An electrocapillary study to test the applicability of the Flory-Huggins isotherm

The Flory-Huggins isotherm with interaction parameter has been tested using accurate electrocapillary data for four aliphatic compounds at the mercury-electrolytic solution interface. When surface coverages derived by differentiation of surface pressure-activity data were tested in the Flory-Huggins isotherm and when all parameters were freely optimized, the equation fit the data very well in all cases, but the size ratio parameter thus obtained was about 0.5. When parameters of the Flory-Huggins isotherm were fixed by limiting properties of surface pressure-activity data directly (with no differentiations performed), the size parameter was about 1.0. The size parameter expected physically is about 3.0. The Flory-Huggins isotherm with realistic size parameters did not fit the data as well as the simpler Frumkin equation in any of the cases considered. The physical basis underlying both models is weak for interaction parameters as large as encountered in aqueous-organic solute systems.