We measure the bond dissociation energy, D0(HC[special characters omitted] − O) ≤ 1.29 ± 0.10 eV (125 ± 11 kJ/mol), of the E-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 Δ fH298(E-HCO3·) ≤ −100 ± 11 kJ/mol respectively, previously unknown experimentally.
|Advisor:||Ervin, Kent M.|
|Commitee:||Cline, Joseph I., Weinstein, Jonathan|
|School:||University of Nevada, Reno|
|School Location:||United States -- Nevada|
|Source:||MAI 50/02M, Masters Abstracts International|
|Keywords:||Bond dissociation energy, Enthalpy of formation, Peroxyformate anion|
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