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.
TY - JOUR
AU - Maksimović, Jelena P.
AU - Tosović, Jelena
AU - Pagnacco, Maja
PY - 2020
UR - https://cer.ihtm.bg.ac.rs/handle/123456789/3776
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 . .
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