A general kinetic model for industrially significant cumene oxidation and cumene hydroperoxide decomposition in the presence of Zn, Cd or Hg 2-ethylhexanoate as catalyst was developed. The model was based on the mass action law, in the form of a stiff system of nonlinear differential equations describing the rates of change in the concentrations of all species in the reaction mixture during the processes. Physically substantiated values of the unknown coefficients of the model (the coefficients of the temperature dependencies of the reaction rate constants) were found as a result of solving the inverse problem. It was done by minimizing the average relative error (using the method of direct search of the zero order) between the data calculated as a result of the numerical solving of the model by the implicit BDF method and the experimental data. The analysis of model sensitivity to changes of its coefficients has been carried out. Through this analysis, the original model is reduced to a simplified form, more convenient for studying the kinetic regularities and the mechanism of the considered chemical processes. The modification of the original model involved in exception from its equations of the terms containing the coefficients that were found as a result of solving the inverse problem, for which change the model is insensitive. A total of 39 terms were excepted out of 179. Thus, a possible mechanism for the cumene oxidation and cumene hydroperoxide decomposition in the presence of Zn, Cd or Hg 2-ethylhexanoate has been substantiated. The developed model was used to study the catalytic activity and thermal stability of Zn, Cd and Hg 2-ethylhexanoates in cumene oxidation and cumene hydroperoxide decomposition. Computational experiments have shown that the catalytic activity of Zn, Cd and Hg 2-ethylhexanoates in cumene oxidation and cumene hydroperoxide decomposition is caused by formation of intermediate adducts ROOH⋅Cat, which turn to be an additional source of free radicals due to their lower thermal stability compared to the original catalyst and cumene hydroperoxide. This phenomenon can be used for practical purposes to increase the rate of cumene hydroperoxide accumulation during cumene oxidation. The kinetic model presented in the article, can be a starting point (model object) for the development of kinetic models of oxidation processes of other aromatic hydrocarbons, catalyzed by nontransition metals due to the formation of intermediate adducts.

开发了在 Zn、Cd 或 Hg 2-乙基己酸酯作为催化剂存在下，具有工业意义的枯烯氧化和枯烯氢过氧化物分解的一般动力学模型。该模型基于质量作用定律，采用非线性微分方程的刚性系统的形式，描述了反应过程中反应混合物中所有物质浓度的变化率。作为求解逆问题的结果，发现了模型未知系数的物理证实值（反应速率常数的温度相关系数）。它是通过最小化通过隐式 BDF 方法对模型进行数值求解而计算出的数据与实验数据之间的平均相对误差（使用零阶直接搜索的方法）来完成的。对模型对其系数变化的敏感性进行了分析。通过这种分析，将原始模型简化为简化形式，更便于研究所考虑的化学过程的动力学规律和机理。原始模型的修改涉及其方程的异常，其中包含作为求解逆问题的结果发现的系数的项，对于该模型的更改不敏感。在 179 项中总共排除了 39 项。因此，在 Zn、Cd 或 Hg 2-乙基己酸存在下枯烯氧化和枯烯氢过氧化物分解的可能机制已得到证实。所开发的模型用于研究 Zn 的催化活性和热稳定性，枯烯氧化和枯烯氢过氧化物分解中的 Cd 和 Hg 2-乙基己酸酯。计算实验表明，Zn、Cd 和 Hg 2-乙基己酸酯在枯烯氧化和枯烯氢过氧化物分解中的催化活性是由中间加合物 ROOH·Cat 的形成引起的，中间加合物 ROOH·Cat 由于其较低的热量而成为自由基的额外来源。与原始催化剂和枯烯氢过氧化物相比，稳定性更高。这种现象可用于实际目的，以增加枯烯氧化过程中氢过氧化枯烯的积累速率。文章中介绍的动力学模型可以作为其他芳烃氧化过程动力学模型开发的起点（模型对象），由于中间加合物的形成，由非过渡金属催化。