Add time:09/02/2019         Source:sciencedirect.com

The adsorption of 3-ethyl-3-hexanol and 4-octanol was studied at the dodecane/water interface using from 0 to 0.02 mole fraction alcohol in the dodecane, and from 20 to 40°C. Standard Gibbs energies of adsorption from the dodecane at 25°C were −21.10 and −21.37 kJ/mole for 3-ethyl-3-hexanol and 4-octanol, respectively. These are about 3 kJ/mole less negative than that reported for 1-octanol and imply weaker adsorption. The standard enthalpies of adsorption from dodecane were −32.5 and −30.1 kJ/mole for the respective alcohols, similar to that for 1-octanol. Since the enthalpies of transfer were previously determined as 40.6 and 44.6 kJ/mole, enthalpies of adsorption from water are quite positive for these alcohols, although almost thermoneutral for 1-octanol. Thus, the larger enthalpies of solution of the branched alcohols in water, compared to 1-octanol, result from hydrophobic interactions in the water, and not from anomalous hydration of the OH group.

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