title: Determination of liquid-liquid critical point composition using 90^{∘} laser light scattering.
abstract: Despite over a century of characterization efforts, liquid-liquid critical point compositions are difficult to identify with good accuracy. Reported values vary up to 10% for even well-studied systems. Here, a technique is presented for high-precision determination of the critical composition of a partially miscible binary liquid system. Ninety-degree laser light-scattering intensities from single-phase samples are analyzed using an equation derived from nonclassical power laws and the pseudospinodal approximation. Results are reported for four liquid-liquid systems (aniline + hexane, isobutyric acid + water, methanol + cyclohexane, and methanol + carbon disulfide). Compared to other methods, the 90^{∘} light-scattering approach has a strong dependence on composition near the critical point, is less affected by temperature fluctuations, and is insensitive to the presence of trace impurities in the samples. Critical compositions found with 90^{∘} light scattering are precise to the parts-per-thousand level and show long-term reproducibility.
authors.affiliation: Department of Chemistry, Willamette University, 900 State Street, Salem, Oregon 97301, USA.
authors.forename: J Charles
authors.initials: JC
authors.lastname: Williamson
authors.affiliation: Department of Chemistry, Willamette University, 900 State Street, Salem, Oregon 97301, USA.
authors.forename: Allison M
authors.initials: AM
authors.lastname: Brown
authors.affiliation: Department of Chemistry, Willamette University, 900 State Street, Salem, Oregon 97301, USA.
authors.forename: Elise N
authors.initials: EN
authors.lastname: Helvie
authors.affiliation: Department of Chemistry, Willamette University, 900 State Street, Salem, Oregon 97301, USA.
authors.forename: Kevin M
authors.initials: KM
authors.lastname: Dean