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| - Oxidative Adsorption of n-Alkanethiolates at Mercury. Dependence of Adsorption FreeEnergy on Chain Length
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| - The oxidative adsorption of n-alkanethiolates(CncH2nc+1S-,nc= 2−8) at Hg inaqueous solutions containing0.5 M NaOH is reported. Oxidative adsorption ofCncH2nc+1S-is characterized by two voltammetric wavescorresponding to the formation of energetically distinct low-densityand high-density surface phases of Hg−SCncH2nc+1.The high-density surface phase (9.8 ×10-10 mol/cm2) corresponds toadsorption of ca. onemonolayer ofCncH2nc+1S-.Electrodeposition of a bulk film of a mercury thiolate complexalso occurs atmore positive potentials in solutions containing short-chainn-alkanethiolates, nc≤ 5. The dependence of theadsorption half-wave potential E1/2 on thesolution concentration ofCncH2nc+1S-indicates that approximatelyone electron is transferred per adsorbed molecule. The free energyof adsorption ΔGads ofCncH2nc+1S-on Hgdecreases by ∼1 kcal/mol per nc, reflectingthe influence of hydrophobic interactions andintermolecularforces on the thermodynamic stability of the monolayer.
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