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Micellar effects upon electron transfer from ferrocenes

 

作者: Clifford A. Bunton,   Giorgio Cerichelli,  

 

期刊: International Journal of Chemical Kinetics  (WILEY Available online 1980)
卷期: Volume 12, issue 8  

页码: 519-533

 

ISSN:0538-8066

 

年代: 1980

 

DOI:10.1002/kin.550120803

 

出版商: John Wiley&Sons, Inc.

 

数据来源: WILEY

 

摘要:

AbstractThe oxidations of ferrocene (FcH) andn‐butylferrocene (FcBu) by ferric salts (nitrate or bromide) are strongly inhibited by aqueous cetyltrimethylammonium bromide and nitrate (CTABr and CTANO3, respectively). The kinetics of inhibition fit a model in which the substrates are distributed between water, and the micelles and binding constantsKsto the micelle can be estimated. The oxidations are strongly catalyzed by micelles of sodium lauryl sulfate (NaLS), and the kinetics can be fitted to a model in which the reaction rate depends upon the concentration of both reactants in the micellar pseudophase and the rate constants in that pseudophase, which for both substrates are very similar to those in water. Some added salts reduce the micellar catalysis by excluding ferric ions from the micelle. The oxidations of FcH and FcBu by ferricyanide ions are too fast to be followed in water, but they are inhibited by anionic micelles of NaLS. By analyzing the rate surfactant profiles using independently measured values ofKsthe second‐order rate constants in water have been estima

 

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