Conclusions
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1.
Ozone forms 1∶1 complexes with benzene, fluorobenzene, chlorobenzene, bromobenzene, toluene, ethylbenzene, and benzyl chloride. Stability constants have been determined for these complexes at -10°C.
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2.
A study of the relation between the logarithm of the equilibrium constant and the Hammettσ-m values for the various substituents log K0=−0.54,ρ=−1.74 has shown the inductive effect from the substituent X to be the principal factor in fixing the equilibrium constant in reactions of the ArX+O3⇆ArX·O3 type.
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3.
The values of the heats of complexing of ozone with mono substituted benzenes (ΔH0) range from −1.4 to −2.6 kcal/mole, while the corresponding entropies of formation (ΔS0) range from −9.9 to −11.8 cal/ (mole·deg), values close to those for aromatic hydrocarbon complexes with acceptors such as iodine, iodine monochloride, and sym-trinitrobenzene.
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Literature cited
P. S. Bailey, J. W. Ward, and R. E. Hornish, J. Am. Chem. Soc.,93, 3552 (1971).
L. A. Hull, I. C. Hisatsune, and J. Heicklen, J. Am. Chem. Soc.,94, 4856 (1972).
P. S. Bailey, J. W. Ward, T. P. Carter, Ir. E. Nieh, C. M. Fischer, and A. Y. Khashab, J. Am. Chem. Soc.,96, 6136 (1974).
V. V. Shereshovets, V. D. Komissarov, and L. G. Galimova, Izv. Akad. Nauk SSSR, Ser. Khim., 2632 (1980).
L. J. Andrews and R. M. Keefer, Molecular Complexes in Organic Chemistry, Holden-Day (1964).
T. W. Nakagawa, L. F. Andrews, and R. M. Keefer, J. Am. Chem. Soc,82, 269 (1960).
A. Weissberger (editor), Technique of Organic Chemistry, Vol. 7, Organic Solvents, Wiley-Interscienee (1955).
L. J. Andrews and R. M. Keefer, J. Am. Chem. Soc.,72, 3113 (1950).
L. P. Hammett, Physical Organic Chemistry, McGraw-Hill (1970).
Chemical Bond Rupture Energies. Ionization Potentials and Electron Affinities [in Russian], Nauka, Moscow (1974).
G. Briegleb, J. Czekalla, and G. Reus, Z. Phys. Chem. (BRD),30, 316 (1961).
G. Briegleb and J. Czekalla, Z. Elektrochem.,59, 184 (1955).
N. Ogimachi, L. J. Andrews, and R. M. Keefer, J. Am. Chem. Soc.,77, 4202 (1955).
R. M. Keefer and L. J. Andrews, J. Am. Chem. Soc,47, 2164 (1955).
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2488–2492, November, 1981.
The authors would like to thank I. R. Akhunov for his help in carrying out the experiments.