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DSC and vapour pressure measurements are presented on some Be, Al and Cr complexes with 2,4-pentanedione tetramethyl-3,5-heptanedione, 1,1,1-trifluoro-2,4-pentanedione and hexafluoro-2,4-pentanedione. Thermodynamic functions are given for the sublimation, vaporization and melting processes of the substances.
Abstract
The molar heat capacity C p,m of 1,2-cyclohexane dicarboxylic anhydride was measured in the temperature range from T=80 to 390 K with a small sample automated adiabatic calorimeter. The melting point T m, the molar enthalpy Δfus H m and the entropy Δfus S m of fusion for the compound were determined to be 303.80 K, 14.71 kJ mol−1 and 48.43 J K−1 mol−1, respectively. The thermodynamic functions [H T-H 273.15] and [S T-S 273.15] were derived in the temperature range from T=80 to 385 K with temperature interval of 5 K. The thermal stability of the compound was investigated by differential scanning calorimeter (DSC) and thermogravimetry (TG), when the process of the mass-loss was due to the evaporation, instead of its thermal decomposition.
Abstract
Both calorimetric determination of displacement adsorption enthalpies ΔH and measurement of adsorbed amounts of lysozyme (Lyz) denatured by 1.8 mol L−1 guanidine hydrochloride (GuHCl) on a moderately hydrophobic packings at 298 K, pH 7.0 and various salt concentrations were carried out. Based on the thermodynamics of stoichiometric displacement theory (SDT) the fractions of thermodynamic functions, which related to four subprocesses of denatured protein refolding on the surface, were calculated and thermodynamic analysis that which one of the subprocesses plays major role for contribution to the thermodynamic fractions was made in detail. The moderately hydrophobic surface can provide denatured Lyz energy and make it gain more conformation with surface coverage or salt concentration increment. The displacement adsorptions of denatured Lyz onto PEG-600 surface are exothermic, more structure-ordered and enthalpy driven processes.
Abstract
The non-isothermal kinetics of dehydration of AlPO4·2H2O was studied in dynamic air atmosphere by TG–DTG–DTA at different heating rates. The result implies an important theoretical support for preparing AlPO4. The AlPO4·2H2O decomposes in two step reactions occurring in the range of 80–150 °C. The activation energy of the second dehydration reaction of AlPO4·2H2O as calculated by Kissinger method was found to be 69.68 kJ mol−1, while the Avrami exponent value was 1.49. The results confirmed the elimination of water of crystallization, which related with the crystal growth mechanism. The thermodynamic functions (ΔH*, ΔG* and ΔS*) of the dehydration reaction are calculated by the activated complex theory. These values in the dehydration step showed that it is directly related to the introduction of heat and is non-spontaneous process.
Abstract
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 m 0(T)-S m 0(0); difference in the enthalpy, H m 0(T)-H m 0(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.
Abstract
Al2O3-Cr2O3 solid solutions with 0, 4, 7, 10 and 20 mol% of corundum were synthesized using a high-pressure/high-temperature apparatus and characterized by X-ray powder diffraction. Calorimetric measurements were carried out using DSC-111 (Setaram). Heat capacity was measured by the enthalpy method in a temperature range of 260–340 K, near magnetic phase transition in pure Cr2O3 (305 K). Magnetic contribution into the heat capacity was derived and found to change irregularly with the composition. Heat capacity of solid solutions remains constant in a relatively wide range of composition, while the C p values of the end members differ significantly. This phenomenon is very important for the modeling of the thermodynamic functions of intermediate solid solutions.
Abstract
A calorimetric investigation was performed on the partition ofn-pentanol in the external oil phase and in the interfacial layer of the water-in-oil microemulsion system sodium dodecyl-benzenesulfonate(DDBS)/n-pentanol/n-heptane/water. The results show that fine changes can be observed in the structure of the water-in-oil emulsion and microemulsion droplets, such as then-pentanol/DDBS mole ratio increase in the interfacial layer; further, the alcohol/surfactant mole ratio α in the interfacial layer of the droplets, and also the standard thermodynamic functions of the alcohol transition from the external phase to the interfacial phase (ΔG e→s o , ΔH c→s o and ΔS e→s o ), can be derived from calorimetric data.
Abstract
The solubility and solubility product of europium trifluoride were measured by radiometric, potentiometric and conductometric methods. There are significant differences in the values of both solubility and solubility product obtained by the three different techniques. Due to reasons discussed in the text, radiometric values seem to be more acceptable than the others. The thermodynamic functions such as ΔH0, ΔG0 and ΔS0 for the dissolution process were also measured. The positive values of ΔH0 and ΔG0 and the negative value of ΔS0 are indicative of the slight solubility of EuF3. The dependence of solubility on pH and also on the fluoride concentration has also been studied. It was confirmed that europium forms a monofoluoride complex in aqueous solution. The stability constant of this complex was estimated.
Abstract
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.
Abstract
Synergic extraction of Eu(III) and Tb(III) with 2-thenoyltrifluoroacetone (HTTA) and tribenzylamine (TBA) as neutral donor ligand has been studied in chloroform from perchlorate media at lower pH range. The stoichiometric composition of the adduct was established as M(TTA)3 · 3TBA for both the elements, having a coordination number 9. The formation constants K3,0 and K3,3 and stability constant 
3,3 of the organic phase reaction have been calculated. The effect of temperature on the extraction has also been studied. The adducts are stabilized by the large exothermic enthalpy change. The calculated thermodynamic functions such as 
H, S and G were used to elucidate the mechanism of synergism in which the coordination numbers of the lanthanide ions increased.
