Calculation of thermodynamic properties of SF<Subscript>6</Subscript> including the critical region. Thermal functions and speed of sound

Specific heats C _v and C _p, entropy S, enthalpy H, and speed of sound W have been calculated using a new thermal equation of state with a small number of variable constants, which includes regular and scale contributions with a new transition function. The calculation results correspond to the accuracy level of the modern reference equations of state with a large number of determined parameters in the regular behavioral region of SF₆ properties; in the critical region, these results make it possible to supplement the existing reference data with the related tables, taking into account the scaling-theory advances. The experimental and tabular data on C _v, C _p, S, H, and W have not been used to determine the constants of the calculation equations (except for isochoric specific heat, C _v, in the ideal-gas state). These data have been applied only for comparison of the calculated values with the experimental and tabular values. To calculate the behavior of thermal properties in the critical region, universal critical indices α, β, and γ have been used according to the threedimensional Ising model. The mean error in describing thermal properties of SF₆ does not exceed the error of the existing experimental data. The calculated values coincide with the modern reference data in the regular region in the entire range of gas and liquid states. The discrepancies in the critical region are due to the application of the scale equation of state (in contrast to the regular equations used previously in this region for composing reference tables).     

Threshold electron impact ionization of SF<Subscript>6</Subscript> molecule

The relative cross sections of a dissociative ionization of SF₆ molecules by electron impact in the near-threshold energy region have been determined. The experiments were performed on a setup providing for ion mass separation and detection using a monopole mass spectrometer. The energy dependences of the cross sections of fragment ion formation have been measured and the corresponding appearance thresholds are determined.     

Preparation of high-purity SF<Subscript>6</Subscript> and AsH<Subscript>3</Subscript> using gas centrifuges

We have developed centrifugal separation technology for ultrapurification of sulfur hexafluoride (SF₆) and arsine (AsH₃). The content of volatile impurities in sulfur hexafluoride (∼0.15 mol %) was reduced by more than a factor of 1500. The purity of the resultant product was 99.9999+ mol %. The impurity content of arsine (∼0.02 mol %) was reduced by more than a factor of 20. The purity of the resultant product was 99.999+ mol %.     

High-temperature thermodynamic properties of LuPO<Subscript>4</Subscript>

The high-temperature enthalpy of lutetium orthophosphate has been determined as a function of temperature in the range 432.92–1744.58 K using drop calorimetry. The present and earlier experimental data have been used to calculate temperature-dependent heat capacity of LuPO₄ in the range 1–1750 K.     

High-temperature thermodynamic properties of the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

High-temperature mass spectrometry is used to investigate vaporization processes and determine SiO₂ activity in the Al₂O₃-SiO₂ system between 1850 and 1970 K. The results are consistent with the known phase equilibria in this system.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 4, 2005, pp. 434–441.Original Russian Text Copyright © 2005 by Bondar, Lopatin, Stolyarova.     

Electrical and thermodynamic properties of Cs<Subscript>0.97</Subscript> Rb<Subscript>0.03</Subscript>H<Subscript>2</Subscript>PO<Subscript>4</Subscript>

The transport properties of Cs_0.97Rb_0.03H₂PO₄ have been studied using polycrystalline samples and single crystals. The mixed salt is isostructural with cesium dihydrogen phosphate and has slightly smaller unitcell parameters. The cation substitution increases the low-temperature ionic conductivity of the material by about two orders of magnitude but has an insignificant effect on the conductivity of the high-temperature phase. The low-temperature conductivity of single-crystal samples exhibits significant anisotropy, with σ _a < σ _b±c . The conductivity of the polycrystalline material is close to σ _b±c . The substitution reduces the temperature of the superionic phase transition by 20°C and enhances the thermal stability of the high-temperature phase at low humidity (1 mol % H₂O).     

Thermoelastic equation of state of boron subphosphide B<Subscript>12</Subscript>P<Subscript>2</Subscript>

Compressibility of boron subphosphide B₁₂P₂ has been studied under quasi-hydrostatic conditions up to 26 GPa and 2600 K using laser-heated diamond anvil cell and angle-dispersive synchrotron X-ray diffraction. 300-K data fit yields the values of bulk modulus B ₀ = 192(11) GPa and its first pressure derivative B ₀′ = 5.5(12). It has been found that at ambient pressure the thermal expansion is quasi-linear up to 1300 K with average volume expansion coefficient α = 17.4(1) × 10^?6 K^?1. The whole set of experimental p–V–T data is well described by the Anderson-Grüneisen model with δ_T = 6.     

Heat capacity and thermodynamic properties of crystalline SrB<Subscript>4</Subscript>O<Subscript>7</Subscript>

The heat capacity of a strontium tetraborate (SrB₄O₇) single crystal has been determined in the temperature range 55–300 K by adiabatic calorimetry, and its Debye characteristic temperature, entropy change, enthalpy increment, and phonon mean free path have been calculated as functions of temperature.     

High-temperature heat capacity and thermodynamic properties of Tb<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript>

Tb₂Sn₂O₇ has been prepared by solid-state reaction in air at 1473 K over a period of 200 h and its isobaric heat capacity has been studied experimentally in the range 350–1073 K. The C _p(T) data for this compound have no extrema and are well represented by the classic Maier–Kelley equation. The experimental C _p(T) data have been used to evaluate the thermodynamic properties of terbium stannate (pyrochlore structure): enthalpy increment H°(T)–H°(350 K), entropy change S°(T)–S°(350 K), and reduced Gibbs energy Ф°(Т).     

Spectral parameters of Nd<Superscript>3+</Superscript> ion in Sr<Subscript>6</Subscript>NdSc(BO<Subscript>3</Subscript>)<Subscript>6</Subscript> crystal

The spectroscopic study of Nd³⁺ in Sr₆NdSc(BO₃)₆ crystal had been performed. Based on the Judd-Ofelt theory to analyze the optical strengths measured in absorption spectra, the following spectral parameters were obtained: intensity parameters are ₂ = 1.108 × 10^–20 cm², ₄ = 2.884 × 10^–20 cm², ₆ = 3.085 × 10^–20 cm², the radiative lifetime is 385 s, the quantum efficiency is 12.5%. The fluorescence branch ratios were calculated: ₁ = 0.423, ₂ = 0.482, ₃ = 0.092, ₄ = 0.005.     

High-temperature heat capacity and thermodynamic properties of TbBiGeO<Subscript>5</Subscript> and DyBiGeO<Subscript>5</Subscript>

Polycrystalline TbBiGeO₅ and DyBiGeO₅ samples have been prepared by solid-state reactions, by firing stoichiometric mixtures of Tb₂O₃ (Dy₂O₃), Bi₂O₃, and GeO₂ in air at 1003, 1073, 1123, 1143, 1173, and 1223 K. The molar heat capacity of the bismuth terbium and bismuth dysprosium germanates has been determined by differential scanning calorimetry. The experimental C _p (T) data obtained in the range 350–1000 K have been used to evaluate the thermodynamic functions of the synthesized oxide compounds: enthalpy increment, entropy change, and reduced Gibbs energy.     

Catalytic effect of Ti<Subscript>5</Subscript>Si<Subscript>3</Subscript> on thermal decomposition of Li<Subscript>3</Subscript>AlH<Subscript>6</Subscript>

Fine Ti₅Si₃ powder has been mechanochemically synthesized from a mixture of elemental Ti and Si powders. When Ti₅Si₃ is added as a catalyst into Li₃AlH₆, it shows a good catalytic ability by reducing the decomposition temperature and improving the decomposition kinetics as well. Although its catalytic effect is not as good as well-known TiCl₃, the use of Ti₅Si₃ has a benefit of releasing more hydrogen than TiCl₃ during dehydrogenation. This can be explained by that Ti₅Si₃, unlike TiCl₃, does not incur any chemical reactions with Li₃AlH₆ and thus remains inert during milling for dispersion.     

Electrical and thermal properties of PTFE-Sr<Subscript>2</Subscript>ZnSi<Subscript>2</Subscript>O<Subscript>7</Subscript> composites

A new polymer-ceramic composite was prepared using PTFE and low loss Sr₂ZnSi₂O₇. The dielectric properties of the composite were studied in the microwave and radiofrequency ranges. The relative permittivity (ε_r) and dielectric loss (tan δ) increased with the filler loading from 0.10 to 0.50 volume fractions (v_f). The observed values of ε_r, thermal conductivity and coefficient of thermal expansion (CTE) were compared with the corresponding theoretical predictions. The ability of the composite towards moisture absorption resistance was studied as a function of filler loading. It was also found that the variation of ε_r was less than 2% in the temperature range 25–90 °C, at 1 MHz. For a filler content of 0.50 v_f, the PTFE/Sr₂ZnSi₂O₇ composite exhibited ε_r = 4.4_, tan δ = 0.003 (at 4–6 GHz), CTE = 38.3 ppm/°C, thermal conductivity = 2.1 W/mK and moisture absorption = 0.09 wt%.     

Anharmonicity in the V<Subscript>2</Subscript>O<Subscript>3</Subscript> molecule and thermodynamic properties of V<Subscript>2</Subscript>O<Subscript>3</Subscript> in the gas phase

A quantum-mechanical calculation of the relative stability, structural parameters, and vibrational frequencies of V₂O₃ molecule isomers for different spin states was carried out using the BPW91/6-311+G(d, p) method. It was shown that the isomer with the C _s structure (nonplanar VOVO rectangle with an O atom attached to it) in the X ⁵ A″ electronic state possesses the maximum stability. The energy of the C _2v symmetry structure was higher than the lowest energy by just 23 cm⁻¹. It definitely indicated the impossibility of usage of the harmonic model in order to calculate the thermodynamic functions of V2O3 (g). A model is proposed based on which the energy levels and vibrational sums of states for this type of motion were calculated for the C _s → C _2v → C _s transition coordinate. These data, as well as results obtained from quantum-mechanical calculations, were used to calculate the thermodynamic functions of V₂O₃ (g) in the temperature range of T = 100–6000 K. The calculations were performed with the five excited electronic states with energies from 1000 to 9000 cm⁻¹ taken into account. A comparison with the data calculated in the “rigid rotator-harmonic oscillator” approximation was performed.     

Composition range and thermodynamic properties of Tl<Subscript>5</Subscript>Se<Subscript>2</Subscript>Br-based solid solutions

The equilibrium subsolidus phase diagram of the TlBr-Tl₂Se-TlSe system has been mapped out using X-ray diffraction analysis and emf measurements on thallium concentration cells. Tl₅Se₂Br has been shown to have a broad homogeneity region. The emf results are used to evaluate the relative partial thermodynamic functions of the thallium in the alloys studied and the standard integral thermodynamic functions (ΔG ⁰(298 K), ΔH ⁰(298 K), S ⁰(298 K)) of the Tl₅Se₂Br-based solid solutions.     

The velocity of streamer propagation toward anode and cathode in He,Xe, N<Subscript>2</Subscript>, and SF<Subscript>6</Subscript>

A simple mechanism of ionization spreading in a dense gas, based on the background electron multiplication wave in an inhomogeneous electric field, is considered. This process is independent of the sign of the field projection onto the direction of propagation. An analytical expression for the velocity of the ionization front propagation is obtained, which agrees well with the results of numerical calculations performed using both the simple background electron multiplication model and a detailed diffusion-drift theory. The ionization wave front velocity as a function of the field strength at the streamer boundary has been tabulated for He, Xe, N₂, and SF₆. Some peculiarities observed in the motion of streamers, such as the velocity jerks, can be related to the recently discovered nonmonotonic dependence of the ionization rate on the field strength.     

Experimental study and critical review of structural,thermodynamic and mechanical properties of superhard refractory boron suboxide B<Subscript>6</Subscript>O

In the present study the analysis of available data on structural, thermodynamic and mechanical properties of B₆O has been performed. Although the compound is known for half a century and has been extensively studied, many properties of this boron-rich solid remain unknown or doubtful. A semi-empirical analysis of our experimental and literature data has allowed us to choose the best values of main thermodynamic and mechanical characteristics among previously reported data, to predict the thermo-elastic equation of state of B₆O, and dependence of its hardness on non-stoichiometry and temperature.     

Magnetic,magnetocaloric properties,and critical behavior in a layered perovskite La<Subscript>1.4</Subscript>(Sr<Subscript>0.95</Subscript>Ca<Subscript>0.05</Subscript>)<Subscript>1.6</Subscript>Mn<Subscript>2</Subscript>O<Subscript>7</Subscript>

We report the results of magnetic, magnetocaloric properties, and critical behavior investigation of the double-layered perovskite manganite La_1.4(Sr_0.95Ca_0.05)_1.6Mn₂O₇. The compounds exhibits a paramagnetic (PM) to ferromagnetic (FM) transition at the Curie temperature T _C = 248 K, a Neel transition at T _N = 180 K, and a spin glass behavior below 150 K. To probe the magnetic interactions responsible for the magnetic transitions, we performed a critical exponent analysis in the vicinity of the FM–PM transition range. Magnetic entropy change (??S _M) was estimated from isothermal magnetization data. The critical exponents β and γ, determined by analyzing the Arrott plots, are found to be T _C = 248 K, β = 0.594, γ = 1.048, and δ = 2.764. These values for the critical exponents are close to the mean-field values. In order to estimate the spontaneous magnetization M _S(T) at a given temperature, we use a process based on the analysis, in the mean-field theory, of the magnetic entropy change (??S _M) versus the magnetization data. An excellent agreement is found between the spontaneous magnetization determined from the entropy change [(??S _M) vs. M ²] and the classical extrapolation from the Arrott curves (µ₀H/M vs. M ²), thus confirming that the magnetic entropy is a valid approach to estimate the spontaneous magnetization in this system and in other compounds as well.     

Structure and microwave dielectric properties of ZnTa<Subscript>2</Subscript>O<Subscript>6</Subscript> ceramics with TiO<Subscript>2</Subscript> and ZrO<Subscript>2</Subscript> additions

Ceramic samples based on ZnTa2O₆ and ZnTa₂O₆–MO₂ (M = Ti, Zr) systems have been obtained by the solid state ceramic route. The phase composition and microstructure of samples were investigated. The effect of the aliovalent substitution of ions Zn²⁺ and Ta⁵⁺ by M⁴⁺ (M = Ti, Zr) in the structure of ZnTa₂O₆ on microwave dielectric properties of ceramics was studied. The way of the compensation of the positive temperature coefficient of resonant frequency of dielectric resonators based on ZnTa₂O₆ ceramics with using the aliovalent substitution of cations was proposed. Dielectric resonators with the high temperature stability of the resonant frequency and high dielectric properties in the microwave range based on the ZnTa₂O₆–ZrO₂ system were obtained for application in electronics.