Ru(III)-catalyzed oxidation of cysteine hydrochloride by methylene blue in acidic medium; synergetic effect of Cu(II): A kinetic study
✍ Scribed by R. Chaturvedi; K. K. Mishra
- Publisher
- John Wiley and Sons
- Year
- 2008
- Tongue
- English
- Weight
- 101 KB
- Volume
- 40
- Category
- Article
- ISSN
- 0538-8066
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✦ Synopsis
Abstract
Cysteine hydrochloride and methylene blue (MB) interact in a molar ratio of 2:1 in acidic medium forming cystine and dihydromethylene blue, and the reaction is catalyzed by Ru(III). At low concentrations (ca. 2.0 × 10^−8^ M), Cu(II) does not catalyze the reaction significantly but at this concentration level the catalytic activity of Ru(III) is found to be augmented by the addition of Cu(II) and the kinetics of Ru(III)‐catalyzed reaction has been studied in the absence and in the presence of externally added Cu(II). The reaction follows a half‐order kinetics in MB that increases to ¾ on increasing [MB] beyond 1.5 × 10^−5^ M in the Ru‐catalyzed reaction. In the Ru–Cu catalyzed reaction; the order in MB is ¾ even at lower concentrations of MB. The order in cysteine is unity. The rate decreases on increasing [MB] in both cases but attains a limiting value at higher concentrations of MB (ca. >2.0 × 10^−5^ M) in the presence of Ru(III) alone. The rate increases on increasing [H^+^] and in Ru‐catalyzed reaction, an optimum is noticed. The rate increases linearly with increasing [Ru(III)], but equilibration of the catalyst with other ingredients of the reaction system decreases the rate. The FTIR spectra of the reaction system exhibit time‐dependent changes in the stretching as well as bending modes of –SH group. The synergetic effect of Cu(II) has been attributed to its ligation with cysteine and its subsequent interaction with Ru(II) produced in situ in the system. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 145–150, 2008