
圖5-14在常壓及288.15K下NBA (1)－Water (2)－NaCl (S)系統液液平衡的預估結果與實驗數據之比較……… 76
圖5-15在常壓及298.15K下NBA (1)－Water (2)－NaCl (S)系統液液平衡的預估結果與實驗數據之比較……... 77
圖5-16在常壓及308.15K下NBA (1)－Water (2)－NaCl (S)系統液液平衡的預估結果與實驗數據之比較……... 78
圖5-17在常壓及298.15K下NBA (1)－Water (2)－KCl (S)系統液液平衡的預估結果與實驗數據之比較……... 79
圖5-18在常壓及298.15K下IBA (1)－Water (2)－NaCl (S)系統液液平衡的預估結果與實驗數據之比較……... 80
圖5-19在常壓及298.15K下SBA (1)－Water (2)－KCl (S)系統液液平衡的預估結果與實驗數據之比較……... 81
圖5-20在常壓及293.15K下NBA (1)－Water (2)－NaCl (S)系統液液平衡的預估結果與實驗數據之比較……... 82
圖5-21在常壓及298.15K下NBA (1)－Water (2)－NaCl (S)系統液液平衡的預估結果與實驗數據之比較……... 83
圖5-22在常壓及303.15K下NBA (1)－Water (2)－NaCl (S)系統液液平衡的預估結果與實驗數據之比較……... 84
圖5-23在常壓及313.15K下NBA (1)－Water (2)－NaCl (S)系統液液平衡的預估結果與實驗數據之比較……... 85
圖5-24在常壓及298.15K下IBA (1)－Water (2)－NaCl (S)系統液液平衡的預估結果與實驗數據之比較……... 86
圖5-25在常壓及298.15K下SBA (1)－Water (2)－NaCl (S)系統液液平衡的預估結果與實驗數據之比較……... 87
圖5-26相平衡示意圖………………………………………………...88
表4-1在常壓下NBA (1)－H2O (2)系統之液液平衡實驗數據與文獻值之比較……………………………….…44
表4-2在常壓下IBA (1)－H2O (2)系統之液液平衡實驗數據與文獻值之比較……………………………….…45
表4-3在常壓下SBA (1)－H2O (2)系統之液液平衡實驗數據與文獻值之比較………………………………….45
表4-4 在常壓及288.15K下NBA (1)－Water (2)－NaCl (S)系統液液平衡實驗數據……………………..….....…46
表4-5在常壓及298.15K下NBA (1)－Water (2)－NaCl (S)系統液液平衡實驗數據………….………………….…47
表4-6在常壓及308.15K下NBA (1)－Water (2)－NaCl (S)系統液液平衡實驗數據………….…………..….....…48
表4-7在常壓及288.15K下NBA (1)－Water (2)－KCl (S)系統液液平衡實驗數據………….……………………49
表4-8在常壓及298.15K下IBA (1)－Water (2)－KCl (S)系統液液平衡實驗數據………….……………..….....…50
表4-9在常壓及298.15K下SBA (1)－Water (2)－KCl (S)系統液液平衡實驗數據………….……………..….....…51
表5-1液液平衡系統TTK-Wilson模式中溶劑與水之交互作用參數值………..………………………….……89
表5-2 Modified Setschenow方程式中參數 與可調參數 ………..90
表5-3 Alcohol (1)－Water (2)－Electrolyte (S)系統液液平衡以不同Setschenow方程式預估兩相組成誤差比較表……...91
表5-4 以本論文所提出之計算方法與文獻計算結果之比較………92
表5-5 NBA(1)－Water(2)－NaCl(S)系統在常壓及288.15K之液液平衡數據…..………………………………………93
表5-6 NBA(1)－Water(2)－NaCl(S)系統在常壓及298.15K之液液平衡數據…..………………………………..…94
表5-7 NBA(1)－Water(2)－NaCl(S)系統在常壓及308.15K之液液平衡數據…..…………………………………..…95
表5-8 NBA(1)－Water(2)－KCl(S)系統在常壓及298.15K之液液平衡數據…..…………………………………..…96
表5-9 IBA(1)－Water(2)－KCl(S)系統在常壓及298.15K之液液平衡數據…..…………………………………..…97
表5-10 SBA(1)－Water(2)－KCl(S)系統在常壓及298.15K之液液平衡數據…..…………………………………..…98
表5-11 NBA(1)－Water(2)－NaCl(S)系統在常壓及293.15K之液液平衡數據…..…………………………………..…99
表5-12 NBA(1)－Water(2)－NaCl(S)系統在常壓及298.15K之液液平衡數據…..……………………………………100
表5-13 NBA(1)－Water(2)－NaCl(S)系統在常壓及303.15K之液液平衡數據…..……………………………………101
表5-14 NBA(1)－Water(2)－NaCl(S)系統在常壓及313.15K之液液平衡數據…..…………………………………….102
表5-15 IBA(1)－Water(2)－NaCl(S)系統在常壓及298.15K之液液平衡數據…..…………………………………….103
表5-16 SBA(1)－Water(2)－NaCl(S)系統在常壓及298.15K之液液平衡數據…..……………………………………104
表5-17 Alcohol(1)－Water(2)－Electrolyte(S)系統液液平衡以飽和點實驗數據內插與所有實驗數據迴歸兩相組成誤差比較表..105
表5-18 Alcohol(1)－Water(2)－Electrolyte(S)系統液液平衡有機相組成計算水相組成誤差比較表………………….106
表5-19 以本論文所提出之計算方法與Tang等人使用NRTL模式之計算結果比較……………………………………107

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