• 作者： Lee, Liang-Sun; Chuang, Min-Lang
• 中文摘要： 超餘摩耳體積與焓，.upsilon./sub E/及h/sub E/，在化工的程序設計裡是相當重要的熱力學性質，尤其應用在混合操作，然而這些熱力學性質無法完全由實驗得到，一部份亦得出計算求得。本論文既存討論由狀態方程式(EOS)計算的可靠性。本論文以雙參數及三參數狀態方程式並組配不同的混合律計算13組非極性及極性混合物的超餘摩耳體積與焓，雙參數EOS有：Redlich-Kwong、 Soave-Redlich-Kwomg、Peng-Robinson及Stryjek-Vera，三參數EOS有： Schmidt-Wenzel、Harmens-Knapp、Patel-Teja及Iwai-Margerum-Lu，而混合律有：van der Waals、van Laar、Redlich-Kister、Huron-Vidal及 Kurihara-Tochigi-Kojima。關聯計算結果說明，對此13組非極性及極性混合物ν/sub E/的計算要比h/sub E/好，三參數EOS並不一定比雙參數EOS好。而以局部組成理論為基礎的混合律要比簡單的混合律好，但是例外的是水-酒精、水-甲醇及環己烷-正十烷。本文討論的混合律中van der Waals混合律用於雙參數 EOS是計算效果最差的一個。它只適合低碳的非極性.upsilon./sub E/及非極性的h/sub E/。
• 英文摘要： In this study, the excess molar volumes, .upsilon./sub E/ and excess enthalpies, h/sub E/, of thirteen polar and nonpolar binary mixtures from literature were correlated by the two-parameter cubic equations of state (EOS) of Redlich-Kwong (RK) (1949), Soave-Redlich-Kwang(SRK) (1972), Peng-Robinson(PR) (1976), Stryjek-Vera(PRSV) (1986a,b), and by the three-parameter Schmidt-Wenzel (SW) (1980), Harmens-Knapp(HK) (1980), Patel-Teja (PT) (1982), and Iwai-Margenim-Lu (IML)(1988) equations of state along with the mixing rules of the van der Waals (vdW), van Laar (vL), Redlich-Kister (RK) (1948), Huron-Vidal(HV) (1979) and Kurihara-Tochigi-Kojima (KTK) (1987). The results show that for the present mixtures the h/sub E/ correlation succeeds in more mixtures than h/sub E/ correlations do by the above equations of state, the three-parameter EOS are not superior to the two-parameter EOS for .upsilon./sub E/ correlation, and in general, the local composition type mixing rules improve correlation except systems of water + methanol, water + ethanol and cyclohexane + n-decane. Compared to other mixing rules, the vdW mixing rule is applicable to the least number of mixtures. It is suitable for nonpolar systems with lower number of carbon for .upsilon./sub E/ correlation and for nonpolar systems for h/sub E/ correlation when incorporated into the two-parameter EOS.
• 中文關鍵字： 狀態方程式; 混合律; 莫耳體積; 焓; 相關性; 熱力學
• 英文關鍵字： State Equation; Mixing Rule; Molar Volume; Enthalpy; Correlation; Thermodynamics