Heat capacity and thermodynamic functions of MnBr2 · 4D2O and MnCl2 · 4D2O

The heat capacities of MnBr₂ · 4D₂O and MnCl₂ · 4D₂O have been experimentally determined from 1.4 to 300 K. The smoothed heat capacity and thermodynamic functions (H°_TH°₀) and S°_T are reported for the two compounds over the temperature range 10 to 300 K. The error in the thermodynamic functions at 10 K is estimated to be 3%. Additional error in the tabulated values arising from the heat capacity data above 10 K is thought to be less than 1%. A λ-shaped heat capacity anomaly was observed for MnCl₂ · 4D₂O at 48 K. The entropy associated with the anomaly is 1.2 ± 0.2 J/mole K.     

Heat capacity and thermodynamic functions of theRFe2 compounds (R =Gd,Tb, Dy,Ho, Er,Tm, Lu) over the temperature region 8 to 300 K

Experimental heat capacity data for the Laves phaseRFe₂ intermetallic compounds (R =Gd, Tb, Dy, Ho, Er, Tm, and Lu) have been determined over the temperature range 8 to 300 K. The error in these data is thought to be less than 1%. Smoothed heat capacity values and the thermodynamic functions, (H°_T ? H°₀) and S°_T, are reported throughout the temperature range for theRFe₂ series. In addition, (G°₂₉₈ ? H°₀) at 298 K is reported for all theRFe₂ compounds. These data were analyzed and it was shown that the maxima in the thermodynamic functions near HoFe₂ are due to the magnetic contribution of the lanthanide element. The lattice contribution to the entropy at 300 K was estimated, and from this quantity the Debye temperature was calculated to be about 300 K, which is in good agreement with the low-temperature heat capacity. Furthermore, this analysis indicates that the apparent electronic specific heat constants, γ′, for TbFe₂, DyFe₂, and HoFe₂, reported earlier, are in error.     

Thermodynamic properties of α-platinum dichloride

The heat capacity of crystalline α-platinum dichloride was measured for the first time in the temperature intervals from 11 to 300 K (vacuum adiabatic microcalorimeter) and from 300 to 620 K (differential scanning calorimetry). In the 300–620 K temperature interval, the C° _p values for α-PtCl₂ (cr) coincide with the heat capacity of CrCl₂ (cr) within the limits of experimental error, which made it possible to estimate the heat capacity of α-PtCl₂ (cr) at higher temperatures. The approximating equation of the temperature dependence of the heat capacity in the interval from 298 to 900 K C° _p (±0.8) = 63.5 + 21.4·10⁻³ T + 0.883·10⁵/T ² (J mol⁻¹ K⁻¹) was derived using the experimental values, as well as the literature data on the heat capacity of CrCl₂ (cr). For the standard conditions, the C° _p,298.15 and S°_298.15 values are 70.92±0.08 and 100.9±0.33 J mol⁻¹ K, respectively; H°_298.15 − H°₀ = 14 120±42 J mol⁻¹. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1136–1138, June, 2008.     

The Entropies of n-Heptane,n-Octane,n-Nonane,and n-Undecane over a Wide Range of the Liquid and Gaseous States

The entropies S of C₇–C₁₁ normal alkanes over the temperature and pressure ranges 300–620 K and 0.5–60 MPa were obtained by the integration of the experimental isobars of isobaric heat capacity C _p . The C _p data were obtained using a flow adiabatic calorimeter with calorimetric flow rate measurements. The entropy values were determined up to critical temperatures by extrapolation from the sides of liquid S′ and gas S″ phases. The p-T-S thermodynamic surfaces of the alkanes under consideration in the liquid and gas phases were constructed. A generalized temperature dependence of S′ and S″ was determined for the homologous series over the temperature range from the triple to critical point within the framework of similarity theory.     

The apparent molar heat capacities and volumes of aqueous NaCl from 0.01 to 3 mol kg−1 in the temperature range 274.65 to 318.15 K

The heat capacities per unit volume of aqueous solutions of NaCl were measured with a flow microcalorimeter. The molality and temperature range covered were 0.01 to 3 mol kg^?1 and 274.65 to 318.15 K. The derived apparent molar heat capacities C₂, φ, when extrapolated to infinite dilution, give standard partial molar heat capacities C₂^o which are in excellent agreement with those of Criss and Cobble. The excess apparent molar heat capacities (C₂, φ - C₂^o) can be used to predict the temperature dependence of (H₂, φ - H₂^o), the excess apparent molar enthalpy. The calculated values of ΔH₂, φ agree within experimental uncertainty with the integral enthalpies of dilution of Ensor and Anderson and of Messikomer and Wood up to 323.15 K. Above this temperature significant differences are observed. The densities of the solutions were also remeasured in the same range of temperature and molality with a flow densimeter, and the derived apparent molar volumes agree with the literature values.     

Thermodynamic properties of carbon dioxide derived from the speed of sound

Thermodynamic properties of CO₂ are derived from speed of sound in the temperature range 300 to 360 K (from 0 to 6 MPa), and 300 to 220 K (from 0 to 90% of the saturation pressure). The density, the specific heat capacity at constant pressure, and the specific heat capacity at constant volume are obtained by numerical integration of differential equations connecting the speed of sound with other thermodynamic properties. The set of differential equations is solved as the initial value problem, with the initial values specified along the isotherm at 300 K in terms of several accurate values of the density and the specific heat capacity at constant pressure. The density, the specific heat capacity at constant pressure and the specific heat capacity at constant volume are derived with the absolute average deviations of 0.018%, 0.19%, and 0.18%, respectively. The results of numerical integration are extrapolated to the saturation line for ρ, c _p , and c _v with the absolute average deviations of 0.056%, 2.31%, and 1.32%, respectively.     

Standard enthalpy and heat capacity of solid tin telluride

The published data on the heat capacity of tin telluride were analyzed. The C _p values were demonstrated to be consistent only at temperatures below 56 K. Some data on the heat capacity of SnTe within 80–453 K were found to differ significantly. The heat capacity C _p was measured on a DSM-2M calorimeter within a temperature range of 350–600 K and other thermodynamic functions of tin telluride were calculated.     

Researches by the method of low-temperature adiabatic calorimetry and quantum chemical computation of vibrational states

The temperature dependence of heat capacity of a natural zinc silicate, hemimorphite Zn₄Si₂O₇(OH)₂·H₂O, over the temperature range 5–320 K has been investigated by the method of low-temperature adiabatic calorimetry. On the basis of the experimental data on heat capacity over the whole temperature interval, its thermodynamic functions C _p (T), S(T) and H(T) ? H(0) have been calculated. The existence of a phase transition in the area of 90–105 K determined on the basis of vibrational spectra has been confirmed, and changes of entropy ΔS _tr. and enthalpy ΔH _tr. of the phase transition have been calculated. Hemimorphite heat capacity has also been determined by the calculation methods according to the valence force field model in LADY program. The values of force constants of valence bonds and angles have been calculated by semi-empirical method PM5. The calculated IR and Raman spectra concordant with the experimental spectra have been obtained. The heat capacity values calculated according to the found vibrational states satisfactorily agree with those experimentally obtained with an accuracy of ±1.7% in the area of 120–200 K, and not more than ±0.8% for the interval of 200–300 K. This fact testifies that the calculation of thermodynamic characteristics is correct.     

Low-temperature heat capacities and thermodynamic properties of rare-earth triisothiocyanate hydrates (III) —Sm(NCS)3 · 6H2O, Gd(NCS)3 · 6H20, Yb(NCS)3 · 6H20 and Y(NCS)3 · 6H20

The heat capacities of four RE isothiocyanate hydrates, Sm(NCS)₃, · 6H₂0, Gd(NCS)₃ · 6H₂0, Yb(NCS)₃, · 6H₂O and Y(NCS)₃, · 6H₂0, have been measured from 13 to 300 K with a fully-automated adiabatic calorimeter. No obvious thermal anomaly was observed for the above-mentioned compounds in the experimental temperature ranges. The polynomial equations for calculating the heat capacities of the four compounds in the range of 13–300 K were obtained by the least-squares fitting based on the experimentalC _P, data. TheC _P, values below 13 K were estimated by using the Debye-Einstein heat capacity functions. The standard molar thermodynamic functions were calculated from 0 to 300 K. Gibbs energies of formation were also calculated. Project supported by the National Natural Science Foundation of China.     

Thermodynamics of 2D polymerized tetragonal phase of fullerene C60 in the range from T→0 to 650 K at standard pressure

By dynamic calorimetry the temperature dependence of heat capacity for two-dimensional (2D) polymerized tetragonal phase of C₆₀ has been determined over the 300-650 K range at standard pressure mainly with an uncertainty ±1.5%. In the range 490-550 K, an irreversible endothermic transition of the phase, caused by the depolymerization of the polymer, has been found and characterized. Based on the experimental data obtained and literature information, the thermodynamic functions of 2D polymerized tetragonal phase of C₆₀, namely, the heat capacity C°_p(T), enthalpy H°(T)−H°(0), entropy S°(T), and Gibbs function G°(T)−H°(0), have been calculated over the range from T→0 to 490 K. From 150 to 330 K in an adiabatic vacuum calorimeter and between 330 and 650 K in a dynamic calorimeter the thermodynamic properties of the depolymerization products have been examined and compared with the corresponding data for the monomeric phase C₆₀.     

Measurements of the isochoric heat capacity,the critical point (TC, ρC) and vapor–liquid coexistence curve (TS, ρS) of high-purity toluene near the critical point

Isochoric heat capacities (C_V, V, T), phase boundary properties (T_S, ρ_S) and the critical (T_C, ρ_C) parameters for high-purity (0.9999+ mole fraction) toluene have been measured with a high temperature, high pressure, nearly constant volume adiabatic calorimeter and quasi-static thermogram technique. Measurements were made at three selected liquid and vapor isochores 777.8, 555.25, and 214.64 kg m⁻³ in the temperature range from 379 to 591 K. For five near-critical isochores 268.68, 281.68, 296.62, 301.52, and 318.28 kg m⁻³, the measurements were made in the immediate vicinity of the coexistence curve in order to accurately determine the phase transition temperatures (T_S, ρ_S) (shape of the coexistence curve near the critical point) and the critical parameters (T_C, ρ_C). The total combined uncertainty of heat capacity, density, and temperature measurements were estimated to be less than 2%, 0.06%, and 15 mK, respectively. The uncertainties reported in this paper are expanded uncertainties at the 95% confidence level with a coverage factor of k = 2. The uncertainty of the phase transition and the critical temperature value was 0.02 K. The Krichevskii parameter for some toluene-containing binary mixtures was calculated. The derived values of the Krichevskii parameter were used to estimate the effect of dilute impurities on the critical parameters of toluene. The measured values of saturated density near the critical point were interpreted in terms of the “complete scaling” theory in order to study singularity behavior of the coexistence curve diameter. The measured isochoric heat capacities and saturated densities were compared with the data reported by other authors and values calculated from an equation of state and other correlations.     

Heat capacity and thermodynamic functions of MnBr2 · 4H2O and MnCl2 · 4H2O

The heat capacities of MnBr₂ · 4H₂O and MnCl₂ · 4H₂O have been experimentally determined from 10 to 300 K. The smoothed heat capacity and the thermodynamic functions (H°_TH°₀) andS°_T are reported for the two compounds over the temperature range 10 to 300 K. The error in these data is thought to be less than 1%. A subtle heat capacity anomaly was observed in MnCl₂ · 4H₂O over the temperature range 52 to 90 K. The entropy associated with the anomaly is of the order 0.4 J/mole K.     

Determination of specific heat capacity and standard molar combustion enthalpy of taurine by DSC

Using XRY-1C calorimeter, the standard molar enthalpy of taurine was determined to be ?2546.2?kJ?mol^?1 . The reliability of the instrument used was tested by using naphthalene as reference material; and through comparing the molar combustion enthalpy of naphthalene measured with its standard value found in literature, the absolute error and relative error were found to be 4.53?kJ?mol^?1 and 0.09%, respectively. The melting point and melting enthalpy of taurine were determined by Differential Scanning Calorimetry (DSC), which was found to be 588.45?K and ?22.197?kJ?mol^?1, respectively. Moreover, using the DSC method, the specific heat capacities C _p of taurine was measured and the relationship between C _p and temperature was established. The thermodynamic basic data obtained are available for the exploiting new synthesis method, engineering design and industry production of taurine.     

Temperature dependence of the thermophysical properties of polycrystallene chalcogenide glasses

The specific heat (C _p), thermal conductivity (λ), thermal diffusivity (a), and electrical conductivity (σ) were measured for polycrystalline HgS and Sb₂S₃ in the temperature range 300–600 K. The measurements were performed with an experimental apparatus based on a socalled flash method. The results showed that the mechanism of heat transfer is mainly due to phonons, whereas the contribution of electrons and bipolars is very small indeed. The energy gap of the samples was also calculated.     

Heat capacities and electrical conductivities of 1-ethyl-3-methylimidazolium-based ionic liquids

We present the heat capacities and electrical conductivities of five [Emim] 1-ethyl-3-methylimidazolium-based ionic liquids: [Emim][BF₄] (tetrafluoroborate), [Emim][CF₃SO₃] (trifluoromethanesulfonate), [Emim][C₂N₃] (dicyanamide), [Emim][C₂H₅SO₄] (ethylsulfate), and [Emim][MDEGSO₄] (2-(2-methoxyethoxy) ethylsulfate). The heat capacities were measured using a differential scanning calorimeter (DSC) over the temperature ranging from (303.2 to 358.2) K. The electrical conductivities were measured over the temperature ranging from (293.2 to 353.2) K using a commercial conductivity meter. The estimated uncertainties of heat capacity C_p and electrical conductivity σ measurements were ±0.015 kJ · kg^?1 · K^?1 and ±0.001 mS · cm^?1, respectively. The measured C_p and σ are presented as a function of temperature. The temperature dependency of the C_P value was correlated using an empirical equation. A modified version of VTF-type (Vogel–Tamman–Fulcher) equation was used to describe the temperature dependency of σ values. The correlations give satisfactory results. Also, the results of this study are in good agreement with the available literature data. The heat capacities and electrical conductivities presented in this work are in good agreement with the available literature data. The results of this study can be applied to numerous chemical processes, since C_p and σ data are essential information for rational design.     

Heat capacity (Cp) and entropy of olivine-type LiFePO4 in the temperature range (2 to 773) K

The heat capacity of olivine-type lithium iron phosphate (LiFePO₄ – LFP) has been measured covering a temperature range from (2 to 773) K. Three different calorimeters were used. The Physical Property Measurement System (PPMS) from Quantum Design was applied in the range between T = (2 and 300) K, a Micro-DSC II from Setaram within the range between T = (283 and 353) K and data between T = (278 and 773) K were measured by means of a Sensys DSC (Setaram) using the Cp-by-step method. Experimental data are given with an error of (1 to 2)% above T = 20 K and up to 8% below 20 K. The data were subdivided into appropriate temperature intervals and fitted using common heat capacity functions. The low temperature results permit the calculation of standard entropies and temperature coefficients of electronic, lattice, as well as magnetic (antiferromagnetic transition at T = 49.2 K) contributions to the heat capacity. The obtained experimental values were compared to results of a recently published first principles phonon study (DFT) and to few available experimental data from the literature.     

The heat capacity of lead from 300 to 850°k: conversion of cp to cv for liquid lead

Abstract

Recent measurements of the heat capacity at constant pressure C_p for lead from 300 to 850°K have shown that C_p for liquid lead decreases continuously from the melting point to 850°K. Using data in the literature of density and velocity of sound, the dilation correction has been applied to C_p to obtain the heat capacity at constant volume C_v for liquid lead. Application of the dilation correction to solid lead gives a C_v curve which uncreases only about one joule/gm-atom-°K from 300 to 600°K, whereas the C_v curve for liquid lead decreases almost 5 joules/gm-atom-°K from 600 to 850°K. A careful assessment of the uncertainty in the quantities used in the dilation correction leads to an uncertainty in C_v of ± 2.5% (about one joule/gm-atom-°K), and thus the decrease in C_v for liquid lead is quite real.     

Low-temperature heat capacity and thermodynamic parameters of γ-aminobutyric acid

Thermodynamic properties of γ-aminobutyric acid were studied in the temperature interval from 5.7 to 300 K using a vacuum adiabatic calorimeter. The curve C _p (T) in the mentioned temperature interval is S-shaped without any anomalies. Based on the smoothed values of heat capacity, the calorimetric entropy $ S_{m}^{0} (T) - S_{m}^{0} (0) $ and the difference in the enthalpies $ H_{m}^{0} (T) - H_{m}^{0} (0) $ were calculated and tabulated. At the standard temperature 298.15 K, these values are equal to 158.1 ± 0.3 J K^?1 mol^?1 and 23020 ± 50 J mol^?1, respectively. At temperatures from 5 to 10 K, the function C _p (T) was found to obey the Debye law C = AT ³. Contrary to what has been supposed previously, the empirical Parks–Huffman rule for estimating entropy in the homologous series was shown to be not valid for the series glycine–β-alanine–γ-aminobutyric acid.     

The heat capacity of titanium di-and tetrachloride over the temperature range 7-314 K

The temperature dependences of the heat capacities of titanium di-and tetrachloride were studied by vacuum adiabatic calorimetry. The parameters of fusion (T _tr, Δ_tr H, and Δ_tr S) were determined for TiCl₄. The thermodynamic functions of the substances were calculated over the temperature range 10–300 K. The results obtained were compared with literature data.     

Study on thermodynamic properties of glyphosate by oxygen-bomb calorimeter and DSC

The combustion enthalpy of glyphosate was determined by XRY-1C oxygen-bomb calorimeter at a constant volume. The standard mole combustion enthalpy and the standard mole formation enthalpy have been calculated to be ?1702.19 and ?1478.36 kJ mol^?1, respectively. For testing the reliability of instrument, glycine and naphthalene were used as reference materials by comparing the measured values with the literature values, the absolute error and relative error are 2.58 kJ mol^?1 and 0.26 % for glycine, respectively, and these of naphthalene are 4.08 kJ mol^?1 and 0.08 %, respectively. Moreover, the constant-pressure heat capacities c _p of glyphosate were measured by differential scanning calorimetry in the temperature range 303.15–365.15 K, and the relationship between c _p and temperature was established. These related studies can provide a thermodynamic basis for their further application.