Ideal solution components

These results indicate that, for all practical purposes, at 100° F and 26 psia, the butane exhibits the behavior of an ideal solution component. However, at 400 psia the solution is not ideal insofar as the behavior of butane is concemed. 

These relationships or laws were discovered in the nineteenth century by investigations of gas or vapor pressures associated with solutions of known composition. Because the gas or vapor was at a fairly low pressure, it acted as an ideal gas, and because it was in equilibrium with the solution, it provided information on the nature of the liquid solution. Today, the original connection with an associated vapor or gas phase is a secondary concern. The relationship between the ideal solution components themselves proves to be more useful, a subject to be discussed in terms of activities, an important topic introduced here and treated more fully in Chapter 8. Before discussing these relationships, we look first at solutions of ideal gases. 

Equations (7.26) provide a relationship between the concentration of an ideal solution component and its Gibbs energy. This is an important milestone. Equations (4.42) and (4.43)... 

If an ideal solution is formed, then the actual molecular A is just Aav (and Aex = 0). The same result obtains if the components are completely immiscible as illustrated in Fig. IV-21 for a mixture of arachidic acid and a merocyanine dye [116]. These systems are usually distinguished through the mosaic structure seen in microscopic evaluation. 

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 vapour pressure of each component is equal to the vapour pressure of the pure substances multiplied by its mol fraction in the solution. The last-named property is merely an expression of Raoult s law, the vapour pressure of a substance is pro-... 

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. 

An ideal gas obeys Dalton s law that is, the total pressure is the sum of the partial pressures of the components. An ideal solution obeys Raoult s law that is, the partial pressure of the ith component in a solution is equal to the mole fraction of that component in the solution times the vapor pressure of pure component i. Use these relationships to relate the mole fraction of component 1 in the equilibrium vapor to its mole fraction in a two-component solution and relate the result to the ideal case of the copolymer composition equation. 

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-... 

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 ... 

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... 

One way to describe this situation is to say that the colligative properties provide a method for counting the number of solute molecules in a solution. In these ideal solutions this is done without regard to the chemical identity of the species. Therefore if the solute consists of several different components which we index i, then nj = S nj j is the number of moles counted. Of course, the total mass of solute in this case is given by mj = Sjnj jMj j, so the molecular weight obtained for such a mixture is given by... 

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 ... 

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. 

Thus the formation of an ideal solution from its components is always a spontaneous process. Real solutions are described in terms of the difference in the molar Gibbs free energy of their formation and that of the corresponding ideal solution, thus ... 

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]. 

All the above deals with gases and gas phase processes. We now turn to non-gaseous components of the system. There are many ways of expressing this. Probably the simplest is to consider an ideal solution of a solute in a solvent. If the solution is ideal, the vapour pressure of the solute is proportional to its concentration, and we may write p = kc, where c is the concentration and k is the proportionality constant. Similarly, = Arc , which expresses the fact that the standard pressure is related to a standard concentration. Thus we may write from equation 20.198 for a particular component... 

The contribution that (46) makes to the free energy of mixing is — kT In Wc and it will be noticed that, if the right-hand side of (47) is multiplied by kT, it becomes identical with (45), which is the total change in the free energy, when an ideal solution is formed from its components. 

In an ideal solution the components A, B, and C. . . are on an equal footing, and there is no distinction between solvent and solute. In this book we are mainly interested in very dilute ionic solutions, where the mole fraction of one component, known as the solvent, is very near unity, and where (at least) two solute species are present, the positive and the negative ions we shall use nA and xA to refer to the solvent particles and shall denote the solute species by B and C. Let us write... 

An ideal solution is one for which all components obey Raoult s law... 

Therefore, it is a sufficient condition for ideal solution behavior in a binary mixture that one component obeys Raoult s law over the entire composition range, since the other component must do the same. 

When deviations from ideal solution behavior occur, the changes in the deviations with mole fraction for the two components are not independent, and the Duhem-Margules equation can be used to obtain this relationship. The allowed combinations"1 are shown in Figure 6.10 in which p /p and P2//>2 are... 

Equation (8.26) relates the melting temperature, T, of an ideal solution to the mole fraction,, v of the (pure) component that freezes from solution. It can be integrated by separating variables and setting the integration limits between T, the melting temperature where the mole fraction is. y, and 7, the melting temperature of the pure component, /, where. v, = 1. The result is... 

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 ... 

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... 

Work in this area has been conducted in many laboratories since the early 1980s. The electrodes to be used in such a double-layer capacitor should be ideally polarizable (i.e., all charges supplied should be expended), exclusively for the change of charge density in the double layer [not for any electrochemical (faradaic) reactions]. Ideal polarizability can be found in certain metal electrodes in contact with elelctrolyte solutions free of substances that could become involved in electrochemical reactions, and extends over a certain interval of electrode potentials. Beyond these limits ideal polarizability is lost, owing to the onset of reactions involving the solvent or other solution components. 

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