Photochemistry of peroxoborates: borate inhibition of the photodecomposition of hydrogen peroxide

Sébastien Rey, Martin Davies

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11 Citations (Scopus)

Abstract

The UV absorbance and photochemical decomposition kinetics of hydrogen peroxide in borate/boric acid buffers were investigated as a function of pH, total peroxide concentration, and total boron concentration. At higher pH borate/boric acid inhibits the photodecomposition of hydrogen peroxide (molar absorptivity and quantum yield of H2O2 and HO2−, (19.0±0.3) m−1 cm−1 and 1, and (237±7) m−1 cm−1 and 0.8±0.1, respectively). The results are consistent with the equilibrium formation of the anions monoperoxoborate, KBOOH=[H+][HOOB(OH)3−]/([B(OH)3][H2O2]), 2.0×10−8, R. Pizer, C. Tihal, Inorg. Chem. 1987, 26, 3639–3642, and monoperoxodiborate, KBOOB=[BOOB2−]/([B(OH)4−][HOOB(OH)3−]), 1.0±0.3 or 4.3±0.9, depending upon the conditions, with molar absorptivity, (19±1) m−1 cm−1 and (86±15) m−1 cm−1, respectively, and respective quantum yields, 1.1±0.1 and 0.04±0.04. The low quantum yield of monoperoxodiborate is discussed in terms of the slower diffusion apart of incipient .OB(OH)3− radicals than may be possible for .OH radicals, or a possible oxygen-bridged cyclic structure of the monoperoxodiborate.
Original languageEnglish
Pages (from-to)9284-9288
JournalChemistry: A European Journal
Volume12
Issue number36
DOIs
Publication statusPublished - Oct 2006

Keywords

  • atmospheric chemistry
  • boron
  • green chemistry
  • hydroxyl radical
  • photolysis

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