Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
권호 표지

Kinetic Studies on the Oxidation of Oxalatoaquamolybdenum(IV) Trimer by Hydrogen Chromate Ion

수소크롬산 이온에 의한 옥살라토아쿠아몰리브덴(IV) 삼합체의 산화반응

  • Chang-Su Kim (Department of Chemistry Education, Taegu University) ;
  • Chang-Yong Kwon (Department of Chemistry Education, Taegu University)
  • 김창수 (大邱大學敎 師範大學 化學敎育科) ;
  • 권창룡 (大邱大學敎 師範大學 化學敎育科)
  • Published : 1986.02.20
Download PDF
⟨ Previous Next ⟩

Abstract

Oxidation of $[Mo_3O_4(C_2O_4)_3(H_2O)_3]^{2-}$ with HCr$O_4^-$ yields the molybdenum(Ⅳ) complex, $[Mo_2O_5(C_2O_4)_2(H_2O)_2]^{2-}$. Stoichiometry for the reaction of $[Mo_3O_4(C_2O_4)_3(H_2O)_3]^{2-}$ with HCr$O_4^-$ are expressed as $2Mo_3^{IV} + 4Cr^{VI} {\to} 3Mo_2^{VI} + 4Cr^{III}$. Observed rate constants are dependent on hydrogen ion concentration. The kinetic data are consistent with a mechanism in which three successive single-electron steps convert $Cr^{VI}$to $Cr^{III}$ by way of intermediate $Cr^V$ and $Cr^{IV}$. Detailed mechanisms are presented and discussed.

HCr$O_4^-$에 의한 $[Mo_3O_4(C_2O_4)_3(H_2O)_3]^{2-}$의 산화는 몰리브덴(IV)화합물, $[Mo_2O_5(C_2O_4)_2(H_2O)_2]^{2-}$를 생성한다. HCr$O_4^-$와 $[Mo_3O_4(C_2O_4)_3(H_2O)_3]^{2-}$의 반응에 대한 화학양론은 $2Mo_3^{IV} + 4Cr^{VI} {\to} 3Mo_2^{VI} + 4Cr^{III}$와 같다. 관찰된 속도상수는 수소이온농도에 의존한다.$Cr^{VI}$는 $Cr^V$와 $Cr^{IV}$를 거쳐서 $Cr^{III}$로 일전자씩 연속적으로 변화한다. 상세한 메카니즘이 논의된다.

Keywords

References

  1. J. Am. Chem. Soc. v.100 A. Bino;F.A. Cotton;Z. Dori
  2. J. Am. Chem. Soc. v.102 R.K. Murmann;M.E. Shelton
  3. Inorg. Chem. v.20 M.A. Harmer;D.T. Richens;A.B. Soares;A.T. Thornton;A.G. Sykes
  4. Inorg. Chem. v.12 G.F. McKnight;G.P. Haight, JR.
  5. J. Am. Chem. Soc. v.86 J.H. Espenson
  6. J. Am. Chem. Soc. v.92 J.H. Espenson
  7. Inorg. Chem. v.22 M.T. Paffett;F.C. Anson
  8. Progress in Inorganic Chemistry v.17 J.K. Beattie;G.P. Haight, JR;S.J. Lippard(Ed.)
  9. Inorg. Chem. v.23 C.S. Kim;R.K. Murmann
  10. Transition Met. Chem. v.9 C.S. Kim;R. K. Murmann;E.O. Schlemper
  11. Inorg. Chem. v.8 R.M. Wing;K.P. Callahan
  12. Quart. Rev. v.20 P.C.H. Mitchell
  13. J. Inorg. Nucl. Chem. v.26 P.C.H. Mitchell
  14. J. Chem. Soc. (A) P.C.H. Mitchell
  15. Inorg. Chem. v.3 F.A. Cotton;S.M. Morehouse;J.S. Wood
  16. Inorg. Chem. v.16 G.R. Cayley;R.S. Taylor;R.K. Wharton;A.G. Sykes
  17. J. Am. Chem. Soc. v.82 J.Y. Tong;E.L. King
  18. J. Am. Chem. Soc. v.85 J.H. Espenson;E.L. King