Thermodynamic properties of bridging clusters in thin films of water between hydrophobic surfaces assessed from...

In the course of a long-term effort to cope with surface force data for thin films of water between hydrophobic surfaces, we have applied the bridging-cluster model (Eriksson, J. C.; Henriksson, U. Bridging-cluster model for hydrophobic attraction . Langmuir 2007, 23, 10026 - 10033) to the recently published surface force isotherms for water films between hexadecylthiolated gold surfaces in the thickness range of 20-100 nm and temperature range of 10-40 °C (Wang, J.; Yoon, R.-H.; Eriksson, J. C. Excess thermodynamic properties of thin water films confined between hydrophobized gold surfaces. J. Colloid Interface Sci. 2011, 364, 257 - 263). We show that these isotherms can be faithfully reproduced on the basis of the bridging-cluster model. The thermodynamic excess properties (ΔGc , ΔHc , and TΔSc) of linear clusters that are assumed to bridge the core of the films were calculated from the experimental surface force isotherms. A crucial step taken was to infer two-dimensional ideal mixing of the clusters with the surrounding film water. We find that ΔHc and TΔSc are both negative quantities, with the latter being larger than the former, which implies a positive excess Gibbs energy of a cluster, ΔGc = ΔHc - TΔSc. Typically, for temperatures between 10 and 40 °C, these cluster properties are of the order of some kBT units, corresponding to 10(-4)-10(-3)kBT per water molecule entailed. Our analysis yields support of the notion that elongated aggregates can arise in thin films of water between hydrophobic surfaces driven by entropy of mixing.