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Daniele S, Baldo MA, Bragato C, et al. Steady-state voltammetry of hydroxide ion oxidation in aqueous solutions containing ammonia. Anal Chem. 2002;74(14):3290-6doi: 10.1021/ac025530n.
Daniele, S., Baldo, M. A., Bragato, C., Abdelsalam, M. E., & Denuault, G. (2002). Steady-state voltammetry of hydroxide ion oxidation in aqueous solutions containing ammonia. Analytical chemistry, 74(14), 3290-6. https://doi.org/10.1021/ac025530n
Daniele, Salvatore, et al. "Steady-state voltammetry of hydroxide ion oxidation in aqueous solutions containing ammonia." Analytical chemistry vol. 74,14 (2002): 3290-6. doi: https://doi.org/10.1021/ac025530n
Daniele S, Baldo MA, Bragato C, Abdelsalam ME, Denuault G. Steady-state voltammetry of hydroxide ion oxidation in aqueous solutions containing ammonia. Anal Chem. 2002 Jul 15;74(14):3290-6. doi: 10.1021/ac025530n. PMID: 12139031.
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Anal Chem. 2002 Jul 15;74(14):3290-6. doi: 10.1021/ac025530n.

Steady-state voltammetry of hydroxide ion oxidation in aqueous solutions containing ammonia.

Analytical chemistry

Salvatore Daniele, M Antonietta Baldo, Carlo Bragato, Mamdouh Elsayed Abdelsalam, Guy Denuault

Affiliations

  1. Department of Physical Chemistry, University of Venice, Italy.

PMID: 12139031 DOI: 10.1021/ac025530n

Abstract

An oxidation process observed in dilute aqueous solutions of ammonia was investigated under steady-state conditions with gold microelectrodes with radii in the range 2.5-30 microm. Over the ammonia concentration range 0.1-10 mM, a well-defined voltammetric wave was observed at approximately 1.4 V versus Ag/AgCl. It was attributed to the oxidation of hydroxide ions that arise from the dissociation of the weak base. The steady-state limiting current was found to depend on the concentration of supporting electrolyte, and in solution with low electrolyte, it was enhanced by migration contribution, as expected for a negatively charged species that oxidizes on a positively charged electrode. In addition, the steady-state limiting current was proportional to both the ammonia concentration and the electrode radius. The overall electrode process was analyzed in terms of a CE mechanism (homogeneous chemical reaction preceding the heterogeneous electron transfer) with a fast chemical reaction when measurements were carried out in solutions containing NH3 at < or = 5 mM and with electrodes having a radius of > or = 5 microm. This was ascertained by comparing experimental and theoretical data obtained by simulation. The formation of the soluble complex species Au(NH3)2+ was also considered as a possible alternative to explain the presence of the oxidation wave. This process however was ruled out, as the experimental data did not fit theoretical predictions in any of the conditions employed in the investigation. Instead, the direct oxidation of NH3, probably to N2O, was invoked to explain the anomalous currents found when the CE process was strongly kinetically hindered. Throughout this study, a parallel was made between the CE mechanism investigated here and that known to occur during the hydrogen evolution reaction from weak acids.

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