Abstract
Experimental rate constants of the reactions of semiquinone radicals with hydroquinones in chlorobenzene at ∼300 K are by almost an order of magnitude higher than the rate constants of the reactions of phenoxyl radicals with phenols, which are equivalent to the former ones by heat effects. To reveal differences in the rate constants of these groups of reactions, we performed quantum chemical calculations of the energy profiles of the reactions and dissociation energies by the B3LYP density functional theory using the GAMESS and GAUSSIAN-03 programs in the 6-31+G* basis set. The solvation energies were calculated in all stationary points on the reaction coordinate by the method of polarized continuum model. In terms of the intersecting parabolas method, the reactions of semiquinone radicals with hydroquinones and phenoxyl radicals with phenols can be attributed to the same class of reactions only in the gas phase. In solvents this class of reactions is divided into two subclasses due to differences in solvation energies of the preliminary complexes and transition states of these reactions.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
E. T. Denisov and I. B. Afanas’ev, Oxidation and Antioxidants in Organic Chemistry and Biology, Taylor and Francis Co., Andover, 2005, 989 pp.
K. B. Piotrovskii and Z. N. Tarasova, Starenie i stabilizatsiya sinteticheskikh kauchukov i vulkanizatorov [Aging and Stabilization of Synthetic Rubbers and Vulcanizers], Khimiya, Moscow, 1980, 264 pp. (in Russian).
Oxidation Inhibition in Organic Materials, Eds J. Pospisil and P. P. Klemchuk, Vols 1, 2, CRC Press, Boca Raton, 1990.
E. T. Denisov and T. G. Denisova, Handbook of Antioxidants, CRC Press, Boca Raton, 2000, 289 pp.
E. B. Burlakova and N. G. Khrapova, Usp. Khim., 1985, 54, 1540 [Russ. Chem. Rev., 1985, 54 (Engl. Transl.)].
E. T. Denisov, Konstanty skorosti gomoliticheskikh zhidkofaznykh reaktsii [Rate Constants of Homolytic Liquid-Phase Reactions], Nauka, Moscow, 1971, 711 pp. (in Russian).
Landolt-Bornstein, Numerical Data and Functional Relationships in Science and Technology. New Series. Group Atomic and Molecular Physics, Springer Verlag, Berlin, 1984, Vol. 13(d).
E. T. Denisov and T. I. Drozdova, Kinet. Katal., 1997, 38, 35 [Kinet. Catal., 1997, 38 (Engl. Transl.)].
V. T. Varlamov, Kinet. Katal., 2001, 42, 836 [Kinet. Catal., 2001, 42 (Engl. Transl.)].
A. V. Antonov and V. T. Varlamov, Kinet. Katal., 2006, 47, 541 [Kinet. Catal., 2006, 47 (Engl. Transl.)].
E. T. Denisov, Mendeleev Commun., 1992, 2, 1.
M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. J. Su, T. L. Windus, M. Dupuis, and J. A. Montgomery, J. Comput. Chem., 1993, 14, 1347.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople, Gaussian 03, Revision C.02, Gaussian, Inc., Wallingford (CT), 2004.
M. Cossi, V. Barone, R. Cammi, and J. Tomasi, Chem. Phys. Lett., 1996, 255, 327.
V. T. Varlamov, Dokl. Akad. Nauk, 1993, 332, 457 [Dokl. Chem., 1993 (Engl. Transl.)].
V. T. Varlamov, Izv. Akad. Nauk, Ser. Khim., 2004, 293 [Russ. Chem. Bull., Int. Ed., 2004, 53, 306].
V. T. Varlamov, B. E. Krisyuk, and A. V. Antonov, Izv. Akad. Nauk, Ser. Khim., 2005, 2244 [Russ. Chem. Bull., Int. Ed., 2005, 54, 2317].
L. R. Mahoney and M. A. Da Rooge, J. Am. Chem. Soc., 1972, 94, 7002.
P. E. M. Siegbahn, L. A. Eriksson, F. Himo, and M. Pavlov, J. Phys. Chem., 1998, B102, 10622.
J. M. Mayer, D. A. Hrovat, J. L. Thomas, and W. T. Borden, J. Am. Chem. Soc., 2002, 124, 11142.
V. B. Luzhkov, Chem. Phys., 2005, 314, 211.
M. J. Lundquist and L. A. Eriksson, J. Phys. Chem., 2000, B104, 848.
Author information
Authors and Affiliations
Additional information
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1495–1501, September, 2006.
Rights and permissions
About this article
Cite this article
Varlamov, V.T., Krisyuk, B.E. Effect of solvation on the kinetic parameters of the reactions of phenoxyl radicals with phenols and semiquinone radicals with hydroquinones. Russ Chem Bull 55, 1549–1556 (2006). https://doi.org/10.1007/s11172-006-0453-2
Received:
Issue Date:
DOI: https://doi.org/10.1007/s11172-006-0453-2