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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 11, Number 4
BKCSDE 11(4)
April 20, 1990 

A Kinetic Study of the Fe(Ⅲ)-Catalyzed Aquation of Bis(malonato)Diaquochromate(Ⅲ) Ion
Jeong-Ae Shim, Jung-Dae Moon, Heung-Jae Park, Sung-Nak Choi*
The bis(malonato)diaquochromate(Ⅲ) ion, Cr(C3H2O4)2- in acidic solution hydrolyzes to give Cr(C3H2O4)+. This reaction is catalyzed by ferric ion and the rate law for this cation catalyzed-aquation in a HClO4/NaClO4 medium, I = 1.00 M, is-d[Cr(C3H2O4)2-]/dt = (k1[Fe3+] + k2[H+])[Cr(C3H2O4)2-] where k1(25℃) = 4.72×10-5 M-1sec-1 (ΔH≠ = 22.5 Kcal/mol, ΔS≠ = - 2.58 eu) and k2(25℃) = 4.75×10-5 M-1sec-1 (ΔH≠ = 21.2 Kcal/mol, ΔS≠ = - 7.13 eu). Rapid preequilibrium association of basic Cr-bound oxygen with Fe3+, followed by rate-determining ring opening, is proposed to account for the k1, hydrolysis pathway.
318 - 323
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