Surface protonation

Jacobs et al. [59,925,926] (Fig. 17). While this scheme conveniently summarizes many features of the observed behaviour, a number of variations or modifications of the mechanisms indicated have been proposed. Maycock and Pai Vemeker [924,933] emphasize the possible role of point defects and suggest, on the evidence of conductivity measurements, that the initial step may be the transfer of either a proton or an electron. Boldyrev et al. [46] suggest that proton conduction permits rapid migration of HC104 within the reactant and this undergoes preferential decomposition in distorted regions. More recently, the ease of proton transfer and the mobilities of other species in or on AP crystals have been investigated by a.c. [360] and d.c. [934] conductivity measurements. Owen et al. [934] could detect no surface proton conductivity and concluded that electron transfer was the initial step in decomposition. At the present time, these inconsistencies remain unresolved. 

Fig. 5.38 Reduction of 10-3m phenylglyoxylic acid at the mercury streaming electrode in acetate and phosphate buffers containing 1 m KN03 (1) pH 5.02, (2) pH 5.45, (3) pH 5.85, (4) pH 6.25. The curves 2, 3 and 4 are shifted by 0.2 V, 0.4 V and 0.6 V with respect to curve 1. The first wave is controlled by the surface protonation reaction while the second is a direct reduction of the acid anion. (According to J. Koryta)...

Fontes tt al. [224,225 addressed the acid—base effects of the zeolites on enzymes in nonaqueous media by looking at how these materials affected the catalytic activity of cross-linked subtilisin microcrystals in supercritical fluids (C02, ethane) and in polar and nonpolar organic solvents (acetonitrile, hexane) at controlled water activity (aw). They were interested in how immobilization of subtilisin on zeolite could affected its ionization state and hence their catalytic performances. Transesterification activity of substilisin supported on NaA zeolite is improved up to 10-fold and 100-fold when performed under low aw values in supercritical-C02 and supercritical-ethane respectively. The increase is also observed when increasing the amount of zeolite due not only to a dehydrating effect but also to a cation exchange process between the surface proton of the enzyme and the sodium ions of the zeolite. The resulting basic form of the enzyme enhances the catalytic activity. In organic solvent the activity was even more enhanced than in sc-hexane, 10-fold and 20-fold for acetonitrile and hexane, respectively, probably due to a difference in the solubility of the acid byproduct. 

Compounds 1-8 have been investigated. 4-Pyridylcarbinol, 1, is of interest because it is one of the electrochemical reduction products of 4-pyridinecarboxaldehyde, the species for which surface protonation reactions were discovered and characterized in earlier work (6). 

Thus, the shift in the titration curve, ACb, at constant pH, is directly related to the extent of Pb(II) binding to the oxide surface. The adsorption of a metal ion decreases the surface protonation. 

The net proton charge (in Coulombs nr2), the charge due to the binding of protons or H+ ions - one also speaks of the surface protonation - is given by... 

Relationship between pH, surface potential, xp or Coulombic term, log P, or Coulombic free energy, AGcoui), and surface charge density, a (or surface protonation) for various ionic strengths of a 1 1 electrolyte for a hydrous ferric oxide surface (P = exp(-Fi //RT). 

Fig. 3.4a gives plots of charge resulting from surface protonation vs pH for various oxides. Dots represent experimental data from different authors (Table 3.1a) from titration curves at ionic strength I = 0.1 M (hematite = 0.2 M). It is interesting to note that the data "of different oxides" can be "normalised" i.e., made congruent, if we chose the master variable... 

Surface protonation isotherms. Dots represent experimental data from titration curves at ionic strength I = 0.1 (Hematite, I = 0.2). References are indicated in Table 3.1. The concentration of protonated sites MOH is given in moles nr2. BET surface data were used to calculate the surface concentration. 

Addition of a ligand, at constant pH, increases surface protonation while the addition of a metal ion (that is specifically adsorbed) lowers surface protonation. 

Surface protonation at the kaolinite surfaces. The excess proton density, Th.v. at the surface hydroxyl group is displayed as a function of pH. Surface protonation is interpreted as a successive protonation of two distinct types of OH groups localized at the gibbsite and edge surfaces. The pHpzc of the edge surface is about 7.5. 

In summary, the model proposed on the basis of acid-base characteristics of kaolinite platelets explains the pH-dependent charge primarily to the protonation of the hydroxyl groups at the basal gibbsite and the edge surface. We will later illustrate how this charge characteristics (surface protonation) influences the reactivity (dissolution characteristics) of kaolinite. 

Similarly, surface protonation tends to increase the dissolution rate, because it leads to highly polarized interatomic bonds in the immediate proximity of the surface central ions and thus facilitates the detachment of a cationic surface group into the solution. On the other hand, a surface coordinated metal ion, e.g., Cu2+ or Al3+, may block a surface group and thus retard dissolution. An outer-sphere surface complex has little effect on the dissolution rate. Changes in the oxidation state of surface central ions have a pronounced effect on the dissolution rate (see Chapter 9). 

One may note that at the same surface coverage, C , different dissolution rates are observed (Fig. 5.5c). At the same surface coverage, C , the extent of surface protonation is about the same thus, the configuration and structure of the surface complex is of influence. 

Under steady state conditions, i.e., if the original surface sites are regenerated completely after the detachment step (Table 5.1) and if it is assumed that surface protonation equilibria are retained and kept constant by controlling the solution pH, one may write... 

If the fraction of surface that is covered with protons is smaller than 1 (%h 1), the surface density of singly, doubly, and triply protonated surface sites (B, C, and D, respectively (see Fig. 5.6)) can be described as probability functions of the surface protonation Cf. ... 

A weakening of the critical metal-oxygen bonds occurs as a consequence of the protonation of the oxide ions neighboring a surface metal center and imparting charge to the surface of the mineral lattice. The concentration (activity) of D should reflect that three of such oxide or hydroxide ions have to be protonated. If there is a certain numer of surface-adsorbed (bound) protons whose concentration (mol nr2) is much lower than the density of surface sites, S (mol 2), the probability of finding a metal center surrounded with three protonated oxide or hydroxide ions is proportional to (CJ/S)3. Thus, as has been derived from lattice statistics by Wieland et al. (1988), the activity of D is related to (C )3, and the rate of proton-promoted dissolution, Rh (mol nrr2 lr1), is proportional to the third power of the surface protonation ... 

The dissolution rate of most oxides increases both with increasing surface protonation and with decreasing surface protonation, equivalent to the binding of OH ligands thus, in the alkaline range the dissolution rate increases with increasing pH (Chou and Wollast, 1984 Schott, 1990 Brady and Walther, 1990) (see Fig. 5.9c). 

Surface protonation and deprotonation are experimentally directly accessible from alkalimetric or acidimetric surface tritrations. The surface concentrations (sMOH ) or <=MO") are nonlinearly related to H+ by surface complex formation equilibria or by semi-empirical relations in other words,... 

But factors other than the surface charge can become important such as the effects of specific adsorption of cations and anions on the degree of surface protonation (see Example 5.1). 

The weathering of silicates has been investigated extensively in recent decades. It is more difficult to characterize the surface chemistry of crystalline mixed oxides. Furthermore, in many instances the dissolution of a silicate mineral is incipiently incongruent. This initial incongruent dissolution step is often followed by a congruent dissolution controlled surface reaction. The rate dependence of albite and olivine illustrates the typical enhancement of the dissolution rate by surface protonation and surface deprotonation. A zero order dependence on [H+] has often been reported near the pHpzc this is generally interpreted in terms of a hydration reaction of the surface (last term in Eq. 5.16). 

Example 5.1 Change in Surface Protonation as a Consequence of Metal Ion or Ligand Adsorption... 

Effect of ligands and metal ions on surface protonation of a hydrous oxide. Specific Adsorption of cations and anions is accompanied by a displacement of alkalimetric and acidimetric titration curve (see Figs. 2.10 and 3.5). This reflects a change in surface protonation as a consequence of adsorption. This is illustrated by two examples ... 

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