The kinetics of solvent extraction is a function of both the various chemical reactions occurring in the system and the rates of diffusion of the various species that control the chemistry of the extraction process.
The dependence of the kinetics on the chemical reactions is easily understood by considering that the final products of any extraction process are usually in a chemical state different from the initial unreacted species. This is true even for the simple partition of neutral molecules between two immiscible liquid phases, where the chemical change is in the solvation environment of the extracted species. More drastic chemical changes take place in the extraction of a metal cation from an aqueous solution by a chelating extractant dissolved in an organic diluent. In the extraction some of the solvation water molecules can be removed from the metal ion, and a new coordination compound, soluble in the organic phase, is formed with the chelating group of the extractant. In addition, the extracting reagent can undergo an acid dissociation reaction and, together with the extractant-metal complex, can undergo changes in aggregation in the organic phase. Consequently, whenever at least one of the chemical steps of the overall reaction mechanism is slow enough, compared with the diffusion rate, the kinet- ics of extraction would depend on the rate of the slow chemical reactions.
For solvent extraction systems, we have two additional complications. First, the chemical reactions can take place, at least in principle, in two bulk phases, since we are dealing with two immiscible liquid layers. Second, the chemical reactions can occur in the two-dimensional region called the liquid\u2013 liquid interface, that separates the two immiscible liquids, or in a thin volume region very close to it. When interfacial chemical reactions are important, the situation is analogous to that describing the kinetics of the chemical reactions encountered in heterogeneous catalysis and in some electrode processes. Al- though a relatively large number of sophisticated techniques are available for studying chemical reactions at solid\u2013fluid interfaces, very few tools have been developed to investigate chemical changes occurring at liquid\u2013liquid interfaces. Our knowledge of such interfacial reactions, therefore, is still limited and is based largely on indirect evidence and speculations.
To understand the dependence of the extraction kinetics on the rate of diffusion of the various chemical species that participate in the extraction reaction, we first have to distinguish between diffusion in the bulk phases and diffusion through the thin layers adjacent to the interface. In most solvent extraction pro- cesses of practical interest, both the aqueous and the organic phase are effi- ciently stirred. It follows that transport of material from the bulk of the phases up to a region very close to the interface can be considered instantaneous and that diffusion in the bulk of the phases can be neglected. Nevertheless, diffu- sional processes can still have an appreciable influence on the solvent extraction kinetics. For example, even when the two phases are vigorously stirred, it is possible to describe interfacial diffusion by assuming the existence of two stag- nant thin layers of finite thickness located on the aqueous and organic side of the interface. This model of the interface, often referred to as the two-film the- ory [1,2], is extremely useful for describing extraction kinetics that are con- trolled by diffusion occurring in proximity to the interface. The two-film model is used throughout our treatment. Other models and theories of higher complex- ity exist for describing diffusional transport in proximity to the interface. These theories (penetration, surface renewal, boundary layer) are described in detail in more advanced books [3,4].
The two films are schematically described inFig. 5.1, in which the pres- ence of an interfacially absorbed layer of extractant molecules is also shown.\u03b4o and\u03b4w represent the thickness of the organic and aqueous films, respectively. In these layers the liquid phases are considered completely stagnant (i.e., no move- ment of the fluids takes place in spite of the mechanical energy that is dissipated in the two-phase system to provoke mixing of the aqueous and organic phases).
These two thin liquid films, which are also called diffusion films, diffusion layers, or Nernst films, have thicknesses that range between 10\u22122 and 10\u22124 cm (in this chapter centimeter-gram-second (CGS) units are used, since most pub- lished data on diffusion and extraction kinetics are reported in these units; com- parison with literature values is, therefore, straightforward).
The description of the diffusion films as completely stagnant layers, having definite and well-identified thicknesses, represents only a practical approxima- tion useful for a simple mathematical description of interfacial diffusion. A
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