Oxidation reactions, mineral surfaces

Oxidation of H2S (reaction (1-35)) occurs under the near-surface environment. Oxygen may be supplied from oxygenated groundwater. These oxidation reactions liberate H+ ion, leading to a decrease in pH. Under low pH conditions intermediate argillic alteration minerals (e.g., kaolinite, sericite) are stable. 

Rate constants for the dissolution and precipitation of quartz, for example, have been measured in deionized water (Rimstidt and Barnes, 1980). Dove and Crerar (1990), however, found that reaction rates increased by as much as one and a half orders of magnitude when the reaction proceeded in dilute electrolyte solutions. As well, reaction rates determined in the laboratory from hydrothermal experiments on clean systems differ substantially from those that occur in nature, where clay minerals, oxides, and other materials may coat mineral surfaces and hinder reaction. 

We take two cases in which mineral surfaces catalyze oxidation or reduction, and one in which a consortium of microbes, modeled as if it were a simple enzyme, promotes a redox reaction. In Chapter 33, we treat the question of modeling the interaction of microbial populations with geochemical systems in a more general way. 

Dissolved iron(III) is (i) an intermediate of the oxidative hydrolysis of Fe(II), and (ii) results from the thermal non-reductive dissolution of iron(III)(hydr)oxides, a reaction that is catalyzed by iron(II) as discussed in Chapter 9. Hence, iron(II) formation in the photic zone may occur as an autocatalytic process (see Chapter 10.4). This is also true for the oxidation of iron(II). As has been discussed in Chapter 9.4, the oxidation of iron(II) by oxygen is greatly enhanced if the ferrous iron is adsorbed at a mineral (or biological) surface. Since mineral surfaces are formed via the oxidative hydrolysis of Fe(II), this reaction proceeds as an autocatalytic process (Sung and Morgan, 1980). Both the rate of photochemical iron(II) formation and the rate of oxidation of iron(II) are strongly pH-dependent the latter increases with... 

Adsorption may influence precipitation by means other than the processes mentioned above. Davies (Chapter 23) discusses the role of the surface as a catalyst for oxidation of adsorbed Mnz+. Redox reactions may contribute substantially to the formation of manganese oxide coatings on mineral surfaces in soils and sediments. 

In all physical and chemical processes, and in particular those of relevance to geochemistry, that involve the oxide/aqueous solution interface, it is important to understand the general, non-specific characteristics of that interface before focussing on those specific processes or mechanisms of interest. Due to the structure of mineral surfaces, the mineral oxide/aqueous solution interface will invariably acquire a net charge or electrostatic potential relative to the bulk solution. The electrical state of the interface will depend in part on the chemical reactions that can take place on the mineral surface, and in part on the electrolytic composition of the aqueous environment. 

Using a simple amphoteric model for the mineral surface, we have demonstrated the role specific chemical binding reactions of potential determining Ions In determining the electrical properties and thermodynamics of the oxide/solution interfaces. A by-product of our study Is that under appropriate conditions, an amphoteric surface can show marked deviations from ideal Nernstlan behaviour. The graphical method also serves to Illustrate the... 

Rates of reductive dissolution of transition metal oxide/hydroxide minerals are controlled by rates of surface chemical reactions under most conditions of environmental and geochemical interest. This paper examines the mechanisms of reductive dissolution through a discussion of relevant elementary reaction processes. Reductive dissolution occurs via (i) surface precursor complex formation between reductant molecules and oxide surface sites, (ii) electron transfer within this surface complex, and (iii) breakdown of the successor complex and release of dissolved metal ions. Surface speciation is an important determinant of rates of individual surface chemical reactions and overall rates of reductive dissolution. 

Coordinative Environment. The coordinative environment of transition metal ions affects the thermodynamic driving force and reaction rate of ligand substitution and electron transfer reactions. FeIIIoH2+(aq) and hematite (a-Fe203) surface structures are shown in Figure 3 for the sake of comparison. Within the lattice of oxide/hydroxide minerals, the inner coordination spheres of metal centers are fully occupied by a regular array of O3- and/or 0H donor groups. At the mineral surface, however, one or more coordinative positions of each metal center are vacant (15). When oxide surfaces are introduced into aqueous solution, H2O and 0H molecules... 

Effect of Oxide Mineralogy on Reductive Dissolution. Oxide/hydrox-ide surface structures and the coordinative environment of metal centers may change substantially throughout the course of a reductive dissolution reaction. Nonstoichiometric and mixed oxidation state surfaces produced during surface redox reactions may exhibit dissolution behavior that is quite different from that observed with more uniform oxide and hydroxide minerals. 

The mixed-potential model demonstrated the importance of electrode potential in flotation systems. The mixed potential or rest potential of an electrode provides information to determine the identity of the reactions that take place at the mineral surface and the rates of these processes. One approach is to compare the measured rest potential with equilibrium potential for various processes derived from thermodynamic data. Allison et al. (1971,1972) considered that a necessary condition for the electrochemical formation of dithiolate at the mineral surface is that the measmed mixed potential arising from the reduction of oxygen and the oxidation of this collector at the surface must be anodic to the equilibrium potential for the thio ion/dithiolate couple. They correlated the rest potential of a range of sulphide minerals in different thio-collector solutions with the products extracted from the surface as shown in Table 1.2 and 1.3. It can be seen from these Tables that only those minerals exhibiting rest potential in excess of the thio ion/disulphide couple formed dithiolate as a major reaction product. Those minerals which had a rest potential below this value formed the metal collector compoimds, except covellite on which dixanthogen was formed even though the measured rest potential was below the reversible potential. Allison et al. (1972) attributed the behavior to the decomposition of cupric xanthate. 

The density of the corrosive current of jamesonite in NaOH solution is basically the same as that in Ca(OH)2 solution, but it is minimal in Na2C03 solution, about a fraction of the fourth of the former. There are obvious appearances of passivation and its breaking-down in strong polarization area in NaCOa solution Because COj ion is easier to form insoluble alkaline carbonate than OH ion, the carbonate salts are passive on the mineral surface to inhibit oxidation reaction. 

There existed oxidation-reduction reactions with the same reaction speed on the sulphide mineral surface in water. One is the self-corrosion of sulphide mineral. Another is the reduction of oxygen. If the equilibrium potential for the anodic reaction and the cathodic reaction are, respectively, E and, and the mineral electrode potential is E, the relationship among them is as follows ... 

According to the mixed potential theory, an anodic reaction can occur only if there is a cathodic reaction proceeding at finite rate at that potential (Rand and Woods, 1984). For the flotation systems, the cathodic reaction is usually given by the reduction of oxygen. The corresponding anodic reaction involves interaction of xanthate on the sulphide minerals in various ways, including the reaction of xanthate with the sulphide mineral (MS) to form metal xanthate and the oxidation of xanthate to dixanthogen (X2) at the mineral surface. 

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