A Fluctuation Equation of State for Prediction of High-Pressure Densities of Ionic Liquids

International audienceDuring this work, we demonstrate, for the first time, that the volumetric properties of pure ionic liquids could be truly predicted as a function of temperature from 219 K to 473 K and pressure up to 300 MPa. This has been achieved by using only density and isothermal compressibility data at atmospheric pressure through the Fluctuation Theory-based Tait-like Equation of State (FT-EoS). The experimental density data of 80 different ionic liquids, described in the literature by several research groups as a function of temperature and pressure, was then used to provide comparisons. Excellent predictive capability of FT-EoS was observed with an overall relative absolute average deviation close to 0.14% for the 15,298 data points examined during this work

Turning molecular springs into nano-shock absorbers: the effect of macroscopic morphology and crystal size on the dynamic hysteresis of water intrusion-extrusion into-from hydrophobic nanopores

Controlling the pressure at which liquids intrude (wet) and extrude (dry) a nanopore is of paramount importance for a broad range of applications, such as energy conversion, catalysis, chromatography, separation, ionic channels, and many more. To tune these characteristics, one typically acts on the chemical nature of the system or pore size. In this work, we propose an alternative route for controlling both intrusion and extrusion pressures via proper arrangement of the grains of the nanoporous material. To prove the concept, dynamic intrusion-extrusion cycles for powdered and monolithic ZIF-8 metal-organic framework were conducted by means of water porosimetry and in operando neutron scattering. We report a drastic increase in intrusion-extrusion dynamic hysteresis when going from a fine powder to a dense monolith configuration, transforming an intermediate performance of the ZIF-8 + water system (poor molecular spring) into a desirable shock-absorber with more than 1 order of magnitude enhancement of dissipated energy per cycle. The obtained results are supported by MD simulations and pave the way for an alternative methodology of tuning intrusion-extrusion pressure using a macroscopic arrangement of nanoporous material

Experimental assessment of the fuel heating and the validity of the assumption of adiabatic flow through the internal orifices of a diesel injector

[EN] In this paper an experimental investigation on the heating experienced by the fuel when it expands through the calibrated orifices of a diesel injector is carried out. Five different geometries corresponding to the control orifices of two different commercial common-rail solenoid injectors were tested. An experimental facility was used to impose a continuous flow through the orifices by controlling the pressures both upstream and downstream of the restriction. Fuel temperature was controlled prior to the orifice inlet and measured after the outlet at a location where the flow is already slowed down. Results were compared to the theoretical temperature increase under the assumption of adiabatic flow (i.e. isenthalpic process). The comparison points out that this assumption allows to predict the fuel temperature change in a reasonable way for four of the five geometries as long as the pressure difference across the orifice is high enough. The deviations for low imposed pressure differences and the remaining orifice are explained due to the low Reynolds numbers (i.e. flow velocities) induced in these cases, which significantly increase the residence time of a fuel particle in the duct, thus enabling heat transfer with the surrounding atmosphere. A dimensionless parameter to quantify the proneness of the flow through an orifice to exchange heat with the surroundings has been theoretically derived and calculated for the different geometries tested, allowing to establish a boundary that defines beforehand the conditions from which heat losses to the ambient can be neglected when dealing with the internal flow along a diesel injector.This work was partly sponsored by “Ministerio de Economía y Competitividad”, of the Spanish government, in the frame of the project “Estudio de la interacción chorro-pared en condiciones realistas de motor”, reference TRA2015-67679-c2-1-R. This support is gratefully acknowledged by the authors.Salvador, F.; Gimeno, J.; Carreres, M.; Crialesi Esposito, M. (2017). Experimental assessment of the fuel heating and the validity of the assumption of adiabatic flow through the internal orifices of a diesel injector. Fuel. 188:442-451. https://doi.org/10.1016/j.fuel.2016.10.061S44245118

Thermodynamic Properties of Dichloromethane, Bromochloromethane, and Dibromomethane under Elevated Pressure: Experimental Results and SAFT-VR Mie Predictions

The speeds of sound in dibromomethane, bromochloromethane, and dichloromethane have been measured in the temperature range from 293.15 to 313.15 K and at pressures up to 100 MPa. Densities and isobaric heat capacities at atmospheric pressure have been also determined. Experimental results were used to calculate the densities and isobaric heat capacities as the function of temperature and pressure by means of a numerical integration technique. Moreover, experimental data at atmospheric pressure were then used to determine the SAFT-VR Mie molecular parameters for these liquids. The accuracy of the model has been then evaluated using a comparison of derived experimental high-pressure data with those predicted using SAFT. It was found that the model provide the possibility to predict also the isobaric heat capacity of all selected haloalkanes within an error up to 6%

Subnanometer Topological Tuning of the Liquid Intrusion/Extrusion Characteristics of Hydrophobic Micropores

Intrusion (wetting)/extrusion (drying) of liquids in/from lyophobic nanoporous systems is key in many fields, including chromatography, nanofluidics, biology, and energy materials. Here we demonstrate that secondary topological features decorating main channels of porous systems dramatically affect the intrusion/extrusion cycle. These secondary features, allowing an unexpected bridging with liquid in the surrounding domains, stabilize the water stream intruding a micropore. This reduces the intrusion/extrusion barrier and the corresponding pressures without altering other properties of the system. Tuning the intrusion/extrusion pressures via subnanometric topological features represents a yet unexplored strategy for designing hydrophobic micropores. Though energy is not the only field of application, here we show that the proposed tuning approach may bring 20-75 MPa of intrusion/extrusion pressure increase, expanding the applicability of hydrophobic microporous materials