Authors:M. Cieslak-Golonka, E. Ingier-Stocka, and A. Bartecki
The activation energy,Ea taken from the thermal decomposition of KMnO4 and AgMnO4 was compared with the energy of the longest wavelength O→Mn ‘charge transfer’ (CT) transition. TheEa and CT correlation was found in these systems. However, such relationship can be valid when in the dissociation process the
electron transfer is assumed to be the rate determining step. Thus, the permanganates as well as the previously studied chromates,
are positive examples showing that in some cases, the energies derived from both methods can be comparable.
Authors:M. Maciejewski, E. Ingier-Stocka, W.-D. Emmerich, and A. Baiker
The complexity of the processes occurring during cobalt oxalate dihydrate (COD) decomposition indicates that an interpretation
of the mechanism based only on the TG curve is of little value. Mass change alone does not allow deeper insight into all of
the potential primary and secondary reactions that could occur. The observed mass changes (TG) and thermal effects (DTA/DSC)
are a superposition of several phenomena and thus do not necessarily reflect COD decomposition alone. Investigation of the
mechanism of decomposition requires the application of different simultaneous techniques that allow the qualitative and quantitative
determination of the composition of the gaseous products.
Composition of the solid and gaseous products of COD decomposition and heats of dehydration and oxalate decomposition were
determined for inert, oxidizing and hydrogen-containing atmospheres. Contrary to previous suggestions about the mechanism
of cobalt oxalate decomposition, the solid product formed during decomposition in helium contains not only metallic Comet, but also a substantial amount of CoO (ca 13 mol%). In all atmospheres, the composition of the primary solid and gaseous
products changes as a result of secondary gas-solid and gas-gas reactions, catalyzed by freshly formed Comet.
The course of the following reactions has been investigated under steady-state and transient conditions characteristic for
COD decomposition: water gas shift, Fischer-Tropsch, CO disproportionation, CoO reduction by CO and H2, Comet oxidation under rich and lean oxygen conditions.
Authors:L. Rycerz, M. Cieślak-Golonka, E. Ingier-Stocka, and M. Gaune-Escard
Several experimental techniques were used to characterise the physicochemical properties of the TbBr3-NaBr system. The phase diagram determined by DSC, exhibits an eutectic and a Na3TbBr6 stoichiometric compound that decomposes peritectically (759 K) shortly after a solid-solid phase transition (745 K). The
eutectic composition, x(TbBr3)=39.5 mol%, was obtained from the Tamman method. This mixture melts at 699 K. With the corresponding enthalpy of about 16.1
kJ mol-1. Diffuse reflectance spectra of the pure components and their solid mixtures (after homogenisation in the liquid state) confirmed
the existence of new phase exhibiting its own spectral characteristics, which may be possibly related to the formation of
Na3TbBr6 in this system. Additionally, the electrical conductivity of TbBr3-NaBr liquid mixtures was measured down to temperatures below solidification over the whole composition range.
Authors:L. Rycerz, E. Ingier-Stocka, M. Golonka-Cieślak, and M. Gaune-Escard
The heat capacity of solid NdBr3 was measured by Differential Scanning Calorimetry in the temperature range from 300 K up to the melting temperature. The
heat capacity of liquid NdBr3 was also determined. These results were least-squares fitted to a temperature polynome. The melting enthalpy of NdBr3 was measured separately. DSC was used also to study phase equilibrium in the NdBr3-LiBr system. The results obtained provided a basis for constructing the phase diagram of the system under investigation.
It represents a typical example of simple eutectic system. The eutectic composition, x(NdBr3)=0.278, was obtained from the Tamman construction. This eutectic mixture melts at 678 K. The electrical conductivity of NdBr3-LiBr liquid mixtures and of pure components was measured down to temperatures below solidification. Reflectance spectra of
the pure components and their solid mixtures (after homogenisation in the liquid state) with different composition were recorded
in order to confirm the reliability of the constructed phase diagram.