Iron cation catalyzed reduction of N2O by CO: gas-phase temperature dependent kinetics
2013 | journal article. A publication with affiliation to the University of Göttingen.
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Melko, Joshua J., Shaun G. Ard, Joseph A. Fournier, Jun Li, Nicholas S. Shuman, Hua Guo, Juergen Troe, and Albert A. Viggiano. "Iron cation catalyzed reduction of N2O by CO: gas-phase temperature dependent kinetics." Physical Chemistry Chemical Physics 15, no. 27 (2013): 11257-11267. https://doi.org/10.1039/c3cp50335f.
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- Authors
- Melko, Joshua J.; Ard, Shaun G.; Fournier, Joseph A.; Li, Jun; Shuman, Nicholas S.; Guo, Hua; Troe, Juergen; Viggiano, Albert A.
- Abstract
- The ion-molecule reactions F-e+ + N2O -> FeO+ + N-2 and FeO+ + CO -> Fe+ + CO2, which catalyze the reaction CO + N2O -> CO2 + N-2, have been studied over the temperature range 120-700 K using a variable temperature selected ion flow tube apparatus. Values of the rate constants for the former two reactions were experimentally derived as k(2) (10(-11) cm(3) s(-1)) = 2.0(+/- 0.3) (T/300)(-1.5(+/- 0.2)) + 6.3(+/- 0.9) exp(-515(+/- 77)/T) and k(3) (10(-10) cm(3) s(-1)) = 3.1(+/- 0.1) (T/300)(-0.9(+/- 0.1)). Characterizing the energy parameters of the reactions by density functional theory at the B3LYP/TZVP level, the rate constants are modeled, accounting for the intermediate formation of complexes. The reactions are characterized by nonstatistical intrinsic dynamics and rotation-dependent competition between forward and backward fluxes. For Fe+ + N2O, sextet-quartet switching of the potential energy surfaces is quantified. The rate constant for the clustering reaction FeO+ + N2O + He -> FeO(N2O)(+) + He was also measured, being k(4) (10(-27) cm(6) s(-1)) = 1.1(+/- 0.1) (T/300)(-2.5(+/- 0.1)) in the low pressure limit, and analyzed in terms of unimolecular rate theory.
- Issue Date
- 2013
- Status
- published
- Publisher
- Royal Soc Chemistry
- Journal
- Physical Chemistry Chemical Physics
- ISSN
- 1463-9076