The molar enthalpies of the solid–solid and solid–liquid phase transitions were determined by differential scanning calorimetry
for pure TbCl3 and KTb2Cl7, RbTb2Cl7, CsTb2Cl7, K3TbCl6, Rb3TbCl6 and Cs3TbCl6 compounds. Both types of compounds, i.e. M3TbCl6 and MTb2Cl7 (M=K, Rb, Cs) melt congruently and show additionally a solid–solid phase transition with a corresponding enthalpy ΔtrsH0 of 6.1, 7.6 and 7.0 kJ mol–1 for potassium, rubidium and caesium M3TbCl6 compounds andΔtrsH0 of 17.1 (rubidium) and of 12.1 and 10.9 kJ mol–1 (caesium) for MTb2Cl7 compounds, respectively. The enthalpies of fusion were measured for all the above compounds with the exception of Rb3TbCl6 and Cs3TbCl6. The heat capacities of the solid and liquid compounds have been determined by differential scanning calorimetry (DSC) in
the temperature range 300–1100 K. The experimental heat capacity strongly increases in the vicinity of a phase transition,
but varies smoothly in the temperature ranges excluding these transformations. Cp data were fitted by an equation, which provided a satisfactory representation up to the temperatures of Cp discontinuity. The measured heat capacities were checked for consistency by calculating the enthalpy of formation of the
liquid phase, which had been previously measured. The results obtained agreed satisfactorily with these experimental data.
Authors:V. V. Deshpande, M. D. Karkhanavala, and U. R. K. Rao
It is shown that the heat of transition of the phase change II → I at 129° on heating KNO3 is dependent on the thermal history of the sample, since it involves two steps, viz., II→ III and III→ I at 2° interval. During cooling, the latter step is fast and truly reversible, though with a temperature hysteresis. The former step is sluggish and is dependent both on temperature and time. Our results indicate that KNO3 can be used for calibration purpose only if the material has not been heated beyond 128° in the immediately preceding three hours.
Authors:H. Honda, A. Oshima, H. Hinode, and M. Wakihara
Enthalpy increment HT-H289K measurements have been made on iron Chevrel phase sulphide Fe2Mo6S7.8, in the temperature range 300 to 500 K by the drop method using a hightemperature Calvet-type twin calorimeter. The first-order phase transition of this sulphide from a triclinic (low-temperature phase) to a rhombohedral (high-temperature phase) occurred at 375 K, and the enthalpy was evaluated to be 6.0 kJ/mol. The heat capacities of iron Chevrel phase sulphide Fe2Mo6S7.8 were also calculated before and after the phase transition.
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 Cp values of the end members differ significantly. This phenomenon is very important for the modeling of the thermodynamic functions
of intermediate solid solutions.
Authors:E. Grell, E. Lewitzki, R. Schneider, G. Ilgenfritz, I. Grillo, and M. von Raumer
Differential scanning calorimetry (DSC) studies of micellar, 60 mM solutions of the octaethyleneglycol alkylethers C14E8 and C16E8 provide evidence for a narrow endothermic transition at 41 and 32C,respectively, characterized by an enthalpy change of
2 kJ mol−1 for both detergents. The observed thermal transition is indicative of a concerted transition of the surfactant molecules,
as illustrated on the basis of a simple molecular model. The effect of co-solvents such as different alcohols on the thermal
transition is investigated. Glycerol markedly lowers the transition temperature whereas the transition is absent in the presence
of at least 10% ethanol. The calorimetric transition correlates with the temperature dependent increase of viscosity and static
light scattering as well as with changes observed by small-angle neutron scattering (SANS). The SANS results provide clear
evidence for a distinct structural change occurring at the transition temperature, which is interpreted as a sphere-to-rod
transition of the detergent micelles. Moreover, the rod length increases with increasing temperature. We suggest that the
process causing the thermal transition acts as the prerequisite of the growth process.
La2Mo2O9 (LMO) was synthesized at lower temperature 973 K (LT-phase) by ceramic route. Differential thermal analysis (DTA) scan of
LT-phase of LMO showed α→β transition at 843 K during heating and β→α conversion via a metastable γ-phase during cooling.
This was also confirmed by thermo-dilatometry and impedance spectroscopy. La2Mo1.95V0.05O9-δ (LMVO), La1.96Sr0.04Mo2O9-δ (LSMO) and La1.96Sr0.04Mo1.95V0.05O9-δ (LSMVO) were prepared in a similar way. These compounds exhibited α→β transition on heating with shift in transition temperature,
but the existence of γ-phase during cooling disappeared. Substitution increased the ionic conductivity of α-phase and reduced
that of β-phase.
Liquid crystal → liquid crystal and liquid crystal → isotropic liquid transitions of several materials are studied using a numberN, whereN is defined as the ratioh′/h, h andh′ being the heights of the transition peaks at heating rates†p and2†p respectively.N is found close to two, which shows that a heat capacity increase occurs near the transition temperature, in agreement with the current theories describing these transitions.