Abstract
The temperature effect of the c-C6H12/c-C6D12 kinetic isotope effect (KIE) and the rate constant ratio c-C6H12/c-C5D10 (k6/k5) in the reactions of cycloalkanes with OH radicals in aqueous solution and in the gas phase has opposite signs. Values for the KIE and k6/k5 decrease with increasing temperature from 5 to 55 °C in the gas phase, while these values increase in solution. We propose that this phenomenon is a consequence of a solvent cage effect.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
R. Atkinson, Atmos. Chem. Phys., 3, 2233–2307 (2003).
G. V. Buxton, C. L. Greenstock, W. P. Helman, and A. B. Ross, J. Phys. Chem., Ref. Data, 17, No. 2, 513–886 (1988).
J. Prousek, Chem. Listy, 89, 11–21 (1995).
I. I. Moiseev, Izv. Akad. Nauk, Ser. Khim., No. 3, 578–588 (1995).
M. Anbar, D. Meyerstein, and P. Neta, J. Chem. Soc., B, No. 8, 742–747 (1966).
G. C. Stevens, R. M. Clarke, and E. J. Hart, J. Phys. Chem., 76, No. 25, 3863–3867 (1972).
T. Berces and A. F. Trotman-Dickeson, J. Chem. Soc., No. 10, 4281–4284 (1961).
B. Hickel, J. Phys. Chem., 79, No. 11, 1054–1059 (1975).
N. Getoff, Appl. Radiat. Isot., 40, 585–594 (1989).
N. Getoff, Radiat. Phys. Chem., 37, 673–680 (1991).
J. Rabani, M. Pick, and M. Simic, J. Phys. Chem., 78, 1049–1051 (1974).
T. Soylemez and R. H. Schuler, J. Phys. Chem., 78, 1052–1062 (1974).
E. S. Rudakov, Reactions of Alkanes with Oxidizing Agents, Metal Complexes and Radicals in Solution [in Russian], Naukova Dumka, Kiev (1985).
E. S. Rudakov, L. K. Volkova, and V. P. Tretyakova, React. Kinet. Catal. Lett., 16, No. 4, 333–337 (1981).
V. V. Goncharuk, G. L. Kamalov, G. A. Kovtun, et al., Catalysis. Mechanisms of Homogeneous and Heterogeneous Catalysis, Cluster Approaches [in Russian], Naukova Dumka, Kiev (2002).
Author information
Authors and Affiliations
Corresponding author
Additional information
__________
Translated from Teoreticheskaya i Éksperimental’naya Khimiya, Vol. 44, No. 1, pp. 35–39, January–February, 2008.
Rights and permissions
About this article
Cite this article
Lobachev, V.L., Rudakov, E.S., Matvienko, Y.V. et al. Kinetics and anomalous temperature dependence of the kinetic isotope effect of reactions of cycloalkanes C5H10, C6H12 and C6D12 with OH radicals in aqueous solutions. Theor Exp Chem 44, 37–41 (2008). https://doi.org/10.1007/s11237-008-9002-4
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11237-008-9002-4