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The Reaction Kinetics of Amino Radicals with Sulfur Dioxide
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July 10, 2015
Abstract
Application of the laser photolysis–laser-induced fluorescence method to the reaction NH2 + SO2 in argon bath gas yields pressure-dependent, third-order kinetics which may be summarized as k = (1.49 ± 0.15) × 10−31 (T/298 K)−0.83 cm6 molecule–2 s–1 over 292–555 K, where the uncertainty is the 95% confidence interval and includes possible systematic errors. The quenching of vibrationally excited NH2 is consistent with a high-pressure limit for NH2 + SO2 of (1.62 ± 0.25) × 10−11 cm3 molecule–1 s–1 over the temperature range 295–505 K, where again the 95% confidence interval is shown. Ab initio analysis yields a H2N–SO2 dissociation enthalpy of 73.5 kJ mol–1, and comparison with RRKM theory and the exponential down model for energy transfer yields 〈ΔE〉down = 350 cm–1 for Ar at room temperature.
Supplementary material
the online version of this article (DOI: 10.1515/zpch-2015-0637) provides supplementary material for authorized users.
Acknowledgement
PM thanks the Robert A. Welch Foundation (Grant B-1174) and the National Science Foundation (Grant CBET-0756144) for support. Computational facilities were purchased in part with NSF Grant CHE-0741936.
Received: 2015-4-29
Accepted: 2015-6-18
Published Online: 2015-7-10
Published in Print: 2015-10-28
©2015 Walter de Gruyter Berlin/Boston
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- Preface
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- The Kinetics of the Reaction C2H5• + HI → C2H6 + I• over an Extended Temperature Range (213–623 K): Experiment and Modeling
- Collisional Relaxation of NCN: An Experimental Study with Laser-Induced Fluorescence
- Reaction of Chlorine Molecules with Unsaturated Submicron Organic Particles
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- Challenging High-Level ab initio Rovibrational Spectroscopy: The Nitrous Oxide Molecule
- Reaction of the CF3 Radical with Various Cations (Ar+, Xe+, O2+, NO+, CO2+, C2F5+)
- Electronic Spectra of Corannulenic Cations and Neutrals in Neon Matrices and Protonated Corannulene in the Gas Phase at 15 K
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