The thermodynamic adsorption profile at a solvated organic-inorganic interface is probed by following the binding and organization of carboxylic acid-terminated alkanethiols of varying chain lengths (C2, C3, and C6) to the surface of gold nanoparticles (NPs) (5.4 ± 0.7, 9.5 ± 0.6, and 19.4 ± 1.1 nm diameter) using isothermal titration calorimetry (ITC). We discuss the effect of alkyl chain length, temperature, and Au NP size on the energetics at an organic-inorganic interface. ITC allows for the quantification of the adsorption constant, enthalpy of adsorption, entropy of adsorption, and the binding stoichiometry in a single experiment. The thermodynamic parameters support a mechanism of stepwise adsorption of thiols to the surface of Au NPs and secondary ordering of the thiols at the organic-inorganic interface. The adsorption enthalpies are chain-length dependent; enthalpy becomes more exothermic as longer chains are confined, compensating for greater decreases in entropy with increasing chain length. We observe an apparent compensation effect: the negative ΔH is compensated by a negative ΔS as the thiols self-assemble on the Au NP surface. A comparison of the thermodynamic parameters indicates thiol-Au NP association is enthalpy-driven because of the large, exothermic enthalpies accompanied by an unfavorable entropic contribution associated with confinement of alkyl chains, reduced trans-gauche interconversion, and the apparent ordering of solvent molecules around the hydrophobic organic thiols (hydrophobic effect). Understanding the thermodynamics of adsorption at NP surfaces will provide critical insight into the role of ligands in directing size and shape during NP synthesis since thiols are a common ligand choice (i.e., Brust method). The ITC technique is applicable to a larger number of structure-directing ligands and solvent combinations and therefore should become an important tool for understanding reaction mechanisms in nanostructure synthesis.

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