General equilibrium condition

In an SVE system, the primary mechanism for contaminant removal from the soil to the vadose zone is the volatilization of contaminants present in the pure or adsorbed phase onto soil into the vapor phase, as the vapor phase is continually extracted. The property that shows the extent to which this transfer can take place during SVE is vapor pressure, which provides an indication of the extent to which each contaminant will partition between the liquid phase and the vapor state at equilibrium conditions. Generally, a contaminant with a greater vapor pressure more readily volatilizes than one with a lesser vapor pressure. 

Although many natural systems are far from equilibrium, many localized regions of natural systems are well described in thermod3mamic and equilibrium terms. As a general rule, if the reactions that redistribute compounds between the reactant and product states are fast, then equilibrium conditions may be applied. In some cases, part of a system can be described in equilibrium terms and part... 

An alternative approach to the solution of the system dynamic equations, is by the natural cause and effect mass transfer process as formulated, within the individual phase balance equations. This follows the general approach, favoured by Franks (1967), since the extractor is now no longer constrained to operate at equilibrium conditions, but achieves this eventual state as a natural consequence of the relative effects of solute accumulation, solute flow in, solute flow out and mass transfer dynamics. 

The electroneutrality condition decreases the number of independent variables in the system by one these variables correspond to components whose concentration can be varied independently. In general, however, a number of further conditions must be maintained (e.g. stoichiometry and the dissociation equilibrium condition). In addition, because of the electroneutrality condition, the contributions of the anion and cation to a number of solution properties of the electrolyte cannot be separated (e.g. electrical conductivity, diffusion coefficient and decrease in vapour pressure) without assumptions about individual particles. Consequently, mean values have been defined for a number of cases. 

The equilibrium conditions given by eqs. (4.15) and (4.16) can in general be expressed through the activity coefficients. Using a solid-liquid phase equilibrium as an example we obtain... 

The purpose of this chapter is to introduce the effect of surfaces and interfaces on the thermodynamics of materials. While interface is a general term used for solid-solid, solid-liquid, liquid-liquid, solid-gas and liquid-gas boundaries, surface is the term normally used for the two latter types of phase boundary. The thermodynamic theory of interfaces between isotropic phases were first formulated by Gibbs [1], The treatment of such systems is based on the definition of an isotropic surface tension, cr, which is an excess surface stress per unit surface area. The Gibbs surface model for fluid surfaces is presented in Section 6.1 along with the derivation of the equilibrium conditions for curved interfaces, the Laplace equation. 

In some undisturbed subsurface systems, an equilibrium is established. Bacteria have acclimated to food sources, water availability, and electron acceptor types. The number and variety of microbial cells are balanced in this system. If the system is aerobic, the microbial activity continues at the rate of oxygen resupply. If the system is anaerobic, the rate of activity cannot exceed the accessibility of alternate electron acceptors. Generally, the subsurface (lower than the plant root zone) is relatively deficient in available carbon and electron acceptors. Under these normal semi-equilibrium conditions, a soil or aquifer system can consume organic materials within a reasonable range. When a chemical release is introduced into a well-established soil system, the system must change to react to this new energy source. The bacterial balance readjusts, in an effort to acclimate to the new carbon source. 

Expressions for the rate of mixing may be developed for any one of the possible mechanisms. Since mixing involves obtaining an equilibrium condition of uniform randomness, the relation between b and time might be expected to take the general form ... 

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