Solutions chemical potential

For precise measurements, diere is a slight correction for the effect of the slightly different pressure on the chemical potentials of the solid or of the components of the solution. More important, corrections must be made for the non-ideality of the pure gas and of the gaseous mixture. With these corrections, equation (A2.1.60) can be verified within experimental error. 

It follows that, because phase equilibrium requires that the chemical potential p. be the same in the solution as in the gas phase, one may write for the chemical potential in the solution ... 

To proceed fiirther, to evaluate the standard free energy AG , we need infonnation (experimental or theoretical) about the particular reaction. One source of infonnation is the equilibrium constant for a chemical reaction involving gases. Previous sections have shown how the chemical potential for a species in a gaseous mixture or in a dilute solution (and the corresponding activities) can be defined and measured. Thus, if one can detennine (by some kind of analysis)... 

We conclude this section by discussing an expression for the excess chemical potential in temrs of the pair correlation fimction and a parameter X, which couples the interactions of one particle with the rest. The idea of a coupling parameter was mtrodiiced by Onsager [20] and Kirkwood [Hj. The choice of X depends on the system considered. In an electrolyte solution it could be the charge, but in general it is some variable that characterizes the pair potential. The potential energy of the system... 

The McMillan-Mayer theory allows us to develop a fomialism similar to that of a dilute interacting fluid for solute dispersed in the solvent provided that a sensible description of W can be given. At the Ihnit of dilution, when intersolute interactions can be neglected, we know that the chemical potential of a can be written as = W (a s) + IcT In where W(a s) is the potential of mean force for the interaction of a solute... 

The McMillan-Mayer theory offers the most usefiil starting point for an elementary theory of ionic interactions, since at high dilution we can incorporate all ion-solvent interactions into a limitmg chemical potential, and deviations from solution ideality can then be explicitly coimected with ion-ion interactions only. Furthemiore, we may assume that, at high dilution, the interaction energy between two ions (assuming only two are present in the solution) will be of the fomi... 

The alternative to direct simulation of two-phase coexistence is the calculation of free energies or chemical potentials together with solution of the themiodynamic coexistence conditions. Thus, we must solve (say) pj (P) = PjjCT ) at constant T. A reasonable approach [173. 174. 175 and 176] is to conduct constant-AT J simulations, measure p by test-particle insertion, and also to note that the simulations give the derivative 3p/3 7 =(F)/A directly. Thus, conducting... 

Next suppose AS , and AH , are both positive. In this case these two partially offset one another, and a plot of AGj resembling that shown in Fig. 8.2b may result. We are particularly interested in the two minima in this curve and the hump between them. A common tangent can always be drawn to two such minima so the above discussion shows that the minima at points P and Q in Fig. 8.2b each have the same values of AjUi and A/i2. Since AjUj is simply the difference between juj and its value for the pure component, the chemical potential for each component is seen to have the same value for both solution P and solution Q in Fig. 8.2b. 

This is an expression of Raoult s law which we have used previously. Freezing point depression. A solute which does not form solid solutions with the solvent and is therefore excluded from the solid phase lowers the freezing point of the solvent. It is the chemical potential of the solvent which is lowered by the solute, so the pure solvent reaches the same (lower) value at a lower temperature. At equilibrium... 

Before pursuing the diffusion process any further, let us examine the diffusion coefficient itself in greater detail. Specifically, we seek a relationship between D and the friction factor of the solute. In general, an increment of energy is associated with a force and an increment of distance. In the present context the driving force behind diffusion (subscript diff) is associated with an increment in the chemical potential of the solute and an increment in distance dx ... 

A reverse osmosis membrane acts as the semipermeable barrier to flow ia the RO process, aHowiag selective passage of a particular species, usually water, while partially or completely retaining other species, ie, solutes such as salts. Chemical potential gradients across the membrane provide the driving forces for solute and solvent transport across the membrane. The solute chemical potential gradient, —is usually expressed ia terms of concentration the water (solvent) chemical potential gradient, —Afi, is usually expressed ia terms of pressure difference across the membrane. 

Solution—Diffusion Model. In the solution—diffusion model, it is assumed that (/) the RO membrane has a homogeneous, nonporous surface layer (2) both the solute and solvent dissolve in this layer and then each diffuses across it (J) solute and solvent diffusion is uncoupled and each is the result of the particular material s chemical potential gradient across the membrane and (4) the gradients are the result of concentration and pressure differences across the membrane (26,30). The driving force for water transport is primarily a result of the net transmembrane pressure difference and can be represented by equation 5 ... 

For the solute flux, it is assumed that chemical potential difference owing to pressure is negligible. Thus the driving force is almost entirely a result of concentration differences. The solute flux, J), is defined as in equation 6 ... 

When it was recognized (31) that the SD model does not explain the negative solute rejections found for some organics, the extended solution—diffusion model was formulated. The SD model does not take into account possible pressure dependence of the solute chemical potential which, although negligible for inorganic salt solutions, can be important for organic solutes (28,29). 

The chemical potential, plays a vital role in both phase and chemical reaction equiUbria. However, the chemical potential exhibits certain unfortunate characteristics which discourage its use in the solution of practical problems. The Gibbs energy, and hence is defined in relation to the internal energy and entropy, both primitive quantities for which absolute values are unknown. Moreover, p approaches negative infinity when either P or x approaches 2ero. While these characteristics do not preclude the use of chemical potentials, the appHcation of equiUbrium criteria is faciUtated by the introduction of a new quantity to take the place of p but which does not exhibit its less desirable characteristics. 

Expressions of supersaturation can then be formulated as follows (/) the difference between the chemical potential of the system and the chemical potential of at saturation, ji — ji where the chemical potential is a function of both temperature and concentration (2) the difference between the solute concentration and the concentration at equiUbrium, c — c (J) the difference between the system temperature at equiUbrium and the actual temperature,... 

The chemical potential in the dyebath solution, is defined in equation 1 where is the standard chemical potential in the solution, R is the gas constant, Tis temperature in K, and a is activity. 

Rate of Diffusion. Diffusion is the process by which molecules are transported from one part of a system to another as a result of random molecular motion. This eventually leads to an equalization of chemical potential and concentration throughout the system, and in the case of dyeing an equihbrium between dye in the fiber and dye in the dyebath. In dyeing there are three stages to diffusion diffusion of dye through the bulk solution of the dyebath to the fiber surface, diffusion through this surface, and diffusion of dye from the surface into the body of the fiber to allow for more dye to diffuse through the surface layer. These processes have been summarized elsewhere (9). 

Perhaps the most significant of the partial molar properties, because of its appHcation to equiHbrium thermodynamics, is the chemical potential, ]1. This fundamental property, and related properties such as fugacity and activity, are essential to mathematical solutions of phase equihbrium problems. The natural logarithm of the Hquid-phase activity coefficient, Iny, is also defined as a partial molar quantity. For Hquid mixtures, the activity coefficient, y, describes nonideal Hquid-phase behavior. 

Since the infinite dilution values D°g and Dba. re generally unequal, even a thermodynamically ideal solution hke Ya = Ys = 1 will exhibit concentration dependence of the diffusivity. In addition, nonideal solutions require a thermodynamic correction factor to retain the true driving force for molecular diffusion, or the gradient of the chemical potential rather than the composition gradient. That correction factor is ... 

Understanding the behavior of all the chemicals involved in the process—raw materials, intermediates, products and by-products, is a key aspect to identifying and understanding the process safety issues relevant to a given process. The nature of the batch processes makes it more likely for the system to enter a state (pressure, temperature, and composition) where undesired reactions can take place. The opportunities for undesired chemical reactions also are far greater in batch reaction systems due to greater potential for contamination or errors in sequence of addition. This chapter presents issues, concerns, and provides potential solutions related to chemistry in batch reaction systems. 

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