Quantum chemical study on the reaction mechanism and kinetics of Cl-initiated oxidation of methyl n-propyl ether

  • Subrata Paul
  • Ramesh Chandra Deka
  • Nand Kishor Gour
Regular Article

Abstract

Oxidation of methyl n-propyl ether (CH3CH2CH2OCH3) molecule initiated by Cl atoms has been carried out using a dual level of quantum chemical investigation to understand the mechanistic pathways and kinetics of the H-atom abstraction reaction. Firstly, geometry optimization and frequency calculations for all the species are performed using BHandHLYP/6-311++G(d,p) level of theory at 298 K, and energetic calculations are further refined using CCSD(T) method with the same basis set to explore all stationary points on potential energy profile. We have observed from the energy profile that H-atom abstraction from –OCH2 group of CH3CH2CH2OCH3 is the kinetically predominant pathway. The reported bond dissociation energy for the dominant path is found to be in good agreement with the experimentally determined value. Further, standard Gibbs free energies (ΔG°298) and standard enthalpies (ΔH°298) analyses also indicate that the H-atom abstraction from –OCH2 group of CH3CH2CH2OCH3 is thermodynamically more favourable than other abstraction channels. The rate coefficients are also reported using canonical transition state theory, which is found to be in good agreement with the experimental data. The atmospheric lifetime of title molecule is also calculated.

Keywords

OVOCs MnPE BHandHLYP CCSD(T) CTST BDE 

Notes

Acknowledgements

SP and NKG are thankful to University Grant Commission (UGC), New Delhi, for providing Dr. D. S. Kothari Post-Doctoral 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

214_2018_2239_MOESM1_ESM.docx (437 kb)
Supplementary material 1 (DOCX 437 kb)

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Subrata Paul
    • 1
  • Ramesh Chandra Deka
    • 1
  • Nand Kishor Gour
    • 1
  1. 1.Department of Chemical SciencesTezpur UniversityTezpurIndia

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