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題名 | Evaluation of Parameter-Free Models for Computations of Heterogeneous Azeotropes of Aqueous Ternary and Quaternary Mixtures=以無參數模式計算三成分及四成分含水混合物的非均相共沸 |
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作者姓名(中文) | 林慶峰; 李亮三; | 書刊名 | Journal of the Chinese Institute of Chemical Engineers |
卷期 | 37:6 民95.11 |
頁次 | 頁567-577 |
分類號 | 460.026 |
關鍵詞 | 均相共沸; 溫度; 無參數模式; Heterogeneous azeotrope; Parameter-free model; |
語文 | 英文(English) |
中文摘要 | 本論文以四種無參數模式來預估及計算三成分及四成分非均相混合物的共沸溫度及組成。本論文是繼續延伸Lee et al., 1996)預估均相共沸混合物性質的演算法。在數學技巧上用以完成非線性計算是採用牛頓-拉普森(Newton-Rapson method)及虛擬弧長連續法(pseudo-archlength continuation)及同倫法(homotopy)的觀念。對於液相活性係數的估算是採用四種無參數模式:Scatchard- Hildebrand (1931),UNIFAC(1975),Vetere-NRTL (1994)和Ash-Wilson (1992)等方法。計算結果發現UNIFAC模式為四種無參數模式中誤差最小的模式。相對於Horsley的數據,其中共沸溫度的平均最小相對誤差 (AARD%)三成份系統為1.7%而四成份系統為1.6%。而組成的AARD%三成份系統為23.9%。對於本論文的數據採用Horsley (1973)的共沸數據書。由本研究計算結果發現很多Horsley中的數據為均相共沸物系統都呈現為非均相行為。此對於實際設計考慮極為重要。 |
英文摘要 | In this study, the capabilities of four parameter-free models for predicting the heterogeneous azeotropic behavior of ternary and quaternary mixtures were evaluated. The present work was basically extended from that of Lee et al. (1996, 1999) on homogeneous azeotrope determination. The mathematical techniques of Newton-Raphson, pseudo-archlength continuation, and the concept of homotopy were used to accomplish the mathematical computations. Four parameter-free models, Schatchard-Hildebrand (1931), UNIFAC (1975), Vetere-NRTL (1994), and Ash-Wilson (1992), were employed for liquid phase activity coefficient estimations. The ternary and quaternary azeotropic mixtures from Horsley's data book (1973) were adopted in this study. The UNIFAC model has the best performance among these four models. The average absolute relative deviations (AARD%) of azeotropic temperatures and compositions estimated by the UNIFAC model were 1.7%, 1.6%, 15.6%, and 23.9% by comparing with Horsley's data for ternary and quaternary mixtures, respectively. It is very interesting to observe that many homogeneous azeotropes in Horsley's data book appeared to be heterogeneous in our calculations. |
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