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| - Competitive Molecular Adsorption at Liquid/Solid Interfaces: A Study by Sum-FrequencyVibrational Spectroscopy
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| - We used sum-frequency vibrational spectroscopy to study competitive adsorption of water−alcohol binaryliquid mixtures at hydrophilic fused silica and hydrophobic alkyl silane-covered substrates. Monitoring thestrength of the methyl stretching modes of alcohols in the mixtures allowed deduction of the surface coverageof alcohols and their adsorption isotherms. It was found that for both types of substrates, alcohol adsorbspreferentially than water at liquid/solid interfaces. The driving force behind preferential alcohol adsorptionappears to be the strong hydrogen-bonding interaction among water molecules as they would like to maintainthe three-dimensional hydrogen-bonding network and minimize loss of hydrogen bonds in the interfaciallayer. The mechanism is believed to be generally true if interaction among molecules of one species issignificantly stronger than other intermolecular interactions in a mixture and the interactions of differentmolecular species with the substrate are about the same.
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