Influence of acid-base equilibria on the rate of the chemical reaction in the advanced oxidation processes: Coumarin derivatives and hydroxyl radical
Само за регистроване кориснике
2023
Аутори
Milanović, ŽikoDimic, Dusan
Antonijević, Marko
Žižić, Milan
Milenkovic, Dejan
Avdović, Edina
Marković, Zoran
Чланак у часопису (Рецензирана верзија)
Метаподаци
Приказ свих података о документуАпстракт
The decomposition and chemical manipulation of stable aromatic pollutants into less toxic products is an
important topic for wastewater management and natural water remediation. The mechanism of the Advanced
Oxidation Process (AOPs) of 4,7-dihydroxycoumarin (4,7-DHC) and 7-hydroxycoumarin (7-HC), as examples of
stable naturally-occurring industrially-important compounds, in the presence of hydroxyl radical (HO•
) in the
aqueous solution has been analyzed using Electron Paramagnetic Resonance spectroscopy (EPR) and Quantum
Mechanics-based test for Overall Free Radical Scavenging Activity (QM-ORSA). The effect of pH values of the me-
dium on the investigated reaction mechanisms has been fully investigated. The rate constants were estimated by
the conventional transition state theory (TST) and Eckart’s method (ZCT_0). Estimated values of the overall rate
constant (koverall) higher than >4.06 × 109 M 1 s 1 at all pH values showed that both compounds undergo a
chemical transformat...ion when exposed to HO•
. When pH increased in the range of 0–14, the koverall increased
from 4.06 × 109 to 1.11 × 1010 (4.7-DHC) and 2.09 × 109 to 1.76 × 1010 M 1s 1 (7-HC). At physiological pH =
7.4 value, 7-HC was ~1.5 times more prone to radical action, as shown by EPR and QM-ORSA, due to the
dominant anionic form. Both compounds were more reactive towards HO•
than Trolox at this pH value. The
ecotoxicity assessment of the starting compounds, intermediates and oxidation products indicated that the
formed products show lower acute and chronic toxicity effects on aquatic organisms than starting compounds,
which is a prerequisite for the development of novel AOPs procedures.
Кључне речи:
4,7-Dihydroxycoumari / 7-Hydroxycoumarin / QM-ORSA / Thermodynamic approach / Kinetic approachИзвор:
Chemical Engineering Journal, 2023, 453, 139648-139661Издавач:
- Elsevier
Финансирање / пројекти:
- Министарство науке, технолошког развоја и иновација Републике Србије, институционално финансирање - 200378 (Институт за информационе технологије, Крагујевац) (RS-MESTD-inst-2020-200378)
- Министарство науке, технолошког развоја и иновација Републике Србије, институционално финансирање - 200122 (Универзитет у Крагујевцу, Природно-математички факултет) (RS-MESTD-inst-2020-200122)
Институција/група
Institut za multidisciplinarna istraživanjaTY - JOUR AU - Milanović, Žiko AU - Dimic, Dusan AU - Antonijević, Marko AU - Žižić, Milan AU - Milenkovic, Dejan AU - Avdović, Edina AU - Marković, Zoran PY - 2023 UR - http://rimsi.imsi.bg.ac.rs/handle/123456789/3164 AB - The decomposition and chemical manipulation of stable aromatic pollutants into less toxic products is an important topic for wastewater management and natural water remediation. The mechanism of the Advanced Oxidation Process (AOPs) of 4,7-dihydroxycoumarin (4,7-DHC) and 7-hydroxycoumarin (7-HC), as examples of stable naturally-occurring industrially-important compounds, in the presence of hydroxyl radical (HO• ) in the aqueous solution has been analyzed using Electron Paramagnetic Resonance spectroscopy (EPR) and Quantum Mechanics-based test for Overall Free Radical Scavenging Activity (QM-ORSA). The effect of pH values of the me- dium on the investigated reaction mechanisms has been fully investigated. The rate constants were estimated by the conventional transition state theory (TST) and Eckart’s method (ZCT_0). Estimated values of the overall rate constant (koverall) higher than >4.06 × 109 M 1 s 1 at all pH values showed that both compounds undergo a chemical transformation when exposed to HO• . When pH increased in the range of 0–14, the koverall increased from 4.06 × 109 to 1.11 × 1010 (4.7-DHC) and 2.09 × 109 to 1.76 × 1010 M 1s 1 (7-HC). At physiological pH = 7.4 value, 7-HC was ~1.5 times more prone to radical action, as shown by EPR and QM-ORSA, due to the dominant anionic form. Both compounds were more reactive towards HO• than Trolox at this pH value. The ecotoxicity assessment of the starting compounds, intermediates and oxidation products indicated that the formed products show lower acute and chronic toxicity effects on aquatic organisms than starting compounds, which is a prerequisite for the development of novel AOPs procedures. PB - Elsevier T2 - Chemical Engineering Journal T1 - Influence of acid-base equilibria on the rate of the chemical reaction in the advanced oxidation processes: Coumarin derivatives and hydroxyl radical EP - 139661 SP - 139648 VL - 453 DO - 10.1016/j.cej.2022.139648 ER -
@article{ author = "Milanović, Žiko and Dimic, Dusan and Antonijević, Marko and Žižić, Milan and Milenkovic, Dejan and Avdović, Edina and Marković, Zoran", year = "2023", abstract = "The decomposition and chemical manipulation of stable aromatic pollutants into less toxic products is an important topic for wastewater management and natural water remediation. The mechanism of the Advanced Oxidation Process (AOPs) of 4,7-dihydroxycoumarin (4,7-DHC) and 7-hydroxycoumarin (7-HC), as examples of stable naturally-occurring industrially-important compounds, in the presence of hydroxyl radical (HO• ) in the aqueous solution has been analyzed using Electron Paramagnetic Resonance spectroscopy (EPR) and Quantum Mechanics-based test for Overall Free Radical Scavenging Activity (QM-ORSA). The effect of pH values of the me- dium on the investigated reaction mechanisms has been fully investigated. The rate constants were estimated by the conventional transition state theory (TST) and Eckart’s method (ZCT_0). Estimated values of the overall rate constant (koverall) higher than >4.06 × 109 M 1 s 1 at all pH values showed that both compounds undergo a chemical transformation when exposed to HO• . When pH increased in the range of 0–14, the koverall increased from 4.06 × 109 to 1.11 × 1010 (4.7-DHC) and 2.09 × 109 to 1.76 × 1010 M 1s 1 (7-HC). At physiological pH = 7.4 value, 7-HC was ~1.5 times more prone to radical action, as shown by EPR and QM-ORSA, due to the dominant anionic form. Both compounds were more reactive towards HO• than Trolox at this pH value. The ecotoxicity assessment of the starting compounds, intermediates and oxidation products indicated that the formed products show lower acute and chronic toxicity effects on aquatic organisms than starting compounds, which is a prerequisite for the development of novel AOPs procedures.", publisher = "Elsevier", journal = "Chemical Engineering Journal", title = "Influence of acid-base equilibria on the rate of the chemical reaction in the advanced oxidation processes: Coumarin derivatives and hydroxyl radical", pages = "139661-139648", volume = "453", doi = "10.1016/j.cej.2022.139648" }
Milanović, Ž., Dimic, D., Antonijević, M., Žižić, M., Milenkovic, D., Avdović, E.,& Marković, Z.. (2023). Influence of acid-base equilibria on the rate of the chemical reaction in the advanced oxidation processes: Coumarin derivatives and hydroxyl radical. in Chemical Engineering Journal Elsevier., 453, 139648-139661. https://doi.org/10.1016/j.cej.2022.139648
Milanović Ž, Dimic D, Antonijević M, Žižić M, Milenkovic D, Avdović E, Marković Z. Influence of acid-base equilibria on the rate of the chemical reaction in the advanced oxidation processes: Coumarin derivatives and hydroxyl radical. in Chemical Engineering Journal. 2023;453:139648-139661. doi:10.1016/j.cej.2022.139648 .
Milanović, Žiko, Dimic, Dusan, Antonijević, Marko, Žižić, Milan, Milenkovic, Dejan, Avdović, Edina, Marković, Zoran, "Influence of acid-base equilibria on the rate of the chemical reaction in the advanced oxidation processes: Coumarin derivatives and hydroxyl radical" in Chemical Engineering Journal, 453 (2023):139648-139661, https://doi.org/10.1016/j.cej.2022.139648 . .