双成分气液相平衡观念介绍.PPT

Introduction to Chemical Engineering Thermodynamics Ji-Sheng Chang Equilibrium between phases The nature of equilibrium Equilibrium:the all values of the thermodynamic properties of the system had been fixed. By macroscopic view:static equilibrium By microscopic view:dynamic equilibrium The phase rule The size of system The size of the system, we have to given an extensive property of the system. Given each one of extensive propertyVtotal, Htotal, Utotal, ... , or total mass The phase rule The phase rule The Gibbs phase rule, tell us that how many properties or variables can to fix the system? For a ? phases and N components system at equilibriumF = 2 - ? + N The phase rule The phase rule The Duhem’s theorem, tell us that how many variables can given the information of the size distribution between equilibrium phases? F = 2F: the degrees of freedom of a system. Simple models for VLE Simple models for vapor/liquid equilibrium Dalton’s law; ideal solution behavior for gas phase Pi = yi P Raoult’s law; ideal solution behavior for liquid phase Pi = xi Pisat Henry’s law; ideal solution behavior for liquid phase Pi = xi Hi,j Simple models for VLE Simple models for vapor/liquid equilibrium Ideal gas behaviorPV=RT; For pure components vapor/liquid system, at equilibrium, P = Pisat Thermodynamic variables The variables T: Temperature P: Pressure ?: chemical potential f: fugacity Pi: partial pressure the suffix and superscript V: vapor phase; L: liquid phase; 1,2: species VLE problems For a binary VLE problems Variables T, P, x1, x2, y1, y2;( P1sat, P2sat) The degrees of freedom from the Gibbs phase rule F = 2 -2 + 2 = 2 Independent equations(1) Independent equations as from the state at equilibrium, TV = TL PV = PL P1V=P1L;  (?1V=?1L; f1V=f1L) P2V=P2L;  (?2V=?2L; f2V=f2L) Independent equations(2) Other equations The physical law The other thermodynamic models Antoine equation Kind of VLE calculation The cases of binar