Heat capacity of gold from 80 to 1000 K

The heat capacity of gold has been measured by laserflash calorimetry in the temperature range 80–1000 K. The results are compared with available low- and high-temperature heat capacities, and revised thermodynamic values of gold are given.     

Heat capacity of a polydiacetylene single crystal from 3 to 300 K

Heat capacities C_p of a polydiacetylene-bis(toluene sulfonate) single crystal and its monomer have been measured in the temperature range from 3 to 300 K. The temperature dependence of C_p for both monomer and polymer crystals differs from that for monoatomic solids. By applying a chain lattice model for a polymer crystal, the temperature dependence of the heat capacity can be described assuming a phonon density of states given by bending and stretching modes of the polymer backbone. With a combination of one-dimensional and three-dimensional elastic continuum approximations, the heat capacity has been calculated and a good fit to the data has been obtained. A small peak in C_p was detected at 161 K for the monomer and at 198 K for the polymer. This may be ascribed to a lower-temperature phase transition in the polydiacetylene crystals evidenced by previous x-ray and spectroscopic measurements.     

Heat capacity and other thermodynamic properties of CoTe2 from 5 to 1 030 K and of CoTe2.315 from 300 to 1 040 K

The heat capacity of orthorhombic (marcasite-type structure) cobalt ditelluride has been measured from 5 to 1 030 K by adiabatic-shield calorimetry with alternate energy inputs and equilibrations. Above 900 K a marked increase in heat capacity occurs which probably signals a change in the composition of the CoTe₂-phase towards higher tellurium content. Values at 298.15 and 1 000 K in J K^–1 mol^–1 of the heat capacity (C _p,m), entropy [S _m ^° (T)–S _m ^° (0)], andGibbs energy function – [G _m ^° (T)–H _m ^° (0)]T ^–1 are 75.23, 114.5, 49.93, and 132.4, 216.2, 139.17, respectively. Consistent with the metallic behavior of CoTe₂, deviation of the heat capacity from theDebye T ³-law was found at low temperatures. Comparison with the heat capacity of FeTe₂ shows aSchottky-like deviation with a maximum of 7.3 J K^–1 mol^–1 at 80 K and evidences the influence of the additional 3 d-electron in cobalt compared to iron. Heat capacity measurements were made on CoTe_2.33 to ascertain the existence range of the CoTe_2+x -phase and the entropy of the associated structural disorder.The portion of this research done at Ann Arbor was supported in part by the Structural Chemistry and Chemical Thermodynamics Program of the Division of Chemistry of the National Science Foundation under Grant No. CHE-7710049.     

Low-temperature heat capacity of sodium borosilicate glasses at temperatures from 13 K to 300 K

Thermodynamic properties of sodium borosilicate glasses {56.7 SiO₂, (43.7  − x)B₂O₃,xNa₂O} wherex =  14.4, 22.9, and 32.5, have been studied. The heat capacity was measured using an adiabatic calorimeter at temperatures between 13 K and 300 K. The thermodynamic functions were calculated from the smoothed values ofC_{p, m} . The results differ from an additive model with pure glassy SiO₂, B₂O₃, and crystalline Na₂O as components. A model based on the assumption that the contribution of structural units of glasses to the heat capacity is equal to those of glasses with the same molecular formula is proposed.     

Heat capacity of β-alanine in a temperature range between 6 and 300?K

Thermodynamic properties of β-alanine in the temperature range 6.3–301 K were studied. No phase transitions were observed for the sample specially prepared to contain no solvent inclusions. At 298.15 K the calorimetric entropy and the difference in the enthalpy values are equal, respectively, to 126.6 JK⁻¹ mol⁻¹ and 19.220 Jmol⁻¹. The C _p (T) in the temperature range 6–16 K can be well described by Debye equation C _p  = AT ³. A comparison of the data on the entropies of glycine polymorphs and of β-alanine was used to show, that the empirical Parks–Huffman rule holds in the case of these compounds.     

Heat capacity measurement of cubic lithium tungsten bronzes from 200 to 800°K

Heat capacities of three cubic lithium tungsten bronze samples (Li_xWO₃) with x values of 0.363, 0.437, and 0.478 were measured from 200 to 800°K. Heat capacities per gram-atom at the same temperature of Li_0.363WO₃ and Li_0.437WO₃ were equal within experimental error and also equal to those of Na_0.485WO₃, Na_0.698WO₃, and Na_0.794WO₃, regardless of the difference of the composition. λ-type heat capacity anomalies were observed around 330, 460, and 590°K in Li_0.363WO₃ and around 330 and 460°K in Li_0.437WO₃ and Li_0.478WO₃, showing the existence of second-order phase transitions. The entropy increments of the transitions were obtained as 1.36, 0.45, and 1.68 J mole^?1 K^?1 for Li_0.363WO₃, 1.09 and 0.59 J mole^?1 K^?1 for Li_0.437WO₃, and 1.42 and 0.50 J mole^?1 K^?1 for Li_0.478WO₃.     

Heat capacity of hafnium mononitride from temperatures of 5 to 350 K: An estimation procedure

Measurements of the heat capacity by quasi-adiabatic, intermittent energy increments from 5 to 350 K show small high heat-capacity anomalies near 7 and 10 K which are attributed to superconducting transitions seen by magnetic measurements on the same carefully synthesized and well-characterized sample of (Hf_0.934Zr_0.057)(N_0.97). Although no previous heat capacity measurements over the cryogenic region are known, the estimated 298.15 K standard entropy values (S/R) vary in the literature from about 200 per cent higher to 5 per cent lower than our measured value of (5.28±0.01)R^–1 when the formula is represented as above. A simple scheme to represent and predict values based on both molar volumes and atomic masses for related materials is presented which seems more reliable on a limited sample than do others despite the intrusion of lanthanide contraction.This revised version was published online in November 2005 with corrections to the Cover Date.     

Heat capacity, enthalpy, entropy, and gibbs energy of terbium diboride as determined from calorimetric measurements within 5–300 K

The heat capacity at constant pressure C _p (T) of terbium diboride synthesized from elements via an intermediate hydride phase was studied experimentally within 5–300 K. A ferromagnetic phase transition manifests itself in the C _p (T) dependence as a sharp maximum at 142.4 ± 0.1 K. The C _p (T) dependence was used to calculate the tempreature dependences of the enthalpy, entropy, and the Gibbs energy and to determine the parameters of the electronic, lattice, and magnetic contributions to the heat capacity of TbB₂.     

Heat capacity and characteristic thermodynamic functions of dysprosium boride DyB62 in the temperature range of 2 to 300 K

Heat capacity at constant pressure C _p (T) of a dysprosium boride DyB₆₂ single crystal obtained by zone melting was studied experimentally in the temperature range of 2 to 300 K. Abnormally high values of dysprosium boride heat capacity were revealed in the range of 2–20 K, due to the magnetic contribution and the effect of disorder in the boride lattice. Temperature changes in DyB₆₂ enthalpy, entropy, Gibbs energy, and standard values of these thermodynamic functions were calculated.     

Heat capacity of amorphous polyhexene-1 between 20 and 300°K: Intramolecular vibrational contribution to Cv below the glass transition

The heat capacity of polyhexene-1 was measured between 20 and 300°K. The apparatus, an adiabatic calorimeter giving results with a random error of 0.2–0.4%, is briefly described. The characterization of the sample by x-ray diffraction patterns established that it was amorphous at all temperatures. Gold foil was incorporated with the sample to increase the apparent thermal diffusivity and so to decrease the time needed for the measurements. The glass transition temperature was found to be 215.5 ± 1°K. On the C_p curve, no subglass anomaly was detected, unlike the results of experiments described elsewhere. The calculation of C_v is discussed, and an explanation is given for the choice of the number of intramolecular vibrational modes per monomer which are assumed to contribute to C_v. A linear continuum model with characteristic temperature θ₁ = 736°K allows us to fit the experimental curve over a temperature range of 140°K.     

Heat capacity of α-glycylglycine in a temperature range of 6 to 440 K

Heat capacity of α-glycylglycine was measured using adiabatic calorimetry (6 to 304 K) and DSC (264 to 443 K), and then thermodynamic functions were calculated. Heat capacity has no anomalies. The molecular crystal melts at 493 K (enthalpy of melting is about 62 kJ mol^–1). The melting is accompanied by decomposition. C _P(T) function for glycylglycine is very similar to those of three glycine polymorphs. The ‘universal’ curve consists of two parts: low-temperature Debye-like function (from 0 to about 120 K) and a straight line (up to the melting point). At very low temperatures rigid molecules oscillate as a whole, and the Debye temperature is proportional to the molecular mass to the power of 3/2.     

Temperature dependence of ESR spectra of methyl methacrylate radicals from 77 K to 300 K

The radicals formed in poly(methyl methacrylate) (PMMA) under vacuum by UV irradiation at room temperature were carefully examined from 77 K to 300 K by electron spin resonance (ESR). The conventional nine-line spectrum was observed with significant overall intensity changes in contrast to previous reports. The intensity decreases greatly as the temperature increases from 77 K to 100 K. The intensity of the ESR spectrum increases as the temperature increases gradually from 100 K to 260 K. The spectral changes were reversible at all temperatures. Three different models are considered to interpret the temperature dependence of the intensity of the ESR spectrum. The results indicate that the ESR spectrum depends on (1) the steady-state concentration of the propagating radical in the polymer, (2) the conformational distributions of the radicals, and (3) the environmental structures of the polymer matrix.     

Heat capacity measurement of U1?yLayO2 (y=0.044, 0.090, 0.142) from 300 to 1500 K

Heat capacities of U_1–yLa_yO₂ were measured by means of direct heating pulse calorimetry in the temperature range from 300 to 1500 K. An anomalous increase in the heat capacity curve of each sample was observed similarly to the case of U_1–yGd_yO₂, found recently in our laboratory. As the lanthanum content of U_1–yLa_yO₂ increased, the onset temperature of an anomalous increase in the heat capacity decreased and the excess heat capacity increased. The enthalpy of activation (H_f) and the entropy of activation (S_f) of the thermally excited process, which cause the excess heat capacity were obtained to be 2.14, 1.63 and 1.50 eV and 39.4, 34.2 and 31.8 J·K^–1·mol^–1 for U_0.956La_0.044O₂, U_0.910La_0.090O₂ and U_0.858La_0.142O₂, respectively. The values at zero La content extrapolated by using the data of H_f and S_f for U_1–yLa_yO₂ were in good agreement with the experimental values of undoped UO₂ so far reported, similarly to the case of Gddoped UO₂. The electrical conductivities of U_1–yLa_yO₂ (y=0.044 and 0.142) were also measured as a function temperature. No anomaly was seen in the electrical conductivity curve. It may be concluded that the excess heat capacity originates from the predominant contribution of the formation of oxygen clusters and from the small contribution of the formation of electron-hole pairs.     

The heat capacity of indium phosphide

The heat capacity of indium phosphide was measured over the temperature range 360–760 K using a DSM-2M differential scanning calorimeter. The thermodynamic functions of InP were calculated. Original Russian Text ? A.S. Pashinkin, A.S. Malkova, M.S. Mikhailova, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 6, pp. 1191–1192.     

Heat capacity of niobium chlorides in the range 6–320 K

The heat capacities of NbCl₅ and Nb₃Cl₈ samples with less than 1·10^–3 mass-% of impurities were determined over the range 6–320 K by an adiabatic calorimeter. An anomaly was found in Nb₃Cl₈ within the 7–13 K range. Comparisons ofC _p values of Nb₃Cl₈ are made with the theoretical works of Tarassov. The qualitative fit is quite good.

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Zusammenfassung Die Wärmekapazitäten von NbCl₅- und Nb₃Cl₈-Proben mit Verunreinigungsgehalten 10^–3 Masse-% wurden mit einem adiabatischen Kalorimeter bei 6 bis 320 K bestimmt. Am Nb₃Cl₈ wurde eine Anomalie bei 7 bis 13 K nachgewiesen. Die C_p-Werte von Nb₃Cl₈ werden mit theorischen Ergebnissen von Tarassov verglichen, die qualitative Übereinstimmung ist gut.

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6–320 NbCl₅ Nb₃Cl₈ , 1· 10^–3 . Nb₃Cl₃ 7–13 . _p Nb₃Cl₈ , .

     

Heat capacity and thermodynamic properties of the alkali metal compounds in the temperature range 300–800 K. I. Cesium and rubidium molybdates

The heat capacities of cesium and rubidium molybdates, Cs₂MoO₄ and Rb₂MoO₄, have been measured by differential scanning calorimetry (DSC) in the temperature range 300–800 K. These values have been combined with published low-temperature heat capacity data for Cs₂MoO₄ to obtain thermodynamic functions to 800 K. For Rb₂MoO₄, however, these functions could not be calculated because low-temperature heat capacities are unavailable. Instead, only heat capacity data are reported.     

Heat capacity of MnAs0.88P0.12 from 10 to 500 K: Thermodynamic properties and transitions

The heat capacity of MnAs_0.88P_0.12 has been measured by adiabatic shield calorimetry from 10 to 500 K. It is shown that very small energy changes are connected with two magnetic order-order transitions, indicating that these can be regarded as mainly “noncoupled” magnetic transitions. At higher temperatures contributions to the excess heat capacity arises from a magnetic order-disorder transition, a conversion from low- to high-spin state for manganese, and a MnP- to NiAs-type structural transition. The observed heat capacity is resolved into contributions from the different physical phenomena, and the character of the transitions is discussed. In particular it is substantiated that the dilational contribution, which includes magnetoelastic and magnetovolume terms as well as normal anharmonicity terms, plays a major role in MnAs_0.88P_0.12. The entropy of the magnetic order-disorder transition is smaller than should be expected from a complete randomization of the spins, assuming a purely magnetic transition. Thermodynamic functions have been evaluated and the respective values of C_p, {S^O_m(T) - S^O_m(0)}, and -{G^O_m(T) - H^O_m(0)}/T at 298.15 K are 68.74, 72.09, and 32.30 J K⁻¹ mole⁻¹, and at 500 K 56.05, 108.12, and 56.64 J K⁻¹ mole⁻¹.     

Heat capacity and thermodynamic properties of germanium disulfide at temperatures from T = (2 to 1240) K

The heat capacity of polycrystalline germanium disulfide α-GeS₂ has been measured by relaxation calorimetry, adiabatic calorimetry, DSC and heat flux calorimetry from T = (2 to 1240) K. Values of the molar heat capacity, standard molar entropy and standard molar enthalpy are 66.191 J · K^?1 · mol^?1, 87.935 J · K^?1 · mol^?1 and 12.642 kJ · mol^?1. The temperature of fusion and its enthalpy change are 1116 K and 23 kJ · mol^?1, respectively. The thermodynamic functions of α-GeS₂ were calculated over the range (0 ? T/K ? 1250).