• 作者： Huang, Jin-Feng; Lee, Liang-Sun
• 中文摘要： 在化工程序設計中經常需要許多熱力學性質,如過剩焓(h/sup E/)、過剩吉伯士能(g/sup E/)及汽液平衡(VLE)數據等,這些熱力學性質不可能完全依賴實驗得到。因此以理論計算提供數據是程序設計不可缺的步驟,但理論計算之模式能愈簡單,愈能同時計算多種熱力學性質及愈準確愈好。而本論文即在修正以往之熱力學模式以同時能準確計算(h/sup E/、g/sup E/及VLE。本論文從理論探討但最終提供可以實際程序所需之熱力學模式。本文蒐集文獻上之實驗數據以證明本論文之優點及貢獻。我們所考慮之模式為熟知之溶液理論之NRTL模式。我們由理論推導而得到再增加一個含兩個參數的組成函數,並將原模式中的交互作用參數(.DELTA.g/sub 21/及.DELTA.g/sub 12/)及.alpha.值(nonrandomness factor)考慮成溫度的函數。我們將文獻中所查得之不同溫度下的過剩焓(h/sup E/)及過剩吉伯士能(g/sup E/)之實驗數據分別決定此一修正模式中.DELTA.g/sub 21/、.DELTA.g/sub 12/和.alpha./sub 12/等溫度函數中的係數以及額外所加之組成函數中的可調節參數。之後這些決定的參數將用來同時估計等溫的雙成分h/sup E/、g/sup E/和VLE,以及等壓的雙成分及三成分VLE。與文獻上與此相當之 Demirel et al.(1992)的方法做一比較,當中其所提假設.DELTA.g/sub 21/、.DELTA.g/sub 12/及.alpha.為溫度函數之NRTL模式,亦使用相同的實驗數據同時決定其中之係數。從結果中我們可以發現本論文所提之修正方法將可改進Demirel et al.的NRTL模式在同時估計h/sup E/、g/sup E/及VLE的能力。此外,本論文所提之修正模式將能僅含雙成分參數而推廣到多成分系統,更具有實際應用之意義。
• 英文摘要： Design of separation equipment for the chemical processes need accurate data of thermodynamic properties, such as excess enthalpy (h/sup E/), excess Gibbs free energy(g/sup E/), and vapor-liquid equilibrium (VLE). Because of the difficulties obtaining all the required data experimentally, the designer often turns to the estimation models. It is often expected that an estimation model should be simple in mathematical form and be applicable to calculate the different thermodynamic properties simultaneously and accurately. To meet such a goal, a modification of the well-known NRTL model was proposed in this work. The modifications were discussed in the manuscript. More than one different isotherm data of h/sup E/ and g/sup E/ were used separately to correlate the temperature-dependent parameters .DELTA.g/sub 21/,.DELTA.g/sub 12/, and .alpha./sub 12/ and the parameters of an additional composition function in this modified NRTL model. And the identical h/sup E/ and g/sup E/ data were also used simultaneously to correlate all the parameters of the NRTL model of Demirel et al. (1992). Those estimated parameters of these two models were then used to estimate: isothermal binary h /sup E/, g/sup E/, VLE, and isobaric binary and ternary VLE. Comparisons were then made among the differently estimated results and the experimental data from literature. It is found that the proposed modifications indeed improved the capability of the NRTL model of Demirel et al. for estimating h/sup E/, g/sup E/, and VLE simultaneously. Finally, it should be mentioned that this modified model can be easily extended to handle multicomponent mixtures merely with the constituent binary pair parameters.
• 中文關鍵字： 理論; 過剩函數; 焓; 局部組成; 氣-液平衡; 極性; 非極性
• 英文關鍵字： Theory; Excess Function; Enthalpy; Local Composition; Vapor- Liquid Equilibria; Polar; Nonpolar