Desorption Reactions

Sorbed pesticides are not available for transport, but if water having lower pesticide concentration moves through the soil layer, pesticide is desorbed from the soil surface until a new equiUbrium is reached. Thus, the kinetics of sorption and desorption relative to the water conductivity rates determine the actual rate of pesticide transport. At high rates of water flow, chances are greater that sorption and desorption reactions may not reach equihbrium (64). NonequiUbrium models may describe sorption and desorption better under these circumstances. The prediction of herbicide concentration in the soil solution is further compHcated by hysteresis in the sorption—desorption isotherms. Both sorption and dispersion contribute to the substantial retention of herbicide found behind the initial front in typical breakthrough curves and to the depth distribution of residues. 

The adsorption of carbon monoxide retards the reduction reaction with the rate constant k, followed by the desorption reaction with a rate constant k in the overall rate equation... 

A third reaction, which goes in parallel with the desorption reaction, is the entry of atomic hydrogen into the steel from the surface adsorbed state ... 

These equations represent the adsorption-desorption reactions and the surface reaction E, P, and B are, respectively, ethene, propene, and 2-butene, and s represents an active site. If the surface reaction is rate deter-... 

Very simply these equations are valid as long as ion backspillover from the solid electrolyte onto the gas-exposed electrode surfaces is fast relative to other processes involving these ionic species (desorption, reaction) and thus spillover-backspillover is at equilibrium, so that the electrochemical potential of these ionic species is the same in the solid electrolyte and on the gas exposed electrode surface. As long as this is the case, equation (5.29) and its consequent Eqs. (5.18) and (5.19) simply reflect the fact that an overall neutral double layer is established at the metal/gas interface. 

The right-hand part of Fig. 7.7 corresponds to the second-order desorption of nitrogen atoms from a rhodium surface. As the desorption reaction corresponds to N -I- N —> N2 -I- 2 the rate is indeed expected to vary with A characteristic feature of second-order desorption kinetics is that the peaks shift to lower temperature with increasing coverage, because of the strong dependence of the rate on coverage. 

Major problems are associated with using the linear distribution coefficient for describing adsorption-desorption reactions in groundwater systems. Some of these problems include the... 

One of the most significant recent insights in surface chemical dynamics is the idea that the principle of detailed balance may be used to infer the properties of a dissociative adsorption reaction from measurements on an associative desorption reaction.51,52 This means, for example, that the observation of vibrationally-excited desorption products is an indicator that the dissociative adsorption reaction must be vibrationally activated, or vice versa the observation of vibrationally-cold desorption products indicates little vibrational promotion of dissociative adsorption. In this spirit, it is... 

It has been proposed that the precursor state [81, 82] for the adsorption-desorption reaction consists of weakly physisorbed CO. This can be CO sitting on an occupied site (COad-CO) or on an sterically unfavorable Pt site. According to Ertl [81], the desorption process occurs through a trapping mechanism on such sites if the surface is saturated by chemisorbed CO the desorption channel involves either a COad-CO potential well or a Pt-CO attractive well which is sterically weakened by the presence of pre-absorbed CO . 

Dang et al. (1994) observed that the experimentally determined solubility lines for Zn2+ in 14 soil solutions from southern Queensland with soil pH from 7.45-8.98 and 0.08-2.07% CaC03 were not undersaturated with respect to the solubility of any known mineral form of Zn. Therefore, they suggested that Zn2+ activity was mainly controlled by adsorption-desorption reactions in these soils. Similar observation on solubility of Cr(VI) in arid soils was reported by Rai et al. (1989). In the absence of a solubility controlling solid phase, Cr(VI) aqueous concentrations under slightly alkaline conditions may be primarily controlled by adsorption/desorption reactions (Rai et al., 1989). Chromuim(VI) is adsorbed by iron and aluminum oxides, and kaolinite and its adsorption decreases with increasing pH. 

In order to test the reversibility of metal-bacteria interactions, Fowle and Fein (2000) compared the extent of desorption estimated from surface complexation modeling with that obtained from sorption-desorption experiments. Using B. subtilis these workers found that both sorption and desorption of Cd occurred rapidly, and the desorption kinetics were independent of sorption contact time. Steady-state conditions were attained within 2 h for all sorption reactions, and within 1 h for all desorption reactions. The extent of sorption or desorption remained constant for at least 24 h and up to 80 h for Cd. The observed extent of desorption in the experimental systems was in accordance with the amount estimated from a surface complexation model based on independently conducted adsorption experiments. 

Two desorption reactions, for paraffins and for olehns, the latter one being reversible... 

Due to the fast kinetics of adsorption/desorption reactions of inorganic ions at the oxide/aqueous interface, few mechanistic studies have been completed that allow a description of the elementary processes occurring (half lives < 1 sec). Over the past five years, relaxation techniques have been utilized in studying fast reactions taking place at electrified interfaces (1-7). In this paper we illustrate the type of information that can be obtained by the pressure-jump method, using as an example a study of Pb2+ adsorption/desorption at the goethite/water interface. 

Having chosen a particular model for the electrical properties of the interface, e.g., the TIM, it is necessary to incorporate the same model into the kinetic analysis. Just as electrical double layer (EDL) properties influence equilibrium partitioning between solid and liquid phases, they can also be expected to affect the rates of elementary reaction steps. An illustration of the effect of the EDL on adsorption/desorption reaction steps is shown schematically in Figure 7. In the case of lead ion adsorption onto a positively charged surface, the rate of adsorption is diminished and the rate of desorption enhanced relative to the case where there are no EDL effects. 

What remains is to relate the surface potential to activation potentials for the adsorption/desorption reaction steps. Defining the activation potentials as iji, ijjf for the activation required to overcome the EDL potential for the adsorption, desorption steps, respectively, allows the intrinsic rate constants to be directly related to the rate constants k, k (4), i.e.,... 

A mechanism is determined from these data by choosing one which is consistent with the overall equilibrium behavior and which correctly matches the rate relationships derived for the postulated mechanism e.g., assuming the bimolecular adsorption/desorption reaction mechanism, as given in Equation 1, and using the kinetic model described above, the following relationship between xp and reactant and product concentrations can be derived (see Appendix C) ... 

If this mechanism is consistent with the experimental relaxation data, then a plot of xp versus the expression in the brackets of Equation 35 will give a straight line with a slope of kjnt and an intercept at the origin. As shown in Figure 11, the data fit this proposed mechanism quite well. Values for i i0, reactant and product concentrations, and K nt input into Equation 35 are from the equilibrium modeling results calculated at each pH value for which kinetic runs were made. Normally a variety of different mechanisms are tested against the experimental data. Several other more complex mechanisms were tested, including those postulated for metal ion adsorption onto y-A O (7) however, only the above mechanism was consistent with the experimental data. Hence it was concluded that the bimolecular adsorption/desorption reaction was the most plausible mechanism for Pb2+ ion adsorption onto a-FeOOH. 

In an interesting analysis of the effects of reduction of dimensionality on rates of adsorption/desorption reactions (26), the bimolecular rate of 10 M- s- has been reported as the lower limit of diffusion control. Based on this value, the rates given in Table III indicate the desorption step is chemical-reaction-controlled, likely controlled by the chemical activation energy of breaking the surface complex bond. On the other hand, the coupled adsorption step is probably diffusion controlled. 

Chemical relaxation methods can be used to determine mechanisms of reactions of ions at the mineral/water interface. In this paper, a review of chemical relaxation studies of adsorption/desorption kinetics of inorganic ions at the metal oxide/aqueous interface is presented. Plausible mechanisms based on the triple layer surface complexation model are discussed. Relaxation kinetic studies of the intercalation/ deintercalation of organic and inorganic ions in layered, cage-structured, and channel-structured minerals are also reviewed. In the intercalation studies, plausible mechanisms based on ion-exchange and adsorption/desorption reactions are presented steric and chemical properties of the solute and interlayered compounds are shown to influence the reaction rates. We also discuss the elementary reaction steps which are important in the stereoselective and reactive properties of interlayered compounds. 

The fast reactions of ions between aqueous and mineral phases have been studied extensively in a variety of fields including colloidal chemistry, geochemistry, environmental engineering, soil science, and catalysis (1-6). Various experimental approaches and techniques have been utilized to address the questions of interest in any given field as this volume exemplifies. Recently, chemical relaxation techniques have been applied to study the kinetics of interaction of ions with minerals in aqueous suspension (2). These methods allow mechanistic information to be obtained for elementary processes which occur rapidly, e.g., for processes which occur within seconds to as fast as nanoseconds (j0. Many important phenomena can be studied including adsorption/desorption reactions of ions at electri fied interfaces and intercalation/deintercalation of ions with minerals having unique interlayer structure. 

The main reasons for investigating the rates of solid phase sorption/desorption processes are to (1) determine how rapidly reactions attain equilibrium, and (2) infer information on sorption/desorption reaction mechanisms. One of the important aspects of chemical kinetics is the establishment of a rate law. By definition, a rate law is a differential equation [108] as shown in Eq. (32) ... 

Suppose (X 2, (X2)2+, and (X)1 are the organic cations of interest which are involved in the adsorption/desorption reactions experiment. 

Alternatively, according to the Volme-Heyrovsky mechanism, the Volmer discharge reaction is followed by the Heyrovsky electrochemical desorption reaction... 

Examples 5 and 15 are for desorption reactions, and therefore Steps 5, 8, and 9 could be relevant. The values for Steps 8 and 9 could not be calculated the partition functions for the mobile species were not available. If Step 5 is to be chosen for Examples 5 and 15, the site densities are low. Such a low site density situation in desorption is not unknown. Hayward, Herley, and Tompkins (JOS) found log L 8 for hydrogen desorption from Ni, and they suggested that, even when surface coverage is large, desorption might take place from only a very few favored sites. 

Is it possible that low site densities are obtained in some desorption reactions because an incorrect assumption is made about the entropy of activation For Step 5 we have assumed that AS = 0. Were we to modify this step to obtain a larger log L, we would have to postulate that the adsorbed molecule loses more entropy as the activated complex forms (4.6 e.u. per unit change in log L) than it does in Step 5 as we have described it. Such a sequence of events is not impossible for a surface reaction. But if the adsorbed molecule is immobile, it is difficult to imagine such a species losing... 

Adsorption/desorption Reactions that involve solute becoming chemically bonded to the surface of a solid. The reverse process releases solutes from the surface of a solid... 

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