臺灣博碩士論文加值系統

本論文主要目的在於探討電解質混合溶劑三成份系統液液平衡，包括實驗量測與理論預估兩部份。
在實驗方面於15、25、35℃下，完成正丁醇(n-butanol , NBA)－水、異丁醇(iso-butanol , IBA)－水及第二丁醇(sec-butanol , SBA)－水二成份系統及正丁醇(n-butanol , NBA)－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25℃時正丁醇(n-butanol , NBA)－水－氯化鉀、異丁醇(iso-butanol , IBA)－水－氯化鉀和第二丁醇(sec-butanol , SBA)－水－氯化鉀之液液平衡數據。
在理論方面，本文以Tan之修正型Wilson模式來計算電解質混合溶液中各別溶劑之活性係數，此模式結合了電解質水溶液蒸汽壓模式，並以Gibbs-Duhem方程式來計算電解質之平均活性係數，配合驟餾計算來預估兩液相之組成，且無須新增可調參數，模擬6組電解質混合溶劑系統之液液平衡時，可發現與實驗數據相當吻合。

The objective of this study is to investigate salt effects on liquid-liquid equilibria (LLE) in mixed solvent systems, including experimental measurements and theoretical predictions. For a temperature range of 15-35oC with an increment of 10oC, the experiments of LLE for binary systems of n-butanol(NBA)- water, iso-butanol(IBA)- water and sec-butanol(SBA)- water and that for ternary system of n-butanol(NBA)- water- NaCl were made and checked with literature data. At a single temperature of 25oC, the LLE data for ternary systems of n-butanol(NBA)- water- KCl, iso-butanol(IBA)- water- KCl and sec-butanol(SBA)- water- KCl were measured in this study.
In theoretical simulation, the activity coefficients of solvents were calculated by Tan''s modified Wilson model, combined with vapor pressure model of electrolyte aqueous solutions. The Gibbs-Duhem equation was used to calculate mean activity coefficient of the electrolyte. Based on the scheme of flash calculation, the mole fractions in both phases were predicted without adding new adjustable parameter. It was found that the theoretical simulations for the six cases reported in this study were in good agreement with experimental data.

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 電解質溶液之濃度單位…………………………………….. 4
2.1.1 重量莫耳濃度(m)與莫耳分率(x)…………………….. 4
2.1.2 離子強度(I)……………………………………….…... 4
2.2 電解質溶液中離子之化勢………………………………….. 5
2.3 電解質平均活性係數……………………………………….. 6
第三章 文獻回顧…………………………………………………….. 7
3.1 電解質溶液之分配平衡…………………………………….. 7
3.2 電解質溶液液液平衡之模擬……………………………….. 9
第四章 理論說明……………………………………………….…… 14
4.1 Tan''s修正型液相活性係數模式…………………………… 14
4.2 電解質水溶液蒸氣壓………………………………….…… 15
4.3 電解質之平均活性係數……………………………………. 16
4.4 電解質溶液之液液平衡的模擬……………………………. 18
第五章 電解質溶液液液平衡實驗…………………………………. 22
5.1 前言…………………………………………………………. 22
5.2 實驗裝置……………………………………………………. 22
5.3 儀器設備……………………………………………………. 23
5.4 實驗藥品……………………………………………………. 24
5.5 實驗方法……………………………………………………. 25
5.5.1非電解質水溶液液液平衡之實驗…………………… 25
5.5.2電解質水溶液液液平衡之實驗……………………… 25
5.6 分析方法……………………………………………………. 26
5.6.1液相中溶劑組成之分析……………………………… 26
5.6.2檢量線的製作………………………………………… 27
5.6.3未知樣品分析………………………………………… 28
5.6.4液相中電解質成份之分析…………………………… 28
5.7結果與討論………………………………………………….. 30
第六章 理論模擬……………………………………………………. 55
第七章 結論…………………………………………………………. 71
參考文獻……………………………………………………….…….. 73
符號說明……………………………………………………….……… 77
作者簡介………………………………………………………………. 80

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