Skip to main content
SpringerLink
Log in

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

  • Research Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Scheme 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  • Anderson SA, Manthata S, Root TW (2005) The decomposition of dimethyl carbonate over copper zeolite catalysts. Appl Catal A Gen 280:117–124

    Article  CAS  Google Scholar 

  • Atkinson R (2007) Rate constants for the atmospheric reactions of alkoxy radicals: an updated estimation method. Atmos Environ 41:8468–8485

    Article  CAS  Google Scholar 

  • Atkinson R, Arey J (2003) Atmospheric degradation of volatile organic compounds. Chem Rev 103:4605–4638

    Article  CAS  Google Scholar 

  • 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 40:6148

    Article  CAS  Google Scholar 

  • 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 121:6028–6035

    Article  CAS  Google Scholar 

  • 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 101:3514–3525

    Article  CAS  Google Scholar 

  • Bohets H, Vekan BV (1999) On the conformational behavior of dimethyl carbonate. Phys Chem Chem Phys 1:1817–1826

    Article  CAS  Google Scholar 

  • 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 25:1475–1482

    Article  CAS  Google Scholar 

  • 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 8:4877–4889

    Article  CAS  Google Scholar 

  • 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 100:12364–12368

    Article  Google Scholar 

  • 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 19:7147

    Article  CAS  Google Scholar 

  • Frisch MJ (2013) Gaussian 09, Revision D01. Gaussian Inc, Wallingford

    Google Scholar 

  • 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):1–17

    CAS  Google Scholar 

  • 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):2874–2883

    Article  CAS  Google Scholar 

  • Gonzalez C, Schlegel HB (1989) An improved algorithm for reaction path following. J Chem Phys 90:2154–2161

    Article  CAS  Google Scholar 

  • 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 108:5979–5989

    Article  CAS  Google Scholar 

  • Huang S, Yan B, Wang S (2015) Recent advances in dialkyl carbonates synthesis and applications. Chem Soc Rev 44:3079–3116

    Article  CAS  Google Scholar 

  • 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 42:5951–5960

    Article  CAS  Google Scholar 

  • 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 9:3149–3162

    Article  CAS  Google Scholar 

  • 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 43:151–174

    Article  CAS  Google Scholar 

  • Lei Y, Jing-yao L, Ze-sheng L (2008) Theoretical studies of the reaction of hydroxyl radical with methyl acetate. J Phys Chem A 112:6364

    Article  CAS  Google Scholar 

  • Martin JML (1996) Ab initio total atomization energies of small molecules-towards the basis set limit. Chem Phys Lett 259:669–678

    Article  CAS  Google Scholar 

  • 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 117:623–638

    Article  CAS  Google Scholar 

  • 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 107:2680–2692

    Article  CAS  Google Scholar 

  • Monks PS (2005) Gas-phase radical chemistry in the troposphere. Chem Soc Rev 34:376–395

    Article  CAS  Google Scholar 

  • North M, Pasquale R, Young C (2010) Synthesis of cyclic carbonates from epoxides and CO2. Green Chem 12:1514

    Article  CAS  Google Scholar 

  • Ono Y (1997) Catalysis in the production and reactions of dimethyl carbonate, an environmentally benign building block Appl. Catal A: Gen 155:133–166

    Article  CAS  Google Scholar 

  • 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 41:6294–6317

    Article  CAS  Google Scholar 

  • Orlando JJ, Tyndall GS, Willington TJ (2003) The atmospheric chemistry of alkoxy radicals. Chem Rev 103:4657–4690

    Article  CAS  Google Scholar 

  • Pacheco MA, Marshall CL (1997) Review of dimethyl carbonate (DMC) manufacture and its characteristics as a fuel additive. Energy Fuel 11:2–29

    Article  CAS  Google Scholar 

  • 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 180:396–406

    Article  CAS  Google Scholar 

  • 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 37:3639–3651

    Article  CAS  Google Scholar 

  • Sakakura T, Kohno K (2009) The synthesis of organic carbonates from carbon dioxide. Chem Commun 11:1312–1330

  • 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 117:4611–4626

    Article  CAS  Google Scholar 

  • 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 118:3479–3490

    Article  CAS  Google Scholar 

  • Shan-Shan P, Li-Ming W (2015) The atmospheric oxidation of o-xylene initiated bu hydroxyl radical. Acta Phys -Chim Sin 31:2259

    Google Scholar 

  • 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 118:4593–4610

    Article  CAS  Google Scholar 

  • 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):7235–7246

    Article  CAS  Google Scholar 

  • Singh HJ, Mishra BK (2011) Ab-initio studies on the decomposition kinetics of CF3OCF2O radical. J Mol Model 17:415–422

    Article  CAS  Google Scholar 

  • Singh HJ, Mishra BK, Rao PK (2012) Computational study on the thermal decomposition and isomerization of the CH3OCF2O* radical. Can J Chem 4:403

    Article  CAS  Google Scholar 

  • 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):8922–8933

    Article  CAS  Google Scholar 

  • Tuan TD, Balamurugan RA, Abdul MS (2015) Efficient ruthenium-catalyzed N-methylation of amine using methonal. ACS Catal 5:4082

    Article  CAS  Google Scholar 

  • Tundo P, Selva M (2002) The Chemistry of dimethyl carbonate. Acc Chem Res 35:706–716

    Article  CAS  Google Scholar 

  • Tundo P, Selva M (2010) ChemInform abstract: the chemistry of dimethyl carbonate. ChemInform 33:49

    Article  Google Scholar 

  • 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):157

    Google Scholar 

  • Vereecken L, Joseph SF (2012) Theoretical studies of atmospheric reaction mechanisms in the troposphere. Chem Soc Rev 41:6259–6293

    Article  CAS  Google Scholar 

  • 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 101:3514

    Article  Google Scholar 

  • 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 38:1197–1204

    Article  CAS  Google Scholar 

  • 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 125:094106

    Article  CAS  Google Scholar 

  • 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):1667–1676

    Article  CAS  Google Scholar 

  • Yang L, J-Y L, Z-S L (2008) Theoretical studies of the reaction of hydroxyl radical with methyl acetate. J Phys Chem A 112:6364–6372

    Article  CAS  Google Scholar 

  • 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 7:9484–9494

    Article  CAS  Google Scholar 

  • 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), 1095–1099

  • 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, 215–241

  • Zhao L, Ye L, Zhang F, Zhang L (2012) Thermal decomposition of 1-pentanol and its isomers: a theoretical study. J Phys Chem A 116:9238–9244

    Article  CAS  Google Scholar 

  • Zheng J, Zhang S, Corchado JC, Chuang YY, Coitino EL, Ellingson BA, Truhlar DG (2016a) GAUSSRATE version

  • 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 version

  • Ziemann PJ, Atkinson R (2012) Kinetics, products, and mechanisms of secondary organic aerosol formation. Chem Soc Rev 41:6582–6605

    Article  CAS  Google Scholar 

Download references

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.

Author information

Authors and Affiliations

  1. Department of Physics, Bharathiar University, Coimbatore, 641 046, India

    Mannangatti Gnanaprakasam & Kittusamy Senthilkumar

  2. Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX, USA

    Lakshmanan Sandhiya

Authors
  1. Mannangatti Gnanaprakasam
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Lakshmanan Sandhiya
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Kittusamy Senthilkumar
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Kittusamy Senthilkumar.

Additional information

Responsible editor: Gerhard Lammel

Electronic supplementary materials

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)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gnanaprakasam, M., Sandhiya, L. & Senthilkumar, K. Mechanism and kinetics of the oxidation of dimethyl carbonate by hydroxyl radical in the atmosphere. Environ Sci Pollut Res 26, 3357–3367 (2019). https://doi.org/10.1007/s11356-018-3831-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-018-3831-z

Keywords

Search

Navigation