Low-temperature thermodynamic properties of <Emphasis Type="SmallCaps">dl</Emphasis>-cysteine

Heat capacity C _p(T) of the crystalline dl-cysteine was measured on heating the system from 6 to 309 K by adiabatic calorimetry; thermodynamic functions were calculated based on these data smoothed in the temperature range 6–273.15 K. The values of heat capacity, entropy, and enthalpy at 273.15 K were equal to 142.4, 153.3, and 213.80 J K⁻¹ mol⁻¹, respectively. At about 300 K, a heat capacity peak was observed, which was interpreted as an evidence of a first-order phase transition. The enthalpy and the entropy of the transition are equal, respectively, to 2300 ± 50 and 7.6 ± 0.1 J K⁻¹ mol⁻¹.     

Thermodynamics of tetraphenylantimony acetophenoneoxymate

In the present research for the first time, the heat capacity C_\textp ^° C_{\text{p}}^{ \circ } of crystalline tetraphenylantimony acetophenoneoxymate Ph₄SbONCPhMe has been measured using the methods of precision adiabatic vacuum calorimetry over the range from 6 to 350 K, the standard thermodynamic functions: heat capacity C_\textp ^° (T ) C_{\text{p}}^{ \circ } (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 K to 350 K. Low-temperature (20 K ≤ T ≤ 50 K) heat capacity data have shown a chain-layered structure topology of the compound under study. The energy of combustion of the compound has been determined in the isothermal combustion calorimeter with a stationary bomb. The standard thermodynamic functions of formation of crystalline Ph₄SbONCPhMe at 298.15 K have been calculated. The differential scanning calorimetry and thermogravimetric analysis studies have shown the compound melts with decomposition and its melting temperature has been estimated. Thermodynamic properties of Ph₄SbONCPhMe, Ph₅Sb and Ph₄SbONCPh₂ have been compared.     

Crystal structure, spectroscopy and thermodynamic properties of MVWO6(M – Li, Na)

In the present work lithium (sodium) vanadium tungsten oxides with brannerite structure is refined by the Rietveld method (space group C2/m, Z=2). IR and Raman spectroscopy was used to assign vibrational bands and determine structural particularities. The diffuse reflectance spectra allow to calculate bandgap for M^IVWO₆(M^I – Li, Na). The temperature dependences of heat capacity have been measured first in the range from 7 to 350 K for these compounds and then between 330 and 640 K, respectively, by precision adiabatic vacuum and dynamic calorimetry. The experimental data were used to calculate standard thermodynamic functions, namely the heat capacity C_p^o(T), enthalpy H^o(T)−H^o(0), entropy S^o(T)−S^o(0) and Gibbs function G^o(T)−H^o(0), for the range from T→0 to 640 K. The differential scanning calorimetry was applied to measure decomposition temperature of compounds under study.     

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 characteristics of triphenylantimony bis(acetophenoneoximate)

The temperature dependence of heat capacity C _p ^° = f(T) of triphenylantimony bis(acetophenoneoximate) Ph₃Sb(ONCPhMe)₂ was measured for the first time in an adiabatic vacuum calorimeter in the range of 6.5–370 K and a differential scanning calorimeter in the range of 350–463 K. The temperature, enthalpy, and entropy of fusion were determined. Treatment of low-temperature (20 K ≤ T ≤ 50 K) heat capacity was performed on the basis of Debye’s theory of the heat capacity of solids and its multifractal model and, as a consequence, a conclusion was drawn on the type of structure topology. Standard thermodynamic functions C _p ^°(T), H°(T) — H°(0), S°(T), and G°(T) — H°(0) were calculated according to the experimental data obtained for the compound mentioned in the crystalline and liquid states for the range of T → 0–460 K. The standard entropy of the formation of crystalline Ph₃Sb(ONCPhMe)₂ was determined at T = 298.15 K.     

Thermodynamics of dimethylene urethane and poly(dimethylene urethane) in the range from T → 0 to 490 K at standard pressure

By high-precision dynamic calorimetry the temperature dependences of heat capacity of dimethylene urethane (DMU) between 320 and 370 K and partially crystalline poly(dimethylene urethane) (PDMU) in the range 326-490 K at standard pressure have been determined within ±1.5%. The thermodynamic characteristics of fusion of the substances, namely the temperature interval of melting, temperature, enthalpy and entropy of fusion, as well as the characteristics of devitrification and glassy state for poly(dimethylene urethane) have been estimated. The first and the second cryoscopic constants have been calculated for dimethylene urethane. The experimental data obtained in the present work and literature findings on the heat capacity of the substances were used to calculate their thermodynamic functions: the heat capacity C°_p (T), enthalpy H°(T)−H°(0), entropy S°(T) and Gibbs function G°(T)−H°(0) over the range from T→0 to (370-480) K. Based on the data, the thermodynamic characteristics of polymerization process with five-membered ring opening Δ_polH°, Δ_polS° and Δ_polG° of dimethylene urethane with the formation of linear partially crystalline poly(dimethylene urethane) have been evaluated.     

The thermodynamic properties of uranyl metaborate

The standard enthalpy of formation of crystalline UO₂(BO₂)₂ at 298.15 K was determined by reaction calorimetry (?2542.5 ± 3.5 kJ/mol). The heat capacity of this compound was measured over the temperature range 6–302 K by adiabatic vacuum calorimetry. The thermodynamic functions were calculated, including the standard entropy (502.8 ± 2.1 J/(mol K)) and Gibbs function of formation (?2392.5 ± 4.0 kJ/mol) at 298.15 K. The standard thermodynamic functions of reactions with the participation of uranyl metaborate were determined and analyzed.     

Thermodynamic properties of triphenylantimony dibenzoate

The temperature dependence of the heat capacity of triphenylantimony dibenzoate Ph₃Sb(OC(O)Ph)₂ is studied in the range of 6–480 K by means of precision adiabatic vacuum calorimetry and differential scanning calorimetry. The melting of the compound is observed in this temperature range, and its standard thermodynamic characteristics are identified and analyzed. Ph₃Sb(OC(O)Ph)₂ is obtained in a metastable amorphous state in a calorimeter. The standard thermodynamic functions of Ph₃Sb(OC(O)Ph)₂ in the crystalline and liquid states are calculated from the obtained experimental data: C_p^°(T), H°(T)–H°(0), S°(T), and G°(T)–H°(0) for the region from T → 0 to 480 K. The standard entropy of formation of the compound in the crystalline state at T = 298.15 K is determined. Multifractal processing of the low-temperature (T < 50 K) heat capacity of the compound is performed. It is concluded that the structure of the compound has a planar chain topology.     

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.     

Structural studies of cyclic ureas: 2. Enthalpy of formation of parabanic acid

Thermophysical and thermochemical studies have been carried out for crystalline parabanic acid. The thermophysical study was made by differential scanning calorimetry, DSC, over the temperature interval between T = (263 and 473) K. Two phase transitions were found: at T = (392.3 ± 1.6) K with the enthalpy of transition of (2.1 ± 0.4) kJ · mol⁻¹ and at T = (509.8 ± 1.5) K, when the compound was scanned to its fusion temperature. The standard (p = 0.1 MPa) molar enthalpy of formation, at T = 298.15 K, for crystalline parabanic acid was determined using static-bomb combustion calorimetry as −(590.2 ± 1.0) kJ · mol⁻¹. The standard molar enthalpy of sublimation, at T = 298.15 K, was derived from the variation of their vapour pressures, measured by the Knudsen-effusion method, with the temperature. These two thermochemical parameters yielded the standard molar enthalpy of formation in the gaseous phase, at T = 298.15 K, as −(470.8 ± 1.2) kJ · mol⁻¹.     

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.     

Thermodynamics of cross-linked and branched (co)polymers based on <Emphasis Type="Italic">tris</Emphasis>- and <Emphasis Type="Italic">bis</Emphasis>-(pentafluorophenyl)germanes

The temperature dependence of the heat capacity of cross-linked and branched (co)polymers based on tris- and bis-(pentafluorophenyl)germanes is studied in the temperature range of 6–7 to 535–570 K, using adiabatic vacuum and differential scanning calorimeters. In the indicated temperature range, physical transformations are revealed and their thermodynamic characteristics are determined. The obtained experimental data are used to calculate the thermodynamic functions of (co)polymers: C _p /°, H°(T) - H°(0), S°(T) - S°(0), and G°(T) - H°(0) in the range of T → 0 to 535 K for the branched (co)polymer and from T → 0 to 500 K for the cross-linked polymer. Their standard entropies of formation are determined at 298.15 K. The obtained results are compared with analogous data for hyperbranched perfluorinated polyphenylenegermane studied earlier. The effect of the structure of polyphenylenegermanes on their thermodynamic properties is analyzed.     

The heat capacities and thermodynamic functions of some derivatives of ferrocene

The heat capacities of benzoylferrocene (BOF), C₅H₅FeC₅H₄COC₆H₅, and benzylferrocene (BF), C₅H₅FeC₅H₄CH₂C₆H₅, have been measured by the low-temperature adiabatic calorimetry in the temperature range from 6 K to 372 K. The purity benzylferrocene and thermodynamic properties – the triple point temperature and the enthalpy of fusion have been obtained. The ideal gas thermodynamic functions (changes of the entropy, enthalpy, and Gibbs free energy) of BOF and BF were derived at T = 298.15 K using the heat capacities and previously determined data on the saturation vapours pressures and the enthalpies of sublimation. The ideal gas enthalpy of formation and absolute entropy of BOF at T = 298.15 K have been obtained from quantum chemical calculations, where as the thermodynamic properties of BF have been estimated by empirical method of group equations. A good agreement between experimental and theoretical values provides an additional check of the reliability of the experimental data.     

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.     

Low-Temperature Heat Capacities and Thermodynamic Properties of Hydrated Nickel L-Threonate Ni（C4H7O5）2·2H2O（S）

Low-temperature heat capacities of the compound Ni（C4H7O5）2·2H2O（S） have been measured with an auto- mated adiabatic calorimeter. A thermal decomposition or dehydration occurred in 350--369 K. The temperature, the enthalpy and entropy of the dehydration were determined to be （368.141 ±0.095） K, （18.809±0.088） kJ·mol ^-1 and （51.093±0.239） J·K^-1·mol^-1 respertively. The experimental values of the molar heat capacities in the temperature regions of 78-350 and 368-390 K were fitted to two polynomial equations of heat capacities （Cp,m） with the reduced temperatures （X）, [X=f（T）], by a least squares method, respectively. The smoothed molar heat capacities and thermodynamic functions of the compound were calculated on the basis of the fitted polynomials. The smoothed values of the molar heat capacities and fundamental thermodynamic functions of the sample relative to the standard reference temperature 298.15 K were tabulated with an interval of 5 K.     

Heat capacity of GdBiGeO<Subscript>5</Subscript> in the temperature range 373–1000 K

Ternary oxide GdBiGeO₅ was synthesized by a ceramic method. The heat capacity of crystalline gadolinium bismuth germanate as a function of temperature in the range 373–1000 K has been studied by differential scanning calorimetry. It has been demonstrated that the temperature dependence of the heat capacity can be described by the classical Maier–Kelley equation. From the experimental C _P = f(T) data, the thermodynamic functions (the change in enthalpy and entropy) of ternary oxide GdBiGeO₅ have been calculated.     

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.     

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.     

Synthesis and study of high-temperature heat capacity of erbium orthovanadate

Orthovanadate ErVO₄ has been prepared by solid-phase synthesis from a stoichiometric mixture of high pure V₂O₅ and chemically pure Er₂O₃ by multistage calcination in air in the temperature range 873–1273 K. The effect of temperature (380–1000 K) on the heat capacity of orthovanadate ErVO₄ was studied by hightemperature calorimetry. Thermodynamic properties of erbium orthovanadate (enthalpy change H°(T)–H°(380 K), entropy change S°(T)–S°(380 K), and reduced Gibbs energy Φ°(T)) have been calculated from the experimental C_p = f(T) data. It has been shown that the specific heat varies in a row of oxides and orthovanadates of Gd-Lu naturally depending on the radius of the R³⁺ ion within the third and fourth tetrads.     

A low-temperature heat capacity study of natural lithium micas

Low-temperature heat capacity of natural zinnwaldite was measured at temperatures from 6 to 303 K in a vacuum adiabatic calorimeter. An anomalous behavior of heat capacity function C _p(T) has been revealed at very low temperatures, where this function does not tend to zero. Thermodynamic functions of zinnwaldite have been calculated from the experimental data. At 298.15 K, heat capacity C _p(T) = 339.8 J K⁻¹mol⁻¹, calorimetric entropy S ^o(Т) – S ^o(6.08) = 329.1 J K⁻¹ mol⁻¹, and enthalpy Н ^o(Т) − Н ^o(6.08) = 54,000 J mol⁻¹. Heat capacity and thermodynamic functions at 298.15 K for zinnwaldite having theoretical composition were estimated using additive method of calculation.