Investigation of the O-O Dissociation Energy of Peroxyformate Anion

Abstract

We measure the bond dissociation energy, D0(E-HCO_2^--O) ≤ 1.29 ± 0.10 eV (125 ± 11 kJ/mol), of the peroxyformate anion using energy-resolved collision-induced dissociation with a guided ion beam tandem mass spectrometer. The peroxyformal radical [HC(O)OO∙], is a known intermediate in combustion of HCO∙. We use our threshold energy measurement in a thermochemical cycle to obtain information about the peroxyformyl radical. The oxygen-oxygen bond dissociation energy connects the peroxyformic acid negative ion thermochemical cycle to that of formic acid, leading to experimental enthalpies of formation for peroxyformic acid, ΔfH298(Z-HCO3H) ≤ ─291 ± 17 kJ/mol and ΔfH298(E-HCO3⋅) ≤ ─100 ± 11 kJ/mol respectively, previously unknown experimentally.