Investigation of the O-O Dissociation Energy of Peroxyformate Anion

Abstract

We measure the bond dissociation energy, D0( ) ≤ 1.29 ± 0.10 eV (125 ± 11 kJ/mol), of the E-peroxyformate anion using energy-resolved collisioninduced 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 formic acid, leading to experimental enthalpies of formation for peroxyformic acid, ΔfH298(Z-HCO3 ) ≤ ─291 ± 17 kJ/mol and ΔfH298(E-HCO3⋅) ≤ ─100 ± 11 kJ/mol respectively, previously unknown experimentally.