화학공학소재연구정보센터
Journal of Chemical Physics, Vol.105, No.22, 9781-9795, 1996
On the Heat of Formation of Carbonyl Fluoride, Cf2O
In light of the recent controversy surrounding its heat of formation, CF2O was reexamined by photoionization mass spectrometry. In particular, the CO+ fragment ion yield curve from CF2O was interpreted in terms of a retarded CO++F-2 process, and a more facile two-step fragmentation to CO++2F. The former process produces a weak, slowly growing tail region without a clear onset, while the latter occurs at higher energy and causes a pronounced growth with a conspicuous onset, which was found to occur at less than or equal to 20.87(+0.03)/(-0.07) eV at 0 K by fitting with a model curve that incorporates "fluctuations" associated with second-generation fragments. This onset leads to Delta H degrees(f 298)(CF2O) greater than or equal to -149.1(+1.4)/(-0.7) kcal/mol, and indicates that the older experimental values for this quantity are too low by at least 3-4 kcal/mol. While the F-2 elimination is retarded by competition with lower energy processes, the two-step process derives its strength from the FCO+ fragment, which assumes the role of a pseudoparent. Thus, the onset of CO++2F is expected to appear reasonably close to the thermochemical threshold. Such an interpretation indicates that recently calculated nb initio values of -145.3+/-1.7 kcal/mol and -145.6+/-1.0 kcal/mol are very likely too high by 3-4 kcal/mol. In addition, the adiabatic ionization potential of CF2O was refined to 13.024+/-0.004 eV, while the 0 K appearance potential of the FCO+ fragment was found by fitting to be less than or equal to 14.752+/-0.005 eV. Together with the suggested value for Delta H degrees(f)(CF2O), these two onsets lead to Delta H degrees(f 298)(CF2O+) = 151.2(+1.4)/(-0.7) kcal/mol and Delta H degrees(f 298)(FCO+) = 173.5(+1.4)/(-0.7) kcal/mol.