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

  • Mannangatti Gnanaprakasam
  • Lakshmanan Sandhiya
  • Kittusamy Senthilkumar
Research Article


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.


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



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)


  1. Anderson SA, Manthata S, Root TW (2005) The decomposition of dimethyl carbonate over copper zeolite catalysts. Appl Catal A Gen 280:117–124CrossRefGoogle Scholar
  2. Atkinson R (2007) Rate constants for the atmospheric reactions of alkoxy radicals: an updated estimation method. Atmos Environ 41:8468–8485CrossRefGoogle Scholar
  3. Atkinson R, Arey J (2003) Atmospheric degradation of volatile organic compounds. Chem Rev 103:4605–4638CrossRefGoogle Scholar
  4. Bhupesh Kumar M, Makroni L, Ramesh CD, AK C (2016) A theoretical insight into atmospheric chemistry of HFE-7100 and perfluoro-butyl formate: reactions with OH radicals and Cl atoms and the fate of alkoxy radicals. New J Chem 40:6148CrossRefGoogle Scholar
  5. Bhuvaneshwari R, Sandhiya L, Senthilkumar K (2017) Theoretical investigation on the reaction mechanism and kinetics of monochloroacetic acid with OH radical. J Phys Chem A 121:6028–6035CrossRefGoogle Scholar
  6. Bilde M, Mogelberg TE, Sehested J, Nielsen OJ, Wallington TJ, Hurley MD, Japar SM, Dill M, Orkin VL, Buckley TJ, Huie RE, Kurylo MJ (1997) Atmospheric chemistry of dimethyl carbonate: reaction with OH radicals, UV spectra of CH3OC(O)OCH2 and CH3OC(O)OCH2O2 radicals, reactions of CH3OC(O)OCH2O2 with NO and NO2, and fate of CH3OC(O)OCH2O radicals. J Phys Chem A 101:3514–3525CrossRefGoogle Scholar
  7. Bohets H, Vekan BV (1999) On the conformational behavior of dimethyl carbonate. Phys Chem Chem Phys 1:1817–1826CrossRefGoogle Scholar
  8. Deka RC, Mishra BK (2014) Theoretical investigation of the atmospheric chemistry of methyl difluoroacetate: reaction with Cl atoms and fate of alkoxy radical at 298 K. Struct Chem 25:1475–1482CrossRefGoogle Scholar
  9. Dillon TJ, Crowley JN (2008) Direct detection of OH formation in the reactions of HO2 with CH3C(O)O2 and other substituted peroxy radicals. Atmos Chem Phys 8:4877–4889CrossRefGoogle Scholar
  10. El Boudali A, Le Calve S, Le Bras GA, Mellouki A (1996) Kinetic studies of OH reactions with a series of acetates. J Phys Chem A 100:12364–12368CrossRefGoogle Scholar
  11. Fethi K, Binod RG, Milan S, Tam V-TM, Lam KH, Aamir F (2017) A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals. Phys Chem Chem Phys 19:7147CrossRefGoogle Scholar
  12. Frisch MJ (2013) Gaussian 09, Revision D01. Gaussian Inc, WallingfordGoogle Scholar
  13. Gnanaprakasam M, Sandhiya L, Senthilkumar K (2017) A theoretical investigation on the mechanism and kinetics of the gas-phase reaction of naphthalene with OH radical. Theor Chem Accounts 136(131):1–17Google Scholar
  14. Gomez-Balderas R, Coote ML, Henry DJ, Radom L (2004) Reliable theoretical procedures for calculating the rate of methyl radical addition to carbon-carbon double and triple bonds. J Phys Chem A 108(15):2874–2883CrossRefGoogle Scholar
  15. Gonzalez C, Schlegel HB (1989) An improved algorithm for reaction path following. J Chem Phys 90:2154–2161CrossRefGoogle Scholar
  16. Hasson AS, Tyndall GS, Orlando JJ (2004) A product yield study of the reaction of HO2 radicals with ethyl peroxy (C2H5O2), acetyl peroxy (CH3C(O)O2), and acetonyl peroxy (CH3C(O)CH2O2) radicals. J Phys Chem A 108:5979–5989CrossRefGoogle Scholar
  17. Huang S, Yan B, Wang S (2015) Recent advances in dialkyl carbonates synthesis and applications. Chem Soc Rev 44:3079–3116CrossRefGoogle Scholar
  18. Huidong Y, Liufang Z, Yaqiang X, Yu C, Liyi Y, Song T (2016) N-Methylation of poorly nucleophilic aromatic amines with dimethyl carbonate. Res Chem Intermed 42:5951–5960CrossRefGoogle Scholar
  19. Jenkin ME, Hurley MD, Wallington TJ (2007) Investigation of the radical product channel of the CH3C(O)O2+HO2 reaction in the gas phase. Phys Chem Chem Phys 9:3149–3162CrossRefGoogle Scholar
  20. Katrib Y, Deiber G, Mirabel P, George C, Mellouki A, Le bras G (2002) Atmospheric Loss Processes of Dimethyl and Diethyl Carbonate. J Atmos Chem 43:151–174CrossRefGoogle Scholar
  21. Lei Y, Jing-yao L, Ze-sheng L (2008) Theoretical studies of the reaction of hydroxyl radical with methyl acetate. J Phys Chem A 112:6364CrossRefGoogle Scholar
  22. Martin JML (1996) Ab initio total atomization energies of small molecules-towards the basis set limit. Chem Phys Lett 259:669–678CrossRefGoogle Scholar
  23. Merza G, Lászlo B, Oszko A, Baán K, Erdohelyi A (2016) The decomposition of dimethyl carbonate over carbon supported Cu catalysts. React Kinet Mech Catal 117:623–638CrossRefGoogle Scholar
  24. Miller JA, Klippenstein SJ (2003) From the multiple-well master equation to phenomenological rate coefficients: reactions on a C3H4 potential energy surface. J Phys Chem A 107:2680–2692CrossRefGoogle Scholar
  25. Monks PS (2005) Gas-phase radical chemistry in the troposphere. Chem Soc Rev 34:376–395CrossRefGoogle Scholar
  26. North M, Pasquale R, Young C (2010) Synthesis of cyclic carbonates from epoxides and CO2. Green Chem 12:1514CrossRefGoogle Scholar
  27. Ono Y (1997) Catalysis in the production and reactions of dimethyl carbonate, an environmentally benign building block Appl. Catal A: Gen 155:133–166CrossRefGoogle Scholar
  28. Orlando JJ, Tyndall GS (2012) Laboratory studies of organic peroxy radical chemistry an overview with emphasis on recent issues of atmospheric significance. Chem Soc Rev 41:6294–6317CrossRefGoogle Scholar
  29. Orlando JJ, Tyndall GS, Willington TJ (2003) The atmospheric chemistry of alkoxy radicals. Chem Rev 103:4657–4690CrossRefGoogle Scholar
  30. Pacheco MA, Marshall CL (1997) Review of dimethyl carbonate (DMC) manufacture and its characteristics as a fuel additive. Energy Fuel 11:2–29CrossRefGoogle Scholar
  31. Rajesh Kumar B, Sravanan S (2016) Partially premixed low temperature combustion using dimethyl carbonate (DMC) in a DI diesel engine for favorable smoke/NOx emissions. Fuel 180:396–406CrossRefGoogle Scholar
  32. Rena X, Harder H, Martinez M, Lesher RL, Oliger A, Simpas XL, Gao HL (2003) OH and HO2 chemistry in the urban atmosphere of New York City. Atoms Environ 37:3639–3651CrossRefGoogle Scholar
  33. Sakakura T, Kohno K (2009) The synthesis of organic carbonates from carbon dioxide. Chem Commun 11:1312–1330Google Scholar
  34. Sandhiya L, Kolandaivel P, Senthilkumar K (2013) Mechanism and kinetics of the atmospheric oxidative degradation of dimethylphenol isomers initiated by OH radical. J Phys Chem A 117:4611–4626CrossRefGoogle Scholar
  35. Sandhiya L, Kolandaivel P, Senthilkumar K (2014) Oxidation and nitration of tyrosine by ozone and nitrogen dioxide- reaction mechanisms, biological and atmospheric implications. J Phys Chem B 118:3479–3490CrossRefGoogle Scholar
  36. Shan-Shan P, Li-Ming W (2015) The atmospheric oxidation of o-xylene initiated bu hydroxyl radical. Acta Phys -Chim Sin 31:2259Google Scholar
  37. Shiroudi A, Deleuze MS, Canneaux S (2014) Theoretical study of the oxidation mechanisms of naphthalene initiated by hydroxyl radicals: the OH-addition pathway. J Phys Chem A 118:4593–4610CrossRefGoogle Scholar
  38. Simmie JM, Somers KP (2015) Benchmarking compound methods (CBS-QB3, CBS-APNO, G3, G4, W1BD) against the active thermochemical tables: a litmus test for cost-effective molecular formation enthalpies. J Phys Chem A 119(28):7235–7246CrossRefGoogle Scholar
  39. Singh HJ, Mishra BK (2011) Ab-initio studies on the decomposition kinetics of CF3OCF2O radical. J Mol Model 17:415–422CrossRefGoogle Scholar
  40. Singh HJ, Mishra BK, Rao PK (2012) Computational study on the thermal decomposition and isomerization of the CH3OCF2O* radical. Can J Chem 4:403CrossRefGoogle Scholar
  41. Somers KP, Simmie JM (2015) Benchmarking Compound methods (CBS-QB3, CBS-APNO, G3, G4, W1BD) against the active thermochemical tables: formation enthalpies of radicals. J Phys Chem A 119(33):8922–8933CrossRefGoogle Scholar
  42. Tuan TD, Balamurugan RA, Abdul MS (2015) Efficient ruthenium-catalyzed N-methylation of amine using methonal. ACS Catal 5:4082CrossRefGoogle Scholar
  43. Tundo P, Selva M (2002) The Chemistry of dimethyl carbonate. Acc Chem Res 35:706–716CrossRefGoogle Scholar
  44. Tundo P, Selva M (2010) ChemInform abstract: the chemistry of dimethyl carbonate. ChemInform 33:49CrossRefGoogle Scholar
  45. Tyndall GS, Cox RA, Granier C, Moortgat GK, Pilling MJ, Ravishankara AR, Wallington TJ (2001) Atmospheric chemistry of small organic peroxy radicals. J Geophys Res 106(12):157Google Scholar
  46. Vereecken L, Joseph SF (2012) Theoretical studies of atmospheric reaction mechanisms in the troposphere. Chem Soc Rev 41:6259–6293CrossRefGoogle Scholar
  47. Wallington TJ, Hurley MD, Japar SM, Dill M (1997) Atmospheric chemistry pf dimethyl carbonate: reaction with OH radicals, UV spectra of CH3OC(O)OCH2 and CH3OC(O)OCH2O2 radicals, reactions of CH3OC(O)OCH2O2 with NO and NO2 and fate of CH3OC(O)OCH2O radicals. J Phys Chem A 101:3514CrossRefGoogle Scholar
  48. Wenger J, Porter E, Collins E, Treacy J, Sidebottom H (1999) Mechanisms for the chlorine atom initiated oxidation of dimethoxymethane and 1,2-dimethoxyethane in the presence of NOx. Chemosphere 38:1197–1204CrossRefGoogle Scholar
  49. Wood GPF, Radom L, Petersson GA, Barnes EC, Frisch MJ, Montgomery JA Jr (2006) A restricted-open-shell complete-basis-set model chemistry. J Chem Phys 125:094106CrossRefGoogle Scholar
  50. Xu X, Alecu IM, Truhlar DG (2011) How well can modern density functional predict internuclear distances at transition states? J Chem Theory Comput 7(6):1667–1676CrossRefGoogle Scholar
  51. Yang L, J-Y L, Z-S L (2008) Theoretical studies of the reaction of hydroxyl radical with methyl acetate. J Phys Chem A 112:6364–6372CrossRefGoogle Scholar
  52. Yu Q, Xie H-B, Li T, Ma F, Fu Z, Wang Z, Li C, Fu Z, Xia D, Chen J (2017) Atmospheric chemical reaction mechanism and kinetics of 1,2-bis (2,4,6-tribromophenoxy) ethane initiated by OH radical: a computational study. RSC Adv 7:9484–9494CrossRefGoogle Scholar
  53. Zhao Y, Truhlar DG (2008a): How well can new-generation density functionals describe the energetics of bond-dissociation reactions producing radicals? J Phys Chem A 112(6), 1095–1099CrossRefGoogle Scholar
  54. Zhao Y, Truhlar G (2008b): The M06 suite of density functions for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor Chem Accounts 120, 215–241CrossRefGoogle Scholar
  55. Zhao L, Ye L, Zhang F, Zhang L (2012) Thermal decomposition of 1-pentanol and its isomers: a theoretical study. J Phys Chem A 116:9238–9244CrossRefGoogle Scholar
  56. Zheng J, Zhang S, Corchado JC, Chuang YY, Coitino EL, Ellingson BA, Truhlar DG (2016a) GAUSSRATE versionGoogle Scholar
  57. Zheng J, Zhang S, Lynch BJ, Corchado JC, Chaung YY, Fast PL, Hu WP, Liu YP, Lynch GC, Nguyen KA, Jackels CF, Ramos AF, Ellingson BA, Melissas VS, Villa J, Rossi I, Coitino EL, Pu J, Albu TV (2016b) POLYRATE versionGoogle Scholar
  58. Ziemann PJ, Atkinson R (2012) Kinetics, products, and mechanisms of secondary organic aerosol formation. Chem Soc Rev 41:6582–6605CrossRefGoogle Scholar

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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