Desorption, phase transfer processes

Many different types of interfacial boundaries can be probed by SECM. The use of the SECM for studies of surface reactions and phase transfer processes is based on its abilities to perturb the local equilibrium and measure the resulting flux of species across the phase boundary. This may be a flux of electrons or ions across the liquid/liquid interface, a flux of species desorbing from the substrate surface, etc. Furthermore, as long as the mediator is regenerated by a first-order irreversible heterogeneous reaction at the substrate, the current-distance curves are described by the same Eqs. (34) regardless of the nature of the interfacial process. When the regeneration kinetics are more complicated, the theory has to be modified. A rather complete discussion of the theory of adsorption/desorption reactions, crystal dissolution by SECM, and a description of the liquid/liquid interface under SECM conditions can be found in other chapters of this book. In this section we consider only some basic ideas and list the key references. 

We begin with simple adsorption/desorption measurements and develop the ideas to include transport in two-dimensional (2D) systems, and phase transfer processes such as dissolution and transport in two-phase systems. Some of the work highlighted complements studies described in Chapter 9 on membrane transport where the tip is mainly used as a detector of localized transport phenomena. 

The two-phase kinetic model developed by Karickhoff (65) is capable of fitting either the sorption or desorption of a sorbing solute. For linear isotherms, the mathematical description given by Karickhoff (1) and others (67, 70, 71) is virtually identical to that of a mass transfer process (72). 

In voltammetric experiments, electroactive species in solution are transported to the surface of the electrodes where they undergo charge transfer processes. In the most simple of cases, electron-transfer processes behave reversibly, and diffusion in solution acts as a rate-determining step. However, in most cases, the voltammetric pattern becomes more complicated. The main reasons for causing deviations from reversible behavior include (i) a slow kinetics of interfacial electron transfer, (ii) the presence of parallel chemical reactions in the solution phase, (iii) and the occurrence of surface effects such as gas evolution and/or adsorption/desorption and/or formation/dissolution of solid deposits. Further, voltammetric curves can be distorted by uncompensated ohmic drops and capacitive effects in the cell [81-83]. 

Since there are twice the phase transfers as there are desorption processes the number of steps (n) is equal to two times Equation 2.68, or... 

Besides fluid mechanics, thermal processes also include mass transfer processes (e.g. absorption or desorption of a gas in a liquid, extraction between two liquid phases, dissolution of solids in liquids) and/or heat transfer processes (energy uptake, cooling, heating, drying). In the case of thermal separation processes, such as distillation, rectification, extraction, and so on, mass transfer between the respective phases is subject to thermodynamic laws (phase equilibria) which are obviously not scale dependent. Therefore, one should not be surprised if there are no scale-up rules for the pure rectification process, unless the hydrodynamics of the mass transfer in plate and packed columns are under consideration. If a separation operation (e.g. drying of hygroscopic materials, electrophoresis, etc.) involves simultaneous mass and heat transfer, both of which are scale-dependent, the scale-up is particularly difficult because these two processes obey different laws. 

If the stationary phase is a solid, the mass transfer process is adsorption and desorption on its surface. This process is very fast and usually does not contribute significantly to the Cs-term. 

A solid-phase microextraction process involves two steps, namely partitioning of the analytes between the coating and the sample, and desorption of the concentrated species into an analytical instrument. In the first step, the coated fibre is exposed and the target analytes are extracted from the sample matrix into the coating. In the second step, the fibre with the concentrated analytes is transferred to an instrument for desorption. A third, clean-up step can also be incorporated by using selective solvents, as in SPE. 

If gaseous, electrochemicaUy active components of the measuring environment are not dissolved in the electrode, then the electrode process will consist of the following stages (also shown in Figure 1.18). They are adsorption-desorption of electrochem-icaUy active gaseous components on gas-electrolyte (GE) and gas-metal (GM) interfaces, ionization reaction (with electron transfer) on the metal-electrolyte (ME) and gas-electrolyte interfaces, and mass-transfer processes on all boundaries of three phases (gas-metal, gas-electrolyte, and metal-electrolyte). Furthermore, mass transfer of electrons and holes on the surface electrolyte layer may also occur. It is evident that the quantity of the current in the stationary state is equal to the quantity of the nonmetal component adsorbing on the gas-metal and gas-electrolyte surfaces as a result of ionization of this component on the ME and GE surfaces. 

SPME is a multiphase equilibrium technique and, therefore, the analytes are not completely extracted from the matrix. Nevertheless, the method is useful for quantitative work and excellent precision and Unearity have been demonstrated. An extraction is complete when the concentration of analytes has reached distribution equilibrium between the sample and coating. This means that once the equihbrium is achieved, the amount extracted is independent of further increase in extraction time. If extraction is terminated before the equihbrium is reached, good precision and reproducibihty is still obtained if incubation temperature, sample agitation, sample pH and ionic strength, sample and headspace volume, extraction and desorption time are kept constant. The theory of the thermodynamic, kinetic and mass transfer processes underlying direct immersion and HS-SPME has been extensively discussed by Pawhszyn [2]. The sensitivity and time required to reach adsorption equilibriiun depends on the partition coefficients between the fiber and the analytes, and the thickness of the phase. Limits of detection and quantitation are often below 1 ppb. 

To appreciate the impact of SECM on the study of phase transfer kinetics, it is useful to briefly review the basic steps in reactions at solid/liquid interfaces. Processes of dissolution (growth) or desorption (adsorption), which are of interest herein, may be described in terms of some, or all, of the series of events shown in Figure 1. Although somewhat simplistic, this schematic identifies the essential elements in addressing the kinetics of interfacial processes. In one limit, when any of the surface processes in Figure 1 (e.g., the detachment of ions or molecules from an active site, surface diffusion of a species across the surface, or desorption) are slow compared to the mass transport step between the bulk solution and the interface, the reaction is kinetically surface-controlled. In the other limit, if the surface events are fast compared to mass transport, the overall process is in a mass transport-controlled regime. 

Although this chapter has focused on phase transfer reactions at solid/ liquid interfaces, many of the techniques and principles are generally applicable to such processes at liquid/liquid and air/liquid interfaces. Studies of adsorption/desorption, absorption, dissolution, and lateral interfacial diffusion at these types of interface are of considerable fundamental and practical importance, and SECM studies in these areas are already appearing. 

When explosive concentrations in soils were sufficiently high to produce free product in the soil, solubilization was the dominant mass transfer process. When concentrations were low, desorption, convection, and dispersion controlled solution phase concentrations. Surfactants generally increased solution phase concentrations of explosives however,... 

In general, two important types of processes occur at the electrode surface in contact with electrolyte solution containing electroactive substances when an appropriate potential is applied a charge (electron) transfer process that causes oxidation or reduction of the substances and an adsorption-desorption process in which adsorbable species from the solution phase are attached to the electrode surface through replacement of preadsorbed species such as solvent molecules. Electrochemical adsorption is characterized by competitive processes depending on the electrode potential. Furthermore the adsorbed state of a species, particularly its orientation to the electrode surface, affects redox reactivity. In situ studies on the adsorption of bioactive substances on an electrode surface are thus of great interest from a bioelectroanalytical standpoint. 

However, the two-sink model as well as other existing adsorption (sink) models do not seem to be able to describe the strong asymmetry between the adsorption/desorption of VOCs on/from indoor surface materials (the desorption process is much slower than the adsorption process). Diffusion combined with internal adsorption is assumed to be capable of explaining the observed asymmetry. Diffusion mechanisms have been considered to play a role in interactions of VOCs with indoor sinks. Dunn and Chen (1993) proposed and tested three unified, diffusion-limited mathematical models to account for such interactions. The phrase unified relates to the ability of the model to predict both the ad/absorption and desorption phases. This is a very important aspect of modeling test chamber kinetics because in actual applications of chamber studies to indoor air quality (lAQ), we will never be able to predict when we will be in an accumulation or decay phase, so that the same model must apply to both. Development of such models is underway by different research groups. An excellent reference, in which the theoretical bases of most of the recently developed sorption models are reviewed, is the paper by Axley and Lorenzetti (1993). The authors proposed four generic families of models formulated as mass transport modules that can be combined with existing lAQ models. These models include processes such as equilibrium adsorption, boundary layer diffusion, porous adsorbent diffusion transport, and conveetion-diffusion transport. In their paper, the authors present applications of these models and propose criteria for selection of models that are based on the boundary layer/conduction heat transfer problem. 

Both chemical and biological agents in either gaseous or liquid form can be adsorbed into adsorbent materials via adsorption, which is a dynamic adsorption-desorption process for forming a monolayer of gaseous or liquid molecules (i.e., adsorbates) on the surface of solid adsorbents such as activated carbon via van der Waals forces. During adsorption, part of the adsorbate molecules in fluid state are transferred on to the solid surface of adsorbents (i.e., adsorption phase). Meanwhile, part of the adsorbate molecules captured on the adsorbent surface are released again to the fluid state (i.e., desorption phase). When the rates of adsorption and desorption become equal, an adsorption equilibrium (or so-called adsorption isotherm)... 

I. Introduction to absorption. As discussed briefly in Section 10.IB, absorption is a ma s-transfer process in which a vapor solute. 4 in a gas mixture is absorbed by means of a liquid in which the solute is more or less soluble. The gas mixture consists mainly of an inert gas and the solute. The liquid also is primarily immiscible in the gas phase i.e., its vaporization into the gas phase is relatively slight. A typical example is absorption of the solute ammonia from an air-ammonia mixture by water. Subsequently, the solute is recovered from the solution by distillation. In the reverse process of desorption or stripping, the same principles and equations hold. 

Heat and mass transfers in porous media are coupled in a complicated way. On the one hand, heat is transported by conduction, convection, and radiation. On the other hand, water moves under the action of gravity and pressure gradient whilst the vapor phase moves by diffusion caused by a gradient of vapor density. Thus, the heat transfer process can be coupled with mass transfer processes with phase changes such as moisture sorption/desorption and evaporation/condensation. 

---