Stéphane Vitu

Nous avons développé une méthode de contributions de groupes permettant d'estimer, en fonction de la température, le coefficient d'interaction binaire (kij) de l'équation d'état de Peng Robinson. Notre approche rend cette équation d'état prédictive. Douze groupes sont définis et il est possible d'estimer les kij pour n'importe quel mélange renfermant des alcanes, des aromatiques, des naphtènes et du CO2. Les diagrammes de phase et lieux des points critiques des systèmes binaires sont bien prédits par le modèle baptisé PPR78 (Predictive 1978, Peng Robinson equation of state). Ce modèle permet également de traiter efficacement les mélanges multiconstituants comme les pétroles bruts et les gaz naturels. A l'aide d'une cellule haute pression, des mesures d'équilibres liquide - vapeur ont été réalisées pour la première fois sur deux systèmes binaires : CO2 méthylcyclopentane et CO2 isopropylcyclohexane. Des mesures ont également été faites sur un mélange renfermant du CO2 et cinq hydrocarbures

In this work, the volumetric properties of nine binary systems composed of ethyl propanoate and n-alkylcyclohexanes (from cyclohexane to decylcyclohexane) were investigated. Densities were measured at atmospheric pressure (101 kPa) over the entire composition range and at temperatures from 288.15 K to 328.15 K. A total of 525 density data points were obtained. Excess molar volumes were derived from the experimental densities and correlated using a Redlich–Kister equation, while mixture densities were modeled with the Jouyban–Acree model. All systems exhibit positive excess molar volumes over the studied temperature and composition ranges, indicating volume expansion upon mixing due to dominant repulsive interactions. The magnitude of the excess molar volume increases with increasing alkyl chain length of the branched naphthenic compound: for an equimolar mixture, V^E is about 0.65 cm³·mol⁻¹ for the methylcylohexane + ethyl propanoate mixture and reaches 0.83 cm³·mol⁻¹ for the heptylcylohexane + ethyl propanoate binary system, although a plateau tendency is observed for longer alkyl chains. Excess molar volumes increase linearly with temperature, with a more pronounced temperature effect for shorter-chain alkylcyclohexanes. The Jouyban–Acree model provides an excellent correlation of the density data, yielding average relative deviations between 0.02% and 0.04%, and allows reliable predictions within the investigated temperature range.

This study is a continuation of a series of works concerning the acquisition of new experimental data related to binary mixtures of branched alkanes with CO₂. A synthetic method was employed to measure phase transition pressures for the systems CO₂ + 2,2-dimethylbutane and CO₂ + 2-methylpentane with an adjustable-volume high-pressure cell. To our knowledge, these binary systems were investigated for the first time in this work. Bubble and dew point pressures were obtained by visual detection at constant composition with an expanded uncertainty ranging from (0.04 to 0.08) MPa. Mixtures were investigated at temperatures ranging from (293.15 to 363.15) K with pressures up to 11 MPa. The Peng-Robinson equation of state was used to correlate the experimental data. An accurate representation of the results has been obtained by using classical mixing rules with temperature-dependent binary interaction parameters regressed against experimental data. The predictive model PPR78 has also provided satisfactory results.

Vapor–liquid equilibrium (VLE) and density data for binary systems of branched alkanes + ethyl acetate are scarce in the literature. In this study, the binary mixtures 3-methylpentane + ethyl acetate and 2,3-dimethylbutane + ethyl acetate were investigated. Density measurements at atmospheric pressure were performed using a vibrating tube density meter at 293.15, 298.15 and 303.15 K. Large and positive excess molar volumes were calculated and correlated using a Redlich–Kister-type equation. Isobaric VLE data at 101.3 kPa were obtained using a Gillespie-type recirculation ebulliometer. Equilibrium compositions were determined indirectly from density measurements. The experimental data were checked for consistency by means of the Fredenslund test and the Wisniak (L-W) test and were then successfully correlated using the NRTL model. The newly studied binary systems display high deviations from ideality and minimum boiling azeotropes, the coordinates of which are reported in this work.