EQUILIBRIA AND KINETICS OF THE REACTIONS BETWEEN HYDROGEN-PEROXIDE AND METHYLTRIOXORHENIUM IN AQUEOUS PERCHLORIC-ACID SOLUTIONS

被引：75

作者：

YAMAZAKI, S

ESPENSON, JH

HUSTON, P

机构：

[1] IOWA STATE UNIV SCI & TECHNOL, AMES LAB, AMES, IA 50011 USA

[2] IOWA STATE UNIV SCI & TECHNOL, DEPT CHEM, AMES, IA 50011 USA

来源：

INORGANIC CHEMISTRY | 1993年 / 32卷 / 22期

关键词：

D O I：

10.1021/ic00074a007

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

In aqueous solutions the colorless compounds CH3ReO3 (=MTO) and H2O2 form 1:1 and 1:2 adducts. The latter is yellow, with epsilon360 = 1.1 X 10(3) L mol-1 cm-1. Peroxide binding to MTO shows cooperativity, as shown by the inversion of the usual order of binding constants. The stepwise equilibrium constants are K1 = 7.7 L mol-1 and K2 = 145 L mol-1 at 25-degrees-C. The buildup of product, which occurs on the stopped-flow time scale at 9-680 mM H2O2, is fit by biexponential kinetics. The equilibria and rates are independent of [H3O+] in the range 10(-1)-10(-3) M. The peroxide complexes decompose more rapidly at lower [H3O+], particularly at pH > 3. Possible structures for 1:1 and 1:2 MOT-H2O2 adducts are presented and discussed.

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页码：4683 / 4687

页数：5

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