Development of an applied variant of the kolmogorov–johnson–mehl theory of crystallization for processing thermal analysis data. Temperatures and enthalpies of melting germanium isotopes

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Resumo

An applied kinetic model has been developed for processing DSC peaks of transitions between states, determining the temperature–time dependence of the degree of transition and combining the fundamental theory of Kolmogorov–Johnson–Mehl crystallization, simplified for practice, with the semi-empirical Erofeev model. In the development of this applied model, the concept of a “thermodynamic factor” is introduced, which allows a transition in the kinetics of phase transformations of condensed matter. The application of the new approach is demonstrated by the example of studying the dependences of temperature and enthalpy of fusion on the average atomic mass of stable germanium isotopes, data on which, as new chemical individuals, are of a fundamental nature and can serve as reference information.

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Sobre autores

A. Kutin

G. G. Devyatykh Institute of Chemistry of High-Purity Substances, Russian Academy of Sciences

Email: plekhovich@ihps-nnov.ru
Rússia, 603951 Nizhny Novgorod

A. Plekhovich

G. G. Devyatykh Institute of Chemistry of High-Purity Substances, Russian Academy of Sciences

Autor responsável pela correspondência
Email: plekhovich@ihps-nnov.ru
Rússia, 603951 Nizhny Novgorod

V. Gavva

G. G. Devyatykh Institute of Chemistry of High-Purity Substances, Russian Academy of Sciences

Email: plekhovich@ihps-nnov.ru

Corresponding Member of the RAS

Rússia, 603951 Nizhny Novgorod

A. Bulanov

G. G. Devyatykh Institute of Chemistry of High-Purity Substances, Russian Academy of Sciences

Email: plekhovich@ihps-nnov.ru
Rússia, 603951 Nizhny Novgorod

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2. Fig. 1. Melting peaks of germanium isotopes. The symbols denote the experimental DSC values: ⁷⁶Ge – line, ⁷⁴Ge – square, ⁷²Ge – cross, ⁷⁰Ge – triangle (a); ⁷³Ge – rhombus, ⁿᵃᵗGe – circle (b); solid lines (color corresponding to the symbols) are the result of processing the experimental DSC values ​​according to equations (2), (13), (15), (16), (16ʹ) by the least squares method with the parameters found from Table 1; α are dashed lines.

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3. Fig. 2. Dependence of the melting point of ⁿᵃᵗGe and its isotopes on the atomic mass M (circles with the corresponding trend line and its equation). The measurement data from [18] are indicated by crosses. The error intervals of the experimental temperature measurement, established by the shift of the peaks during triple thermal cycling (0.14 K), are plotted against the values ​​calculated using the FP model Tₜᵣ.

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4. Fig. 3. Enthalpies (ΔₜᵣH) and dimensionless entropies of melting ΔₜᵣS = ΔₜᵣH/RTₜᵣ, calculated using the FP model depending on the atomic mass of M ⁿᵃᵗGe and its isotopes.

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