Hematite surface reduction

This discrepancy might be explained if after about an hour the reaction approached equilibrium and slowed due to a diminishing thermodynamic drive. If the Fe+++ produced did not precipitate on the hematite surface, and did not form either hematite or goethite (FeOOH), it would accumulate in solution and weaken the drive for uranyl reduction. As the saturation index for hematite reached about 1.7, or about 1.25 for goethite, reaction would cease. 

By following the reaction scheme proposed by dos Santos Afonso and Stumm (22) for the reductive dissolution of hematite surface sites (Scheme 1), we were able to explain perfectly the observed pH pattern of the oxidation rate of H2S. The rate is proportional to the concentration of inner-sphere surface complexes of HS" formed with either the neutral (>FeOH) or the protonated (>FeOH2+) ferric oxide surface sites. 

Wavelet analysis has great potential in image processing applications of interest in mineralogy (see Moktadir and Sato (2000) for an illustrative example for silicon). As an illustration, in Figure 4 we show a version of Equation (3) over a one-dimensional trace across a two-dimensional AFM image of a hematite surface where there are some traces of bacterially mediated reduction reactions. One-dimensional wavelets with the second-derivative of the Gaussian function, also known as Mexican-hat wavelets because of their... 

Rate of the photochemical reductive dissolution of hematite, = d[Fe(II)]/dt, in the presence of oxalate as a function of the wavelength at constant incident light intensity (I0 = 1000 peinsteins "1 lr1). The hematite suspensions were deaerated initial oxalate concentration = 3.3 mM pH = 3. (In order to keep the rate of the thermal dissolution constant, a high enough concentration or iron(II), [Fe2+] = 0.15 mM, was added to the suspensions from the beginning. Thus, the rates correspond to dissolution rates due to the surface photoredox process). 

Similar photo-induced reductive dissolution to that reported for lepidocrocite in the presence of citric acid has been observed for hematite (a-Fe203) in the presence of S(IV) oxyanions (42) (see Figure 3). As shown in the conceptual model of Faust and Hoffmann (42) in Figure 4, two major pathways may lead to the production of Fe(II)ag i) surface redox reactions, both photochemical and thermal (dark), involving Fe(III)-S(IV) surface complexes (reactions 3 and 4 in Figure 4), and ii) aqueous phase photochemical and thermal redox reactions (reactions 11 and 12 in Figure 4). However, the rate of hematite dissolution (reaction 5) limits the rate at which Fe(II)aq may be produced by aqueous phase pathways (reactions 11 and 12) by limiting the availability of Fe(III)aq for such reactions. The rate of total aqueous iron production (d[Fe(aq)]T/dt = d [Fe(III)aq] +... 

FeOOCH3 had an area of ca. 60 m g (Morales et ah, 1989). Samples formed from hematite via magnetite by a reduction/oxidation process had length/width ratios of 1-6.3 and corresponding surface areas of 5.S-9.5 m g" (Morales et al., 1994). 

A solid state reaction in which the surface layers of magnetite are converted into maghemite appears to be involved as more chromate is adsorbed, further reduction is halted (Peterson et al., 1996). XAS showed that although adsorbed chromate was not reduced on the (112) plane of hematite, small amounts were reduced on (001) it was suggested that some Fe had been produced on the latter plane during annealing under vacuum (Kendlewicz et al., 1999). 

Desorption of the reduced metal ion is the rate determining step and is assisted by protons and oxalate ions. The reoxidized surface complex also desorbs owing to its altered molecular structure and is thus available for further reaction. The reductive dissolution step is faster than the initial complexation process. Photochemical dissolution of hematite in acidic oxalate solution is faster when air is excluded from the system (by purging with N2) than when air is present (Taxiarchou et al. 1997). 

Biological reductive dissolution by Shewanella putrifaciens of Fe oxides in material from four Atlantic pleistocene sediments (ca. 1.5-41 g/kg Fe oxides) was compared with that of the synthetic analogues (ferrihydrite, goethite, hematite) (Zachara et al. 1998). In the presence of AQDS as an electron shuttle, the percentage of bio-reduc-tion of the three oxides was increased from 13.3 %(fh) 9.2%(gt) and 0.6%(hm) to 94.6% 32.8% and 9.9% with part of the Fe formed being precipitated as vivianite and siderite, but not as magnetite. The quinone was reduced to hydroquinone which in turn, and in agreement with thermodynamics, reduced the Fe as it had much better access to the oxide surface than did the bacteria themselves. 

Al substitution (0.09-0.16 mol mol ) had no definite effect on the photochemical dissolution of substituted goethite in oxalate at pH 2.6 (Cornell Schindler, 1987). On the other hand, Al substitution depressed the initial (linear) stage of dissolution of synthetic goethites and hematites in mixed dithionite/citrate/bicarbonate solutions (Fig. 12.22) (Torrent et al., 1987). As the variation in initial surface area has already been accounted for, the scatter of data in this figure is presumably due to variations in other crystal properties such as disorder and micropores. Norrish and Taylor (1961) noted that as Al substitution in soil goethites increased, the rate of reductive dissolution dropped (see also Jeanroy et al., 1991). 

Dos Santos Alfonso and Stumm (1992) suggested that the rate of reductive dissolution by H2S of the common oxides is a function of the formation rate of the two surface complexes =FeS and =FeSH. The rate (10 mol m min ) followed the order lepidocrocite (20) > magnetite (14) > goethite (5.2) > hematite (1.1), and except for magnetite, it was linearly related to free energy, AG, of the reduction reactions of these oxides (see eq. 9.24). A factor of 75 was found for the reductive dissolution by H2S and Fe sulphide formation between ferrihydrite and goethite which could only be explained to a small extent by the difference in specific surface area (Pyzik Sommer, 1981). 

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