Fe ion reduction

The cake produced by the digestion is extracted with cold water and possibly with some diluted acids from the subsequent processes. During the cake dissolution it is necessary to maintain the temperature close to 65°C, the temperature of iron sulfate maximum solubiUty. To prevent the reoxidation of the Fe " ions during processing, a small amount of Ti " is prepared in the system by the Ti reduction. The titanium extract, a solution of titanium oxo-sulfate, iron sulfate, and sulfuric acid, is filtered off. Coagulation agents are usually added to the extract to faciUtate the separation of insoluble sludge. 

Iron atoms pass into solution in the water as Fe leaving behind two electrons each (the anodic reaction). These are conducted through the metal to a place where the oxygen reduction reaction can take place to consume the electrons (the cathodic reaction). This reaction generates OH ions which then combine with the Fe ions to form a hydrated iron oxide Fe(OH)2 (really FeO, H2O) but instead of forming on the surface where it might give some protection, it often forms as a precipitate in the water itself. The reaction can be summarised by... 

A sheet of steel of thickness 0.50 mm is tinplated on both sides and subjected to a corrosive environment. During service, the tinplate becomes scratched, so that steel is exposed over 0.5% of the area of the sheet. Under these conditions it is estimated that the current consumed at the tinned surface by the oxygen-reduction reaction is 2 X 10 A m -. Will the sheet rust through within 5 years in the scratched condition The density of steel is 7.87Mg m . Assume that the steel corrodes to give Fe " ions. The atomic weight of iron is 55.9. 

Finally, in a recent study by Walling and El-Taliawi (216) it was shown that solvolytically generated vinyl cations may be reduced by Fe ions in solution to the corresponding vinyl radical. When 2-buten-2-yl triflate was solvolyzed in concentrated ferrous perchlorate solution in the presence of acrylonitrile monomer, polymerization of the acrylonitrile was observed. No such polymerization occurred under identical conditions in the absence of Fe ions. It seems that the polymerization of acrylonitrile was initiated by the vinyl radicals formed by reduction of the intermediate vinyl cation by Fe as follows (216) ... 

Concerning the role of the active site Fe ion, it has been argued that the observed FTIR band shifts (typically 20 cm ) resulting from one-electron redox changes are too small to correspond to metal-based redox processes, whose band shifts should amount to about 100 cm per electron (90, 101). There is, however, one example where the shift in f(CN ) upon one-electron reduction of a Fe(III) center is only of... 

Samec Z, Weber J (1973) The influence of chemisorbed sulfur on the kinetic parameters of the reduction of Fe " ions on a platinum electrode on the basis of the Marcus theory of electron transfer. J Electroanal Chem Interfacial Electrochem 44 229-238... 

The thionine reduction prodnct TH is anodically reoxidized to thionine, while the Fe ions are cathodically rerednced to Fe ions. Thns, the chemical composition of the system will not change dnring cnrrent flow. The potential difference between the electrodes that can be used to extract electrical energy is 0.2 to 0.4 V under current flow. The conversion factor of Inminous to electrical energy is very low in such cells, about 0.1%. This is due to the numerous side reactions, which drastically lower the overall efficiency. Moreover, the stability of such systems is not high. Therefore, the chances for a practical use are not evident so far. 

A similar study was conducted by Dimitrijevi6 et al. with neutral solutions of a-Fe203. The yield of Fe was found to be very low. However, a large Fe yield was found after dissolution of the colloid by hydrochloric acid under an argon atmosphere. This showed that electrons donated by the free radicals penetrated deep into the colloidal particles to reduce iron to F, . Buxton et al. observol in a study on the reductive dissolution of colloidal Fe304 that Fe ions in this material are less readily released into the aqueous phase than reduced Fe ions. 

Fe(III)(hydr)oxides introduced into the lake and formed within the lake - Strong affinity (surface complex formation) for heavy metals, phosphates, silicates and oxyanions of As, Se Fe(III) oxides even if present in small proportions can exert significant removal of trace elements. - At the oxic-anoxic boundary of a lake (see Chapter 9.6) Fe(III) oxides may represent a large part of settling particles. Internal cycling of Fe by reductive dissolution and by oxidation-precipitation is coupled to the cycling of metal ions as discussed in Chapter 9. 

Another example of heterogeneous catalysis by oxo-ions is the one-step oxidation of benzene to phenol with nitrous oxide, N2O. Fe/MFI catalysts have, again been found to be very active. This catalysis was discovered by Iwamoto and has been extensively studied by the group of G. Panov in Novosibirsk. " Preparations of Fe/MFI which appear highly active for this reaction display poor activity for NOj reduction and those which are optimum for that process, are poor for benzene oxidation. This shows that different sites are used. Work by Jia et al. revealed that the active sites for benzene oxidation appear to be Fe-oxo-ions containing only one Fe ion. This does not necessarily mean that the sites are mononuclear. A recent work by Zhu et al. has rather suggested that the site consists of one Fe and one Al + ion, the latter ion having left the zeolite framework. ... 

A comma separates the formulas Fe and Fe for the ions involved in the reduction half-reaction. The formulas are not separated by a vertical line, because there is no phase boundary between these ions. The Fe and Fe " ions exist in the same aqueous solution. 

The most probable levels ered and eox of the reductant and oxidant may be derived from the standard Fermi level, ES)ii Ty>Y. and the reorganization energy, X. As an example. Fig. 2-42 shows the standard Fermi level e e.3,/r,j ) (= - 5.27 eV) with the most probable levels er,2 d hydrated Fe and Fe ions,... 

At this point it is not known if the proton taken up during reduction of Ni is still present. Note that the CN bands in the FTIR spectra do not shift, suggesting no changes in electron density on the Fe ion. The CO band, however, shifts 18 cm to higher frequency. Thus far there is no reasonable explanation for this behaviour we do not yet know where H2 (presumably as H /H+) is precisely bound. As mentioned above, in the presence of mediating dyes, an H2-producing reaction... 

Similar PDOS distribution can be seen on the ZnS surface doped with Fe ions. The dominant state in valence band is Fe (3d) orbital, and the conduction band is composed of S (3p) and Zn (4p) orbital. This result indicates that doping Cu or Fe ions on the ZnS surface reduces the band gap of the ZnS. This kind of reduction will produce lot of surface state in bulk ZnS forbidden band. 

A lot of work show that the existence of Fe ions on solid surface can catalyze the reduction of oxygen. It indicates that the rate of oxygen reduction on marmatite is larger than rate of reduction on (Zn, Cu)S, this will cause the mixed potential of marmatite to be higher than that of (Zn, Cu)S and ZnS. This process can be illustrated in Fig. 9.17. 

However, near-stoichiometric Fe " ion binding to NifU-1 or NifU was observable only in experiments conducted at 2°C in anaerobic samples that had been pretreated with dithiothreitol to ensure reduction of any intrasubunit or intersubunit disulfides. At room temperature, <10% of the NifU-1 or NifU was in a Fe bound form, and colorimetric analysis indicates that the remainder of the Fe is in solution was in the form of free Fe " ion. Hence this mononuclear Fe -bound species is more likely to be an intermediate in the reduction of Fe ion by NifU or NifU-1 rather than an initial step in cluster assembly on the NifU-1 domain of NifU. In this connection, it is important to note that Fe is rapidly reduced to Fe by cysteine in aqueous solution (Schubert, 1932). The physiological significance (if any) of the apparent ferric reductase activity associated with the NifU-1 domain of NifU remains to be established. 

The reduction of U(VI) by sulfate-reducing bacteria appears to occur at the cell surface of the anaerobes, since the reduced products of these elements accumulates in the environment outside of the cell. The proteins of cyt Cs and cyt c have been demonstrated to function as nonspecific metal dehydrogenases however, these cytochromes are found in the periplasm and not in the outer membrane. Thus, if it were analogous to Fe(III) reduction, uranyl ions would most appropriately be reduced by a cytochrome in the outer membrane of the sulfate reducers. As demonstrated by Laishley and Bryant (see Chapter 18) cytochromes are located in the outer membrane of certain sulfate reducers however, their role in reduction of U(VI) remains to be demonstrated. 

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