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Aromaticity, electronic structure and molecular dimension in the adsorption of organic compounds on mercury—I. The metal/adsorbate interaction

✍ Scribed by L. Benedetti; C. Fontanesi


Publisher
Elsevier Science
Year
1994
Tongue
English
Weight
748 KB
Volume
39
Category
Article
ISSN
0013-4686

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✦ Synopsis


AI&met-The adsorbability of a wide series of aromatic derivatives (38) on mercury from aqueous solution at constant potential (E or close to it) cannot be simply accounted for by the " aromaticity * of the compounds, at any rate rnoa%Iated by substituent groups on the aromatic moiety, even if the adsorbates show a common planar disposition on the surface in the adsorbed state. The interfacial activity can be successfully related to the process of formation of a "soft-soft" couple (in the Pearson's concept) between mercury and the organic, in competition with the "hard-soft" couple between the metal and water. De-sorption is then explained with a higher "hard" character of mercury at increasing negative potential. In this view, the feasibility of a partial charge transfer, as expressed by I, calculated for neutral organic adsorbates, corresponding to a positive AN value (AN, fractional number of electrons transferred from the adsorbate to the mercury) can be confirmed. A simple relation between adsorbability and "'bulkyness" of the compounds, in relation to the dislodgement of water molecules from the surface occurring in the adsorption process is proposed and discussed.


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