Hematite oxidizing conditions

Figure 1 illustrates that in reduced aquifers uranium would not be mobile. It also shows that uranium can be precipitated well into the field of stability of hematite under oxidizing conditions. This common association between uranium mineralization and hematite needs to be taken into account in any exploration program. 

It is assumed that in such rocks oxides—hematite and magnetite—were essential minerals as well as siderite. The association of siderite with magnetite and fayalite in equilibrium with graphite in reducing conditions has already been examined now it remains to analyze in detail the particulars of metamorphism in oxidizing conditions in equilibrium with a hematite-magnetite buffer. 

The first surface challenge can be addressed by strong oxidation conditions [46] and careful hematite preparation, but the slow water oxidation kinetics are probably intrinsic to hematite. Nevertheless, methods have recently been found to increase the oxidation rate and thus reduce the overpotential. For example, the water oxidation by cobalt has been extensively studied and is known to be particularly rapid [114]. Indeed the treatment of Fe203 photoanodes (prepared by APCVD) with a monolayer of Co " resulted in a ca. 0.1 V reduction of the photocurrent onset potential [105]. Since this treatment also increased the plateau photocurrent it is good evidence that the reaction rate was increased, and the Co " did not just fill surface traps. Following the report of a remarkably effective cobalt-phosphate (Co-Pi)- based water oxidation catalyst [115], the overpotential was reduced even further on hematite photoanodes by Gamelin and coworkers [116]. Their results are shown in Fig. 4.11. 

Shock-synthesis experiments were carried out over a range of peak shock pressures and a range of mean-bulk temperatures. The shock conditions are summarized in Fig. 8.1, in which a marker is indicated at each pressure-temperature pair at which an experiment has been conducted with the Sandia shock-recovery system. In each case the driving explosive is indicated, as the initial incident pressure depends upon explosive. It should be observed that pressures were varied from 7.5 to 27 GPa with the use of different fixtures and different driving explosives. Mean-bulk temperatures were varied from 50 to 700 °C with the use of powder compact densities of from 35% to 65% of solid density. In furnace-synthesis experiments, reaction is incipient at about 550 °C. The melt temperatures of zinc oxide and hematite are >1800 and 1.565 °C, respectively. Under high pressure conditions, it is expected that the melt temperatures will substantially Increase. Thus, the shock conditions are not expected to result in reactant melting phenomena, but overlap the furnace synthesis conditions. 

Adsorption of Pentavalent Sb Ions on Hematite. So far as we know, there are no experimental data on the adsorption equilibrium of dilute pentavalent Sb ions on metal oxides. Therefore, the pH dependence of the adsorption of pentavalent Sb ions on hematite was measured. Carrier-free pentavalent Sb-119 ions were adsorbed on 30 mg of hematite (prefired at 900°C for 2 hours) from 10 cm3 of 0.25 mol/dm3 LiCl solutions at 24 1°C. The amount of antimony employed in each run is estimated to be about 50 ng. The adsorption proceeds with a measurable rate and attains an apparent equilibrium after shaking for several hours. The reaction is second order with respect to the concentration of pentavalent Sb ions in the solution (13) The values given in Figure 4 are those obtained after 22 hours equilibration. As seen in Figure 4, strong adsorption of pentavalent Sb ions is observed below pH 7, while the percent adsorbed diminishes abruptly above that. Most of the Sb ions adsorbed on hematite from solutions of pH 2-5 are not desorbed by subsequent adjustment to alkaline conditions. Results on desorption of Sb ions pre-adsorbed at pH 4 are shown in Figure 4. 

Adsorption Methods. Five grams of hematite were first conditioned in 0.001 M NaCl at pH 4.1. After the SDS had been added to the slurry and the pH adjusted as required, the samples were conditioned on a rotating shaker for two hours. The solutions were then centrifuged, and the supernatant liquid analyzed for its SDS content. The amount of SDS adsorbed was calculated as the difference between the initial amount added and the residual amount measured. Experimental results showed that two hours was sufficient time for equilibrium to be reached. Somasundaran ( ) observed similar equilibrium adsorption times for sulfonate adsorption on aluminum oxide. 

There are structural analogues of a number of iron oxides in the Fe-H-O system. Under certain conditions, continuous solid solutions exist between the two members of a pair. The magnetite-ulvospinel and the hematite-ilmenite pairs are well-known examples. The principle in going from the Fe oxide to the Ti-containing phase is to replace two Fe by one Fe" and one Ti , thereby increasing the unit cell size. 

Hematite, wiistite, maghemite and magnetite are semiconductors magnetite displays almost metallic properties. For a compound to be a semiconductor, the essential characteristic is that the separation between the valence band of orbitals and the conduction band is less than 5 eV this condition is met for the above oxides. In a semiconductor the Fermi level (i. e. the level below which all electron energy levels are filled) lies somewhere between the valence band and the conduction band. 

There are only a few cases where the dissolution of an iron oxide by all three types of processes under comparable conditions has been investigated. Banwart et al. (1989) found that at pH 3, the rate of dissolution of hematite increased in the order, protonation < complexation < reduction with a factor of 350 between the extremes. A similar factor (400) was found for goethite (Zinder et al, 1986) (Fig. 12.15). Hematite dissolution processes were also compared in the pH range similar to that found in neutral environments (Fig. 12.16). Again, dissolution by simple protonation was extremely slow, whereas reduction, especially when aided by Fe complexing ligands, was particularly effective (Banwart et al, 1989). It can, thus, be concluded that reduction, particularly when assisted by protonation and complexation will be the main mechanism for Fe transport in global ecosystems. 

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