Molar volume thermodynamic properties

Equations 175 through 179 allow calculation of thermodynamic properties from volume-expHcit equations of state, ie, equations expHcitiy solvable for volume. If an equation of state is solvable expHcitiy for pressure but not for volume, then alternative formulas must be used, where p is molar density and subscript p/n = 1/E indicates constancy of total volume. Eor equations 180, 181, and 183, T and x are constant for equation 182, Tis constant. 

The addition of solute will also influence the cmc of the surfactant, which in turn means that a correction is needed for the overall partial molar quantity, F This has been taken into account in the models proposed by Roux et al. and DeLisi et al. ° The models have been applied to different thermodynamic properties, mostly volumes and heat capacities, and for different surfactant-solute systems. 

At the vapor-liquid boundary, a single-phase system splits into two phases,i each with its own properties (molar volume, enthalpy, entropy, etc.). The precise conditions under which phase splitting occurs is an important problem in thermodynamics. Up to this point we have relied on tabulated values and empirical equations, such as the Antoine equation, to establish the relationship between saturation temperature and pressure. In this chapter we develop a connection between the conditions at saturation and the equation of state. The key thermodynamic property that makes this connection possible is the Gibbs energy. 

P rtl IMol r Properties. The properties of individual components in a mixture or solution play an important role in solution thermodynamics. These properties, which represent molar derivatives of such extensive quantities as Gibbs free energy and entropy, are called partial molar properties. For example, in a Hquid mixture of ethanol and water, the partial molar volume of ethanol and the partial molar volume of water have values that are, in general, quite different from the volumes of pure ethanol and pure water at the same temperature and pressure (21). If the mixture is an ideal solution, the partial molar volume of a component in solution is the same as the molar volume of the pure material at the same temperature and pressure. 

The concept of equilibrium is central in thermodynamics, for associated with the condition of internal eqmlibrium is the concept of. state. A system has an identifiable, reproducible state when 1 its propei ties, such as temperature T, pressure P, and molar volume are fixed. The concepts oi state a.ndpropeity are again coupled. One can equally well say that the properties of a system are fixed by its state. Although the properties T, P, and V may be detected with measuring instruments, the existence of the primitive thermodynamic properties (see Postulates I and 3 following) is recognized much more indirectly. The number of properties for wdiich values must be specified in order to fix the state of a system depends on the nature of the system and is ultimately determined from experience. 

Temperature, pressure, and composition are thermodynamic coordinates representing conditions imposed upon or exhibited by the system, andtne functional dependence of the thermodynamic properties on these conditions is determined by experiment. This is quite direct for molar or specific volume which can be measured, and leads immediately to the conclusion that there exists an equation of. state relating molar volume to temperature, pressure, and composition for any particular homogeneous PVT system. The equation of state is a primaiy tool in apphcations of thermodyuamics. 

Thermodynamics gives limited information on each of the three coefficients which appear on the right-hand side of Eq. (1). The first term can be related to the partial molar enthalpy and the second to the partial molar volume the third term cannot be expressed in terms of any fundamental thermodynamic property, but it can be conveniently related to the excess Gibbs energy which, in turn, can be described by a solution model. For a complete description of phase behavior we must say something about each of these three coefficients for each component, in every phase. In high-pressure work, it is important to give particular attention to the second coefficient, which tells us how phase behavior is affected by pressure. 

In addition to deciding on the method of normalization of activity coefficients, it is necessary to undertake two additional tasks first, a method is required for estimating partial molar volumes in the liquid phase, and second, a model must be chosen for the liquid mixture in order to relate y to x. Partial molar volumes were discussed in Section IV. This section gives brief attention to two models which give the effect of composition on liquid-phase thermodynamic properties. 

From the Debye-Hiickel expressions for lny , one can derive equations to calculate other thermodynamic properties. For example L2, the relative partial molar enthalpy,q and V2, the partial molar volume are related to j by the equations... 

The form of equations (8.11) and (8.12) turns out to be general for properties near a critical point. In the vicinity of this point, the value of many thermodynamic properties at T becomes proportional to some power of (Tc - T). The exponents which appear in equations such as (8.11) and (8.12) are referred to as critical exponents. The exponent 6 = 0.32 0.01 describes the temperature behavior of molar volume and density as well as other properties, while other properties such as heat capacity and isothermal compressibility are described by other critical exponents. A significant scientific achievement of the 20th century was the observation of the nonanalytic behavior of thermodynamic properties near the critical point and the recognition that the various critical exponents are related to one another ... 

A chart which correlates experimental P - V - T data for all gases is included as Figure 2.1 and this is known as the generalised compressibility-factor chart.(1) Use is made of reduced coordinates where the reduced temperature Tr, the reduced pressure Pr, and the reduced volume Vr are defined as the ratio of the actual temperature, pressure, and volume of the gas to the corresponding values of these properties at the critical state. It is found that, at a given value of Tr and Pr, nearly all gases have the same molar volume, compressibility factor, and other thermodynamic properties. This empirical relationship applies to within about 2 per cent for most gases the most important exception to the rule is ammonia. 

In open systems consisting of several components the thermodynamic properties of each component depend on the overall composition in addition to T and p. Chemical thermodynamics in such systems relies on the partial molar properties of the components. The partial molar Gibbs energy at constantp, Tand rij (eq. 1.77) has been given a special name due to its great importance the chemical potential. The corresponding partial molar enthalpy, entropy and volume under the same conditions are defined as... 

The so-called glass transition temperature, Tg, must be considered below this temperature the liquid configuration is frozen in a structure corresponding to equilibrium at Tg. Around Tg a rather abrupt change is observed of several properties as a function of temperature (viscosity, diffusion, molar volume). Above 7 , for instance, viscosity shows a strong temperature dependence below Tg only a rather weak temperature dependence is observed, approximately similar to that of crystal. Notice that 7 is not a thermodynamically defined temperature its value is determined by kinetic considerations it also depends on the quenching rate. 

This is an appropriate point to remark on some of the thermodynamic aspects of the complicated random network structure envisaged for the liquid. Now, the thermodynamic properties of ices II and III are very similar 1h The ice II ice III transition (249 K, 3.4 kbar) involves only a very small change in volume, namely 0.26 cm3/mole, 1.6% of the molar volume), a small change in entropy 1.22 cal/° mole, and a small change in enthalpy, 304 cal/mole. Similarly, the ice I ice II,... 

Abstract Isotope effects on the PVT properties of non-ideal gases and isotope effects on condensed phase physical properties such as vapor pressure, molar volume, heats of vaporization or solution, solubility, etc., are treated in some thermodynamic detail. Both pure component and mixture properties are considered. Numerous examples of condensed phase isotope effects are employed to illustrate theoretical and practical points of interest. 

In this chapter, we shall consider the methods by which values of partial molar quantities and excess molar quantities can be obtained from experimental data. Most of the methods are applicable to any thermodynamic property J, but special emphasis will be placed on the partial molar volume and the partial molar enthalpy, which are needed to determine the pressure and temperature coefficients of the chemical potential, and on the excess molar volume and the excess molar enthalpy, which are needed to determine the pressure and temperature coefficients of the excess Gibbs function. Furthermore, the volume is tangible and easy to visualize hence, it serves well in an initial exposition of partial molar quantities and excess molar quantities. 

The amount of H2O in amorphous silica (number n of H2O molecules per unit formula) varies between 0.14 and 0.83 (Frondel, 1962). Nevertheless, the thermodynamic properties of the phase are not particularly affected by the value of n (Walther and Helgeson, 1977). The molar volume of opal is 29 cm /mole. The same volume of a-quartz may be adopted for chalcedony see table 5.68 for the other polymorphs. 

TABLE 11.2 Measured Thermodynamic Properties (in SI Units) of Some Common Fluids at 20° C, 1 atm Molar Heat Capacity CP, Isothermal Compressibility jS7, Coefficient of Thermal Expansion otp, and Molar Volume V, with Monatomic Ideal Gas Values (cf. Sidebar 11.3) Shown for Comparison... 

Special classes of apparatus are used for the determination of particular thermodynamic properties, such as activity coefficients at infinite dilution, Henry s constants, or partial molar volumes at infinite dilution [105,106]. These data, together with a thermodynamic model, can be used for the calculation of the compositions of the coexisting phases at equilibrium, and for that reason - in this context - these methods are considered as indirect methods of measurement. 

The thermodynamic properties of a perfect gas are. of course, especially simple. For example, the difference between the molar heal capacities at constant pressure and constant volume is equal to the gas constant R,... 

Figure 17.5 Derived thermodynamic properties at T — 298.15 K and p = 0.1 MPa for (2Cic-CfiHi2 + X2n-CjHi4) (a) excess molar heat capacities obtained from the excess molar enthalpies (b) relative partial molar heat capacities obtained from the excess molar heat capacities (c) change of the excess molar volume with temperature obtained from the excess molar volumes and (d) change of the excess molar enthalpies with pressure obtained from the excess molar volumes.

The thermodynamic properties at T = 298.15 K shown in Figure 18.11 come from S. Causi, R. De Lisi, and S. Milioto, Thermodynamic properties of N-octyl-, N-decyl- and N-dodecylpyridinium chlorides in water , J. Solution Chem., 20, 1031-1058 (1991). Results at the other two temperatures are courtesy of K. Ballerat-Busserolles, C. Bizzo, L. Pezzimi, K. Sullivan, and E. M. Woolley, Apparent molar volumes and heat capacities at aqueous n-dodecyclpyridium chloride at molalities from 0.003 molkg-1 to 0.15 molkg-1, at temperatures from 283.15 K. to 393.15 K, and at the pressure 0.35 MPa , J. Chem. Thermodyn., 30, 971-983 (1998). 

As described above, the activation volume is the difference in partial molar volume between the transition state and the initial state. From a synthetic point of view this could often be approximated by the difference in the molar volume between the reactant(s) and product(s). Partial molar activation volumes, which can be divided into a structural part and a solvent-dependent part, are of considerable value in speculating about the nature of the transition state. This thermodynamic property has led to many studies on the mechanism of organic reactions. 

Finally, the thermodynamic properties of a system considered as variables may be classified as either intensive or extensive variables. The distinction between these two types of variables is best understood in terms of an operation. We consider a system in some fixed state and divide this system into two or more parts without changing any other properties of the system. Those variables whose value remains the same in this operation are called intensive variables. Such variables are the temperature, pressure, concentration variables, and specific and molar quantities. Those variables whose values are changed because of the operation are known as extensive variables. Such variables are the volume and the amount of substance (number of moles) of the components forming the system. 

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