Reactions of Fe+ and FeO+ with C2H2, C2H4, and C2H6: Temperature-Dependent Kinetics

We present the first temperature-dependent rate constants and branching ratios for the reactions of Fe+ and FeO+ with C2H2, C2H4, and C2H6 from 170 to 700 K. Fe+ is observed to react only by association with the three hydrocarbons, with temperature dependencies of T(expn -2) to T(expn -3). FeO+ reacts with C2H2 and C2H4 at the collision rate over the temperature range, and their respective product branchings show similar temperature dependences. In contrast, the reaction with ethane is collisional at 170 K but varies as T(expn -0.5), while the product branching remains essentially flat with temperature. These variations in reactivity are discussed in terms of the published reactive potential surfaces. The effectiveness of Fe+ as an oxygen-transfer catalyst toward the three hydrocarbons is also discussed.
The original document contains color images. Published in the Journal of Physical Chemistry A, v117 p10178-10185, 12 Sep 2013. Prepared in collaboration with the Sterling Chemistry Laboratory, Yale University, New Haven, CT. Sponsored in part by DoD.