Cl-initiated photo-oxidation reactions of methyl propionate in atmospheric condition

Abstract

Cl-initiated photo-oxidation reaction of methyl propionate was investigated experimentally using relative rate method. Gas chromatography/mass spectrometry (GC-MS) and GC/infrared spectroscopy (GC-IR) were used as analytical tools to follow the concentrations of reactants and products during reaction. The gas-phase kinetics of methyl propionate with Cl atoms was measured over the temperature range of 263–363 K at 760 Torr in N2 atmosphere using C2H6 and C2H4 as reference compounds. The temperature-dependent rate coefficient for the reaction of methyl propionate with Cl atom was obtained as k(T) = [(3.25 ± 1.23) × 10−16] T2 exp [− (33 ± 4) / T] cm3 molecule−1 s−1. Theoretical calculations were also performed at CCSD(T)/cc-pVDZ//B3LYP/6-31G(d,p) level of theory, and the rate coefficients for H abstraction reactions were evaluated using canonical variational transition state theory (CVT/SCT) with interpolated single point energy (ISPE) method over the temperature range of 200–400 K. The rate coefficients over the studied temperature range yielded the Arrhenius expression k(T) = (7.22 × 10−16) T1.5 exp (466 / T) cm3 molecule−1 s−1. The reaction mechanism based on product analysis, thermochemistry, branching ratios, atmospheric implications, degradation pathways, and cumulative lifetime of methyl propionate is also presented in this manuscript.

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Acknowledgments

Authors wish to acknowledge Professor D.G. Truhlar for providing the GAUSSRATE 2009A as well as POLYRATE 2008 programs. The authors acknowledge Mr. V. Ravichandran and HPCE for supercomputing facility. BR acknowledges the Department of Science and Technology, Government of India for the financial support.

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Correspondence to Rajakumar Balla.

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Responsible editor: Gerhard Lammel

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Supporting Information.

Vibrational frequencies and structural parameters of reactants, transition states, and products obtained at the B3LYP/6-31G (d, p) level of theory. The details of the products of Cl initiated oxidation of methyl propionate. Variational plots of TS2, TS3, TS4, and TS5. IRC plots for the transition states. Mass spectrum, chromatograms and IR spectrum of each product obtained for the reaction of Methyl propionate with Cl atom.

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Balan, R.C., Balla, R. Cl-initiated photo-oxidation reactions of methyl propionate in atmospheric condition. Environ Sci Pollut Res 25, 20999–21010 (2018). https://doi.org/10.1007/s11356-018-2062-7

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Keywords

  • Methyl propionate
  • Atmospheric oxidants
  • Rate coefficients
  • Cumulative lifetimes
  • Product analysis and relative rate method