CaltechAUTHORS
  A Caltech Library Service

Kinetics and mechanism of the reduction of cobalt(II) 4,4',4",4"'-tetrasulfophthalocyanine by 2-mercaptoethanol under anoxic conditions

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 . http://resolver.caltech.edu/CaltechAUTHORS:20150814-112038008

Full text is not posted in this repository. Consult Related URLs below.

Use this Persistent URL to link to this item: http://resolver.caltech.edu/CaltechAUTHORS:20150814-112038008

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/j100338a083DOIArticle
http://pubs.acs.org/doi/abs/10.1021/j100338a083PublisherArticle
ORCID:
AuthorORCID
Hoffmann, Michael R.0000-0002-0432-6564
Additional Information:© 1989 American Chemical Society. Received: August 18, 1987.
Record Number:CaltechAUTHORS:20150814-112038008
Persistent URL:http://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:14 Aug 2015 21:10

Repository Staff Only: item control page