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

Kevin M. Dean, Christopher B. Babayco, Daniel R.B. Sluss, J. Charles Williamson

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

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 Tcx. 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°, 24°, and 90° 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 Tcx to the onset of decreased transmitted light or increased 2° 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 Tcx 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° scattering is collected along with transmitted or 2° data, the accuracy of Tcx is limited to 0.05 K for near-critical samples. Visual determination of Tcx remains the more accurate approach in this case.

Original languageEnglish (US)
Article number074506
JournalJournal of Chemical Physics
Volume133
Issue number7
DOIs
StatePublished - Aug 21 2010
Externally publishedYes

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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