Ferric ion reduction

Ferric-ion complexes are important in acid-sulfate leaching because ferric ion can be generated from fenous ion using air or oxygen in situ. The reduction of ferric iron to ferrous occurs as the ferric-ion complex diffuses through fluid-filled pores and channels in the rock matrix and encounters reactive metals or sulfides. In most instances, as already discussed, the rate of ferric ion reduction is a diffusion-limited process. The oxidation of ferrous iron to ferric in aqueous solution becomes of primary importance because of its in situ regeneration capacity under appropriate oxidation potentials. 

Historically, ferrous sulfamate, Fe(NH2S02)2, was added to the HNO scmbbing solution in sufficient excess to ensure the destmction of nitrite ions and the resulting reduction of the Pu to the less extractable Pu . However, the sulfate ion is undesirable because sulfate complexes with the plutonium to compHcate the subsequent plutonium purification step, adds to corrosion problems, and as SO2 is an off-gas pollutant during any subsequent high temperature waste solidification operations. The associated ferric ion contributes significantly to the solidified waste volume. 

Bromide ndIodide. The spectrophotometric determination of trace bromide concentration is based on the bromide catalysis of iodine oxidation to iodate by permanganate in acidic solution. Iodide can also be measured spectrophotometricaHy by selective oxidation to iodine by potassium peroxymonosulfate (KHSO ). The iodine reacts with colorless leucocrystal violet to produce the highly colored leucocrystal violet dye. Greater than 200 mg/L of chloride interferes with the color development. Trace concentrations of iodide are determined by its abiUty to cataly2e ceric ion reduction by arsenous acid. The reduction reaction is stopped at a specific time by the addition of ferrous ammonium sulfate. The ferrous ion is oxidi2ed to ferric ion, which then reacts with thiocyanate to produce a deep red complex. 

The yield of 3-hydroxyquinoline relative to the amount of quinoline consumed is low but is increased markedly by the presence of ascorbic acid. This was attributed to the regeneration of ferrous ions by reduction of the ferric ion formed in the first step of the reaction. 

The reaction between ferric ion, Fe+3, and cuprous ion, Cu+, to produce ferrous ion, Fe+2, and cupric ion, Cu+2, is plainly an oxidation-reduction reaction ... 

Because of the presence of Cu+ ion, ferric ion is reduced. Chemists say that Cu+ ion acts as a reducing agent in this reaction—Cu+ ion is the agent that caused the reduction of ferric ion. At the same time, Cu+ is oxidized because of the presence of ferric ion. Hence, Fe+ is called an oxidizing agent in this reaction. 

The extent to which natural systems are described by the Nemst equation depends on the relative rates at which electrons are transferred to and from various substances. These rates vary over several orders of magnitude. For example, the reduction of the hydrated ferric ion. 

Samec Z, Weber J (1972) Reduction of ferric ion on a rotating platinum electrode of the turbulent type in the presence and absence of adsorbed sulfur. J Electroanal Chem Interfacial Electrochem 38 115-126... 

The reduction of iodine by Fe(II) is, of course, the reverse of the ferric ion-iodide ion reaction (p. 408) and it influences the kinetics of the latter. However, the direct reaction has been studied, the rate expression being ... 

Indeed, when present in concentrations sufficient to overwhelm normal antioxidant defences, ROS may be the principal mediators of lung injury (Said and Foda, 1989). These species, arising from the sequential one-electron reductions of oxygen, include the superoxide anion radical, hydrogen peroxide, hypochlorous ions and the hydroxyl radical. The latter species is thought to be formed either from superoxide in the ptesence of iron ions (Haber-Weiss reaction Junod, 1986) or from hydrogen peroxide, also catalysed by ferric ions (Fenton catalysis Kennedy et al., 1989). 

Oxidation- reduction An inert metal dips into a solution containing ions in two different oxidation states. An example consists of a platinum wire dipping into a solution containing ferrous and ferric ions. Such a cell is described by Pt Fe2 (c,). Fe3 (c2). The comma is used to separate the two chemical species which are in the same solution. These electrodes are similar to the gas electrodes, except that the two species involved in the electrode reaction are ions. The electrode reaction in the example is Fe3 + e Fe2, and there is the possibility of the electrode either donating or accepting electrons. 

The data of Table 6.11 create a wealth of information on the free energies of inorganic reactions. Although reported as emfs, these data are readily transformed into free energies by the expression AG° = —n i it. Such free-energy data are of considerable utility in determining equilibrium properties and, in particular, the equilibrium constant for the overall cell reaction. The possibility of the reduction of ferric ion to ferrous ion by zinc as a reduct-ant is considered as an example. The reaction in which one would be interested might be executed in the cell... 

Biochemical waste transformation occurred at low waste concentrations, resulting in the production of methane. Additional microbial degradation of the waste resulted in the reduction of sulfates to sulfides and ferric ions to ferrous ions. 

Except for deposition of Prussian blue from the mixture of ferric and ferricya-nide ions, its electrosynthesis from the single ferricyanide solution is reported [13]. Ferricyanide ions are not extremely stable even in aqueous solution, which is noticed in the change of color after a few days of storage. Thus, the coordination sphere can be destroyed also in the course of electrochemical reactions. The mentioned processes may lead to formation of ferric-ferricyanide complex or free ferric ions. The reduction of the resulting mixture leads to the formation of Prussian blue. 

Of course, superoxide may reduce ferric to ferrous ions and by this again catalyze hydroxyl radical formation. Thus, the oxidation of ferrous ions could be just a futile cycle, leading to the same Fenton reaction. However, the competition between the reduction of ferric ions by superoxide and the oxidation of ferrous ions by dioxygen depends on the one-electron reduction potential of the [Fe3+/Fe2+] pair, which varied from +0.6 to —0.4 V in biological systems [173] and which is difficult to predict.)... 

On the other hand, the formation of radicals from hydroperoxides and ferrous ion is a reduction reaction apparently uncomplicated by any catalytic effect of the ferric ion produced.462... 

One of the most ingenious ways in which corrosion is inhibited is to strap a power pack to each leg (just above the level of the sea) and apply a continuous reductive current. An electrode couple would form when a small portion of the iron oxidizes. The couple would itself set up a small voltage, itself promoting further dissolution. The reductive current coming from the power pack reduces any ferric ions back to iron metal, which significantly decreases the rate at which the rig leg corrodes. 

Most commonly, iron is discussed as being in either the ferrous (Fe2+) or ferric (Fe3+) state. Changes between these two depend on the soil s pH and Eh (where Eh is a measure of the oxidation-reduction potential of soil) as discussed in Chapter 9. Add conditions and low Eh values tend to lead to the production of ferrous ion, while high pH and high Eh values result in the predominance of ferric ion. It should be noted that the ferrous ion is more soluble than the ferric ion and, thus, it will be more available to plants. 

In the simplest case in which the trivalent Fe-57 ions are completely incorporated into the cooperative antiferromagnetic system of the bulk substrate, the Fe-57 ions are expected to align parallel or antiparallel to the magnetic ions of the substrate in a similar manner as the ferric ions of the substrate. When the trivalent Fe-57 ions are on the surface, however, their magnetization is considered to be reduced to some extent due to reduction in the number of neighboring magnetic metal ions interacting with them. 

Worked Example 3.15. An electrochemical charge of 96.5 C is passed through an aqueous solution of ferric ion, thus causing the reduction reaction Fe " " -I-e Fe ". The solution originally contained 0.01 mol of Fe. How much ferric ion remains after the passage of current ... 

The energetics of peptide-porphyrin interactions and peptide ligand-metal binding have also been observed in another self-assembly system constructed by Huffman et al. (125). Using monomeric helices binding to iron(III) coproporphyrin I, a fourfold symmetric tetracarboxylate porphyrin, these authors demonstrate a correlation between the hydropho-bicity of the peptide and the affinity for heme as well as the reduction potential of the encapsulated ferric ion, as shown in Fig. 12. These data clearly demonstrate that heme macrocycle-peptide hydrophobic interactions are important for both the stability of ferric heme proteins and the resultant electrochemistry. 

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