Radical adsorption/desorption reactions

Sedlak and Andren (1991b) modeled hydroxyl radical reaction kinetics in the presence of particulate. They found that the reaction kinetics for PCB oxidation in the presence of particulate resulted from the complex interplay between solution-phase OH reactions and reversible adsorption-desorption reactions. A model predicting the reaction kinetics can be described by the following equation ... 

Thus, the addition of compounds to reaction mixtures can influence the catalytic activity of zeolites. The effect may be increased conversion or a shorter reaction time. The effects may be caused by surface modification or by variation in adsorption-desorption in the system reagent-product-zeolite. Sometimes the properties of the zeolite change so radically that it is possible to talk about the action of new catalytic systems. 

There are three major groups of processes that contribute to chamber wall effects the introduction of free radicals through wall reactions, the adsorption or desorption of oxidised nitrogen species (NOy), and off-gassing of organics that can lead to OH to HO2 conversion and therefore supplement ozone production in the system (Killus and Whitten, 1990). 

Here reactions (29)-(33) are heterogeneous reactions of adsorption-desorption of CF2 and CFz radicals on the silicon surface kgi — kgs are rate constants of heterogeneous reactions the reaction (34) is the reaction of spontaneous silicon etching is the etching rate constant. The designation (s) is used for radicals adsorbed on the wafer surface. 

Fig. 3 Contaminant pathways summary. Contaminants are generically identified as X, X, Xj, and X (a molecule), X + (a cation), and X (a radical). The arrows for both unit cell and catalyst layer levels refer to species movements. At the catalyst level, arrows indicate either species adsorption/desorption or reactions between species. BP bipolar plate, CL catalyst layer, FFC flow-field channel, GDL gas-diffusion layer, M membrane...

Carboxylates, which are chiral in the a-position totally lose their optical activity in mixed Kolbe electrolyses [93, 94]. This racemization supports either a free radical or its fast dynamic desorption-adsorption at the electrode. A clearer distinction can be made by looking at the diastereoselectivity of the coupling reaction. Adsorbed radicals should be stabilized and thus react via a more product like transition state... 

Reduction to the neutral radical appears as an irreversible wave at -0.9 V. Neither anodic peak exhibits the shape characteristic of stripping a solid coating from the electrode hence precipitation of the radical cation or neutral radical on the electrode is not evident (11-13). The sharp peaks at +0.46 V are tentatively assigned to desorption and adsorption of the CiebpyMe2 there are no anticipated redox reactions at that potential. 

As was suggested in a previous paper dthe steady state etching of solid material by exposure to gas phase particles with or without a plasma is usually described by the following sequence of steps (1) nondissociative adsorption of gas phase species at the surface of the solid being etched (2) dissociation of this absorbed gas (i.e., dissociative chemisorption) (3) reaction between adsorbed radicals and the solid surface to form an adsorbed product molecule, e.g., SiF fads) (4) desorption of the product molecule into the gas phase and (5) the removal of nonreactive residue (e.g., carbon) from the surface. 

Here M and T represent methylcyclohexane and toluene in the gas phase, and Ttt represents adsorbed toluene. The first step in the above reaction sequence represents the adsorption of methylcyclohexane with subsequent reaction to form toluene, while the second step is the desorption of toluene from the surface. Very likely the first step represents a series of steps involving partially dehydrogenated hydrocarbon molecules or radicals. However, at steady-state conditions the rates of the intermediate steps would all be equal, and the kinetic analysis is, therefore, not complicated by this factor. To account for the near zero-order behavior of the reaction, it was suggested that the active catalyst sites were heavily covered with... 

The rate of H2Oz consumption and the OH production were directly related to total iron concentration. The concentrations of hydroxyl radical produced were controlled by the rate of reaction with dissolved constituents. Rate constants for adsorption (ka) and desorption (kd) of PCBs from particles were calculated by regression of data from 1.5 to 5 hr. Adsorption rate constants were estimated from Equation (6.130) assuming that the partitioning rate constants between 2 and 5 hr without OH could be used for calculation of equilibrium partition coefficients Ky)... 

Kiperman [31] also warns that detection of free radicals in the postcatalyst volume in itself cannot serve as concrete proof of their direct participation in the process. The relation also has to be revealed between the nature of these radicals formed in the volume and the intermediates of the true heterogeneous component of the reaction. Obviously, sophisticated analytical and characterization procedures are needed to elucidate the nature of the species reacting on and desorbing from a catalytic surface. A powerful tool to study adsorption and desorption of radicals from surface is laser-induced fluorescence, applied to hydroxyl and oxygen radicals by a number of researchers cf. Ref 37. Such techniques will continue to aid in the elucidation of heterogeneous-homogeneous mechanisms. 

The stereochemistry of the products and the regioselectivity of the coupling reaction indicates that adsorption of saturated alkyl radicals is relatively unimportant [20]. Carboxylates which are chiral and non-racemic at the a-position totally lose their optical activity in mixed heterocoupling [21, 22]. This racemization indicates either a free radical as intermediate or its fast desorption-adsorption at the anode. These findings are further supported by the decarboxylation of 3 and 4, which both form the same 1 2 1 mixture of transfrans-, cis,trans- and c ,c -coupled dimer, whilst 5-7 show a slight diastereoselectivity [23, 24]. The latter could be due to some adsorption caused by the phenyl group or double bond and/or by a more effective facial shielding of the radicals (see Chapter 3.3). 

The kinetics of chain-reaction polymerization is illustrated in Fig. 3.28 for a free radical process. Analogous equations, except for termination, can be written for ionic polymerizations. Coordination reactions are more difficult to describe since they may involve solid surfaces, adsorption, and desorption. Even the crystallization of the macromolecule after polymerization may be able to influence the reaction kinetics. The rate expressions, as given in Appendix 7, Fig. A7.1, are easily written under the assumption that the chemical equations represent the actual reaction path. Most important is to derive an equation for the kinetic chain length, v, which is equal to the ratio of propagation to termination-reaction rates. This equation permits computation of the molar mass distribution (see also Sect. 1.3). The concentration of the active species is very small and usually not known. First one must, thus, ehminate [M ] from the rate expression, as shown in the figure. The boxed equation is the important equation for v. 

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