三(O,O′-二异丙基二硫代磷酸酯)合钴(Ⅲ)和双(O,O′-二乙基二硫代磷酸酯)合镍(Ⅱ)及其吡啶加合物的热行为和热分解反应动力学

THERMAL BEHAVIOR AND DECOMPOSITION KINETICS OF TRI(O, O′ DIISOPROPYLDITHIOPHOSPHATE) COBALT(Ⅲ) AND BIS(O, O′ DIETHYLDITHIOPHOSPHATE) NICKEL (Ⅱ) AND ITS ADDUCTS WITH PYRIDINE

用ＴＧ－ＤＴＧ－ＤＳＣ热分析技术研究了三（Ｏ，Ｏ′－二异丙基二硫代磷酸酯）合钴（Ⅲ）、双（Ｏ，Ｏ′－二乙基二硫代磷酸酯）合镍（Ⅱ）及其后者与吡啶或４－甲基吡啶加合物在氮气气氛中的热行为；用传统的微商法（Ａ－Ｂ－Ｓ）和积分法（Ｃ－Ｒ法）以及分别由Ｍａｌｅｋ、Ｄｏｌｌｉｍ ｏｒｅ 提出的两种新型的热分析动力学方法协同处理ＴＧ 数据，获得了四种配合物的热分解反应动力学参数Ｅ和Ａ，确定了反应机理。对它们的热行为和分子结构之间的关系进行了讨论；并试就本文所用的几种数据处理方法作了比较。

Thermal behavior of tri(O, O′ diisopropyldithiophosphate) cobalt (Ⅲ), Co(dptp) 3 and bis(O, O′ diethyldithiophosphate) nicke (Ⅱ), Ni(detp) 2 and its adducts with pyridine Ni(detp) 2(Py) 2, or 4 methylpyridine, Ni(detp) 2(MPy) 2 in a dynamic nitrogen atmosphere was investigated by TG DTG and DSC techniques. Some conventional kinetic methods: differential method (Achar Brindley Sharp method) and integral method (Coats Redfern method), and two newly proposed kinetic methods by Malek and Dollimore respectively were jointly used to process the TG data to obtain the thermal decomposition kinetic parameters, E and A to determine the kinetic model functions for all title complexes. In addition, their thermal behavior and decomposition patterns were discussed and interpreted in terms of their structural features. Finally, the four kinetic methods used in the present paper were compared.$$$$