雙參數離子活性係數模式應用

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林信益(Hsin-Yi Lin) 查詢紙本館藏

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化學工程與材料工程學系

論文名稱

雙參數離子活性係數模式應用

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摘要(中)

Lin and Lee (Fluid Phase Equilibria, vol. 205, (2003) 69-83)在其發表的論文中提出電解質水溶液中，離子活性係數肇因於離子水合作用之部份以solvation parameter表示，而肇因於離子間作用力之部份則以approaching parameter表示，本研究以Lin and Lee的二參數個別離子活性係數模式，並以Vera (AIChE J. vol. 50 (2004) 445-462)中以離子選擇性電極(ion selective electrode, ISE)測量所得的個別離子活性係數實驗值迴歸求得14種1:1型式、2種1:2型式及6種2:1型式共22種電解質個別離子活性係數參數，並成功預測單一電解質水溶液滲透係數及多電解質水溶液的平均活性係數及滲透係數，更可預測多電解質中單一離子的個別離子活性係數。
本研究進一步將利用含共同離子的二元電解質水溶液之滲透係數迴歸出2種1:1型式、5種2:1型式、3種1:2型式及2種2:2型式，共12種電解質個別離子活性係數參數，並成功預測單一電解質水溶液滲透係數及多電解質水溶液的平均活性係數、滲透係數及多電解質中單一離子的個別離子活性係數。
電解質水溶液之熱容量是相當重要的熱力學性質，本研究利用溶液過剩性質及Lin and Lee的二參數個別離子活性係數模式推演出電解質水溶液熱容量預測模式，並利用前述迴歸所得參數成功預測28種電解質水溶液的熱容量。

摘要(英)

In the study of Lin and Lee (Fluid Phase Equilibria, vol.205, (2003) 69-83), it was concluded that, in the electrolyte solution, the ion activity coefficient is contributed by two parts: one is solvation which is expressed by solvation parameter, the other is ion-ion interaction which is expressed by approaching parameter. In this study, the Lin and Lee ‘s two-parameter individual ion activity coefficient model was adopted to regress the Vera’s experimental data measured with ISEs (AIChE J., vol.50 (2004) 445-462). The individual-ion-activity-coefficient parameters of 22 electrolytes, including 14 electrolytes of 1:1 type, 2 electrolytes of 1:2 type and 6 electrolytes of 2:1 type, were obtained. Using these parameters, the osmotic coefficients of aqueous uni-electrolyte solutions and the mean activity coefficients and osmotic coefficients of aqueous multi-electrolyte solutions have been predicted successfully. Even more, the individual ion activity coefficient of certain an ion in the aqueous multi-electrolyte solution can also be predicted.
Furthermore, the two-parameter individual ion activity coefficient model was adopted to regress the experimental data of osmotic coefficients of aqueous bi-electrolyte solutions containing common ions. The individual-ion-activity-coefficient parameters of 12 electrolytes, including 2 electrolytes of 1:1 type, 5 electrolytes of 2:1 type, 3 electrolytes of 1:2 type and 2 electrolytes of 2:2 type, were obtained. Using these parameters, the osmotic coefficients of aqueous uni-electrolyte solutions and the mean activity coefficients and osmotic coefficients of aqueous multi-electrolyte solutions, and the individual ion activity coefficient of certain an ion in the aqueous multi-electrolyte solution have been predicted successfully.
Heat capacity is an important thermodynamic property of aqueous electrolyte solutions. In this study, the predictive model of heat capacity of aqueous electrolyte solutions was also deduced by using the solution excess property and Lin and Lee’s two-parameter individual ion activity coefficient model, and, using the above regressed parameters, the heat capacities of 28 aqueous electrolyte solutions has been successfully predicted.

論文目次

中文摘要 Ⅰ
英文摘要 Ⅱ
目錄 Ⅲ
表目錄 Ⅴ
圖目錄 Ⅷ
符號說明 Ⅸ
第一章緒論 1
第二章電解質水溶液熱力學性質 3
2.1 電解質溶液之濃度單位 3
2.1.1 重量莫耳濃度 3
2.1.2 離子強度 3
2.1.3 莫耳分率 3
2.1.4 莫耳分率之離子強度 3
2.2 標準狀態 (standard state) 3
2.3 電解質平均活性係數 5
2.4 溶液之滲透係數 5
2.5 溶液之熱容量 6
第三章文獻回顧 7
3-1 電解質平均活性係數與溶液滲透係數模式之回顧 7
3-2 電解質溶液個別離子活性係數相關文獻之回顧 11
3-3 Lin & Lee電解質平均活性係數估算模式之回顧 13
第四章電解質水溶液個別活性係數關聯 19
4-1 利用個別離子活性係數實驗數據關聯 Lin & Lee 模式參數 19
4-2 利用共同離子混合水溶液滲透係數實驗數據關聯 Lin & Lee 模式 20
第五章電解質水溶液熱力學性質預估 24
5-1 二元及三元電解混合水溶液中滲透係數預估 24
5-2 單一電解質水溶液熱容量預估 26
第六章個別離子活性係數測量之爭論 31
6-1 Vera團隊的發現 31
6-2 Vera的失誤 35
6-3 Malatesta的觀點 36
6-4 我們的看法 39
第七章結論與未來展望 40
參考文獻 42
表 48
圖 83

參考文獻

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指導教授

李亮三(Liang-Sun Lee)

審核日期

2005-12-30

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