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.     

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.     

Thermodynamic study of the sublimation of crystalline tris(1,1,1-trifluoro-2,4-pentanedionate)ruthenium(III) and tris(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate)ruthenium(III)

The Knudsen mass-loss effusion technique was used to measure the vapour pressures at different temperatures of two crystalline ruthenium complexes: tris(1,1,1-trifluoro-2,4-pentanedionate)ruthenium(III) {Ru(tfacac)₃}, between T =  350.20 K and T =  369.17 K and tris(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate)ruthenium(III) {Ru(hfacac)₃} between T =  299.15 K and T =  313.14 K. From the temperature dependence of the vapour pressure of the crystalline compounds, the standard molar enthalpies of sublimation were derived by the Clausius–Clapeyron equation and the molar entropies of sublimation at equilibrium pressures were calculated. By using an estimated value for the heat capacity differences between the gas and the crystal phases the standard, p^o =  10⁵Pa, molar enthalpies, entropies, and Gibbs energies of sublimation at T =  298.15 K, were derived:     

An experimental setup for isobaric heat capacities for viscous fluids at high pressure: Squalane,bis(2-ethylhexyl) sebacate and bis(2-ethylhexyl) phthalate

A high-pressure flow calorimeter has been used to determine highly accurate isobaric heat capacities for different viscous fluids, squalane (SQN), bis(2-ethylhexyl) sebacate (DEHS) and bis(2-ethylhexyl) phthalate (DEHP) from T = (293.15 to 353.15) K and up to 30 MPa. The experimental device was adapted for viscous liquids at high pressure and it can measure heat capacities with an estimated total uncertainty better than 1%. The isobaric heat capacity values were analysed together with their temperature and pressure dependences. In addition, a fitting equation of the experimental molar isobaric heat capacity for these viscous fluids as a function of temperature and pressure was proposed.     

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.     

Calorimetric measurements and first principles to study the (Ag-Li) liquid system

Integral molar enthalpies of mixing were determined by drop calorimetry for (Ag-Li) liquid alloys at two temperatures (1253 and 873) K. The integral molar enthalpies of mixing are negative in the entire range of concentrations. For the mole fraction of lithium X_Li = 0.5664, minimum value of the integral enthalpy of mixing of at ΔH_m = −11.679 kJ/mol was observed. For (Ag-Li) liquid alloys, between T = (873 and 1253) K no temperature dependence was observed. Ab initio molecular dynamics was used to simulate liquid phase structures at T = 873 K (Li-rich side) and at T = 1250 K (Ag-rich phase) for subsequent calculation of the vibrational energy, respectively. Our measured and calculated data were compared with literature data.     

Thermal properties of [Cr(NH3)6](BF4)3 studied by adiabatic and relaxation calorimetry

Four (solid–solid) phase transitions were detected in the temperature range of (9 to 300) K in polycrystalline [Cr(NH₃)₆](BF₄)₃ at T_C1 = 240.7 K, T_C2 = 108.0 K, T_C3 = 91.9 K, and T_C4 = 61.3 K by adiabatic calorimetry. The measurements by relaxation calorimetry were followed on lowering temperature from 20 K down to 0.35 K under six different external magnetic field values (9, 7, 5, 3, 1 and 0) T. For non-zero values of applied magnetic field well-defined Schottky anomaly appears. Magnetic heat capacity was calculated assuming the zero-field splitting for the decoupled Cr(III) ions. There is no discrepancy between the observed and calculated values. Isothermal magnetization curve recorded up to 5 T was measured at temperature of 1.8 K.     

Physicochemical properties of {1-methyl piperazine (1) + water (2)} system at T = (298.15 to 343.15) K and atmospheric pressure

Densities (ρ) and viscosities (η) of aqueous 1-methylpiperazine (1-MPZ) solutions are reported at T = (298.15 to 343.15) K. Refractive indices (n_D) are reported at T = (293.15 to 333.15) K, and surface tensions (γ) are reported at T = (298.15 to 333.15) K. Derived excess properties, except excess viscosities (Δη), are found to be negative over the entire composition range. The addition of 1-MPZ reduces drastically the surface tension of water. The temperature dependence of surface tensions is explained in terms of surface entropy (S^S) and enthalpy (H^S). The measured and derived properties are used to probe the microscopic liquid structure of the bulk and surface of the aqueous amine solutions.     

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 thermodynamic properties of DyBr3(s) and DyI3(s) from T=5 K to their melting temperatures

Low-temperature calorimetric measurements have been performed on DyBr₃(s) in the temperature range (5.5 to 420 K ) and on DyI₃(s) from T=4 K to T=420 K. The data reveal enhanced heat capacities below T=10 K, consisting of a magnetic and an electronic contribution. From the experimental data on DyBr₃(s) a C⁰_p,m (298.15 K) of (102.2±0.2) J·K⁻¹·mol⁻¹ and a value for {S⁰_m (298.15 K) − S⁰_m (5.5 K)} of (205.5±0.5) J·K⁻¹·mol⁻¹, have been obtained. For DyI₃(s), {S⁰_m (298.15 K) − S⁰_m (4 K)} and C⁰_p,m (298.15 K) have been determined as (226.9±0.5) J·K⁻¹·mol⁻¹ and (103.4±0.2) J·K⁻¹·mol⁻¹, respectively. The values for {S⁰_m (5.5 K) − S⁰_m (0)} for DyBr₃(s) and {S⁰_m (4 K) − S⁰_m (0)} for DyI₃(s) have been calculated, giving S⁰_m (298.15 K)=(212.3±0.9) J·K⁻¹·mol⁻¹ in case of DyBr₃(s) and S⁰_m (298.15 K) =(233.1±0.7) J·K⁻¹·mol⁻¹ for DyI₃(s). The high-temperature enthalpy increment has been measured for DyBr₃(s) in the temperature range (525 to 799 K) and for DyI₃(s) in the temperature range (525 to 627 K). From the results obtained and enthalpies of formation from the literature, thermodynamic functions for DyBr₃(s) and DyI₃(s) have been calculated from T→0 to their melting temperatures at 1151.0 K and 1251.5 K, respectively.     

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.     

PVT,viscosity, and surface tension of ethanol: New measurements and literature data evaluation

In this work, the results of density, viscosity, and surface tension measurements for ethanol are presented. Ethanol with stated mass fraction purity greater than 0.998 was further purified using molecular sieves. Density was measured within the temperature and pressure ranges, respectively, T = (278.15 to 353.15) K and p = (0.1 to 35) MPa by means of a vibrating tube densimeter, model DMA 512P from Anton Paar with an estimated uncertainty of ±0.5 kg · m^?3. The experimental (p, ρ, T) results have been correlated by Tait equation. From this equation the isobaric expansivity, the isothermal compressibility, and the thermal pressure coefficient have been calculated. Viscosity was measured over the range T = (273.15 to 346.15) K using an Ubbelohde viscometer with a Schott–Geräte automatic measuring unit (Model AVS-470) with the associated uncertainty of ±0.001 mPa · s. The measured values were combined with selected values from the literature covering the range T = (223 K to 503) K, and the VTF model has been fitted to all the data. The surface tension of the liquid was measured using a tensiometer KSV Sigma 70 with a Du-Noüy ring for the range of T = (274.77 to 318.99) K with an uncertainty of ±0.01 mN · m^?1. Using these data and critically assessed data of other authors compiled from the literature, a form of the IAPWS equation was used to correlate the surface tension within the temperature range 223 K up to the critical temperature.     

Thermophysical properties of hydroxyl ammonium ionic liquids

The thermophysical properties of hydroxyl ammonium ionic liquids: density ρ, T = (293.15 to 363.15) K; dynamic viscosity η, T = (298.2 to 348.2) K; and refractive indices n_D, T = (293.15 to 333.15) K have been measured. The coefficients of thermal expansion α, values were calculated from the experimental density results using an empirical correlation for T = (293.15 to 363.15) K. The variation of volume expansion of ionic liquids studied was found to be independent of temperature within the range covered in the present work. The thermal decomposition temperature ‘T_d’ for all the six hydroxyl ammonium ionic liquids is also investigated using thermogravimetric analyzer (TGA).     

Physical properties of (jojoba oil + n-hexane) compared with other (vegetable oil + n-hexane) mixtures

Vapour pressures, densities, and viscosities of (jojoba oil + n-hexane) were measured and correlated over the temperature interval (298.15 to 318.15) K and used to calculate the activity coefficients of the components, excess thermodynamics functions, excess molar volumes, isobaric thermal expansibilities, excess viscosities, and the excess Gibbs free energies of activation for viscous flow. The reported results are compared with the corresponding values for commercial (oil + n-hexane) mixtures (cottonseed, soybean, sunflower, corn, olive, grape pip, Vaseline, and linalool oils) reported in the literature. As a by-product of this investigation, the vapour pressures of 1-methoxy-2-propanol from T = (298 to 392) K, 2-ethyl-6-methylaniline from T = (313 to 448) K, and N-methoxyisopropanol-6-ethyl-2-methylaniline from T = (407 to 535) K were measured using an ebulliometric method. A remarkable similarity between the excess properties for all oils is observed, but the behaviour of the excess thermodynamic functions in the case of (n-hexane + jojoba oil), especially in the n-hexane rich region, is quite different.     

Phase transitions and thermodynamic properties of (NH4)3VO2F4 cryolite

Calorimetric measurements performed in a wide temperature range on (NH₄)₃VO₂F₄ have shown the presence of four heat capacity anomalies at T₁ = 438 K, T₂ = 244 K, T₃ = 210.2 K, T₄ = 205.1 K associated with the first order phase transitions. In accordance with the permittivity behavior, the structural transformations are of nonferroelectric nature. Pressure dependence of the phase transition temperatures has been studied by DTA under pressure. The entropy of phase transitions is analyzed mainly in the framework of the orientational disordering of NH₄⁺ and VO₂F₄^3? ions in a cubic phase.     

Heat capacities and thermodynamic functions of hexagonal ice from T = 0.5 K to T = 38 K

The heat capacity of water in the form of hexagonal ice was measured between T = 0.5 K and T = 38 K using a semi-adiabatic calorimetric method. Since heat capacity data below T = 2 K have never been measured for water, this study presents the lowest measured values of the specific heat of water to date. Fits of the data were used to generate thermodynamic functions of water at smoothed temperatures between 0.5 K and 38 K. Both our experimental heat capacities and calculated enthalpy increments agree well with previously published values and thus supplement other studies well.     

Measurements of the viscosity of carbon dioxide at temperatures from (253.15 to 473.15) K with pressures up to 1.2 MPa

The viscosity of carbon dioxide was measured over the temperature range T = (253.15 to 473.15) K with pressures up to 1.2 MPa utilizing a new rotating-body viscometer. The relative expanded combined uncertainty (k = 2) in viscosity (including uncertainties of temperature and pressure) was (0.20 to 0.41)%. The instrument was specifically designed for measurements at low gas densities and enables measurements of the dynamic viscosity at temperatures between T = 253.15 K and T = 473.15 K with pressures up to 2 MPa. For carbon dioxide, the fluid specific measuring range with regard to pressure was limited to 1.2 MPa due to the formation of disturbing vortices inside the measuring cell at higher pressures. The model function for the viscosity measurement was extended in such a way that the dynamic viscosity was measured relative to helium. Therefore, the influence of the geometry of the concentric cylindrical system inside the measuring cell became almost negligible. Moreover, a systematic offset resulting from a small but inevitable eccentricity of the cylindrical system was compensated for. The residual damping, usually measured in vacuum, was calibrated in the entire temperature range using viscosity values of helium, neon and argon calculated ab initio; at T = 298.15 K recommended reference values were used. A viscosity dependent offset of the measured viscosities, which was observed in previously published data, did not occur when using the calibrated residual damping. The new carbon dioxide results were compared to other experimental literature data and to the correlation, which is currently considered the reference for viscosities of carbon dioxide.     

Dichloromethane: Revision and extension of pρT relationships for the liquid

In spite of the great importance of the PVT data of dichloromethane, only limited information on these data seems to be available in the literature. In this work, we present experimental densities of the liquid dichloromethane over the ranges T = (270 to 330) K and p = (0.1 to 30) MPa using a vibrating tube densimeter, model DMA 512P from Anton Paar with an estimated uncertainty lower than ±0.5 kg · m^?3. The high consistency of our data compared with those measured by other authors allows that all the experimental results have been combined and correlated together with the Tait equation in the temperature and pressure ranges T = (244 to 430) K and p = (0.1 to 101) MPa. From the Tait equation, thermomechanical coefficients as the isothermal compressibility, isobaric expansivity, thermal pressure, and internal pressure were calculated. Some of the measurements of density were made at pressures lower than the critical pressure which enabled us to obtain very reliable values for the density of the saturated liquid within the range T = (270.0 to 330.0) K. These data were combined with other values existing in the literature, which made it possible to extend the information on the saturated liquid density to the range T = (208 to 399) K. From these data, a new equation describing the saturated liquid density of dichloromethane was found covering the entire temperature range between the triple and the critical temperatures. A new equation for the vapour pressure was found by using selected values from the literature covering the entire temperature range between the triple and the critical temperatures.     

High-temperature calorimetry of zirconia: Heat capacity and thermodynamics of the monoclinic–tetragonal phase transition

The high-temperature heat capacity of zirconia was directly measured by differential scanning calorimetry between T = (1050 and 1700) K and derived from the heat content measured by transposed temperature drop calorimetry between T = (970 and 1770) K, including the monoclinic–tetragonal (m–t) phase transition region. The enthalpy and entropy of the m–t phase transition are (5.43 ± 0.31) kJ · mol⁻¹ and (3.69 ± 0.21) J · K⁻¹ · mol⁻¹, respectively. Values of thermodynamic functions are provided from room temperature to 2000 K.