气相色谱法研究配合物的热稳定性(ⅩⅤ)-表面配合物热分解动力学方法

Studies on Thermal Stability of Coordination Compounds by Gas Chromatography(XV)-A Kinetic Method for Thermal Decomposition of Surface Complexes

研究了表面配合物的热分解动力学问题,计算了若干MgO的表面Madelung常数,并把H_(2)C_(3)O_(4)-MgO体系的热分解动力学问题转化为均匀表面的迭加问题处理。对于更复杂的体系,基于表面能量的不均匀性,提出了动力学方程。

This paper deals with the kinetic problem of the thermal decomposition of surface coordination compounds.Considering the different influence of various crystal planes,several surface Maderung constants of MgO were computed,and the decomposition kinetics of H_(2)C_(2)O_(4)-MgO system was treated,as an accumulation of homogeneous surfaces For more complicated systems,according to the energetic heterogeneity on the surface,a kinetic equation has been proposed:da/dt=Ae^(-(E+C_(1)α+C_(2)α^(2))/RT)(1-α)^(n) where a denotes the degree of conversion,t the time,Athe frequency factor,Ethe initial activation energy,Rthe gas constant,Tthe temperature,n the reaction order,and C_(1) and C_(2) arc constants.The calculated results arc in agreement with those of experiments.