Leung, Ping Sang K. and Betterton, Eric A. and Hoffmann, Michael R. (1989) Kinetics and mechanism of the reduction of cobalt(II) 4,4',4",4"'-tetrasulfophthalocyanine by 2-mercaptoethanol under anoxic conditions. Journal of Physical Chemistry, 93 (1). pp. 430-433. ISSN 0022-3654. doi:10.1021/j100338a083. https://resolver.caltech.edu/CaltechAUTHORS:20150814-112038008
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Abstract
The kinetics and mechanism of reduction of cobalt(II) 4,4’,4’’,4'’’-tetrasulfophthalocyanine by 2-mercaptoethanol to yield cobalt(I) tetrasulfophthalocyanine and 2-hydroxyethyl disulfide under anoxic conditions were investigated and the following rate law was found: v = -d[Co^(II)TSP]_T/dt = k_2K_1[RSH]_T[Co^(II)TSP]_T{2(1 + ɑ_H+ /Ka_1,+ Ka_2/ɑ_H+)(l+ ɑ[RSH]_T)}, where k_2 is a rate constant for the rate-limiting electron-transfer step, and K_1 is the equilibrium constant for the complexation of a CoTSP dimer with thioethanol; K_(a1) and K_(a2) are the apparent acid dissociation constants of HOC_2H_4SH and HOC_2H_4S^-, respectively; ɑ is K_1/(1 + ɑ_(H+)/K_(a1)+ K_(a2)/ɑ_(H+)):ɑ_H+ is the hydrogen ion activity. A nonlinear least-squares fit of the experimental data to the above rate law gave k_2 = 228 ± 3.8 s^(-l) and K_1 = 117 ± 2.5 M^(-1) at 27 ºC at µ = 0.4 M.
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| Additional Information: | © 1989 American Chemical Society. Received: August 18, 1987. | |||||||||
| Issue or Number: | 1 | |||||||||
| DOI: | 10.1021/j100338a083 | |||||||||
| Record Number: | CaltechAUTHORS:20150814-112038008 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20150814-112038008 | |||||||||
| Official Citation: | Kinetics and mechanism of the reduction of cobalt(II) 4,4',4",4"'-tetrasulfophthalocyanine by 2-mercaptoethanol under anoxic conditions Ping Sang K. Leung, Eric A. Betterton, and Michael R. Hoffmann The Journal of Physical Chemistry 1989 93 (1), 430-433 DOI: 10.1021/j100338a083 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 59536 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Ruth Sustaita | |||||||||
| Deposited On: | 14 Aug 2015 21:10 | |||||||||
| Last Modified: | 10 Nov 2021 22:22 |
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