二價單電解質水溶液之個別離子活性係數
量測與關聯

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姓名

褚建榮(Chien-Jung Chu) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

二價單電解質水溶液之個別離子活性係數量測與關聯
(Measurement and Correlation of the Individual Ionic Activity Coefficients for the 2:1 Type of Aqueous Solutions of Single Electrolytes. )

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摘要(中)

摘要
本研究目的是以實驗方法量測CaCl2、MgCl2及BaCl2
2：1單電解質水溶液在溫度298.15 K下、不同濃度的個別離子活性係數；並且量測CaCl2單電解質水溶液在不同溫度下、不同濃度的個別離子活性係數。因為缺乏鎂及鋇離子選擇性電極，所以本實驗使用氯離子選擇性電極來量測電動勢，以無因次電位法來計算Cl-的活性係數，接著使用平均離子活性係數之文獻值，計算出Ca2+、Mg2+及Ba2+的活性係數。
實驗結果顯示，個別離子活性係數不僅與濃度、溫度有關，而且與其相對離子也有很大的關係。在溫度效應下，固定濃度的單電解質水溶液其離子活性係數隨著溫度的升高而減小。在298.15 K時，相對離子皆為Cl-的2：1單電解質水溶液，陽離子活性係數的大小順序依次為Mg2+＞Ca2+＞Ba2+，且其相對Cl-活性係數皆不相同。
把個別離子活性係數以Khoshkbarchi-Vera方程式及雙離子參數離子活性係數模式（two-ionic-parameter approach）來關聯，均有不錯的結果。最後，使用雙離子參數離子活性係數模式關聯數據所得到的參數，計算2：1單電解質水溶液的滲透壓係數，並與文獻值作比較，其平均相對誤差（AARD）小於2﹪。

摘要(英)

Abstract
In this study, the ionic activity coefficients of Ca2+, Mg2+, Ba2+, and Cl- were determined. The activity coefficients of Ca2+ and Cl- were measured with individual ion selective electrode (ISE). Due to the lack of ion selective electrode of magnesium and barium, the activity coefficients of these ions were calculated by using the literature data of the mean activity coefficients of the salts of these anions.
The experimental results show that the individual ion activity coefficients depend on concentration, temperature and the nature of its counterion. The ionic activity coefficient in aqueous solution decreases with increasing temperature at constant concerntration. The activity coefficient of the cation in the presence of Cl- decreases in the order of: Mg2+＞Ca2+＞Ba2+.
The Khoshkbarchi-Vera equation and the two-ionic-parameter approach were used to correlate the the individual ion activity coefficients with good accuracy. Finally, the approaching and solvation parameters of two-ionic-parameter approach were used to calculate the osmotic coefficient for these 2:1 electrolytes in aqueous solutions. The average absolute relative deviations (AARD) of the osmotic coefficient are ＜2﹪.

關鍵字(中)

★ 滲透壓係數
★ 活性係數
★ 電解質溶液

關鍵字(英)

★ activity coefficient
★ osmotic coefficient
★ electrolyte solution

論文目次

目錄
中文摘要 Ⅰ
英文摘要 Ⅱ
目錄 Ⅲ
圖目錄 Ⅵ
表目錄 Ⅷ
符號說明 Ⅸ
第一章緒論 1
第二章文獻回顧 3
2-1 電解質溶液個別離子活性係數相關文獻之回顧 3
2-2 電解質溶液平均活性係數模式相關文獻之回顧 5
第三章理論說明 8
3-1 電解質溶液之熱力學基本性質 8
3-1-1離子強度 8
3-1-2電解質之活性係數 8
3-2 Güntelberg方程式 9
3-3 水合理論 10
3-4 電化學與熱力學之關係 12
3-4-1電化學電池之作功 12
3-4-2能士特方程式(Nernst Equation) 12
3-5 個別離子活性係數之理論計算 13
3-6 個別離子活性係數實驗數據之關聯 17
3-7 電解質水溶液滲透壓係數之計算 19
第四章實驗方法 22
　前言 22
4-1 實驗裝置 22
4-2 實驗藥品 22
4-3 實驗設備 23
4-4 實驗步驟 23
4-4-1電極的校正 23
4-4-2量測電化學電池之電動勢 24
第五章實驗結果與討論 26
5-1 實驗結果 26
5-2 討論 26
第六章結論與未來展望 29
參考文獻 31
圖 34
表 44
附錄 55

參考文獻

參考文獻
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指導教授

李亮三(Liang-Sun Lee)

審核日期

2003-6-30

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