Two causes for the kinetic compensation effect (KCE) were recognized for a given solidstate reaction at various heating rates. One is due to any change in the range of reaction. This KCE is quantitative and meaningful, provided thatF(α) remains constant under the given conditions. The other is due to misestimation of the appropriate rate law, which in turn leads to a superficial KCE. It was also shown that the existence of an isokinetic point does not necessarily imply the occurrence of a meaningful KCE.
A “true” kinetic compensation effect was established using the most appropriate kinetic functionF(α) for the non-isothermal decomposition of solids at various heating rates. It is likely that the correct kinetic mechanismF(α) is responsible for the “true” kinetic compensation effect, whereas an inappropriateF(α) would lead to “false” one.
Thermoanalytical (TA) and hot-stage microscopic techniques were employed to investigate the complicated behaviour of the non-isothermal
dehydration of single crystals of α-NiSO4·6H2O. Non-isothermal dehydration to the tetrahydrate proceeds in two stages: (1) surface nucleation and growth of nuclei, followed
by advancement of reaction fronts inward; (2) random nucleation and growth near the reaction front as well as in the bulk.
Corresponding TA curves were interpreted to represent diffusional removal of evolved water vapour through the surface layer
created in stage (1). The dehydration process of the tetrahydrate to the monohydrate is explained on the basis of textural
structures produced in the previous step. Crack formation in the surface layer and rapid escape of the water vapour were observed
in this step.
Effects of sample mass on the kinetics of isothermal dehydration of crushed crystals of Li2SO4·H2O were investigated using conventional TG. The process was characterized by a combination of Avrami-Erofeyev and contracting
geometry models. Distribution of the fractional reaction, α, in particles within the sample assembly as well as the change
in the rate of gross diffusion of the evolved water vapour appear responsible for the sample-mass-dependent kinetic parameters
obtained for the system.
The degree of coordination between the kinetic information from the thermonalytical measurements and the kinetic theory of
the solid-state reactions was investigated through the microscopic study of the thermal dehydration of several inorganic salt
hydrates. An accommodation function was applied to the conventional kinetic model functionsf(α), in an attempt to reduce the disagreement between the actual process and the idealized one assumed in formulatingf(α). The significance of the non-integral kinetic exponent in the kinetic model function was discussed with its physico-chemical
For the quantitative analyses of evolved CO2and H2O during the thermal decomposition of solids, calibration curves, i.e. the amounts of evolved gases vs. the corresponding
peak areas of mass chromatograms measured by TG-MS, were plotted as referenced by the reaction stoichiometry of the thermal
decomposition of sodium hydrogencarbonate NaHCO3. The accuracy and reliability of the quantitative analyses of the evolved CO2and H2O based on the calibration curves were evaluated by applying the calibration curves to the mass chromatograms for the thermal
decompositions of copper(II) and zinc carbonate hydroxides. It was indicated from the observed ratio of evolved CO2and H2O that the compositions of copper(II) and zinc carbonate hydroxides examined in this study correspond to mineral malachite,
Cu2CO3(OH)2, and hydrozincate, Zn5(CO3)2(OH)6, respectively. Reliability of the present analytical procedure was confirmed by the fairly good agreement of the mass fraction
of the evolved gases calculated from the analytical values with the total mass-loss during the thermal decompositions measured
Nickel sulfide (NiS) fire assay was used for the pre-concentration of Ir and Au in rock samples. The beads obtained after
fire assay were irradiated directly with neutrons to determine Ir and Au. To suppress the reaction of 58Ni(n,p)58Co, the fire assay was carried out by using a small amount of Ni (0.0625 g) and the NiS bead samples were irradiated by neutrons
with high Cd ratios. Analytical results of Ir and Au for rock samples were close to literature values, confirming that our
procedure of INAA with pre-concentration can be applied to rock samples for the determination of ppb to sub-ppb level of Ir
The effect of atmospheric water vapor on the kinetic rate behavior of the thermal decomposition of copper(II) carbonate hydroxide,
Cu2CO3(OH)2, was investigated by means of TG-DTA coupled with a programmable humidity controller. With increasing water vapor pressure
p(H2O) from 0.8 to 10.6 kPa, a systematic reduction of the reaction temperature of the thermal decomposition was observed as the
continuous trend from the previous works at the lower p(H2O). Through a comparative kinetic analysis of the reaction at different p(H2O), a catalytic action of the atmospheric water vapor on the nucleation process at the first half of the reaction was identified
as the possible origin of the reduction of the reaction temperature.