金属乙酰丙酮酸蒸气热裂解机理的质谱研究

A. Bykov, A. E. Turgambaeva, I. Igumenov, P. P. Semyannikov
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引用次数: 8

摘要

采用高温分子束源,在160 ~ 650℃的温度范围内,研究了乙酰丙酮酸铝(III)和乙酰丙酮酸钪(Al(aa) 3和Sc(aa) 3)的热分解过程,并对反应区出口气相组成进行了质谱采样。提出了乙酰丙酮酸铝(III)和乙酰丙酮酸钪(III)蒸气的热分解方案。确定了这些配合物的共同热裂解机理是由于Mg 2+、Al 3+、Sc 3+和Hf 4+离子具有共同的电子结构。根据该方案,该过程沿着三条平行路线进行,其中一条路线仅适用于具有两个以上配体的配合物,在这种情况下,由配体片段的循环二聚化产生的气体产物形成。建立了氧和氢对气态产物组成的影响以及配合物蒸汽的热分解机理。根据温度曲线,计算了一级反应的动力学参数有效值。
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Mass Spectrometric Study of Thermolysis Mechanism of Metal Acetylacetonates Vapour
The processes of thermal decomposition of aluminium(III) and scandium(III) acetylacetonates (Al(aa) 3 and Sc(aa) 3 ) were investigated in the 160-650°C temperature range using a high-temperature molecular beam source with mass spectrometric sampling of the gas phase composition directly at the outlet from the reaction zone. A scheme of thermal decomposition of aluminium(III) and scandium(III) acetylacetonates vapour is suggested. It is established that the common mechanism of thermolysis of these complexes is due to the commonness of electronic structure of ions Mg 2+ , Al 3+ , Sc 3+ and Hf 4+ . According to the scheme, the process proceeds along three parallel routes, one of them being possible only for complexes possessing more than two ligands, in this case the gaseous products resulting from cyclic dimerization of ligand fragments are formed. The influence of oxygen and hydrogen on the composition of the gaseous products and the mechanism of thermolysis of the complexes vapour are also established. From temperature curves, the effective values of kinetic parameters in Arrhenius equation are calculated for the first order reaction.
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