Mass Spectrometric Study of Copper(II) β-Diketonates Vapour Thermolysis Mechanism and Kinetics

A. E. Turgambaeva, A. Bykov, I. Igumenov
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引用次数: 7

Abstract

Vapour thermolysis processes of copper(II) bis-chelate complexes with different β-diketones in the 160-640°C temperature range were studied by using the high-temperature source of a molecular beam with mass spectrometric recording of the gas phase composition directly at the outlet from the thermal reactor. Schemes of a heterogeneous decomposition of these compounds vapour were suggested on the basis of temperature dependences of the thermolysis gaseous products composition. It was established that the mechanisms of thermal conversion of copper(II) complexes with fluorinated and non-fluorinated ligands were not similar. A comparison of the thermal behaviour of the complexes with fluorinated and non-fluorinated ligands in vacuum, hydrogen and oxygen was carried out. Effective values of kinetic parameters in the Arrhenius equation were calculated for the first-order reaction on initial compound from the temperature dependence of the rate constant. The sequence of copper(II) complexes with β-diketones having different end substituents according to the thermal stability was revealed from the values of the thermal decomposition activation energy.
铜(II) β-二酮酸酯蒸气热裂解机理及动力学的质谱研究
采用分子束高温源,研究了不同β-二酮铜(II)双螯合物在160 ~ 640℃温度范围内的蒸汽热裂解过程,并在热反应器出口直接用质谱法记录了气相组成。根据热分解产物组成的温度依赖性,提出了这些化合物蒸汽的非均相分解方案。结果表明,铜(II)配合物与氟化配体和非氟化配体的热转化机理不相似。比较了含氟和非氟配体配合物在真空、氢和氧条件下的热行为。根据反应速率常数的温度依赖性,计算了初始化合物一级反应的动力学参数有效值。根据热分解活化能的值,揭示了铜(II)配合物与端取代基不同的β-二酮配合物的热稳定性顺序。
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