Combined voltammetry and in situ infrared spectroscopy of tetramethylthiourea on gold in aqueous acid solutions

The voltammetric behaviour of tetramethylthiourea (TMTU) dissolved in aqueous perchloric and sulphuric acid solutions on polycrystalline gold combined with in situ Fourier transform infrared reflection absorption spectroscopy (FTIRRAS) was investigated. Conventional and triangular modulated voltamme...

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Autores principales: Bolzán, Agustín Eduardo, Iwasita, T., Arvia, Alejandro Jorge
Formato: Articulo
Lenguaje:Inglés
Publicado: 2005
Materias:
Acceso en línea:http://sedici.unlp.edu.ar/handle/10915/119201
https://www.sciencedirect.com/science/article/abs/pii/S001346860500592X
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id I19-R120-10915-119201
record_format dspace
institution Universidad Nacional de La Plata
institution_str I-19
repository_str R-120
collection SEDICI (UNLP)
language Inglés
topic Ciencias Exactas
Química
Tetramethylthiourea
Electro-oxidation
FTIRRAS
Gold
Electrodissolution
spellingShingle Ciencias Exactas
Química
Tetramethylthiourea
Electro-oxidation
FTIRRAS
Gold
Electrodissolution
Bolzán, Agustín Eduardo
Iwasita, T.
Arvia, Alejandro Jorge
Combined voltammetry and in situ infrared spectroscopy of tetramethylthiourea on gold in aqueous acid solutions
topic_facet Ciencias Exactas
Química
Tetramethylthiourea
Electro-oxidation
FTIRRAS
Gold
Electrodissolution
description The voltammetric behaviour of tetramethylthiourea (TMTU) dissolved in aqueous perchloric and sulphuric acid solutions on polycrystalline gold combined with in situ Fourier transform infrared reflection absorption spectroscopy (FTIRRAS) was investigated. Conventional and triangular modulated voltammetry and rotating disc electrode data demonstrate the occurrence of two redox surface processes in the potential ranges −0.1 ≤ E ≤ −0.3 V and 0.7 ≤ E ≤ 0.8 V (versus SHE), respectively. These processes would involve the participation of TMTU adsorbates. The redox surface process observed in the range −0.1 to −0.3 V can be related to the electrosorption of TMTU. The absence of infrared absorption bands from these adsorbates agrees with a flat, almost parallel adsorption of TMTU molecules on gold that has been already reported. In the range 0.4 V ≤ E ≤ 0.8 V both electrochemical and spectroscopic data indicate the anodic formation of soluble gold–TMTU complex and tetramethylformamidine disulphide (TMFDS<sup>2+</sup>) ions presumably via Au(TMTU)<sup>+</sup> adsorbates. The kinetics of soluble gold– TMTU complex ion formation is under diffusion control, whereas the formation of TMFDS2+ ions behaves as a rather irreversible process with the anodic slope, derived from current–potential curves, ∂E/∂ log I = 0.120 V decade−1 at 298 K. At E > 1.2 V, the global electro-oxidation of both TMTU and TMFDS<sup>2+</sup> species yields carbon dioxide, sulphate ions and carbonyl-containing compounds, as indicated by IR spectra. These reactions involve the participation of oxygen-containing adsorbates produced from water electro-oxidation on gold.
format Articulo
Articulo
author Bolzán, Agustín Eduardo
Iwasita, T.
Arvia, Alejandro Jorge
author_facet Bolzán, Agustín Eduardo
Iwasita, T.
Arvia, Alejandro Jorge
author_sort Bolzán, Agustín Eduardo
title Combined voltammetry and in situ infrared spectroscopy of tetramethylthiourea on gold in aqueous acid solutions
title_short Combined voltammetry and in situ infrared spectroscopy of tetramethylthiourea on gold in aqueous acid solutions
title_full Combined voltammetry and in situ infrared spectroscopy of tetramethylthiourea on gold in aqueous acid solutions
title_fullStr Combined voltammetry and in situ infrared spectroscopy of tetramethylthiourea on gold in aqueous acid solutions
title_full_unstemmed Combined voltammetry and in situ infrared spectroscopy of tetramethylthiourea on gold in aqueous acid solutions
title_sort combined voltammetry and in situ infrared spectroscopy of tetramethylthiourea on gold in aqueous acid solutions
publishDate 2005
url http://sedici.unlp.edu.ar/handle/10915/119201
https://www.sciencedirect.com/science/article/abs/pii/S001346860500592X
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AT arviaalejandrojorge combinedvoltammetryandinsituinfraredspectroscopyoftetramethylthioureaongoldinaqueousacidsolutions
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