Contaminant Geochemistry by B. Berkowitz, et al.

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By B. Berkowitz, et al.

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The second law of thermodynamics, as formulated by Kelvin, states that “no process is possible in which the sole result is the absorption of heat from a reservoir and its complete conversion into work”; in other words, in any natural process involving a transfer of energy, some energy is converted irreversibly into heat that cannot be involved in further exchange. The second law of thermodynamics, therefore, is a recognition of spontaneous and nonspontaneous processes and the fact that natural processes have a sense of direction.

This perturbation derives from several sequences. Near the ion, water molecules are dominated by a dense electromagnetic field, resulting in the formation of the primary solvation shell. In the next zone, called the secondary solvation shell, water molecules interact weakly with the ion. An example of such behavior of an electrolyte solution near a clay surface was discussed by Sposito (1984). It was shown that the primary solvation shell of a monovalent cation contains between three and six water molecules that exchange relatively rapidly with the surrounding bulk liquid.

However, in the subsurface, when mainly anthropogenic-induced effects are involved, various changes do occur over “observable” time scales, ranging from seconds to years. Under these conditions an apparent equilibrium may be reached. , Stumm and Morgan 1995; 30 2 Selected Geochemical Processes Sposito 1981), and the reader is directed to such sources for ample information on this topic. In a closed system when temperature and pressure are constant, the sum of chemical potentials of all components is fixed; in contrast, in an open system, the chemical potential of all components is influenced by both the thermodynamic parameters of the phases and various parameters outside the system.

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