Kinetic Analysis by High Pressure and High Vacuum Apparatus for the Nucleophilic Substitution Reaction

고압 및 고진공장치를 이용한 친핵성치환반응에 대한 속도론적 분석

  • 김세경 (한양대학교 자연과학대학 화학과)
  • Received : 2004.05.13
  • Accepted : 2004.08.20
  • Published : 2004.10.25


Kinetics have been studied by high vacuum and high pressure apparatus under various temperatures and pressures for the nucleophilic substitution reaction. Rate constants, activated parameters and Hammett ${\rho}$-values are determined. The values of ${\Delta}V^{\ddag}$, ${\Delta}{\beta}^{\ddag}$ and ${\Delta}S^{\ddag}$ are all negative. The Hammett ${\rho}$-values are negative for the nucleophile (${\rho}x$) over the pressure range studied. Consequently the rate constant increases as the pressure increases, and some decrease in vacuum. So these reactions proceed in typical $S_N2$ reaction mechanism.


high pressure;high vacuum;kinetics


  1. J. B. Hyne, J. Am. Chem. Soc., 88, 2104(1966).
  2. I. Lee, N. I. Kim and S. C. Sohn, Tetrahedron Lett., 23, 4723(1983).
  3. L. P. Hammett, J. Am. Chem. Soc., 19, 156(1975).
  4. A. J. Ellis, W. S. Fyfe and R. I. Rutherford, J. Chem. Phys., 31, 176(1959).
  5. E. Whalley, Advances in Physical Organic Chemistry, Academic Press, N.Y., p.93(1964).
  6. S. W. Benson and J. A. Berson, J. Am. Chem. Soc., 86, 259(1964).
  7. S. J. Dickson and J. B. Hyne, Can. J. Chem., 49, 2394(1971).
  8. S. D. Yohi, J. H. Park and K. A. Lee, Bull. Chem. Soc. Jpn., 60, 1149(1987).
  9. Y. Kondo, H. Tojima and N. Tokura, Bull. Chem. Soc. Jpn., 45, 3579(1972).
  10. J. B. Hyne and H. S. Golinkin, Can. J. Chem., 44, 2193(1966).
  11. Y. Kondo, H. Tojima and N. Tokura, Bull. Chem. Soc. Jpn., 45, 3579(1972).
  12. B. L. Archer and R. F. Hudson, J. Chem. Soc., 24, 3258(1950).
  13. M. Charton, Progr. Phys. Org. Chem., 10, 81(1973).
  14. K. Tamura and Y. Ogo, Bull. Chem. Soc. Jpn., 46, 2988(1973).