Activity, 5.9, 5.11 ideal solution

A solution which obeys Raoult s law over the full range of compositions is called an ideal solution (see Example 7.1). Equation (8.22) describes the relationship between activity and mole fraction for ideal solutions. In the case of nonideal solutions, the nonideality may be taken into account by introducing an activity coefficient as a factor of proportionality into Eq. (8.22). 

Osmotic pressure is one of four closely related properties of solutions that are collectively known as colligative properties. In all four, a difference in the behavior of the solution and the pure solvent is related to the thermodynamic activity of the solvent in the solution. In ideal solutions the activity equals the mole fraction, and the mole fractions of the solvent (subscript 1) and the solute (subscript 2) add up to unity in two-component systems. Therefore the colligative properties can easily be related to the mole fraction of the solute in an ideal solution. The following review of the other three colligative properties indicates the similarity which underlies the analysis of all the colligative properties ... 

In equation 21 the vapor phase is considered to be ideal, and all nonideaHty effects are attributed to the Hquid-phase activity coefficient, y. For an ideal solution (7 = 1), equation 21 becomes Raoult s law for the partial pressure,exerted by the Hquid mixture ... 

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... 

Activity coefficients are equal to 1.0 for an ideal solution when the mole fraction is equal to the activity. The activity (a) of a component, i, at a specific temperature, pressure and composition is defined as the ratio of the fugacity of i at these conditions to the fugacity of i at the standard state [54]. 

Units It should be noted that in the S.I. the activity of a solute is defined with reference to a standard state, i.e. an ideal solution of molality 1 mol kg". Thus the relative activity of a metal ion in solution is given by... 

There are several different scales 011 which the activity of a solute may be defined.1 In thermodynamic expressions for a solute in a non-ideal solution the activity on the molality scale plays the same part that is played by the molality of a solute in an ideal solution. Since the activity is expressed in the same units as the molality, the ratio of the activity to the molality—the activity coefficient—is a pure number whose value is independent of these units it is also indopendont of the particular b.q.s. that has been adopted. Thus the numerical values of all activities and molalities would change in the same ratio, if at any time a new choice were made for the b.q.s. 

For ideal solutions, the activity coefficient will be unity, but for real solutions, 7r i will differ from unity, and, in fact, can be used as a measure of the nonideality of the solution. But we have seen earlier that real solutions approach ideal solution behavior in dilute solution. That is, the behavior of the solvent in a solution approaches Raoult s law as. vi — 1, and we can write for the solvent... 

Figure 6.12 Activity (ai and a ) for. yi(C4H9)20 +. V2CCI4 at 7= 308.15 K. The dashed lines are the ideal solution predictions.

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... 

If one of the partners in a second-order reaction is not an ion, then in ideal solutions there will be little effect of added salts on the rate. The activity coefficient of a nonelectrolyte does not depend strongly on ionic strength the way that the activity coefficients of ions do. In a reaction with only one participating ion, it and the transition... 

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 activity is a measure of the tendency of a substance to react relative to its reacting tendency in the standard state. Here we relate activity to c/c for ideal solutions. For ideal gases and ideal solvents, the activity approaches P/P and X, respectively. Although c is taken to be 1.0 M, Equation (8) works best when c is much less than 1.0 M. 

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... 

Fig. 108.—The activity of benzene in solution with rubber plotted against the volume fraction of rubber. The solid curve represents smoothed experimental data of Gee and Treloar. The upper dashed curve represents the calculated ideal curve for an ideal solution of a solute with M = 280,000 dissolved in benzene. The diagonal dashed curve corresponds to ai — Vi. (From the data of Gee and Treloar. )...

If the reaction mixture can be considered to be an ideal solution, the activity coefficients are... 

In an ideal solution the components obey Raoult s law. The activity equals the mole fraction ... 

The equality of activity and mole fraction in an ideal solution has interesting consequences. These consequences, in fact, are the characteristics of an ideal solution, and are presented in the following. 

An ideal solution is an exception rather than the rule. Real solutions are, in general, nonideal. Any solution in which the activity of a component is not equal to its mole fraction is called non-ideal. The extent of the nonideality of a solution, i.e., the extent of its deviation from... 

The zinc will be inclined to depart spontaneously from the high-activity amalgam to that with a corresponding low activity. For example, if c1 is greater than c2, E is positive and the reaction advances in the direction specified. It may be added that metals in mercury constitute fairly ideal solutions, and that the emfs are almost correctly calculated by using concentrations instead of activities. 

For a solution of a non-volatile substance (e.g. a solid) in a liquid the vapour pressure of the solute can be neglected. The reference state for such a substance is usually its very dilute solution—in the limiting case an infinitely dilute solution—which has identical properties with an ideal solution and is thus useful, especially for introducing activity coefficients (see Sections 1.1.4 and 1.3). The standard chemical potential of such a solute is defined as... 

Activity ax is termed the rational activity and coefficient yx is the rational activity coefficient This activity is not directly given by the ratio of the fugacities, as it is for gases, but appears nonetheless to be the best means from a thermodynamic point of view for description of the behaviour of real solutions. The rational activity corresponds to the mole fraction for ideal solutions (hence the subscript x). Both ax and yx are dimensionless numbers. 

For ideal solutions, the activity coefficients are unity, giving ... 

The most important aspect of the simulation is that the thermodynamic data of the chemicals be modeled correctly. It is necessary to decide what equation of state to use for the vapor phase (ideal gas, Redlich-Kwong-Soave, Peng-Robinson, etc.) and what model to use for liquid activity coefficients [ideal solutions, solubility parameters, Wilson equation, nonrandom two liquid (NRTL), UNIFAC, etc.]. See Sec. 4, Thermodynamics. It is necessary to consider mixtures of chemicals, and the interaction parameters must be predictable. The best case is to determine them from data, and the next-best case is to use correlations based on the molecular weight, structure, and normal boiling point. To validate the model, the computer results of vapor-liquid equilibria could be checked against experimental data to ensure their validity before the data are used in more complicated computer calculations. 

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