The heat, equilibrium, and kinetics of adsorption of 1-ethoxy-2-propanol vapours on granulated activated carbon were determined simultaneously by a reaction calorimeter SETARAM C80 D at T=298.15 K at various relative vapour pressures (0.1< p/ps<0.8). The adsorption isotherm was correlated by the Freundlich equation. It was observed that the enthalpies of adsorption decrease slightly with increasing of the relative vapour pressure of the adsorptive. The rate of adsorption were calculated from analysis of the heat flux signals and it was found that the mass-transfer coefficient for 1-ethoxy-2-propanol vapours in granulated activated carbon increased with increasing relative vapour pressure of the adsorptive.
The kinetics of the thermal decomposition of ammonium perchlorate at temperatures between 215 and 260°C is studied, in this
work, by measuring the sample mass loss as a function of time applying the isothermal thermogravimetric method.
From the maximum decomposition rate – temperature dependence two different decomposition stages, corresponding to two different
structural phases of ammonium perchlorate, are identified. For the first region (215–235°C), corresponding to the orthorhombic
phase, the mean value of the activation energy of 146.3 kJ mol–1, and the pre-exponential factor of 3.43⋅1014 min–1 are obtained, whereas for the second region (240–260°C), corresponding to the cubic phase, the mean value of the activation
energy of153.3 kJ mol–1, and the pre-exponential factor of 4.11⋅1014 min–1 are obtained.
The thermal decomposition behavior of hard coal fly ash (HCA2), obtained from the combustion of an Australian hard coal in
thermoelectric power plants, in different atmospheres (air, N2 and N2-H2 mixture), was studied using thermogravimetry (TG), infrared-evolved gas analysis (IR-EGA), differential scanning calorimetry
(DSC) and thermodilatometry (DIL) techniques. It was found that changing of the applied atmosphere affects the carbon content
of the ash which results in different thermal decomposition behaviors. In air, the carbon content was oxidized to carbon dioxide
before the decomposition of carbonate. In N2 or in N2-H2 atmospheres, the carbon content acts as a spacer causing a fewer points of contact between calcium carbonate particles, thus
increasing the interface area which results in a decrease of the carbonate decomposition temperature. Following the carbonate
decomposition, the iron oxide content of the ash undergoes a reductive decomposition reaction with the unburned carbon. This
oxidation-reduction reaction was found to be fast and go to completion in presence of the N2-H2 mixture than in the pure nitrogen atmosphere due to the reducing effect of the hydrogen.
The kinetics of the carbonate decomposition step, in air and N2-H2 mixture was performed under non-isothermal conditions using different integral methods of analysis. The dynamic TG curves
obeyed the Avrami-Erofeev equation (A2) in air, and phase boundary controlled reaction equation (R2) in N2-H2 mixture. The change in the reaction mechanism and the difference in the calculated values of activation parameters with the
change of the atmosphere were discussed in view of effect of the atmosphere on the carbon content of the ash.
Kinetics of oxidation of Fe-Cr steel containing 25 wt.-percent Cr was studied as a function of temperature (1023–1173 K) for
up to 480 h in flowing air, which corresponds to SOFC cathode environment operating conditions. The oxidation process was
found to be a parabolic, suggesting that the diffusion of ionic defects in the scale is the slowest, rate determining step
and it occurs predominantly by short-circuit diffusion paths. Comparison of the determined activation energy of oxidation
of the studied steel with literature data indicates that at 1098–1173 K the chromia scale grows by the outward solid-state
diffusion of chromium interstitials, whereas at 1023–1098 K — through a significant contribution of counter-current oxygen/chromium
diffusion along Cr2O3 grain boundaries. The oxide scales were composed mainly of Cr2O3 with a continuous thin Mn1.5Cr1.5O4 spinel layer on top of the chromia scale. The oxidation test results on Fe-25Cr steel demonstrate the applicability of the
commercial type DIN 50049 stainless steel as interconnect for SOFC.
Authors:Tongshan Sun, Yuting Zhao, Jaihui Jin and Daqing Wang
Four complexes of rare earth bromides with amino acids, REBr3·3L·3H2O (RE=La, Nd;L=glycine or alanine) were prepared and characterized by means of chemical analysis, elemental analysis, molar conductivity,
thermogravimetry, IR spectra and X-ray diffraction. Their thermal decomposition kinetics from ambient temperature to 500°C
were studied by means of TG-DTG techniques under non-isothermal conditions. The kinetic parameters (activation energyE and pre-exponential constantA) and the most probable mechanisms of thermal decomposition were obtained by using combined differential and integral methods.
The thermal decomposition processes of these complexes are distinguished as being of two different types, depending mainly
on the nature of the amino acid.
A modified first order kinetic law, which describes the roles of bound and unbound vacancies, is proposed in order to predict
defect decay and short-range-order kinetics of quenched binary alloys during linear heating experiments. The model has been
applied to differential scanning calorimetry (DSC) curves of Cu–5 at%Zn quenched from different temperatures. Activation energy
for migration of solute-vacancy complexes was also assessed from the kinetics of short-range-order using DSC traces. A value
of 89.50.32 kJ mol–1 was obtained. The relative contribution of bound and unbound vacancies to the ordering process as influenced by quenching
temperature was determined. In conjunction, a parametric study of the initial total defect concentration and effective energy
for defect migration was performed in order to envisage their influence on the calculated DSC profiles.
Authors:M. Suşeska, M. Rajiş, S. Matečiş-Mušaniş, S. Zeman and Z. Jalový
TNAZ (1,3,3-trinitroazetidine) is a relatively new, powerful, steam castable, strained ring explosive. Owing these characteristics
it is of considerable interest to the energetic material community. A relatively high vapour pressure, volume contraction
and formation of shrinkage cavities in the solidification of its melt may be considered as some of its disadvantages. The
kinetics and heats of TNAZ sublimation and evaporation were studied by the non-isothermal and isothermal thermogravimetry
method. The activation energy of 94-102 kJ mol-1 was found for TNAZ sublimation, while the activation energy of 60-81 kJ mol-1 was found for TNAZ evaporation. The enthalpy of TNAZ sublimation at the melting temperature was found to be 95 kJ mol-1, and the enthalpy of TNAZ evaporation equals 66 kJ mol-1.
The accuracy and scope of application of previously reported approximations of the temperature integral were evaluated. The
exact solution was obtained independently by solving the temperature integral numerically be Simpson's rule, the trapezoidal
rule and the Gaussian rule.
Two new approximations have been proposed:
whereX=E/RT. The first equation gives higher accuracy, with a deviation of less than 1% and 0.1% from the exact solution forX≥7 andX≥10, respectively. The second equation has a wider scope of application, with a deviation of less than 1% forX≥4 and of less than 0.1% forX≥35.