Thermodynamic properties of some polymeric forms of fullerite C<Subscript>60</Subscript> at temperatures ranging from 0 to 320 K

The temperature dependences of the heat capacityC ⁰ _p of fullerites C₆₀ were studied at temperatures ranging from 5 to 320 K in an adiabatic vacuum calorimeter with an accuracy of 0.4–0.2%. The fullerite C₆₀ samples were prepared by treating the starting fullerite C₆₀ under 8 GPa at 920 and 1270 K and “quenched” by a sharp decrease in pressure to −10⁵ Pa and in temperature to ∼300 K. Fullerite C₆₀(8 GPa, 920 K), a crystalline polymer with layered structure formed by polymerized fullerene C₆₀ molecules, was obtained at 920 K and 8 GPa. Fullerite C₆₀(8 GPa, 1270 K), a three-dimensional polymer with a graphite-like structure formed by fragments of decomposed C₆₀ molecules and containing many C(sp³)−C(sp³) bonds, was obtained at 1270 K and 8 GPa. Both polymers are metastable polymeric phases. The anomalous character of the temperature dependence of the heat capacity was revealed in the 49–66 K range for the polymer formed at 1270 K. The thermodynamic functions of the substances under study were calculated for the 0–320 K region along with entropies of their formation from graphite. The entropies of transformation of the starting fullerite C₆₀ into metastable phases and that of intertransformation of phases were estimated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 277–281, February, 2000.     

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.     

Thermochemical properties of the Fe-analogue of cryolite, Na3FeF6

Relative enthalpies for low-and high-temperature modifications of Na₃FeF₆ and for the Na₃FeF₆ melt have been measured by drop calorimetry in the temperature range 723–1318 K. Enthalpy of modification transition at 920 K, δ_trans H(Na₃FeF₆, 920 K) = (19 ± 3) kJ mol⁻¹ and enthalpy of fusion at the temperature of fusion 1255 K, δ_fusH(Na₃FeF₆, 1255 K) = (89 ± 3) kJ mol⁻¹ have been determined from the experimental data. Following heat capacities were obtained for the crystalline phases and for the melt, respectively: C _p(Na₃FeF₆, cr, α) = (294 ± 14) J (mol K)⁻¹, for 723 = T/K ≤ 920, C _p(Na₃FeF₆, cr, β) = (300 ± 11) J (mol K)⁻¹ for 920 ≤ T/K = 1233 and C _p(Na₃FeF₆, melt) = (275 ± 22) J (mol K)⁻¹ for 1258 ≤ T/K ≤ 1318. The obtained enthalpies indicate that melting of Na3FeF6 proceeds through a continuous series of temperature dependent equilibrium states, likely associated with the production of a solid solution.      

Temperature dependence of the thermodynamic parameters of cobalt(II) clathrochelate: X-ray diffraction and calorimetric characteristics of the low temperature structural phase transition

The temperature dependence of heat capacity of the polycrystalline sample of cobalt(II) clathrochelate in a range of 6–300 K is studied. Based on the smoothed dependence C _p(T), the entropy and enthalpy values in a temperature range of 8–300 K and their standard values at 298.15 K are calculated. In the C _p(T) curve in a range of 50–70 K, a process is recorded whose entropy and enthalpy are 1.2 J·(K·mol⁻¹) and 68 J·mol⁻¹ respectively. A comparison of the results with the data of a multitemperature X-ray diffraction study makes it possible to attribute this process to the structural phase transition.     

Thermodynamic studies of (R)-BINOL-menthyl dicarbonates

The (R)-BINOL-menthyl dicarbonates, one of the most important compounds in catalytic asymmetric synthesis, was synthesized by a convenient method. The molar heat capacities C _p,m of the compound were measured over the temperature range from 80 to 378 K with a small sample automated adiabatic calorimeter. Thermodynamic functions [H _T–H _298.15] and [S _T–S _298.15] were derived in the above temperature range with a temperature interval of 5 K. The thermal stability of the substance was investigated by differential scanning calorimeter (DSC) and a thermogravimetric (TG) technique.     

Heat Capacities and Thermodynamic Properties of a H2O + Li2B4O7 Solution in the Temperature Range from 80 to 356 K

The molar heat capacities of an aqueous Li₂B₄O₇ solution were measured with a precision automated adiabatic calorimeter in the temperature range from 80 to 356 K at a concentration of 0.3492 mol⋅kg⁻¹. The occurrence of a phase transition was determined based on the changes in the curve of the heat capacity with temperature. A phase transition was observed at 271.72 K corresponding to the solid-liquid phase transition; the enthalpy and entropy of the phase transition were evaluated to be Δ H _m = 4.110 kJ⋅mol⁻¹ and Δ S _m = 15.13 J⋅K⁻¹⋅mol⁻¹, respectively. Using polynomial equations and thermodynamic relationship, the thermodynamic functions [H _T −H _298.15] and [S _T −S _298.15] of the aqueous Li₂B₄O₇ solution relative to 298.15 K were calculated in temperature range 80 to 355 K at intervals of 5 K. Values of the relative apparent molar heat capacities of the aqueous Li₂B₄O₇ solution, C _p,φ, were calculated at every 5 K in temperature range from 80 to 355 K from the experimental heat capacities of the solution and the heat capacities of pure water.     

Thermal properties of seed proteins

The sample of LiCoO₂ was synthesized, and the heat capacity was measured by adiabatic calorimetry between 13 and 300 K. The smoothed values of the heat capacity were calculated from the data. The thermodynamic functions, standard enthalpy, entropy and Gibbs energy, of LiCoO₂ were calculated from the heat capacity and the numerical values are tabulated at selected temperatures from 15 to 300 K. The heat capacity, enthalpy, entropy, and Gibbs energy at T=298.15 K are 71.57 J K^–1mol^–1, 9.853 kJ mol^–1, 52.45 J K^–1 mol^–1, –5.786 kJ mol^–1, respectively. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermodynamic Properties of Hydrofullerene C60H36 from 5 to 340 K

The temperature dependence of the molar heat capacity (C⁰ _p) of hydrofullerene C₆₀H₃₆ between 5 and 340 K was determined by adiabatic vacuum calorimetry with an error of about 0.2%. The experimental data were used for the calculation of the thermodynamic functions of the compound in the range 0 to340 K. It was found that at T=298.15 K and p=101.325 kPa C⁰ _p (298.15)=690.0 J K⁻¹ mol⁻¹,H^o(298.15)−H^o(0)= 84.94 kJ mol⁻¹,S^o(298.15)=506.8 J K⁻¹ mol⁻¹, G^o(298.15)−H^o(0)= −66.17 kJ mol⁻¹. The standard entropy of formation of hydrofullerene C₆₀H₃₆ and the entropy of reaction of its formation by hydrogenation of fullerene C₆₀ with hydrogen were estimated and at T=298.15 K they were Δ_fS^o= −2188.4 J K⁻¹ mol⁻¹ and Δ_rS^o= −2270.5 J K⁻¹mol⁻¹, respectively. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermodynamic investigation of room temperature ionic liquid

The molar heat capacities of the room temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF₄) were measured by an adiabatic calorimeter in temperature range from 80 to 390 K. The dependence of the molar heat capacity on temperature is given as a function of the reduced temperature X by polynomial equations, C _P,m (J K^–1 mol^–1)= 195.55+47.230 X–3.1533 X ²+4.0733 X ³+3.9126 X ⁴ [X=(T–125.5)/45.5] for the solid phase (80~171 K), and C _P,m (J K^–1 mol^–1)= 378.62+43.929 X+16.456 X ²–4.6684 X ³–5.5876 X ⁴ [X=(T–285.5)/104.5] for the liquid phase (181~390 K), respectively. According to the polynomial equations and thermodynamic relationship, the values of thermodynamic function of the BMIBF₄ relative to 298.15 K were calculated in temperature range from 80 to 390 K with an interval of 5 K. The glass translation of BMIBF₄ was observed at 176.24 K. Using oxygen-bomb combustion calorimeter, the molar enthalpy of combustion of BMIBF₄ was determined to be Δ_c H _m ^o= – 5335±17 kJ mol^–1. The standard molar enthalpy of formation of BMIBF₄ was evaluated to be Δ_f H _m ^o= –1221.8±4.0 kJ mol^–1 at T=298.150±0.001 K.     

Anomalies in Heat Capacity Measurements of RuO2-TiO2 System

DSC was used for heat capacity measurements of pure RuO₂ in the temperature range from 300 to 1170 K of solid solutions corresponding to the compositions of (Ti_1−x Ru_x )O₂ (x ≤0.15 and x ≥0.85) and in the temperature range from 300 to 1550 K of pure TiO2. The analysis of experimental data obtained within ±2% of accuracy has shown that the characteristic temperatures representing the harmonic lattice vibrations do not strongly depend on the chemical composition x . It was demonstrated that non-harmonic heat capacity is strongly correlated to x. The existence of additional excess heat capacity was observed with the mixed oxide solid solution samples of low Ru content and explained by the defect formation model. This revised version was published online in August 2006 with corrections to the Cover Date.     

Low-temperature thermodynamic properties of <Emphasis Type="Italic">L</Emphasis>-cysteine

Heat capacity C _p(T) of the orthorhombic polymorph of L-cysteine was measured in the temperature range 6–300 K by adiabatic calorimetry; thermodynamic functions were calculated based on these measurements. At 298.15 K the values of heat capacity, C _p; entropy, S _m⁰(T)-S _m⁰(0); difference in the enthalpy, H _m⁰(T)-H _m⁰(0), are equal, respectively, to 144.6±0.3 J K⁻¹ mol⁻¹, 169.0±0.4 J K⁻¹ mol⁻¹ and 24960±50 J mol⁻¹. An anomaly of heat capacity near 70 K was registered as a small, 3–5% height, diffuse ‘jump’ accompanied by the substantial increase in the thermal relaxation time. The shape of the anomaly is sensitive to thermal pre-history of the sample.     

Pressure perturbation calorimetry of poly(ethylene) glycol solutions in water

The physico-chemical properties of poly(ethylene) glycol solutions in water have been studied with use of pressure perturbation calorimetry. The three PEGs of average molecular mass (M_r) 6000, 10000, 20000 were used. The concentration of polymers was changed in the range 0–30% mass per volume (w/v%). On the basic of VP-DSC measurements with use of PPC technique the dependencies of thermal expansion coefficient (α) and excess specific heat capacity (C_p,exc) on temperature were determinated for PEG–water solutions.     

Heat capacity of methacetin in a temperature range of 6 to 300 K

Heat capacity of methacetin (N-(4-methoxyphenyl)-acetamide) has been measured in the temperature range 5.8–300 K. No anomalies in the C _p(T) dependence were observed. Thermodynamic functions were calculated. At 298.15 K, the values of entropy and enthalpy are equal to 243.1 J K⁻¹ mol⁻¹ and 36360 J mol⁻¹, respectively. The heat capacity of methacetin in the temperature range 6–10 K is well fitted by Debye equation C _p = AT ³. The thermodynamic data obtained for methacetin are compared with those for the monoclinic and orthorhombic polymorphs of paracetamol.     

Heat capacity of crystalline GaN

The heat capacity of gallium nitride has been measured by DSC method using DuPont Thermal Analyst 2100, DSC 951 unit in the temperature range (300–850 K). The temperature dependence of the heat capacity can be presented in the following form: C _p=32.960+0.162·10⁻¹ T+2360170T ⁻²-775370000T ⁻³.     

Thermodynamic properties of graphite-like nanostructures prepared by thermobaric treatment of fullerite C60

Temperature dependences of the heat capacities of disordered graphite-like nanostructures prepared by the thermobaric treatment of fullerite C₆₀ (p = 2 and 8 GPa, T = 1373 K) were measured in the temperature ranges from 7 to 360 K in an adiabatic vacuum calorimeter and from 330 to 650 K in a differential scanning calorimeter. At T < 50 K, the dependences obtained were analyzed using the Debye theory of the heat capacity of solids and its multifractal version. The fractal dimensions D were determined and some conclusions on the heterodynamic character of the structures studied were made. The thermodynamic functions C _p ^o T), H ^o(T) − H ^o(0), S ^o(T) − S ^o(0), and G ^o(T) − H ^o(0) were calculated in the temperature range from T → 0 to 610 (650) K. The thermodynamic properties of the graphite-like nanostructures studied and some carbon allotropes were compared. The standard entropies of formation Δ_f S ^o of the graphite nanostructures studied and diamond were calculated along with the standard entropies of the reactions of their synthesis from the face-centered cubic phase of fullerite C₆₀ and their interconversions at T = 298.15 K. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1940–1945, September, 2008.     

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.     

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.     

C80 Calorimeter Studies of the Thermal Behavior of LiPF 6 Solutions

The thermal behavior of several LiPF₆ solutions was studied using a C80 calorimeter. It was found that oxygen might react with the solvents and decrease their thermal stability. The dissolution of LiPF₆ influences the thermal behavior remarkably with more heat generation and a lower onset temperature. Furthermore, the exothermic peak of LiPF₆ based on an electrolyte containing diethyl carbonate (DEC) was found around 185 ^∘C, which is 9.5–13.6 ^∘C lower than that containing dimethyl carbonate (DMC), which may be due to the relative activity of C₂H₅— and CH₃— in DEC and DMC, respectively.     

Thermal oxide synthesis and characterization of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanorods and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires

Fe₃O₄ nanorods and Fe₂O₃ nanowires have been synthesized through a simple thermal oxide reaction of Fe with C₂H₂O₄ solution at 200–600°C for 1 h in the air. The morphology and structure of Fe₃O₄ nanorods and Fe₂O₃ nanowires were detected with powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The influence of temperature on the morphology development was experimentally investigated. The results show that the polycrystals Fe₃O₄ nanorods with cubic structure and the average diameter of 0.5–0.8 μm grow after reaction at 200–500°C for 1 h in the air. When the temperature was 600°C, the samples completely became Fe₂O₃ nanowires with hexagonal structure. It was found that C₂H₂O₄ molecules had a significant effect on the formation of Fe₃O₄ nanorods. A possible mechanism was also proposed to account for the growth of these Fe₃O₄ nanorods. Supported by the Fund of Weinan Teacher’s University (Grant No. 08YKZ008), the National Natural Science Foundation of China (Grant No. 20573072) and the Doctoral Fund of Ministry of Education of China (Grant No. 20060718010)     

镥晶体的绝热量热法测试和热力学函数

文章合成了Lu(NO₃)₃(C₂H₅O₂N)_4.H₂O,用红外和元素分析对其进行了表征。用高精度全自动绝热量热仪,测定了该配合物80-382 K温区的热容, 利用实验热容数据, 根据热容与焓、熵的热力学关系, 求出了配合物85-350 K温区内每隔5 K相对于298.15K的标准热力学函数(HT - H298.15)m和(ST - S298.15)m.在80-350 K温度区间内,配合物的热容随温度升高而增大,没有相转移点和热力学吸收峰的出现,该配合物在此温度区间内是稳定存在的。