Reaction mechanism surface protonation

Chemical, or abiotic, transformations are an important fate of many pesticides. Such transformations are ubiquitous, occurring in either aqueous solution or sorbed to surfaces. Rates can vary dramatically depending on the reaction mechanism, chemical stmcture, and relative concentrations of such catalysts as protons, hydroxyl ions, transition metals, and clay particles. Chemical transformations can be genetically classified as hydrolytic, photolytic, or redox reactions (transfer of electrons). 

It is well accepted7 that the electroreduction of proton to dihydrogen (Equation (1)) at metal surfaces proceeds via the Volmer-Heyrowsky-Tafel reaction mechanism depicted in Equations (2) (4). 

The surface proton adsorption which occurs after Step 2, however, complicates the determination of the heat content change resulting from anion adsorption. In order to make this correction, the heat associated with proton adsorption must be determined from the previous potentiometric-calorimetric titrations. Proton adsorption on goethite is exothermic, and Figure 1 provides an average value of -29.6 kj/mol near pH 4. This value, when multiplied by the moles of protons required to return to pH 4 after anion adsorption, allows correction for the heat associated with proton adsorption. This correction, however, is based on the assumption that the proposed two-step anion adsorption mechanism described above represents the only surface reactions which occur during anion adsorption. As such, the results obtained by this procedure are model dependent and are best used for comparative purposes. 

The 42-residue peptide KO-42 folds in solution into a hairpin helix-loop-helix motif that dimerizes to form a four-helix bundle. On the surface of the folded motif there are six histidines with assigned piC values in the range 5.2 to 7.2 (Fig. 1) and the second-order rate constant for the hydrolysis of mono-p-nitro-phenyl fumarate is 1140 times larger than that of the 4-methylimidazole-cataly-zed reaction at pH 4.1 and 290 K [13]. The reaction mechanism was found to be pH dependent as the kinetic solvent isotope effect was 2.0 at pH 4.7 and 1.0 at pH 6.1 and the pH dependence showed that the reaction rate depended on residues in their unprotonated form with piCj, values around 5. It was thus established that there are functional cooperative reactive sites that contain protonated and unprotonated His residues. 

In the catalytic mechanism, the two consecutive reactions are likely to have radically different rate constants. If the reaction for the proton discharge is relatively small compared with that for the catalytic desorption, the former reaction will determine the rate of the overall reaction in steady state. The catalytic reaction will react quickly when there are adsorbed H atoms to deal with. Since the recombination reaction is assumed here to have a relatively high rate constant (k2), then as soon as some H atoms arrive on the surface, they will form adsorbed H, which will recombine to H2. After gathering a few H2 s together, these will nucleate to form a tiny bubble, which will grow and detach itself from the electrode surface. Because the recombination rate constant is large, the adsorbed H is quickly removed, and 0H remains small. 

The reaction mechanism of amine deamination and disproportionation has been put forward by analogy with other eliminations, namely dehydration and dehydrochlorination [149,155], its characteristic feature being the cooperation of acidic and basic sites. In the deamination, /3-hydrogen and the NR2 group (R is hydrogen or alkyl) are eliminated by an E2-like mechanism on alumina, but by an El-like mechanism on silica-alumina. The nature of the acidic sites is not clear, protons from surface hydroxyls or aluminium ions are possible candidates. However, it seems... 

Figure I. Potential reaction mechanisms for 3-APTHS (a)-(c) condensation attachment mechanism (d) attachment of molecule via donation of nitrogen lone pair electrons and (e) attachment of molecule via protonation of amine with surface hydroxyl group.

Aminosilanes contain the catalyzing amine function in the organic chain. The reaction of aminosilanes with silica gel in dry conditions is therefore self-catalyzed. They show direct condensation, even in completely dry conditions. Upon addition of the aminosilane to the silica substrate, the amine group may form hydrogen bonds or proton transfer complexes with the surface silanols. This results in a very fast adsorption, followed by direct condensation. This reaction mechanism of APTS with silica gel in dry conditions, is displayed in figure 8.9. After liquid phase reaction, the filtered substrate is cured, in order to consolidate the modification layer. 

The key feature of this reaction mechanism is the fact that a certain proton mobility is induced on the surface silanols by the interaction with ammonia.23 The excellent leaving group, H20, is subsequently replaced by NH3. The rate-limiting step in this reaction is the formation and desorption of the water molecule. This mechanism could explain why Fink was able to reach a much higher degree of ammoniation, using a flow system, compared to other researchers using a static system. 

Especially researchers from the states of the former USSR have performed detailed studies on the reaction mechanism of SOCl2 with the silica surface.32 It was suggested that the anomalously low temperature of chlorination of the silica surface is related to the initial process of electrophilic substitution of a proton of the silanol group, the formation of intermediate compounds and their decomposition, according to reaction scheme (E). 

Examples are the oxygen electrode, Equation (1), or the hydrogen electrode (i.e. the H+/H2 reaction), Equation (2). Electron transfer proceeds regularly with the reacting species adsorbed at an electrode surface. In many cases, electrocatalysis by the electrode metal plays an important role. Associated chemical reactions, such as protonation and dissociation, render the reaction mechanisms complex. This is true in particular for the oxygen electrode. 

As with the hquid phase reaction, one mechanism involves the reaction of the acac ligands with the acidic, surface protons by the following reaction ... 

The reaction mechanism of Clemmensen reduction has not completely been clarified, but it is well known that the alcohol is not an intermediate. As summarized in Scheme 3, the reduction is thought to occur on the zinc metal surface, and involves protonation of the carbonyl function and a concomitant... 

DeNOx reaction involves a strongly adsorbed NH3 species and a gaseous or weakly adsorbed NO species, but differ in their identification of the nature of the adsorbed reactive ammonia (protonated ammonia vs. molecularly coordinated ammonia), of the active sites (Br0nsted vs. Lewis sites) and of the associated reaction intermediates [16,17]. Concerning the mechanism of SO2 oxidation over DeNOxing catalysts, few systematic studies have been reported up to now. Svachula et al. [18] have proposed a redox reaction mechanism based on the assumption of surface vanadyl sulfates as the active sites, in line with the consolidated picture of active sites in commercial sulfuric acid catalysts [19]. Such a mechanism can explain the observed effects of operating conditions, feed composition, and catalyst design parameters on the SO2 SO3 reaction over metal-oxide-based SCR catalysts. 

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