Thermophysical properties of 1-hexanol over the temperature range from 303 K to 503 K and at pressures from the saturation line to 400 MPa

Isobaric thermal expansivities, _P(T,p), of 1-hexanol have been measured in a pressure-controlled scanning calorimeter from just above the saturation vapour pressure to 400 Mpa at temperatures from 302.6 K to 503.15 K. The specific volume isotherm, v(T_R,p), at T_R=302.6 K has been derived from measurements of isothermal compressibilities up to 400 MPa and from the specific density at atmospheric pressure. Specific volumes, isothermal compressibilities, thermal pressure coefficients, and isobaric and isochoric heat capacities for the whole pressure and temperature range are derived from these data and from literature data on the saturation vapour pressures and on the isobaric heat capacities at atmospheric or saturation vapour pressure.     

Partial molal volumes,expansibilities, and compressibilities for aqueous alcohol solutions between 5°C and 40°C

Density and ultrasound measurements have been carried out for aqueous solutions of primary and secondary alcohols and ,-diols at 5, 10, 20, and 40°C. The density data have been used to calculate partial molal volumes and expansibilities at infinite dilution. The ultrasound data have been used to calculate isentropic partial molal compressibilities which have been converted to isothermal values by using the expansibility data and literature data on partial molal heat capacities. The difference between the isentropic and isothermal partial molal compressibilities is practically zero at 5°C, and increases only slightly with temperature. Group partial molal compressibilities have been evaluated. The hydrophobic group compressibilities increase with temperature while the hydrophilic group compressibilities remain constant or decrease with temperature.     

Thermodynamic and transport properties of (1-Butanol + 1,4-Butanediol) at temperatures from (298.15 to 318.15) K

Densities and kinematic viscosities have been measured for (1-butanol + 1,4-butanediol) over the temperature range from (298.15 to 318.15) K. The speeds of sound within the temperature range from (293.15 to 318.15) K have been measured as well. Using these results and literature values of isobaric heat capacities, the molar volumes, isentropic and isothermal compressibility coefficients, molar isentropic and isothermal compressibilities, isochoric heat capacities as well as internal pressures were calculated. Also the corresponding excess and deviation values (excess molar volumes, excess isentropic and isothermal compressibility coefficients, excess molar isentropic and isothermal compressibilities, different defined deviation speed of sound and dynamic viscosity deviations) were calculated. The excess values are negative over the whole concentration and temperature range. The excess and deviation values are expressed by Redlich–Kister polynomials and discussed in terms of the variations of the structure of the system caused by the participation of the two different alcohol molecules in the dynamic intermolecular association process through hydrogen bonding at various temperatures. The predictive abilities of Grunberg–Nissan and McAllister equations for viscosities of mixtures have also been examined.     

The stage of nonisothermal nucleation of supercritical particles of a new phase under nonstationary conditions of particle diffusion growth and heat transfer to a medium

An analytical theory has been formulated for the stage of nonisothermal nucleation of supercritical particles in a metastable medium with instantaneously generated initial supersaturation. The theory takes into account the nonuniformities of metastable substance concentration and temperature, which result from the nonstationary diffusion of the substance to growing particles and the nonstationary transfer of the heat of the phase transition from the particles to the medium. The formulated theory extends the approach based on the concept of excluded volume that has recently been used in the theory of the stage of nucleation under isothermal conditions. This approach implies that the nucleation intensity of new particles is suppressed in spherical diffusion regions with certain sizes that surround previously nucleated supercritical particles and remaining unchanged in the rest of the medium. It has been shown that, when self-similar solutions are used for nonstationary equations of substance diffusion to particles and heat transfer from the particles, the ratio between the excluded volume and the particle volume is independent of particle size, thereby enabling one to analytically solve the integral equation for the excluded volume throughout a system as a time function at the stage of nucleation. The main characteristics of the phase transition have been found for the end of the stage of nucleation. Comparison has been carried out with the characteristics obtained in terms of the isothermal and nonisothermal nucleation theory upon uniform vapor consumption and heat dissipation (the mean-field approximation of vapor supersaturation and temperature).     

Thermodynamic properties in the molecular dynamics ensemble applied to the gaussian core model fluid

The thermodynamic properties of pressure, energy, isothermal pressure coefficient, thermal expansion coefficient, isothermal and adiabatic compressibilities, isobaric and isochoric heat capacities, Joule-Thomson coefficient, and speed of sound are considered in a classical molecular dynamics ensemble. These properties were obtained using the treatment of Lustig [J. Chem. Phys. 100, 3048 (1994)] and Meier and Kabelac [J. Chem. Phys. 124, 064104 (2006)], whereby thermodynamic state variables are expressible in terms of phase-space functions determined directly from molecular dynamics simulations. The complete thermodynamic information about an equilibrium system can be obtained from this general formalism. We apply this method to the gaussian core model fluid because the complex phase behavior of this simple model provides a severe test for this treatment. Waterlike and other anomalies are observed for some of the thermodynamic properties of the gaussian core model fluid.     

Pressure and temperature dependence of hydrophobic hydration: volumetric, compressibility, and thermodynamic signatures

The combined effect of pressure and temperature on hydrophobic hydration of a nonpolar methanelike solute is investigated by extensive simulations in the TIP4P model of water. Using test-particle insertion techniques, free energies of hydration under a range of pressures from 1 to 3000 atm are computed at eight temperatures ranging from 278.15 to 368.15 K. Corresponding enthalpy, entropy, and heat capacity accompanying the hydration process are estimated from the temperature dependence of the free energies. Partial molar and excess volumes calculated using pressure derivatives of the simulated free energies are consistent with those determined by direct volume simulations; but direct volume determination offers more reliable estimates for compressibility. At 298.15 K, partial molar and excess isothermal compressibilities of methane are negative at 1 atm. Partial molar and excess adiabatic (isentropic) compressibilities are estimated to be also negative under the same conditions. But partial molar and excess isothermal compressibilities are positive at high pressures, with a crossover from negative to positive compressibility at approximately 100-1000 atm. This trend is consistent with experiments on aliphatic amino acids and pressure-unfolded states of proteins. For the range of pressures simulated, hydration heat capacity exhibits little pressure dependence, also in apparent agreement with experiment. When pressure is raised at constant room temperature, hydration free energy increases while its entropic component remains essentially constant. Thus, the increasing unfavorability of hydration under raised pressure is seen as largely an enthalpic effect. Ramifications of the findings of the authors for biopolymer conformational transitions are discussed.     

Computational study of the melting-freezing transition in the quantum hard-sphere system for intermediate densities. I. Thermodynamic results

The points where the fluid-solid (face-centered-cubic) transition takes place in the quantum hard-sphere system, for reduced densities 0.85>rhoN*>0.5 (reduced de Broglie wavelengths lambdaB*相似文献   

Binary mixtures of cyclohexanone, 2-butanone, 1,4-dioxane and 1,2-dimethoxyethane

Densities and sound velocities of binary mixtures of cyclohexanone, 2-butanone, 1,4-dioxane and 1,2-dimethoxyethane were measured at 298.15 K and also the densities at 303.15 K. Excess volumes were determined from densities. Isentropic compressibilities were determined from densities and sound velocities, and excess thermal expansion factors were determined from excess volumes of two temperatures. Excess isothermal compressibilities and excess isochoric heat capacities were then estimated using excess isobaric heat capacities previously reported. Excess volumes and excess isentropic and isothermal compressibilities were negative except for cyclohexanone+1,4-dioxane system. This revised version was published online in August 2006 with corrections to the Cover Date.     

Topological transformation of the phase diagram of a potassium perchlorate-water-tetrahydrofuran ternary system in the temperature range of 40 to 140°C

Phase equilibria and critical phenomena in a potassium perchlorate-water-tetrahydrofuran ternary system are studied by visual polythermal means in the range of 40 to 140°C; the solubility diagram of the liquid subsystem is characterized by the presence of isolated binodal curve. The temperature of formation for the critical node of the monotectic state (107.3°C) and the dependences of the composition that corresponds to the critical points of solubility in the delayering field vs. temperature in the ranges of 70.3 to 107.3°C and 137.1 to 140.2°C are determined. The topological transformation of the investigated ternary system’s phase diagram upon a change in temperature is studied using isothermal sections of the system’s temperature concentration prism, plotted at nine temperatures. It is found that potassium perchlorate has only a salting-in effect on mixtures of water and tetrahydrofuran at temperatures below 107.3°C; at higher temperatures, it has both a salting-in and a salting-out effect, depending on its concentration and the composition of mixed solvent. It is shown that potassium perchlorate’s effect of salting tetrahydrofuran out of aqueous solutions grows slightly with an increase in temperature.     

Self-consistent field equations in the distribution function theory of polymeric liquids

In the distribution function approach to the conformational and thermodynamic properties of polymeric liquids site-site (pair) distribution functions are essential components of the theory. These site-site pair distribution functions are basically mean fields obeying integral equations. In our recent works, a set of self-consistent field equations has been proposed for site-site pair correlation functions which allow us to study conformational and thermodynamic properties of polymeric liquids. In this article, we present a short review of the theory and its applications to a number of aspects of polymeric liquids we have made until now. We also present a self-consistent version of the polymer reference interaction site model where the integral equations for the intramolecular site-site correlation functions are obtained from the Kirkwood hierarchy on the basis of the present theory. The present theory is shown to predict correctly the scaling properties associated with swollen and collapsed polymers in good and poor solvents, respectively. At finite densities, self-consistent solutions of the intra- and intermolecular equations yield the structures and thermodynamics of polymer melts which are favorably compared with Monte Carlo simulation results. Self-consistent theory results are found to be more accurate than the non-self-consistent approaches that use an ideal Gaussian chain conformation distribution function. © 1995 John Wiley & Sons, Inc.     

核磁共振法测绘相图 Ⅰ.PrCl_3-CH_3CONH_2-D_2O体系

本文用~1HNMR方法,利用带同轴毛细管的样品管,测定了PrCl_3CH_3CONH_2-D_2O体系的三元等温相图。利用化学位移及积分面积比求得平衡体系中液相及固相的组成。核磁共振方法具有快速、准确、样品用量少的特点。     

The role of temperature in nucleation processes

Heat and mass transfers are coupled processes, also in nucleation. In principle, a nucleating cluster would have a different temperature compared to the surrounding supersaturated old phase because of the heat release involved with attaching molecules to the cluster. In turn a difference in temperature across the cluster surface is a driving force for the mass transfer to and from the cluster. This coupling of forces in nonisothermal nucleation is described using mesoscopic nonequilibrium thermodynamics, emphasizing measurable heat effects. An expression was obtained for the nonisothermal nucleation rate in a one-component system, in the case where a temperature difference exists between a cluster distribution and the condensed phase. The temperature is chosen as a function of the cluster size only, while the temperature of the condensed phase is held constant by a bath. The generally accepted expression for isothermal stationary nucleation is contained as a limiting case of the nonisothermal stationary nucleation rate. The equations for heat and mass transport were solved for stationary nucleation with the given cluster distribution and with the temperature controlled at the boundaries. A factor was defined for these conditions, determined by the heat conductivity of the surrounding phase and the phase transition enthalpy, to predict the deviation between isothermal and nonisothermal nucleation. For the stationary state described, the factor appears to give small deviations, even for primary nucleation of droplets in vapor, making the nonisothermal rate smaller than the isothermal one. The set of equations may lead to larger and different thermal effects under different boundary conditions, however.     

Pair correlation function integrals: computation and use

We describe a method for extending radial distribution functions obtained from molecular simulations of pure and mixed molecular fluids to arbitrary distances. The method allows total correlation function integrals to be reliably calculated from simulations of relatively small systems. The long-distance behavior of radial distribution functions is determined by requiring that the corresponding direct correlation functions follow certain approximations at long distances. We have briefly described the method and tested its performance in previous communications [R. Wedberg, J. P. O'Connell, G. H. Peters, and J. Abildskov, Mol. Simul. 36, 1243 (2010); Fluid Phase Equilib. 302, 32 (2011)], but describe here its theoretical basis more thoroughly and derive long-distance approximations for the direct correlation functions. We describe the numerical implementation of the method in detail, and report numerical tests complementing previous results. Pure molecular fluids are here studied in the isothermal-isobaric ensemble with isothermal compressibilities evaluated from the total correlation function integrals and compared with values derived from volume fluctuations. For systems where the radial distribution function has structure beyond the sampling limit imposed by the system size, the integration is more reliable, and usually more accurate, than simple integral truncation.     

The calculation of vapor-liquid coexistence curve of Morse fluid: application to iron

The vapor-liquid coexistence curve of Morse fluid was calculated within the integral equations approach. The critical point coordinates were estimated. The parameters of Morse potential, fitted for elastic constants in solid phase, were used here to apply the results of present calculations to the determination of iron binodal. The properties of copper and sodium were considered in an analogous way. The calculations of pair correlation functions and isobars at liquid phase have shown that only for sodium these potential parameters allow one to obtain agreement with the measurements data. For iron another parameters are necessary to get this agreement in liquid phase. However, they give rise to very low critical temperature and pressure with respect to the estimates of other authors. Consequently, one can suppose that Morse potential is possibly inapplicable to the calculation of high temperature properties of non-alkali metals in disordered phases.     

Thermodynamics of aqueous mixtures of nonelectrolytes. III. Compressibilities and isochoric heat capacities of water-n-alcohol mixtures at 25°C

Speeds of ultrasound in binary mixtures of water with methanol, ethanol, and 1-propanol were measured at 25°C over the whole composition range by a pulseecho-overlap method. Excess isentropic compressibilities, excess isothermal compressibilities and excess isochoric heat capacities were derived from the results in combination with the results of our previous studies of thermal expansibilities and isobaric heat capacities.Publication issued as NRCC No. 19497     

Pressure-energy correlations in liquids. V. Isomorphs in generalized Lennard-Jones systems

This series of papers is devoted to identifying and explaining the properties of strongly correlating liquids, i.e., liquids with more than 90% correlation between their virial W and potential energy U fluctuations in the NVT ensemble. Paper IV [N. Gnan et al., J. Chem. Phys. 131, 234504 (2009)] showed that strongly correlating liquids have "isomorphs," which are curves in the phase diagram along which structure, dynamics, and some thermodynamic properties are invariant in reduced units. In the present paper, using the fact that reduced-unit radial distribution functions are isomorph invariant, we derive an expression for the shapes of isomorphs in the WU phase diagram of generalized Lennard-Jones systems of one or more types of particles. The isomorph shape depends only on the Lennard-Jones exponents; thus all isomorphs of standard Lennard-Jones systems (with exponents 12 and 6) can be scaled onto a single curve. Two applications are given. One tests the prediction that the solid-liquid coexistence curve follows an isomorph by comparing to recent simulations by Ahmed and Sadus [J. Chem. Phys. 131, 174504 (2009)]. Excellent agreement is found on the liquid side of the coexistence curve, whereas the agreement is less convincing on the solid side. A second application is the derivation of an approximate equation of state for generalized Lennard-Jones systems by combining the isomorph theory with the Rosenfeld-Tarazona expression for the temperature dependence of the potential energy on isochores. It is shown that the new equation of state agrees well with simulations.     

Heat capacities and thermodynamic functions of d-ribose and d-mannose

The heat capacities of d-ribose and d-mannose have been studied over the temperature range from 1.9 to 440 K for the first time using a combination of Quantum Design Physical Property Measurement System and a differential scanning calorimeter. The purity, crystal phase and thermal stability of these two compounds have been characterized using HPLC, XRD and TG–DTA techniques, respectively. The heat capacities of d-Mannose have been found to be larger than those of d-ribose due to its larger molecular weight, and the solid–liquid transition due to the sample melting has also been detected in the heat capacity curve. The heat capacities of these two compounds have been fitted to a series of theoretical models and empirical equations in the entire experimental temperature region, and the corresponding thermodynamic functions have been derived based on the curve fitting in the temperature range from 0 to 440 K. Moreover, the phase transition enthalpy and melting temperature of these two compounds have also been determined from the heat flows obtained in DSC measurements.

     

On the accurate direct computation of the isothermal compressibility for normal quantum simple fluids: application to quantum hard spheres

A systematic study of the direct computation of the isothermal compressibility of normal quantum fluids is presented by analyzing the solving of the Ornstein-Zernike integral (OZ2) equation for the pair correlations between the path-integral necklace centroids. A number of issues related to the accuracy that can be achieved via this sort of procedure have been addressed, paying particular attention to the finite-N effects and to the definition of significant error bars for the estimates of isothermal compressibilities. Extensive path-integral Monte Carlo computations for the quantum hard-sphere fluid (QHS) have been performed in the (N, V, T) ensemble under temperature and density conditions for which dispersion effects dominate the quantum behavior. These computations have served to obtain the centroid correlations, which have been processed further via the numerical solving of the OZ2 equation. To do so, Baxter-Dixon-Hutchinson's variational procedure, complemented with Baumketner-Hiwatari's grand-canonical corrections, has been used. The virial equation of state has also been obtained and several comparisons between different versions of the QHS equation of state have been made. The results show the reliability of the procedure based on isothermal compressibilities discussed herein, which can then be regarded as a useful and quick means of obtaining the equation of state for fluids under quantum conditions involving strong repulsive interactions.     

Monte Carlo simulation of polymer mixtures: recent progress

The phase diagram of symmetrical polymer blends (A,B) confined into thin films is studied, considering both the effect of finite film thickness D and of surface forces at the confining walls that either prefer both the same species, or different species. In the case of <“>neutral<”> walls confinement enhances the compatibility of the blend. The critical temperature is depressed, the coexistence curve gets flattened (reflecting a crossover from 3‐dimensional to 2‐dimensional critical behavior). But if both walls preferentially attract species A, then also the critical composition of the blend is shifted to the A‐rich side of the phase diagram, and the coexistence curve exhibits a bulge just above the wetting transition temperature. If one wall attracts A and the other B, lateral phase separation sets in via a first order transition. Above this transition, an interface parallel to the walls is stabilized in the system.