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Environmental Science and Pollution Research

, Volume 25, Issue 5, pp 4387–4405 | Cite as

Theoretical investigations on the kinetics of Cl atom initiated reactions of series of 1-alkenes

  • S. Vijayakumar
  • B. RajakumarEmail author
Research Article
  • 129 Downloads

Abstract

The temperature-dependent rate coefficients were calculated for the reactions of Cl atoms with propene (R1), 1-butene (R2), 1-pentene (R3), and 1-hexene (R4) over the temperature range of 200–400 K. Canonical variational transition state theory (CVT) with small curvature tunneling (SCT) and conventional transition state theory (CTST) in combination with MP2/6-31G(d,p), MP2/6-31G+(d,p), and MP2/6–311 + G(d,p) level of theories were used to calculate the kinetic parameters. The obtained rate coefficients at 298 K for the reactions of Cl atoms with propene, 1-butene, 1-pentene, and 1-hexene are 1.36 × 10−10 cm3 molecule−1 s−1, 1.53 × 10−10 cm3 molecule−1 s−1, 4.61 × 10−10 cm3 molecule−1 s−1, and 4.76 × 10−10 cm3 molecule−1 s−1, respectively. In all these reactions, strong negative temperature dependence was observed over the studied temperature range. Cl atom addition across the double bond is the most dominant pathway. The contribution of abstraction channels towards their global rate coefficients was observed to be increasing from propene to 1-hexane. Atmospheric implications such as effective lifetimes and thermodynamic parameters of the test molecules were investigated in the present study.

Keywords

Alkenes Atmospheric oxidants Rate coefficients Cumulative lifetimes Marine boundary layers 

Notes

Acknowledgements

We gratefully acknowledge the Department of Science and Technology (DST), Government of India for their financial support and also we thank Mr.V. Ravichandran, High Performance Computing Environment (HPCE), IIT Madras for computer resources.

Supplementary material

11356_2017_638_MOESM1_ESM.docx (353 kb)
ESM 1 (DOCX 353 kb)

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Copyright information

© Springer-Verlag GmbH Germany 2017

Authors and Affiliations

  1. 1.Department of ChemistryIndian Institute of Technology MadrasChennaiIndia

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