High‐temperature mutual solubilities of hydrocarbons and water. Part II: Ethylbenzene, ethylcyclohexane, and n‐octane

Abstract

In Part I (Tsonopoulos and Wilson, 1983), the mutual solubilities of three Ca hydrocarbons (benzene, cyclohexane, n-hexane) and water were experimentally investigated and, together with critically selected literature data, were correlated up to the three-phase critical end point. The present paper extends this analysis to the mutual solubilities of three Cs hydrocarbons (ethylbenzene, ethylcyclohexane, n-octane) and water, which have been measured at the threephase equilibrium pressure up to the critical temperatures (568,561 and 539 K, respectively), A thermodynamic analysis of these new measurements and of available literature data has been performed up to the three-phase critical end point. Information is also provided on vapor-phase equilibrium compositions. The solubility of hydrocarbons in water has been used to calculate Henry's constants, while the solubility and volatility of water in hydrocarbons has been successfully correlated with several modifications of the Redlich-Kwong equation of state. SCOPEThe importance of hydrocarbon/water mutual solubilities to the design and operation of process equipment in refineries and petrochemical pIants was discussed by Tsonopoulos and Wilson (1983) [this reference will be cited as TW (1983)J The same reference also discussed the correlation and prediction of mutual solubilities, Henry's constants for hydrocarbons in water, and the use of equations of slate. All these were applied to Ce hydrocarbons, for which much more is known than for other hydrocarbons.Our work continues with CS hydrocarbons to study the effect of carbon number on mutual solubilities. But we have also expanded the scope of our study by including experimental data for the vapor composition and the three-phase critical end point, the highest temperature at which the vapor and the two liquid phases coexist.

Mutual solubilities of hydrocarbons and water with the CPA EoS

“…The CPA EoS was successfully applied to extreme conditions of temperature and pressure, lower deviations would be expected if the CPA EoS was used to model narrow ranges of temperature and pressure. For higher n-alkanes from pentane to decane mutual solubilities were available at the three-phase equilibrium pressure [1,[55][56][57][58]. As before a single, temperature independent, binary interaction parameter was enough to adequately describe the phase equilibria.…”

IUPAC-NIST Solubility Data Series. 81. Hydrocarbons with Water and Seawater—Revised and Updated. Part 3. C6H8–C6H12 Hydrocarbons with Water and Heavy Water

“…The solubility of cyclohexane in water at 20°C was reported to be 0.10 g(1)/mL (2). The corresponding mass percent and mole fraction, x 1 , calculated by the compiler are 0.010 g(1)/100 g sln and 2.1•10…”

Experimental and molecular modelling study of the three-phase behaviour of (propane+carbon dioxide+water) at reservoir conditions

“…[25,26]. Regarding systems consisting of various (hydrocarbons + water), it is worth highlighting the extensive work of Tsonopoulos et al [27][28][29][30][31] as well as the IUPAC-NIST reviews [32][33][34][35][36][37][38][39][40], albeit both studies focused on heavier hydrocarbons than propane. For completeness, previous work on the (propane + water) mixture is here briefly reviewed.…”