Reactions of (CO2)2+ and (CO)2+ association ions

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Abstract
The reactons of (CO2)2+ and (CO)2+ with various additives have been investigated using the NBS high‐pressure photoionization mass spectrometer at total pressures of 0.4–1.0 torr of either CO2 or CO. The additives include CH4, CD4, C2H2, O2, H2O, 15,14N2O, and CO in both CO2 and 13CO2. Second‐ and third‐order rate coefficients based on an ambipolar diffusion model are reported for 25 separate reaction pairs at 295°K, as well as sequential cationic reaction mechanisms. An approximate value of 225 ± 3 kcal/mol (941 ± 13 kJ/mol) was derived for ΔHf (CO)2+ based on the kinetics observed in various CO‐additive mixtures. Some projections regarding the utility of the data under other conditions are also included.