Extended Veytsman statistics for the solid–fluid transition in the framework of lattice fluid

Lattice fluid can describe a vapor–liquid transition but not a solid–fluid transition. In this work, we propose a simple and analytic term which yields a solid–fluid transition when coupled with a lattice based equation of state (EOS). The proposed term is derived based on the two assumptions that (1) solid can be considered as highly associated phase affected by strong attractive force and (2) this force is distinct from the conventional attractive forces yielding a vapor–liquid transition. To formulate these assumptions, we extend Veytsman statistics by modifying its density dependency. The derived term was combined with a quasi-chemical nonrandom lattice fluid theory (QLF) developed by the authors. The combined model was found to require only two parameters besides 3 QLF parameters for physical properties calculation of three phases. When tested against equilibrium properties of 8 components, the combined model was found to closely reproduce melting pressure, sublimation pressure, and vapor pressure, but underestimate solid density as well as heat of melting at the triple point temperature. It was found that the present approach can yield a solid–liquid transition at all temperatures.     

Supercritical fluid chromatography—mass spectrometry coupling

Over the past five years, an increasing number of studies have been published on supercritical fluid chromatography (SFC) and combined supercritical fluid chromatography—mass spectrometry (SFC—MS), demonstrating their advantages for the separation and analysis of non-volatile or thermally labile compounds. Further technological developments are expected to make SFC (and specially SFC—MS) a puissant, routine analytical tool that is complementary to gas chromatography (GC) (and GC—MS) and liquid chromatography (LC) (and LC—MS). Because of supercritical fluid properties, SFC—MS may be more easily implemented than LC—MS and better performance may be obtained for some types of substances or when complex mixtures must be analysed.     

Small-scale structure in fluid cholesterol–lipid bilayers

Cholesterol is the single most abundant molecule in animal plasma membranes, in the range of 20–30 mol%, where it is known to modulate the lipid-bilayer component of the membrane and lead to increased mechanical stability, lower permeability, larger thickness, and a distinct lateral organization. The phase equilibria of membranes with cholesterol and the associated large- and small-scale structure have turned out to be a particularly elusive problem. With the proposal that lipid domains and so-called ‘rafts’, characterized by high local levels of cholesterol in a liquid-ordered phase, are important for a wide range of cellular functions, an understanding and a quantitative assessment of the nature of these cholesterol-induced structures and their types of ordering have become urgent. Recent progress in neutron diffraction studies of lipid–cholesterol model membranes has now revealed details of the lateral ordering, and combined with earlier molecular model studies a picture emerges of the membrane as a locally structured liquid with small ordered ‘domains’ of a highly dynamic nature.     

Double-diffusive Cattaneo–Christov squeezing flow of micropolar fluid

Journal of Thermal Analysis and Calorimetry - An incompressible magnetized flow of micropolar fluid is confined between two disks. The lower disk is stationary, while the upper disk moves in upward...     

Determination of illicit and medicinal drugs and their metabolites in oral fluid and preserved oral fluid by liquid chromatography–tandem mass spectrometry

An LC-MS/MS method using 0.5 ml of oral fluid was developed for the determination of morphine, codeine, 6-monoacetylmorphine, methadone, amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine, 3,4-methylenedioxy-N-ethylamphetamine, benzoylecgonine, cocaine, delta-9-tetrahydrocannabinol, zolpidem, zopiclone, alprazolam, clonazepam, oxazepam, nordiazepam, lorazepam, flunitrazepam, diazepam, diphenhydramine and amitriptyline. The method was fully validated in terms of linearity (the method was linear between 1–5 μg/L and 100–200 μg/L) recoveries (7.5–82.6%), within-day and between-day precisions and accuracies (CV and MRE, both <15%), limits of detection (0.5 μ g/L) and quantitation (the lowest point on the calibration curve), relative ion intensities, freeze-and-thaw stability and matrix effect. The method was applied to preserved oral fluid collected by a special commercial device, the StatSure Saliva Sampler™.     

Liquid-liquid phase separation of binary Lennard-Jones fluid in slit nanopores

The capillary phase separation of a binary mixture of two truncated and shifted Lennard-Jones (LJ) Ar liquids in slit-shaped oxygen nanopores is examined. The LJ parameters—ε(Ar(A)–Ar(A))=ε(Ar(B)–Ar(B))=0.8ε(Ar(A)–Ar(B)) and 0.5ε(Ar(A)–O)?=?ε(Ar(B)–O)—were used to distinguish the two Ar liquids. The cut off distance for Ar was 3.5σ. We employed a molecular dynamics (MD) technique in which a pore space was connected with a bulk solution to easily determine the equilibrium bulk concentration. Liquid phase isotherms were obtained for pores with widths ranging from 5.5σ to 9.5σ, and the relation between the pore width and the phase separation concentration was determined. Each simulation was run until the bulk concentration attained equilibrium (1–2 μs). The MD results show that the Patrick model overestimates the bulk concentration for a given pore size. We proposed a modified Patrick model in which the pore wall potential is considered. In our model, the Gibbs-Tolman-Koenig-Buff effect is not considered for the interfacial tension since two surfaces of tension exist on both sides of the equimolar dividing surface of the two-Ar liquid phase. The two surfaces of tension neutralized Gibbs-Tolman-Koenig-Buff effect each other. The present simple model successfully describes the relation to prove its reliability.     

Patterns of solid–fluid phase equilibria: new possibilities?

Thermodynamic phase space patterns of solid–liquid–vapor (slg) behavior in binary systems are reviewed. The van der Waals equation of state is used in combination with a common mathematical artifice for the solid–phase fugacity function to map out the slg loci for a model binary homologous series of solvent+solute mixtures as a function of the solute characterization. The computational results suggest the possible existence of a richer thermodynamic phase space topography than previously envisioned.     

Retention behaviour of carboxylic acid methyl esters in supercritical fluid chromatography

The study on retention behavior in supercritical fluid chromatography (SFC) is necessary to understand the mechanism of the various interactions in SFC. The retention of SFC in carboxylic acid methyl ester/polymethylsiloxane/CO2 system was studied systematically and the retention behavior of this kind of compounds under various typical operation conditions was described using the method of an alternative unified theory of chromatographic retention. The results illustrated that expression: Ink.= a + b/T + cp + dp/T + ep2/T can be used to describe quantitatively the retention behavior of carboxylic acid methyl ester/polymethylsiloxane/CO2 system in the ranges of reduced density from 0.549 to 1.411. It was also found that the entropy of solute in stationary phase is dependent on the density of supercritical fluid (SF) under typical operating conditions of SFC.     

Modified Carnahan—Starling—Van Der Waals equation for supercritical fluid extraction

The capability of a modified Carnahan—Starling—Van der Waals equation of state to correlate binary solid or liquid solubility data in a supercritic     

Roton excitations in Bose–Einstein condensates and a fluid–solid transition

Several authors have recently discussed the existence of roton excitations in Bose–Einstein condensates (BECs) and considered how a roton dip in the dispersion curve of elementary excitations may be related to the formation of a spatially modulated ground state. Here attention is drawn to a theoretical study of Minguzzi et al. on interatomic correlations in a BEC from dipole–dipole interactions induced by laser light of increasing intensity. Attractive interactions in superfluid ⁴He and repulsive interactions in ‘untuned’ BECs are then compared and contrasted, the experiments of Woods and Cowley and of Greiner et al. providing the focus respectively. It is stressed that, contrary to a very recent assertion by Nazario and Santiago, ⁴He is crucially different from BECs at the lowest temperatures.     

Does confining the hard-sphere fluid between hard walls change its average properties?

We use grand canonical transition-matrix Monte Carlo and discontinuous molecular dynamics simulations to generate precise thermodynamic and kinetic data for the equilibrium hard-sphere fluid confined between smooth hard walls. These simulations show that the pronounced inhomogeneous structuring of the fluid normal to the confining walls, often the primary focus of density functional theory studies, has a negligible effect on many of its average properties over a surprisingly broad range of conditions. We present one consequence of this insensitivity to confinement: a simple analytical equation relating the average density of the confined fluid to that of the bulk fluid with equal activity. Nontrivial implications of confinement for average fluid properties do emerge in this system, but only when the fluid is both (i) dense and (ii) confined to a gap smaller than approximately three particle diameters. For this limited set of conditions, we find that "in-phase" oscillatory deviations in excess entropy and self-diffusivity (relative to the behavior of the bulk fluid at the same average density) occur as a function of gap size. These paired thermodynamic/kinetic deviations from bulk behavior appear to reflect the geometric packing frustration that arises when the confined space cannot naturally accommodate an integer number of particle layers.     

Cerium oxide nanofiber–based electrochemical immunosensor for detection of sepsis in biological fluid

Sepsis causes life-threatening complications with the highest burden of death and medical expenses in hospitals worldwide. Despite the progression of targeted therapies for sepsis, the challenge of early diagnosis of sepsis-related biomarkers remains. The analysis of the TNF-α and sTREM-1 in biological fluids provides essential information for effective treatments. In this work, we report developing an electrochemical immunosensor for the rapid detection of TNF-α and sTREM-1 proteins in human plasma samples. First, using the electrospinning process, cerium oxide nanofibers were synthesized. Subsequently, the antibodies corresponding to the targeted proteins are immobilized onto the surface-functionalized working electrodes using NHS/EDC chemistry. The proposed immunosensor’s performance in a biological fluid was assessed using an analytical electrochemistry approach. The limit of detection for the electrochemical immunosensors was 0.51 and 0.41 pg/mL for TNF-α and sTREM-1, respectively, with high selectivity and sensitivity for the use as a point of care device.

     

An improved heat conduction analysis in swirling viscoelastic fluid with homogeneous–heterogeneous reactions

Journal of Thermal Analysis and Calorimetry - This paper studies an unsteady magnetohydrodynamic (MHD) Maxwell fluid flow on a rotating as well as a vertically moving disk in the presence of...     

Thermodynamics for fluid mixtures near to and far from the vapor–liquid critical point

To describe thermodynamic properties of fluid mixtures near to and far from the vapor–liquid critical point, we need a method where a classical equation-of-state is augmented with a correction based on renormalization group (RG) theory. The advantage of the method described here is that, subject to well-defined assumptions, it can be applied not only to binary mixtures but to mixtures containing any number of components. While our method is based on White’s recursion procedure, our extension to mixtures is based on the isomorphism assumption and on an approximation suggested by Kiselev. To illustrate, calculations are presented for the critical loci of some alkane mixtures containing one discrete component and one pseudo-component whose composition is characterized by a continuous distribution of molecular weight. While critical loci calculated with the RG correction are similar to those calculated by the classical equation-of-state alone, inclusion of the RG correction provides better agreement with experiment.     

2D polyaniline with exchangeable interlayer fluid for fast and stable volumetric dual ion storage

Two-dimensional(2D) layered materials are widely applied in energy devices including lithium-ion battery and supercapacitor due to their unique properties,such as tunable interlayer structure,numerous active sites,large aspect ratio versatile interlayer chemistry.In this work,2D layered tungstate acidlinked polyaniline(TALP) presented a fluid-in-solid structure,which allowed facile exchange of the interlayer fluid from moisture to conventional Li⁺ containing electrolyte.With fast and stable dual ion storage(Li⁺ and PF₆^-),TALP demonstrates high-rate volumetric capacity(39 mAh cm_-3 at 2000 mA g^-1) and good stability(2000 cycles at 200 mA g^-1) within the working potential window of 1.5-4.5 V versus Li⁺/Li.     

Surface tension curvature correction for fluid–vapour interface by thermodynamics of curved boundary layers

Thermodynamics of curved boundary layers is used to study surface properties of Lennard–Jones fluids and an equation is obtained for the surface tension of the spherical interfaces. The work of cavity formation inside a fluid is utilised to calculate the surface tension. The scaled particle theory (SPT) equation of Pierotti and Stillinger are properly modified. The calculations by the modified Stillinger equation predicts the surface tension in any radius of curvature and the results are in good agreement with the experimental data. But for Pierotti equation, due to low sensitivity to temperature, good agreement obtained only at low temperatures.     

Can the speed of sound be used for detecting critical states of fluid mixtures?

The phenomenology of sound speeds in fluid mixtures is examined near and across critical lines. Using literature data for binary and ternary mixtures, it is shown that the ultrasound speed along an isotherm-isopleth passes through a minimum value in the form of an angular (or V-shaped) point at critical states. The relation between critical and pseudo-critical coordinates is discussed. For nonazeotropic fixed-composition fluid mixtures, pseudo-critical temperatures and pressures are found to be lower than the corresponding critical temperatures and pressures. The analysis shows that unstable pseudo-critical states cannot be detected using acoustic methods. The thermodynamic link between sound speeds and isochoric heat capacities is formulated and discussed in terms of p-Vm-T derivatives capable of being calculated using cubic equations of state. Based on the Griffiths-Wheeler theory of critical phenomena, a new specific link between critical sound speeds and critical isochoric heat capacities is deduced in terms of the rate of change of critical pressures and critical temperatures along the p-T projection of the critical locus of binary fluid mixtures. It is shown that the latter link can be used to obtain estimates of critical isochoric heat capacities from the experimental determination of critical speeds of sound. The applicability domain of the new link does not include binary systems at compositions along the critical line for which the rate of change in pressure with temperature changes sign. The new equation is combined with thermodynamic data to provide approximate numerical estimates for the speed of sound in two mixtures of carbon dioxide and ethane at different temperatures along their critical isochores. A clear decrease in the sound speed is found at critical points. A similar behavior is suggested by available critical heat capacity data for several binary fluid mixtures. Using an acoustic technique, the critical temperature and pressure were determined for three different mixtures of methane and propane, and compared with literature data obtained using conventional methods. It is concluded that acoustic-based techniques are reliable to determine, for the most part, critical surfaces of fluid mixtures. The remaining few cases where the present analysis cannot be applied could be tested by the thermodynamic calculation of critical sound speeds using crossover equations of state in conjunction with experimentally determined critical isochoric heat capacities.     

Characteristics of an oxa-diamide–HNO3 extractant in the supercritical fluid extraction of uranium

An extractant is required in the recovery process to drive the uranium to a stage that enables it to be extracted using the extraction solvent. This paper proposes the composition of a composite extractant, N,N,N′,N′-tetrabutyl-3-oxapentane-diamide–HNO₃ (TBODA–HNO₃) as an extractant, to successfully achieve the objective using supercritical carbon dioxide (sc-CO₂). The composite TBODA–HNO₃ extractant has a chemical composition of TBODA(HNO₃)_1.0(H₂O)_1.5. The U(IV) in the UO₂ containing solid phase is directly oxidized to U(VI) in the form of $ {\rm UO}_{2}^{2 + } $ in sc-CO₂, which contains a CO₂-soluble TBODA–HNO₃ extractant at 200 atm and 50 °C. The resulting $ {\rm UO}_{2}^{2 + } $ /TBODA complex can be consequently extracted using acetone-modified sc-CO₂. The chemical composition of the $ {\rm UO}_{2}^{2 + } $ /TBODA complex, which can be extracted by nonpolar sc-CO₂, is proposed in the form of an ion pair: [UO₂(TBODA)₂]²⁺–2( $ {\rm NO}_{3}^{ - } $ ).     

Synchrotron FTIR microscopy of synthetic and natural CO2–H2O fluid inclusions

Fluid inclusions provide a record of the physical and chemical composition of fluids that flow through the Earth's crust. Here, we describe a novel use of synchrotron Fourier Transform Infrared (FTIR) microscopy to map three parameters in individual fluid inclusions: (1) very low concentrations of CO₂, (2) variations of the state of CO₂ and (3) variations in water structure. The intensity of the synchrotron light source allows compositional mapping of individual fluid inclusions, which provides high-resolution images of the distribution of different CO₂ and H₂O species within individual inclusions. High resolution spectra of the CO₂, recorded here for the first time in fluid inclusions, show the rotational lines of CO₂ gas. The results reveal predicted as well as unexpected distributions of CO₂ gas in the inclusions.