jp077596y_si_001.pdf (129.57 kB)
Absolute Proton Affinity for Acetaldehyde
journal contribution
posted on 2008-01-17, 00:00 authored by John C. TraegerDissociative photoionization mass spectrometry has been used to measure appearance energies for the
1-hydroxyethyl cation (CH3CHOH+) formed from ethanol and 2-propanol. Molecular orbital calculations
for these two unimolecular fragmentation reactions suggest that only methyl loss from ionized 2-propanol
does not involve excess energy at the threshold. The experimental appearance energy of 10.31 ± 0.01 eV for
this latter process results in a 298 K heat of formation of 593.1 ± 1.2 kJ mol-1 for CH3CHOH+ and a
corresponding absolute proton affinity for acetaldehyde of 770.9 ± 1.3 kJ mol-1. This value is supported by
both high-level ab initio calculations and a proposed upward revision of the absolute isobutene proton affinity
to 803.3 ± 0.9 kJ mol-1. A 298 K heat of formation of 52.2 ± 1.9 kJ mol-1 is derived for the tert-butyl
radical.