David Bessières

Simultaneous estimation of phase behavior and second-derivative properties using the statistical associating fluid theory with variable range approach.

A modified statistical associating fluid theory (SAFT) with variable range version is presented using the family of m-n Mie potentials. The use of this intermolecular potential for modeling repulsion-dispersion interactions between the monomer segments, together with a new method for optimizing the molecular parameters of the equation of state, is found to give a very accurate description of both vapor-liquid equilibria and compressed liquid bulk properties (volumetric and derivative properties) for long-chain n-alkanes. This new equation improves other SAFT-like equations of state which fail to describe derivative properties such as the isothermal compressibility and the speed of sound in the condensed liquid phase. Emphasis is placed on pointing out that the key for modeling the latter properties is the use of a variable repulsive term in the intermolecular potential. In the case of the n-alkanes series, a clear dependence of the characteristic molecular parameters on increasing chain length is obtained, demonstrating their sound physical meaning and the consistency of the new fitting procedure proposed. This systematic method for optimizing the model parameters includes data on the saturation line as well as densities and speed of sound data in the condensed liquid phase, and the results show undoubtedly that the model performance is enhanced and its range of applicability is now widened, keeping in any case a good balance between the accuracy of the different estimated properties.

Interfacial Properties of Water/CO2: A Comprehensive Description through a Gradient Theory−SAFT-VR Mie Approach

The Gradient Theory of fluid interfaces is for the first time combined with the SAFT-VR Mie EOS to model the interfacial properties of the water/CO(2) mixture. As a preliminary test of the performance of the coupling between both theories, liquid-vapor interfacial properties of pure water have been determined. The complex temperature dependence of the surface tension of water can be accurately reproduced, and the interfacial thickness is in good agreement with experimental data and simulation results. The water/CO(2) mixture presents several types of interfaces as the liquid water may be in contact with gaseous, liquid, or supercritical CO(2). Here, the interfacial tension of the water/CO(2) mixture is modeled accurately by the gradient theory with a unique value of the crossed influence parameter over a broad range of thermodynamic conditions. The interfacial density profiles show a systematic adsorption of CO(2) in the interface. Moreover, when approaching the saturation pressure of CO(2), a prewetting transition is highlighted. The adsorption isotherm of CO(2) is computed as well in the case of a gas/liquid interface and compared with experimental data. The good agreement obtained is an indirect proof of the consistency of interfacial density profiles computed with the gradient theory for this mixture and confirms that the gradient theory is suitable and reliable to describe the microstructure of complex fluid interfaces.

Interfacial properties of the Mie n−6 fluid: Molecular simulations and gradient theory results

In a first part, interfacial properties of a pure monoatomic fluid interacting through the Mie n-6 potential (n=8, 10, 12, and 20) have been studied using extensive molecular simulations. Monte Carlo and molecular dynamics simulations have been employed, using, respectively, the test area approach and the mechanic route. In order to yield reference values, simulations have been performed with a cutoff radius equal to 10sigma, which is shown to be sufficient to avoid long range corrections. It is shown that both approaches provide results consistent with each other. Using the molecular simulations results, it is demonstrated that a unique scaling law is able to provide an accurate estimation of the surface tension whatever the repulsive exponent n, even far from the critical point. Furthermore, it is shown that the surface tension of the Mie n-6 fluid is as well accurately described by a unique Parachors law. Density profiles are shown to be well represented by the tanh mean field profile, with slight deviations for the lowest temperatures and the smallest n. In addition, the interfacial width is shown to increase when n decreases (for a given reduced temperature) and to follow the usual scaling behavior for not too low temperature. In a second part, interfacial properties of the Mie n-6 fluid computed by the gradient theory, coupled with an equation of state based on the Barker-Henderson perturbation theory, have been compared with those obtained by molecular simulations. It is demonstrated that, even far from the critical point, the gradient theory is efficient to compute surface tensions and density profiles of this model fluid, provided the equation of state accurately model the phase behavior of the fluid involved (which is not the case for n=8 in this study).

On the isobaric thermal expansivity of liquids

The temperature and pressure dependence of isobaric thermal expansivity, α(p), in liquids is discussed in this paper. Reported literature data allow general trends in this property that are consistent with experimental evidence to be established. Thus, a negative pressure dependence is to be expected except around the critical point. On the other hand, α(p) exhibits broad regions of negative and positive temperature dependence in the (T, p) plane depending on the nature of the particular liquid. These trends are rationalized here in terms of various molecular-based equations of state. The analysis of the Lennard-Jones, hard sphere square well and restricted primitive model equations allows understanding the differences in the α(p) behavior between liquids of diverse chemical nature (polar, nonpolar, and ionic): broader regions of negative temperature and positive pressure dependencies are obtained for liquids characterized by larger ranges of the interparticle potential. Also, using the statistical associating fluid theory (SAFT) allowed the behavior of more complex systems (basically, those potentially involving chain and association effects) to be described. The effect of chain length is rather simple: increasing it is apparently equivalent to raise the interaction range. By contrast, association presents a quite complex effect on α(p), which comes from a balance between the dispersive and associative parts of the interaction potential. Thus, if SAFT parameters are adjusted to obtain low association ability, α(p) is affected by each mechanism at clearly separate regions, one at low temperature, due to association, and the other to dispersive forces, which has its origin in fluctuations related with vapor-liquid transition.

Thermophysical properties of n-tridecane from 313.15 to 373.15 K and up to 100 MPa from heat capacity and density data

Isobaric heat capacities of liquid n-tridecane were measured at temperatures from 313.15 to 373.15 K and at pressures up to 100 MPa using a calorimetric device based on a Calvet calorimeter (Setaram C80). These experimental data combined with the additional knowledge of density data were used to calculate the following properties at pressures up to 100 MPa: isochoric heat capacity, isentropic compressibility and ultrasound velocity.

Thermodynamic properties of the Mie n-6 fluid: a comparison between statistical associating fluid theory of variable range approach and molecular dynamics results.

Molecular dynamics (MD) simulations of direct and derivative thermodynamic properties of the Mie n-6 fluid (n=8, 10, and 12) have been performed for liquid to supercritical states. Using the results, an in depth test of the monomer-monomer interaction estimation of a recently derived statistical associating fluid theory of variable range (SAFT-VR) equation of state [Lafitte et al., J. Chem. Phys., 124, 024509 (2006)] has been carried out based on the Mie n-6 potential. For pure fluids, using an appropriate scaling, MD simulations show that density and isometric heat capacity are nearly independent of n, whereas sound velocity and thermal pressure coefficient tend to increase with n. In addition, the results show that predictions provided by the equation of state are consistent with those coming from MD and catch correctly the trends of each property with n except for the heat capacity. The comparison is next extended to binary mixtures with components differing only in the value of the n parameter and which demonstrate the reliability of the scheme (MX1b) used by Lafitte et al. to deal with this parameter in the SAFT-VR equation of state. In addition, a new empirical one-fluid approximation of the n parameter is proposed thanks to MD simulations, which very favorably compare with the one-fluid model on n previously proposed in the literature. The consistency of this approximation is addressed by making use of it in combination with the SAFT-VR Mie equation of state. It is shown that using such an approach, which is easier to handle than the MX1b one, yields slightly improved results compared to those of the MX1b.

Measurement and Calculation of Heat Capacity of Heavy Distillation Cuts Under Pressure up to 40 MPa

Isobaric heat capacities of natural mixtures were determined up to 40 MPa with a modified C-80 Setaram calorimeter equipped with cells designed for high pressures. The systems investigated were heavy distillation cuts with respective boiling points of 150, 200, 250 and 300°C. These experimental data were used as discriminatory values to test thermodynamic models and more precisely to choose among the great number of equations of state and mixing rules proposed in the literature, the most appropriate for the characterization of the heavy components.

Analysis of the orientational order effect on n-alkanes: Evidences on experimental response functions and description using Monte Carlo molecular simulation

Short-range correlations of the molecular orientations in liquid n-alkanes have been extensively studied from depolarized Rayleigh scattering and thermodynamic measurements. These correlations between segments induce structural anisotropy in the fluid bulk. This phenomenon, which is characteristic of linear chain molecules when the constituting segments are nor freely jointed, but interact through a given angular potential, is then present in the linear n-Cn series, increasing its magnitude with chain length, and it is therefore less relevant or even completely absent in branched alkanes. This intermolecular effect is clearly revealed in second-order excess magnitudes such as heat capacities when the linear molecule is mixed with one whose structure approaches sphericity. The mixing process of different aspect ratio chain molecules is thought to modify the original pure fluid structure, by producing a diminution of the orientational order previously existing between pure n-alkane chains. However, second-order thermodynamics quantities of pure liquids C(P), ( partial differentialv/ partial differentialT)(P), and ( partial differentialv/ partial differentialP)(P) are known to be very sensitive to the specific interactions occurring at the microscopic level. In other words, the behavior of these derived properties versus temperature and pressure can be regarded as response functions of the complexity of the microscopic interactions. Thus, the purpose of the present work is to rationalize the orientational order evolution with both temperature and molecular chain length from the analysis of pure fluid properties. To this aim, we focused on two linear alkanes, n-octane (n-C(8)) and n-hexadecane (n-C(16)), and two of their branched isomers, i.e., 2,2,4-trimethylpentane (br-C(8)) and 2,2,4,4,6,8,8-heptamethylnonane (br-C(16)). For each compound, we propose a combined study from direct experimental determination of second-order derivative properties and Monte Carlo simulations. We performed density rho, speed of sound c, and isobaric heat capacity C(P) measurements in broad ranges of pressure and temperature allowing a complete thermodynamic characterization of these compounds. Monte Carlo simulations provide a link between the molecular scale model and the experimental thermodynamic properties. Additional information about the microscopic structure of the simulated fluid model was derived, through the calculation of the radius of gyration and average end-to-end distances. Orientational order is clearly revealed by the experimental residual heat capacity trend of pure linear alkanes. The close agreement observed between this experimental macroscopic property and the calculated theoretical structural parameters support the conclusion that the orientational order between segments of linear molecules should be regarded as a conformational effect due to the flexibility of the chain.

Heat Capacity of a Synthetic Distillation Cut+n-Hexane System under Pressure

Isobaric heat capacities of synthetic mixtures were determined up to 40 MPa with a modified C-80 Setaram calorimeter equipped with cells designed for high pressures. The system investigated was a pseudo-binary hexane+synthetic cut, the latter consisting of compounds of the three chemical families that occur most frequently in natural effluents (paraffins, naphthenes and aromatics). The additional knowledge of density vs. pressure and temperature affords the specific heat γ ratio.

CO2 and CH4 Adsorption Behavior of Biomass Based Activated Carbons

The aim of the present study is to provide new insights into the CO2 and CH4 adsorption using a set of biomass-based activated carbons obtained by physical and chemical activation of olive-stones. The adsorption behavior is analyzed by means of pure gas adsorption isotherms up to 3.2 MPa at two temperatures (303.15 and 323.15 K).The influence of the activation method on the adsorption uptake is studied in terms of both textural properties and surface chemistry. For three activated carbons the CO2 adsorption was more important than that of CH4. The chemically activation resulted in higher BET surface area and micropore volume that lead to higher adsorption for both CO2 and CH4. For methane the presence of mesopores seems to facilitate the access of the gas molecules into the micropores while for carbon dioxide, the presence of oxygen groups enhanced the adsorption capacity.