Interfacial transfer processes

The spontaneous stirring enhances significantly mass exchange between the two media and thus is very efficient for interfacial transfer processes (liquid-liquid extraction, purification of biochemical compounds..)... 

Equipment Absorption, stripping, and distiUation operations are usually carried out in vertical, cylindrical columns or towers in which devices such as plates or packing elements are placed. The gas and liquid normally flow countercurrently, and the devices serve to provide the contacting and development of interfacial surface through which mass transfer takes place. Background material on this mass transfer process is given in Sec.. 5. 

Interfacial Area The effective area of contact between gas and liquid is that area which participates in the gas-liqiiid mass-exchange process. This area may be less than the actual interfacial area because of stagnant pools where liquid reaches satiiradon and no longer par-dcipates in the transfer process. 

The several industrial applications reported in the hterature prove that the energy of supersonic flow can be successfully used as a tool to enhance the interfacial contacting and intensify mass transfer processes in multiphase reactor systems. However, more interest from academia and more generic research activities are needed in this fleld, in order to gain a deeper understanding of the interface creation under the supersonic wave conditions, to create rehable mathematical models of this phenomenon and to develop scale-up methodology for industrial devices. 

Derivatized semiconductor photoelectrodes offer a way to design photosensitive interfaces for effecting virtually any redox process. Manipulation of interfacial charge transfer processes has been demonstrated using hydrolytically unstable redox... 

Duonghung D, Ramsden J, Gratzel M (1982) Dynamics of interfacial electron-transfer processes in colloidal semiconductor systems. J Am Chem Soc 104 2977-2985... 

Electron transfer processes leading to a product adsorbed in the interfacial region o are of practical interest. These processes include the deposition of a metal such as Cu or Pd at ITIES, the preparation of colloidal metal particles with catalytic properties for homogeneous organic reactions, or electropolymerization. 

Although the correlation between ket and the driving force determined by Eq. (14) has been confirmed by various experimental approaches, the effect of the Galvani potential difference remains to be fully understood. The elegant theoretical description by Schmickler seems to be in conflict with a great deal of experimental results. Even clearer evidence of the k t dependence on A 0 has been presented by Fermin et al. for photo-induced electron-transfer processes involving water-soluble porphyrins [50,83]. As discussed in the next section, the rationalization of the potential dependence of ket iti these systems is complicated by perturbations of the interfacial potential associated with the specific adsorption of the ionic dye. 

Within the potential range where Ru(bpy)3 remains in the aqueous phase, photocurrent responses are clearly observed with a slow rising time of the order of 10 s as shown in Fig. 14(a). According to the convention employed by these authors, positive currents correspond to the transfer of a negative charge from water to DCE. No photoresponses were observed in the absence of either the dye in the aqueous phase or TCNQ in DCE. Further analysis of the interfacial behavior of the product TCNQ revealed that the ion transfer occurred outside of the polarizable window [cf. Fig. 14(d)], confirming that these photoresponses are not affected by coupled ion-transfer processes. An earlier report also showed photoeffects for the photoreduction of the viologen under similar conditions [131]. 

Between 0.20 and 0.30 V, a decay of the initial photocurrent and a negative overshoot after interrupting the illumination are developed. This behavior resembles the responses observed at semiconductor-electrolyte interfaces in the presence of surface recombination of photoinduced charges [133-135] but at a longer time scale. These features are in fact related to the back-electron-transfer processes within the interfacial ion pair schematically depicted in Fig. 11. 

The influence of an interfacial kinetic barrier on the transfer process is readily illustrated by fixing the concentrations and the diffusion coefficients of Red for the two phases and examining the current response of the UME as K is varied. For illustrative purposes, we arbitrarily set and y = 1, i.e., initially the equilibrium conditions are such that there are equal concentrations of the target solute in the two phases, and the solute diffusion coefficient is phase-independent. Figure 17 shows the chronoamperometric characteristics for several K values from zero up to 1000. Under the defined conditions, these values of K reflect the ease with which the transfer process can respond to a perturbation of the local concentration of Red in phase 1, due to electrolytic depletion. 

The theoretical results described have implications for the design of experimental approaches for the study of transfer processes across the interface between two immiscible phases. The current response in SECMIT is clearly sensitive to the relative diffusion coefficients and concentrations of a solute in the two phases and the kinetics of interfacial transfer over a wide range of values of these parameters. 

The interfacial transfer kinetics were then investigated by perturbing the equilibrium, through the depletion of Cu + in the aqueous phase, by reduction to Cu at an UME located in close proximity to the aqueous-organic interface. This process promoted the transfer of Cu into the aqueous phase, via the transport and decomplexation of the cupric ion-oxime complex, resulting in an enhanced steady-state current at the UME. Approach curve measurements of i/i oo) vs. d allowed the kinetics of the transfer process to be determined unambiguously [9,18]. 

The driving force for the transfer process was the enhanced solubility of Br2 in DCE, ca 40 times greater than that in aqueous solution. To probe the transfer processes, Br2 was recollected in the reverse step at the tip UME, by diffusion-limited reduction to Br . The transfer process was found to be controlled exclusively by diffusion in the aqueous phase, but by employing short switching times, tswitch down to 10 ms, it was possible to put a lower limit on the effective interfacial transfer rate constant of 0.5 cm s . Figure 25 shows typical forward and reverse transients from this set of experiments, presented as current (normalized with respect to the steady-state diffusion-limited current, i(oo), for the oxidation of Br ) versus the inverse square-root of time. 

M sulfuric acid to air [34]. As discussed above, for the aqueous-DCE interface, the rate of this irreversible transfer process (with the air phase acting as a sink) was limited only by diffusion of Bt2 in the aqueous phase. A lower limit for the interfacial transfer rate constant of 0.5 cm s was found [34]. 

Many of the electrochemical techniques described in this book fulfill all of these criteria. By using an external potential to drive a charge transfer process (electron or ion transfer), mass transport (typically by diffusion) is well-defined and calculable, and the current provides a direct measurement of the interfacial reaction rate [8]. However, there is a whole class of spontaneous reactions, which do not involve net interfacial charge transfer, where these criteria are more difficult to implement. For this type of process, hydro-dynamic techniques become important, where mass transport is controlled by convection as well as diffusion. 

In the majority of methods described thus far, the interfacial kinetics are deduced by measuring concentration changes in the bulk of the solution rather than at the interface, where the reaction occurs. This introduces a time lag, limiting the resolution of the measurement in the determination of interfacial kinetics. A more direct approach is to identify the interfacial flux. This can be achieved in the electrolyte dropping electrode, via the current flow, but this method is only applicable to net charge-transfer processes at externally polarized interfaces. 

The description of the ion transfer process is closely related to the structure of the electrical double layer at the ITIES [50]. The most widely used approach is the combination of the BV equation and the modified Verwey-Niessen (MVN) model. In the MVN model, the electrical double layer at the ITIES is composed of two diffuse layers and one ion-free or inner layer (Fig. 8). The positions delimiting the inner layer are denoted by X2 and X2, and represent the positions of closest approach of the transferring ion to the ITIES from the organic and aqueous side, respectively. The total Galvani potential drop across the interfacial region, AgCp = cj) — [Pg.545]

When ionizabie compounds are concerned, the situation is complicated by the fact that all the species present may transfer from one phase to the other depending on the interfacial potential difference, so that the transfer process of the solute is entirely determined by the thermodynamic cycle described in Fig. 4. 

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