Liquid densities, heat capacities, refractive index and excess quantities for {protic ionic liquids plus water} binary system

Densities, rho, of aqueous solutions of the room temperature protic ionic liquid (PIL), pyrrolidinium nitrate are determined at the atmospheric pressure over the temperature range from (283.15 to 323.15) K and within the whole composition range. The molar isobaric heat capacities, C(p), and refractive index, n(D), of {PIL + water} binary system are measured at 298.15 K. The excess molar volumes V(E), excess molar isobaric heat capacities C(p)(E), and deviation from ideality of refractive index Delta(phi)n, of pyrrolidinium nitrate aqueous solutions were deduced from the experimental results as well as apparent molar volumes V(phi), partial molar volumes (V) over bar (m,i), and thermal expansion coefficients alpha(p). The V(E) values were found to be positive over the entire composition range at all temperatures studied therein, whereas deviations from ideality were negative for refractive index Delta(phi)n. The volumetric properties of binary mixtures containing water and four other protic ionic liquids, such as pyrrolidinium hydrogen sulfate, pyrrolidinium formiate, collidinium formate, and diisopropyl-ethylammonium formate were also determined at 298.15 K. Results have been then discussed in terms of molecular interactions and molecular structures in these binary mixtures. (C) 2009 Elsevier Ltd. All rights reserved.

Structure and thermal properties of salicylate-based-protic ionic liquids as new heat storage media. COSMO-RS structure characterization and modeling of heat capacities

During this research, we present a study on the thermal properties, such as the melting, cold crystallization, and glass transition temperatures as well as heat capacities from 293.15 K to 323.15 K of nine in-house synthesized protic ionic liquids based on the 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate ([H-Im-C₁OC_n][Sal]) with n = 3–11. The 3D structures, surface charge distributions and COSMO volumes of all investigated ions are obtained by combining DFT calculations and the COSMO-RS methodology. The heat capacity data sets as a function of temperature of the 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate are then predicted using the methodology originally proposed in the case of ionic liquids by Ge et al. 3-(Alkoxymethyl)-1H-imidazol-3-ium salicylate based ionic liquids present specific heat capacities higher in many cases than other ionic liquids that make them suitable as heat storage media and in heat transfer processes. It was found experimentally that the heat capacity increases linearly with increasing alkyl chain length of the alkoxymethyl group of 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate as was expected and predicted using the Ge et al. method with an overall relative absolute deviation close to 3.2% for temperatures up to 323.15 K.

High-Pressure Densities and Derived Thermodynamic Properties of Imidazolium-Based Ionic Liquids

This work addresses the experimental measurements of the pressure (0.10 <p/MPa <10.0) and temperature (293.15 <T/K <393.15) dependence of the density and derived thermodynamic properties, such as the isothermal compressibility, the isobaric expansivity, the thermal pressure coefficient, and the pressure dependence of the heat capacity of several imidazolium-based ionic liquids (ILs), namely, 1-butyl-3-methylimidazolium tetrafluoroborate, [bmim][BF4]; 3-methyl-1-octylimidazolium tetrafluoroborate, [omim][BF4]; 1-hexyl-3-methylimidazolium hexafluorophosphate, [hmim][PF6]; 3-methyl-1-octylimidazolium hexafluorophosphate, [omim][PF6]; 1-butyl-2,3-dimethylimidazolium hexafluorophosphate, [bmmim][PF6]; and 1-butyl-3-methylimidazolium trifluoromethansulfonate, [bmim][CF3SO3]. These ILs were chosen to provide an understanding of the influence of the cation alkyl chain length, the number of cation substitutions, and the anion influence on the properties under study. The influence of water content in the density was also studied for the most hydrophobic IL used, [omim][PF6]. A simple ideal-volume model was employed for the prediction of the imidazolium molar volumes at ambient conditions, which proved to agree well with the experimental results.

PVT Property Measurements for Some Aliphatic Esters from (298 to 393) K and up to 35 MPa

The results of PVT measurements of the liquid phase within the temperature range of (298 to 393) K and up to 35 MPa are presented for some aliphatic esters. Measurements were made by means of a vibrating-tube densimeter, model DMA 512P from Anton Parr. The calibration of the densimeter was performed with water and n-heptane as reference fluids. The experimental PVT data have been correlated by a Tait equation. This equation gives excellent results when used to predict the density of the esters using the method proposed by Thomson et al. (AIChE J. 1982, 28, 671-676). Isothermal compressibilities, isobaric expansivities, thermal pressure coefficients, and changes in the isobaric heat capacity have been calculated from the volumetric data.

Temperature-Driven Mixing-Demixing Behavior of Binary Mixtures of the Ionic Liquid Choline Bis(trifluoromethylsulfonyl)imide and Water

The ionic liquid (2-hydroxyethylammonium)trimethylammonium) bis(trifluoromethylsulfonyl)imide (choline bistriflimide) was obtained as a supercooled liquid at room temperature (melting point = 30 degrees C). Crystals of choline bistriflimide suitable for structure determination were grown from the melt in situ on the X-ray diffractometer. The choline cation adopts a folded conformation, whereas the bistriflimide anion exhibits a transoid conformation. The choline cation and the bistriflimide anion are held together by hydrogen bonds between the hydroxyl proton and a sulfonyl oxygen atom. This hydrogen bonding is of importance for the temperature-dependent solubility proper-ties of the ionic liquid. Choline bistriflimide is not miscible with water at room temperature, but forms one phase with water at temperatures above 72 degrees C (equals upper critical solution temperature). H-1 NMR studies show that the hydrogen bonds between the choline cation and the bistriflimide anion are substantially weakened above this temperature. The thermophysical properties of water-choline bistriflimide binary mixtures were furthermore studied by a photopyroelectric technique and by adiabatic scanning calorimetry (ASC). By photothermal analysis, besides highly accurate values for the thermal conductivity and effusivity of choline bistriflimide at 30 degrees C, the detailed temperature dependence of both the thermal conductivity and effusivity of the upper and lower part of a critical water-choline bistriflimide mixture in the neighborhood of the mixing-demixing phase transition could be determined with high resolution and accuracy. Together with high resolution ASC data for the heat capacity, experimental values were obtained for the critical exponents alpha and beta, and for the critical amplitude ratio G(+)/G(-). These three values were found to be consistent with theoretical expectations for a three dimensional Ising-type of critical behavior of binary liquid mixtures.

Thermophysical Properties of Amino Acid-Based Ionic Liquids

Ionic liquids (ILs) having either cations or anions derived from naturally occurring amino acids have been synthesized and characterized as amino acid-based ionic liquids (AAILs) In this work, the experimental measurements of the temperature dependence or density. viscosity, heat capacity, and thermal conductivity of several AAILs, namely, tributylmethylammonium serinate ([N-444][Ser], tributylmethylammonium taurmate ([N-444][Tau]) tributylmethylammonium lysinate a [N-444][ Lys]), tributylmethylammonium threonate ([N-444][Thr]), tetrabutylphosphonium serinate ([P-4444][Ser]), tetrabutylphosphonium taurmate ([P-4444][Tau]), tetrabutylphosphonium lysinate ([P-4444][Lys]), tetrabutylphosphonium threonate P-4444 Thr tetrabutylphosphonium prolinate P-4444 ((Pro(), tetrabutylphosphonium valinate ([P-4444][Val]), and tetrabutylphosphonium cysteinate ([P-4444][Cys]), are presented The influence of cations and anions on studied properties is discussed. On the basis of experimental data. the QSPR (quantitative structure property relationship) correlations and group contribution methods for thermophysical properties of AAILs have been developed, which form the basis for the development of the computer-aided molecular design (CAMD) of AAILs It has also been demonstrated that that the predictive data obtained by con elation methods ale in good agreement with the experimental data The correlations developed, herein. can thus be used to evaluate the studied thermophysical properties of AAILs for use in process design or in the CAMD of new AAILs

A scheme for entanglement extraction from a solid

Some thermodynamical properties of solids, such as heat capacity and magnetic susceptibility, have recently been shown to be linked to the amount of entanglement in a solid. However, this entanglement may appear a mere mathematical artefact of the typical symmetrization procedure of many-body wavefunction in solid state physics. Here we show that this entanglement is physical, demonstrating the principles of its extraction from a typical solid-state system by scattering two particles off the system. Moreover, we show how to simulate this process using present day optical lattice technology. This demonstrates not only that entanglement exists in solids but also that it can be used for quantum information processing or as a test of Bell's inequalities.

Biomass-derived Oxymethylene Ethers as Diesel Additives: A Thermodynamic Analysis

Conversion of biomass for production of liquid fuels can help in reducing the greenhouse gas (GHG) emissions which are predominantly generated by combustion of fossil fuels. Adding oxymethylene ethers (OMEs) in conventional diesel fuel has the potential to reduce soot formation during the combustion in a diesel engine. OMEs are downstream products of syngas, which can be generated by the gasification of biomass. In this research, a thermodynamic analysis has been conducted through development of data intensive process models of all the unit operations involved in production of OMEs from biomass. Based on the developed model, the key process parameters affecting the OMEs production including equivalence ratio, H2/CO ratio, and extra water flow rate were identified. This was followed by development of an optimal process design for high OMEs production. It was found that for a fluidized bed gasifier with heat capacity of 28 MW, the conditions for highest OMEs production are at an air amount of 317 tonne/day, at H2/CO ratio of 2.1, and without extra water injection. At this level, the total OMEs production is 55 tonne/day (13 tonne/day OME3 and 9 tonne/day OME4). This model would further be used in a techno-economic assessment study of the whole biomass conversion chain to determine the most attractive pathways.

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%.

Thermal Properties of Alkyl-triethylammonium bis{(trifluoromethyl)sulfonyl}imide Ionic Liquids

In this work, we address the thermal properties of selected members of a
homologous series of alkyltriethylammonium bisf(trifluoromethyl)sulfonylgimide ionic
liquids. Their phase and glass transition behavior, as well as their standard isobaric heat
capacities at 298.15 K, were studied using differential scanning calorimetry (DSC),
whereas their decomposition temperature was determined by thermal gravimetry analysis.
DSC was further used to measure standard molar heat capacities of the studied ionic liquids
and standard molar heat capacity as a function of temperature for hexyltriethylammonium,
octyltriethylammonium, and dodecyltriethylammonium bisf(trifluoromethyl)sulfonylgimide
ionic liquids. Based on the data obtained, we discuss the influence of the alkyl chain
length of the cation on the studied ionic liquids on the measured properties. Using viscosity
data obtained in a previous work, the liquid fragility of the ionic liquids is then discussed.
Viscosity data were correlated by the VTF equation using a robust regression along a
gnostic influence function. In this way, more reliable VTF model parameters were obtained than in our previous work and a good estimate of the liquid fragility of the ionic liquids was made.

High Pressure Speed of Sound and Related Thermodynamic Properties of 1-Alkyl-3-methylimidazolium Bis[(trifluoromethyl)sulfonyl]imides (from 1-Propyl- to 1-Hexyl-)

The knowledge of thermodynamic high-pressure speed of sound in ionic liquids (ILs) is a crucial way either to study the nature of the molecular interactions, structure and packing effects or to determine other key thermodynamic properties of ILs essential for their applications in any chemical and industrial processes. Herein, we report the speed of sound as a function temperature at pressures up to 101 MPa in four ultrapure ILs: 1-propyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, 1-pentyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, and 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, taking into consideration their relaxation behavior. Additionally, to further improve the reliability of the speed of sound results, the density, isentropic compressibility, and isobaric heat capacity as a function of temperature and pressure are calculated using an acoustic method.

Effect of Turbine Inlet Temperature on Rotor Blade Tip Leakage Flow and Heat Transfer

One of the most critical gas turbine engine components, the rotor blade tip and casing, is exposed to high thermal load. It becomes a significant design challenge to protect the turbine materials from this severe situation. The purpose of this paper is to study numerically the effect of turbine inlet temperature on the tip leakage flow structure and heat transfer. In this paper, the effect of turbine inlet temperature on the tip leakage flow structure and heat transfer has been studied numerically. Uniform low (LTIT: 444 K) and high (HTIT: 800 K) turbine inlet temperature, as well as non-uniform inlet temperature have been considered. The results showed the higher turbine inlet temperature yields the higher velocity and temperature variations in the leakage flow aerodynamics and heat transfer. For a given turbine geometry and on-design operating conditions, the turbine power output can be increased by 1.33 times, when the turbine inlet temperature increases 1.80 times. Whereas the averaged heat fluxes on the casing and the blade tip become 2.71 and 2.82 times larger, respectively. Therefore, about 2.8 times larger cooling capacity is required to keep the same turbine material temperature. Furthermore, the maximum heat flux on the blade tip of high turbine inlet temperature case reaches up to 3.348 times larger than that of LTIT case. The effect of the interaction of stator and rotor on heat transfer features is also explored using unsteady simulations. The non-uniform turbine inlet temperature enhances the heat flux fluctuation on the blade tip and casing.

Effect of turbine inlet temperature on blade tip leakage flow and heat transfer

One of the most critical gas turbine engine components, rotor blade tip and casing, are exposed to high thermal load. It becomes a significant design challenge to protect the turbine materials from this severe situation. As a result of geometric complexity and experimental limitations, Computational Fluid Dynamics (CFD) tools have been used to predict blade tip leakage flow aerodynamics and heat transfer at typical engine operating conditions. In this paper, the effect of turbine inlet temperature on the tip leakage flow structure and heat transfer has been studied numerically. Uniform low (LTIT: 444 K) and high (HTIT: 800 K) turbine inlet temperature have been considered. The results showed the higher turbine inlet temperature yields the higher velocity and temperature variations in the leakage flow aerodynamics and heat transfer. For a given turbine geometry and on-design operating conditions, the turbine power output can be increased by 1.48 times, when the turbine inlet temperature increases 1.80 times. Whereas the averaged heat fluxes on the casing and the blade tip become 2.71 and 2.82 times larger, respectively. Therefore, about 2.8 times larger cooling capacity is required to keep the same turbine material temperature. Furthermore, the maximum heat flux on the blade tip of high turbine inlet temperature case reaches up to 3.348 times larger than that of LTIT case. The effect of the interaction of stator and rotor on heat transfer features is also explored using unsteady simulations.

Influencing effect of heat-treatment on radon emanation and exhalation characteristic of red mud

The reuse of industrial by-products is important for members of numerous industrial sectors. However, though the benefits of reuse are evident from an economical point of view, some compounds in these materials can have a negative effect on users' health.In this study, the radon emanation and exhalation features of red mud were surveyed using heat-treatment (100-1200 °C). As a result of the 1200°C-treated samples, massic radon exhalation capacity reduced from 75 ± 10 mBq kg^-1 h^-1 to 7 ± 4 mBq kg^-1 h^-1, approximately 10% of the initial exhalation rate.To find an explanation for internal structural changes, the porosity features of the heat-treated samples were also investigated. It was found that the cumulative pore volume reduced significantly in less than 100 nm, which can explain the reduced massic exhalation capacity in the high temperature treated range mentioned above.SEM snapshots were taken of the surfaces of the samples as visual evidence for superficial morphological changes. It was found that the surface of the high temperature treated samples had changed, proving the decrement of open pores on the surface.