Issue 20, 1996

Bromide electrosorption on the low-index faces of silver

Abstract

Bromide adsorption on the three low-index faces of silver was investigated from mixed c mol dm–3 KBr +(0.02 –c) mol dm–3 KPF6 solutions over a range of c from 1 × 10–6 to 5 × 10–3 mol dm–3 using the potential-step chronocoulometric technique. The adsorption behaviour on the Ag(110) face shows significant differences with respect to that on the Ag(111) and Ag(100) faces. Thus, the plot of the applied potential E vs. the specifically adsorbed charge density σi of the bromide ions, for σi equal and opposite to the charge density σM on the metal, shows a rather abrupt decrease in slope with a decrease in σi. Moreover, the plots of σivs.σM at constant c intersect for σi≈–35 µC cm–2. This behaviour is explained by a decrease in the negative value of the surface potential due to electron smoothing with an increase in |σi| on Ag(110). The potential difference across the inner layer, once plotted against |σi| at constant σM, attains a maximum value before shifting linearly towards more negative values with a further increase in |σi|; this behaviour, observed on all three low-index faces, is interpreted on the basis of a molecular model of the inner layer which accounts for the reorientation of the water dipoles and for the screening by the inhomogeneous electron gas.

Article information

Article type
Paper

J. Chem. Soc., Faraday Trans., 1996,92, 3747-3756

Bromide electrosorption on the low-index faces of silver

M. L. Foresti, M. Innocenti, H. Kobayashi, G. Pezzatini and R. Guidelli, J. Chem. Soc., Faraday Trans., 1996, 92, 3747 DOI: 10.1039/FT9969203747

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