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Mechanistic investigation of the atmospheric oxidation of bis(2-chloroethyl) ether (ClCH2CH2OCH2CH2Cl) by OH and NO3 radicals and Cl atoms: a DFT approach

  • Subrata Paul
  • Nand Kishor GourEmail author
  • Ramesh Chandra DekaEmail author
Original Paper
  • 41 Downloads

Abstract

The oxidation of bis(2-chloroethyl) ether (ClCH2CH2OCH2CH2Cl) in the atmosphere, as initiated by various oxidants (OH and NO3 radicals and Cl atoms), was examined using the functional M06-2X in conjunction with the basis set 6–31 + G(d,p). We explored the oxidation pathways and reaction energies (enthalpies and Gibb’s free energies) for the abstraction of H from the –CH2Cl and –OCH2 sites of ClCH2CH2OCH2CH2Cl by oxidants. The energy profile shows that H abstraction from the −OCH2 site of the title molecule by each atmospheric oxidant is more likely than H abstraction from the other site. The resulting radical ClCH2CHOCH2CH2Cl was found to more stable than any other product, as shown by their reaction energies. The rate constants of the oxidation reactions were also calculated using canonical transition state theory in the temperature range 298–400 K. The calculated total rate constant at 298 K is consistent with the reported experimental rate constant. The branching ratio percentages and global atmospheric lifetime of the title molecule are also reported herein.

Keywords

HCE BCEE H abstraction M06-2X Rate constant 

Notes

Acknowledgments

Dr. S.P. and Dr. N.K.G. are grateful to the University Grant Commission (UGC), New Delhi for providing financial support in the form of a Dr. D.S. Kothari Postdoctoral Fellowship (award letter nos. F.4-2/2006(BSR)/CH/16-17/0152 and F.4-2/2006(BSR)/CH/14-15/0217).

Supplementary material

894_2019_3923_MOESM1_ESM.doc (88 kb)
ESM 1 (DOC 87 kb)

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Chemical SciencesTezpur UniversityTezpurIndia

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