Reduction of Fe

The cathodic reaction (the right-hand cell) is the reduction of Fe + to Fe +... 

Reduction of Fe + to Fe + occurs at the working electrode, making it the cathode in the electrochemical cell. 

Any Fe + lost in this fashion must be replaced by the additional reduction of Fe +, reducing the current efficiency and increasing the time needed to reach the titration s end point. The net result is that the reported concentration of Cr207 is too large. 

Schematic showing transport of Fe(CN)6 toward the electrode and Fe(CN)6 away from the electrode following the reduction of Fe(CN)6 -.

Xanthine oxidase, mol wt ca 275,000, present in milk, Hver, and intestinal mucosa (131), is required in the cataboHsm of nucleotides. The free bases guanine and hypoxanthine from the nucleotides are converted to uric acid and xanthine in the intermediate. Xanthine oxidase cataly2es oxidation of hypoxanthine to xanthine and xanthine to uric acid. In these processes and in the oxidations cataly2ed by aldehyde oxidase, molecular oxygen is reduced to H2O2 (133). Xanthine oxidase is also involved in iron metaboHsm. Release of iron from ferritin requires reduction of Fe " to Fe " and reduced xanthine oxidase participates in this conversion (133). 

In this work, a method based on the reduction potential of ascorbic acid was developed for the sensitive detennination of trace of this compound. In this method ascorbic acid was added on the Cr(VI) solution to reduced that to Cr(III). Cr(III) produced in solution was quantitatively separated from the remainder of Cr(VI). The conditions were optimized for efficient extraction of Cr(III). The extracted Cr(III) was finally mineralized with nitric acid and sensitively analyzed by electro-thermal atomic absorption spectrometry. The determinations were carried out on a Varian AA-220 atomic absolution equipped with a GTA-110 graphite atomizer. The results obtained by this method were compared with those obtained by the other reported methods and it was cleared that the proposed method is more precise and able to determine the trace of ascorbic acid. Table shows the results obtained from the determination of ascorbic acid in two real samples by the proposed method and the spectrometric method based on reduction of Fe(III). 

Cr(VI)] increase the rate by raising the potential of the alloy into the transpassive region, the converse applies in the acid (Fe2(S04)j test, since reduction of Fe to Fe during the test will result in a decrease in the redox potential and the whole sample will corrode with hydrogen evolution. 

The electronic absorption spectra of the products of one-electron electrochemical reduction of the iron(III) phenyl porphyrin complexes have characteristics of both iron(II) porphyrin and iron(III) porphyrin radical anion species, and an electronic structure involving both re.sonance forms Fe"(Por)Ph] and tFe "(Por—)Ph has been propo.sed. Chemical reduction of Fe(TPP)R to the iron(II) anion Fe(TPP)R) (R = Et or /7-Pr) was achieved using Li BHEt3 or K(BH(i-Bu)3 as the reductant in benzene/THF solution at room temperature in the dark. The resonances of the -propyl group in the F NMR spectrum of Fe(TPP)(rt-Pr) appear in the upfield positions (—0.5 to —6.0 ppm) expected for a diamagnetic porphyrin complex. This contrasts with the paramagnetic, 5 = 2 spin state observed... 

The reduced alkyl complexes are reoxidized by O2 to the iron(lll) alkyls. The corresponding diamagnetic phthalocyanine iron(ll) alkyl complexes, rFe(Pc)R), were prepared by two-electron reduction of Fe(Pc) by LiAIFl4 to give [Fe(Pc) (actually the Fe(I) phthalocyanine radical anion) followed by reaction with Mel, Etl or i-PrBr. The methyl compound, [Fe(Pc)CHi] was characterized by X-ray crystallography. ... 

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... 

Kashefi K, DR Lovley (2000) Reduction of Fe(lll), Mn(lV), and toxic metals and 100°C by Pyrobaculum islandicum. Appl Environ Microbiol 66 1050-1056. 

Iron was present as Fe " in the calcined precursors. For all the catalysts the reduction procedure described in Sec. 2.1 resulted in incomplete reduction of the Fe to metallic iron. This is in agreement with the findings of previous authors [6,11]. The individual percentage reductions of Fe to Fe°, as determined by the separate gravimetric and volumetric measurements (Sec. 2.2), are shown in Table 1. The values are calculated on the assumption that all the Fe is reduced to Fe prior to the onset of reduction to Fe°. There is good agreement between the two methods. Table 1 also records the actual Fe/(Fe + Mg) ratio in the catalysts as determined by atomic absorption spectroscopy (AAS) on the calcined precursors. 

The release of iron from intracellular ferritin stores is thought to involve the reduction of Fe to Fe " (Funk et al., 1985) and one would expect this reduction to be fecilitated by the low oxygen tension, increased levels of reducing species and the low pH shown by nuclear magnetic resonance (NM to be as low as 6.9 after only 6 h of cold storage (Fuller et al., 1988). Exogenous redox-active quinones such as adriamycin have been shown to catalyse lipid peroxidation in the presence of ferritin under hypoxic conditions (Vile and Winterbourne, 1988), and lipid peroxidation is stimulated in micro-somes in the presence of purified ferritin and flavin... 

The ET reaction between aqueous Fe(CN)g and the neutral species, TCNQ, has been investigated extensively with SECM, in parallel with microelectrochemical measurements at expanding droplets (MEMED) [84], which are discussed in Chapter 13. In the SECM studies, a Pt UME in the aqueous phase generated Fe(CN)g by reduction of Fe(CN)g. TCNQ was selected as the organic electron acceptor, because the half-wave potential for TCNQ ion transfer from DCE to water is 0.2 V more positive than that for ET from Fe(CN)g to TCNQ [85]. This meant that the measured kinetics were not compromised by TCNQ transfer from DCE to the aqueous phase within the potential window of these experiments. 

FIG. 22 Dependence of ET rates on CIO4 concentration in the aqueous phase for the reduction of TCNQ in DCE by aqueous Fe(CN)6. The aqueous phase contained 0.1 M Li2S04 with various concentrations of NaC104, while the DCE phase contained 0.1 M TEIAP. The SECM approach curves for the generation of Fe(CN)6 by the reduction of Fe(CN)g present in the bulk aqueous phase, were obtained with a 25 pm diameter Pt UME. From top to bottom, the first four solid experimental curves are shown for [CIO4 ] = 0.01, 0.025, 0.1, and 0.25 M. For the bottom solid line, there was no TCNQ in the DCE phase. The dashed lines are the corresponding theoretical curves for ki2 = 0.3, 0.2, 0.04, 0.015, and 0 cm s ... 

These observations for Fe(Cp)2 in the presence of the polymer-bound Cr complex are consistent with Fe(Cp)2+, generated electrochemically, undergoing a reaction with Cr(CN-[P])c resulting in the chemical reduction of Fe(Cp)2+ and oxidation of the Cr species. Therefore, when the cathodic part of the Fe(Cp)2 /Fe(Cp)2+ wave is scanned, little ferricenium ion remains to be reduced electrochemically. As a result, the ferrocene molecule has effected the transfer of electrons from the polymer to the electrode. 

The reduction of Fe(III) by carotenoids may have deleterious consequences. The reduced iron Fe(II) can react with hydrogen peroxide leading to the formation of hydroxyl radical, the most reactive free radical encountered in biological systems (Equation 15.10) ... 

In the first experiment 10 ml of 500 ppm solutions of FeCl3 were sonicated for 15, 30, 45 and 60 min. To examine the reduction of Fe(III) to Fe(II), 0.1 ml of the sonicated sample was transferred to a 10 ml volumetric flask and mixed with 0.5 ml of 2,000 ppm K3[Fe(CN)6] solution before making up to the mark with distilled water. Final concentration of this sonicated sample in 10 ml of volumetric flask was 5 ppm. UV-vis absorbance at >.max 795 was recorded. Sonication reduced Fe3+ to Fe2+, which reacted with K3[Fe(CN)6], already added in the solution, to form blue colour due to prussian blue. Continuous sonication gradually increased the concentration and intensity of prussian blue complex, as is clear from the Table 10.1. 

Table. 10.1 Increase in absorbance with sonication due to reduction of Fe(III) to Fe(II)...

In the enterocyte as it enters the absorptive zone near to the villus tips, dietary iron is absorbed either directly as Fe(II) after reduction in the gastrointestinal tract by reductants like ascorbate, or after reduction of Fe(III) by the apical membrane ferrireductase Dcytb, via the divalent transporter Nramp2 (DCT1). Alternatively, haem is taken up at the apical surface, perhaps via a receptor, and is degraded by haem oxygenase to release Fe(II) into the same intracellular pool. The setting of IRPs (which are assumed to act as iron biosensors) determines the amount of iron that is retained within the enterocyte as ferritin, and that which is transferred to the circulation. This latter process is presumed to involve IREG 1 (ferroportin) and the GPI-linked hephaestin at the basolateral membrane with incorporation of iron into apotransferrin. (b) A representation of iron absorption in HFE-related haemochromatosis. 

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