Heat capacities,third-law entropies and thermodynamic functions of the negative thermal expansion material Zn2GeO4 from T=(0 to 400) K

The molar heat capacity of Zn₂GeO₄, a material which exhibits negative thermal expansion below ambient temperatures, has been measured in the temperature range 0.5⩽(T/K)⩽400. At T=298.15 K, the standard molar heat capacity is (131.86 ± 0.26) J · K⁻¹ · mol⁻¹. Thermodynamic functions have been generated from smoothed fits of the experimental results. The standard molar entropy at T=298.15 K is (145.12 ± 0.29) J · K⁻¹ · mol⁻¹. The existence of low-energy modes is supported by the excess heat capacity in Zn₂GeO₄ compared to the sums of the constituent binary oxides.     

Heat capacities of the mixtures of ionic liquids with acetonitrile

Isobaric specific heat capacities were measured for {1-hexyl-3-methylimidazolium tetrafluoroborate (HMIMBF₄) + acetonitrile (MeCN)} and {1-methyl-3-octylimidazolium tetrafluoroborate (OMIMBF₄) + acetonitrile} within the whole range of composition and temperatures from (283.15 to 323.15) K. The excess molar heat capacities were calculated from the experimental results and satisfactorily fitted to Redlich–Kister type polynomials for several selected temperatures. Negative deviations from the additivity of molar heat capacities were observed within the whole composition range of (HMIBMF₄ + MeCN) and (OMIMBF₄ + MeCN). The results obtained have been interpreted in terms of interactions between ionic liquids and acetonitrile.     

The high-temperature heat capacity of LnPO4 (Ln = La,Ce, Gd) by drop calorimetry

The high-temperature heat capacity of three lanthanide orthophosphates of monazite structure have been measured in the temperature range (450 to 1570) K. The data have been analysed in terms of a lattice term, represented by the 4f⁰ and 4f⁷ compounds LaPO₄ and GdPO₄, and an electronic term for CePO₄. The calculated excess heat capacity thus obtained is in reasonable agreement with that calculated from the crystal field energies.     

Low-temperature thermodynamic properties of Ir(C5H7O2)3: Connection of entropy with the molecule volume for tris-acetylacetonates of metals

The heat capacity of Ir(C₅H₇O₂)₃ has been measured by the adiabatic method within the temperature range (5 to 305) K. The thermodynamic functions (entropy, enthalpy, and reduced Gibbs free energy) at 298.15 K have been calculated using the obtained experimental heat capacity data. A connection has been found between the entropy and the volume of the elementary crystalline cell for β-acetylacetonates of some metals. The reasons for this interdependence are discussed. The values of entropies at T = 298.15 K have been calculated for all the metal acetylacetonates on which there are structural data.     

The high-temperature heat capacity of ThPd3 and UPd3

The enthalpy increments of UPd₃ and ThPd₃ have been measured using the drop calorimetry for temperature range (480 to 1290) K. The heat capacity curves have been derived using the simultaneous linear regression of our data and the low temperature heat capacity data from previous studies. Furthermore the Schottky contributions for UPd₃ were determined by comparing the ThPd₃ and UPd₃ heat capacity functions and correlated with the theoretical values calculated from the crystal field energy levels.     

Heat capacities,third-law entropies and thermodynamic functions of the geometrically frustrated antiferromagnetic spinels GeCo2O4 and GeNi2O4 from T=(0 to 400) K

The molar heat capacities of GeCo₂O₄ and GeNi₂O₄, two geometrically frustrated spinels, have been measured in the temperature range from T=(0.5 to 400) K. Anomalies associated with magnetic ordering occur in the heat capacities of both compounds. The transition in GeCo₂O₄ occurs at T=20.6 K while two peaks are found in the heat capacity of GeNi₂O₄, both within the narrow temperature range between 11.4<(T/K)<12.2. Thermodynamic functions have been generated from smoothed fits of the experimental results. At T=298.15 K the standard molar heat capacities are (143.44 ± 0.14) J · K⁻¹ · mol⁻¹ for GeCo₂O₄ and (130.76 ± 0.13) J · K⁻¹ · mol⁻¹ for GeNi₂O₄. The standard molar entropies at T=298.15 K for GeCo₂O₄ and GeNi₂O₄ are (149.20 ± 0.60) J · K⁻¹ · mol⁻¹ and (131.80 ± 0.53) J · K⁻¹ · mol⁻¹ respectively. Above 100 K, the heat capacity of the cobalt compound is significantly higher than that of the nickel compound. The excess heat capacity can be reasonably modeled by the assumption of a Schottky contribution arising from the thermal excitation of electronic states associated with the CO²⁺ ion in a cubic crystal field. The splittings obtained, 230 cm⁻¹ for the four-fold-degenerate first excited state and 610 cm⁻¹ for the six-fold degenerate second excited state, are significantly lower than those observed in pure CoO.     

Heat capacities of aqueous solutions containing diethanolamine and N-methyldiethanolamine

In this work, we present new results for heat capacities of aqueous mixtures of diethanolamine with N-methyldiethanolamine over the temperature range (303.2 to 353.2) K with a differential scanning calorimeter. For mole fractions of water ranging from 0.2 to 0.8, 16 concentrations of the (DEA + MDEA + water) systems were investigated. For the binary system, (DEA + MDEA), heat capacities of nine concentrations were also measured. A Redlich–Kister-type equation for representing excess molar heat capacity was applied to correlate the measured C_p of aqueous alkanolamine solutions. For a total of 176 data points for the (DEA + MDEA + water) system, the overall average absolute percentage deviation of the calculations are 16.5% and 0.2% for the excess molar heat capacity and the molar heat capacity, respectively. The heat capacities presented in this study are, in general, of sufficient accuracy for most engineering-design calculations.     

Low temperature heat capacity Study of Fe(PO3)3 and Fe2P2O7

The heat capacities of two iron phosphates, Fe(PO₃)₃ and Fe₂P₂O₇, have been measured over the temperature range from (2 to 300) K using the heat capacity option of a Quantum Design Physical Property Measurement System (PPMS). A phase transition related to magnetic ordering has been found in the heat capacity at T = 8.76 K for Fe(PO₃)₃ and T = 18.96 K for Fe₂P₂O₇, which are comparable with literature values from magnetic measurements. By fitting the experimental heat capacity values, the thermodynamic functions, magnetic heat capacities, and magnetic entropies have been determined. Additionally, theoretical fits at low temperatures suggest that Fe₂P₂O₇ has an anisotropic antiferromagnetic contribution to the heat capacity and a large linear term likely caused by oxygen vacancies. Further data fitting in a series over widened temperature regions found that this linear term exists only below 15 K and disappears gradually from (15 to 17) K.     

Effect of the temperature on the physical properties of pure 1-propyl 3-methylimidazolium bis(trifluoromethylsulfonyl)imide and characterization of its binary mixtures with alcohols

In this paper, physical properties of a high purity sample of the ionic liquid 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [PMim][NTf₂], and its binary mixtures with methanol, ethanol, 1-propanol, and 2-propanol were measured at atmospheric pressure. The temperature dependence of density, refractive index and speed of sound (293.15 to 343.15) K and dynamic viscosity (298.15 to 343.15) K were studied at atmospheric pressure by conventional techniques for the pure ionic liquid. For its mixtures with alcohols, density, speed of sound, and refractive index were measured at T = 298.15 K over the whole composition range. The thermal expansion coefficient of the [PMim][NTf₂] was calculated from the experimental results using an empirical equation, and values of the excess molar volume, excess refractive index, and excess molar isentropic compressibility for the binary systems at the above mentioned temperature, were calculated and fitted to the Redlich–Kister equation. The heat capacity of the pure ionic liquid at T = 298.15 K was determined using DSC.     

Liquid heat capacity of the solvent system (piperazine + n-methyldiethanolamine + water)

A new set of values for the heat capacity of aqueous mixtures of piperazine (PZ) and n-methyldiethanolamine (MDEA) at different concentrations and temperatures are reported in this paper. The differential scanning calorimetry technique was used to measure the property over the range T = 303.2 K to T = 353.2 K for mixtures containing 0.60 to 0.90 mole fraction water with 15 different concentrations of the system (PZ + MDEA + H₂O). Heat capacity for four concentrations of the binary system (PZ + MDEA) was also measured. A Redlich–Kister-type equation was adopted to estimate the excess molar heat capacity, which was used to predict the value of the molar heat capacity at a particular concentration and temperature, which would then be compared against the measured value. A total of 165 data points fit into the model resulted in a low overall average absolute deviation of 4.6% and 0.3% for the excess molar heat capacity and molar heat capacity, respectively. Thus, the results presented here are of acceptable accuracy for use in engineering process design.     

The standard thermodynamic functions of fullerene chloride,C60Cl30

The heat capacity of a crystal solvate of fullerene chloride, C₆₀Cl₃₀·0.09 Cl₂, was measured by vacuum adiabatic calorimetry in the temperature range from (25 to 371.5) K. The thermodynamic functions (changes of the enthalpy, entropy, and Gibbs free energy) of C₆₀Cl₃₀·0.09 Cl₂ have been derived. On the basis of obtained data and the enthalpy of formation of C₆₀Cl₃₀ determined before, the entropy and Gibbs free energy of formation of the fullerene chloride were calculated at T = 298.15 K.     

Structural and electrochemical investigation of Li2MgSnO4 anode for lithium batteries

Hexagonal Li₂MgSnO₄ compound was synthesized at 800 °C using Urea Assisted Combustion (UAC) method and the same has been exploited as an anode material for lithium battery applications. Structural investigations through X-ray diffraction, Fourier Transform Infra Red spectroscopy and ⁷Li NMR (Nuclear Magnetic Resonance spectroscopy) studies demonstrated the existence of hexagonal crystallite structure with a = 6.10 and c = 9.75. An average crystallite size of ∼400 nm has been calculated from PXRD pattern, which was further evidenced by SEM images. An initial discharge capacity of ∼794 mA h/g has been delivered by Li₂MgSnO₄ anode with an excellent capacity retention (85%) and an enhanced coulombic efficiency (97–99%). Further, the Li₂MgSnO₄ anode material has exhibited a steady state reversible capacity of ∼590 mA h/g even after 30 cycles, thus qualifying the same for use in futuristic lithium battery applications.     

Heat capacity of hafnia at low temperature

The low temperature (2 to 300) K heat capacity of monoclinic hafnia (HfO₂) was measured using the heat capacity option of a Quantum Design Physical Property Measurement System (PPMS). The thermodynamic functions in this temperature range were derived by curve fitting. The standard entropy and enthalpy of hafnia at T = 298.15 K was calculated to be 56.15 ± 0.57 J · mol^?1 · K^?1 and 9.34 ± 0.09 kJ · mol^?1, respectively. The results are in fairly good agreement with old data, which only covered temperatures from (50 to 298) K. Hafnia has a higher heat capacity than zirconia at all temperatures from (2 to 300) K.     

High-temperature calorimetry of (La1−xLnx)PO4 solid solutions

The enthalpy increment of the monazite-type solid solutions of LaPO₄ with NdPO₄, EuPO₄ and GdPO₄ has been measured by drop calorimetry at T = 1000 K. The results show deviations (excess enthalpy) from ideal behaviour that have been interpreted in terms of lattice strains resulting from the ion size effects of substitution of La³⁺ by Ln³⁺. For (La_0.5Gd)_0.5PO₄ also the temperature dependence has been determined for T = (515 to 1565) K, indicating that the excess enthalpy decreases with increasing temperature.     

Calorimetric analysis of NaF and NaLaF4

Heat flux calorimetry was used to measure the heat capacity of NaF between 630 K and 1100 K. The results agreed well with previous measurements known from the literature. Similar experiments were performed on NaLaF₄. This compound was synthesized from NaF and LaF₃ and analyzed by X-ray diffraction. The heat capacity of NaLaF₄ was determined for two temperature ranges: from 4 K to 400 K, for which adiabatic calorimetry, and from 623 K to 1213 K for which differential scanning heat flux calorimetry was used. The two heat capacity series fit smoothly; the resulting C_p,m function was used in a reassessment of the binary system (NaF + LaF₃).     

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.     

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.     

Densities,excess volumes,isobaric expansivity,and isothermal compressibility of the (1-ethyl-3-methylimidazolium ethylsulfate + methanol) system at temperatures (283.15 to 333.15) K and pressures from (0.1 to 35) MPa

Densities of pure 1-ethyl-3-methylimidazolium ethylsulfate ionic liquid – [C₂mim][EtSO₄] and its mixtures with methanol have been measured with an accuracy of ±0.2 kg · m^?3, over the temperature range (283.15 to 333.15) K and pressure range (0.1 to 35) MPa, using a vibrating tube densimeter. Excess volumes have been calculated directly from the experimental densities. The latter data have been correlated by the Tait equation with the temperature dependent parameters for the pure ionic liquid and by a van Laar-type equation, involving parameters dependent on temperature and pressure for the mixtures. The isobaric expansivity, isothermal compressibility, and related excess properties have been calculated. The exceptionally strong influence of pressure and temperature on these properties has been observed.     

Size-dependence of the heat capacity and thermodynamic properties of hematite (α-Fe2O3)

The heat capacity of a 13 nm hematite (α-Fe₂O₃) sample was measured from T = (1.5 to 350) K using a combination of semi-adiabatic and adiabatic calorimetry. The heat capacity was higher than that of the bulk which can be attributed to the presence of water on the surface of the nanoparticles. No anomaly was observed in the heat capacity due to the Morin transition and theoretical fits of the heat capacity below T = 15 K show a small T³ dependence (due to lattice contributions) with no T^3/2 dependence. This suggests that there are no magnetic spin-wave contributions to the heat capacity of 13 nm hematite. The use of a large linear term to fit the heat capacity below T = 15 K is most likely due to superparamagnetic contributions. A small anomaly within the temperature range (4 to 8) K was attributed to the presence of uncompensated surface spins.     

Volumes,heat capacities,and compressibilities of the mixtures of acetonitrile and 2-methoxyethanol

Heat capacities and speed of sound of (acetonitrile + 2-methoxyethanol) mixtures at 298.15 K and the densities of the same mixtures at T = (308.15 and 318.15) K were determined over the whole composition range. The excess of molar volume and isobaric heat capacity of the mixture, the partial molar volumes and heat capacities of both components of the mixture as well as the adiabatic and isothermal coefficients of compressibility and their excess were calculated from the obtained experimental data. The internal pressure of the examined system was also calculated. The results of investigations were analyzed and discussed. The behavior of the analyzed functions is similar to that observed in the case of the mixtures of acetonitrile with some aprotic solvents examined earlier.