Kinetic Studies on the Oxidation of Oxalate Complex of Oxomolybdenum (V) of Hydrogen Chromate Ion

수소크롬산 (VI) 이온에 의한 몰리브덴 (V) 의 옥살산착물의 산화반응

  • Chang-Yong Kwon (Department of Chemistry Education, Taegu University) ;
  • Chang-Su Kim (Department of Chemistry Education, Taegu University)
  • 권창룡 (大邱大學校 師範大學 化學敎育科) ;
  • 김창수 (大邱大學校 師範大學 化學敎育科)
  • Published : 1986.04.20

Abstract

Oxidation of $[Mo_2O_4(C_2O_4)_2(OH_2)_2]^{2-}$ with hydrogen chromate yields the molybdenum (VI) complex, $[Mo_2O_4(C_2O_4)_2(OH_2)_2]^{2-}$. Stoichiometry for the reaction of $[Mo_2O_4(C_2O_4)_2(OH_2)_2]^{2-}$ with hydrogen chromate are expressed as ${3Mo_2}^V+2Cr^{VI}\;{\rightleftharpoons}\;{3Mo_2}_{VI}+2Cr^{III}$. Observed rate constants are dependent on $[H+]^2$. 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 $Cr^{IV}$. Mechanism of the reaction are presented and discussed.

수소크롬산이온에 의한 $[Mo_2O_4(C_2O_4)_2(OH_2)_2]^{2-}$의 산화는 $[Mo_2O_5(C_2O_4)_2(OH_2)_2]^{2-}$를 생성한다. 수소크롬산이온과 $[Mo_2O_4(C_2O_4)_2(OH_2)_2]^{2-}$의 반응에 대한 화학양론은 ${3Mo_2}^V+2Cr^{VI}\;{\rightleftharpoons}\;{3Mo_2}_{VI}+2Cr^{III}$와 같다. 관찰된 속도상수는 $[H+]^2$에 의존한다. $Cr^{VI}$Cr^V$$Cr^{IV}$를 거쳐서 $Cr^{III}$로 일전자씩 연속적으로 변화한다. 이들 반응에 대한 상세한 메카니즘이 제시되며 이에 대해서 논의된다.

Keywords

References

  1. Inorg. Chem. v.4 F.A. Cotton;S.M. Morehouse
  2. Inorg. Chem. v.19 R.K. Murmann
  3. J.C.S. Dalton C.D. Garner;M.R. Hyde;F.E. Mabbs;V.I. Routledge
  4. Inorg. Chem. v.16 G.R. Cayley;R.S. Taylor;R.K. Wharton;A.G. Sykes
  5. J.C.S. Dalton R.K. Wharton;J.F. Ojo;A.G. Sykes
  6. Inorg. Chem. v.16 G.R. Cayler;R.S. Taylor;R.K. Wharton;A.G. Sykes
  7. Inorg. Chem. v.12 G.F. McKnight;G.P. Haight, Jr.
  8. J. Inorg. Nucl. Chem. v.26 P.C.H. Mitchell
  9. J. Am. Chem. Soc. v.75 J.Y. Tong;E.L. King
  10. J. Korean Chem. Soc. v.30 C.S. Kim;C.Y. Kwon
  11. Inorg. Chem. v.23 C.S. Kim;R.K. Murmann
  12. Transition Met. Chem. v.9 C.S. Kim;R.K. Murmann;E.O. Schlemper
  13. J. Am. Chem. Soc. v.83 J.Y. Tong;E.L. King
  14. J. Am. Chem. Soc. v.85 J.H. Espenson;E.L. King
  15. J. Am. Chem. Soc. v.86 J.H. Espenson