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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 30, Number 1
JKCSEZ 30(1)
February 20, 1986 

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

수소크롬산 이온에 의한 옥살라토아쿠아몰리브덴(Ⅳ) 삼합체의 산화반응
Author
Chang-Su Kim, Chang-Yong Kwon

김창수, 권창룡
Keywords
Abstract
HCrO4-에 의한 [Mo3O4(C2O4)3(H2O)3]2-의 산화는 몰리브덴(Ⅳ)화합물, [Mo2O5(C2O4)2(H2O)2]2-를 생성한다. HCrO4-와 [Mo3O4(C2O4)3(H2O)3]2-의 반응에 대한 화학양론은 2Mo3Ⅳ + 4CrⅥ → 3Mo2Ⅵ + 4CrⅢ와 같다. 관찰된 속도상수는 수소이온농도에 의존한다. CrⅥ는 CrⅤ와 CrⅣ를 거쳐서 CrⅢ로 일전자씩 연속적으로 변화한다. 상세한 메카니즘이 논의된다.

Oxidation of [Mo3O4(C2O4)3(H2O)3]2- with HCrO4- yields the molybdenum(Ⅳ) complex, [Mo2O5(C2O4)2(H2O)2]2-. Stoichiometry for the reaction of [Mo3O4(C2O4)3(H2O)3]2- with HCrO4- are expressed as 2Mo3Ⅳ + 4CrⅥ → 3Mo2Ⅵ + 4CrⅢ. 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 CrⅥ to CrⅢ by way of intermediate CrⅤ and CrⅣ. Detailed mechanisms are presented and discussed.

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