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Determination of the entropy of formation of the Pt(111)∣ perchloric acid solution interface. Estimation of the entropy of adsorbed hydrogen and OH species

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Abstract

The entropy of formation of the interface between a Pt(111) electrode and a 0.1-M HClO4 solution is calculated here for the first time from the temperature dependence of total charge vs potential curves following a thermodynamic analysis based on the electrocapillary equation. From this quantity, the absolute entropies of specifically adsorbed species (hydrogen and OH) can be estimated. The present method is an alternative treatment of data that overcomes some of the limitations involved in the approach that uses a generalized isotherm. However, it requires additional experimental data: the temperature coefficient of the potential of zero total charge of the working electrode and the temperature coefficient of the reference electrode. Comparison of the results obtained by both approaches shows that, for hydrogen adsorption, the agreement is reasonable, but the differences are larger for OH adsorption, thus showing the limitations inherent in the treatment based on the generalized isotherm.

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Acknowledgements

B. Álvarez-Ruiz is gratefully acknowledged for providing the experimental data. Financial support from the Ministerio de Educación y Ciencia (MEC) (Spain) through project CTQ 2006-04071/BQU is gratefully acknowledged. NG thanks the MEC (Spain) for the award of a Formación de Personal Univeritario grant. VC acknowledges financial support from the MEC and the Generalitat Valenciana under the Ramon y Cajal program.

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Authors and Affiliations

  1. Instituto Universitario de Electroquímica, Universidad de Alicante, Apartado 99, 03080, Alicante, Spain

    Nuria Garcia-Araez, Victor Climent & Juan M. Feliu

Authors
  1. Nuria Garcia-Araez
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  2. Victor Climent
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  3. Juan M. Feliu
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Correspondence to Juan M. Feliu.

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Dedicated to Professor Oleg Petrii on the occasion of his 70th birthday on August 24, 2007.

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Garcia-Araez, N., Climent, V. & Feliu, J.M. Determination of the entropy of formation of the Pt(111)∣ perchloric acid solution interface. Estimation of the entropy of adsorbed hydrogen and OH species. J Solid State Electrochem 12, 387–398 (2008). https://doi.org/10.1007/s10008-007-0417-y

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  • DOI: https://doi.org/10.1007/s10008-007-0417-y

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