Evidence for the Existence of an Effective Interfacial Tension between Miscible Fluids: Isobutyric Acid−Water and 1-Butanol−Water in a Spinning-Drop Tensiometer

Abstract

We report definitive evidence for an effective interfacial tension between two types of miscible fluids using spinning-drop tensiometry (SDT). Isobutyric acid (IBA) and water have an upper critical solution temperature (UCST) of 26.3 degrees C. We created a drop of the IBA-rich phase in the water-rich phase below the UCST and then increased the temperature above it. Long after the fluids have reached thermal equilibrium, the drop persists. By plotting the inverse of the drop radius cubed (r(-)(3)) vs the rotation rate squared (omega(2)), we confirmed that an interfacial tension exists and estimated its value. The transition between the miscible fluids remained sharp instead of becoming more diffuse, and the drop volume decreased with time. We observed droplet breakup via the Rayleigh-Tomotika instability above the UCST when the rotation rate was decreased by 80%, again demonstrating the existence of an effective interfacial tension. When pure IBA was injected into water above the UCST, drops formed inside the main drop even as the main drop decreased in volume with time. We also studied 1-butanol in water below the solubility limit. Effective interfacial tension values measured over time were practically constant, while the interface between the two phases remains sharp as the volume of the drop declines. The effective interfacial tension was found to be insensitive to changes in temperature and always larger than the equilibrium interfacial tension. Although these results may not apply to all miscible fluids, they clearly show that an effective interfacial tension can exist and be measured by SDT for some systems.