Advertisement

Environmental Science and Pollution Research

, Volume 26, Issue 3, pp 2345–2352 | Cite as

Computational investigations on the HO2 + CHBr2O2 reaction: mechanisms, products, and atmospheric implications

  • Yizhen TangEmail author
  • Chenggang Lu
  • Jingyu Sun
  • Youxiang Shao
  • Ying Gao
  • Zhihao Fu
Research Article
  • 32 Downloads

Abstract

Using quantum chemistry methods, mechanisms and products of the CHBr2O2 + HO2 reaction in the atmosphere were investigated theoretically. Computational result indicates that the dominant product is CHBr2OOH + O2 formed on the triplet potential energy surface (PES). While CBr2O + OH + HO2 produced on the singlet PES is subdominant to the overall reaction under the typical atmospheric condition below 300 K. Due to higher energy barriers surmounted, other products including CBr2O2 + H2O2, CBr2O + HO3H, CH2O + HO3Br, CHBrO + HO3 + Br, and CHBr2OH + O3 make minor contributions to the overall reaction. In the presence of OH radical, CHBr2OOH generates CHBr2O2 and CBr2O2 + H2O subsequently, which enters into new Br-cycle in the atmosphere. The substitution effect of alkyl group and halogens plays negligible roles to the dominant products in the RO2 + HO2 (X = H, CH3, CH2OH, CH2F, CH2Cl, CH2Br, CH2Cl, and CH2Br) reactions in the atmosphere.

Keywords

CHBr2O2 HO2 Mechanisms Halogen effect Atmospheric reaction 

Notes

Funding information

This work has been supported by the National Natural Science Foundation of China (No. 41775119, 21507027), Focus on Research and Development Plan in Shandong Province (2018GSF117017).

References

  1. Albritton DL, Watson RT (1993) Methyl Bromide: Its Atmospheric Science, Technology and Economics, Montreal Protocol Assessment Supplement. UNEP, Nairobi, KenyaGoogle Scholar
  2. Anderson JG (1976) The absolute concentration of OH(X2π) in the Earth's stratosphere. Geophys Res Lett 3:165–168CrossRefGoogle Scholar
  3. Anglada JM, Olivella S, Sole A (2006) Mechanistic study of the CH3O2+ HO2→ CH3O2H + O2 reaction in the gas phase. Computational evidence for the formation of a hydrogen-bonded Diradical complex. J Phys Chem A 110:6073–6082CrossRefGoogle Scholar
  4. Anglada JM, Olivella S, Sole A (2007) New insight into the gas-phase bimolecular self-reaction of the HOO radical. J Phys Chem A 111:1695–1704CrossRefGoogle Scholar
  5. Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648–5652CrossRefGoogle Scholar
  6. Catoire V, Lesclaux R, Lightfoot PD, Rayez MT (1994) Kinetic study of the reaction of CH2ClO2 with itself and with HO2, and theoretical study of the reactions of CH2ClO, between 251 and 600 K. J Phys Chem 98:2889–2898CrossRefGoogle Scholar
  7. Catoire V, Lesclaux R, Schneider WF, Wallington TJ (1996) Kinetics and Mechanisms of the Self-Reactions of CCl3O2 and CHCl2O2 Radicals and Their Reactions with HO2. J Phys Chem 100:14356–14371CrossRefGoogle Scholar
  8. Frisch MJ, Trucks GW, Schlegel HB, Gill PWM, Johnson BG, Robb MA, Cheeseman JR, Keith TA, Petersson GA, Pople JA et al (2010) Gaussian 09. Gaussian, Inc., Wallingford, CTGoogle Scholar
  9. Gligorovski S, Strekowski R, Barbati S, Vione D (2015) Environmental implications of hydroxyl radicals OH. Chemi Rev 115:13051–13092CrossRefGoogle Scholar
  10. Hossaini R, Chipperfield MP, Monge-Sanz BM, Richards NAD, Atlas E, Blake DR (2010) Bromoform and dibromomethane in the tropics: a 3-D model study of chemistry and transport. Atmos Chem Phys 10:719–735CrossRefGoogle Scholar
  11. Hou H, Wang BS (2005) Systematic Computational Study on the Reactions of HO2 with RO2: The HO2 + CH3O2(CD3O2) and HO2 + FCH2O2 Reactions. J Phys Chem A 109:451–460CrossRefGoogle Scholar
  12. Hou H, Wang BS (2007) Ab initio study of the reaction of propionyl (C2H5CO) radical with oxygen (O2). J Chem Phys 127:054306CrossRefGoogle Scholar
  13. Hou H, Deng LZ, Li JC, Wang BS (2005) A systematic computational study of the reactions of HO2 with RO2: the HO2 + CH2ClO2, CHCl2O2, and CCl3O2 reactions. J Phys Chem A 109:9299–9309CrossRefGoogle Scholar
  14. Johnson D, Price DW, Marston G (2004) Correlation-type structure activity relationships for the kinetics of gas-phase RO2 self-reactions and reaction with HO2. Atmosp Environ 38:1447–1458CrossRefGoogle Scholar
  15. Krishnan R, Binkley JS, Seeger R, Pople JA (1980) Self-consistent molecular orbital methods. XX. A basis set for correlated wave functions. J Chem Phys 72:650–654CrossRefGoogle Scholar
  16. Krysztofiak G, Catorie V, Poulet G, Marécal V, Pirre M, Louis F, Canneaux S, Josse B (2012) Detailed modeling of the atmospheric degradation mechanism of brominated very-short lived species. Atmosp. Environ. 59:514–532CrossRefGoogle Scholar
  17. Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the Electron density. Phys Rev B 37:785–789CrossRefGoogle Scholar
  18. Lightfoot PD, Cox RA, Crowley JN, Destriau M, Hayman GD (1992) Organic Peroxy radicals: kinetics, spectroscopy and tropospheric chemistry. Atmosp. Environ. 26:1805–1961CrossRefGoogle Scholar
  19. McGivern WS, Francisco JS, North SW (2004) Investigation of the atmospheric oxidation pathways of Bromoform and Dibromomethane: initiation via UV photolysis and hydrogen abstraction. J Phys Chem A 108:7247–7252CrossRefGoogle Scholar
  20. Montzka SA, Reimann S (2011) Ozone-depleting substances (ODSs) and related chemicals. Chapter 1 in scientific assessment of ozone depletion: 2010, global ozone research and monitoring project report no. World Meteorological Organization, Geneva, p 52Google Scholar
  21. Orlando JJ, Tyndall GS, Wallington TJ (2003) The atmospheric chemistry of Alkoxy radicals. Chem Rev 103:4657–4689CrossRefGoogle Scholar
  22. Shao YX, Hou H, Wang BS (2014) Theoretical study of the mechanisms and kinetics of the reactions of hydroperoxy (HO2) radicals with hydroxymethylperoxy (HOCH2O2) and methoxymethylperoxy (CH3OCH2O2) radicals. Phys Chem Chem Phys 16:22805–228011CrossRefGoogle Scholar
  23. Tang YZ, Wang BS, Wang RS (2008) Theoretical study on mechanisms and kinetics of NCCO + O2 reaction. J Phys Chem A 112:5295–5299CrossRefGoogle Scholar
  24. Tang YZ, Sun JY, Zhang YJ, Wang RS (2014) The atmospheric degradation pathways of BrCH2O2: computational calculation on mechanisms of the reaction with HO2. Chemosphere 111:545–553CrossRefGoogle Scholar
  25. Villenave E, Lesclaux R (1995) The UV absorption spectra of BrCH2 and BrCH2O2 and the reaction kinetics of BrCH2O2 with itself and with HO2 at 298 K. Chem Phys Lett 236:376–384CrossRefGoogle Scholar
  26. Wallington TJ, Dagaut P, Kurylo MJ (1992) Ultraviolet absorption cross-sections and reaction kinetics and mechanisms for Peroxy radicals in the gas phase. Chem Rev 92:667–710CrossRefGoogle Scholar
  27. Wallington TJ, Hurley MD, Schneider WF (1996) Atmospheric chemistry of CH3Cl: mechanistic study of the reaction of CH2ClO2 radicals with HO2. Chem Phys Lett 251:164–173CrossRefGoogle Scholar
  28. Wei WM, Zheng RH (2007) Theoretical study on the reaction mechanism of CH2ClO2 with HO2. J Mol Struct THEOCHEM 812:1–11CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.School of Environmental and municipal engineeringQingdao University of TechnologyQingdaoPeople’s Republic of China
  2. 2.College of Chemistry and Environmental engineeringHubei Normal UniversityHuangshiPeople’s Republic of China
  3. 3.School of Materials Science and Engineering, PCFM LabSun Yat-sen UniversityGuangzhouPeople’s Republic of China

Personalised recommendations