Thermochemical investigations of associated solutions: calculation of solute--solvent equilibrium constants from solubility measurements.
A simple solution model that has lead to successful predictive equations for the partial molar excess properties of a solute in simple binary solvent mixtures containing only nonspecific interactions is extended to include association between the solute and one of the solvent components. An expression is derived and tested for its ability to describe anthracene solubilities in binary solvent mixtures containing benzene. The best description of the experimental solubilities requires the formation of a 1:1 anthracene-benzene complex, with a molarity-based equilibrium constant of KcAC approximately equal to 0.107 M-1. In comparison, a stoichiometric complexation model which attributes all solubility enhancement to the formation of anthracene-benzene complexes requires a somewhat larger equilibrium constant (KcAC approximately equal to 0.228 M-1) to describe the solubility behavior of anthracene in the benzene-n-heptane system. The results of these calculations illustrate that the determination of solute-solvent equilibrium constants from solubility data depends on the theoretical model used and the manner in which nonspecific interactions are incorporated into the model.
Solubility in binary solvent systems I: Specific versus nonspecific interactions.
Solubilities are reported for benzil in carbon tetrachloride-alkane (isooctane, n-octane, cyclooctane) systems at 25 degrees and in similar binary mixtures containing cyclohexane plus alkane. The results of these measurements are compared to solution models previously developed for solubility in systems containing specific solute-solvent interactions and to models for purely nonspecific interactions. A stoichiometric complexation model based primarily on specific solute-solvent interactions requires several equilibrium constants to mathematically describe the experimental solubilities in binary carbon tetrachloride mixtures. However, there was no direct experimental evidence to suggest complexation between benzil and carbon tetrachloride. In comparison, expressions derived from the Nearly Ideal Binary Solvent (NIBS) model for nonspecific interactions predict experimental solubilities with a maximum deviation of 5% and an overall deviation of 1.0%. The success of the NIBS approach for this system is significant because the mole fraction solubility of benzil changes by a factor of 14 in the carbon tetrachloride-isooctane system.
A bifunctional Cr/Yb/Tm:Ca3Ga2Ge3O12 phosphor with near-infrared long-lasting phosphorescence and upconversion luminescence.
Currently, upconversion nanocrystals and long-lasting phosphorescent particles have attracted extensive research interest for their possible applications as bioimaging probes. However, there are few reports concerning the achievement of both upconversion luminescence of lanthanide ions and long-lasting phosphorescence of transition metal ions in a sole host so far. Herein, we demonstrate a novel calcium gallium germanium garnet (Ca3Ga2Ge3O12) host where lanthanide ions such as Tm(3+)/Yb(3+) and transition metal ions such as Cr(3+) can be easily incorporated through substituting the Ca(2+) and Ga(3+) respectively. This Cr/Yb/Tm:Ca3Ga2Ge3O12 phosphor exhibits both broadband near-infrared long-lasting phosphorescence of Cr(3+) with an afterglow time of more than 7000 s and near-infrared to near-infrared upconversion luminescence of Tm(3+). Impressively, it is evidenced that the addition of Yb(3+)/Tm(3+) into Cr:Ca3Ga2Ge3O12 not only results in Tm(3+) upconversion luminescence but also greatly increases Cr(3+) afterglow time. Based on excitation/emission, three-dimensional thermoluminescence, and time-resolved luminescence spectra, the related long-lasting phosphorescence and upconversion luminescent mechanisms are systematically discussed as well.