| Abstract: | 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。 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. |
