Search Results
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
Isoproturon [N'-(p-cumenyl)-N,N-dimethylurea] was synthesized, and the low-temperature heat capacities were measured with a small sample precise automatic adiabatic calorimeter over the temperature range from 78 to 342 K. No thermal anomaly or phase transition was observed in this temperature range. The melting and thermal decomposition behavior of isoproturon was investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). The melting point and decomposition temperature of isoproturon were determined to be 152.4 and 239.0C. The molar melting enthalpy, and entropy of isoproturon, ΔH m and ΔS m, were determined to be 21.33 and 50.13 J K-1 mol-1, respectively. The fundamental thermodynamic functions of isoproturon relative to standard reference temperature, 298.15 K, were derived from the heat capacity data.
Abstract
Equilibrium adiabatic heat-capacity measurements have been made on zone refined samples of CeB6 and PrB6. Companion measurements made on LaB6, NdB6, and GdB6 have been reported elsewhere. These show cooperative lambda-type anomalies associated with antiferro-magnetic ordering. Except for lanthanum hexaboride, Schottky internal crystal field levels result in significant contributions to the thermodynamic functions. The gross thermodynamic properties at 298.15 K heat capacity (Cp/R), entropy increment (ΔT 0,m S 0/R), and Gibbs energy function are correlated with the nature of the lanthanide. For LaB6, CeB6, PrB6, NdB6, and GdB6 the three properties are, respectively: {11.654, 12.014, 11.997, 11.916, 11.695} Cp/R; {10.001, 11.803, 12.430, 12.558, 13.982} S0/R, and finally {4.379, 5.912, 6.232, 6.451, 7.905}Φ0 m/R.
Abstract
The thermodynamic properties of carbosilane dendrimer of second generation with terminal methoxyundecylene groups were studied between 6 and 340 K by adiabatic vacuum calorimetry: the temperature dependence of the molar heat capacity Cp 0 was measured, the physical transformations were established and their thermodynamic characteristics were obtained. The experimental data were used to calculate the thermodynamic functions Cp 0 (T), H 0(T)-H 0(0), S0(T), G 0(T)-H 0(0) of the compound in the range 0 to 340 K. from the relation Cp 0 (T) the fractal dimension of the dendrimer was experimentally determined. The heat capacity of the dendrimer was compared with the corresponding additive values calculated from the properties of its constituents - a dendritic matrix (carbosilane dendrimer of second generation) and the corresponding amount of moles of methyl ester of 11-(tetramethyldisiloxy)undecanoic acid serving as terminal groups.
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
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
Synthesis and characterization of N,N,N',N'-tetrabutylsuccinamide (TBSA)was carried out and used for the extraction of U(VI) and Th(IV) from nitricacid solutions. Toluene was found to be the most suitable diluent for TBSAcompared with the other diluents tested. Extraction distribution ratios (D)of U(VI) and Th(IV) have been studied as a function of aqueous HNO 3 concentrations,NO3 – ion concentration, TBSA concentration and temperature.The results obtained indicated that U(VI) and Th(IV) are mainly extractedas UO2 (NO3 ) 2 . 2TBSA and Th(NO3 ) 4 . TBSA, respectively, and the IR spectra of the extractedspecies have been investigated. The values of thermodynamic functions havebeen calculated. Back-extraction of U(VI) and Th(IV) from organic phases wasalso studied.
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.
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
Phases may be smaller than visible to the human eye. In order to characterize a microphase, a phase smaller than 1 μm, one must consider surface area and free energy in addition to the standard thermodynamic functions. As one approaches nanometer sizes, one also needs to know the changing thermodynamic functions within the phases. The Gibbs–Thomson equation can be used to characterize microphases, but not nanophases. For the latter, the glass transition is needed to assess the properties in the interior. In order to classify condensed phases as liquid, solid, mesophase, or crystal, one needs to consider the molecular motion in addition to the molecular structure. Most important are large-amplitude displacements in form of translation, rotation, and conformational motion. An operational definition based on experiments and an updated classification of the phases is given. The surprising result is the observation that crystals, earlier assumed prime examples of solids, can have order–disorder transitions to more mobile mesophases, as well as a glass transition without change in crystal structure, i.e., under certain condition, they cannot be identified as a solid. To these observations, one has to add the fact that large-amplitude motion may start gradually to a more mobile phase without abrupt changes in structure. These observations limit the usefulness of the 80-year-old classification of transitions as being of first or second order. Quantitative thermal analysis is shown to be an important tool to identify the possible total of 57 different condensed states in terms of their macroscopic properties as well as molecular structure and motion.
