Ideal solutions formation from pure components

Figure 14.2. Thermodynamics of formation of ideal solution from pure components.

Ideal Adsorbed Solution Theory. Perhaps the most successful approach to the prediction of multicomponent equiUbria from single-component isotherm data is ideal adsorbed solution theory (14). In essence, the theory is based on the assumption that the adsorbed phase is thermodynamically ideal in the sense that the equiUbrium pressure for each component is simply the product of its mole fraction in the adsorbed phase and the equihbrium pressure for the pure component at the same spreadingpressure. The theoretical basis for this assumption and the details of the calculations required to predict the mixture isotherm are given in standard texts on adsorption (7) as well as in the original paper (14). Whereas the theory has been shown to work well for several systems, notably for mixtures of hydrocarbons on carbon adsorbents, there are a number of systems which do not obey this model. Azeotrope formation and selectivity reversal, which are observed quite commonly in real systems, ate not consistent with an ideal adsorbed... 

Scamehorn et. al. (20) also presented a simple, semi—empirical method based on ideal solution theory and the concept of reduced adsorption isotherms to predict the mixed adsorption isotherm and admicellar composition from the pure component isotherms. In this work, we present a more general theory, based only on ideal solution theory, and present detailed mixed system data for a binary mixed surfactant system (two members of a homologous series) and use it to test this model. The thermodynamics of admicelle formation is also compared to that of micelle formation for this same system. 

For ideal solutions, the partial pressure of a component is directly proportional to the mole fraction of that component in solution and depends on the temperature and the vapor pressure of the pure component. The situation with group III-V systems is somewhat more complicated because of polymerization reactions in the gas phase (e.g., the formation of P2 or P4). Maximum evaporation rates can become comparable with deposition rates (0.01-0.1 xm/min) when the partial pressure is in the order of 0.01-1.0 Pa, a situation sometimes encountered in LPE. This problem is analogous to the problem of solute loss during bakeout, and the concentration variation in the melt is given by equation 1, with l replaced by the distance below the gas-liquid interface and z taken from equation 19. The concentration variation will penetrate the liquid solution from the top surface to a depth that is nearly independent of zlDx and comparable with the penetration depth produced by film growth. As result of solute loss at each boundary, the variation in solute concentration will show a maximum located in the melt. The density will show an extremum, and the system could be unstable with respect to natural convection. 

The constant KV) which is called the ionic product of water, may be computed from equations (V-44) and (V-46), if partial molal free energies (potentials) of formation of all the reaction components in the corresponding standard states are known. For such standard states we select both the state of a hypothetical ideal solution with molal concentration of hydrogen and hydroxyl ions equalling unity and the state of hypothetical, absolutely undissociatcd pure water. Since in actual diluted solutions the activity of undissociated water hardly differs from the activity in its standard state, aji2 in the equation (V-51) may be considered as equalling unity so that then Km = K . The following expression is valid for a temperature of 25° C ... 

The adsorption of binary mixtures of anionic surfactants in the bilayer region has also been modeled by using just the pure component adsorption isotherms and ideal solution theory to describe the formation of mixed admicelles (3 ). Positive deviation from ideality in the mixed admicelle phase was reported, and the non-ideality was attributed to the planar shape of the admicelle. However, a computational error was made in comparison of the ideal solution theory equations to the experimental data, even though the theoretical equations presented were correct. Thus, the positive deviation from ideal mixed admicelle formation was in error. 

The formation of azeotropes, or constant-boiling blends, is known to be a function of the non-ideality of the azeotropic solution, combined with the difference in boiling point between the two pure components. In general, the deviations from ideality can be attributed to contributions from dispersion interactions, dipole/dipole interactions, dipole-induced dipole interactions and hydrogen bonding, this last being one of the most important contributors to azeotrope formation. Ref. 3, Appendix 2 has much more details. 

In many solutions strong interactions may occur between like molecules to form polymeric species, or between unlike molecules to form new compounds or complexes. Such new species are formed in solution or are present in the pure substance and usually cannot be separated from the solution. Basically, thermodynamics is not concerned with detailed knowledge of the species present in a system indeed, it is sufficient as well as necessary to define the state of a system in terms of the mole numbers of the components and the two other required variables. We can make use of the expressions for the chemical potentials in terms of the components. In so doing all deviations from ideal behavior, whether the deviations are caused by the formation of new species or by the intermolecular forces operating between the molecules, are included in the excess chemical potentials. However, additional information concerning the formation of new species and the equilibrium constants involved may be obtained on the basis of certain assumptions when the experimental data are treated in terms of species. The fact that the data may be explained thermodynamically in terms of species is no proof of their existence. Extra-thermodynamic studies are required for the proof. 

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