The thermal decomposition of nitrocellulose (NC) 12.1% N, has been studied with regard to kinetics, mechanism, morphology and the gaseous products thereof, using thermogravimetry
(TG), differential thermal analysis (DTA), IR spectroscopy, differential scanning calorimetry (DSC) and hot stage microscopy.
The kinetics of the initial stage of thermolysis ofNC in condensed state has been investigated by isothermal high temperature infrared spectroscopy (IR). The decomposition ofNC in KBr matrix in the temperature range of 142–151°C shows rapid decrease in O−NO2 band intensity, suggesting that the decomposition of NC occurs by the rupture of O−NO2 bond. The energy of activation for this process has been determined with the help of Avrami-Erofe'ev equation (n=1) and is ≈188.35 kJ·mol−1. Further, the IR spectra of the decomposition products in the initial stage of thermal decomposition ofNC, indicates the presence of mainly NO2 gas and aldehyde.
The thermal stability, kinetics and glass forming ability of an Fe77C5B4Al2GaP9Si2 bulk amorphous alloy have been studied by differential scanning calorimetry. The activation energy, frequency factor and
rate constant corresponding to the multiple crystallization steps were determined by the Kissinger method. X-ray diffraction
and transmission electron microscopy studies revealed that the crystallization starts with the primary precipitation of α-Fe
from the amorphous matrix. The kinetics of nucleation of the α-Fe nanoparticles was investigated by two different methods,
i.e. isothermal annealing and continuous heating after partial annealing.
The effect of the water vapor pressure on the thermal dehydration of manganese(II) formate dihydrate was studied by means
of isothermal gravimetry under various water vapor pressure, ranging from 4.6 to 24.4 torr.
The kinetics of dehydration was described by a two-dimensional phase-boundary model,R2. The rate of dehydration decreased with increasing atmospheric water vapor pressure, but the Smith-Topley phenomenon was
not observed for the present dehydration. The activation energy and the frequency factor for the dehydration were 110–170
kJ·mol−1 and 1010–1016 cm·s−1, respectively. These values increased with increasing water vapor pressure, and were much larger than those reported for
the dehydration in vacuum.
The kinetics of thermal decomposition of a series of uranyl nitrate complexes with N-alkylcaprolactams (alkyl=C2H5, C4H9, C6H13, C8H17, C10H21 or C12H25) was studied by means of non-isothermal gravimetry under a nitrogen atmosphere. From the TG-DTG curves, the kinetic parameters
relating to the loss of two molecules of coordinated ligand were obtained by employing two groups of methods: (I) a group
of conventional methods involving the Coast-Redfern, Freeman-Carroll, Horowitz-Metzger, Dharwadkar-Karkhanavala and Doyle
(modified by Zsakó) equations; (II) a new method were suggested by J. Máleket al.. The results obtained using two types of methods were compared, and it emerged that the results of method II were much more
meaningful and reasonable in this work. Additionally, the effects of the molecular structure of the ligands on the kinetic
data and models were studied and are discussed.
The curing reactions of the epoxy resins tetraglycidyl diaminodiphenyl methane (TGDDM) and tetraglycidyl methylenebis (o-toluidine) (TGMBT) using diaminodiphenyl sulfone (DDS), diaminodiphenyl methane (DDM) and diethylenetriamine (DETA) as curing agents were studied kinetically by differential scanning calorimetry. The dynamic scans in the temperature range 20°–300°C were analyzed to estimate the activation energy and the order of reaction for the curing process using some empirical relations. The activation energy for the various epoxy systems is observed in the range 71.9–110.2 kJ·mol−1. The cured epoxy resins were studied for kinetics of thermal degradation by thermogravimetry in a static air atmosphere at a heating rate of 10 deg·min−1. The thermal degradation reactions were found to proceed in a single step having an activation energy in the range 27.6–51.4 kJ·mol−1.
Correlations were determined between heat capacity and temperature and phase change enthalpy of Ba(OH)2·8H2O. The phase diagram and DSC curve of the binary system Na2CO3·10H2O−Na2HPO4·12H2O were determined The kinetics of the dehydrating reaction of Ba(OH)2·8H2O, Na2CO3·10H2O and Na2HPO4·12H2O were measured and theoretically analyzed by TG.
The kinetics of thermal decomposition of Sn(II), Pb(II), Cd(II) and Hg(II) alginate gels have been studied using thermogravimetry (TG) and derivative thermogravimetry (DTG) in static air. The thermal dehydration of each gel complex was found to occur in one step, whereas the decomposition of the dehydrated complexes occurred in two steps. The kinetic parameters were computed by different models and a tentative decomposition mechanism consistent with the kinetic observations is discussed.
Reaction kinetics of the formation of TiC by calciothermic reduction of TiO2 in presence of carbon have been investigated using thermal analysis (TG-DTA) of a powder mixture of TiO2, Ca, and C in argon atmosphere at different heating rates. Both the reaction initiation and the peak temperatures are found
to increase with heating rates. The appearance of exothermic peaks in the DTA plots after Ca melting indicates the reduction
of TiO2 by liquid calcium and formation of TiC by in-situ reaction of Ti with C. The apparent activation energy of the process has
been found to be 170.80.5 kJ mol-1.
Authors:S.-J. Tian, G.-X. Xi, Q.-T. Cheng, X.-D. Lou and J.-H. Li
The inclusion complex of benzaldehyde (BA) with β-cyclodextrin (β-CD) was prepared and was studied by thermal analysis and
X-ray diffractometry. The composition of the complex was identified by TG and elemental analysis as β-CDBA9H2O. TG and DSC studies showed that the thermal dissociation of β-CDBA9H2O took place in three stages: dehydration in the range 70-120C; dissociation of β-CDBA in the range 235-270C; and decomposition
of β-CD above 280C. The kinetics of dissociation of β-CDBA in flowing dry nitrogen was studied by means of TG both at constant
temperature and at linearly increasing temperature. The results showed that the dissociation of β-CDBA was dominated by a
one-dimensional random nucleation and subsequent growth process (A2). The activation energy E was 124. 8 kJ mol-1, and the pre-exponential factor A 5.041011 min-1.
Authors:D. Choudhury, R. Borah, R. Goswamee, H. Sharmah and P. Rao
Pyrolysis of petroleum refinery sludge has received global acclamation as a clean conversion technique for providing solution
of sludge disposal as well as efficient resource utilization. This communication reports the kinetics study of pyrolysis of
petroleum refinery sludge. Experiments were carried out by means of thermogravimetric analysis at different heating rates
of 5, 10 and 20�C min−1. The pyrolytic reaction is significant in the temperature range of 200–350�C and analysis and evaluation of kinetic parameters
is done in the 100–500�C region of non-isothermal TG curves obtained in nitrogen atmosphere.
The activation energy is calculated by iso-conversional method, then other kinetic parameters are determined by considering
single reaction and two reaction global kinetic model. Two-reaction model is found to fit satisfactorily the experimental