Proton- and deuteron-transfer reactions to ethane and ETHANE-D6 (cas 1632-99-1): Internal-energy effects in the formation and decomposition of C2H7+

Add time:07/13/2019    Source:sciencedirect.com

A tandem-ICR mass spectrometer was used to study internal-energy effects in proton (deuteron) transfer to ethane. Product distributions for reactions of ArD+, D3+, N2H+, CO2H+, CO2D+, CD5+, N2OD+, and COD+ with ethane (or ethane-d6) and rate constants for reaction of ArD+, D3+, CO2D+, and CD5+ are reported as a function of the average number of relaxing collisions the reactant ion undergoes before reaction. The competing reaction of hydride-ion abstraction (or short-lived, unequilibrated proton transfer) decreases relative to proton transfer [followed by X2 (X=H or D) elimination from a species in which H and D atoms are equivalent] as the available energy is decreased for the more energetic reactants. For the less energetic species, large isotope effects were noted in the formation of C2X5+ product ions. The metastable decomposition of C2H6D+ and C2D6H+ ions were also examined by injecting these ions into the ICR spectrometer and monitoring the C2X5+ product ions; the expected very large isotope effects were observed.The reverse reaction of C2H5+ with D2 was also examined and found to be very slow (10−12 > k > 10−13 cm3 mol−1 s−1); the rate increases as internal or translational energy is increased. The C2H3D2+/C2H4D+ product ratio is 1.2±0.1 and independent of C2H5+ translational or internal energy. These observations are consistent with the hypothesis that an activation-energy barrier impedes formation of a C2H5D2+ intermediate.

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