Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
권호 표지

The Electronic Structure and Reactivity of Transition Metal Complexes (III). Effect of Pressure on the Aquation of $[Cr(NH_3)_5(DMF)]^{3+}$ Ion

전이금속 착물의 전자구조 및 화학적 반응성 (제 3 보) $[Cr(NH_3)_5(DMF)]^{3+}$ 이온의 수화반응에 미치는 압력효과

  • Jong-Jae Chung (Department of Chemistry, Kyungpook National University) ;
  • Choi Jong-Ha (Department of Chemistry, Andong National University) ;
  • Eun-Ki Kim (Department of Chemistry, Kyungpook National University)
  • Published : 1989.12.20
Download PDF
⟨ Previous Next ⟩

Abstract

Rates for aquation of $[Cr(NH_3)_5(DMF)]^{3+}$ ion in aqueous acidic solution have been measured by spectrophotometric method at various temperatures and pressures. The volume of activation for the aquation is small negative and lies in the limited range -2.76 ∼ -3.65 $cm^3mol^{-1}$. The entropy and compressibility coefficient of activation are small negative values. From the results of thermodynamic activation parameters, it can be inferred that the aquation of $[Cr(NH_3)_5(DMF)]^{3+}$ ion proceeds through an associative interchange($I_a$) mechanism.

$[Cr(NH_3)_5(DMF)]^{3+}$ 이온의 수화반응 속도를 분광광도법을 이용하여 온도와 압력을 변화시켜 가면서 측정하였다. 활성화부피(${{\Delta}V_0}^{\neq}$)는 -2.76∼-3.65$cm^3mol^{-1}$의 범위로 작은 음의 값을 나타내었다. 활성화 엔트로피(${\Delta}S^{\neq}$) 및 활성화 압축률계수(${\Delta}{\beta}^\neq$)도 모두 작은 음의 값을 가졌다. 이러한 열역학적인 활성화 파라미터로부터 이 착이온의 수화반응은 교환회합($I_a$) 메카니즘으로 진행됨을 알 수 있었다.

Keywords

References

  1. Ligand Substitution Process C. H. Langford;H. B. Gray
  2. Mechanisms of Inorganic Reactions F. Basolo;R. G. Pearson
  3. Prog. Inorg. Chem. v.13 K. Kustin;J. Swinehart
  4. Coord. Chem. Rev. v.23 D. A. House
  5. The Study of Kinetics, and Mechanism of Reactions of Transition Metal Complexes R. G. Wilkins
  6. Coord. Chem. Rev. v.17 T. W. Swaddle
  7. Pure Appl. Chem. v.38 D. R. Stranck
  8. Chem. Rev. v.78 T. Asano;W. J. le Noble
  9. Acc. Chem. Res. v.12 G. A. Lawrance;D. R. Stranks
  10. Inorg. Chem. v.21 G. A. Lawrance
  11. Coord. Chem. Rev. v.36 D. A. Palmer;H. Kelm
  12. Inorganic High Pressure Chemistry R. van Eldik(ed.)
  13. Can. J. Chem. v.51 G. Guastalla;T. W. Swaddle
  14. J. Inorg. Nucl. Chem. v.43 P. Riccieri;E. Zinato
  15. High Temp. High Press. v.7 H. Lentz;S. O. Oh
  16. Phil. Mag. v.3 E. A. Guggenheim
  17. Chemical Kinetics and Reaction Mechanisms F. Wilkinson
  18. J. Am. Chem. Soc. v.70 E. Grunward;S. Winstein
  19. Coord. Chem. Rev. v.4 J. R. Perumarredi
  20. Symmetry in Bonding and Spectra B. E. Douglas;C. A. Hollingsworth
  21. Aust. J. Chem. v.23 W. W. Fee;J. N. MacB. Harrowfield
  22. Inorg. Chem. v.19 J. Glerup;O. Monsted;C. E. Shaffer
  23. Coord. Chem. Rev. v.48 L. G. Vanquickenbornne;A. Ceulemans
  24. Personal Communicaiton A. B. P. Lever
  25. Inorganic Electronic Spectroscopy A. B. P. Lever