Isochoric temperature coefficient of surface tension andS o-parameter of quasi-spherical molecular liquids

The Sharma parameterS _o which is characteristic of molten alkali halides and polymers has also been shown to be characteristic of a wide variety of liquids. Calculated data using the volume expansivity of the liquid establish the constancy of theS _o-parameter which retains, on an average, a constant value of 1·11 for quasi-spherical molecular liquids. It is shown thatS _o-parameter is also related to volume expansivity of the surface layer of the liquid, temperature coefficient of surface tension of liquids and describes the temperature and volume or pressure dependence of thermodynamic Grüneisen parameter and isochoric heat capacity with significant contribution for influencing the thermoacoustic and surface tension properties of liquids.     

Modified grüneisen and anderson-grüneisen relations for quasispherical molecular liquids

The validity of the expression for the Grüneisen parameter of liquids has been tested by obtaining expressions for the heat capacity ratio, isothermal and adiabatic Anderson-Grüneisen parameters,C ₁-parameter, Rao’s acoustical parameter, Beyer’s non-linearity parameter, and relate them to the Grüneisen parameter. The calculated values for five liquefied gases comparising of quasi-spherical molecules are reasonably satisfactory and explain the experimental results for the variation of heat capacity ratio, Beyer’s nonlinearity parameter andC ₁-parameter with temperature for liquid state. It is shown that the isochoric temperature derivative of the sound speed, specified heat ratio and the compressibility are dominant factors with significant contribution for influencing the thermo-acoustic properties of liquids.     

The Rise and Fall of Anomalies in Tetrahedral Liquids

The thermodynamic liquid-state anomalies and associated structural changes of the Stillinger-Weber family of liquids are mapped out as a function of the degree of tetrahedrality of the interaction potential, focusing in particular on tetrahedrality values suitable for modeling C, H₂O, Si, Ge and Sn. We show that the density anomaly, associated with a rise in molar volume on isobaric cooling, emerges at intermediate tetrahedralities (e.g. Ge, Si and H₂O) but is absent in the low (e.g. Sn) and high (e.g. C) tetrahedrality liquids. The rise in entropy on isothermal compression associated with the density anomaly is related to the structural changes in the liquid using the pair correlation entropy. An anomalous increase in the heat capacity on isobaric cooling exists at high tetrahedralities but is absent at low tetrahedralities (e.g. Sn). Structurally, this heat capacity anomaly originates in a sharp rise in the fraction of four-coordinated particles and local tetrahedral order in the liquid as its structure approaches that of the tetrahedral crystal.     

Measuring the configurational heat capacity of liquids

A high electric field impedance experiment on supercooled molecular liquids is employed to transfer energy to the slow modes by absorption from the field and detect the increase of their "configurational temperature", T(cfg), via the change of the relaxation times. This allows us to determine the configurational heat capacity, which accounts for most of the excess heat capacity for stronger liquids, but for only half of the heat capacity step in the case of more fragile systems. It is also observed that T(cfg) gradually approaches the phonon temperature on the structural relaxation time scale.     

Anomalous heat capacity of Agx and the nonlinear temperature dependence of the formation energy of Frenkel defects

Abstract

The nonlinear decrease of Gibbs free energy (g_F) for the formation of Frenkel defects in Agx accounts for the anomalous increase of electrical conductivity and self-diffusion in this system. Using an analytical expression for g_F(T) the excess heat capacity for Frenkel defects is calculated. A comparison with experimental data indicates that all the anomalies of heat capacity at high temperature is not accounted for. A contribution from Schottky defects is thus probable.     

Loci of extrema of thermodynamic response functions for the Lennard–Jones fluid

Lines of extrema along isotherms and isobars for the residual isochoric heat capacity, the residual isobaric heat capacity, the isobaric thermal expansivity, and the isothermal compressibility of the Lennard–Jones fluid have been studied from popular equations of state due to Johnson et al. [Mol. Phys. 78, 591 (1993)], Kolafa and Nezbeda [Fluid Phase Equilib. 100, 1 (1994)], and Mecke et al. [Int. J. Thermophys. 17, 391 (1996)]. On depicting such loci in the pressure–temperature plane, the characteristic behaviour of thermodynamic response functions in the ideal-gas limit (at high enough temperatures or low enough pressures), the close-packed-fluid limit (at low enough temperatures or high enough pressures) as well as in the liquid, critical, and supercritical regions is identified. The present analysis is informative itself, but it also stimulates further work in order to tackle more complicated cases of study including associated fluids.     

Comment on: An intermolecular potential for nitrogen from a multi-property analysis

A paper by Cappelletti et al. (1998, Molec. Phys. 93, 485) utilizes classical trajectory effective cross-sections to predict the rotational collision number for nitrogen gas. It is suggested that use of the rotational heat capacity, rather than the total internal heat capacity, will give a more meaningful conversion of the cross-sections into relaxation time. In addition, an error in the formula for first-order collision number is corrected.     

Shock compression of simple liquids: Implications for deuterium

Abstract

This report summarizes research on shock-compressed liquids: argon, xenon, nitrogen, and hydrogen. The purpose is to illustrate the common thread that connects all of these studies with the recent work on deuterium.     

Spin–lattice relaxation phenomena in the magnetic state of a suggested Weyl semimetal CeAlGe

ABSTRACT

In this work, we report the results of DC susceptibility, AC susceptibility and related technique, resistivity, transverse and longitudinal magnetoresistance and heat capacity on polycrystalline magnetic semimetal CeAlGe. This compound undergoes antiferromagnetic type ordering around 5.2 K (T¹). Under the application of external magnetic fields, parallel alignment of magnetic moments is favoured above 0.5?T. At low field and temperature, frequency and AC field amplitude response of AC susceptibility indicate the presence of spin–lattice relaxation phenomena. The observation of spin–lattice interaction suggests the presence of the Rashba–Dresselhaus spin–orbit interaction which is associated with inversion and time-reversal symmetry breaking. Additionally, the presence of negative and asymmetric longitudinal magnetoresistance indicates anomalous velocity contribution to the magnetoresistance due to the Rashba–Dresselhaus spin–orbit interaction which is further studied by heat capacity.     

Sizes and series of m35–atomic clusters in icosahedral quasicrystals and in m35–approximant crystals. Theory and examples

Abstract

A critical examination of the behaviour of three fragile glass forming liquids viz. Salol, α-phenyl-o-cresol and o-terphenyl, has been carried out using differential scanning calorimetry and dielectric relaxation technique (frequency: 10⁶-10^?3 Hz). Our study reveals two sub-T_g processes designated as β- and γ-processes, in addition to the primary (α-) process. The β-process has an activation energy of 36–50 kJ/mol. in these liquids, and is found to be intramolecular in nature. Our results along with the published viscosity data on these liquids indicate a decoupling of the viscous modes from the α-modes in the region of T_g, with the latter still retaining its non-Arrhenius character. The nature of this decoupling has been discussed in detail.     

Effect of γ irradiation on the heat capacity of Rb2ZnBr4 in the vicinity of phase transitions

Heat capacity of Rb₂ZnBr₄ as a function of γ irradiation dose has been measured within the 85–300 K range by the adiabatic calorimeter technique. It is shown that, as the irradiation dose increases, the heat capacity peak in the vicinity of the incommensurate-commensurate first-order phase transition (PT) decreases, and the transition temperature T _c increases. The heat capacity peak in the region of the second-order PT at T ₃=112 K does not depend on γ irradiation, both in magnitude and in position, just as the heat capacity throughout the remainder of the temperature range studied. Fiz. Tverd. Tela (St. Petersburg) 40, 1106–1108 (June 1998)     

<Emphasis Type="Italic">Comment on</Emphasis>¶Low temperature specific heat of blue bronze K <Emphasis Type="Bold">0.30</Emphasis>MoO <Emphasis Type="Bold">3</Emphasis>, by J. Odin,J.C. Lasjaunias,K. Biljaković, K. Hasselbach,and P. Monceau

Eur. Phys. J. B 24, 315 (2001) Here we comment on a recently published paper on the presence of a phason contribution in the low temperature heat capacity data of the charge-density-wave compounds K_0.3MoO₃ and (TaSe₄)₂I. We have shown that the anomaly in the C _P / T ³ data reported by Odin et al. is straightforwardly interpreted in terms of low energy phonon modes resulting from the peculiar topology of these compounds. Received 21 February 2002 Published online 19 July 2002     

Carbon–ionic liquid double-layer capacitors

A series of electrochemical capacitors, based on activated carbon powders (ACP, specific surface area 870 and 2600 m²/g) and ionic liquids as electrolytes, were prepared and tested. The ionic liquids consisted of 1-ethyl-3-methyl imidazolium (EMIm⁺), 1-butyl-3-methyl imidazolium (BMIm⁺) and 1-methyl-1-propyl pyrrolidinium (BMPy⁺) cations, as well as of tetrafluoroborate, hexafluorophosphate and bis((trifluoromethyl)sulfonyl) imide anions. A typical capacitor consisted of two electrodes each with a mass of ca. 15–30 mg, and showed a capacity of ca. 0.35–1.5 F; this leads to a specific capacity of the carbon electrode material within the range of 45 (ACP 870 m²/g)–180 F/g (ACP 2600 m²/g). The specific capacity expressed versus total surface of carbon material was within the range of 5.2–6.9 μF/cm². The electrochemical stability window of ionic liquids determined at the glassy carbon electrode is within the range of ca. 3.0–4.2 V. The energy stored in a capacitor based on activated carbons and ionic liquids may be high, due to a broad practical electrochemical stability window of ca. 3 V. Ionic liquids are characterised by negligible vapour pressure; such a capacitor emits no volatile organic compounds and may be regarded as environmentally friendly.     

Comparative study of the heat capacity of icosahedral quasicrystals in solid and liquid states

The heat capacity of icosahedral quasicrystals Al₆₃Cu₂₅Fe₁₂ and Al₆₂Cu_25.5Fe_12.5 has been studied at high temperatures up to 1700 K, which is by almost 400 K higher than the melting point of the material. It has been shown that the melt exhibits an excess heat capacity with respect to that determined by the Dulong-Petit law and that is a direct extension of the excess heat capacity of the solid state. It has been concluded that the excess heat capacity is related, as a whole, to the short-range order in the quasicrystal structure. This circumstance allows the identification of the orbital hybridization as the most probable mechanism of formation of the pseudogap in the electronic structure of the quasicrystals.     

Disappearance of the heat capacity peak of Sc3In around the curie temperature in high magnetic fields

The low temperature (1.3–20.0 K) heat capacity of the weak itinerant electron ferromagnet Sc₃In was measured in magnetic fields up to ～ 10 T. The heat capacity peak observed around T_c = 6.0 K in zero field becomes smaller with increasing fields and at 9.98 T its magnetic entropy is ≈ 18% of the zero field value. Above T_c, the spin fluctuation contribution to the heat capacity, which is enhanced by the magnetic field at lower fields (?5 T), is quenched at higher fields (?5 T). This depression of the spin fluctuation contibution to the heat capacity by the high magnetic fields occurs at lower magnetic fields than had been considered possible heretofore. Our results suggest that the itinerant ferromagnetism is Sc₃In is completely quenched at 12 T.     

On the specific heat of Fermi liquids

The contributions of long-wavelength spin fluctuations to the specific heat of Fermi liquids is consistently calculated on the basis of the Landau theory of Fermi liquids. More satisfactory estimations of the Landau parameter F₁^a for liquid ³He are obtained.     

Structural Disorder in Supercritical Aqueous Ionic Solutions as seen by MD-EXAFS

Because of their inherent structural disorder, liquids are challenging systems for structural studies. This is even more so for high temperature/high pressure fluids such as supercritical (SC) ones. By combining Molecular Dynamics simulations with Extended X-ray Absorption Fine Structure spectroscopy, we have recently elucidated the structure of the Br m hydration shell in low concentrated solutions from ambient to supercritical conditions [1]. The densities explored correspond to pressures up to 450 bar. In this paper, we show that this combination of techniques has been an essential tool to correctly interpret the experimental signals. Indeed, the occurrence of drastic different local environment of the ions in solutions, typical of liquids and magnified in supercritical conditions, can be seriously misleading if not taken into account.     

Calorimetric fragility of maltitol

The heat capacity of maltitol has been measured with an adiabatic calorimeter for the crystal from 100 K to 425 K (T _m = 420 K), for the glass from 249 K to T _g (around 311 K) and for the liquid from T _g to 400 K. The heat of melting is 55.068 kJ/mol. The calorimetric glass transition occurs at about T _g = 311 K with a sudden jump of the heat capacity ΔC _p (T _g ) of about 243.6 J/(K mol). The excess entropy between the undercooled liquid and the crystal was calculated from the heat capacity data and was used to estimate the Kauzmann temperature T _K which was found 50 K below T _g . ΔC _p (T _g ) and T _K for maltitol were compared to other compounds like sugars, polyol and hydrogen bonded liquids. It has been found that the glass former maltitol is a "fragile" liquid on the thermodynamic point of view.     

Performance of a Single-Family Heat Pump at Different Working Conditions Using Small Quantity of Propane as Refrigerant

The performance of a domestic heat pump that uses a low quantity of propane as refrigerant has been experimentally investigated. The heat pump consists of two minichannel aluminium heat exchangers, a scroll compressor, and an electronic expansion valve. It was charged with the minimum amount of refrigerant propane required for the stable operation of the heat pump without permitting refrigerant vapor into the expansion valve at incoming heat source fluid temperature to the evaporator of +10°C. The inlet temperature of the heat source fluid passing through the evaporator was varied from +10°C to ?10°C while holding the condensing temperature constant at 35°C, 40°C, 50°C, and 60°C, respectively. The minimum refrigerant charges required at above-tested condensing temperatures were found to decrease when the condensing temperature increased and were recorded as 230 g, 224 g, 215 g, and 205 g, respectively. The results confirm that a heat pump with 5 kW capacity can be designed with less than 200 g charge of refrigerant propane in the system. Due to the high solubility of propane in compressor lubrication oil, the amount of refrigerant which may escape rapidly in case of accident or leakage is less than 150 g.     

Raman Spectrum of the Fluorination Products of RbC1

Abstract

Compounds with high fluorinating capacity are obtained when rubidium and cesium chlorides are fluorinated in a stream of elemental fluorine. Best results are obtained when the, temperature is kept in the range of 140–170°C. These products were first assumed to be polyfluorides, MF₃, of Rb and Cs ¹. It was later assumed by various researchers ² that the products are really tetrafluorohalates of Rb and Cs, formulated as MC1F₄. One of the authors was himself involved in the problem of trying to establish the structure of these products. It is, however, a very difficult problem since pure products giving constant analytical results were not obtained. During the fluorination process, which is an exothermic one, enough heat is evolved to melt the reaction medium and the temperature rises above that needed to decompose the products. It is therefore impossible to obtain reliable analytical data, the products being a mixture of regular fluorides, MF, and the active, fluorinating, ones. No final proof has therefore been found for the C1F^? ₄ structure.