TY  - 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 . .