Thermodynamic properties and phase equilibria in alloys of Bi—Tm system

The thermochemical properties of the melts of the Bi—Tm system at a temperature of 1100 K in the range of compositions 0 ≤ xTm ≤ 0,2 were determined for the first time by the calorimetry method. It is established that the minimum value of the enthalpy of mixing of these liquid alloys is equal to –75,7 ± 0,5 kJ / mol at xTm = 0,65. = = –150,7 ± 16,7 kJ / mol, = –230,9 ± 21,8 kJ / mol. The activities of the components and molar particles of associates were calculated according to the model of an ideal associated solution (IAR), using data on the thermochemical properties of melts of the Bi—Tm system. It was found that the activities of the components in these metallic solutions show very large negative deviations from ideal solutions with a high content of TmBi and Tm2Bi associates. The obtained dependences of the first i i melts of the Bi—Tm system on temperature showed a large steepness of the Bi Bi curve in contrast to the gradual decrease of exothermic values Tm of Tm. This indicates large changes in the structure of the Bi atom with increasing temperature. Excess integral and partial Gibbs energies of Bi-Tm system melt mixing calculated from component activities The absolute values of G in the whole concentration range are smaller than H (G min = –41,8 kJ / mol at xTm = 0,58), and the function G of is more asymmetric, which is caused by the entropy contribution (entropy of mixing of the studied melts is negative, and Smin min = −30,5 J / mol ∙ K at xTm = 0,65). Keywords: thermochemical properties, compounds, melts, Bi, Tm.

Thermodynamic properties of alloys binary In—Pr (Nd) and ternary In—Pr (Nd)—Ni systems

The thermochemical properties of In—Pr system melts in the range of compositions 0 < xIn < 0,4 and In—Nd in the whole concentration range at 1573 ± 1 K were investigated by isoperibolic calorimetry. The obtained data for the In—Pr system melts were extrapolated to the unexplored concentration interval, taking into account that at xPr = 1 the integral and partial mixing for Pr enthalpy are equal to zero. It was found that the first partial for Pr and the minimum enthalpy of mixing are equal to –139 ± 11 and –40,3 ± 0,2 kJ / mol, respectively. For the In—Nd system the first partial for In and Nd, the minimum enthalpy of mixing is equal to −131,7 ± 11, −140,6 ± 12 і –43,3  0,2 kJ / mol, respectively. Comparison of ΔHmin, melts of the five previously studied In—Ln systems from the ordinal number Ln (zLn) together with the data obtained in this work showed that they are described by a single trend line. For ΔHmin of melts of In—Eu (Yb) systems there are very insignificant deviations from the trend line. But for the size factor, these deviations from the trend line are more significant. The enthalpies of formation of some intermetallics of In—Ln systems are known, and most of them belong to the compound LnIn3. But there is no complete agreement between these data. The results of the most modern work show less dependence on the serial number of lanthanide and are more exothermic for heavy lanthanides, compared with other data. Keywords: thermochemical properties, compounds, melts, In, Pr, Nd.

Group Contribution Revisited: The Enthalpy of Formation of Organic Compounds with “Chemical Accuracy” Part II

Group contribution (GC) methods to predict thermochemical properties are eminently important to process design. We present a group contribution parametrization for the heat of formation of organic molecules exhibiting chemical accuracy, maximum 1 kcal/mol (4.2 kJ/mol) difference between experiment and model values while minimizing the number of parameters avoiding overfitting and therewith avoiding reduced predictability. Compared to the contemporary literature, this was successfully achieved by employing available literature high-quality and consistent experimental data, optimizing parameters group by group, and introducing additional parameters when chemical understanding was obtained supporting these. A further important result is the observation that the applicability of the group contribution approach breaks down with increasing substitution levels, i.e., more heavily alkyl-substituted molecules, the reason being a serious influence of substitution on the conformation of the flexible part of the entire molecule within particular valence angles and torsional angles affected, which cannot be accounted for by additional GC parameters with fixed numerical values.