Iron cation catalyzed reduction of N2O by CO: gas-phase temperature dependent kinetics

Literature Information

Publication Date 2013-05-31
DOI 10.1039/C3CP50335F
Impact Factor 3.676
Authors

Joshua J. Melko, Shaun G. Ard, Joseph A. Fournier, Jun Li, Nicholas S. Shuman, Hua Guo, Albert A. Viggiano


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Abstract

The ion–molecule reactions Fe+ + N2O → FeO+ + N2 and FeO+ + CO → Fe+ + CO2, which catalyze the reaction CO + N2O → CO2 + N2, 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 k2 (10−11 cm3 s−1) = 2.0(±0.3) (T/300)−1.5(±0.2) + 6.3(±0.9) exp(−515(±77)/T) and k3 (10−10 cm3 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 k4 (10−27 cm6 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.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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