Thermodynamic properties of saturated and compressed liquid difluorochloromethane

In an isochoric study the thermodynamic behaviour of liquid difluorochloromethane was experimentally investigated. New measurements of (p, ?, T) have been carried out at densities from 0.83 to 1.36 g·cm^?3 (reduced densities from 1.6 to 2.7) and pressures up to 60 MPa. In addition new results for the vapour pressure of liquid difluorochloromethane are reported at temperatures from 312 to 369 K. Saturated liquid densities were obtained from the extrapolation of the isochoric results to the vapour-liquid coexistence curve.     

The embedded atom model of molten lead

The method for calculating the embedded atom potential for liquid metals from the diffraction structural data close to the melting point was applied to lead at temperatures from 613 to 20000 K. The embedded atom potential parameters were adjusted using the data on the lead structure at 613–1173 K, the thermodynamic properties of lead over the temperature range 613–2000 K, and the results of shock wave experiments. The embedded atom potential and molecular dynamics method allowed the structural characteristics of the liquid metal to be successfully predicted up to 1173 K. The calculated bulk compression modulus at 613 K was close to its actual value. The self-diffusion coefficients along the liquid-vapor equilibrium line increased as the temperature rose following the power law with the exponent close to 2.03. The properties of lead under extremal conditions were calculated up to the temperature 20000 K and density 20.721 g/cm³. At 1000 K and a density of 18.156 g/cm³, close agreement with the experimental pressure (101.5 GPa) was obtained. The potential found fairly well described the properties of crystalline lead. At the same time, the embedded atom potential adjusted to describe the properties of the crystalline phase only poorly described the properties of liquid lead at increased densities.     

Totally inclusive cubic equation of state with five parameters for pure fluids

A totally inclusive cubic equation of state (cubic EOS) is proposed. Although, its form is fairly simple as compared with the present cubic equations, it can include all of them as special cases. The EOS has five parameters. By fitting the experimental critical isothermal for six typical substances combining the critical conditions, the generalized expressions for the five parameters at critical temperature are established. The temperature coefficients of the five parameters for 43 substances are determined by fitting the experimental data of vapor pressure and saturated liquid density. These coefficients are correlated with the critical compressibility factor and acentric factor to obtain the generalized expressions. The predicted saturated vapor pressure, saturated liquid density, critical isothermal and coexistence curve near the critical point show that the equation gives the best results when compared with the Redlich–Kwong–Soave (RKS) and Peng–Robinson (PR) EOS.     

Scaled equations for the coexistence curve,the capillary constant and the surface tension of n-alkanes

A review of experimental data of several fluids shows that their coexistence curve follows a power law in reduced temperature at the approach of the critical point, with an universal exponent equal to 0.325, their capillary constant a power law with an universal exponent equal to 0.925 and their surface tension a power law with an universal exponent equal to 1.26. In the critical region, the concept of two-scale-factor universality was used to predict the density difference amplitude, the capillary constant amplitude, and the surface tension amplitude between near critical vapor and liquid phases. A comparison with amplitudes determined from experimental data is given. In order to extend this universality all along the liquid–gas coexistence curve from the triple point to the critical point for n-alkanes, a mean field approximation was used far away from T_C. We show that the density difference, the capillary constant and the surface tension can be calculated with a reasonable accuracy by generalized scaled equations adding only two empirical constants. A comparison between calculated and experimental data is presented.     

Low-coordination phases of both crystalline and fluid states of alkali metals under extreme conditions of high and low densities,respectively

After a brief summary of early work, involving the present authors, relating to low coordination phases of some alkalis in either dense crystalline states at high pressure (e.g. Li) or low density metallic fluids near criticality (Cs and Rb), contact is made with the very recent density functional study by Pickard and Needs (Phys. Rev. Lett. 102, 146401 (2009)). Whereas these authors predict three- and four-fold coordination numbers for extremely high pressure crystalline phases of Li, we stress here the remarkable behaviour of the heavy alkali metallic fluids Cs and Rb along the liquid–vapour coexistence curve towards the critical point. Coordination numbers ～8?10 near melting then reduce, as the density is lowered, to 2 at or near the critical point.     

Critical Properties of Argon

Abstract

Measurements of P-V-T properties of argon in the critical region are reported. Isothermal compressibilities have been calculated from the data for liquid and vapor along the coexistence curve and for the gas above the critical temperature at the critical density. Densities of the liquid and vapor along the coexistence curve were measured, and the critical temperature, pressure and density of argon were redetermined. These data are compared with those of other workers; in addition critical indices which represent the manner in which these properties vary as one approaches the critical point were determined and compared with the predictions of several theoretical estimates of these quantities.     

A New Technique for Modelling the Structure of Expanded Liquid Metals Along the Liquid-Vapour Coexistence Curve

Abstract

We have developed a simple technique for modelling the structure of expanded liquid metals along the liquid vapour coexistence curve which may be characterised as a ‘correlated percolation’ method. Starting from a model for the liquid at high density, e.g. near the triple point, obtained either by molecular dynamics simulation or reverse Monte Carlo modelling, we keep the size of the model and the atomic positions fixed and remove atoms, according to criteria which depend on the coordination number distribution, until the required lower density, corresponding to a higher temperature, is reached. Small random Gaussian displacements are then added to the position of each atom to account for the increased temperature. The structure factor of the resulting model is quite close to that measured experimentally. Changes in the structure factor as the liquid expands can thus be separated into the effects of density fluctuations and temperature (or entropy).     

New pressure-density-temperature measurements and new rational equations for the saturated liquid and vapour densities of oxygen

The results of pressure, density, temperature (p, ?, T) measurements in the temperature range from 65 K to 300 K, for pressures up to 7.2 MPa, and for densities from 0.3 mol dm^?3 to 39 mol dm^?3, are presented for pure oxygen. Using the experimental results, new values for the densities of saturated liquid and vapour are evaluated. To check the accuracy of these results, corresponding sets reported in the literature are critically analysed to determine the most reliable p, ?, T set for oxygen. Finally, new equations for the densities of saturated liquid and vapour are developed using a statistical procedure.     

Pressure effects on the transitions between disordered phases in supercooled liquid silicon

We investigate the pressure effects on the transitions between the disordered phases in supercooled liquid silicon through Monte Carlo simulations and efficient methods to compute free energies. Our calculations, using an environment dependent interatomic potential for Si, indicate that at zero pressure the liquid-liquid phase transition, between the high density liquid and the low density liquid, occurs at a temperature 325K below melting. We found that the liquid-liquid transition temperature decreases with increasing pressure, following the liquid-solid coexistence curve. As pressure increases, the liquid-liquid coexistence curve approaches the region where the glass transition between the low density liquid and the low density amorphous takes place. Above 5 GPa, our calculations show that the liquid-liquid transition is suppressed by the glassy dynamics of the system. We also found that above 5 GPa, the glass transition temperature is lower than that at lower pressures, suggesting that under these conditions the glass transition occurs between the high density liquid and the high density amorphous.     

An adiabatic low-temperature calorimeter for heat capacity measurement of small samples

A small sample adiabatic calorimeter for measuring heat capacities in the temperature range 60–350 K using the Nernst method has been constructed. The sample cell of the calorimeter is 6 cm³ in the internal volume, equipped with a miniature platinum thermometer and surrounded by two adiabatic shields. Two sets of 6-junction chromel-copel thermocouples were mounted between the cell and the shields to indicate the temperature differences between them. The adiabatic conditions of the cell were automatically controlled by two sets of temperature controller. A mechanical pump was used to pump out the vapour of liquid nitrogen in the cryostat to solidify N₂ (1), and 60 K or even lower temperature was obtained. The performance of this apparatus was evaluated by heat capacity measurements on α-alumina. The deviations of experimental results from a smoothed curve lie within ±0.2%, while the inaccuracy is within ±0.5% compared with the recommended reference data in the wole temperature range.     

Vapour—liquid equilibrium in binary mixtures formed by benzene or cyclohexane with 1-chloropropane or 1-chlorobutane

The vapour—liquid equilibria (VLE) for the binary systems formed by 1-chloropropane with benzene and cyclohexane at 308.15 K and 318.15 K, and for systems formed by 1-chlorobutane with the same hydrocarbons at 308.22 K, 328.27 K and 348.31 K have been determined by a total pressure ebulliometric method. The accuracy of these results was proved by comparing the heat of mixing data calculated from these VLE results with those obtained by direct measurements (Amaya, 1961; Grolier et al., 1973). The experimental data and the results of correlation by means of the Redlich—Kister equation are given. The systems with benzene were found to be nearly ideal, while those with cyclohexane exhibit positive deviations (G^E = 220–260 J mole^?1 for an equimolar mixture). New vapour pressure versus temperature data for 1-chlorobutane are reported.     

A new apparatus for measuring the vapour pressure of liquid mixtures excess Gibbs free energy of octamethylcyclotetrasiloxane + cyclohexane at 308.15 K

A new apparatus for measuring the vapour pressure of liquid mixtures is described. In conjunction with an automatic pressure controller, a capacitance manometer is used as a null device to isolate the liquid and vapour. The vapour pressure is measured with a precision mercury manometer. The continuous-dilution technique for sample introduction has been incorporated in the new apparatus, so that the composition range of a mixture can be covered in two runs. The accuracy of each measured quantity is: pressure, 3 Pa; temperature (IPTS-68), 0.002 K; volume, 0.002 cm³. G^E for cyclohexane + octamethylcyclotetrasiloxane (abbreviated throughout this paper as omcts) at 308.15 K has been determined: the minimum value of ?68 J mol^?1 occurs near x₂(omcts) = 0.5.     

Thermodynamic and Structural Characterization of the Transformation from a Metastable Low‐Density to a Very High‐Density Form of Supercooled TIP4P‐Ew Model Water

We explore the phase diagram of the metastable TIP4P‐Ew liquid model water from 360 K down to 150 K at densities ranging from 0.950 to 1.355 g cm^?3. In addition to the low‐density/high‐density (LDL/HDL) liquid–liquid transition, we observe a structural high‐density/very high‐density (HDL/VHDL) transformation for the lowest temperatures at 1.30 g cm^?3. The characteristics of the isobars and isotherms suggest the presence of a stepwise HDL/VHDL transition with first‐order‐like appearance. In addition, we also identify an apparent pretransition at 1.24 g cm^?3, which suggests that the experimentally detected LDA/VHDA transformation might evolve into a multiple‐step process with different local structures representing local minima in the free‐energy landscape. Such a scenario is supported by a pronounced correlation between the isothermal density dependence of the pressure, with a stepwise increase of the oxygen coordination number, due to the appearance of interstitial water molecules.     

Some Properties of a Model Liquid of C 60 Buckyballs

Utilizing the results of published simulations for the liquid C 60 phase using a model of rigid C 60 molecules, it is pointed out that the liquid phase has a critical compressibility ratio Z c = p c /( c k B T c ) in terms of the usual critical thermodynamic variables (critical pressure p c , critical density c and critical temperature T c ), of 0.32. This is to be compared with the value 0.29 for the heavy condensed rare gases Ar, Kr and Xe, in spite of their much lower T c , and with the prediction of 0.27 from Dieterici's phenomenological equation of state. The global shape of the coexistence curve, as embodied in the behaviour of the normalized difference density ( l m g )/ c versus the average density ( l + g )/2 c , where l and g are the liquid and the gas densities, respectively, is also consistent with the shape of the coexistence curve of insulating fluids. Going beyond the assumption of rigid C 60 molecules has interesting consequences on the stability and observability of the liquid phase, and those effects are discussed.     

A nonadditive methanol force field: bulk liquid and liquid-vapor interfacial properties via molecular dynamics simulations using a fluctuating charge model

We study the bulk and interfacial properties of methanol via molecular dynamics simulations using a CHARMM (Chemistry at HARvard Molecular Mechanics) fluctuating charge force field. We discuss the parametrization of the electrostatic model as part of the ongoing CHARMM development for polarizable protein force fields. The bulk liquid properties are in agreement with available experimental data and competitive with existing fixed-charge and polarizable force fields. The liquid density and vaporization enthalpy are determined to be 0.809 g/cm3 and 8.9 kcal/mol compared to the experimental values of 0.787 g/cm3 and 8.94 kcal/mol, respectively. The liquid structure as indicated by radial distribution functions is in keeping with the most recent neutron diffraction results; the force field shows a slightly more ordered liquid, necessarily arising from the enhanced condensed phase electrostatics (as evidenced by an induced liquid phase dipole moment of 0.7 D), although the average coordination with two neighboring molecules is consistent with the experimental diffraction study as well as with recent density functional molecular dynamics calculations. The predicted surface tension of 19.66+/-1.03 dyn/cm is slightly lower than the experimental value of 22.6 dyn/cm, but still competitive with classical force fields. The interface demonstrates the preferential molecular orientation of molecules as observed via nonlinear optical spectroscopic methods. Finally, via canonical molecular dynamics simulations, we assess the model's ability to reproduce the vapor-liquid equilibrium from 298 to 423 K, the simulation data then used to obtain estimates of the model's critical temperature and density. The model predicts a critical temperature of 470.1 K and critical density of 0.312 g/cm3 compared to the experimental values of 512.65 K and 0.279 g/cm3, respectively. The model underestimates the critical temperature by 8% and overestimates the critical density by 10%, and in this sense is roughly equivalent to the underlying fixed-charge CHARMM22 force field.     

Low density observations of Rb and Cs chains along the liquid–vapour coexistence curves to the critical point in relation to quantum-chemical predictions on the metal-insulator transitions in Li and Na rings

Recent ab initio predictions concerning the metal-insulator (MI) transition in rings of the light alkali atoms, Li and Na, are compared and contrasted with experimental facts concerning diluted Rb and Cs alkalis. The main focus here is on the local coordination number as a function of density as these two heavy alkali metallic fluids are taken along the liquid–vapour coexistence curve towards the critical point, which in these cases coincides with the MI transition. Also recorded are the results of experiments in which Cs chains are observed at large interatomic spacing outside semiconducting substrates of InSb and GaAs.     

Polyaniline impregnated activated carbon fabric: Adsorption and protection studies against nerve agent sarin

The synergistic effect of polyaniline (PANI) was explored in detail by conducting experiments with liquid and vapour sarin (GB) exposure tests. For that, different samples were prepared and breakthrough behaviour, liquid sarin elution profile and dynamic adsorption of vapour were studied at a different doping level of PANI and activated carbon fabric (PANI-ACF) was optimized to achieve optimum breakthrough behaviour. The results reveal that PANI-ACF of a surface density of 1.2–1.27 g/cm² has a high surface area (914–980 m²/g) and micropore volume (0.20–0.22 (mL/g). Specific breakthrough volume (BTV), breakthrough time (BTT) and average breakthrough concentration rate were determined and found to be 243 L/g, 220–350 min and 0.004–0.0014 μg h^?1cm^?2 respectively which is much better than only ACF. Hence, PANI reinforced ACF applies to selective adsorption of nerve agent sarin and consecutively in chemical nerve agent protection.     

Phase equilibrium data and thermodynamic modelling of the system (propane + DMF + methanol) at high pressures

Reported in this work are phase equilibrium data at high pressures for the binary and ternary systems formed by {propane + N,N-dimethylformamide (DMF) + methanol}. Phase equilibrium measurements were performed in a high-pressure, variable-volume view cell, following the static synthetic method for obtaining the experimental bubble and dew points transition data over the temperature range of (363 to 393) K, pressures up to 11.5 MPa and overall mole fraction of the lighter component varying from 0.1 to 0.995. For the systems investigated, vapour–liquid (VLE), liquid–liquid (LLE) and vapour–liquid–liquid (VLLE) phase transitions were visually recorded. Results show that the systems investigated present UCST (upper critical solution temperature) phase transition curves with an UCEP (upper critical end point) at a temperature higher than the propane critical temperature. The experimental data were modelled using the Peng–Robinson equation of state with the Wong–Sandler and the classical quadratic mixing rules, affording a satisfactory representation of the experimental data.     

A new form of the equation of state for pure substances and its application to oxygen

Schmidt, R. and Wagner, W., 1985. A new form of the equation of state for pure substances and its application to oxygen. Fluid Phase Equilibria, 19: 175–200.A new wide range equation of state is presented and expressed analytically in the form of the free energy as a function of density and temperature. This fundamental equation contains, in addition to pure polynomial and “BWR”-terms, new exponential functions especially convenient for the critical region. To guarantee an effective structure, the combination of the terms of the equation was found by using an optimization method recently developed. As a result, the optimized function for the free energy is capable of representing the thermodynamic surface of oxygen in the range 54 ≤ T ≤ 300 K, 0 < p ≤ 818 bar and 0 < ρ ≤ 41 mol dm^?3 within the experimental uncertainty of the data available. With the exception of very few items of data, this statement is also valid for the whole coexistence curve and the critical region. Extrapolations of this new equation beyond the range of data yield physically meaningful results.