Solubility of Solid Polycyclic Aromatic Hydrocarbons in Pressurized Hot Water:  Correlation with Pure Component Properties

Abstract

A semiempirical relationship was developed to correlate solubility of solid polycyclic aromatic hydrocarbons (PAHs) in pressurized hot water using only pure-component properties. The required properties of water include cohesive energy density, internal pressure, and relative permittivity (dielectric constant), all at the particular temperature and pressure. The required properties of PAHs include triple-point temperature, enthalpy of fusion, the molar volume of the subcooled liquid, and the molar volume of the solid. The correlation was developed from experimental solubility data of eight 2- to 5-ring PAHs at temperatures within 313−498 K, with the solubility (equilibrium mole fraction) ranging within 10-11 to 10-3. Considering the wide range of the source data, the extreme nonideality of water−PAH systems, and the absence of any water−PAH interaction parameters, the correlation provides an adequate reproduction of the source data. Further, the correlation yields a relatively reasonable prediction of PAH solubilities outside the range of the source data, namely, at environmentally relevant conditions of 298.15 K and 0.1 MPa. In addition to the correlation, new data on aqueous solubilities of fluorene and fluoranthene are also reported.

Direct and Indirect Applications of Sub- and Supercritical Water in Food-Related Analysis

“…8.4 Activity coefficients of oxygenated aromatic solutes in saturated aqueous solutions: ○, xanthene; Â, anthrone; e, xanthone; *, thioxanthone; Δ, 9,10-anthraquinone. Anthracene (Karásek et al 2006b) r is shown for reference. The lines serve just to guide the eye.…”

Analysis of Predictive Thermodynamic Models for Estimation of Polycyclic Aromatic Solid Solubility in Hot Pressurized Water

“…In recent years, many efforts have been made to develop semi-empirical approaches [10][11][12][13] to correlate the solubility *Address correspondence to this author at the Instituto de Investigación en Ciencias de la Alimentación CIAL (CSIC-UAM) C/Nicolás Cabrera 9, Universidad Autónoma de Madrid, 28049 Madrid, Spain; Tel: +34910017927; Fax: +34910017900; E-mail: tiziana.fornari@uam.es of solids in HPW, based on the use of solute and solvent (water) physical properties. For example, Miller et al [10] developed a simple equation to relate the effect of increasing temperature on the solubility of polycyclic aromatic hydrocarbons (PAHs) in liquid water at high temperatures.…”

“…Another semi-empirical relationship, presented by Karásek et al [13], uses the temperature dependency of pure water physical properties (internal pressure, cohesive energy density and dielectric constant) to correlate the activity coefficients of PAHs in water as a function of temperature. Pure solute physical properties (fusion enthalpy, triple-point temperature, subcooled liquid molar and solid molar volumes) are employed to calculate the ratio of the solute fugacity in the solid and subcooled liquid states, and high degree of correlation of the experimental solubility data was achieved [13].…”

“…Pure solute physical properties (fusion enthalpy, triple-point temperature, subcooled liquid molar and solid molar volumes) are employed to calculate the ratio of the solute fugacity in the solid and subcooled liquid states, and high degree of correlation of the experimental solubility data was achieved [13].…”

“…The above mentioned approaches [10][11][12][13] are based on the use of physical properties of both the solute and water (i.e. no energy interactions between like or unlike molecules are considered) and are good correlative methods but are not predictive tools.…”