Environmental Science and Pollution Research

, Volume 25, Issue 26, pp 26144–26156 | Cite as

Kinetics, mechanism, and global warming potentials of HFO-1234yf initiated by O3 molecules and NO3 radicals: insights from quantum study

  • Subrata Paul
  • Ramesh Chandra Deka
  • Nand Kishor GourEmail author
Research Article


In the present investigation, the oxidation of HFO-1234yf (2,3,3,3-tetrafluoropropene) with O3 molecule and NO3 radical is studied by quantum chemical methods. The possible reaction pathways of the titled molecule with O3 molecule and NO3 radical are analyzed using M06-2X meta-hybrid density functional with the 6-311++G(d,p) basis set. We have further employed a series of single-point energy calculations by using a potentially high-level couple cluster method with single and double excitations, including perturbative corrections ((CCSD(T)) at the same basis set. The addition reaction of HFO-1234yf with O3 molecule is initiated by the formation of primary ozonide complex, which leads to the formation of various carbonyl compounds and Criegee intermediates. The calculated energy barriers and thermochemical parameters inferred that decomposition of C˙H2OO˙ and CF3CFO is slightly more preferred over the formation of CF3C˙FOO˙ and CH2O. Further, the NO3 radical addition at α- and β-sits of CF3CF〓CH2 molecule is analyzed in details. The individual and overall rate constants for each reaction pathways are calculated by using canonical transition state theory over the temperature range of 250–450 K. We have observed that the computed rate constants are in good agreement with the available experimental data. Atmospheric lifetimes and global warming potentials of the HFO-1234yf are also reported in this manuscript.


HFO-1234yf POZ TSs Lifetime GWPs 


Funding information

Dr. SP and Dr. NKG are thankful to University Grant Commission (UGC), New Delhi for providing Dr. D. S. Kothari Post-Doctoral Fellowship (award letter no: F.4-2/2006(BSR)/CH/16-17/0152 and F.4-2/2006(BSR)/CH/14-15/0217).

Supplementary material

11356_2018_2633_MOESM1_ESM.doc (78 kb)
ESM 1 (DOC 78 kb)


  1. Atkinson R (1991) Kinetics and mechanisms of the gas phase reactions of the NO3 radical with organic compounds. J Phys Chem Ref Data 20:459–507CrossRefGoogle Scholar
  2. Balaganesh M, Rajakumar B (2014) Mechanism, kinetics and atmospheric fate of CF3CHCH2, CF3CFCH2, and CF3CFCF2 by its reaction with OH-radicals: CVT/SCT/ISPE and hybrid meta-DFT methods. J Mol Graph Model 48:60–69CrossRefGoogle Scholar
  3. Bravo I, Aranda A, Hurley MD, Marston G, Nutt DR, Shine KP, Smith K, Wallington TJ (2010) Infrared absorption spectra, radiative efficiencies, and global warming potentials of perfluorocarbons: comparison between experiment and theory. J Geophys Res Atmos 115:D24CrossRefGoogle Scholar
  4. Bravo I, Marston G, Nutt DR, Shine KP (2011) Radiative efficiencies and global warming potentials using theoretically determined absorption cross-sections for several hydrofluoroethers (HFEs) and hydrofluoropolyethers (HFPEs). J Quant Spectrosc Radiat Transf 112:1967–1977CrossRefGoogle Scholar
  5. Du B, Feng C, Zhang W (2009) Theoretical studies on the reaction mechanisms and rate constants for OH radicals with CF3CFCH2. Chem Phys Lett 479:37–42CrossRefGoogle Scholar
  6. Elakiya C, Shankar R, Vijayakumar S, Kolandaivel P (2017) A theoretical study on the reaction mechanism and kinetics of allyl alcohol (CH2〓CHCH2OH) with ozone (O3) in the atmosphere. Mol Phys 115:895–911CrossRefGoogle Scholar
  7. Farman JC, Gardiner BG, Shanklin JD (1985) Large losses of total ozone in Antarctica reveal seasonal ClOx/NOx interaction. Nature 315:207–210CrossRefGoogle Scholar
  8. Finlayson-Pitts BJ, Pitts Jr-JN (1999). Chemistry of the upper and lower atmosphere: theory, experiments, and applications. San Diego:Academic PressGoogle Scholar
  9. Frisch MJ, Trucks GW, Schlegel HB et al (2009) Gaussian 09. Gaussian, Inc, WallingfordGoogle Scholar
  10. Galano A, Muñoz-Rugeles L, Alvarez-Idaboy JR, Bao JL, Truhlar DG (2016) Hydrogen abstraction reactions from phenolic compounds by peroxyl radicals: multireference character and density functional theory rate constants. J Phys Chem A 120:4634–4642CrossRefGoogle Scholar
  11. Gonzalez C, Schlegel HB (1989) An improved algorithm for reaction path following. J Chem Phys 90:2154–2161CrossRefGoogle Scholar
  12. Gour NK, Sarma PJ, Mishra BK, Deka RC (2017) Night-time reaction of 2-chloroethyl methyl ether (CH3OCH2CH2Cl) initiated by NO3 radical: a theoretical insight. Comput Theor Chem 1110:1–7CrossRefGoogle Scholar
  13. Hammitt JK, Jain AK, Adams JL, Wuebbles DJ (1996) A welfare-based index for assessing environmental effects of greenhouse-gas emissions. Nature 381:301–303CrossRefGoogle Scholar
  14. Henne S, Shallcross DE, Reimann S, Xiao P, Brunner D, O’Doherty S, Buchmann B (2012) Future emissions and atmospheric fate of HFC-1234yf from mobile air conditioners in Europe. Environ Sci Technol 46:1650–1658CrossRefGoogle Scholar
  15. Hodnebrog Ø, Etminan M, Fuglestvedt JS, Marston G, Myhre G, Nielsen CJ, Shine KP, Wallington TJ (2013) Global warming potentials and radiative efficiencies of halocarbons and related compounds: a comprehensive review. Rev Geophys 51:300–378CrossRefGoogle Scholar
  16. Hurley MD, Wallington TJ, Javadi MS, Nielsen OJ (2008) Atmospheric chemistry of CF3CFCH2: products and mechanisms of Cl atom and OH radical initiated oxidation. Chem Phys Lett 450:263–267CrossRefGoogle Scholar
  17. Johnson D, Marston G (2008) The gas-phase ozonolysis of unsaturated volatile organic compounds in the troposphere. Chem Soc Rev 37:699–716CrossRefGoogle Scholar
  18. Johnston HS, Heicklen J (1962) Tunnelling corrections for unsymmetrical Eckart potential energy barriers. J Phys Chem 66:532–533CrossRefGoogle Scholar
  19. Kaiser EW, Wallington TJ (2012) Relative rate study of the kinetics, mechanism, and thermodynamics of the reaction of chlorine atoms with CF3CF〓CH2 (HFO-1234yf) in 650–950 Torr of N2 or N2/O2 diluent at 296–462 K. J Phys Chem A 116:5958–5971CrossRefGoogle Scholar
  20. Karagulian F, Rossi MJ (2005) The heterogeneous chemical kinetics of NO3 on atmospheric mineral dust surrogates. Phys Chem Chem Phys 7:3150–3162CrossRefGoogle Scholar
  21. Kazil J, McKeen S, Kim SW, Ahmadov R, Grell GA, Talukdar RK, Ravishankara AR (2014) Deposition and rainwater concentrations of trifluoroacetic acid in the United States from the use of HFO-1234yf. J Geophys Res Atmos 119:14059–14079CrossRefGoogle Scholar
  22. Laidler KJ (2004) Chemical kinetics, 3rd edn. Pearson Education, DelhiGoogle Scholar
  23. Logan JA (1985) Tropospheric ozone: seasonal behavior, trends, and anthropogenic influence. J Geophys Res Atoms 90:10463–10482CrossRefGoogle Scholar
  24. Molina MJ, Rowland FS (1974) Stratospheric sink for chlorofluoromethanes: chlorine atom-catalysed destruction of ozone. Nature 249:810–812CrossRefGoogle Scholar
  25. Nielsen OJ, Javadi MS, Andersen MS, Hurley MD, Wallington TJ, Singh R (2007) Atmospheric chemistry of CF3CFCH2: kinetics and mechanisms of gas-phase reactions with Cl atoms, OH radicals, and O3. Chem Phys Lett 439:18–22CrossRefGoogle Scholar
  26. Orkin VL, Huie RE, Kurylo MJ (1997) Rate constants for the reactions of OH with HFC-245cb (CH3CF2CF3) and some fluoroalkenes (CH2CHCF3, CH2CFCF3, CF2CFCF3, and CF2CF2). J Phys Chem A 101:9118–9124CrossRefGoogle Scholar
  27. Papadimitriou VC, Kambanis KG, Lazarou YG, Papagiannakopoulos P (2004) Kinetic study for the reactions of several hydrofluoroethers with chlorine atoms. J Phys Chem 108:2666–2674CrossRefGoogle Scholar
  28. Papadimitriou VC, Lazarou YG, Talukdar RK, Burkholder JB (2011) Atmospheric chemistry of CF3CF〓CH2 and (Z)-CF3CF〓CHF: cl and NO3 rate coefficients, Cl reaction product yields, and thermochemical calculations. J Phys Chem A 115:167–181CrossRefGoogle Scholar
  29. Papadimitriou VC, Talukdar RK, Portmann RW, Ravishankara AR, Burkholder JB (2008) CF3CF〓CH2 and (Z)-CF3CF〓CHF: temperature dependent OH rate coefficients and global warming potentials. Phys Chem Chem Phys 10:808–820CrossRefGoogle Scholar
  30. Pinnock S, Hurley MD, Shine KP, Wallington TJ, Smyth TJ (1995) Radiative forcing of climate by hydrochlorofluorocarbons and hydrofluorocarbons. J Geophys Res Atmos 100:23227–23238CrossRefGoogle Scholar
  31. Prinn RG, Huang J, Weiss RF, Cunnold DM, Fraser PJ, Simmonds PG, McCulloch A, Harth C, Salameh P, O'doherty S, Wang RH (2001) Evidence for substantial variations of atmospheric hydroxyl radicals in the past two decades. Science 292:1882–1888CrossRefGoogle Scholar
  32. Rao PK, Gejji SP (2017) Molecular insights for the HFO-1345fz+ X (X = Cl, O3 or NO3) reaction and fate of alkoxy radicals initiated by Cl: DFT investigations. J Fluor Chem 204:65–75CrossRefGoogle Scholar
  33. Rienstra-Kiracofe JC, Allen WD, Schaefer HF (2000) The C2H5 + O2 reaction mechanism: high-level ab-initio characterizations. J Phys Chem A 104:9823–9840CrossRefGoogle Scholar
  34. Solomon KR, Velders GJ, Wilson SR, Madronich S, Longstreth J, Aucamp PJ, Bornman JF (2016) Sources, fates, toxicity, and risks of trifluoroacetic acid and its salts: relevance to substances regulated under the Montreal and Kyoto Protocols. J Toxicol Enviro Health, Part B 19:289–304CrossRefGoogle Scholar
  35. Stocker TF, Dahe Q, Plattner GK, Tignor M (2015) IPCC workshop on regional climate projections and their use in impacts and risk anal-ysis studies. Instituto Nacional de Pesquisas Espaciais, São José dos Campos, Brazil,15–18 SeptemberGoogle Scholar
  36. Vereecken L, Crowley JN, Amedro D (2015) Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF3OCF〓CF2. Phys Chem Chem Phys 17:28697–28704CrossRefGoogle Scholar
  37. Wallington TJ, Schneider WF, Worsnop DR, Nielsen OJ, Sehested J, Debruyn WJ, Shorter JA (1994) The environmental impact of CFC replacements HFCs and HCFCs. Environ Sci Technol 28:320A–326ACrossRefGoogle Scholar
  38. Wayne RP, Barnes I, Biggs P, Burrows JP, Canosa-Mas CE, Hjorth J, Le Bras G, Moortgat GK, Perner D, Poulet G, Restelli G (1991) The nitrate radical: physics, chemistry, and the atmosphere. Atmos Environ Part A 25:1–203CrossRefGoogle Scholar
  39. WMO (World Meteorological Organization) (2014) Scientific assessment of ozone depletion: Global Ozone Research and Monitoring Project-Report No. 55, Geneva, Switzerland pp 416,
  40. Yang F, Deng F, Pan Y, Zhang Y, Tang C, Huang Z (2017) Kinetics of hydrogen abstraction and addition reactions of 3-hexene by OH radicals. J Phys Chem A 121:1877–1889CrossRefGoogle Scholar
  41. Zhao Y, Truhlar DG (2006) A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions. J Chem Phys 125:19410–1–19410-18CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Department of Chemical SciencesTezpur UniversityTezpurIndia

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