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研究生: 孫紹倫
Shao-Lun Sun
論文名稱: 單一電解質水溶液之汽化熱,凝固點下降,沸點上升之預測
The prediction of the enthalpy of vaporization, depression of freezing point, and elevation of boiling point of single electrolyte solutions.
指導教授: 李亮三
Liang-Sun Lee
口試委員:
學位類別: 碩士
Master
系所名稱: 工學院 - 化學工程與材料工程學系
Department of Chemical & Materials Engineering
畢業學年度: 94
語文別: 中文
論文頁數: 44
中文關鍵詞: 電解質水溶液活性係數凝固點下降沸點上升汽化熱
外文關鍵詞: enthalpy of vaporization, epression of freezing point, elevation of boiling point, electrolyte solution, activity coefficient
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  • 電解質水溶液在化工製程,環境工程,醫學工程,石油工業,石化工業等,都是常遭遇到的混合物。因為電解質的加入,使得原本只含有溶劑的液體,會因此而改變其原有的熱力學性質,也使得溶液偏離了理想性。為了描述溶液偏離理想溶液的程度,通常引入活性係數作為考慮。而Lin and Lee (2003)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分,即是電解質水溶液中離子與溶劑分子之間短距離作用力,以媒合參數(solvation parameter)表示,而肇因於離子與離子之間的長距離作用力之部分則以趨近參數(approaching parameter)表示。相對於非電解質的熱力學性質,電解質水溶液的熱力學性質的文獻數據較少,所以本研究便應用Lin and Lee (2003)所提出之個別離子活性係數模式,使用已經求得之趨近參數以及媒合參數並搭配熱力學之方程式,來對11種單一電解質水溶液之汽化熱(enthalpy of vaporization)、18種單一電解質水溶液之凝固點下降(depression of Freezing point)、以及13種單一電解質水溶液之沸點上升(elevation of Boiling point)進行預估,並將預估的結果與文獻值進行比較,並得到了不錯的結果。


    Electrolyte solutions are always met in the process of chemical engineering, environment engineering, biomedical engineering, the petroleum industry, and petrifaction industry. Because of adding the electrolytes, the thermodynamic properties of the original solvent were changed, and were made deviation from ideality. In order to describe the degree of the solution deviating from the ideal solution, we usually take activity coefficient for consideration. In the study of Lin and Lee (2003), it was proposed that, in the electrolyte solution, the ion activity coefficient is contributed by two parts: one is salvation which is expressed by salvation parameter which is the short-range interaction between ion and water molecule, the other is the long-range interaction between ions which is expressed by approaching parameter. In this study, we use the ion activity coefficient model of Lin and Lee (2003), the known salvation parameter and approaching parameter, and using some thermodynamic equations to calculate the enthalpies of vaporization of 11 kinds of single electrolyte solutions, freezing point depressions of 18 kinds of single electrolyte solutions, and boiling point elevations of 13 kinds of the single electrolyte solutions then compare them with the literature data, and the results were predicted successfully.

    中文摘要 I 英文摘要 II 目錄 III 表目錄 V 圖目錄 VI 符號說明 VII 第一章 緒論 1 第二章 文獻回顧 3 第三章 熱力學理論 12 3.1電解質溶液之濃度單位 12 3.1.1 重量莫耳濃度 12 3.1.2 離子強度 12 3.1.3 莫耳分率 12 3.2 Lin and Lee模式 13 第四章 電解質水溶液熱力學性質預測 18 4.1 汽化熱之預測 18 4.2 凝固點下降之預測 22 4.3 沸點上升之預測 25 第五章 預估結果與討論 28 第六章 結論與未來展望 31 參考文獻 33 表 37 圖 41

    Angell, C. A.; Ogunl, M.; SlChlna, W. J., Heat Capacity of Water at Extremes of Supercooling and Superheating. J. Phys. Chem. 86(1982) 998-1002.
    Apelblat, A.; Korin, E., The Vapour Pressures of Saturated Aqueous Solutions of Sodium Chloride, Sodium Bromide, Sodium Nitrate, Potassium Iodate, and Rubidium Chloride at Temperatures from 227 K to 323 K. J. Chem. Thermodynamics 30(1998) 59-71.
    Apelblat, A., Vapour Pressures of H216O and H218O, and Saturated Aqueous Solutions of KCl from T=298 K to T=318 K by the isoteniscopic method. J. Chem. Thermodynamics 30(1998) 1191-1198.
    Apelblat, A.; Korin, E., The Vapour Pressures of Saturated Aqueous Solutions of Ammonium Iodide, Potassium Iodide, Potassium Nitrate, Strontium Chloride, Lithium Sulphate, Sodium Thiosulphate, Magnesium Nitrate, and Uranyl Nitrate from T=(278 to 323) K. J. Chem. Thermodynamics 30(1998) 459-471.
    Apelblat, A.; Korin, E., The Molar Enthalpies of Solution and Vapour Pressures of Saturated Aqueous Solutions of Some Cesium Salts. J. Chem. Thermodynamics 38(2006) 152-157.
    Apelblat, A.; Manzurola, E., Solubilities and Vapour Pressures of Saturated Aqueous Solutions of Sodium Tetraborate, Sodium Carbonate, and Magnesium Sulfate and Freezing-Temperature Lowerings of Sodium Tetraborate and Sodium Carbonate Solutions. J. Chem. Thermodynamics 35(2003) 221-238.
    Bahe, L. W., Structure in Concentrated Solutions of Electrolytes. Field Dielectric Gradient Forces and Energies. J. Phys. Chem. 76(1972) 1062-1071.
    Bancroft, W. D.; Davis, H.L., The Boiling-Points of Aqueous Solutions. J. Phys. Chem. 33(1929) 591-604.
    Bromely, L. A., Thermodynamic Properties of Strong Electrolytes in Aqueous Solutions. AIChE J. 19(1973) 313-320.
    De Coppet, L. C., On the Molecular Depression of the Freezing-Point of Water Produced by Some Very Concentrated Saline Solutions. J. Phys. Chem. 8(1904) 531-538.
    Ghosh, S.; Patwardhan, V. S., Aqueous Solutions of Single Electrolytes: A Correlation Based on Ionic Hydration. Chem. Eng. Sci. 45(1990) 79-87.
    Guggenheim, E. A.; Stokes, R. H., Equilibrium Properties of Aqueous Solutions of
    Single Strong Electrolytes, Pergamon, Oxford, 1969.
    Haghtalab, A.; Vera, J. H., A Nonrandom Factor Model for the Excess Gibbs Energy
    of Electrolyte Solutions. AIChE J. 34(1988) 803-813.
    Hamer, W. J.; Wu, Y. C., Osmotic Coefficients and Mean Activity Coefficients of
    Uni-Univalent Electrolytes in Water at 25℃. J. phys. Chem. Ref. Data. 1(1972)
    1047-1054.
    Hunter, J. B.; Bliss, H., Thermodynamics Properties of Aqueous Salt Solutions. Ind.
    Eng. Chem. 36(1944) 945-953.
    Jin, G.; Donohue, M. D., An Equation of State for Electrolyte Solutions.1. Aqueous Systems Containing Strong Electrolytes. Ind. Eng. Chem. Res. 27(1988) 1073-1084.
    Lanier, R. D., Activity Coefficients of Sodium Chloride in Aqueous Three Component
    Solutions by Cation-Sensitive Glass Electrodes. J. Phy. Chem. 69(1965 ) 3992-3998.
    Lin, C. L.; Tseng, H. C.; Lee, L. S., A Three Characteristic Parameter Correlation
    Model for Strong Electrolyte Solutions. Fluid Phase Equilibria. 152(1998) 169-185.
    Lin, C. L.; Lee, L. S., A Two-Ionic-Parameter Approach for Ion Activity Coefficients
    of Aqueous Electrolyte Solutions. Fluid Phase Equilivria. 205(2003) 69-88.
    Lin, H. Y.; Lee, L. S., Estimations of Activity Coefficients of Constituent Ions in
    Aqueous Electrolyte Solutions with Two-Ionic-Parameter Approach. Fluid Phase
    Equilibria 237(2005) 1-8.
    Lu, X.; Zhang, L., Prediction of Activity Coefficients of Electrolytes in Aqueous Solutions at High Temperatures. Ind. Eng. Chem. Res. 35(1996) 1777-1784.
    Murphy, D. M.; Koop, T., Review of the Vapour Pressures of Ice and Supercooled Water for Atmospheric Applications. Q. J. R. Meteorol. Soc. 131(2005) 1539-1565.
    Pan, C. F., Activity and Osmotic Coefficients in Dilute Aqueous Solutions of Bi-Univalent Electrolytes at 25℃. J. Chem. Eng. Data 22(1977) 234-237.
    Pitzer, K. S., Thermodynamics of Electrolytes. I. Theoretical Basis and General
    Equations. J. Phys. Chem. 77(1973) 268-277.
    Pitzer, K. S.; Mayorga, G., Thermodynamic of Electrolytes. II. Activity and Osmotic
    Coefficients for Strong Electrolytes with One or Both Ions Univalent. J. Phys. Chem.
    77(1973) 2300-2307.
    Pitzer, K. S.; Kim, J. J., Thermodynamics of Electrolytes. IV. Activity and Osmotic
    Coefficients for Mixed Electrolytes. J. Am. Chem. Soc.96(1974) 5701-5707.
    Prem, P. S., A Model for Ionic Behavior in Aqueous Solution. Activity Coefficients of
    Electrolytes at 298.15 K. J. Am. Chem. Soc. 99(1977) 1312-1315.
    Rodebush, H. W., The Freezing Points of Concentrated Solutions and The Free
    Energy of Solution of Salts. J. Am. Chem. Soc. 40(1918) 1204-1213.
    Rysselberghe P. V.; Eisenberg S., Activity Coefficients in Concentrated Aqueous Solutions of Strong Electrolytes Described by a Formula Containing the Mean Ionic Diameter as Single Parameter. J. Am. Chem. Soc. 61(1939) 3030-3037.
    Saxton, B.; Smith, R. P., The Activity Coefficient of Potassium Chloride in Aqueous Solution from Boiling Point Data. J. Am. Chem. Soc. 54(1932) 2626-2636.
    Stokes, R. H.; Robinson, R. A., Ionic Hydration and Activity in Electrolyte Solutions.
    J. Am. Chem. Soc. 70(1948) 1870-1878.
    Verma, M. P., Steam Tables for Pure Water as An ActiveX Component in Visual Basic
    6.0, Computers Geosci. 29(2003) 1155-1163.
    Weast, R. C., Ed, CRC Handbook of Chemistry and Physics, 81st ed. pp 8-58 – 8-84.
    Zaytsev, I. D.; Aseyev, G. G., Properties of Aqueous Solutions of Electrolytes, CRC
    Press, Boca Raton, FL(1992).

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