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Mechanism of the gas-phase decomposition of trifluoro-, trichloro-, and tribromomethanols in the presence of hydrogen halides

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Abstract

Ab initio calculations at the G2 level were used in a theoretical analysis of the kinetics of the decomposition of trifluoro-, trichloro-, and tribromomethanols. The high-pressure limiting rate coefficients kdiss,∞ for the thermal dissociation of CF3OH, CCl3OH, and CBr3OH were calculated using the conventional transition state theory. The results of potential surface calculations show that in the presence of the hydrogen halides HX (X = F, Cl, and Br), considerably lower energy pathways are accessible for the decomposition of CF3OH, CCl3OH, and CBr3OH. The mechanism of the reactions appears to be complex and consists of three consecutive elementary processes with the formation of pre- and post-reaction adducts. The presence of hydrogen halides considerably decreases the energy barrier for the bimolecular decomposition of the alcohols CF3OH, CCl3OH, and CBr3OH. Results of this study indicate that hydrogen halides can considerably accelerate the homogeneous decomposition of perhalogenated methanols when they are present in the reaction area at sufficiently high concentrations. However, the atmospheric concentrations of hydrogen halides are too small for efficient removal of atmospheric CF3OH, CCl3OH, and CBr3OH.

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Acknowledgments

This research was supported by Wroclaw Medical University under grant no. ST-263. The Wroclaw Center of Networking and Supercomputing is acknowledged for the generous allotment of computer time.

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Authors and Affiliations

  1. Department of Physical Chemistry, Wroclaw Medical University, pl. Nankiera 1, 50-140, Wroclaw, Poland

    Katarzyna Brudnik, Jerzy T. Jodkowski, Dariusz Sarzyński & Andrzej Nowek

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  1. Katarzyna Brudnik
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  2. Jerzy T. Jodkowski
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  3. Dariusz Sarzyński
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  4. Andrzej Nowek
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Correspondence to Jerzy T. Jodkowski.

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Brudnik, K., Jodkowski, J.T., Sarzyński, D. et al. Mechanism of the gas-phase decomposition of trifluoro-, trichloro-, and tribromomethanols in the presence of hydrogen halides. J Mol Model 17, 2395–2409 (2011). https://doi.org/10.1007/s00894-011-0988-5

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  • DOI: https://doi.org/10.1007/s00894-011-0988-5

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