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Experimental and mechanistic study of the inhibitory effects by phenolics on the oscillations of the Orbàn–Epstein Reaction

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Abstract

The system KSCN–H2O2–CuSO4–NaOH, also known as the Orbàn–Epstein oscillatory reaction, is exposed to external perturbations by several phenolic compounds: catechol, resorcinol, hydroquinone, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, caffeic acid, and ferulic acid. As a result of the performed perturbation in most examined cases, oscillations have been inhibited for some characteristic time, and resumed afterwards. The evaluated inhibition time is typical for each substance and strongly dependent on its concentration. The chemical mechanism of the interaction between the Orbàn–Epstein system and phenolic compounds is briefly discussed. Numerical simulations are performed using the original Orbàn–Epstein model with 30 reactions, extended by three reactions describing the interaction with inhibitory substances. The rate constants of three added reactions are adjusted to fit experimental inhibition times, and compared among used compounds. The observed effects are discussed further in relation with the bond dissociation enthalpy theory. Unlike other tested compounds, 2,5-dihydroxybenzoic acid remains off from predicted order of activity.

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Acknowledgement

Support from the Ministry of Education, Science and Technological Development of the Republic of Serbia, grants 172015 and 45001, is gratefully acknowledged.

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Authors and Affiliations

  1. Dipartimento di Chimica “G. Ciamician”, Università di Bologna, Via Selmi 2, Bologna, Italy

    Rinaldo Cervellati & Emanuela Greco

  2. Faculty of Pharmacy, University of Belgrade, Vojvode Stepe 450, Belgrade, Serbia

    Slavica M. Blagojević

  3. Institute of General and Physical Chemistry, University of Belgrade, Studentski trg 12-16, Belgrade, Serbia

    Stevan N. Blagojević

  4. Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, Belgrade, Serbia

    Slobodan Anić

  5. Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Njegoševa 12, Belgrade, Serbia

    Željko D. Čupić

Authors
  1. Rinaldo Cervellati
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  2. Emanuela Greco
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  3. Slavica M. Blagojević
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  4. Stevan N. Blagojević
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  5. Slobodan Anić
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  6. Željko D. Čupić
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Correspondence to Rinaldo Cervellati.

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Cervellati, R., Greco, E., Blagojević, S.M. et al. Experimental and mechanistic study of the inhibitory effects by phenolics on the oscillations of the Orbàn–Epstein Reaction. Reac Kinet Mech Cat 123, 125–139 (2018). https://doi.org/10.1007/s11144-017-1306-8

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  • DOI: https://doi.org/10.1007/s11144-017-1306-8

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