Partial molar functions

Partial derivatives Response functions partial molar properties... 

Since we make the simplifying assumption that the partial molar volumes are functions only of temperature, we assume that, for our purposes, pressure has no effect on liquid-liquid equilibria. Therefore, in Equation (23), pressure is not a variable. The activity coefficients depend only on temperature and composition. As for vapor-liquid equilibria, the activity coefficients used here are given by the UNIQUAC equation. Equation (15). ... 

Along the three-phase line liquid-clathrate-gas the variation of the composition with temperature is considerable (cf. CD in Fig. 3), because when applying Eq. 27 to this equilibrium, the relatively small quantity AH = 0.16 kcal/mole has to be replaced by the much larger difference/ —//ql between the partial molar heat functions of / -hydroquinone and the liquid phase, which amounts to about —6 kcal/mole. The argon content of the solid reaches a minimum at the quadruple point. 

By measuring the partial molar heat of solution as a function of temperature for infinitely dilute concentrations of Cu, Ag, and Au in liquid tin, Oriani and Murphy51 have determined ACp for the liquid solutes to be 1.0, 0, and 3.0 cal/deg mole respectively. These numbers bear no relationship to the sign of the heat of solution, or to atom-size disparity, but seem to be related to the deviation from unity of the ratio of the masses of the components. 

Since Eqs. (5) and (6) are not restricted to the vapor phase, they can, in principle, be used to calculate fugacities of components in the liquid phase as well. Such calculations can be performed provided we assume the validity of an equation of state for a density range starting at zero density and terminating at the liquid density of interest. That is, if we have a pressure-explicit equation of state which holds for mixtures in both vapor and liquid phases, then we can use Eq. (6) to solve completely the equations of equilibrium without explicitly resorting to the auxiliary-functions activity, standard-state fugacity, and partial molar volume. Such a procedure was discussed many years ago by van der Waals and, more recently, it has been reduced to practice by Benedict and co-workers (B4). 

The difficulties encountered in the Chao-Seader correlation can, at least in part, be overcome by the somewhat different formulation recently developed by Chueh (C2, C3). In Chueh s equations, the partial molar volumes in the liquid phase are functions of composition and temperature, as indicated in Section IV further, the unsymmetric convention is used for the normalization of activity coefficients, thereby avoiding all arbitrary extrapolations to find the properties of hypothetical states finally, a flexible two-parameter model is used for describing the effect of composition and temperature on liquid-phase activity coefficients. The flexibility of the model necessarily requires some binary data over a range of composition and temperature to obtain the desired accuracy, especially in the critical region, more binary data are required for Chueh s method than for that of Chao and Seader (Cl). Fortunately, reliable data for high-pressure equilibria are now available for a variety of binary mixtures of nonpolar fluids, mostly hydrocarbons. Chueh s method, therefore, is primarily applicable to equilibrium problems encountered in the petroleum, natural-gas, and related industries. 

In Eq. (128), the superscript V stands for the vapor phase v2 is the partial molar volume of component 2 in the liquid phase y is the (unsym-metric) activity coefficient and Hffl is Henry s constant for solute 2 in solvent 1 at the (arbitrary) reference pressure Pr, all at the system temperature T. Simultaneous solution of Eqs. (126) and (128) gives the solubility (x2) of the gaseous component as a function of pressure P and solvent composition... 

Volume is an extensive property. Usually, we will be working with Vm, the molar volume. In solution, we will work with the partial molar volume V, which is the contribution per mole of component i in the mixture to the total volume. We will give the mathematical definition of partial molar quantities later when we describe how to measure them and use them. Volume is a property of the state of the system, and hence is a state function.1 That is... 

Equation (5.16) can be integrated. We expect the partial molar properties to be functions of composition, and of temperature and pressure. For a system at constant temperature and constant pressure, the partial molar properties would be functions only of composition. We will start with an infinitesimal quantity of material, with the composition fixed by the initial amounts of each component present, and then increase the amounts of each component but always in that same fixed ratio so that the composition stays constant. When we do this. Z, stays constant, and the integration of equation... 

A variety of procedures can be used to determine Z, as a function of composition.2 Care must be taken if reliable values are to be obtained, since the determination of a derivative or a slope is often difficult to do with high accuracy. A number of different techniques are employed, depending upon the accuracy of the data that is used to calculate Z, and the nature of the system. We will now consider several examples involving the determination of V,- and Cpj, since these are the properties for which absolute values for the partial molar quantity can be obtained. Only relative values of //, and can be obtained, since absolute values of H and G are not available. For H, and we determine H, — H° or — n°, where H° and are values for H, and in a reference or standard state. We will delay a discussion of these quantities until we have described standard states. 

The volume of a solution is sometimes expressed as a function of composition and the partial molar volume is then obtained by differentiation. For example, Klotz and Rosenburg2 have expressed the volume of aqueous sodium chloride solutions at 298.15 K and ambient pressure as a function of the molality m of the solution by the equation ... 

Figure 5.3 shows V and V2 for the (benzene + cyclohexane) system as a function of mole fraction, obtained in this manner.3 Shown on the graph are Fm, i and F, 2, the partial molar volumes (which are the molar volumes) of the pure benzene and pure cyclohexane. The opposite ends of the curves gives Vf and Vf, the partial molar volumes in an infinitely dilute solution. We note that... 

Plot an appropriate volume unit vs. mole fraction of acetic acid. Determine the partial molar volumes of water and acetic acid at X2 = 0, 1, and several intermediate compositions (at least three). Plot V and V2 as a function of. Y2. 

Relative partial molar enthalpies can be used to calculate AH for various processes involving the mixing of solute, solvent, and solution. For example, Table 7.2 gives values for L and L2 for aqueous sulfuric acid solutions7 as a function of molality at 298.15 K. Also tabulated is A, the ratio of moles H2O to moles H2S(V We note from the table that L — L2 — 0 in the infinitely dilute solution. Thus, a Raoult s law standard state has been chosen for H20 and a Henry s law standard state is used for H2SO4. The value L2 = 95,281 Tmol-1 is the extrapolated relative partial molar enthalpy of pure H2SO4. It is the value for 77f- 77°. 

In the case of reciprocal systems, the modelling of the solution can be simplified to some degree. The partial molar Gibbs energy of mixing of a neutral component, for example AC, is obtained by differentiation with respect to the number of AC neutral entities. In general, the partial derivative of any thermodynamic function Y for a component AaCc is given by... 

In a similar way, we now look at the molar Gibbs function of each component i within a mixture. Component i could be a contaminant. But because i is only one part of a system, we call the value of Gm for material i the partial molar Gibbs function. The partial molar Gibbs function is also called the chemical potential, and is symbolized with the Greek letter mu, p. 

Figure 5.18 depicts graphically the relationship in Equation (5.12), and shows the partial molar Gibbs function of the host material as a function of temperature. We first consider the heavy bold lines, which relate to a pure host material, i.e. before contamination. The figure clearly shows two bold lines, one each for the material when solid and another at higher temperatures for the... 

Figure 5.19 The chemical potential /j, (the partial molar Gibbs function) of a species in a mixture is obtained as the slope of a graph of Gibbs function G as a function of composition...

In connection with the development of the thermodynamic concept of partial molar quantities, it is desirable to be familiar with a mathematical relationship known as Euler s theorem. As this theorem is stated with reference to homogeneous functions, we will consider briefly the namre of these functions. 

The volume function then is homogeneous of the first degree, because the parameter X, which factors out, occurs to the first power. Although an ideal solution has been used in this illustration. Equation (2.31) is true of all solutions. However, for nonideal solutions, the partial molar volume must be used instead of molar volumes of the pure components (see Chapter 9). 

Although the function / is a homogeneous function of the mole numbers of degree 1, the partial molar quantities, and are homogeneous functions of degree 0 that is, the partial molar quantities are intensive variables. This statement can be proved by the following procedure. Let us differentiate both sides of Equation (2.32) with respect to x ... 

Therefore the state in which the solute has a partial molar Gibbs function of p.2 can be found from the following limit, because 72 approaches unity as m2 approaches zero ... 

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. 

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