Enthalpies of dissolution of benzo-15-crown-5 ether (B15C5) in mixtures of acetonitrile with water and in solutions of NaI and NaBPh4 (I=0.05 mol dm−3) in these mixtures were measured at 298.15 K. From the obtained results and appropriate literature data, the thermodynamic functions of B15C5/Na+ complex formation in acetonitrile-water mixtures were determined. The enthalpies of transfer of the complex B15C5/Na+ from pure acetonitrile to the examined mixtures were calculated and are discussed.
The phase diagrams of binary organic systems of benzidine with pyrogallol andp-nitrophenol give a double simple eutectic type phase diagram showing formation of a 1∶1 molecular complex with congruent melting point and two eutectics. The growth data on the pure components, the eutectics and the molecular complexes, determined by measuring the rate of movement of growth front in a capillary, justify the square relationship between growth velocity and undercooling. While enthalpy of mixing values suggest intermolecular hydrogen bonding, the excess thermodynamic functions reveal strong interactions among the components forming eutectics and addition compounds.
The (R)-BINOL-menthyl dicarbonates,
one of the most important compounds in catalytic asymmetric synthesis, was
synthesized by a convenient method. The molar heat capacities Cp,m
of the compound were measured over the temperature range from 80 to 378 K
with a small sample automated adiabatic calorimeter. Thermodynamic functions
[HT–H298.15] and [ST–S298.15] were derived in the
above temperature range with a temperature interval of 5 K. The thermal stability
of the substance was investigated by differential scanning calorimeter (DSC)
and a thermogravimetric (TG) technique.
The temperature dependence of the molar heat capacities of the tellurites Fe2(TeO3)3, Fe2TeO5 and Fe2Te4O11 were determined. By statistical manipulation of the values obtained, the parameters in the equations for the corresponding
compounds showing this dependence were determined using the least-squares method. These equations together with the standard
molar entropies were used to determine the thermodynamic functions Δ0TSm0, ΔTT,Hm0 and (Φm0 + Δ0T’Hm0 / T) for T’=298.15 K.
The molar heat capacity, Cp,m, of a complex of holmium chloride coordinated with L-aspartic acid, Ho(Asp)Cl2·6H2O, was measured from 80 to 397 K with an automated adiabatic calorimeter. The thermodynamic functions HT-H298.15 and ST-S298.15 were derived from 80 to 395 K with temperature interval of 5 K. The thermal stability of the complex was investigated by
differential scanning calorimeter (DSC) and thermogravimetric (TG) technique, and the mechanism of thermal decomposing of
the complex was determined based on the structure and the thermal analysis experiment.
The results of recent developments on modelling of supramolecular ordering and physicochemical properties of molecular mixtures
have been reviewed. The main attention is paid to the unified approach based on a generalized quasichemical model for a set
of thermodynamic, dielectric and optical properties of mixtures, self-organized by specific bonding. Interrelations between
thermodynamic, as well as dielectric, and optical properties of liquid mixtures, reflecting different molecular parameters,
and the characteristics of quasichemical processes are presented. Applications for thermodynamic functions of mixing, permittivity,
coefficients Rayleigh light scattering in molecular mixtures are considered. Data on thermodynamics of aggregation in mixtures
have been obtained.
Phase diagrams of urea-α-naphthol and urea-benzoic acid systems, determined by the thaw-melt method, show the formation of
simple eutectic in each case. The growth velocity data, determined at different undercooling (ΔT) by observing the rate of
movement of interface in a capillary, obey the Hillig-Turnbull equation, v=u(ΔT)n, where u and n are constants depending on the nature of the materials. Using enthalpy of fusion, undercooling (ΔT) and melting
point data, entropy of fusion, interfacial energy, enthalpy of mixing, critical radius size and excess thermodynamic functions
were calculated. The microstructural investigations give characteristic features of the eutectics.
The temperature dependence of the molar heat capacities of the tellurites PbTeO3, Pb2Te3O8 and Ge(TeO3)2 are determined. By statistical manipulation of the values obtained, the parameters in the equations for the corresponding compounds showing this dependence are determined using the least-squares method. These equations and the standard molar entropies are used to determine the thermodynamic functions Δ0TSm0, ΔTTHm0 and (Φm0+Δ0THm0/T) for T′=298.15 K.
Heat capacity of stoichiometric homogeneous spinel MgFe2O4 was measured from 5 to 305 K and thermodynamic functions were derived for temperatures up to 725 K using our previous high-temperature
experimental data for the same sample.
Anomaly in Cp was found at very low temperatures. Experimental data below 20 K contain large (up to 25% near 5 K) error arising from the
difference in the thermal history between the experimental series.
Magnetic contribution to the low-temperature heat capacity was tested, and the linear function was found to fit experimental
data better than the three-halves power derived from the spin-wave theory.
Synthetic enstatite MgSiO3 was crystallized from a melt, quenched into water, and then annealed at 873 K. The product is the monoclinic polymorph with
the unit cell parameters of a=0.9619(7), b=0.8832(3), c=0.5177(4) nm, β=108.27(5)°. Heat capacity was measured from 6 to 305 K using an adiabatic vacuum calorimeter. Thermodynamic
functions for clinoenstatite differ by about 5% from those predicted after a thermodynamic model in the literature, but are
very close to those measured for orthorhombic enstatite.