Professional Documents
Culture Documents
Schaum's Theory & Problems of Thermodynamics
Schaum's Theory & Problems of Thermodynamics
V, then V,—Vy=Vgy and by the idesl-gas law, V,=RT/Ps, Then (4.38) becomes ain Posty aut ‘An identical expression is obtained for Hy, the Intent heat of sublimation. This equation is known as the Clausivs-Clapeyron equation, and it allows an approximate value for the latent heat to be determined from data for the saturation pressure alone. No volumetric data are required. 4) ‘More specifically, (4.6) indicates that the value of Hyp (or of Hv) is given by the slope of a plot of In P* versus 1/T. It is a fact, however, that such plots made of ex- perimental data produce lines that are nearly straight, which implies through (4.4) that the latent heat of vaporization Hj, is independent of temperature. This is far from true. In fact, Hip must become zero at the critical point, where the phases become identical. The difficulty is that (4.4) is based on assumptions which have approximate validity only at low pressures, at pressures well below the critical pressure for any pure substance considered. 43 VAPOR PRESSURES AND LATENT HEATS ‘The Clapeyron equation provides a vital connection between the properties of different phases, It is usually applied to the calculation of latent heats of vaporization and sub- limation from vapor-pressure and volumetric data:104 PROPERTIES OF PURE SUBSTANCES [CHAP. 4 aH = Taves For this, we need accurate representations of P™* as a function of T. As stated following Example 4.4, a plot of In P= versus 1/T generally yields a line that is very nearly straight. ‘This suggests a vapor-pressure equation of the form a B mP™ = A-F 5) where A and B are constants. ‘This equation is useful for many purposes, but it does not represent data sufficiently well to provide accurate values of derivatives. ‘The Antoine equation is more satisfactory, and has found wide use: B mew = A- 78a 46) where A, B, and C are constants. When extensive vapor-pressure data of high accuracy are available, it is found dif- ficult to represent them faithfully by any simple equation. An equation that is usually satisfactory has the form B Inpt = A- peg + DP + EMT 7) where A, B,C, D, and E are constants. Equations for the representation of vapor-pressure data are empirical. Again, thermodynamics provides no model for the behavior of substances, either in general or individually. 44 PROPERTIES OF TWO-PHASE SYSTEMS When a phase change of a pure substance is brought about at constant T and P, the molar properties of the individual phases do not change. We start with a given amount of a substance in phase a, for which the molar (or unit-mass) properties are V*, Us, Hs, S*, etc. If we gradually carry out a change at constant 7 and P to give finally the same ‘quantity of the substance in phase 2, then it will have the molar (or unit-mass) properties Y#, U?, He, $8, ete. Intermediate states of the system will be made up of the two phases a and f in varying amounts, but each phase will always have the same set of molar (or unit-mass) properties, If we want an average molar (or unit-mass) property over the entire two-phase system, we need a weighted sum of the properties of the individual phases, If we let z be the fraction of the total number of moles (or of the total mass) of the system that exists in phase 2, then the average properties of the two-phase system are given by 1 —2)U" + 20" 1 —2)S* + 2S# V = (1-2)Ve + 2ve u H = (1—-a)H* + 2H? s ‘These equations can be represented in general by M 2)Me + 2M? 8) @ where M represents any molar (or unit-mass) thermodynamic property. When # = 0, Me Ms, and when Z—1, M= MP, In between these limits M is a linear funetion of =.CHAP. 4) PROPERTIES OF PURE SUBSTANCES 105 ‘This is most clearly seen by rewriting (4.8) in the form M = Me + x(a —M%) or [= ae + aaa re) Example 45. Rewrite (J.8) and (J.0) in the subscript notation of the steam tables for the ease of the volume of a two-phase system of liquid and vapor. In thia case Mf becomes V, and the are written as perscripts « and f become subscripts f and g. Then (4.8) and (0) v A-2Vj+2Vy and V = Vi t2Vy ‘The last equation has a simple, physical interpretation: the mixture has at least the ‘volume of saturated liquid but has in addition the volume gained by vaporization of the fraction of the system represented by 2. For liquid-vapor systems the mass fraction « which is vapor is called the quality. 45 VOLUME EXPANSIVITY AND ISOTHERMAL COMPRESSIBILITY OF SOLIDS AND LIQUIDS ‘The volume expansivity # and isothermal compressibility x were defined by (3.17) and (8.18): = yr). + = Hm). Experimental values for these quantities are tabulated in handbooks of data, and for solids and liquids such tabulations take the place of an equation of state when used in conjunction with w = par — «dP (8.19) Both # and x are generally positive numbers; however fi can take on negative values in ‘unusual cases, as it does for liquid water between 0 and 4(°C). Both f and « are in general functions of temperature and pressure. Normally, both # and « increase with increasing temperature, though there are exceptions. The effect of pressure is usually quite small, an increase in pressure invariably causing « to decrease and usually, but not always, causing 6 also to decrease. ‘When both f and « are weak functions of 7 and P or where the changes in T and P are relatively small, # and « may be treated as constants, and (3.19) may be integrated to give: nfs = Als—T,) ~ (Pe~ ) (4.10) ‘This is a different order of approximation than the assumption of incompressibility, for which f and « are taken to be zero, as discussed in Example 3.12, When f and « cannot be considered constant as a reasonable approximation, (8.29) must be integrated more generally: A ny "par — fea un Since V is a state function, the value of In(V2/V;) must be independent of the path of inte- gration for given states 1 and 2. This means that one may choose any path at all leading From’nste to ate 2 andthe cote To made on the basi Of convenience, Diferent paths