| Summary: | This work describes the mathematical modeling of the thermal decomposition of the complex compound [Ni(En)<sub>3</sub>](ClO<sub>4</sub>)<sub>2</sub> (En = C<sub>2</sub>H<sub>8</sub>N<sub>2</sub> = ethylenediamine) in an inert atmosphere under non-isothermal conditions. This process is characterized by several simultaneous and intense stages: elimination of ethylenediamine from the nickel coordination sphere, decomposition of perchlorate anions, and explosive-like oxidation of free or bound ethylenediamine. These stages overlap and merge into a one step on the differential thermogravimetric curve. Typically, this curve is modeled as a one-stage process during kinetic analysis. In this paper, for the first time, the data from the dynamic mass-spectral thermal analysis and thermogravimetric analysis were modeled using the hybrid genetic algorithm, and the results were compared. A two-stage scheme of [Ni(En)<sub>3</sub>](ClO<sub>4</sub>)<sub>2</sub> thermolysis was proposed and the kinetic parameters for each stage were obtained. It was shown that the decomposition of [Ni(En)<sub>3</sub>](ClO<sub>4</sub>)<sub>2</sub> begins with the elimination of one molecule of ethylenediamine (stage A), then the perchlorate anions quickly decompose with the evolution of oxygen (stage B). We believe that the resulting <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mrow><mi>ClO</mi></mrow><mrow><mn>4</mn><mo>−</mo><mi mathvariant="normal">x</mi></mrow><mo>−</mo></msubsup></mrow></semantics></math></inline-formula> (x = 1–3), as stronger oxidizing agents, instantly start an explosive-like exothermic process of ethylenediamine oxidation (stage B).
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