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.07.015 . 24. Caires , FJ , Lima , LS , Carvalho , CT , Giagio , RJ , Ionashiro , M . Thermal behaviour of malonic acid, sodium malonate and its compounds with some bivalent transition metal ions . Thermochim Acta . 2010

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Abstract  

An ion chromatographic method has been developed for the determination of traces of Li+, Na+, K+, Ca2+, Mg2+, Sr2+, Fe3+, Cu2+, Ni2+, Co2+, Zn2+, Cd2+, Mn2+ in UO2, ThO2 powders and sintered (Th,U)O2 pellets. This new method utilizes poly-(butadiene-maleic acid) (PBDMA) coated silica cation exchange column and mixed functionality column of anion and cation exchange to achieve the separation of alkali, alkaline earths and transition metal ions, respectively. It involves matrix separation after sample dissolution by solvent extraction with TBP (tri butyl phosphate)-TOPO (tri octyl phosphine oxide)/CCl4. Interference of transition metal ions in the determination of alkali, alkaline earth metal ions are removed by using pyridine 2,6-dicarboxylic acid (PDCA) in the tartaric acid mobile phase. Mobile phase composition is optimized for the base line separation of alkali, alkaline earth and transition metal ions. Linear calibration graphs in the range 0.01–20 μg mL−1 were obtained with regression coefficients better than 0.999. The respective relative standard deviations were also determined. Recoveries of the spiked samples are within ±10% of the expected value. The developed method is authenticated by comparison with certified standards of UO2 and ThO2 powders.

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have been used to characterize complexes of bivalent transition metal ions [ 9 , 10 ]. However, they are not found in the literature thermal studies involving all metal-ions with oxamates, as well as the characterization of the gaseous products

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Abstract  

Tracer studies using65Zn and58Co showed that of the four forms ofMethanosarcina hydrogenases, the A form has about 15% of acid labile zinc, while the hydrogenase D has about 50% of cobalt of the total bound activity in the cell and the other two forms B and C have neither zinc nor cobalt. However, all hydrogenases are known to contain iron, sulfur and probably nickel in trace amounts. All air-oxidized forms of hydrogenases catalyze the reduction of methyl viologen after a finite incubation period. The reduction is revealed by an increase in the absorption peak at 602 nm. On -irradiation, all the four hydrogenases changed to more stable oxidized forms, as indicated by an increase in the optical absorption in the visible region at 405 nm. The irradiated samples showed a greater time lag before they could reduce methyl viologen, the time lag increasing with the -dose. The irradiated enzymes could be reactivated by flushing with H2. The zinc-bearing hydrogenase A alone appeared to be immune to -radiation in its ability to reduce methyl viologen. This may be due to the zinc having no unpaired electrons to interact with -radiation or the primary radiolytic products.

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Abstract  

The thermal behaviour of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pd(II) complexes of uracil was studied by TG, DTG and DTA in a dynamic nitrogen atmosphere. Two processes occur in the isolated uracil complexes: dehydration and pyrolytic decomposition. In the hydrated complexes, the first stage observed was the loss of water molecules, which was followed by decomposition of the uracil. The thermal dehydration of the complexes occurred in from one to three steps. The final decomposition products were found to be the respective metal oxides, except in the cases of the Co(II) and Pd(II) complexes, which produced metallic cobalt and palladium, respectively. The order of reaction and energy of activation for the dehydration stage were evaluated.

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Abstract  

The complexes formed by the chemically modified chloromethylated poly(styrene)-PAN (CMPS-PAN) as a resin chelating ion exchanger were characterized by infrared and potentiometry. The thermal degradation of pure CMPS-PAN resin and its complexes with Au3+, Cr3+, Cu2+, Fe3+, Mn2+ and Pt4+ in air atmosphere has been studied using thermal gravimetry (TG) and derivative thermal gravimetry (DTG). The results showed that four different steps accompany the decomposition of CMPS-PAN resin and its complexes with the metal ions. These stages were affected by the presence of the investigated metal ions. The thermal degradation of CMPS-PAN resin in the presence of the ions showed different stability of the resin in the following decreasing order: Au3+>Pt4+>Mn2+>Cu2+>Cr3+>Fe3+. On the basis of the applicability of a non-isothermal kinetic equation, the decomposition process was a first-order reaction. The activation energy, Ea, the entropy change, ΔS *, the enthalpy change, ΔH * and the Gibbs free energy of activation, ΔG * were calculated by applying the theory of the reaction rates. The effect of the different central metal ions on the calculated thermodynamic activation parameters was discussed.

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