An Investigation of the System Cr(III)/Cr(II) by Digital Polarography, at Different Cr(III) Concentrations, at Varying pH, and in Different Supporting Electrolytes

Citation

Rathjen, Nancy Katherine (1969) An Investigation of the System Cr(III)/Cr(II) by Digital Polarography, at Different Cr(III) Concentrations, at Varying pH, and in Different Supporting Electrolytes. Master's thesis, California Institute of Technology. doi:10.7907/N5V3-H153. https://resolver.caltech.edu/CaltechTHESIS:05042010-123622070

Abstract

One of the implications of Marcus theory of electron transfer is that d, the electrochemical transfer coefficient, would not be constant, but would be a function of potential. Recent work has tended to confirm this implication. To examine this possible potential-dependence d, the system Cr(III)/Cr(II) was investigated by digital polarography, at different Cr(III) concentrations, at varying pH, and in different supporting electrolytes. Most of the resulting rate data do suggest a potential-dependence of d. Apparent heats of activation were obtained for three of the supporting electrolytes investigated, and from these a calculation was made of the magnitude of the potential-dependence predicted by Marcus theory. There was little correlation between the magnitude of the potential-dependence predicted by Marcus theory, and that actually found.

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