Acoustical and excess properties of {1-hexanol + n-hexane, or n-octane, or n-decane} at (298.15, 303.15, and 308.15) K

Densities (ρ) and speeds of sound (u) for the binary mixtures of 1-hexanol with n-hexane, n-octane and n-decane have been measured over the entire composition range at 298.15, 303.15 and 308.15 K. The dynamic viscosities (η) for these systems have been measured at 298.15 K. From experimental data, excess molar volumes (V_m^E), molar isentropic compressibility (K_s,m), excess molar isentropic compressibility (K_s,m^E), deviation in speed of sound (u^D) from their ideal values (u^id) in an ideal mixture, and excess free volumes (V_f^E) have been calculated. The excess functions have also been correlated with the Redlich–Kister polynomial equation. The viscosity data have been analysed in terms of some semi-empirical equations. The theoretical values of speed of sound (u) and isentropic compressibility (κ_S) have also been estimated using the Prigogine–Flory–Patterson (PFP) theory with the van der Waals (vdW) potential energy model and the results have been compared with experimental values. The effect of chain-length of n-alkanes as well as the temperature on the excess properties has also been studied.     

Viscosity and excess molar volume of binary mixtures of methanol with n-butylamine and di-n-butylamine at 303.15, 313.15 and 323.15 K. Characterization in terms of ERAS model

The excess molar volume V_m^E, viscosity deviation Δη, and excess Gibbs energy of activation ΔG^?E of viscous flow have been investigated from the density ρ and viscosity η measurements of binary mixtures of methanol with n-butylamine and di-n-butylamine over the entire range of mole fractions at 303.15, 313.15, and 323.15 K. The systems studied exhibit very strong cross association through strong O–H…N bonding between –OH and –NH– groups. As a consequence of this strong intermolecular association, both the systems have very large negative V_m^E and positive Δη and ΔG^?E over entire range of composition and at all the temperatures of investigation. V_m^E of the studied mixtures is consistently described by the ERAS model. The values of cross association constants K_AB illustrate that cross-associates are more pronounced in primary amine mixtures than that in secondary amine.     

Solidification of 3He in a porous glass

NMR relaxation measurements of ³He in porous high silica glass within a temperature range of 0.5 to 4.2 K at various applied pressures up to 14.6 MPa are reported. The onset of solidification of ³He in the pores was observed at excess pressures ≈ 2.3?4.7 MPa above the bulk melting pressure between 1.3 and 2.1 K. The specific heat of ³He in the porous glass was measured to supplement the NMR measurements and the result confirmed the solidification.     

Measurements of the viscosity of compressed gaseous and liquid methane

The shear viscosity coefficient of compressed gaseous and liquid methane has been measured at temperatures between 100 and 300 K and at pressures up to 30 MPa (4350 psia) with a torsionally oscillating quartz crystal viscometer. The estimated precision and accuracy of the measurements are about 0.5% and 2%, respectively. The measurements have been compared with an equation previously proposed for calculating the viscosity of gaseous and liquid methane. Most of the differences between the equation and the measurements reported here are within our experimental error. Larger differences (up to 6%) are reported at the lowest temperature (100 K) and high pressures, and along a supercritical isotherm at 200 K (T ≈ 1.05 T_c).     

Generation of microcellular poly(methyl methacrylate) by compressed gases

Abstract

Generation of microcellular poly(methy1 methacrylate) (PMMA) was studied in CO₂ and N₂O at pressures from 2 to 15MPa at three temperatures, 293.2K, 308.2K, and 323.2 K. The average diameter d and average number density N of voids generated by a rapid expansion of compressed gases in PMMA were measured by use of an optical microscope. Effects of gases, temperature, and pressure on the d and N values were examined. Even at pressure below glass transition pressure of PMMA with both gases, voids of diameter being as small as those found at high pressure, 15MPa, were obtained at each temperature. However, the void density of PMMA at lower pressure by both gases was not so good as those obtained at high pressures.     

Density, viscosity, and excess properties of the binary mixture of diethylene glycol monomethyl ether + water at T = (293.15, 303.15, 313.15, 323.15, 333.15) K under atmospheric pressure

Densities and viscosities have been measured as a function of composition for the binary liquid mixture of diethylene glycol monomethyl ether CH₃O(CH₂)₂O(CH₂)₂OH + water at T = (293.15, 303.15, 313.15, 323.15, 333.15) K under atmospheric pressure. Densities were determined using a capillary pycnometer. Viscosities were measured with Ubbelohde capillary viscometer. From the experimental data, the excess molar volumes V^E, and viscosity deviations δη, and the excess energies of activation for viscous flow ΔG^*E were calculated. These data have been correlated by the Redlich–Kister type equations to obtain their coefficients and standard deviations. The results suggest that molecular interaction between diethylene glycol monomethyl ether and water is strong.     

Microwave dielectric response of binary mixture of N,N-dimethylformamide with propylene glycol using TDR method

Dielectric relaxation study of N,N-dimethylformamide (DMF) has been carried out with propylene glycol (PLG) at different temperatures. Time domain reflectometry (TDR) in reflection mode has been used to measure the reflection coefficient in frequency range of 10 MHz to 20 GHz. The dielectric parameters static dielectric permittivity (? ₀) and relaxation time (τ) have been obtained by Fourier transform and least squares fit methods. The experimental results show nonlinear variation in dielectric permittivity and relaxation time with volume fraction of PLG confirm the structural formation due to the intermolecular interaction between N,N-dimethylformamide and PLG. The variation in excess permittivity (ε ^E), excess inverse relaxation times (1/τ)^E, Kirkwood correlation factors (g ^eff, g ^f), activation enthalpy (ΔH) and entropy (ΔS) are also calculated to study the binary mixture interaction.     

Mass-spectroscopic study of the diffusion and solubility of helium in submicrocrystalline palladium

By the method of helium thermal desorption from submicrocrystalline palladium presaturated in the gaseous phase, the diffusion coefficient D _eff and solubility coefficient C _eff of helium are measured in the range P=0–3 MPa and T=293–508 K. The pressure dependence of C _eff flattens at high pressures. At low saturation pressures, the temperature dependences of the diffusion and solubility coefficients may be divided into (1) high-temperature (400–508 K) and (2) low-temperature (293–400 K) ranges described by the exponentials D _{1, 2}=D ₀exp (−E _{1, 2} ^D /kT) and C _{1, 2}=C ₀exp (−E _{1, 2} ^S /kT). The energies of diffusion activation are E ₂ ^D =0.0036±0.0015 eV and E ₁ ^D =0.33±0.03 eV, and the solution energies are E ₂ ^S =−0.025±0.008 eV and E ₁ ^S =0.086±0.008 eV in the low-and high-temperature ranges, respectively. Mechanisms behind the diffusion and solution of helium are discussed.     

Densities, speeds of sound and viscosities of binary liquid mixtures of octan-2-ol with benzene and halobenzenes at 298.15 and 303.15 K

Densities ρ, speeds of sound u, viscosities η and refractive indices n_D of binary mixtures of octan-2-ol with benzene, chlorobenzene and bromobenzene have been measured over the entire range of composition at 298.15 and 303.15 K and atmospheric pressure. From the experimental data, excess molar volumes V^E, isentropic compressibilities κ_S, excess isentropic compressibilities κ_S^E, and deviations of speeds of sound u^D, have been calculated at 298.15 and 303.15 K. These excess functions have been fitted to the Redlich-Kister polynomial equation. The viscosity data have been correlated using Kendall-Monroe, Grunberg-Nissan, Tamura-Kurata, Hind-Mclaughlin Ubbelohde and Katti-Chaudhary viscosity models, and McAllister's three-body interaction model at different temperatures.     

ESR studies on the pressure and temperature dependence of electron self-exchange kinetics between tetrathiafulvalene (TTF) and its radical cation in ionic liquids and organic solvents

The question whether chemical reactions and diffusion processes in ionic liquids are comparable with those taking place in classical organic liquids is a current issue in the literature. Pressure- and temperature-dependent investigations on simple electron self-exchange reactions between the two partners of a redox couple are good tools to get a better understanding of how the solvent influences such reactions. The electron self-exchange reaction between tetrathiafulvalene (TTF) and its radical cation has been investigated in two ionic liquids and two organic solvents using electron spin resonance (ESR) line broadening experiments at variable temperature and pressure. Rate constants are reported for the ionic liquids 1-ethyl-3methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim⁺][Tf₂N^?]) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim⁺][Tf₂N^?]) within a temperature range of 298 K ≤ T ≤ 368 K and a pressure range of 0.1 MPa ≤ p ≤ 100 MPa. The self-exchange reaction of the redox couple [TTF/TTF^?+] has been found to be diffusion-controlled in the used ionic liquids over the entire temperature range. The observed rate constants in ionic liquids at higher pressures are larger than those predicted by common diffusion, and suggest that the electron transfer takes place within a solvent cage. Also, the self-exchange reaction of the [TTF/TTF^?+] redox couple in classical solvents (dimethylphthalate (DMP) and acetonitrile) was investigated and compared to the results with those obtained in ionic liquids. The high viscosity of the ionic liquids makes it difficult to extract the electron transfer rate constants reliably, making interpretation within the framework of the Marcus Theory impossible.     

Effects of pressure and temperature on the solubility of monosodium L-glutamate monohydrate in water

Abstract

The solubility of monosodium L-glutamate monohydrate (MSG.H₂O) in water was measured at pressures in the range of 0.10-300MPa and 298.15K. The density of MSG solution at high concentrations and heat of solution at saturated concentration were also measured at atmospheric pressure. The solubility, m_s, increased with increasing pressure and the pressure coefficient, Θ_p, [?(? In m_s,? p)_T] at 0.10 MPa was (2.0 ± 0.1) × 10-¹⁰Pa-1. It agrees well with (2.1 ±0.2)× 10-¹⁰ Pa-¹ thermodynamically estimated using the partial molar volume, the activity coefficient of the solute in solution, and the molar volume of the crystal. The excellent agreement at 0.10MPa gives us confidence in the solubility data at higher pressures. The heat of solution data and other pertinent values were used to calculate the temperature coefficient of solubility, Θ_T [? (? In m_s/?(1/T))_p], by a thermodynamic equality. The resulting Θ_T compares well with the data directly measured by Ogawa.     

Scaling of the shear viscosity of the system nitrobenzene—n-hexane in the critical region

The shear viscosity of the system nitrobenzene—n-hexane was measured along the isochores near the critical concentration. By applying the empirical formula η = η_idε^-Φ _sp, the critical exponent of the shear viscosity Φ was determined.     

Study of acoustic parameters of binary mixtures of a nonpolar liquid with polar liquid at different frequencies

The densities (ρ) and ultrasonic velocities (C) of binary mixture of diisopropyl ether (DIPE) and bromobenzene (BB) have been measured at different frequencies (1 MHz, 3 MHz and 5 MHz) over the entire range of mole fraction of diisopropyl ether (DIPE) at temperature 303 K. The intermolecular free length (L _f ), isentropic compressibility (β), acoustic impedance (Z) and excess values of isentropic compressibility (β ^E ) and acoustic impedance (Z^E) have been computed using values of ultrasonic velocity (C) and density (ρ). The ultrasonic velocity, intermolecular free length are positive whereas the excess values of isentropic compressibility and acoustic impedance are negative over the entire composition range of DIPE which indicates presence of specific interactions between unlike molecules. The results are discussed in the light of intermolecular interactions occurring in the mixtures.      

Effect of High Pressure on Acid Phosphatase in Milk

Acid phosphatase activity was measured in whole milk, skim milk, acid and rennet wheys before and after subjecting samples to high hydrostatic pressures for 10 min. Whole and skim milks exhibited a significant drop in activity following treatment at pressures in excess of 200 MPa. While rennet whey exhibited similar characteristics, acid whey was more pressure resistant and required pressures in excess of 500 MPa before exhibiting a net loss in activity. Most of the activity was lost in the first 10 min of pressurisation.     

Thermophysical properties of binary mixtures (dimethyl carbonate + ketones) at T = (303.15, 308.15 and 313.15) K

The densities ρ, viscosities η, and refractive indices n_D of binary mixtures of dimethyl carbonate (DMC) with acetophenone, cyclopentanone, cyclohexanone, and 3-pentanone have been measured over the entire range of composition at the temperatures 303.15, 308.15 and 313.15 K and at atmospheric pressure. The density values were used to calculate excess molar volumes V^E, and other excess functions of interest such as deviations in viscosity Δη, excess Gibb's free energies of activation of viscous flow ΔG^E and deviations in molar refraction ΔR. The measured viscosities were compared with those predicted using the Grunberg-Nissan, Eyring-Margules, Soliman-Marshall, and McAllister four body models. Furthermore the refractive indices data have been correlated using Lorentz-Lorentz, Weiner, Newton, Gladstone-Dale, Eykman, and Eyring-John equations and a satisfactory agreement was found for all the binary systems studied in the present work.     

Far-infrared optical excitations in multiferroic TbMnO<Subscript>3</Subscript>

We provide a detailed study of the reflectivity of multiferroic TbMnO₃ for wave numbers from 40 cm^-1 to 1000 cm^-1 and temperatures 5 K < T < 300 K. Excitations are studied for polarization directions E || a, the polarization where electromagnons are observed, and for E || c, the direction of the spontaneous polarization in this material. The temperature dependencies of eigenfrequencies, damping constants and polar strengths of all modes are studied and analyzed. For E || a and below the spiral ordering temperature of about 27 K we observe a transfer of optical weight from phonon excitations to electromagnons, which mainly involves low-frequency phonons. For E || c an unusual increase of the total polar strength and hence of the dielectric constant is observed indicating significant transfer of dynamic charge probably within manganese-oxygen bonds on decreasing temperatures.     

Internal pressure,ultrasonic velocity and viscosity of multi-component liquid systems

Ultrasonic velocity, density and viscosity were measured in two ternary liquid systems namely,n-pentane +n-hexane + benzene(I) andn-hexane + cyclohexane + benzene(II) and one quaternary liquid system,n-pentane +n-hexane + benzene + toluene (III). The experimental as well as literature values of thermal expansion coefficient and iso-thermal compressibility of pure liquid components were utilized to deduce the ideal value of internal pressure and excess internal pressure for the above liquid systems at 298·15K using two different approaches. In the conventional approach one needs the experimental values ofα andβ _T of mixtures for computing internal pressure, which was not possible. The second method which is proposed here utilizes only the density, ultrasonic velocity and viscosity data of the mixture. This method is used in computing internal pressure and its excess value for multicomponent liquid systems. A satisfactory agreement has been observed.     

Study of the electrical properties of thin SmS films at high pressures

The pressure-induced shift of impurity levels under hydrostatic compression (?1.9 × 10^?2 meV/MPa) at T = 300 K has been derived from measurements of the behavior with temperature of the electrical resistance of thin polycrystalline SmS films on glass substrates at different pressures. The difference between the pressure-induced shifts of impurity levels in thin films and single crystals has been attributed to the effect of elastic properties of the substrate material. It has been shown that the semiconductor-metal phase transition in SmS films does not occur at pressures of up to 1000 MPa, because the impurity levels triggering the mechanism of phase transition at such pressures are not in the conduction band.     

Liquid mixture excess properties by the hard sphere model

The excess properties of mixing were calculated for seven systems Ar-CH₄; Ar-N₂; Ar-O₂; Ar-CO; CO-CH₄; O₂-N₂; N₂-CO, using the Caranhan and Starling equation of state of rigid spheres and the Longuet-Higgins and Widom model. Two sets of calculations were done one using the experimentalG ^E to calculateS ^E ,H ^E andV ^E , and the other making use of Miller’s cross parameter values. The calculated values are compared with those of Snider and Herrington and Miller’s values and also with the experimental values. The agreement was found to be good.     

Dechanneling of MeV protons in tungsten

Abstract

A systematic investigation of the dechanneling of protons in tungsten has been completed for the <111> axial direction and also for the (110) plane. Measurements at room temperature have been made at energies of 0.5, 2.0, 3.5, 8.0 and 12.0 MeV; at 2.0 MeV, the effect of target temperature has been investigated over the range 77–873°K. In the axial case, the dechanneling rate increases strongly with the vibrational amplitude _ρ, but not as strongly as the ρ² dependence reported by the Catania group (Refs. 4–7) for silicon and germanium. Also, unlike silicon and germanium, the tungsten axial data exhibit practically no energy dependence and so cannot be fitted by the zρ²/E scaling parameter suggested by the Catania group. On the other hand, the planar dechanneling data in tungsten exhibit the predicted (E ^?1)dependence and relatively littie temperature dependence, in good agreement with previous work.