New insight into 3-picoline—deuterium oxide (D2O) mixtures of limited miscibility with the lower critical consolute temperature

Abstract

Coexistence curves in mixtures of limited miscibility with the lower critical consolute temperature (LCT), of 3-picoline with deuterium oxide (D2O), and D2O/H2O have been determined. They were tested with respect to the order parameter, the diameter of the binodal, and coordinates of the critical consolute point (critical temperature {T}_{mathrm{C}} and critical concentration {phi }_{mathrm{C}}). Studies were carried out using the innovative method based on the analysis of relative volumes occupied by coexisting phases, yielding high-resolution data. The clear violation of the Cailletet-Mathew law of rectilinear diameter for the LCT mixtures of limited miscibility is evidenced. For the order parameter, the new distortion-sensitive analysis method yielded the evidence for the model-value of the order parameter critical exponent beta =0.326pm 0.003, up to ca. 1 K from {T}_{mathrm{C}}. Finally, the simple & easy method for determining the critical concentration by testing relative volumes of coexisting phases (or alternatively fractional meniscus heights, h) is presented. The significance of the invariant value {h}_{mathrm{C}}=hleft({T}_{mathrm{C}},{phi }_{mathrm{C}}right)=1/2 is highlighted. The appearance of the milky & bluish critical opalescence is also shown.Graphical abstract