Surface activity coefficients of spread monolayers of behenic acid salts at air–water interface

The pressure–area isotherms of ionized monolayers of behenic acid at air–water interface at pH 12.0 have been obtained from the Langmuir film balance experiments under various physico-chemical conditions. The value of the measured surface pressure at a given area per molecule is equal to the sum of the ideal pressure, cohesive pressure and electrical pressure. The electrical pressure term is regarded as the sum of the pressure originating from the Gouy–Chapman double layer including discrete ion effect, ion binding and monolayer hydration effect. At a given area, the deviation of the measured surface pressure from its ideal value has been calculated in terms of the apparent surface compressibility coefficients, surface fugacity coefficients for gaseous monolayer and surface activity coefficients of solute forming two-dimensional solutions in the monolayer phase respectively. Values of all these coefficients have been calculated for different compositions of the monolayer using non-ideal gas model and Raoultʹs and Henryʹs laws modified for two-dimensional non-ideal solutions respectively. Values of these coefficients may be higher or lower than unity depending upon ionic strengths and nature of inorganic salts present in the sub-phase. Using these values of surface activity coefficients, the standard free energies of formation, of spread monolayers of salts of behenic acid have been calculated at different standard states of reference.