화학공학소재연구정보센터
Langmuir, Vol.27, No.12, 7963-7965, 2011
Reply to "Should the Gibbs Analysis Be Revised?"
Plots of surface tension vs log [surfactant] show a steep linear decline until the CMC is reached. Conventional "Gibbs analysis" declares that the air/water interface is saturated with surfactant throughout this linear region, thereby enabling an area-per-molecule to be determined. We have previously provided evidence from four independent experimental methods that cast doubt on the "saturated interface" concept. In the preceding paper, Laven and de With question our results with deceptively authoritative but specious arguments devoid of any new experiments (e.g., they explain our conductance data by postulating the presence of two different coexisting micellar structures). However, consider the Gibbs analysis from strictly an intuitive standpoint. The Gibbs analysis demands that surfactant in the bulk phase (even at submillimolar concentrations) causes a dramatic decline in the surface tension of an interface that is already saturated. The Gibbs analysis also forces the conclusion that initial saturation of the interface (at the high end of the linear decline) has little effect on the surface tension. We thus maintain our position that the surface tension declines sharply because the air-water interface adsorbs more and more surfactant as surfactant is added to the bulk phase.