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Abstract:

The oscillatory picric acid/CTAB two-phase system-as introduced by Yoshikawa and Matsubara [J. Am. Chem. Soc. 1984, 106, 4423-4427]-has been revisited. UV-vis spectroscopic studies were presented that provide a clearer and new insight into the possible kinetic mechanism for the oscillatory behavior. It was shown that the key process in the system is the formation of 1:1 ion pairs between picrate and CTA+ at the liquid/liquid interface that desorb and move into the organic phase. Kinetic UV-vis experiments also showed that the presence of alcohol-which was essential to observe oscillatory behavior-inhibits the formation of ion pairs. In the course of this process, this inhibition is released presumably due to the transfer of the alcohol from the interface into the organic phase. The corresponding inhibition/acceleration dynamics were observed in a subsystem experiment as S-shaped, autocatalytic-like kinetics with respect to the ion-pair formation. A new mechanism based on Langmuir-Hinshelwood kinetics was proposed that includes the competitive adsorption of CTA+, picrate, and the alcohol at the liquid/liquid interface. The release of inhibition, which depends on the concentration of vacant interface sites and which occurs autocatalytically, expresses the key process for the nonlinear behavior. Computer simulations were performed which confirm that the proposed kinetic mechanism is dynamically reasonable.

Registro:

Documento: Artículo
Título:On the origin of electrochemical oscillations in the picric acid/CTAB two-phase system
Autor:Pimienta, V.; Etchenique, R.; Buhse, T.
Filiación:Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Av. Univ. No 1001, Col. Chamilpa, 62210 Cuernavaca, Morelos, Mexico
Laboratoire des IMRCP, UMR au CNRS No 5623, Université Paul Sabatier, 118 route de Narbonne, 31062 Toulouse Cedex, France
DQIAyQF, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, CP 1428, Buenos Aires, Argentina
Palabras clave:Alcohols; Computer simulation; Electrochemistry; Interfaces (materials); Ions; Oscillations; Reaction kinetics; Ultraviolet spectroscopy; Electrochemical oscillations; Organic acids
Año:2001
Volumen:105
Número:44
Página de inicio:10037
Página de fin:10044
DOI: http://dx.doi.org/10.1021/jp013350w
Título revista:Journal of Physical Chemistry A
Título revista abreviado:J Phys Chem A
ISSN:10895639
CODEN:JPCAF
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v105_n44_p10037_Pimienta

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Citas:

---------- APA ----------
Pimienta, V., Etchenique, R. & Buhse, T. (2001) . On the origin of electrochemical oscillations in the picric acid/CTAB two-phase system. Journal of Physical Chemistry A, 105(44), 10037-10044.
http://dx.doi.org/10.1021/jp013350w
---------- CHICAGO ----------
Pimienta, V., Etchenique, R., Buhse, T. "On the origin of electrochemical oscillations in the picric acid/CTAB two-phase system" . Journal of Physical Chemistry A 105, no. 44 (2001) : 10037-10044.
http://dx.doi.org/10.1021/jp013350w
---------- MLA ----------
Pimienta, V., Etchenique, R., Buhse, T. "On the origin of electrochemical oscillations in the picric acid/CTAB two-phase system" . Journal of Physical Chemistry A, vol. 105, no. 44, 2001, pp. 10037-10044.
http://dx.doi.org/10.1021/jp013350w
---------- VANCOUVER ----------
Pimienta, V., Etchenique, R., Buhse, T. On the origin of electrochemical oscillations in the picric acid/CTAB two-phase system. J Phys Chem A. 2001;105(44):10037-10044.
http://dx.doi.org/10.1021/jp013350w