The oxidative adsorption of n- alkanethiolates (C n c H 2 n c +1 S -, n c = 2−8) at Hg in aqueous solutions containing 0.5 M NaOH is reported. Oxidative adsorption of C n c H 2 n c +1 S - is characterized by two voltammetric waves corresponding to the formation of energetically distinct low-density and high-density surface phases of Hg−SC n c H 2 n c +1 . The high-density surface phase (9.8 × 10 -10 mol/cm 2 ) corresponds to adsorption of ca. one monolayer of C n c H 2 n c +1 S - . Electrodeposition of a bulk film of a mercury thiolate complex also occurs at more positive potentials in solutions containing short-chain n- alkanethiolates, n c ≤ 5. The dependence of the adsorption half-wave potential E 1/2 on the solution concentration of C n c H 2 n c +1 S - indicates that approximately one electron is transferred per adsorbed molecule. The free energy of adsorption Δ G ads of C n c H 2 n c +1 S - on Hg decreases by ∼1 kcal/mol per n c, reflecting the influence of hydrophobic interactions and intermolecular forces on the thermodynamic stability of the monolayer.
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Stevenson et al. (1998) studied this question.
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