Theoretical investigations on the kinetics of Cl atom initiated reactions of series of 1-alkenes
- 129 Downloads
The temperature-dependent rate coefficients were calculated for the reactions of Cl atoms with propene (R1), 1-butene (R2), 1-pentene (R3), and 1-hexene (R4) over the temperature range of 200–400 K. Canonical variational transition state theory (CVT) with small curvature tunneling (SCT) and conventional transition state theory (CTST) in combination with MP2/6-31G(d,p), MP2/6-31G+(d,p), and MP2/6–311 + G(d,p) level of theories were used to calculate the kinetic parameters. The obtained rate coefficients at 298 K for the reactions of Cl atoms with propene, 1-butene, 1-pentene, and 1-hexene are 1.36 × 10−10 cm3 molecule−1 s−1, 1.53 × 10−10 cm3 molecule−1 s−1, 4.61 × 10−10 cm3 molecule−1 s−1, and 4.76 × 10−10 cm3 molecule−1 s−1, respectively. In all these reactions, strong negative temperature dependence was observed over the studied temperature range. Cl atom addition across the double bond is the most dominant pathway. The contribution of abstraction channels towards their global rate coefficients was observed to be increasing from propene to 1-hexane. Atmospheric implications such as effective lifetimes and thermodynamic parameters of the test molecules were investigated in the present study.
KeywordsAlkenes Atmospheric oxidants Rate coefficients Cumulative lifetimes Marine boundary layers
We gratefully acknowledge the Department of Science and Technology (DST), Government of India for their financial support and also we thank Mr.V. Ravichandran, High Performance Computing Environment (HPCE), IIT Madras for computer resources.
- Finlayson-Pitts BJ, Pitts JN Jr (1986) Atmospheric chemistry: fundamentals and experimental techniques. Wiley-Interscience, New YorkGoogle Scholar
- Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA et al (2010) Gaussian 09, revision B.01. Gaussian, Inc., WallingfordGoogle Scholar
- Gonzalez-Lafont A, Truong TN, Truhlar DG (1991) Interpolated variational transition state theory: practical methods for estimating variational transition state properties and tunneling contributions to chemical reaction rates from electronic structure calculations. J Chem Phys 95:8875–8894CrossRefGoogle Scholar
- Graedel TE (1978) Chemical compounds in the atmosphere. Academic Press, New YorkGoogle Scholar
- Keene WC. (1995) In Naturally produced organohalogens (eds A. Grimvall, E.W. B. de Leer) inorganic Cl cycling in the marine boundary layer: A Review. Academic Publishers, 363–373Google Scholar
- Kent JA (2007) Kent and Riegel’s hand book of Industrial Chemistry and Biotechnology (11th edn, Vol. 1)Google Scholar
- Zheng J, Zhang S, Corchado JC, Chuang YY, Coitiño EL, Ellingson BA, Truhlar DG (2010) GAUSSRATE, version 2009-A. University of Minnesota, MinneapolisGoogle Scholar
- Zheng J, Zhang S, Lynch BJ, Corchado JC, Chuang YY, Fast PL, Hu WP, Liu YP, Lynch GC, Nguyen KA et al (2009) POLYRATE, version, vol 2008. University of Minnesota, MinneapolisGoogle Scholar