The Use of Hybrid Genetic Algorithm in the Kinetic Analysis of Thermal Decomposition of [Ni(C<sub>2</sub>H<sub>8</sub>N<sub>2</sub>)<sub>3</sub>](ClO<sub>4</sub>)<sub>2</sub> with Overlapping Stages
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 at...
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2022-12-01
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| author | Kirill A. Dmitruk Oksana V. Komova Alexander A. Paletsky Andrey G. Shmakov Svetlana A. Mukha Vladislav R. Butenko Alena A. Pochtar Olga V. Netskina |
| author_facet | Kirill A. Dmitruk Oksana V. Komova Alexander A. Paletsky Andrey G. Shmakov Svetlana A. Mukha Vladislav R. Butenko Alena A. Pochtar Olga V. Netskina |
| author_sort | Kirill A. Dmitruk |
| collection | DOAJ |
| description | 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). |
| first_indexed | 2024-03-11T09:55:47Z |
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| id | doaj.art-3574c35090d54e55a375a258004aaf3c |
| institution | Directory Open Access Journal |
| issn | 1996-1944 |
| language | English |
| last_indexed | 2024-03-11T09:55:47Z |
| publishDate | 2022-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Materials |
| spelling | doaj.art-3574c35090d54e55a375a258004aaf3c2023-11-16T15:46:50ZengMDPI AGMaterials1996-19442022-12-011619010.3390/ma16010090The Use of Hybrid Genetic Algorithm in the Kinetic Analysis of Thermal Decomposition of [Ni(C<sub>2</sub>H<sub>8</sub>N<sub>2</sub>)<sub>3</sub>](ClO<sub>4</sub>)<sub>2</sub> with Overlapping StagesKirill A. Dmitruk0Oksana V. Komova1Alexander A. Paletsky2Andrey G. Shmakov3Svetlana A. Mukha4Vladislav R. Butenko5Alena A. Pochtar6Olga V. Netskina7Boreskov Institute of Catalysis SB RAS, 5 Akademika Lavrentieva Ave., Novosibirsk 630090, RussiaBoreskov Institute of Catalysis SB RAS, 5 Akademika Lavrentieva Ave., Novosibirsk 630090, RussiaBoreskov Institute of Catalysis SB RAS, 5 Akademika Lavrentieva Ave., Novosibirsk 630090, RussiaVoevodsky Institute of Chemical Kinetics and Combustion SB RAS, 3 Institutskaya Str., Novosibirsk 630090, RussiaBoreskov Institute of Catalysis SB RAS, 5 Akademika Lavrentieva Ave., Novosibirsk 630090, RussiaBoreskov Institute of Catalysis SB RAS, 5 Akademika Lavrentieva Ave., Novosibirsk 630090, RussiaBoreskov Institute of Catalysis SB RAS, 5 Akademika Lavrentieva Ave., Novosibirsk 630090, RussiaBoreskov Institute of Catalysis SB RAS, 5 Akademika Lavrentieva Ave., Novosibirsk 630090, RussiaThis 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).https://www.mdpi.com/1996-1944/16/1/90thermal analysisdynamic mass-spectral thermal analysistwo-step kineticsCoats–Redfern kineticstris(ethylenediamine)nickel(II) perchlorate |
| spellingShingle | Kirill A. Dmitruk Oksana V. Komova Alexander A. Paletsky Andrey G. Shmakov Svetlana A. Mukha Vladislav R. Butenko Alena A. Pochtar Olga V. Netskina The Use of Hybrid Genetic Algorithm in the Kinetic Analysis of Thermal Decomposition of [Ni(C<sub>2</sub>H<sub>8</sub>N<sub>2</sub>)<sub>3</sub>](ClO<sub>4</sub>)<sub>2</sub> with Overlapping Stages Materials thermal analysis dynamic mass-spectral thermal analysis two-step kinetics Coats–Redfern kinetics tris(ethylenediamine)nickel(II) perchlorate |
| title | The Use of Hybrid Genetic Algorithm in the Kinetic Analysis of Thermal Decomposition of [Ni(C<sub>2</sub>H<sub>8</sub>N<sub>2</sub>)<sub>3</sub>](ClO<sub>4</sub>)<sub>2</sub> with Overlapping Stages |
| title_full | The Use of Hybrid Genetic Algorithm in the Kinetic Analysis of Thermal Decomposition of [Ni(C<sub>2</sub>H<sub>8</sub>N<sub>2</sub>)<sub>3</sub>](ClO<sub>4</sub>)<sub>2</sub> with Overlapping Stages |
| title_fullStr | The Use of Hybrid Genetic Algorithm in the Kinetic Analysis of Thermal Decomposition of [Ni(C<sub>2</sub>H<sub>8</sub>N<sub>2</sub>)<sub>3</sub>](ClO<sub>4</sub>)<sub>2</sub> with Overlapping Stages |
| title_full_unstemmed | The Use of Hybrid Genetic Algorithm in the Kinetic Analysis of Thermal Decomposition of [Ni(C<sub>2</sub>H<sub>8</sub>N<sub>2</sub>)<sub>3</sub>](ClO<sub>4</sub>)<sub>2</sub> with Overlapping Stages |
| title_short | The Use of Hybrid Genetic Algorithm in the Kinetic Analysis of Thermal Decomposition of [Ni(C<sub>2</sub>H<sub>8</sub>N<sub>2</sub>)<sub>3</sub>](ClO<sub>4</sub>)<sub>2</sub> with Overlapping Stages |
| title_sort | use of hybrid genetic algorithm in the kinetic analysis of thermal decomposition of ni c sub 2 sub h sub 8 sub n sub 2 sub sub 3 sub clo sub 4 sub sub 2 sub with overlapping stages |
| topic | thermal analysis dynamic mass-spectral thermal analysis two-step kinetics Coats–Redfern kinetics tris(ethylenediamine)nickel(II) perchlorate |
| url | https://www.mdpi.com/1996-1944/16/1/90 |
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