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A. Heiss J. Tardieu De Maleissye V. Viossat K. A. Sahetchian I. G. Pitt 《国际化学动力学杂志》1991,23(7):607-622
The reaction pathways of n-butoxy and s-butoxy radicals have been investigated by TLC and HPLC analysis of end products, particularly peroxides and carbonyl compounds. The butoxy radicals were produced by the pyrolysis of very low concentrations of the corresponding dibutylperoxide in an atmosphere of oxygen and nitrogen, at atmospheric pressure. The decomposition reaction (3) s-BuO → C2H5 + CH3CHO and the reaction (2) s-BuO + O2 → HO2 + CH3COC2H5 have been studied, and the ratio k3/k2 has been determined in the temperature range 363–503 K by kinetic modeling of the formation of the observed acetaldehyde and methylethylketone. The rate constant k3 obtained was: A good agreement was observed between experimental data and RRKM theory. The implications of the results for atmospheric chemistry and combustion are discussed. At room temperature, the reaction with O2, yielding HO2 radicals and methylethylketone is, by far, the main channel for s-BuO radicals. In the field of low temperature combustion, the decomposition of s-BuO radicals producing C2H5 and CH3CHO is the main pathway; the route s-BuO + O2 decreases tremendously in importance as the temperature is raised above 393 K. 相似文献
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Pascale Lemoine Vincente Viossat Elie Dayan Dung Nguyen-Huy Bernard Viossat 《Journal of chemical crystallography》2010,40(10):852-858
Abstract
Two ternary complexes of manganese(II) indole-2-carboxylate (2-IC−) or isoquinolinecarboxylate (IQC−) with 1,10-phenanthroline (phen) in methanol or in dimethylacetamide (DMA) were synthesized and studied by X-ray diffraction and IR spectra. [Mn(C9H6NO2)2(C12H8N2)2]·CH4O (1) crystallizes in the triclinic space group P-1 with cell parameters of a = 10.548(2) ?, b = 14.168(3) ?, c = 14.580(3) ?, α = 62.35(2)°, β = 69.16(2)°, γ = 78.61(2)°, V = 1802.4(6) ?3 and Z = 2; [Mn(C10H6NO2)2(C12H8N2)].C4H9NO (2) crystallizes in the monoclinic space group P21/a with cell parameters of a = 15.304(5) ?, b = 12.871(5) ?, c = 17.421(5) ?, β = 114.39(1), V = 3125(2) ?3 and Z = 4. In 1, Mn is six-coordinate by two bidentate phen ligands and two 2-IC− ligands and exhibits a very distorted octahedral geometry. This complex is solvated by methanol involved in hydrogen bonding. In 2, Mn atom is surrounded by one bidentate phen ligand and two bidentate IQC− ligands. The complex exhibits a distorted octahedral geometry around the MnII atom. The crystal structure is completed by a disordered DMA solvate molecule. The IR spectra of both compounds are slightly different in the range 4000–2400 cm−1 which may be attributed to hydrogen bond lack in 2. 相似文献8.
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