Phase Equilibria for Binary Aqueous Systems from a Near-Critical Water Reaction Apparatus

Abstract

For any valid study of reaction kinetics the phase equilibria involved must be known. We present an apparatus designed to measure both phase equilibria and kinetics for reactions in near-critical water. Liquid−liquid mutual solubilities are reported for the benzene−water and toluene−water systems from 200 to 275 °C at the three-phase pressures and 172 bar. These data were found to be in good agreement with data reported in the literature. Additionally, the near-critical water reaction apparatus was used to verify one-phase regions for the phenol−water and p-cresol−water systems from 250 to 300 °C at 172 bar.

Modeling Studies on the Transport of Benzene and H2S in CO2-Water Systems

“…Usually, the mutual solubilities are measured along the three-phase equilibrium line, at given reported vapor pressures, such as in Chandler et al (1998), Anderson and Prausnitz (1986), and Jou and Mather (2003). Some researchers (e.g., Sanemasa et al, 1982; were more interested in the solubility at low temperatures and measured the solubility of benzene in water at vapor-liquid equilibrium.…”

“…Vapor pressure (bar) Mole fraction of benzene in water Chandler et al, 1998Anderson and prausnitz 1986Chen and Wagner, 1994Jou and Mather, 2003 (Miller and Hawthorne, 2000)) and along the three-phase pressure curve (Neely et al, 2008) at saturation temperatures.…”

“…Generally, the solubilities calculated by TMVOC_REACT reproduce the measured data reasonably well, within acceptable margins for the objectives of this study. Chandler et al, 1998Anderson and prausnitz, 1986Chen and Wagner, 1994Jou and Mather, 2003 calculated by TMVOC The log(K) derived from vapor-liquid-liquid equilibrium reflects the equilibrium of benzene in water with benzene in vapor. However, as shown in the phase diagram of benzene ( Figure A3), benzene would be in the liquid state in the temperature and pressure range of most geological environments.…”

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

“…Consequently, there have been numerous measurements of the aqueous solubilities of organics at high temperatures (Dohrn et al 2010;Fonseca et al 2011;Š kerget et al 2011). Although some of the studies have covered the solutes that are liquid at the measurement temperatures (Yang et al 1997;Chandler et al 1998;Miller and Hawthorne 2000a, b), a significant part of these efforts have dealt with the solubilities of organic nonelectrolyte solids. The main reason is probably that the solid phase at equilibrium with the aqueous solution remains a pure solid solute as opposed to most situations when the solute is a liquid at the measurement temperature.…”

Spectroscopic study of mutual solubilities of water and benzene at high temperatures and pressures

“…The transferring of a sample without disturbing equilibrium and/or without composition change is rather difficult, particularly at high temperatures and pressures. 10,21 Therefore most of the solubility data of the water-benzene system have been limited at the three-phase equilibrium pressures, 9,10,13,21 and a few other pressures at higher temperatures. [22][23][24][25] In addition, effect of pressure on the mutual solubilities has not been fully understood, in contrast to the temperature effect, namely the significant increase in the mutual solubilities with increasing temperature.…”