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  • Author or Editor: L. I. Myachina x
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The effect of the dispersity of the sample on the topochemical mechanism and on the kinetic parameters of thermolysis (A s→Bs + Cg) under non-isothermal conditions is discussed. For correctness of the experiment, a ratio of maximum and minimum particle diameters ≤ 6 is a necessary condition. The topochemical mechanism of the process should be determined separately for the initial and final stages.

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Dehydratation kinetics of aquo-acido complex EDTA chelates CaML · nH2O (M= =Mn, Co, Ni, Cu, Zn, Cd, Ca,n=2 ... 5) were studied under non-isothermal conditions. The existence of two isokinetic temperatures (β 1=42°,β 2=216°) has been detected with a reliability of 95 %. The compensation effect found is explained by the change in the number of bonds formed in the sequence of equal-type dehydratation reactions of analogously built-up, but not isostructural compounds.

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The informative capacity of thermal analysis in the evaluation of the thermal stability of coordination compounds involving the evolution of volatile ligands is discussed. The temperature of decomposition under quasi-equilibrium conditions (Q-derivatograph, quasi-isobaric, quasi-isothermal operation) is suitable for characterizing the thermodynamic stability of compounds. The initial temperature of decomposition at linear heating indicates the reaching of a defined value of the rate constant (depending on the sensitivity of the sensing device of the instrument and on experimental conditions). The temperature sequence of increasing thermal stability may not coincide with the sequence of increasing activation energy values, since in the majority of cases it demands on the value of activation enthropy.

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