Water redox potentials

The coordination chemistry of vanadium is strongly influenced by the oxidizing/reducing properties of the metallic centre, and the chemistry of vanadium ions in aqueous solution is limited to oxidation states +2, +3, +4 and +5, although V2+ can reduce water. Redox potentials are given in Table 1 and an E vs. pH diagram is shown in Figure 1. 

Under aerobic conditions the redox potential deviates widely from the potentials of soil redox couples. In anaerobic soils, redox potentials may be more quantitatively related to ion activities. The Fe24" and perhaps Mn2+ concentrations are high and tend to dominate the redox potential. The range of redox potentials that have been measured in soils is shown in Fig. 4.7. The envelope around those data was considered by the investigators to be the extreme limits of likely redox potentials and pH values in soils and natural waters. Redox potentials can closely approach the H+-H2 potential, because it is nearly reversible at the platinum electrode. 

When combining the RuOEP CO with a transition metal, such as ruthenium or platinum, the bandedge shift increases up to 0.48 electron volts (eV) in the positive direction. These combination treatments allowed overlap of the water redox potentials to occur in the dark. The effect of pH on the flat band potential of an untreated electrode and... 

Drastic change in ground water redox potential. Depending on the nature of change there are oxidation and reduction brirriers. Oxidation barrier is usually caused by penetration in the subsurface of surface water rich in O. Reduction barrier is usually associated with penetration of deep no-oxygen water to the surface. 

Hence, the reduction and oxidation potentials depend in the same way on the pH as the band positions, i.e., by —59 mV per pH unit. This means that the band positions of most metal oxides are fixed with respect to the water redox potentials. 

Band edges that straddle the water redox potentials... 

Honeyman, B.D., R.A. Hamish, T. McKibben, J.R. Spear, and S. Winkler. 1999. Actinide migration studies at the Rocky Rats Environmental Technology Site The effect of soil-water redox potential on 239,240py solubility. Report to Kaiser-Hill, Rocky Flats Environ. Technol. Site. 

When the water ligands around a cation are replaced by other ligands which are more strongly attached, the redox potential can change dramatically, for example for the cobalt(II)-cobalt(III) system we have... 

In an aquo-complex, loss of protons from the coordinated water molecules can occur, as with hydrated non-transition metal ions (p. 45). To prevent proton loss by aquo complexes, therefore, acid must usually be added. It is for these conditions that redox potentials in Chapter 4 are usually quoted. Thus, in acid solutions, we have... 

As a result, the electromotive force (EMF) of the cell is zero In the presence of fluoride ions, cerium(IV) forms a complex with fluoride ions that lowers the cerium(IV)-cerium(IIl) redox potential The inner half-cell is smaller, and so only 5 mL of cerium(IV)-cenum (III) solution is added To the external half-cell, 50 mL of the solution is added, but the EMF of the cell is still zero When 10 mL of the unknown fluonde solution is added to the inner half-cell, 100 mL of distilled water IS added to the external half-cell The solution in the external half-cell is mixed thoroughly by turning on the stirrer, and 0 5 M sodium fluonde solution is added from the microburet until the null point is reached The quantity of known fluonde m the titrant will be 10 times the quantity of the unknown fluoride sample, and so the microburet readings must be corrected prior to actual calculations... 

The term aggressive is often used to imply some approximately quantitative estimate of the likelihood of corrosion and depends on measuring factors such as soil water (resistivity), pH, redox potential, salt concentrations and bacterial populations in order to establish criteria for the prediction of corrosion rates . Similar measurements for predicting corrosion... 

The precautions generally applicable to the preparation, exposure, cleaning and assessment of metal test specimens in tests in other environments will also apply in the case of field tests in the soil, but there will be additional precautions because of the nature of this environment. Whereas in the case of aqueous, particularly sea-water, and atmospheric environments the physical and chemical characteristics will be reasonably constant over distances covering individual test sites, this will not necessarily be the case in soils, which will almost inevitably be of a less homogeneous nature. The principal factors responsible for the corrosive nature of soils are the presence of bacteria, the chemistry (pH and salt content), the redox potential, electrical resistance, stray currents and the formation of concentration cells. Several of these factors are interrelated. 

Ultraviolet spectroscopy metal in water complexes, 2, 309 redox potentials and, 1,498 Ultraviolet-visible spectroscopy, 1, 243 Umbellicomplexone metallofluorescent indicator, 1. 558 Undecametallic complexes, 1, 167 Uni thiol chelating agent heavy metal poisoning, 6. 767 Unsaturated compounds hydrogenation... 

The Table shows a great spread in Kd-values even at the same location. This is due to the fact that the environmental conditions influence the partition of plutonium species between different valency states and complexes. For the different actinides, it is found that the Kd-values under otherwise identical conditions (e.g. for the uptake of plutonium on geologic materials or in organisms) decrease in the order Pu>Am>U>Np (15). Because neptunium is usually pentavalent, uranium hexavalent and americium trivalent, while plutonium in natural systems is mainly tetravalent, it is clear from the actinide homologue properties that the oxidation state of plutonium will affect the observed Kd-value. The oxidation state of plutonium depends on the redox potential (Eh-value) of the ground water and its content of oxidants or reductants. It is also found that natural ligands like C032- and fulvic acids, which complex plutonium (see next section), also influence the Kd-value. 

In Figure 2 the solubility and speciation of plutonium have been calculated, using stability data for the hydroxy and carbonate complexes in Table III and standard potentials from Table IV, for the waters indicted in Figure 2. Here, the various carbonate concentrations would correspond to an open system in equilibrium with air (b) and closed systems with a total carbonate concentration of 30 mg/liter (c,e) and 485 mg/liter (d,f), respectively. The two redox potentials would roughly correspond to water in equilibrium wit air (a-d cf 50) and systems buffered by an Fe(III)(s)/Fe(II)(s)-equilibrium (e,f), respectively. Thus, the natural span of carbonate concentrations and redox conditions is illustrated. 

Hostettler, J. D. (1984). Electrode reaction, aqueous electrons, and redox potentials in natural waters. Am. J. Sci. 284,734-759. 

Therefore, polysulfide ions play a major role in the global geological and biological sulfur cycles [1, 2]. In addition, they are reagents in important industrial processes, e.g., in desulfurization and paper production plants. It should be pointed out however that only sulfide, elemental sulfur and sulfate are thermodynamically stable under ambient conditions in the presence of water, their particular stabihty region depending on the redox potential and the pH value [3] ... 

Results from other studies support the rapid degradation of methyl parathion in soils with a high water (i.e., low oxygen) content (Adhya et al. 1981, 1987 Brahmaprakash et al. 1987). Experiments in flooded and nonflooded soils showed that the redox potential affected both the rate of degradation and the transformation products of methyl parathion (Adhya et al. 1981, 1987). Transformation to volatile products was suggested by Brahmaprakash et al. (1987) as the reason that significant amounts of " C from labeled methyl parathion could not be accounted for, especially in flooded soils. 

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