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Type of Document	Dissertation
Author	Jones, Janet Gretchen
URN	etd-09232002-120547
Persistent URL	http://resolver.caltech.edu/CaltechETD:etd-09232002-120547
Title	Ligand bridging in the oxidation of chromium(II) at mercury electrodes
Degree	PhD
Option	Chemistry
Advisory Committee	Advisor Name Title unknown Committee Member
Keywords	none
Date of Defense	1966-06-30
Availability	restricted
Abstract 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.
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