研究生热力学第4章节.pptVIP

TOPIC 4 NON-IDEAL FLUID BEHAVIOR Homogeneous fluids are normally divided into two classes, liquids and gases (vapors). Gas: A phase that can be condensed by a reduction of temperature at constant pressure. Liquid: A phase that can be vaporized by a reduction of pressure at constant temperature. The distinction cannot always be made unambiguously, and the two phases become indistinguishable at the critical point. THE CRITICAL POINT Critical point: The maximum pressure and temperature where a pure material can exist in vapor-liquid equilibrium. Beyond Tc and Pc, the designation of gas vs. liquid is arbitrary. At the critical point, the meniscus between phases slowly fades and dissappears. If one moves around the critical point, it is possible to get from the liquid to the vapor field without crossing a phase boundary. THE P-V DIAGRAM We can use the lever rule on a P-V diagram to determine the proportion of vapor vs. liquid at any given pressure. The bending of the isotherms in the vapor field from the ideal hyperbolic shape as the critical point is approached indicates non-ideality. The P-V diagram illustrates the difficulty in developing an equation of state for all regions for a pure substance. However, this can be done for the vapor phase. MOST GENERAL EQUATION OF STATE VIRIAL EQUATION OF STATE The most generally applicable EOS PV = a + bP + cP2 + … a, b, and c are constants for a given temperature and substance. In principle, an infinite series is required, but in practice, a finite number of terms suffice. At low P, PV ? a + bP. The number of terms necessary to accurately describe the PVT properties of gases increases with increasing pressure. I. THE COMPRESSIBILITY FACTOR THE COMPRESSIBILITY FACTOR Z ? PV/RT = 1 + B’P + C’P2 + D’P3 + … or Z = 1 + B/V + C/V2 + D/V3 + … The virial equation of state is the only one which has a firm basis in theory. It follows from statistical mechanics. It can be used to represent both liquids and gases. The term B/V arises due to