XANES Spectroelectrochemistry: A New Method for Determining Formal Potentials

Autor:	Mark R. Antonio, Clayton Williams,§ and, L. Soderholm, S. R. Wasserman
Rok vydání:	1999
Předmět:	Electrolysis Valence (chemistry) Absorption spectroscopy Chemistry Analytical chemistry Electrochemistry XANES Analytical Chemistry law.invention chemistry.chemical_compound law Bulk electrolysis Perchloric acid Electrochemical potential
Zdroj:	Analytical Chemistry. 71:4622-4628
ISSN:	1520-6882 0003-2700
DOI:	10.1021/ac990080t
Popis:	Proof-of-concept experiments are presented outlining the use of X-ray absorption near-edge structure (XANES) in the determination of formal potentials. Two redox couples of Np in 1 M perchloric acid are used for the demonstration. XANES data obtained as a function of applied potential are used to quantitatively determine the relative concentrations of Np(VI)/Np(V) and Np(IV)/Np(III). Bulk electrolysis is done in the X-ray beam with the solution maintained under electrochemical control. Relative concentrations are extracted from the data using a principal component (factor) analysis. The formal potentials of the two redox couples determined using this method agree with those previously published. The results establish in situ XANES spectroelectrochemistry as a viable method for determining formal potentials. Examples, taken from environmental or heteropolyanion chemistry, are discussed for which this methodology will provide information currently unavailable from other established techniques.
Databáze:	OpenAIRE
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