在熱力學與化學工程學中,氣液平衡(;縮寫為VLE)描述某一化學物質於氣液兩相中的分布情形。
熱力學表示式
純物質系統
若液體與氣體皆為純物質,即僅由單一物質所組成而不存在雜質,則兩相間的平衡狀態可以下列方程表示之:
:P^{liq} = P^{vap}\,;
:T^{liq} = T^{vap}\,;且
:\tilde{G}^{liq} = \tilde{G}^{vap}
其中,P^{vap}\,及P^{liq}\,分別為氣液兩相的壓力;T^{vap}\,及T^{liq}\,分別為氣液兩相的溫度;而\tilde{G}^{vap}及\tilde{G}^{liq}分別為氣液兩相的莫耳吉布斯自由能。也就是說,當兩相達平衡時,其溫度、壓力和莫耳吉布斯自由能皆相等。
等價地,熱力學上常以逸度的概念來表達氣液平衡狀態,並可以下列方程表示之:
:f^{\,liq}(T_s,P_s) = f^{\,vap}(T_s,P_s)
其中,f^{\,vap}(T_s,P_s)及f^{\,liq}(T_s,P_s)分別為在系統溫度及壓力下的氣液兩相之逸度。以逸度進行計算是更為方便的,由於液體的逸度近似上是與壓力無關的,並經常以「逸度係數」\phi=f/P\,(若為理想氣體,其值為1)來計算。
多成分系統
於多成分系統中,即氣液兩相由多種分子所組成,其平衡關係是更為複雜的。對系統中的所有組成物質,兩相間的平衡狀態可以下列方程表示之:
:P^{liq} = P^{vap}\,;
:T^{liq} = T^{vap}\,;且
:\bar{G}_i^{liq} = \bar{G}_i^{vap}
其中,及為各相的溫度及壓力,而\bar{G}_i^{vap}及\bar{G}_i^{liq}分別為各相之偏莫耳吉布斯自由能(亦稱為化學勢)。偏莫耳吉布斯自由能被定義為:
:\bar{G}_i \ \stackrel{\mathrm{def}}{=}\ \frac{\partial G}{\partial n_i}
其中,為外延的吉布斯自由能,而為組成物質的物量。
參見
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*多特蒙德資料庫
*芬斯克方程
*閃蒸
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*過冷
*過熱蒸汽
外部連結
*[https://web.archive.org/web/20100219001912/http://lorien.ncl.ac.uk/ming/distil/distilpri.htm Distillation Principals] by Ming T. Tham, University of Newcastle upon Tyne (scroll down to Relative Volatility)
- [https://web.archive.org/web/20070310171923/http://lorien.ncl.ac.uk/ming/distil/distilvle.htm Introduction to Distillation: Vapor Liquid Equilibria]
- [https://web.archive.org/web/20070711065620/http://www.et.byu.edu:8080/~rowley/VLEfinal/background2.htm VLE Thermodynamics] (Chemical Engineering Dept., Prof. Richard Rowley, Brigham Young University)
- [https://www.nist.gov/srd/nist103b.cfm NIST Standard Reference Database 103b] (Describes the extensive VLE database available from NIST)
- [http://www.ddbst.com/en/EED/VLE/VLEindex.php Some VLE data sets and diagrams for mixtures of 30 common components] , a small subset of the Dortmund Data Bank
- [http://www.ognition.com/1480/where-can-i-get-the-phase-equilibrium-data Where can I get the vapor-liquid phase equilibrium data?] Reference to the various phase equilibrium data sources
- George Schlowsky, Alan Erickson, and Thomas A. Schafer, Modular Process Systems, Inc., [https://web.archive.org/web/20151208081630/http://modularprocess.com/wp-content/uploads/2015/07/Article-GeneratingYourOwnVLE-ChE-1995.pdf Operations & Maintenance - Generating your own VLE Data], Chemical Engineering, March 1995, McGraw-Hill, Inc.
參考文獻
化工熱力學
平衡化學
蒸餾
物質狀態
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