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Mechanism and kinetics of the oxidation of dimethyl carbonate by hydroxyl radical in the atmosphere

  • Mannangatti Gnanaprakasam
  • Lakshmanan Sandhiya
  • Kittusamy Senthilkumar
Research Article
  • 42 Downloads

Abstract

The mechanism and kinetics for the reaction of dimethyl carbonate (DMC) with OH radical have been studied by using quantum chemical methods. Four reaction pathways were identified for the initial reaction. In the first two pathways, hydrogen atom abstraction is taking place and alkyl radical intermediate is formed with the energy barrier of 6.4 and 7.9 kcal/mol. In the third pathway, OH addition reaction to the carbonyl carbon (C2) atom of DMC and intermediate, I2, is formed with an energy barrier of 11.9 kcal/mol. In the fourth pathway, along with CH3O, methyl hydrogen carbonate is formed. For this C–O bond breaking and O–H addition reaction, the energy barrier is 27 kcal/mol. The calculated enthalpy and Gibbs energy values show that the studied initial reactions are exothermic and exoergic except the OH addition reaction. For the initial reactions, the rate constants were calculated by using canonical variational transition state theory (CVT) with small curvature tunneling (SCT) correction over the temperature range of 278–1200 K. At 298 K, the calculated rate coefficient for the in-plane and out-of-plane hydrogen atom abstraction reaction pathway is 2.30 × 10−13 and 0.02 × 10−13 cm3 molecule−1 s−1. Further, the reaction between alkyl radical intermediate formed from the first pathway and O2 is studied. The reaction of alkyl peroxy radical intermediate with atmospheric oxidants, HO2, NO, and NO2 is also studied. It was found that the formic (methyl carbonic) anhydride is the end product formed from the atmospheric oxidation and secondary reactions of DMC.

Keywords

Dimethyl carbonate (DMC) H-atom abstraction reaction Reaction mechanism Transition state Rate constant 

Notes

Acknowledgements

The authors are thankful to UGC and Department of Science and Technology (DST), India, for funding the establishment of a high-performance computing facility under the SAP and PURSE programs.

Supplementary material

11356_2018_3831_MOESM1_ESM.docx (981 kb)
ESM 1 The optimized structure of the possible conformers of c,c-SC1 and t,c-SC2 of the reactive species involved in the DMC in reactant, transition state, intermediate complex and intermediates are shown in Figures S1, S2, and S3. The optimized structure of the reactive species involved in the secondary reactions of alkyl radical intermediate, I1a are shown in Figure S4. Harmonic vibrational frequencies, ZPEs and absolute energy values of reactant complex, transition states, intermediate complex, intermediate and product calculated at M06-2X/6-311++G(d,p) level of theory are summarized in Tables S1 and S2. The relative energy (∆Etot kcal/mol), enthalpy (∆H298 kcal/mol) and Gibbs free energy (∆G298 kcal/mol) of the reactive species involved in the initial reaction in c,c-SC1 conformer of dimethyl carbonate with OH radical is summarized in Table S3. Cartesian coordinates of the transition state involved in the studied reactions calculated at M06-2X/ 6-311++G(d,p) level of theory are summarized in Table S4. Relative Energy (∆Etot kcal/mol), enthalpy (∆H298 kcal/mol) and Gibbs energy (∆G298 kcal/mol) of the reactive species involved in the initial reaction of (t,c-SC2 conformer) of dimethyl carbonate with OH radical calculated at M06-2X/6-311++G(d,p) level of theory are summarized in Table S5. The calculated CVT, TST, TST(SCT), and CVT(SCT) rate coefficients (cm3 molecule−1 s−1) and branching ratio of alkyl radical intermediates formed from initial reactions (R1a and R1b ) of c,c-SC1 conformer of DMC are summarized in Table S6. The relative energy (∆Etot kcal/mol), enthalpy (∆H298 kcal/mol) and Gibbs energy (∆G298 kcal/mol) of reactant, transition state, intermediate and product involved in the secondary reactions of I1a is summarized in Table S7. (DOCX 980 kb)

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Copyright information

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

Authors and Affiliations

  • Mannangatti Gnanaprakasam
    • 1
  • Lakshmanan Sandhiya
    • 2
  • Kittusamy Senthilkumar
    • 1
  1. 1.Department of PhysicsBharathiar UniversityCoimbatoreIndia
  2. 2.Department of Chemistry and BiochemistryTexas Tech UniversityLubbockUSA

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