Authors:B. V. Lebedev, V. G. Vasil'yev, and N. N. Novosyolova
The heat capacityCpo of polypropanal was studied in a vacuum adiabatic calorimeter between 11 and 330 K, and in an ADKTTM automatic differential calorimeter from 320 to 370 K. The thermodynamic parameters of melting and glass transition of polypropanal were also determined. From the results, the thermodynamic functions of the polymer were calculated in the range 0 K to 360 K. The enthalpy of depolymerization of polypropanal to the starting monomer was measured in a DAK-1-1 differential automatic microcalorimeter. From the results of this study and literature data on the thermodynamic properties of propanal., the enthalpy, entropy and Gibbs function of bulk polymerization of propanal were estimated from 0 K to 330 K. Ceiling limiting temperatures of transitions of the liquid monomer to crystalline and high-elasticity polymer were determined.
Authors:Małgorzata Jóźwiak, Adam Bald, and Andrzej Jóźwiak
The thermodynamic functions of complex formation of benzo-15-crown-5 ether (B15C5) and sodium cation (Na+) in acetone–water mixtures at 298.15 K have been calculated. The equilibrium constants of B15C5/Na+ complex formation have been determined by conductivity measurements. The enthalpic effect of complex formation has been measured
by the calorimetric method. The complexes are enthalpy-stabilized but entropy-destabilized in acetone–water mixtures. The
effects of hydrophobic hydration, preferential solvation of B15C5 by a molecule of water and acetone, respectively and the
solvation of Na+ on the complex formation processes have been discussed. The calculated thermodynamic functions of B15C5/Na+ complex formation and the effect of benzene ring on the complex formation have been compared with analogous data obtained
in dimethylsulfoxide–water mixtures. The effect of carbonyl atom replacement in acetone molecule by sulphur atom (DMSO molecule)
on the thermodynamic functions of complex formation has been analysed.
Authors:N. Smirnova, B. Lebedev, T. Bykova, A. Markin, and D. Tur
By adiabatic vacuum and dynamic calorimetry, heat capacity for poly[bis(trifluoroethoxy)phosphazene] has been determined over the 6–620 K range. Physical transformations of the polymer on its heating
and cooling have been detected and characterized. Smoothed heat capacity Cp0(T) and standard thermodynamic functions (H0(T)-H0(0), S0(T) and G0(T)-H0(0)) of poly[bis(trifluoroethoxy)phosphazene] have been evaluated for the temperature range from T→0 to 560 K. The standard entropy of formation ΔfS0 at T=298.15 K has been also determined. Fractal dimensions D in the heat capacity function of the multifractal variant of Debye’s theory of heat capacity of solids characterizing the
heterodynamics of the tested polymer have been determined.
The temperature dependence of the molar heat capacity (C0p) 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 C0p (298.15)=690.0 J K−1 mol−1,Ho(298.15)−Ho(0)= 84.94 kJ mol−1,So(298.15)=506.8 J K−1 mol−1, Go(298.15)−Ho(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 ΔfSo= −2188.4 J K−1 mol−1 and ΔrSo= −2270.5 J K−1mol−1, respectively.
Authors:V. Bessergenev, Yu. Kovalevskaya, L. Lavrenova, and I. Paukov
Low-temperature heat capacity of the coordination compound of nickel(II) nitrate with 4-amine-1,2,4-triazole was measured in the temperature range from 11 to 317 K using a computerized vacuum adiabatic calorimeter. The thermodynamic functions have been derived from the smoothed experimental data over the whole temperature interval covered and at standard conditions. At 298.15 K, the heat capacity is 574.7±1.2 J K-1 mol-1, the entropy is 599.2±1.2 J K-1 mol-1, the enthalpy is 91070±200 J mol-1, and the reduced Gibbs energy is 293.7±1.2 J K-1 mol-1. The results on Cp(T) were compared with those for Cu(NH2trz)3(NO3)2·0.5H2O. It was revealed that the slope of the curve dCp/dT (T) changes essentially for both compounds at 110-120 K. It implies that additional degrees of freedom appear in the heat capacity at these temperatures.
Authors:V. I. Pet’kov, E. A. Asabina, A. V. Markin, N. N. Smirnova, and D. B. Kitaev
Summary The thermodynamic data for NZP compounds MZr2(PO4)3 (M=Na, K, Rb, Cs, Zr0.25) and Na5D(PO4)3 (D=Ti, Zr) are reported. The heat capacities of the phosphates were measured between T=7 and T=640 K. The standard enthalpies entropies, and Gibbs functions of formation at T=298.15 K were derived. The obtained thermodynamic characteristics of phosphates of the NZP type structure and literature data are summarized. Thermodynamic functions of reactions of solid-state synthesis were calculated and the usability of ceramic technology for obtaining NZP compounds was proved.
Authors:T. Tojo, T. Atake, T. Mori, and H. Yamamura
The heat capacity of 9.70 and 11.35 mol% yttria stabilized zirconia ((ZrO2)1–x(Y2O3)x; x=0.0970, 0.1135) was measured by adiabatic calorimetry between 13 and 300 K, and some thermodynamic functions were calculated and given in a table. A large excess heat capacity extending from the lowest temperature to room temperature with a broad maximum at about 75 K was found in comparison with the heat capacity calculated from those of pure zirconia and yttria on the basis of simple additivity rule. The shape of the excess heat capacity is very similar to the Schottky anomaly, which may be attributed to a softening of lattice vibration. The amount of the excess heat capacity decreased with increasing yttria doping, while the maximum temperature did not vary. The relationships among the excess heat capacity, defect structure and interatomic force constants, and also the role of oxygen vacancy were discussed.
Authors:M.-H. Wang, Z.-C. Tan, Q. Shi, L.-X. Sun, and T. Zhang
heat capacities of 2-benzoylpyridine were measured with an automated adiabatic
calorimeter over the temperature range from 80 to 340 K. The melting point,
molar enthalpy, ΔfusHm,
and entropy, ΔfusSm,
of fusion of this compound were determined to be 316.49±0.04 K, 20.91±0.03
kJ mol–1 and 66.07±0.05 J mol–1
K–1, respectively. The purity of the compound
was calculated to be 99.60 mol% by using the fractional melting technique.
The thermodynamic functions (HT–H298.15) and (ST–S298.15) were calculated based
on the heat capacity measurements in the temperature range of 80–340
K with an interval of 5 K. The thermal properties of the compound were further
investigated by differential scanning calorimetry (DSC). From the DSC curve,
the temperature corresponding to the maximum evaporation rate, the molar enthalpy
and entropy of evaporation were determined to be 556.3±0.1 K, 51.3±0.2
kJ mol–1 and 92.2±0.4 J K–1
mol–1, respectively, under the experimental
Authors:N. Manin, A. Fini, A. Manin, and G. Perlovich
Enthalpies of solution and dilution of aqueous solutions of sodium diclofenac salt were measured by isoperibolic calorimeter
at 293.15, 298.15, 303.15, 308.15 and 318.15 K. The concentration of the electrolyte was restricted to solubility salt at
various temperatures and did not exceed 0.035–0.057 mol kg−1 values depending on the studied temperature. The virial coefficients were derived from Pitzer’s model and the excess thermodynamic
functions of both the solution and the components of the solution were calculated. The analysis of thermodynamic characteristics
of the solution from concentration and temperatures was carried out and discussed.
The temperature dependencies of the molar heat capacities of ZnTeO3, Zn2Te3O8, CdTeO3 and CdTe2O5 are determined. The experimental data are statistically processed using the least squares method to determine the parameters in the equations for the corresponding compounds: Cp,m=a+b(T/K)-c(T/K)-2. These equations and the standard molar entropies are used to determine ΔT0S0m, ΔTTH0m and (Φ0m+ΔT,0H0m/T) for T'=298.15 K.