Abstract
Gas-phase reaction mechanisms of ozone with cis/trans-3-hexenyl acetate and cis/trans-2-hexenyl acetate are performed using density functional theory. The reactions are initiated by the formation of the primary ozonides which are followed by the reactions of biradicals with H2O or NO. The formation of the secondary ozonide (SOZ) is also studied. On the basis of the above DFT calculations, the modified multichannel RRKM theory is used to evaluate the rate constants. At 298 K and 101 kPa, the calculated total rate constants are 9.84 × 10−17, 1.39 × 10−17, 2.50 × 10−17, and 7.37 × 10−17 cm3 mol−1 s−1 for cis-3-hexenyl acetate, trans-2-hexenyl acetate, cis-2-hexenyl acetate, and trans-3-hexenyl acetate, respectively. Our results are in good agreement with experimental values. The total rate coefficients are almost pressure-independent in the range of 0.01–10,000 Torr, but show temperature dependence over the whole study range (200–2,000 K). In addition, branching ratios of the favorable reaction channels are obtained.
Similar content being viewed by others
References
Graedel TE (1978) Chemical Compounds in the Atmosphere. Academic, New York
Wine AM, Arey J, Atkinson R, Aschmann SM, Long WD, Morrison CL (1991) Atmos Environ 25A:1063–1075
Winter M, Willhalm B (1964) Helv Chirn Acta 47:1215–1227
Smith DF, Kleindienst TE, Hudgens EE, McIver CD, Bufalini J (1992) Int J Che Kinet 24:199–215
Wallington TJ, Andino JM, Potts AR, Rudy SJ, Siegl WO, Zhang Z, Kurylo MJ, Huie RE (1993) Environ Sci Technol 27:98–104
Mellouki A, Le Bras G, Sidebottom H (2003) Chem Rev 103:5077–5096
Arey J, Winer AM, Atkinson R, Aschmann SM, Long WD, Momson CL, Olszyk DM (1991) J Geophys Res 96:9329–9336
Grosjean E, Grosjean D (1999) J Atmos Chem 32:205–232
Atkinson R, Arey J, Aschmann SM, Corchnoy SB, Shu Y (1995) Int J Chem Kinet 27:941–955
Picquet-Varrault B, Scarfogliero M, Doussin JF (2010) Sci Technol 44:4615–4621
Vogel B, Fiedler F, Vogel H (1995) J Geophys Res 100:22907
Saxena P, Hildemann LM (1996) J Atmos Chem 24:57–109
McKeen SA, Hsie E-Y, Trainer M, Tallamraju R, Liu SC (1991) J Geophys Res 96:15377–15394
Atkinson R, Carter WPL (1984) Chem Rev 84:437–470
Le Calvé S, Mellouki A, Le Bras G, Treacy J, Wenger J, Sidebottom H (2000) J Atmos Chem 37:161–172
Grosjean E, Grosjean D, Seinfeld JH (1996) Int J Chem Kinet 28:373–382
He MX, Cao HJ, Sun YH, Han DD, Hu JT (2012) Atmos Environ 49:197–205
He MX, Sun YH, Cao HJ, Han DD, Hu JT (2012) Struct Chem 23:201–208
Grosjean E, Grosjean D (1998) Int J Chem Kinet 30:21–29
Grosjean E, Grosjean D (1997) J Atmos Chem 27:271–289
Hou H, Wang BS (2007) J Chem Phys 127:054306
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
Gonzalez C, Schlegel HB (1989) J Chem Phys 90:2154–2161
Gonzalez C, Schlegel HB (1990) J Phys Chem 94:5523–5527
Jiang L, Xu YS, Ding AZ (2010) J Phys Chem 114:12452–12461
Zhang D, Zhang R (2002) J Am Chem Soc 124:2692–2703
Zhang D, Zhang R (2005) J Chem Phys 122:114308
Wang BS, Gu YS, Kong FN (1999) J Phys Chem 103:2060–2065
Astholz DC, Troe J, Wieters W (1979) J Chem Phys 70:5107–5116
Stein SE, Rabinovitch BS (1973) J Chem Phys 58:2438–2445
Criegee R (1957) Record of Chem Progress 18:111
Criegee R (1962) In Peroxide Reaction Mechanisms. London, New York
Kohlmiller CK, Andrews L (1981) Am Chem Soc 103:2578–2583
Anachkov MP, Rakovsky SK, Zaikov GE (2007) J Appl Polym Sci 104:427–433
Razumovskii SD, Zaikov GE (1980) Russ Chem Rev 49:1163–1180
Neeb P, Moortgat GK (1999) J Phys Chem 103:9003–9012
Acknowledgments
This work was supported financially by the National Nature Science Foundation of China (NSFC No. 21077067), Foundation for Excellent Young and Middle-Aged Scientists of Shandong Province (BS2009SW037, BS2010SF016), and China Postdoctoral Science Special Foundation (200902560).
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Li, J., Sun, Y., Cao, H. et al. Mechanisms and kinetics of the ozonolysis reaction of cis-3-hexenyl acetate and trans-2-hexenyl acetate in atmosphere: a theoretical study. Struct Chem 25, 71–83 (2014). https://doi.org/10.1007/s11224-013-0226-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11224-013-0226-0