TY - JOUR

T1 - The Use of Hybrid Genetic Algorithm in the Kinetic Analysis of Thermal Decomposition of [Ni(C2H8N2)3](ClO4)2 with Overlapping Stages

AU - Dmitruk, Kirill A

AU - Komova, Oksana V

AU - Paletsky, Alexander A

AU - Shmakov, Andrey G

AU - Mukha, Svetlana A

AU - Butenko, Vladislav R

AU - Pochtar, Alena A

AU - Netskina, Olga V

N1 - Funding: This research was funded by the Ministry of Science and Higher Education of the Russian Federation (project No. 075-15-2020-781).

PY - 2023/1

Y1 - 2023/1

N2 - This work describes the mathematical modeling of the thermal decomposition of the complex compound [Ni(En)3](ClO4)2 (En = C2H8N2 = 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)3](ClO4)2 thermolysis was proposed and the kinetic parameters for each stage were obtained. It was shown that the decomposition of [Ni(En)3](ClO4)2 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 ClO4-x- (x = 1-3), as stronger oxidizing agents, instantly start an explosive-like exothermic process of ethylenediamine oxidation (stage B).

AB - This work describes the mathematical modeling of the thermal decomposition of the complex compound [Ni(En)3](ClO4)2 (En = C2H8N2 = 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)3](ClO4)2 thermolysis was proposed and the kinetic parameters for each stage were obtained. It was shown that the decomposition of [Ni(En)3](ClO4)2 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 ClO4-x- (x = 1-3), as stronger oxidizing agents, instantly start an explosive-like exothermic process of ethylenediamine oxidation (stage B).

KW - Coats–Redfern kinetics

KW - dynamic mass-spectral thermal analysis

KW - thermal analysis

KW - tris(ethylenediamine)nickel(II) perchlorate

KW - two-step kinetics

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85145651658&origin=inward&txGid=b304b2a3ab48e07df9c7b77423a071fe

UR - https://www.mendeley.com/catalogue/2567ce92-91da-3ab8-8bd5-0debae5b2f28/

U2 - 10.3390/ma16010090

DO - 10.3390/ma16010090

M3 - Article

C2 - 36614426

VL - 16

JO - Materials

JF - Materials

SN - 1996-1944

IS - 1

M1 - 30

ER -