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Mechanistic and kinetic study on the ozonolysis of ethyl vinyl ether and propyl vinyl ether

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Abstract

The reaction mechanisms for ozonolysis of ethyl vinyl ether (EVE) and propyl vinyl ether (PVE) have been investigated using the density functional theory (DFT) and ab initio method. Cycloaddition reactions of O3 to EVE and PVE are highly exothermic by 52.91 and 53.17 kcal/mol, respectively. Major products (formaldehyde, ethyl formate, and propyl formate) resulting from the both reactions are identified by comparing them with the experimental results. Further reactions of the most energy-rich Criegee intermediates (C2H5OCHOO and C3H7OCHOO) have been proposed in the presence of NO and H2O in which the main products are ethyl formate and propyl formate. The Multichannel Rice–Ramsperger–Kassel–Marcus (RRKM) approach is employed to calculate the total and individual rate constants for major product channels over a wide range of temperatures and different pressures. In the temperature range of 200–2500 K, the main path is the production of ethyl formate with k EVE+O3 = 4.67 × 10−12 exp(−3029/T), for the EVE with O3 reaction and k PVE+O3 = 3.58 × 10−12 exp(−2858/T) for the PVE with O3 reaction. At 298 K and 760 torr, the rate constants calculated are 1.80 × 10−16 and 2.45 × 10−16 cm3 molecule−1 s−1 for ozonolysis of EVE and PVE, which are consistent with the experimental results. The total rate constants show positive temperature dependence over the temperature range of 200–2000 K but pressure independence in the range of 0.01–10000 Torr. Estimation of branching ratios of several products is also performed. The influence of carbon chain length on reactivity toward ozone is examined.

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References

  1. Scarfogliero M, Picquet-Varrault B, Salce J, Durand-Jolibois R, Doussin JF (2006) Kinetic and mechanistic study of the gas-phase reactions of a series of vinyl ethers with the nitrate radical. J Phys Chem A 110:11074–11081

    Article  CAS  Google Scholar 

  2. Pschl U (2005) Atmospheric aerosols: composition, transformation, climate and health effects. Angew Chem Int Ed 44:7520–7540

    Article  Google Scholar 

  3. Jang M, Kamens RM (1999) Newly characterized products and composition of secondary aerosols from the reaction of α-pinene with ozone. Atmos Environ 33:459–474

    Article  CAS  Google Scholar 

  4. Kalberer M, Yu J, Cocker DR, Flagan RC, Seinfeld JH (2000) Aerosol formation in the cyclohexene-ozone system. Environ Sci Technol 34:4894–4901

    Article  CAS  Google Scholar 

  5. Thiault G, Thévent R, Mellouki A, Le Bras G (2002) OH and O3-initiated oxidation of ethyl vinyl ether. Phys Chem Chem Phys 4:613–619

    Article  CAS  Google Scholar 

  6. Mellouki A, Le Bras G, Sidebottom H (2003) Kinetics and mechanisms of the oxidation of oxygenated organic compounds in the gas phase. Chem Rev 103:5077–5096

    Article  CAS  Google Scholar 

  7. Wang L, Ge MF, Wang WG (2009) Kinetic study of the reactions of chlorine atoms with ethyl vinyl ether and propyl vinyl ether. Chem Phys Lett 473:30–33

    Article  CAS  Google Scholar 

  8. Sun XY, He MX, Zhang QZ, Wang WX, Jalbout AF (2008) Quantum chemical study on the atmospheric photooxidation of methyl vinyl ether (MVE). J Mol Struct 868:87–93

    CAS  Google Scholar 

  9. Zhou SM, Barnes I, Zhu T, Bejan I, Benter T (2006) Kinetic study of the gas-phase reactions of OH and NO3 radicals and O3 with selected vinyl ethers. J Phys Chem A 110:7386–7392

    Article  CAS  Google Scholar 

  10. Mellouki A (2006) Proceedings of the NATO ARW “environmental simulation chambers—application to atmospheric chemical processes”, Zakopane, Poland, 1–4 Oct 2004. NATO Science Series, IV. Earth and Environmental Sciences, Springer, Dordrecht, pp 163–170

  11. Barnes I, Zhou SM, Klotz B (2005) In Final reports of the EU project MOST; contract EVK2-CT-2001-00114; European Union: Brussels

  12. Grosjean E, Grosjean D (1999) The reaction of unsaturated aliphatic oxygenates with ozone. J Atmos Chem 32:205–232

    Article  CAS  Google Scholar 

  13. Dai SG (2006) Environmental chemistry. Higher Education Press, Beijing, p 18

    Google Scholar 

  14. He MX, Wang H, Sun XY, Zhang QZ, Wang WX (2009) Sensitivity of hydrogenated silicon nanodot on small polar molecules. J Theor Comput Chem 8:261–277

    Article  CAS  Google Scholar 

  15. Qu XH, Wang H, Zhang QZ, Shi XY, Xu F, Wang WX (2009) Mechanistic and kinetic studies on the homogeneous gas-phase formation of PCDD/Fs from 2,4,5-trichlorophenol. Environ Sci Technol 43:4068–4075

    Article  CAS  Google Scholar 

  16. Zhang QZ, Yu WN, Zhang RX, Zhou Q, Gao R, Wang WX (2010) Quantum chemical and kinetic study on dioxin formation from the 2,4,6-TCP and 2,4-DCP precursors. Environ Sci Technol 44:3395–3403

    Article  CAS  Google Scholar 

  17. Xu F, Wang H, Zhang QZ, Zhang RX, Qu XH, Wang WX (2010) Kinetic properties for the complete series reactions of chlorophenols with OH radicals relevance for dioxin formation. Environ Sci Technol 44:1399–1404

    Article  CAS  Google Scholar 

  18. Frisch MJ, Trucks GW, Schlegel HB, Gill PWM, Johnson BG, Robb MA, Cheeseman JR, Keith TA, Petersson GA, Montgomery JA, Raghavachari K, Allaham MA, Zakrzewski VG, Ortiz JV, Foresman JB, Cioslowski J, Stefanov BB, Nanayakkara A, Challacombe M, Peng CY, Ayala PY, Chen W, Wong MW, Andres JL, Replogle ES, Gomperts R, Martin RL, Fox DJ, Binkley JS, Defrees DJ, Baker J, Stewart JP, Head-Gordon M, Gonzales C, Pople JA (2003). Gaussian 03. Gaussian Inc., Wallingford

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

    Article  CAS  Google Scholar 

  20. Gonzalez C, Schlegel HB (1990) Reaction path following in mass-weighted internal coordinates. J Phys Chem 94:5523–5527

    Article  CAS  Google Scholar 

  21. Zhang D, Zhang R (2005) Ozonolysis of a-pinene and b-pinene: kinetics and mechanism. J Chem Phys 122:114308

    Article  Google Scholar 

  22. Zhang D, Zhang R (2002) Mechanism of OH formation from ozonolysis of isoprene: a quantum—chemical study. J Am Chem Soc 124:2692–2703

    Article  CAS  Google Scholar 

  23. Zhang D, Zhang RY, Park J, North SW (2002) Hydroxy peroxy nitrites and nitrates from OH initiated reactions of isoprene. J Am Chem Soc 124:9600–9605

    Article  CAS  Google Scholar 

  24. Jiang L, Xu YS, Ding AZ (2010) Reaction of stabilized criegee intermediates from ozonolysis of limonene with sulfur dioxide: ab initio and DFT study. J Phys Chem A 114:12452–12461

    Article  CAS  Google Scholar 

  25. Hou H, Wang BS (2007) Ab initio study of the reaction of propionyl (C2H5CO) radical with oxygen (O2). J Chem Phys 127:054306

    Article  Google Scholar 

  26. Wang F, Sun H, Sun JY, Jia XJ, Zhang YJ, Tang YZ, Pan XM, Su ZM, Hao LZ, Wang RS (2010) Mechanistic and kinetic study of CH2O+O3 reaction. J Phys Chem A 114:3516–3522

    Article  CAS  Google Scholar 

  27. Wang BS, Gu YS, Kong FN (1999) Theoretical investigation of the reaction of O(3P) with CH2Cl. J Phys Chem A 103:2060–2065

    Article  CAS  Google Scholar 

  28. Hou H, Li AX, Hu HY, Li YZ, Li H, Wang BS (2005) Mechanistic and kinetic study of the CH3CO+O2 reaction. J Chem Phys 122:224304

    Article  Google Scholar 

  29. Stein SE, Rabinovitch BS (1973) Accurate evaluation of internal energy level sums and densities including anharmonic oscillators and hindered rotors. J Chem Phys 58:2438–2445

    Article  CAS  Google Scholar 

  30. Astholz DC, Troe J, Wieters W (1979) Unimolecular processes in vibrationally highly excited cycloheptatrienes. I. Thermal isomerization in shock waves. J Chem Phys 70:5107–5116

    Article  CAS  Google Scholar 

  31. Troe J (1977) Theory of thermal unimolecular reactions at low pressures. I. Solutions of the master equation. J Chem Phys 66:4745–4757

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This study was supported financially by the National Nature Science Foundation of China (NSFC Nos. 20877049, 21077067, 20737001), Independent Innovation Foundation of Shandong University (IIFSDU, project No. 2009JC016), Foundation for Excellent Young and Middle-Aged Scientists of Shandong Province (BS2009SW037).

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  1. Environment Research Institute, Shandong University, Jinan, 250100, People’s Republic of China

    Dandan Han, Haijie Cao, Yanhui Sun & Maoxia He

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  1. Dandan Han
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  2. Haijie Cao
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Correspondence to Maoxia He.

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Han, D., Cao, H., Sun, Y. et al. Mechanistic and kinetic study on the ozonolysis of ethyl vinyl ether and propyl vinyl ether. Struct Chem 23, 499–514 (2012). https://doi.org/10.1007/s11224-011-9899-4

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