Insight into the Origin of Pyrocatechol Inhibition on Oscillating Bray-Liebhafsky Reaction: Combined Experimental and Theoretical Study
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Chemical Society of Japan
Metapodaci
Prikaz svih podataka o dokumentuApstrakt
The pyrocatechol inhibitory effect on the oscillatory Bray-Liebhafsky (BL) reaction is reported. Obtained results are compared with those available in the literature (R. Cervellati et al, Helvetica Chimica Acta 2001) for Briggs-Rauscher (BR) reaction with pyrocatechol addition. The two orders of magnitude larger calibration curve slope obtained in BR in comparison to BL reaction, suggests that different reactions are responsible for inhibitory effects in these systems. The potential explanation of pyrocatechol behavior is given by employing the ultraviolet-visible (UV/VIS) spectroscopy, density functional theory, and coupled cluster computational methods. The last two were employed for the first time to discover potential candidates among unstable chemical species HIO, HIO2, I2O, HOO•, HO•, IO•, IO2•, and I• of the BL (and BR) system for reaction with pyrocatechol. The calculated reaction rate constants for the hydrogen atom transfer reactions between pyrocatechol and free radical inte...rmediates indicate the following order of reactivity: HO• > IO• > HOO• > IO2•. The same order of reactivity is also observed in the case of a thermodynamic investigation. In addition, kinetic insight indicates that the inhibitory behavior of pyrocatechol could not be explained with one particular chemical reaction in the BL (or in the BR) oscillatory system.
Ključne reči:
Oscillatory reaction / Pyrocatechol / Computational methodsIzvor:
Bulletin of the Chemical Society of Japan, 2020, 93, 5, 676-684Izdavač:
- Chemical Society of Japan
Finansiranje / projekti:
- Dinamika nelinearnih fizičkohemijskih i biohemijskih sistema sa modeliranjem i predviđanjem njihovih ponašanja pod neravnotežnim uslovima (RS-172015)
- Sinteza, modelovanje, fizičko-hemijske i biološke osobine organskih jedinjenja i odgovarajućih kompleksa metala (RS-172016)
- Ministarstvo prosvete, nauke i tehnološkog razvoja Republike Srbije, Ugovor br. 200146 (Univerzitet u Beogradu, Fakultet za fizičku hemiju) (RS-200146)
Napomena:
- This is the peer-reviewed version of the manuscript: Jelena P. Maksimović , Jelena Tošović , Maja C. Pagnacco, Bulletin of the Chemical Society of Japan, 2020, 93, 5, 676-684, doi: https://doi.org/10.1246/bcsj.20190296
- The published version: https://cer.ihtm.bg.ac.rs/handle/123456789/3776
DOI: 10.1246/bcsj.20190296
ISSN: 0009-2673
WoS: 000532690000005
Scopus: 2-s2.0-85086148155
Institucija/grupa
IHTMTY - JOUR AU - Maksimović, Jelena P. AU - Tosović, Jelena AU - Pagnacco, Maja PY - 2020 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/3853 AB - The pyrocatechol inhibitory effect on the oscillatory Bray-Liebhafsky (BL) reaction is reported. Obtained results are compared with those available in the literature (R. Cervellati et al, Helvetica Chimica Acta 2001) for Briggs-Rauscher (BR) reaction with pyrocatechol addition. The two orders of magnitude larger calibration curve slope obtained in BR in comparison to BL reaction, suggests that different reactions are responsible for inhibitory effects in these systems. The potential explanation of pyrocatechol behavior is given by employing the ultraviolet-visible (UV/VIS) spectroscopy, density functional theory, and coupled cluster computational methods. The last two were employed for the first time to discover potential candidates among unstable chemical species HIO, HIO2, I2O, HOO•, HO•, IO•, IO2•, and I• of the BL (and BR) system for reaction with pyrocatechol. The calculated reaction rate constants for the hydrogen atom transfer reactions between pyrocatechol and free radical intermediates indicate the following order of reactivity: HO• > IO• > HOO• > IO2•. The same order of reactivity is also observed in the case of a thermodynamic investigation. In addition, kinetic insight indicates that the inhibitory behavior of pyrocatechol could not be explained with one particular chemical reaction in the BL (or in the BR) oscillatory system. PB - Chemical Society of Japan T2 - Bulletin of the Chemical Society of Japan T1 - Insight into the Origin of Pyrocatechol Inhibition on Oscillating Bray-Liebhafsky Reaction: Combined Experimental and Theoretical Study VL - 93 IS - 5 SP - 676 EP - 684 DO - 10.1246/bcsj.20190296 ER -
@article{ author = "Maksimović, Jelena P. and Tosović, Jelena and Pagnacco, Maja", year = "2020", abstract = "The pyrocatechol inhibitory effect on the oscillatory Bray-Liebhafsky (BL) reaction is reported. Obtained results are compared with those available in the literature (R. Cervellati et al, Helvetica Chimica Acta 2001) for Briggs-Rauscher (BR) reaction with pyrocatechol addition. The two orders of magnitude larger calibration curve slope obtained in BR in comparison to BL reaction, suggests that different reactions are responsible for inhibitory effects in these systems. The potential explanation of pyrocatechol behavior is given by employing the ultraviolet-visible (UV/VIS) spectroscopy, density functional theory, and coupled cluster computational methods. The last two were employed for the first time to discover potential candidates among unstable chemical species HIO, HIO2, I2O, HOO•, HO•, IO•, IO2•, and I• of the BL (and BR) system for reaction with pyrocatechol. The calculated reaction rate constants for the hydrogen atom transfer reactions between pyrocatechol and free radical intermediates indicate the following order of reactivity: HO• > IO• > HOO• > IO2•. The same order of reactivity is also observed in the case of a thermodynamic investigation. In addition, kinetic insight indicates that the inhibitory behavior of pyrocatechol could not be explained with one particular chemical reaction in the BL (or in the BR) oscillatory system.", publisher = "Chemical Society of Japan", journal = "Bulletin of the Chemical Society of Japan", title = "Insight into the Origin of Pyrocatechol Inhibition on Oscillating Bray-Liebhafsky Reaction: Combined Experimental and Theoretical Study", volume = "93", number = "5", pages = "676-684", doi = "10.1246/bcsj.20190296" }
Maksimović, J. P., Tosović, J.,& Pagnacco, M.. (2020). Insight into the Origin of Pyrocatechol Inhibition on Oscillating Bray-Liebhafsky Reaction: Combined Experimental and Theoretical Study. in Bulletin of the Chemical Society of Japan Chemical Society of Japan., 93(5), 676-684. https://doi.org/10.1246/bcsj.20190296
Maksimović JP, Tosović J, Pagnacco M. Insight into the Origin of Pyrocatechol Inhibition on Oscillating Bray-Liebhafsky Reaction: Combined Experimental and Theoretical Study. in Bulletin of the Chemical Society of Japan. 2020;93(5):676-684. doi:10.1246/bcsj.20190296 .
Maksimović, Jelena P., Tosović, Jelena, Pagnacco, Maja, "Insight into the Origin of Pyrocatechol Inhibition on Oscillating Bray-Liebhafsky Reaction: Combined Experimental and Theoretical Study" in Bulletin of the Chemical Society of Japan, 93, no. 5 (2020):676-684, https://doi.org/10.1246/bcsj.20190296 . .