Abstract
The intersecting parabolas model (IPM) is used to analyze the measured kinetic parameters for the concerted molecular decomposition of chloroalkanes RCl to olefin and HCl. According to this model, the configuration of the transition state is formed by three atoms: C…H…Cl. The activation energy E and the rate constant k for 12 previously unstudied reactions of concerted molecular decomposition of RCl are calculated based on the enthalpy of reaction by using the IPM algorithms. The factors that influence the activation energy E for RCl decomposition are established: the enthalpy of reaction, energy of stabilization of radical R•, presence of a π bond adjacent to the reaction center, and dipole–dipole interaction for the decomposition of polychloroalkanes. The values of E and k for reverse reactions of addition of HCl to olefins are evaluated. The energy spectrum of partial activation energies for the concerted molecular decomposition of RCl is constructed.
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References
C. K. Ingold, Structure and Mechanism in Organic Chemistry (Cornell Univ., Ithaca, 1969).
E. T. Denisov, O. M. Sarkisov, and G. I. Likhtenshtein, Chemical Kinetcs: Fundamentals and New Developments (Elsevier, Amsterdam, 2003), p. 268.
M. G. Safarov, F. A. Valeev, V. G. Safarova, and L. Kh. Faizullina, Principles of Organic Chemistry (Khimiya, Moscow, 2012), p. 116 [in Russian].
N. N. Semenov, Selected Works, Vol. 3: On Some Problems of Chemical Kinetics and Reaction Ability (Nauka, Moscow, 2005) [in Russian].
S. Benson, Thermochemical Kinetics (Wiley, New York, 1968), p. 111.
E. S. Swinbourne, in Comprehensive Chemical Kinetics, Ed. by C. H. Bamford and C. F. H. Tipper (Elsevier, Amsterdam, 1972), Vol. 5, p. 149.
S. W. Benson and H. E. O’Neal, Kinetic Data on Gas Phase Unimolecular Reactions (NSRDS-NBS 21, Gaithersburg, 1970), p. 628.
E. T. Denisov and T. S. Pokidova, Russ. Chem. Rev. 81, 415 (2012).
L. L. Bladow, C. J. Stopera, W. D. Thweatt, and M. Page, J. Phys. Chem. A 112, 11931 (2008).
L. L. Bladow, C. J. Stopera, W. D. Thweatt, and M. Page, J. Phys. Chem. A 114, 4304 (2010).
E. T. Denisov, Russ. Chem. Rev. 66, 859 (1997).
E. T. Denisov, Khim. Fiz. 11, 1328 (1992).
I. V. Aleksandrov, Teor. Eksp. Khim. 12, 878 (1976).
NIST Standart Reference Database 17, NIST Chemical Kinetics Database, Ver. 6.0 (Gaithersburg, 1994).
D. Stull, E. Westrum, and G. Sinke, Chemical Thermodynamics of Organic Compounds (Wiley, New York, 1969; Mir, Moscow, 1971).
E. S. Domalski and E. D. Hearing, J. Phys. Chem. Ref. Data 22, 805 (1993).
W. Tsang, J. Chem. Phys. 41, 2487 (1964).
H. Hartman, H. Heydtmann, and G. Rinck, Z. Phys. Chem. 28, 71 (1961).
D. H. R. Barton and P. F. Onyon, J. Am. Chem. Soc. 72, 988 (1950).
H. Hartman, H. G. Bosche, and H. Heydtmann, Z. Phys. Chem. 42, 329 (1964).
K. E. Howlett, J. Chem. Soc., 945 (1953).
K. E. Howlett, J. Chem. Soc., 4487 (1952).
A. Maccoll and S. C. Wong, J. Chem. Soc. B, 1492 (1968).
P. J. Thomas, J. Chem. Soc., 136 (1961).
R. I. Failes and V. R. Stimson, Aust. J. Chem. 20, 1553 (1967).
H. Heydtmann and G. Rinck, Z. Phys. Chem. (Neue Folge) 30, 250 (1961).
E. S. Swinbourne, J. Chem. Soc., 4668 (1960).
E. S. Swinbourne, Aust. J. Chem. 11, 314 (1958).
D. H. R. Barton, A. J. Head, and R. J. Williams, J. Chem. Soc., 453 (1952).
M. R. Bridge, D. H. Davies, A. Maccoll, and R. A. Ross, J. Chem. Soc. B, 805 (1968).
A. Maccoll and S. C. Wong, J. Chem. Soc. B, 1492 (1968).
C. J. Harding, A. Maccoll, and R. A. Ross, J. Chem. Soc. B, 634 (1969).
E. T. Denisov, T. G. Denisova, and T. S. Pokidova, Handbook of Free Radical Initiators (Wiley, Hoboken, New Yersey, 2003).
Y.-R. Luo, Comprehensive Handbook of Chemical Bond Energies (CRC, Boca Raton, FL, 2007), p. 9.
Handbook of Chemistry and Physics (CRC, Boca Raton, FL, 2004–2005), p. 5.
H. C. Brown and Y. Okamoto, J. Am. Chem. Soc. 79, 1913 (1957).
L. Hammet, Physical Organic Chemistry: Reaction Rates, Equilibria and Mechanisms (McGraw-Hill, New York, 1970).
E. T. Denisov and T. G. Denisova, Pet. Chem. 55, 85 (2015).
E. T. Denisov and T. G. Denisova, Application of Thermodynamics to Biological and Materials Science, Ed. by T. Mazutani (InTech, Rijeka, Croatia, 2011), p. 405.
E. T. Denisov, Zh. Fiz. Khim. 68, 1206 (1994).
E. T. Denisov, Kinet. Catal. 49, 313 (2008).
E. T. Denisov, Kinetics of Homogeneous Chemical Reactions (Vyssh. Shkola, Moscow, 1988), p. 72 [in Russian].
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Original Russian Text © T.S. Pokidova, E.T. Denisov, 2016, published in Khimicheskaya Fizika, 2016, Vol. 35, No. 5, pp. 23–35.
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Pokidova, T.S., Denisov, E.T. Parabolic model of the concerted molecular decomposition of chloroalkanes. Russ. J. Phys. Chem. B 10, 394–406 (2016). https://doi.org/10.1134/S1990793116030064
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DOI: https://doi.org/10.1134/S1990793116030064