Bulletin of the Korean Chemical Society

  • 제6권5호
  • /
  • Pages.259-263
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  • 1985
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  • 0253-2964(pISSN)
  • /
  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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The Effect of Pressure on the Solvolysis of Benzylchlorides(Ⅰ). p-Methylbenzyl Chloride in Ethanol-Water Mixtures

  • 발행 : 1985.10.20
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초록

Rate Constants for the solvolysis of p-methylbenzyl chloride in various ethanol-water mixtures were studied at 30 and $40^{\circ}C$ under various pressures up to 1600 bar. The rates of reaction were increased with increasing temperature and pressure, and decreased with increasing solvent composition of ethanol mole fraction. From the rate constants, the values of the activation parameters (${\Delta}V^{\neq},{\Delta}{\beta}^{\neq},{\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$) were evaluated. The values of ${\Delta}V^{\neq}\;and\;{\Delta}{\beta}^{\neq}$ exhibit the extremum behavior at about 0.30 mole fraction of ethanol. This behavior is discussed in terms of solvent structure variation (electrostriction). From the relation between the reaction rate and the dielectric constant of solvent or the number of water molecule participated in the transition state, it could be postulated that the reaction proceeds through $S_N1$ mechanism.

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참고문헌

  1. J. Org. Chem. v.35 W.J. leNoble;A. Shurpik
  2. The Theory of Rate Processes S. Glasstone;K. J. Laidler;H. Eyring
  3. J. Amer. Chem. Soc. v.84 S.W. Benson;J.A. Berson
  4. Physics and Chemistry of the Voyage of H.M.S. Challenger v.2 P.G. Tait
  5. J. Amer. Chem. Soc. v.89 H. S. Golinkin;I. Lee;J.B. Hyne
  6. J. Chem. Phys. v.2 J. G. Kirkwood
  7. Ann. N.Y. Acad. Soc. v.39 J. K. Laidler;H. Eyring
  8. J.Chem. Soc. D. A. Brown;R. F. Hudson
  9. Solvent Effect on Chemical Phenomena E. S. Amis;J. F. Hinton
  10. J. Amer. Chem. Soc. v.53 Jeffries Wyman
  11. J. Amer. Chem. Soc. v.54 Gosta Akerlof
  12. Can. J. Chem. v.53 M. L. Tonnet;E. whalley
  13. J. Phys. Chem. v.65 B.B. Owen;R.C. Miller;C.E. Milner
  14. J. Korean Chem. Soc. v.25 O. C. Kwun(et al.)
  15. J. Chem. Soc. V. J. Hilton;E. G. Jefferson
  16. Acta Chem. Scand. v.19 A. Kivinen
  17. Proceedings of NATO Advanced Study Institute High Pressure Chemistry H. Kelm(ed.)
  18. Bull. Korean Chem. Soc. v.5 J. G. Jee;O. C. Kwun(et al.)
  19. Liquid Phase High Pressure Chemistry N. S. Isaacs
  20. Advances in Physical Organic Chemistry v.2 E. Whalley
  21. Inter. J. Chem. Kinetics v.1 K. J. Laidler;R. Martin
  22. Can. J. Chem. v.49 M. J. Mackinon;J. B. Hyne
  23. Phill. Mag. v.2 E. A. Guggenheim