Surface charge of oxides

Equation (3.43) was used in many original publications and in compilations of thermodynamic data (temperature effects on PZC and calorimetric) on surface charging of oxides [543-545]. Machesky [544] summarized also temperature effects on specific adsorption, which are discussed in detail in Chapter 4. Most AH values reported in Refs, [543-545] are negative, i.e. proton adsorption is exothermic and the pHo decreases when T increases. Moreover, more negative AJTads is observed for oxides whose PZC falls at high pH. However, different representations of the temperature effects on PZC than that based on Eqs. (3.42) and (3.43) have been also used, thus, special caution must be exercised by comparison of results reported in different sources. In some publications the surface reaction responsible for the proton adsorption is defined in such way that... 

Tewari, P.H. and Campbell, A.B., The surface charge of oxides and its role in deposition and transport of radioactivity in water-cooled nuclear reactors, in Proceedings of the Symposium on Oxide-Electrolyte Interfaces, Alwitt, R.S., ed.. The Electrochemical Society, Princeton, 1973, p. 102. 

Kosmuiski, M., The role of the activity coefficients of surface groups in the formation of surface charge of oxides, Pol. J. Chem.. 66, 1867, 1992. 

Park (1967) summarized the factors controlling the sign and magnitude of surface charge of oxide and mineral oxides, especially hydrous metal oxides. 

Several mechanisms can cause surface charges of oxide particles [JOL 94] [HUN 87]. The main ones are i) the reaction of hydroxyl groups present at the srrrface of oxides, ii) the adsorption of specific iorrs or charged polyelectrolytes called... 

In adsorptive stripping voltammetry the deposition step occurs without electrolysis. Instead, the analyte adsorbs to the electrode s surface. During deposition the electrode is maintained at a potential that enhances adsorption. For example, adsorption of a neutral molecule on a Hg drop is enhanced if the electrode is held at -0.4 V versus the SCE, a potential at which the surface charge of mercury is approximately zero. When deposition is complete the potential is scanned in an anodic or cathodic direction depending on whether we wish to oxidize or reduce the analyte. Examples of compounds that have been analyzed by absorptive stripping voltammetry also are listed in Table 11.11. 

An important property of the surface behaviour of oxides which contain transition metal ions having a number of possible valencies can be revealed by X-ray induced photoelectron spectroscopy. The energy spectrum of tlrese electrons give a direct measure of the binding energies of the valence electrons on the metal ions, from which the charge state can be deduced (Gunarsekaran et al., 1994). 

Thus titanium by itself cannot function as an efficient anode for the passage of positive direct current into an electrolyte. The surface film of oxide formed upon the titanium has, however, a most useful property while it will not pass positive direct current into an electrolyte (more correctly, while it will not accept electrons from negatively charged ions in solution), it will accept electrons from, or pass positive current to, another metal pressed on to it. Hence a piece of titanium which has pressed on to its surface a small piece of platinum will pass positive direct current into brine and into many electrolytes, at a high current density, via the platinum, without undue potential rise, and without breakdown of the supporting titanium . ... 

Various mechanisms for electret effect formation in anodic oxides have been proposed. Lobushkin and co-workers241,242 assumed that it is caused by electrons captured at deep trap levels in oxides. This point of view was supported by Zudov and Zudova.244,250 Mikho and Koleboshin272 postulated that the surface charge of anodic oxides is caused by dissociation of water molecules at the oxide-electrolyte interface and absorption of OH groups. This mechanism was put forward to explain the restoration of the electret effect by UV irradiation of depolarized samples. Parkhutik and Shershulskii62 assumed that the electret effect is caused by the accumulation of incorporated anions into the growing oxide. They based their conclusions on measurements of the kinetics of Us accumulation in anodic oxides and comparative analyses of the kinetics of chemical composition variation of growing oxides. 

Finally, we should note that the extent of oxidation or reduction needed to cause a surface charge of this type need not be large and the acquisition of charge, whether positive or negative, is fast and requires no more than a millisecond after immersing the electrodes in their respective half-cells. 

We will demonstrate how the surface charge of a hydrous oxide (a-FeOOH) can be calculated from an experimental titration curved (e.g., Fig. 2.2). 

Thus, the net surface charge of a hydrous oxide is determined by the proton transfer and reactions with other cations or anions. In general, the net surface charge density of a hydrous oxide is given by... 

As we have seen, the net surface charge of a hydrous oxide surface is established by proton transfer reactions and the surface complexation (specific sorption) of metal ions and ligands. As Fig. 3.5 illustrates, the titration curve for a hydrous oxide dispersion in the presence of a coordinatable cation is shifted towards lower pH values (because protons are released as consequence of metal ion binding, S-OH + Me2+ SOMe+ + H+) in such a way as to lower the pH of zero proton condition at the surface. 

The surface charge of metal oxides (due to surface protonation) as a function of pH can be predicted if their pHpzc are known with the help of the relationship given in Fig. 3.4. Fig. 7.6 exemplifies the effect of various solutes on the colloid stability of hematite at pH around 6.5 (pH = 10.5 for Ca2+ and Na+) (Liang and Morgan, 1990). 

Simple electrolyte ions like Cl, Na+, SO , Mg2+ and Ca2+ destabilize the iron(Hl) oxide colloids by compressing the electric double layer, i.e., by balancing the surface charge of the hematite with "counter ions" in the diffuse part of the double... 

The phenomena of surface precipitation and isomorphic substitutions described above and in Chapters 3.5, 6.5 and 6.6 are hampered because equilibrium is seldom established. The initial surface reaction, e.g., the surface complex formation on the surface of an oxide or carbonate fulfills many criteria of a reversible equilibrium. If we form on the outer layer of the solid phase a coprecipitate (isomorphic substitutions) we may still ideally have a metastable equilibrium. The extent of incipient adsorption, e.g., of HPOjj on FeOOH(s) or of Cd2+ on caicite is certainly dependent on the surface charge of the sorbing solid, and thus on pH of the solution etc. even the kinetics of the reaction will be influenced by the surface charge but the final solid solution, if it were in equilibrium, would not depend on the surface charge and the solution variables which influence the adsorption process i.e., the extent of isomorphic substitution for the ideal solid solution is given by the equilibrium that describes the formation of the solid solution (and not by the rates by which these compositions are formed). Many surface phenomena that are encountered in laboratory studies and in field observations are characterized by partial, or metastable equilibrium or by non-equilibrium relations. Reversibility of the apparent equilibrium or congruence in dissolution or precipitation can often not be assumed. 

Parks, G. A. (1967), "Aqueous Surface Chemistry of Oxides and Complex Oxide Minerals Isoelectric Point and Zero Point of Charge," in Equilibrium Concepts in Natural Water Systems, Advances in Chemistry Series, No. 67, American Chemical Society, Washington, DC. 

Co/pH and V o/pH results are sensitive to different aspects of the surface chemistry of oxides. Surface charge data allow the determination of the parameters which describe counterion complexation. Surface potential data allow the determination of the ratio /3 —< slaDL- Given assumptions about the magnitude of the site density Ns and the Stern capacitance C t, this quantity can be combined with the pHp2C to yield values of Ka and Ka2. Surface charge/pH data contain direct information about the counterion adsorption capacitances in their slope. To find the equilibrium constants for adsorption, a plot such as those in Figures 7 and 8 can be used, provided that Ka and Kai are independently known from V o/pH curves. 

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