Abstract
It has long been recognized that the key intermediates for the majority of the reactions of organic molecules in the gas phase, and frequently in the liquid phase as well, are free radicals. An important prerequisite for the description of the behavior of such systems is their thermodynamic properties. At first glance it may be surprising that thermodynamic properties should have any applicability to transient species that are present in trace quantities and disappear in short times. Indeed, if the kinetic properties of such systems are known, then thermodynamic properties are not really necessary and can in fact be derived from the kinetics. In reality, however, kinetic properties may be unavailable or difficult to measure. Thermodynamic properties serve as limits for kinetics and more generally as a basis for the estimation and evaluation of kinetic information [1]. More directly, through the equilibrium constant, rate constants for the reverse direction can be directly calculated from that in the forward direction. There are other physical situations where local thermodynamic equilibrium turns out to be a satisfactory approximation and kinetic information is not important.
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsPreview
Unable to display preview. Download preview PDF.
References
Benson, S. W. (1976) Thermochemical Kinetics. John Wiley and Sons, New York.
O’neal, H. E. and Benson, S. W. (1993) In Free Radicals, Vol 2, J. K. Kochi (ed.) John Wiley and Sons, New York, p. 272.
Berkowitz, J., Ellison, G. B. and Gutman, D. J. (1994) Phys. Chem., 98, 2744.
Mcmillen, D. F. and Golden, D. M. (1982) Annu. Rev. Phys. Chem., 33, 493.
Tsang, W. (1978) Int. J. Chem. Kin., 10, 821.
Tsang, W. (1981) Comparative Rate Single Pulse Shock Tube in the Thermal Stability of Polyatomic Molecules. In Shock Tubes in Chemistry, A. Lifshitz (ed.), Marcel Dekker, New York, p. 59.
Stull, D. R., Westrum, E. F. Jr., and Sinke, G. C. (1969) The Chemical Thermodynamics of Organic Compounds. John Wiley and Sons, New York.
Kerr, J. A. and Lloyd, A. C. (1968) Quart. Rev., 22, 549.
Kerr, J. A. and Parsonage, M. J. (1972) Evaluated Kinetic Data on Gas Phase Addition Reactions. Butterworths, London.
Harris, G. W. and Pitts, J. N. (1982) J. Chem. Phys., 77, 3995.
Brouard, M., Lightfoot, P. D. and Pilling, J. (1986) Phys. Chem., 90, 445.
Gutman, D. (1990) Acc. Chem. Res., 23, 375.
Seakins, P. W. and Pilling, M. J. (1991) J. Phys. Chem., 95, 9874.
Parmar, S. S. and Benson, S. W. (1989) J. Amer. Chem. Soc., 111, 57.
Castelhano and Griller (1982) J. Amer. Chem. Soc., 104, 3655.
Hiatt, R. and Benson, S. W. (1972) J. Amer. Chem. Soc., 94, 25, 6886.
Hiatt, R. and Benson, S. W. (1972) Int. J. Chem. Kin., 4,151, 479
Dobis, O. and Benson, S. W. (1987) Int. J. Chem. Kin., 19, 691.
Russell, J. J., Seetula, J. A., Senkan, S. M. and Gutman, D. (1988) Int. J. Chem. Kin., 20, 759.
Russell, J. J., Seetula, J. A. and Gutman, D. (1988) J. Amer. Chem. Soc., 110, 3092.
Seetula, J. A., Russell,J. J. and Gutman, D. (1990) J. Amer. Chem. Soc., 112, 1347.
Gov, C. A. and Pritchard, H. O. (1965) J. Phys. Chem., 69, 3040.
Nicovich, J. N., Van Dijk, C. A., Kreutter, K. D. and Wine, P. H. (1991) J. Phys. Chem., 95, 9890.
Comber, J. W. and Whittle, E. (1966) Trans. Faraday Soc., 62, 1553.
Parmar, S. S. and Benson, S. W. (1988) J. Phys. Chem., 92, 2652.
Kaiser, E. W. and Wallington, T. J. (1995) Kinetics of the Reactions of Cl with C2H4(k1) and C2H2(k2): An upper limit to the Vinyl Radical Yield, J. Phys. Chem., in press.
Russell, J. J., Senkan, S. M., Seetula, J. A. and Gutman, D. (1989) J. Phys. Chem., 93, 5184.
Cui, J. P., He, Y. Z. and Tsang, W. (1988) Energy and Fuel, 2, 1086.
Parkes, D. and Quinn, C. P. (1953) J. Chem. Soc., Faraday Trans., 1, 72.
Cao, J. R. and Back (1984) Int. J. Chem. Kin., 16, 961.
Pacey, P. D. and Wimalaseba, J. H. (1984) J. Phys. Chem., 88, 5657.
Fettis, G. C., Knox, J. H. and Trotman-Dickenson, A. F. (1960) J. Chem. Soc., 4177.
Knox, J. H. and Musgrave, R. G. (1967) Trans. Faraday Soc., 63, 2201.
Seakins, P. W., Pilling, M. J., Niranen, J. T., Gutman, D. and Krasnoperov, L. N. (1992) J. Phys. Chem., 96, 9847.
Tsang, W. (1970) Int. J. Chem. Kin., 2, 23.
Tsang, W. (1978) Int. J. Chem. Kin., 10, 687.
King, K. D. and Nguyen, T. T. (1979) J. Phys. Chem., 83, 1940.
King, K. D. (1978) Int. J. Chem. Kin., 10, 545.
Tsang, W. (1978) Int. J. Chem. Kin., 10, 599.
Roth, W. R., Bauer, F., Beitat, A., Ebbrecht, T. and Wustfeld, M. (1991) Chem. Ber., 124, 1453.
Tulloch, J. M., Macpherson, M. T., Morgan C. A. and Pilling, M. J. (1982) J. Phys. Chem., 86, 3812.
Tsang, W. and Walker, J. A. (1992) J. Phys. Chem., 96, 8378.
Wagner, H. G. and Zellner, R. (1992) Ber. Bunsenges Physik Chem, 76, 667.
Tsang, W., J. (1985) Amer. Chem. Soc., 107, 2872.
Fettis, G. C. and Knox, J. H. (1964) In Progress in Reaction Kinetics, Porter, G. (ed.), Pergamon, New York, Chapter 1.
Seetula, J. A. and Gutman, D. (1990) J. Phys. Chem., 94, 7529.
Chekov, E. E., Tsailingol’s, A. L. and Ioffe, I. I. (1968) Chem. Abstr., 68, 48759k.
Benson, S. W., Kondo, O. and Marshall, R. M. (1987) Int. J. Chem. Kin., 19, 829.
Muller-Markgraf, W., Rossi, M. J. and Golden, D. M. (1989) J. Amer. Chem. Soc., 111, 956.
Watkins, K. W. and Ward, W. W. (1974) Int. J. Chem. Kin., 6, 855.
Tsang, W. (1984) Int. J. Chem. Kin., 16, 1543.
Niiranen, J. T., Gutman, D. and Krasnoperov, L. (1992) J. Phys. Chem., 96, 5881.
Nicovich, J. M., Shackelford, C.J. and Wine, P. J. (1990) J. Photochem. Photobio. A, 51, 141.
Seetula, J. A. and Gutman, D. J. (1992) Phys. Chem., 96, 5401.
Buckley, E. and Whittle, E. (1966) Trans. Faraday Soc., 58, 536.
Cruickshank, F. R. and Benson, S. W. (1969) J. Phys. Chem., 73, 733.
Dobe, S., Otting, M., Temps, F., Wagner, H. G. and Ziemer, H. (1993) Ber. Bunsenges. Phys. Chem., 97, 887.
Hippler, H. and Troe, J. (1990) J. Phys. Chem., 94, 3803.
Walker, J. A. and Tsang, W. (1990) J. Phys. Chem., 94, 3324.
Lin, C. Y. and Lin, M. C. (1986) J. Phys. Chem., 90, 425.
Suryan, M. M., Kafafi, S. A. and Stein, S. E. (1989) J. Amer. Chem. Soc., 111, 1423.
Knyazev, V. D., Dubinsky, I. A., Slagle, I. R. and Gutman, D. (1995) The Unimolecular Decomposition of tertbutyl Radicals, J. Phys. Chem., in press.
Szwarc, M. (1950) Chem. Rev., 47, 75.
Tsang, W. (1990) J. Phys. Chem. Ref. Data, 19, 1.
Demore, W. B., Sander, S. P., Golden, D. M., Hampson, R. F., Kurylo, M. J., Howard, C. J., Ravishankara, A. R., Kolb, C. J. and Molina, M. J. Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, Evaluation No. 10. JPL Publication 92–20, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, California.
Tsang, W. and Walker, J. A., unpublished results.
Robaugh, D. and Tsang, W. (1986) J. Phys. Chem., 90, 5363.
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1996 Chapman & Hall
About this chapter
Cite this chapter
Tsang, W. (1996). Heats of Formation of Organic Free Radicals by Kinetic Methods. In: Martinho Simões, J.A., Greenberg, A., Liebman, J.F. (eds) Energetics of Organic Free Radicals. Structure Energetics and Reactivity in Chemistry Series (SEARCH series), vol 4. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-0099-8_2
Download citation
DOI: https://doi.org/10.1007/978-94-009-0099-8_2
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-010-6532-0
Online ISBN: 978-94-009-0099-8
eBook Packages: Springer Book Archive