Simultaneous volume and enthalpy relaxation

The ratio between the relaxed enthalpy and volume (so-called aging modulus, K_a) was expressed in frame of the Tool-Narayanaswamy-Moynihan theory. The common case where various experimental arrangements are used for measuring these quantities was analyzed. It was found that relatively small differences between the conditions of enthalpy and volume relaxation experiments may cause a significant shift of observed K_a value. The sensitivity of K_a modulus to the difference between the enthalpy and volume relaxation conditions is significantly higher in the case of organic polymeric glasses in comparison with silicate and chalcogenide glasses. The reason for such grouping resides in higher values of glass transition temperature and lower values of activation enthalpy of inorganic glasses.     

Enthalpy,volume and structural relaxation in glass-forming silicate melts

Through structural relaxation, the configuration of a viscous liquid changes to allow the Gibbs free energy to be minimum in response to temperature variations. In this review, the practical importance of relaxation in silicate melts is first illustrated by configurational heat capacity and entropy and their connection with viscosity via Adam-Gibbs theory. Relaxation effects on thermal expansion and compressibility are then examined, and the similarity of the kinetics of structural, enthalpy and volume relaxation is pointed out. Turning to microscopic mechanisms, we finally stress the importance of Si-O bond exchange and its decoupling with the motion of network-modifying elements near the glass transition. This revised version was published online in August 2006 with corrections to the Cover Date.     

Primary and secondary relaxations in bis-5-hydroxypentylphthalate

Broadband dielectric spectroscopy was used to study the relaxation dynamics in bis-5-hydroxypentylphthalate (BHPP) under both isobaric and isothermal conditions. The relaxation dynamics exhibit complex behavior, arising from hydrogen bonding in the BHPP. At ambient pressure above the glass transition temperature T(g), the dielectric spectrum shows a broad structural relaxation peak with a prominent excess wing toward higher frequencies. As temperature is decreased below T(g), the excess wing transforms into two distinct peaks, both having Arrhenius behavior with activation energies equal to 58.8 and 32.6 kJmol for slower (beta) and faster (gamma) processes, respectively. Furthermore, the relaxation times for the beta process increase with increasing pressure, whereas the faster gamma relaxation is practically insensitive to pressure changes. Analysis of the properties of these secondary relaxations suggests that the beta peak can be identified as an intermolecular Johari-Goldstein (JG) process. However, its separation in frequency from the alpha relaxation, and both its activation energy and activation volume, differ substantially from values calculated from the breadth of the structural relaxation peak. Thus, the dynamics of BHPP appear to be an exception to the usual correlation between the respective properties of the structural and the JG secondary relaxations.     

Molecular packing in highly stable glasses of vapor-deposited tris-naphthylbenzene isomers

Physical vapor deposition of organic molecules can produce glasses with high kinetic stability and low enthalpy. Previous experiments utilizing wide-angle x-ray scattering (WAXS) have shown that, relative to the ordinary glasses prepared by cooling the supercooled liquid, such glasses exhibit excess scattering characteristic of anisotropic packing. We have used vapor deposition to prepare glasses of four isomers of tris-naphthylbenzene (TNB), and measured both the WAXS patterns and the kinetic stability. While vapor-deposited glasses of all four TNB isomers exhibit high and nearly uniform kinetic stability, the level of excess scattering varies significantly. In addition, for α,α,β-TNB, glasses of essentially identical kinetic stability can have excess scattering levels that vary by a factor of two. These results indicate that anisotropic packing is not the source of kinetic stability in vapor-deposited glasses but rather a secondary feature that depends upon the chemical structure of the glass-forming molecules. We also show that the time required for these stable vapor-deposited glasses to transform into the supercooled liquid greatly exceeds the structural relaxation time τ(α) of the liquid and scales approximately as τ(α) (0.6). The kinetic stability of the vapor-deposited TNB glasses matches that expected for ordinary glasses that have been aged for 10(2) to 10(7) years.     

Excess enthalpy,density, and heat capacity for binary systems of alkylimidazolium-based ionic liquids + water

Experimental measurements of excess molar enthalpy, density, and isobaric molar heat capacity are presented for a set of binary systems ionic liquid + water as a function of temperature at atmospheric pressure. The studied ionic liquids are 1-butyl-3-methylpyridinium tetrafluoroborate, 1-ethyl-3-methylimidazolium ethylsulfate, 1-butyl-3-methylimidazolium methylsulfate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, and 1-ethyl-3-methylimidazolium trifluoromethanesulfonate. Excess molar enthalpy was measured at 303.15 K whereas density and heat capacity were determined within the temperature range (293.15 to 318.15) K. From experimental data, excess molar volume and excess molar isobaric heat capacity were calculated. The analysis of the excess properties reveals important differences between the studied ionic liquids which can be ascribed to their capability to form hydrogen bonds with water molecules.     

Thermal analysis and dilatometry of glasses formed under elevated pressure

Densified glasses, formed from the liquid state by cooling at 5°C/hr under elevated pressures of up to 517 MN/m², were studied by thermal analysis and dilatometry at ambient pressure. The materials studied were polystyrene, poly(methyl methacrylate), phenolphthalein, sucrose, and a 1 : 1 mixture by weight of potassium and calcium nitrate. Enthalpies of the densified glasses were found to be up to 2–6 J/g greater than the enthalpies of the glasses formed at atmospheric pressure. The major enthalpy and volume relaxation on heating the densified glasses was found to be not correlated The upper temperature limit of the glass-transition region remained constant for all glasses cooled at various pressures, while the lower temperature limit of the polymeric glasses decreased up to 55°C with increasing pressure. The interpretation of the data suggests that an additional, significant volume relaxation occurred on depressurization at room temperature for all glasses analyzed.     

Molecular association ofn-alcohols in nonpolar solvents. excess volumes and viscosities ofn-pentanol+n-octane mixtures at 0, 5, 25, 35 and 45°C

Densities and viscosities of n-pentanol +n-octane mixtures in the temperature range 0 to 45°C are reported. The data are discussed in terms of molar excess volumes, molar excess fluidities and molar excess activation energies of viscous flow in order to obtain structural information of the mixtures. It is shown that the structural modifications of n-pentanol and n-octane upon mixing, significantly contribute to the parameters governing the viscous flow and the volume of the mixtures.     

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.     

Study of molecular interactions in binary mixtures of formamide with 2-methoxyethanol and 2-ethoxyethanol at varying temperatures

The thermophysical properties of binary mixtures of formamide with 2-methoxyethanol and 2-ethoxyethanol have been investigated in this article. Densities, refractive index, ultrasonic velocity and viscosity for the two binary mixtures viz. formamide with 2-methoxyethanol and 2-ethoxyethanol have been measured over the entire composition range at 293, 303 and 313 K and at atmospheric pressure. The excess molar volume, the molar refraction deviation, excess Gibb's free energy of activation for viscous flow, excess isentropic compressibility, deviation in viscosity, excess free volume and excess molar enthalpy have been computed using experimental data. These excess parameters have been correlated with Redlich–Kister polynomial equation. The results have been interpreted on the basis of strength of intermolecular interaction occurring in these mixtures. Densities, refractive index and ultrasonic velocity were correlated with second-order polynomial equation. The molar volume and excess partial molar volume at infinite dilution have also been calculated for both the mixtures.     

The physicochemical characteristics of heteroassociates in the N,N-dimethylformamide-water system

The data on proton magnetic spin-spin relaxation, refractometry, acoustic spectroscopy, densimetry, and excess enthalpy of mixing of the N,N-dimethylformamide-water system are reviewed. The molar volumes, molar refractions, electronic polarizabilities, and isothermal compressibilities of heteroassociates formed in the N,N-dimethylformamide-water binary system were calculated.     

A highly selective diethyldithiocarbamate extraction system in activation analysis of copper,indium, manganese and zinc

A versatile separation system based on the extraction of dithiocarbamates and applicable to the determination of copper, managanese, zinc and indium in a wide selection of materials by activation analysis is described. After the dissolution of the sample and a few simple operations which eliminate specific interferences, depending upon the material (e. g. sodium and gold in the NBS Standard Reference Glasses), carbamates are extracted under specific conditions by addition of appropriate complexing agents and selective stripping. Extreme separation factors permit interference-free counting using a sodium iodide detector. For example, indium is separated from a hundred thousand fold excess of manganese in the determination of the two elements in Orchard Leaves. Results are also presented for all four elements in Bowen's Kale, NBS Bovine Liver, and for Cu, In and Mn in the 0.02 ppm and 1 ppm SRM glasses.     

Thermophysical properties of the binary mixtures (1,8-cineole + 1-alkanol) at T = (298.15 and 313.15) K and at atmospheric pressure

This work presents the measurements of the density, speed of sound, refractive index and enthalpy of binary mixtures containing {1,8-cineole + 1-alkanol (ethanol, 1-propanol, 1-butanol, and 1-pentanol)} at two temperatures (298.15 and 313.15) K and atmospheric pressure. The determination of excess molar volume, speed of sound deviation, refractive index deviation, molar refraction, molar refraction deviation, excess isentropic compressibility, and excess molar enthalpy are also given. Redlich–Kister equation was used to fit these derivate properties. The experimental data of the constituent binaries were analysed to discuss the nature and strengths of intermolecular interactions. Eventually some models, SAFT and PC-SAFT for density, Free Length and Collision Factor for speed of sound, Gladstone-Dale Arago-Biot for refractive index, and UNIFAC for excess molar enthalpy, among others, were successfully applied.     

Thermodynamics of liquid mixtures of krypton+ethane

The total vapour pressure, the excess Gibbs energy Q^E (at 115.77 K), the excess enthalpy H^E (at 117.0 K) and the excess molar volume V^E (at 115.77 K) are reported for liquid mixtures of krypton and ethane. The results are interpreted in the light of some recent statistical theories of liquid mixtures.     

Thermodynamics of Organic Mixtures Containing Amines. II. Excess Molar Volumes at 25°C for Methylbutylamine + Alkane Systems and Eras Characterization of Linear Secondary Amine + Alkane Mixtures

Excess molar volumes, at 25°C and atmospheric pressure for methylbutyl amine + n-hexane; + cyclohexane; + n-octane; n-decane; + n-dodecane; + n-tetradecane, or + n-hexadecane systems are reported from densities measured with a vibrating-tube densimeter. The excess functions, molar enthalpy, and volume, for linear secondary amine + n-alkane systems are discussed in terms of interactional and structural effects. In addition, these solutions, which include amines from dimethyl to dioctylamine, are studied in the framework of the ERAS model. The corresponding ERAS parameters are reported. The agreement between experimental data and ERAS results is good for excess enthalpies, excess Gibbs energies, and excess molar volumes. The larger discrepancies are found for the excess volumes when strong free-volume effects are present in the investigated mixtures. The variation with temperature of the thermodynamic properties is well described by ERAS.     

Comparison Between Volume and Enthalpy Relaxations in Non-crystalline Solids Based on the Fictive Relaxation Rate

The volume and enthalpy relaxation rate of inorganic glasses and organic polymeric materials subjected to temperature jump T has been analyzed. It is shown that the relaxation behavior in isothermal conditions can be compared on the basis of the fictive relaxation rate defined as R_f=(dT_f/dlogt)_i. No significant difference between volume and enthalpy relaxation rate has been found for all materials examined. A simple equation relating the R_f and parameters of Tool-Naraynaswamy-Moynihan (TNM) phenomenological model has been derived. This equation predicts increasing R_f with the magnitude of temperature jump. It seems that correct determination of TNM parameters might be problematic for slowly relaxing polymers as the effect of these parameters becomes comparable with experimental uncertainty.This revised version was published online in November 2005 with corrections to the Cover Date.     

过剩热焓松弛CO_2和甲苯在PET薄膜中渗透的影响

本文研究了非晶态、未取向PET薄膜样品在低于T_g温度以下热处理,结构的变化和过剩热焓松弛对CO_2和甲苯溶剂在样品中渗透速率的影响。结果表明,随退火时间增加,从T_g转变吸热峰确定的过剩热焓松弛量、 T_g温度、密度增加,而反式构象含量减少。除分子链堆砌密度提高或自由体积下降外,没有发现非晶相有结构上的变化。因此,CO_2在样品中随退火时间的增加渗透速率下降。然而,由于样品脆性增加和甲苯的溶胀作用,样品表面出现裂纹,使甲苯在样品中的表观渗透速率增加。     

Excess molar properties for binary systems of alkylimidazolium-based ionic liquids + nitromethane. Experimental results and ERAS-model calculations

Density, isobaric molar heat capacity, and excess molar enthalpy were experimentally determined at atmospheric pressure for a set of binary systems ionic liquid + nitromethane. The studied ionic liquids were: 1-butyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-ethyl-3-methylimidazolium ethylsulfate, 1-butyl-3-methylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, and 1-butyl-3-methylimidazolium trifluoromethanesulfonate. Density and heat capacity were obtained within the temperature range (293.15 to 318.15) K whereas excess molar enthalpy was measured at 303.15 K; excess molar volume and excess molar isobaric heat capacity were calculated from experimental data. The ERAS-model was applied in order to study the microscopic mechanisms involved in the mixing process. Although the studied compounds are not self-associated, ERAS-model describe adequately the experimental results if cross-association between both compounds is considered.     

Physicochemical Properties, <Superscript>1</Superscript>H-NMR,Ab Initio Calculations and Molecular Interaction in Binary Mixtures of <Emphasis Type="Italic">N</Emphasis>-methylimidazole with Methanol

Over the full molar fraction range, the density, viscosity, refractive index, conductivity and pH at the temperatures (298.15, 308.15, and 318.15) K, mixing enthalpy at T?=?298.15 K, and ¹H-NMR were measured for the binary mixtures of x N-methylimidazole (hereafter abbreviated to N-mim)?+?(1???x) methanol, together with ab initio calculations. The thermodynamic parameters of activation for viscous flow were calculated and analyzed. The excess molar volume, viscosity deviation, deviation for the logarithm of viscosity, refractive index deviation and the excess refractive index, excess Gibbs energy of activation of viscous flow and the molar mixing enthalpy were calculated and fitted with a Redlich–Kister equation. The partial molar mixing enthalpies and the protons’ chemical shift changes of N-mim and methanol were calculated and explained. An increase in temperature leads to the excess molar volume becoming more negative, whereas the deviations for the logarithm of viscosity, viscosity deviation and the excess Gibbs energy of activation of viscous flow become less positive; in contrast the refractive index deviation and the excess refractive index become less positive at first and then become more positive. The activation of the viscous fluid is a more ordered process. The physicochemical properties, ab initio calculations, combined with the ¹H-NMR results reveal that the molecular interactions among unlike molecules is stronger than that between like ones. There is an ionization process and hydrogen bond interaction between N-mim and methanol, the predominant interaction is N-mim:methanol?=?1:1 hydrogen-bonded network, where the methyl groups of methanol and N-mim, respectively, are electron-withdrawing and electron-donating groups.     

Preferential binding of fluorine to aluminum in high peralkaline aluminosilicate glasses

For two series of fluoride-containing aluminosilicate glasses of high peralkaline type, we apply 27Al, 19F, 29Si, and 23Na NMR spectroscopy to understand the structural changes introduced by the addition of alkali fluorides. Adding fluoride in concentrations above the solubility limit causes crystallization of different phases in sodium and potassium glasses despite identical composition. However, the NMR spectra reveal that the structural evolution of the precrystallized states is similar in both series. In particular, fluorine coordinates exclusively to alkaline cations and aluminum. No indication of direct bonding with silicon was found from 19F --> 29Si cross-polarization experiments. In contrast to other glass systems, double resonance experiments in these peralkaline systems show that halide addition produces at most a minor fraction of tetrahedral aluminum containing fluorine in its coordination sphere. Instead, the fluorine addition prior to crystallization converts up to about 20% of the initial tetrahedral aluminum (1 mol % in absolute units) to 5- and 6-fold coordinated aluminum. A minor portion of five-coordinated aluminum groups is considered as the intermediate to the growing fraction of octahedral aluminum in the silicate matrix. The initialization of the crystallization process is correlated with the saturation of the silicate matrix by octahedral aluminum clusters segregating out under further doping by fluoride. It is suggested that the formation of the nonframework Al-F bonds is responsible for structural relaxation, reflected by the reduction of the glass transition temperature.     

High‐Pressure Influence on the Rate of Diels–Alder Cycloaddition Reactions of Maleic Anhydride with Some Dienes

The rate constants for temperature and pressure range, enthalpy, entropy, and volume of activation and reaction were measured in toluene solution for the Diels–Alder cycloaddition reaction of maleic anhydride ( 1 ) with a very active diene, 9,10‐dimethylanthracene ( 4 ), and with a very inactive diene, 9‐phenylanthracene ( 6 ), which is less reactive in the reaction with 1 by five orders of magnitude. Reaction rates under pressure up to 2600 bar were measured by using a high‐pressure optical cell, adjusted to a UV‐spectrophotometer. The volume of reaction was determined by two independent methods: by the difference of the partial molar volumes of the reactants and by the dependence of a specific volume of solution on the adduct concentration during the reaction. All parameters of activation and reaction were discussed.