ЗАЛЕЖНІСТЬ ЕНЕРГІЇ АКТИВАЦІЇ ВІДНОВЛЕННЯ БІС-ГІДРОКСИЕТИЛІМІНОДІАЦЕТАТНИХ КОМПЛЕКСІВ ПАЛАДІЮ(II) ВІД ПЕРЕНАПРУГИ
The kinetic (exchange currents, apparent elect-ron transfer coefficients) and energetic (activation energies of diffusion and electron-transfer reaction) parameters of electroreduction of palladium (II) bis-hydroxyethyliminodiacetate complexes from an ele-ctrolyte containing an excess of free ligand...
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| Date: | 2019 |
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2019
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oai:ojs2.1444248.nisspano.web.hosting-test.net:article-112019-04-19T09:18:26Z DEPENDENCE ACTIVATION ENERGY OF THE ELECTROREDUCTION OF PALLADIUM(II) BIS-HYDROXYETHYLIMINODIACETATE COMPLEXES ON THE OVERPOTENTIAL ЗАВИСИМОСТЬ ЭНЕРГИИ АКТИВАЦИИ ВОССТАНОВЛЕНИЯ БИС-ГИДРОКСИЭТИЛИМИНОДИАЦЕТАТНЫХ КОМПЛЕКСОВ ПАЛЛАДИЯ (II) ОТ ПЕРЕНАПРЯЖЕНИЯ ЗАЛЕЖНІСТЬ ЕНЕРГІЇ АКТИВАЦІЇ ВІДНОВЛЕННЯ БІС-ГІДРОКСИЕТИЛІМІНОДІАЦЕТАТНИХ КОМПЛЕКСІВ ПАЛАДІЮ(II) ВІД ПЕРЕНАПРУГИ Kublanovskii, Valeriy Nikitenko, Vasyl The kinetic (exchange currents, apparent elect-ron transfer coefficients) and energetic (activation energies of diffusion and electron-transfer reaction) parameters of electroreduction of palladium (II) bis-hydroxyethyliminodiacetate complexes from an ele-ctrolyte containing an excess of free ligand have been determined. A method is proposed for calculating the actual activation energy of the electrode process that is controlled by mixed kinetics, based on the dif-fusion activation energy, transition reaction and the ratio of surface and volume concentrations of potenti-al-determining ions in the solution under study or the ratio of the limiting diffusion current jd and dischar-ge current jk of palladium (II) hydroxyethyliminodi- acetate complexes. The actual activation energy Af of the electrode process, which is controlled by mixed kinetics, is calculated based on the diffusion activati-on energy, transition reaction and the ratio of the li-miting diffusion current jd and discharge current jk of palladium (II) bis-hydroxyethyliminodiacetate com-plexes. The contribution of the activation energy of the transition stage (slow discharge) and the diffusion activation energy of bis -hydroxyethyliminodiacetate palladium (II) complexes to the actual activation ener-gy of the electrode process limited by mixed kine-tics is determined. The dependence of actual activation energy on electrode process overpotential has been stu-died. The actual activation energy Af of the electro-de process varies from the value of the activation ener-gy of the transition reaction At (63.4 kJ×mol–1) to the value of the diffusion activation energy Ad (22.5 kJ ×mol–1). The activation energy calculated according to Tyomkin can be considered as the actual activation energy Af of the discharge stage at a given polarizati-on DE only with a purely kinetic control of the pro-cess rate. The activation energy experimentally deter-mined by the temperature-kinetic method according to the Arrhenius equation and calculated by the pro-posed method is the actual activation energy Af of the electrode process, controlled by mixed kinetics. There is a coincidence of the experimentally determi-ned by the Gorbachev method and the actual Af acti-vation energy of electrode process controlled by mi-xed kinetics calculated by the proposed method. A good agreement between the calculated and experi-mentally determined values of the actual activation energy of the electrode process is observed. V.I.Vernadsky Institute of General and Inorganic Chemistry 2019-02-15 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/11 10.33609/0041-6045.85.1.2019.32-37 Ukrainian Chemistry Journal; Vol. 85 No. 1 (2019): Ukrainian Chemistry Journal; 32-37 Украинский химический журнал; Том 85 № 1 (2019): Украинский химический журнал; 32-37 Український хімічний журнал; Том 85 № 1 (2019): Український хімічний журнал; 32-37 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/11/4 |
| institution |
Ukrainian Chemistry Journal |
| baseUrl_str |
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| datestamp_date |
2019-04-19T09:18:26Z |
| collection |
OJS |
| language |
English |
| format |
Article |
| author |
Kublanovskii, Valeriy Nikitenko, Vasyl |
| spellingShingle |
Kublanovskii, Valeriy Nikitenko, Vasyl ЗАЛЕЖНІСТЬ ЕНЕРГІЇ АКТИВАЦІЇ ВІДНОВЛЕННЯ БІС-ГІДРОКСИЕТИЛІМІНОДІАЦЕТАТНИХ КОМПЛЕКСІВ ПАЛАДІЮ(II) ВІД ПЕРЕНАПРУГИ |
| author_facet |
Kublanovskii, Valeriy Nikitenko, Vasyl |
| author_sort |
Kublanovskii, Valeriy |
| title |
ЗАЛЕЖНІСТЬ ЕНЕРГІЇ АКТИВАЦІЇ ВІДНОВЛЕННЯ БІС-ГІДРОКСИЕТИЛІМІНОДІАЦЕТАТНИХ КОМПЛЕКСІВ ПАЛАДІЮ(II) ВІД ПЕРЕНАПРУГИ |
| title_short |
ЗАЛЕЖНІСТЬ ЕНЕРГІЇ АКТИВАЦІЇ ВІДНОВЛЕННЯ БІС-ГІДРОКСИЕТИЛІМІНОДІАЦЕТАТНИХ КОМПЛЕКСІВ ПАЛАДІЮ(II) ВІД ПЕРЕНАПРУГИ |
| title_full |
ЗАЛЕЖНІСТЬ ЕНЕРГІЇ АКТИВАЦІЇ ВІДНОВЛЕННЯ БІС-ГІДРОКСИЕТИЛІМІНОДІАЦЕТАТНИХ КОМПЛЕКСІВ ПАЛАДІЮ(II) ВІД ПЕРЕНАПРУГИ |
| title_fullStr |
ЗАЛЕЖНІСТЬ ЕНЕРГІЇ АКТИВАЦІЇ ВІДНОВЛЕННЯ БІС-ГІДРОКСИЕТИЛІМІНОДІАЦЕТАТНИХ КОМПЛЕКСІВ ПАЛАДІЮ(II) ВІД ПЕРЕНАПРУГИ |
| title_full_unstemmed |
ЗАЛЕЖНІСТЬ ЕНЕРГІЇ АКТИВАЦІЇ ВІДНОВЛЕННЯ БІС-ГІДРОКСИЕТИЛІМІНОДІАЦЕТАТНИХ КОМПЛЕКСІВ ПАЛАДІЮ(II) ВІД ПЕРЕНАПРУГИ |
| title_sort |
залежність енергії активації відновлення біс-гідроксиетилімінодіацетатних комплексів паладію(ii) від перенапруги |
| title_alt |
DEPENDENCE ACTIVATION ENERGY OF THE ELECTROREDUCTION OF PALLADIUM(II) BIS-HYDROXYETHYLIMINODIACETATE COMPLEXES ON THE OVERPOTENTIAL ЗАВИСИМОСТЬ ЭНЕРГИИ АКТИВАЦИИ ВОССТАНОВЛЕНИЯ БИС-ГИДРОКСИЭТИЛИМИНОДИАЦЕТАТНЫХ КОМПЛЕКСОВ ПАЛЛАДИЯ (II) ОТ ПЕРЕНАПРЯЖЕНИЯ |
| description |
The kinetic (exchange currents, apparent elect-ron transfer coefficients) and energetic (activation energies of diffusion and electron-transfer reaction) parameters of electroreduction of palladium (II) bis-hydroxyethyliminodiacetate complexes from an ele-ctrolyte containing an excess of free ligand have been determined. A method is proposed for calculating the actual activation energy of the electrode process that is controlled by mixed kinetics, based on the dif-fusion activation energy, transition reaction and the ratio of surface and volume concentrations of potenti-al-determining ions in the solution under study or the ratio of the limiting diffusion current jd and dischar-ge current jk of palladium (II) hydroxyethyliminodi-
acetate complexes. The actual activation energy Af of the electrode process, which is controlled by mixed kinetics, is calculated based on the diffusion activati-on energy, transition reaction and the ratio of the li-miting diffusion current jd and discharge current jk of palladium (II) bis-hydroxyethyliminodiacetate com-plexes. The contribution of the activation energy of the transition stage (slow discharge) and the diffusion activation energy of bis -hydroxyethyliminodiacetate palladium (II) complexes to the actual activation ener-gy of the electrode process limited by mixed kine-tics is determined. The dependence of actual activation energy on electrode process overpotential has been stu-died. The actual activation energy Af of the electro-de process varies from the value of the activation ener-gy of the transition reaction At (63.4 kJ×mol–1) to the value of the diffusion activation energy Ad (22.5 kJ ×mol–1). The activation energy calculated according to Tyomkin can be considered as the actual activation energy Af of the discharge stage at a given polarizati-on DE only with a purely kinetic control of the pro-cess rate. The activation energy experimentally deter-mined by the temperature-kinetic method according to the Arrhenius equation and calculated by the pro-posed method is the actual activation energy Af of the electrode process, controlled by mixed kinetics. There is a coincidence of the experimentally determi-ned by the Gorbachev method and the actual Af acti-vation energy of electrode process controlled by mi-xed kinetics calculated by the proposed method. A good agreement between the calculated and experi-mentally determined values of the actual activation energy of the electrode process is observed. |
| publisher |
V.I.Vernadsky Institute of General and Inorganic Chemistry |
| publishDate |
2019 |
| url |
https://ucj.org.ua/index.php/journal/article/view/11 |
| work_keys_str_mv |
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2025-09-24T17:43:23Z |
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2025-09-24T17:43:23Z |
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