Manganese oxidation rate

Since Mn is both soluble in iron oxides and mobile to the same extent as Fe, the addition of Mn to steels has little effect on the overall scaling rate in air or oxygen. Jackson and Wallwork have shown that between 20% and 40% manganese must be added to steel before the iron oxides are replaced by manganese oxides. However, Mn supresses breakaway oxidation in CO/CO2 possibly by reducing the coalescence of pores in the oxide scale. 

Backes C.A., McLaren R.G., Rate A.W., Swift R.S. Kinetics of cadmium and cobalt desoprtion from iron and manganese oxides. Soil Sci Soc Am J 1995 59 778-785. 

Terrestrial plants take up nickel from soil primarily via the roots (NRCC 1981 WHO 1991). The nickel uptake rate from soil is dependent on soil type, pH, humidity, organic content, and concentration of extractable nickel (NAS 1975 WHO 1991). For example, at soil pH less than 6.5 nickel uptake is enhanced due to breakdown of iron and manganese oxides that form stable complexes with nickel (Rencz and Shilts 1980). The exact chemical forms of nickel that are most readily accumulated from soil and water are unknown however, there is growing evidence that complexes of nickel with organic acids are the most favored (Kasprzak 1987). In addition to their uptake from the soils, plants consumed by humans may receive several milligrams of nickel per... 

The processes described and their kinetics is of importance in the accumulation of trace metals by calcite in sediments and lakes (Delaney and Boyle, 1987) but also of relevance in the transport and retention of trace metals in calcareous aquifers. Fuller and Davis (1987) investigated the sorption by calcareous aquifer sand they found that after 24 hours the rate of Cd2+ sorption was constant and controlled by the rate of surface precipitation. Clean grains of primary minerals, e.g., quartz and alumino silicates, sorbed less Cd2+ than grains which had surface patches of secondary minerals, e.g., carbonates, iron and manganese oxides. Fig. 6.11 gives data (time sequence) on electron spin resonance spectra of Mn2+ on FeC03(s). 

Based upon thermodynamic data given in Table I, oxidant strength decreases in the order NijO > Mn02 > MnOOH > CoOOH > FeOOH. Rates of reductive dissolution in natural waters and sediments appear to follow a similar trend. When the reductant flux is increased and conditions turn anoxic, manganese oxides are reduced and dissolved earlier and more quickly than iron oxides (12, 13). No comparable information is available on release of dissolved cobalt and nickel. 

Experiments examining the influence of calcium and phosphate on the reductive dissolution of manganese oxides by hydroquinone have, in fact, shown inhibition by adsorbed ions (33). As the total phosphate in solution is increased, the rate of Mn + release diminished in proportion to the phosphate surface coverage. 

The most direct evidence for surface precursor complex formation prior to electron transfer comes from a study of photoreduc-tive dissolution of iron oxide particles by citrate (37). Citrate adsorbs to iron oxide surface sites under dark conditions, but reduces surface sites at an appreciable rate only under illumination. Thus, citrate surface coverage can be measured in the dark, then correlated with rates of reductive dissolution under illumination. Results show that initial dissolution rates are directly related to the amount of surface bound citrate (37). Adsorption of calcium and phosphate has been found to inhibit reductive dissolution of manganese oxide by hydroquinone (33). The most likely explanation is that adsorbed calcium or phosphate molecules block inner-sphere complex formation between metal oxide surface sites and hydroquinone. 

The importance of bacteria in mediating Mn(II) oxidation in certain environments is evident. But, the mechanisms whereby bacteria oxidize Mn(II) are poorly understood. Some bacteria synthesize proteins or other materials that enhance the rate of Mn(II) oxidation (.52). Other strains of bacteria require oxidized manganese to oxidize Mn(II) (53), suggesting that they may catalyse the oxidation of Mn(II) on the manganese oxide surface. Other bacteria may catalyse the oxidation of Mn(II) on iron oxide surfaces, as iron is associated with manganese deposits on bacteria collected in the eastern subtropical North Pacific (54). 

The rates of Mn(II) removal in some natural waters are similar to the Mn(II) oxidation rates predicted on the basis of these laboratory studies. However, in other cases the rate of manganese removal in natural waters is much faster than that expected on the basis of this work. In these systems significant manganese removal may occur as the result of adsorption, bacterially mediated oxidation, or biological uptake. 

Hem, J.D. "Chemical Equilibria and the Rates of Manganese Oxidation" U.S. Geol. Survey- Water Supply Paper 1667A, 1963. 

Carlson, L. Schwertmann, U. (1981) Natural ferrihydrites in surface deposits from Finland and their association with silica. Geochim. Cosmochim. Acta 45 421-429 Carlson, L. Schwertmann, U. (1987) Iron and manganese oxides in Finnish ground water treatment plants. Wat. Res. 21 165-170 Carlson, L. Schwertmann, U. (1990) The effect of CO2 and oxidation rate on the formation of goethite versus lepidocrocite from an Fe(II) system at pH 6 and 7. Clay Min. 25 65-71... 

A similar oxidation-reduction mechanism in the carbon monoxide oxidation reaction on oxide catalysts has been proposed by Benton (71), Bray (72), Frazer (73), and Schwab (74). In this reaction also, Mooi and Selwood (57) found that a decrease in the percentage of iron oxide, manganese oxide or copper oxide on the alumina support first increased the rate, and then at lower percentages decreased the rate, of carbon monoxide oxidation, indicating that valence stabilization is again operative in these cases. 

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