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Electrochemical Oxidation of the Phospha‐ and Arsaethynolate Anions, PCO – and AsCO –
Author(s) -
Tambornino Frank,
Tanner Eden E. L.,
Amin Hatem M. A.,
Holter Jennifer,
Claridge Tim,
Compton Richard G.,
Goicoechea Jose M.
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201801503
Subject(s) - chemistry , aqueous solution , electrochemistry , cyclic voltammetry , diffusion , redox , arsenic , inorganic chemistry , electron transfer , electrode , analytical chemistry (journal) , organic chemistry , physics , thermodynamics
The anions PCO – and AsCO – are shown to be electroactive and are studied in aqueous and non‐aqueous solutions. Cyclic voltammetry is used to extract fundamental physicochemical parameters such as oxidation peak potentials, and transfer and diffusion coefficients of the anions to better understand the nature of the oxidation process. Variation of the potential scan rate reveals that electro‐oxidation of PCO – with the release of CO is controlled by diffusion and is a one‐electron irreversible process yielding phosphorus‐containing deposits. In contrast, the oxidation of AsCO – is a near electrochemically reversible process, forming pure arsenic deposits, with a chemically irreversible follow‐up reaction. For both anions, the electrode surface is substantially “blocked” by the reaction products. The formed deposits were characterized by scanning electron microscopy and energy dispersive X‐ray spectroscopy.