Jones, Janet Gretchen (1967) Ligand bridging in the oxidation of chromium(II) at mercury electrodes. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-09232002-120547
Controlled potential electrolysis and electrochemical relaxation techniques have been used to investigate the mechanism of oxidation of chromium(II) at mercury electrodes in the presence of chloride, bromide, and iodide. It is shown that the major path for the oxidation is through a bridged activated complex of the type Hg---X--Cr.
Kinetic parameters have been determined for the bromide-dependent path and the halide-independent path. Equations have been derived to predict from kinetic data the product distribution between two competing reactions.
It is suggested that the activated complex is formed with halide adsorbed on the electrode surface.
The limitations of chronopotentiometry at hanging mercury drop electrodes have been investigated and corrections are given for spherical diffusion effects at times greater than 0.1 sec. It is demonstrated that reverse current chronopotentiometry under these conditions is a qualitatively unreliable technique.
|Item Type:||Thesis (Dissertation (Ph.D.))|
|Degree Grantor:||California Institute of Technology|
|Division:||Chemistry and Chemical Engineering|
|Thesis Availability:||Restricted to Caltech community only|
|Defense Date:||30 June 1966|
|Default Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Imported from ETD-db|
|Deposited On:||25 Sep 2002|
|Last Modified:||26 Dec 2012 03:02|
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