High-Pressure Ion–Molecule Reactions in Carbon Monoxide and Carbon Monoxide–Methane Mixtures

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Abstract
In carbon monoxide at pressures above 0.2 torr, the principal product ion is C2O2+ formed by a three‐body process. The rate constant for the reaction is 1.43 × 10−28 cm6 molecule−2·sec−1. Above about 0.8 torr, the reaction appears to approach equilibrium with an equilibrium constant of 1482 referred to 1 atm as standard. At pressures of methane above 0.2 torr and small additions of CO, the only reaction observed in the protonation of CO by CH5+ with a rate constant of 5.54 × 10−10 cm3 molecule−1·sec−1. All other reactions are endothermic and are not observed. At pressures of carbon monoxide above 0.2 torr, the addition of small amounts of methane results in an H‐atom transfer reaction to CO+ with a rate constant of 13.7 × 10−10 cm3 molecule−1·sec−1. In addition, C2O2+ reacts to form HCO+, C2H3O+, and C3H3O+ with rate constants of 9.44, 4.37, and 0.76 × 10−10 cm3 molecule−1·sec−1, respectively.