Ideal Liquid Solutions

Let us consider a mixture forming an ideal solution, that is, an ideal liquid pair. Applying Raoult s law to the two volatile components A and B, we have ... 

There is a parallel between the composition of a copolymer produced from a certain feed and the composition of a vapor in equilibrium with a two-component liquid mixture. The following example illustrates this parallel when the liquid mixture is an ideal solution and the vapor is an ideal gas. 

We define Fj to be the mole fraction of component 1 in the vapor phase and fi to be its mole fraction in the liquid solution. Here pj and p2 are the vapor pressures of components 1 and 2 in equihbrium with an ideal solution and Pi° and p2° are the vapor pressures of the two pure liquids. By Dalton s law, Plot Pi P2 Pi/Ptot these are ideal gases and p is propor-... 

Vapor pressure lowering. Equation (8.20) shows that for any component in a binary liquid solution aj = Pj/Pi°. For an ideal solution, this becomes... 

At equilibrium, a component of a gas in contact with a liquid has identical fugacities in both the gas and liquid phase. For ideal solutions Raoult s law applies ... 

Liquid solutions are often most easily dealt with through properties that measure their deviations, not from ideal gas behavior, but from ideal solution behavior. Thus the mathematical formaUsm of excess properties is analogous to that of the residual properties. 

Denotes excess thermodynamic property Denotes value for an ideal solution Denotes value for an ideal gas Denotes liquid phase... 

The residual Gibbs energy and the fugacity coefficient are useful where experimental PVT data can be adequately correlated by equations of state. Indeed, if convenient treatment or all fluids by means of equations of state were possible, the thermodynamic-property relations already presented would suffice. However, liquid solutions are often more easily dealt with through properties that measure their deviations from ideal solution behavior, not from ideal gas behavior. Thus, the mathematical formahsm of excess properties is analogous to that of the residual properties. 

When Eq. (4-282) is applied to XT E for which the vapor phase is an ideal gas and the liquid phase is an ideal solution, it reduces to a veiy simple expression. For ideal gases, fugacity coefficients and are unity, and the right-hand side of Eq. (4-283) reduces to the Poynting factor. For the systems of interest here this factor is always veiy close to unity, and for practical purposes <1 = 1. For ideal solutions, the activity coefficients are also unity. Equation (4-282) therefore reduces to... 

Raoult s Law. The molar composition of a liquid phase (ideal solution) in equilibrium with its vapor at any temperature T is given by... 

At the same time it is recognized that the pairs of substances which, on mixing, are most likely to obey Raoult s law are those whose particles are most nearly alike and therefore interchangeable. Obviously no species of particles is likely to fulfill this condition better than the isotopes of an element. Among the isotopes of any element the only difference between the various particles is, of course, a nuclear difference among the isotopes of a heavy element the mass difference is trivial and the various species of particles are interchangeable. Whether the element is in its liquid or solid form, the isotopes of a heavy element form an ideal solution. Before discussing this problem we shall first consider the solution of a solid solute in a liquid solvent. 

We will see later that this same equation applies to the mixing of liquids or solids when ideal solutions form. 

Figure 8.14 Relationship between the (p. v) and (/. x) (vapor + liquid) phase diagrams for an ideal solution.

In our discussion of (vapor + liquid) phase equilibria to date, we have limited our description to near-ideal mixtures. As we saw in Chapter 6, positive and negative deviations from ideal solution behavior are common. Extreme deviations result in azeotropy, and sometimes to (liquid -I- liquid) phase equilibrium. A variety of critical loci can occur involving a combination of (vapor + liquid) and (liquid -I- liquid) phase equilibria, but we will limit further discussion in this chapter to an introduction to (liquid + liquid) phase equilibria and reserve more detailed discussion of what we designate as (fluid + fluid) equilibria to advanced texts. 

Since Raoult s law activities become mole fractions in ideal solutions, a simple substitution of.Y, — a, into equation (6.161) yields an equation that can be applied to (solid + liquid) equilibrium where the liquid mixtures are ideal. The result is... 

Figure 8.20 (Solid + liquid) phase equilibria for [.viQHf, +. yl.4-C6H4(CH,)2 - The circles are the experimental results the solid lines are the fit of the experimental results to equation (8.31) the dashed lines are the ideal solution predictions using equation (8.30) the solid horizontal line is at the eutectic temperature and the diamonds are (.v, T) points referred to in the text.

Figure 8.21 gives the ideal solution prediction equation (8.36) of the effect of pressure on the (solid + liquid) phase diagram for. yiC6H6 + xj 1,4-C6H4(CH3)2. The curves for p — OA MPa are the same as those shown in Figure 8.20. As... 

Figure 8.23 (Solid + liquid) phase diagram for (. 1CCI4 +. yiCHjCN), an example of a system with large positive deviations from ideal solution behavior. The solid line represents the experimental results and the dashed line is the ideal solution prediction. Solid-phase transitions (represented by horizontal lines) are present in both CCI4 and CH3CN. The CH3CN transition occurs at a temperature lower than the eutectic temperature. It is shown as a dashed line that intersects the ideal CH3CN (solid + liquid) equilibrium line.

Consider an ideal binary mixture of the volatile liquids A and B. We could think of A as benzene, C6H6, and B as toluene (methylbenzene, C6H< CH ), for example, because these two compounds have similar molecular structures and so form nearly ideal solutions. Because the mixture can be treated as ideal, each component has a vapor pressure given by Raoult s law ... 

We use a different measure of concentration when writing expressions for the equilibrium constants of reactions that involve species other than gases. Thus, for a species J that forms an ideal solution in a liquid solvent, the partial pressure in the expression for K is replaced by the molarity fjl relative to the standard molarity c° = 1 mol-L 1. Although K should be written in terms of the dimensionless ratio UJ/c°, it is common practice to write K in terms of [J] alone and to interpret each [JJ as the molarity with the units struck out. It has been found empirically, and is justified by thermodynamics, that pure liquids or solids should not appear in K. So, even though CaC03(s) and CaO(s) occur in the equilibrium... 

A very simple treatment can be carried out by assuming that the liquid phase is a series of ideal solutions of lead and thallium, and that in the solid phase isomorphous replacement of thallium atoms in the PbTl3 structure by lead atoms occurs in the way corresponding to the formation of an ideal solution. For the liquid phase the free energy would then be represented by the expression... 

Any convenient model for liquid phase activity coefficients can be used. In the absence of any data, the ideal solution model can permit adequate design. 

The activities of the various components 1,2,3. .. of an ideal solution are, according to the definition of an ideal solution, equal to their mole fractions Ni, N2,. . . . The activity, for present purposes, may be taken as the ratio of the partial pressure Pi of the constituent in the solution to the vapor pressure P of the pure constituent i in the liquid state at the same temperature. Although few solutions conform even approximately to ideal behavior at all concentrations, it may be shown that the activity of the solvent must converge to its mole fraction Ni as the concentration of the solute(s) is made sufficiently small. According to the most elementary considerations, at sufficiently high dilutions the activity 2 of the solute must become proportional to its mole fraction, provided merely that it does not dissociate in solution. In other words, the escaping tendency of the solute must be proportional to the number of solute particles present in the solution, if the solution is sufficiently dilute. This assertion is equally plausible for monomeric and polymeric solutes, although the... 

At the outset it will be profitable to deal with an ideal solution possessing the following properties (i) there is no heat effect when the components are mixed (ii) there is no change in volume when the solution is formed from its components (iii) the vapoim pressiure of each component is equal to the vapour pressure of the pime substances multiplied by its mol fraction in the solution. The last-named property is merely an expression of Raoult s law, viz., the vapour pressiure of a substance is proportional to the number of mols of the substance present in unit volume of the solution, applied to liquid-liquid systems. Thus we may write ... 

All in aqueous solution at 25°C standard states are 1 M ideal solution with an infinitely dilute reference state, and the pure liquid for water equilibrium constants from reference 100, except as noted. 

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