Anomalous Concentration Dependence of Surface Tension and Concentration-Concentration Correlation Functions of Binary Non-Electrolyte Solutions.

The concentration dependence of the surface tension of several binary mixtures of non-electrolytes has been measured at 298.15 K. The mixtures have been chosen since they presented a so-called "W-shape" concentration dependence of the excess constant pressure heat capacity and high values of the concentration-concentration correlation function. This behavior was interpreted in terms of the existence of anomalously high concentration fluctuations that resemble those existing in the proximities of critical points. However, no liquid-liquid phase separation has been found in any of these mixtures over a wide temperature range. In this work, we have extended these studies to the liquid-air interfacial properties. The results show that the concentration dependence of the surface tension shows a plateau and the mixing surface tension presents a "W-shape" behavior. To the best of our knowledge, this is the first time that this behavior is reported. The weak anomalies of the surface tension near a liquid-liquid critical point suggest that the results obtained cannot be considered far-from-critical effects. The usual approach of substituting the activity by the concentration in the Gibbs equation for the relative surface concentration has been found to lead to large errors and the mixtures to have a fuzzy and thick liquid/vapor interface.