The accuracy of liquid-liquid phase transition temperatures determined from semiautomated light scattering...

The synthetic-method determination of liquid-liquid coexistence curves using semiautomated light scattering instrumentation and stirred samples is based on identifying the coexistence curve transition temperatures (T(cx)) from sudden changes in turbidity associated with droplet formation. Here we use a thorough set of such measurements to evaluate the accuracy of several different analysis methods reported in the literature for assigning T(cx). More than 20 samples each of weakly opalescent isobutyric acid+water and strongly opalescent aniline+hexane were tested with our instrumentation. Transmitted light and scattering intensities at 2 degrees , 24 degrees , and 90 degrees were collected simultaneously as a function of temperature for each stirred sample, and the data were compared with visual observations and light scattering theory. We find that assigning T(cx) to the onset of decreased transmitted light or increased 2 degrees scattering has a potential accuracy of 0.01 K or better for many samples. However, the turbidity due to critical opalescence obscures the identification of T(cx) from the light scattering data of near-critical stirred samples, and no simple rule of interpretation can be applied regardless of collection geometry. At best, when 90 degrees scattering is collected along with transmitted or 2 degrees data, the accuracy of T(cx) is limited to 0.05 K for near-critical samples. Visual determination of T(cx) remains the more accurate approach in this case.