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Using Gas-Phase Molecular Descriptors to Predict Dechlorination Rates of Chloroalkanes by Zerovalent Iron

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School of Natural Resources, University of Nebraska-Lincoln, Lincoln, Nebraska 68583, and Department of Physics and Astronomy, University of Nebraska-Lincoln, Lincoln, Nebraska 68588
Cite this: Environ. Sci. Technol. 2007, 41, 4, 1200–1205
Publication Date (Web):January 18, 2007
https://doi.org/10.1021/es061746l
Copyright © 2007 American Chemical Society

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    Abstract

    Reductive dehalogenation of chlorinated compounds is the most important process occurring within the zerovalent iron (Fe0) barrier. The relative reaction rates of individual halocarbons with Fe0 can vary considerably. This variability has been the stimulus for using various chemical descriptors for a priori predictions of transformation rates via linear free-energy relationships (LFERs). Our objective was to determine the efficacy of four molecular descriptors to describe the transformation rates of three chloromethanes, three chloroethanes, and six chloropropanes by Fe0. This was accomplished by generating an internally consistent set of rate constants under controlled environmental conditions (16 °C, anaerobic) and regressing the surface-area normalized rate constants (kSA) against (i) energy of the lowest unoccupied molecular orbital (ELUMO); (ii) vertical attachment energies (VAE); (iii) thermal electron attachment rate constants; and (iv) the molar response from a commercial electron capture detector (ECD). Results showed good correlations between kSA's and all four descriptors (r2:  0.72−1.0), but a separate trend line was required for the chloromethanes and the chloro- ethanes/propanes. Given the availability and ease with which ECD response can be obtained, this physical measurement may provide a practical means of determining relative rates of reactivity of various halocarbons in permeable reactive iron barriers.

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     School of Natural Resources.

    *

     Corresponding author phone:  (402) 472-1502; fax:  (402) 472-7904; email:  [email protected].

     Department of Physics and Astronomy.

    Cited By

    This article is cited by 10 publications.

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    2. Paul G. Tratnyek Alexandra J. Salter-Blanc James T. Nurmi James E. Amonette Juan Liu Chongmin Wang Alice Dohnalkova Donald R. Baer . Reactivity of Zerovalent Metals in Aquatic Media: Effects of Organic Surface Coatings. 2011, 381-406. https://doi.org/10.1021/bk-2011-1071.ch018
    3. David M. Cwiertny, William A. Arnold, Tamar Kohn, Lisa A. Rodenburg, and A. Lynn Roberts . Reactivity of Alkyl Polyhalides toward Granular Iron: Development of QSARs and Reactivity Cross Correlations for Reductive Dehalogenation. Environmental Science & Technology 2010, 44 (20) , 7928-7936. https://doi.org/10.1021/es1018866
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    5. Romain Rodrigues, Stéphanie Betelu, Stéfan Colombano, Theodore Tzedakis, Guillaume Masselot, Ioannis Ignatiadis. In Situ Chemical Reduction of Chlorinated Organic Compounds. 2020, 283-398. https://doi.org/10.1007/978-3-030-40348-5_6
    6. Chao Lei, Fengyi Liang, Jing Li, Wenqian Chen, Binbin Huang. Electrochemical reductive dechlorination of chlorinated volatile organic compounds (Cl-VOCs): Effects of molecular structure on the dehalogenation reactivity and mechanisms. Chemical Engineering Journal 2019, 358 , 1054-1064. https://doi.org/10.1016/j.cej.2018.10.105
    7. Binbin Huang, Jimei Long, Wenqian Chen, Yuanyuan Zhu, Guangming Zeng, Chao Lei. Linear free energy relationships of electrochemical and thermodynamic parameters for the electrochemical reductive dechlorination of chlorinated volatile organic compounds (Cl-VOCs). Electrochimica Acta 2016, 208 , 195-201. https://doi.org/10.1016/j.electacta.2016.04.182
    8. Jin Luo, Jiwei Hu, Xionghui Wei, Liya Fu, Lingyun Li. Dehalogenation of persistent halogenated organic compounds: A review of computational studies and quantitative structure–property relationships. Chemosphere 2015, 131 , 17-33. https://doi.org/10.1016/j.chemosphere.2015.02.013
    9. Paul G. Tratnyek, Richard L. Johnson, Gregory V. Lowry, Richard A. Brown. IN SITU Chemical Reduction For Source Remediation. 2014, 307-351. https://doi.org/10.1007/978-1-4614-6922-3_10
    10. Sierra Rayne, Kaya Forest, Ken J. Friesen. Linear free energy relationship based estimates for the congener specific relative reductive defluorination rates of perfluorinated alkyl compounds. Journal of Environmental Science and Health, Part A 2009, 44 (9) , 866-879. https://doi.org/10.1080/10934520902958625

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