Pender, Celia (1987) A study of adsorption on electrodes using infrared spectroscopy. University of Southampton, Doctoral Thesis.
Abstract
This thesis presents an in-situ study of benzonitrile and its mono fluoro derivatives adsorbed on a polycrystalline gold electrode. Electrochemically modulated infrared spectroscopy (EMIRS) produced adsorbate spectra and differential capacitance measurements were used to corroborate their findings. Benzonitrile and ortho fluoro benzonitrile were shown to adsorb in an upright position via the nitrogen lone pair electrons. As well as forming this adsorbate the meta and para fluoro derivatives were found to adsorb in a flat orientation via electron donation from the gold to the organic Π* antibonding levels. Extensive studies of para fluorobenzonitrile showed this latter adsorbate to be the stronger of the two. In addition the N-bonded adsorbate was greatly effected by the electrolyte cation. In the concluding chapter attempts were made to rationalize the adsorption behaviour of the different nitriles in terms of their electron energy levels. (D75977/87)
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