998 resultados para IRON 57


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The determination of bi- and trivalent iron in proximity, in mineral waters has gained in significance, on biological and technical grounds. This short paper describes the procedure of the determination of bivalent iron and total iron in a water sample.

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Most of the humic substances which occur in natural waters have an iron content of a few percent, indicated by the mg/1 content of organically-bonded carbon. This iron is apparently bound in a complex with the humic substances, for it quite plainly differs in its chemical and physico-chemical properties from what one would expect from the purely inorganic iron-water system. The deviations range from the solubility to the redox behaviour, and thus are frequently the basis of analytical and technical difficulties. The key to the solution of most of this problem lies in a better understanding of the aforementioned bonds between the iron and the humic substances. This paper studies the iron content of the humic substance concentration from a bog lake sample and the complexing of iron by humic substances from the surface of the bog lake.

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This partial translation of the original paper provides the summary of this study of the mechanism of mass transfer in the formation of hydrothermal deposits of sulphides. For determining the solubility of sulphides of iron, the radioactive isotope Fe59 was used. The solubility of two sulphides was determined.

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These minutes report on colloquium on the methodology of radiation measurement under water. The meeting was held on 3-5 January 1957, at the Biological Station, Lunz, Austria. The participants of the colloquium discussed various methodologies of radiation measurements, basic methods such as Secchi Disc and underwater photometer as well as specialist equipment like the absolute radiation apparatus.

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Absolute f-values for 7 transitions in the first spectra of 4 elements have been measured using the atomic beam absorption technique. The equivalent widths of the absorption lines are measured with a photoelectric scanner and the atomic beam density is determined by continuously weighing a part of it with a sensitive automatic microbalance. The complete theory is presented and corrections are calculated to cope with gas absorption by the deposit on the microbalance pan and atoms which do not stick to the pan. An additional correction for the failure of the assumption of effusive flow in the formation of the atomic beam at large densities has been measured experimentally.

The following f-values were measured:

Fe: fλ3720 = 0.0430 ± 8%

Cu: fλ3247 = 0.427 ± 4.5%, fλ3274 = 0.206 ± 4.7%, fλ2492 = 0.0037 ± 9%

Cd: fλ3261 = 0.00190 ± 7%, fλ2288 = 1.38 ± 12%

Au: fλ2428 = 0.283 ± 5.3%

Comparison with other accurately measured f-values, where they exist, shows agreement within experimental errors.

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A study of the geochemical cycling of iron and manganese in a seasonally stratified lake, Esthwaite water is described. This work is based on speculative ideas on environmental redox chemistry of iron which were proposed by C.H. Mortimer in the 1940's. These observations have been verified and some speculations confirmed, along with a new understanding of the manganese cycle, and detailed information on the particulate forms of both iron and manganese. Details on the mechanisms and transformations of iron have also emerged.

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Several new ligand platforms designed to support iron dinitrogen chemistry have been developed. First, we report Fe complexes of a tris(phosphino)alkyl (CPiPr3) ligand featuring an axial carbon donor intended to conceptually model the interstitial carbide atom of the nitrogenase iron-molybdenum cofactor (FeMoco). It is established that in this scaffold, the iron center binds dinitrogen trans to the Calkyl anchor in three structurally characterized oxidation states. Fe-Calkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-Calkyl interaction. The anionic (CPiPr3)FeN2- species can be functionalized by a silyl electrophile to generate (CPiPr3)Fe-N2SiR3. This species also functions as a modest catalyst for the reduction of N2 to NH3. Next, we introduce a new binucleating ligand scaffold that supports an Fe(μ-SAr)Fe diiron subunit that coordinates dinitrogen (N2-Fe(μ-SAr)Fe-N2) across at least three oxidation states (FeIIFeII, FeIIFeI, and FeIFeI). Despite the sulfur-rich coordination environment of iron in FeMoco, synthetic examples of transition metal model complexes that bind N2 and also feature sulfur donor ligands remain scarce; these complexes thus represent an unusual series of low-valent diiron complexes featuring thiolate and dinitrogen ligands. The (N2-Fe(μ-SAr)Fe-N2) system undergoes reduction of the bound N2 to produce NH3 (~50% yield) and can efficiently catalyze the disproportionation of N2H4 to NH3 and N2. The present scaffold also supports dinitrogen binding concomitant with hydride as a co-ligand. Next, inspired by the importance of secondary-sphere interactions in many metalloenzymes, we present complexes of iron in two new ligand scaffolds ([SiPNMe3] and [SiPiPr2PNMe]) that incorporate hydrogen-bond acceptors (tertiary amines) which engage in interactions with nitrogenous substrates bound to the iron center (NH3 and N2H4). Cation binding is also facilitated in anionic Fe(0)-N2 complexes. While Fe-N2 complexes of a related ligand ([SiPiPr3]) lacking hydrogen-bond acceptors produce a substantial amount of ammonia when treated with acid and reductant, the presence of the pendant amines instead facilitates the formation of metal hydride species.

Additionally, we present the development and mechanistic study of copper-mediated and copper-catalyzed photoinduced C-N bond forming reactions. Irradiation of a copper-amido complex, ((m-tol)3P)2Cu(carbazolide), in the presence of aryl halides furnishes N-phenylcarbazole under mild conditions. The mechanism likely proceeds via single-electron transfer from an excited state of the copper complex to the aryl halide, generating an aryl radical. An array of experimental data are consistent with a radical intermediate, including a cyclization/stereochemical investigation and a reactivity study, providing the first substantial experimental support for the viability of a radical pathway for Ullmann C-N bond formation. The copper complex can also be used as a precatalyst for Ullmann C-N couplings. We also disclose further study of catalytic Calkyl-N couplings using a CuI precatalyst, and discuss the likely role of [Cu(carbazolide)2]- and [Cu(carbazolide)3]- species as intermediates in these reactions.

Finally, we report a series of four-coordinate, pseudotetrahedral P3FeII-X complexes supported by tris(phosphine)borate ([PhBP3FeR]-) and phosphiniminato X-type ligands (-N=PR'3) that in combination tune the spin-crossover behavior of the system. Low-coordinate transition metal complexes such as these that undergo reversible spin-crossover remain rare, and the spin equilibria of these systems have been studied in detail by a suite of spectroscopic techniques.

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Póster presentado en The Energy and Materials Research Conference - EMR2015 celebrado en Madrid (España) entre el 25-27 de febrero de 2015

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Front cover. Contents.

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Charles Darwin Foundation for the Galapagos Islands. Map