Reaction routes leading to CO2 and CO in the briggs-rauscher oscillator: Analogies between the oscillatory BR and BZ reactions

Norbert Muntean, Gabriella Szabó, M. Wittmann, Thuy Lawson, János Fülöp, Z. Noszticzius, Lavinia Onel

Research output: Contribution to journalArticle

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Abstract

With Fenton-type experiments, it is shown that the intense CO 2/CO evolution in the Briggs-Rauscher (BR) reaction is due to decarboxylation/decarbonylation of organic free radicals. The metal ion applied in the Fenton-type experiments was Fe2+ or Ti3+ or Mn 2+ combined with H2O2 or S2Og 2- as a peroxide, whereas the organic substrate was malonic acid (MA) or a 1:1 mixture of MA and iodomalonic acid (IMA). Experiments with a complete BR system applying MA or the MA/IMA mixture indicate that practically all CO2 and CO comes from IMA. The decarboxylation/decarbonylation mechanisms of various iodomalonyl radicals can be analogous to that of the bromomalonyl radicals studied already in the Belousov-Zhabotinsky (BZ) reaction. It is found that an intense CO2/CO evolution requires the simultaneous presence of H2O2, IO3-, Mn2+, and IMA. It is suggested that the critical first step of this complex reaction takes place in the coordination sphere of Mn2+. That first step can initiate a chain reaction where organic and hydroperoxyl radicals are the chain carriers. A chain reaction was already found in a BZ oscillator as well. Therefore, the analogies between the BR and BZ oscillators are due to the fact that in both mechanisms, free radicals and, in most cases, also transition-metal complexes play an important role.

Original languageEnglish
Pages (from-to)9102-9108
Number of pages7
JournalJournal of Physical Chemistry A
Volume113
Issue number32
DOIs
Publication statusPublished - Aug 13 2009

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Carbon Monoxide
routes
oscillators
acids
Acids
Free Radicals
decarboxylation
Experiments
Coordination Complexes
Peroxides
free radicals
Transition metals
Metal ions
malonic acid
peroxides
Substrates
metal ions
transition metals
Decarboxylation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Reaction routes leading to CO2 and CO in the briggs-rauscher oscillator : Analogies between the oscillatory BR and BZ reactions. / Muntean, Norbert; Szabó, Gabriella; Wittmann, M.; Lawson, Thuy; Fülöp, János; Noszticzius, Z.; Onel, Lavinia.

In: Journal of Physical Chemistry A, Vol. 113, No. 32, 13.08.2009, p. 9102-9108.

Research output: Contribution to journalArticle

Muntean, Norbert ; Szabó, Gabriella ; Wittmann, M. ; Lawson, Thuy ; Fülöp, János ; Noszticzius, Z. ; Onel, Lavinia. / Reaction routes leading to CO2 and CO in the briggs-rauscher oscillator : Analogies between the oscillatory BR and BZ reactions. In: Journal of Physical Chemistry A. 2009 ; Vol. 113, No. 32. pp. 9102-9108.
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