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1.
The thermal decomposition of three new reagent cyclohexylamine- p-tolylglyoxime (L 1H 2), tertiarybutyl amine- p-tolylglyoxime (L 2H 2) and secondary butylamine- p-tolylglyoxime (L 3H 2 and their Co-complexes were studied by both isothermal and nonisothermal methods. As expected, the complex structure of Co-complexes,
different steps with different activation energies were realized in decomposition process. Model-fitting and model-free kinetic
approaches were applied to nonisothermal and isothermal data. The kinetic triplet ( f(α), A and E) related to nonisothermal model-fitting method can not be meaningfully compared with values obtained from isothermal method.
The complex nature of the multi-step process of the studied compounds was more easily revealed using a wider temperature range
in nonisothermal isoconversional method. 相似文献
2.
Thermal analysis is one of the most widely used methods for studying the solid state of pharmaceutical substances.
TG/DTG and DSC curves provide important information regarding the physical properties of the pharmaceutical compounds (stability,
compatibility, polymorphism, kinetic analysis, phase transitions etc.).
The purpose of a kinetic investigation is to calculate the kinetic parameters and the kinetic model for the studied process.
The results are further used to predict the system’s behaviour in various circumstances.
A kinetic study regarding the diazepam, nitrazepam and oxazepam thermal decomposition was performed, under non-isothermal
and isothermal conditions and in a nitrogen atmosphere, for the temperature steps: 483, 498, 523, 538 and 553 K. The TG/DTG
data were processed by three methods: isothermal model-fitting, Friedman’s isothermal-isoconversional and Nomen-Sempere non-parametric
kinetics.
In the model-fitting methods the kinetic triplets ( f(α), A and E
a) that defines a single reaction step resulted in being at variance with the multi-step nature of diazepines decomposition.
The model-free approach represented by isothermal and non-isothermal isoconversional methods, gave dependences of the activation
energies on the extent of conversion.
It is very difficult to obtain an accord with the similar data which resulted under non-isothermal conditions from a previous
work.
The careful treatment of the kinetic parameters obtained in different thermal conditions was confirmed to be necessary, as
well as a different strategy of experimental data processing. 相似文献
3.
The thermal decomposition of potassium iodate (KIO 3) has been studied by both non-isothermal and isothermal thermogravimetry (TG). The non-isothermal simultaneous TG–differential
thermal analysis (DTA) of the thermal decomposition of KIO 3 was carried out in nitrogen atmosphere at different heating rates. The isothermal decomposition of KIO 3 was studied using TG at different temperatures in the range 790–805 K in nitrogen atmosphere. The theoretical and experimental
mass loss data are in good agreement for the thermal decomposition of KIO 3. The non-isothermal decomposition of KIO 3 was subjected to kinetic analyses by model-free approach, which is based on the isoconversional principle. The isothermal
decomposition of KIO 3 was subjected to both conventional (model fitting) and model-free (isoconversional) methods. It has been observed that the
activation energy values obtained from all these methods agree well. Isothermal model fitting analysis shows that the thermal
decomposition kinetics of KIO 3 can be best described by the contracting cube equation. 相似文献
4.
A critical study of the use of isoconversional methods for the kinetic analysis of non-isothermal data corresponding to processes
with either a real or an apparent variation of the activation energy, E, with the reacted fraction, α, has been carried out using for the first time simulated curves. It has been shown that the
activation energies obtained from model-free methods are independent of the heating rate. However, the activation energy shows
a very strong dependence of the range of heating rates used for simulating the curves if the apparent change of E with α is caused by overlapping processes with different individual activation energies. This criterion perhaps could be
used for determining if a real dependence between E and α is really occurring. 相似文献
5.
The purpose of this investigation is to calculate the kinetic parameters and the kinetic model for the studied process. The results are further used to predict the system’s behaviour in various circumstances. A kinetic study regarding the ketoprofen—involving active substance’s thermal decomposition—was performed under isothermal conditions and in a nitrogen atmosphere, for the temperature steps: 260; 265; 270; 275; and 280 °C. The thermogravimetry/derivative thermogravimetry data were processed by three differential methods: isothermal–isoconversional, Friedman’s isothermal–isoconversional, and isothermal model-fittings. The obtained results are in good accordance with those obtained under non-isothermal conditions of a previous study, and confirm the necessity for the kinetic parameters to be determined, under different thermal conditions, by the adequate calculation methods. 相似文献
7.
This study describes the physico-geometrical mechanism and overall kinetics for the multistep thermal dehydration of barium titanyl oxalate tetrahydrate (BTO). The thermal dehydration kinetics of BTO was studied at four different linear heating rates under non-isothermal conditions. The reaction kinetics was performed using differential scanning calorimetry (DSC) and the curves obtained were analysed using different isoconversional model-free equations and the values are found to be compatible with each other. The kinetic deconvolution principle is used for identifying the partially overlapped kinetic processes of the thermal dehydration of BTO, and it occurs in two stages. The overall reaction kinetics parameters calculated via kinetic deconvolution of the sample indicate the multistep nature of the process and the kinetic analysis of the non-isothermal data of this reaction model shows that the reaction is best described by Sestak–Berggren (m, n) empirical kinetic model. The prepared sample was identified and characterized by means of FT-IR, XRD, SEM, and TEM. 相似文献
9.
The curing of a thermosetting powder coating was studied by means of differential scanning calorimetry (DSC). The isothermal
cure was simulated by non-isothermal experiments. The results of the simulation were compared with experimental isothermal
data. From non-isothermal isoconversional procedures (free model), it was concluded that these permit simulation of the isothermal
cure but do not enable us to determine the complete kinetic triplet ( A preexponential factor, E activation energy, f(a) and/or g(a) function of conversion). Non-isothermal procedures based on a single heating rate or on master curves present difficulties
for determination of all the kinetic parameters, due to the compensation effect between preexponential factor and activation
energy. The kinetic triplet can be determined by a combination of various non-isothermal methods or by using experimental
isothermal data in addition to non-isothermal data.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
10.
A kinetic study on the thermal decomposition of 3-nitro and 4-nitro-benzaldehyde-2,4-dinitrophenylhydrazones was carried out. The isothermal and dynamic differential scanning calorimetric curves were recorded for solids and melts, respectively. The standard isoconversional analysis of the obtained curves from both isothermal and nonisothermal analysis suggests an autocatalytic decomposition mechanism. This mechanism is also supported by the temperature dependence of the observed induction periods. Based on the results of the model-free method from nonisothermal regime, the kinetic model was derived and the kinetic parameters were obtained by means of a multivariate nonlinear regression. 相似文献
11.
The application of thermal method is of great importance regarding the pharmaceutical problems such as the control of raw materials, the determination of purity, the qualitative and quantitative analysis of drug formulation, tests of thermal stability and compatibility and the determination of kinetic parameters etc. The purpose of a kinetic investigation is to calculate the kinetic parameters and the determination of the kinetic model for the studied process. The results are further used to predict the system’s behaviour in various circumstances. A kinetic study regarding the piroxicam—active substance’s thermal decomposition was performed under isothermal conditions and nitrogen atmosphere, for the temperature steps: 200, 205, 210, 215 and 220 °C. The TG/DTG data were processed by three differential methods: isothermal—isoconversional, Friedman’s isothermal isoconversional and isothermal model-fitting. The obtained results are in good accord between them, as well as with those obtained under non-isothermal conditions from a previous work and confirm the necessity of the kinetic parameters determining in different thermal conditions, by the adequate calculation methods. 相似文献
12.
The thermal decomposition of un-irradiated and gamma-irradiated potassium bromate (KBrO 3) was performed under non-isothermal conditions at different heating rates (5, 10, 15 and 20 K min ?1). The data was analysed using isoconversional and non-isoconversional methods. The kinetic parameters of thermal decomposition process were obtained by three model-free isoconversional methods: Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose and Friedman. Irradiation enhances the decomposition and the effect increases with the irradiation dose. The activation energy decreases on irradiation. Kinetic analysis of data in view of various solid-state reaction models showed that the decomposition of un-irradiated and irradiated anhydrous KBrO 3 is best described by the Avrami–Erofeev model equation, [?ln(l? α)] 1/2 = kt. 相似文献
13.
Pyrolysis, one possible alternative to recover valuable products from waste plastics, has recently been the subject of renewed interest. In the present study, the isoconversion methods, i.e., Vyazovkin model-free approach is applied to study non-isothermal decomposition kinetics of waste PET samples using various temperature integral approximations such as Coats and Redfern, Gorbachev, and Agrawal and Sivasubramanian approximation and direct integration (recursive adaptive Simpson quadrature scheme) to analyze the decomposition kinetics.The results show that activation energy ( Eα) is a weak but increasing function of conversion ( α) in case of non-isothermal decomposition and strong and decreasing function of conversion in case of isothermal decomposition. This indicates possible existence of nucleation, nuclei growth and gas diffusion mechanism during non-isothermal pyrolysis and nucleation and gas diffusion mechanism during isothermal pyrolysis. Optimum Eα dependencies on α obtained for non-isothermal data showed similar nature for all the types of temperature integral approximations. 相似文献
14.
The thermal polymerization kinetics of dimethacrylate monomers was studied by differential calorimetry using non-isothermal
experiments. The kinetic analysis compared the following procedures: isoconversional method (model-free method), reduced master
curves, the isokinetic relationship (IKR), the invariant kinetic parameters (IKP) method, the Coats-Redfern method and composite
integral method I. Although the study focused on the integral methods, we compared them to differential methods. We saw that
even relatively complex processes (in which the variations in the kinetic parameters were only slight) can be described reasonably
well using a single kinetic model, so long as the mean value of the activation energy is known ( E). It is also shown the usefulness of isoconversional kinetic methods, which provide with reliable kinetic information suitable
for adequately choosing the kinetic model which best describes the curing process. For the system studied, we obtained the
following kinetic triplet: f(α)=α 0.6(1−α) 2.4, E=120.9 kJ mol −1 and ln A=38.28 min −1. 相似文献
15.
The kinetics involved in the thermal decomposition of Kapton ® polyimide 100HN under nitrogen atmosphere were studied by applying various fitting techniques to the isothermal and non-isothermal gravimetric data. The correlation of the reaction mechanism fitting, the analytical model fitting and the isoconversional method to these data was examined in relation to the kinetic parameters and the kinetic predictions. The mechanisms for solid-state reactions fit the isothermal data very well but result in highly uncertain values for the kinetic parameters when applied to the non-isothermal data. Isoconversional methods show that the apparent activation energy depends on the extent of conversion but do not provide information for the reaction order and the pre-exponential factor. Three single heating-rate analytical models by Coats-Redfern, MacCallum-Tanner and van Krevelen were analysed using the non-isothermal data. A multi-heating rate model is proposed and its validity is compared to the single-heating rate models on the basis of kinetic predictions. 相似文献
16.
The thermal decomposition of strontium acetate hemihydrate has been studied by TG-DTA/DSC and TG coupled with Fourier transform
infrared spectroscopy (FTIR) under non-isothermal conditions in nitrogen gas from ambient temperature to 600°C. The TG-DTA/DSC
experiments indicate the decomposition goes mainly through two steps: the dehydration and the subsequent decomposition of
anhydrous strontium acetate into strontium carbonate. TG-FTIR analysis of the evolved products from the non-oxidative thermal
degradation indicates mainly the release of water, acetone and carbon dioxide. The model-free isoconversional methods are
employed to calculate the E
a of both steps at different conversion α from 0.1 to 0.9 with increment of 0.05. The relative constant apparent E
a values during dehydration (0.5<α<0.9) of strontium acetate hemihydrate and decomposition of anhydrous strontium acetate (0.5<α<0.9)
suggest that the simplex reactions involved in the corresponding thermal events. The most probable kinetic models during dehydration
and decomposition have been estimated by means of the master plots method. 相似文献
17.
Solid bisphenol-A epoxy resin of medium molecular weight was cured using a Lewis acid initiator (erbium(III) trifluoromethanesulfonate) in three different proportions (0.5, 1 and 2 phr). A kinetic study was performed in a differential scanning calorimeter. The complete kinetic triplet was determined (activation energy, pre-exponential factor, and integral function of the degree of conversion) for each system. A kinetic analysis was performed with an integral isoconversional procedure (model-free), and the kinetic model was determined both with the Coats-Redfern method (the obtained isoconversional E value being accepted as the effective activation energy) and through the compensation effect. All the systems followed the same isothermal curing model simulated from non-isothermal ones. The “nucleation and growth” Avrami kinetic model A3/2 has been proposed as the polymerization kinetic model. The addition of initiator accelerated the reaction having higher influence when low temperatures were applied. 相似文献
18.
In the case of a complex mechanism of two parallel independent reactions, peak maximum evolution methods and model-fitting
methods give only a mean value of the kinetic parameters, while isoconversional methods are useful to describe the complexity
of the mechanism. Isothermal and non-isothermal isoconversional methods can be used to elucidate the kinetics of the process.
Nevertheless, isothermal isoconversional methods can be limited by restrictions on the temperature regions experimentally
available because of duration times or detection limits.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
20.
Anion exchange reactions of nanodimensional layered metal hydroxide compounds are utilized to create materials with targeted physical and chemical properties and also as a means for controlled release of intercalated anions. The kinetics of this important class of reaction are generally characterized by model-based approaches. In this work, a different approach based on isothermal, isoconversional analysis was utilized to determine effective activation energies with respect to extent of reaction. Two different layered metal hydroxide materials were chosen for reaction with chloride anions, using a temperature range of 30-60 °C. The concentrations of anions released into solution and the changes in polycrystalline solid phases were evaluated using model-based (Avrami-Erofe'ev nucleation-growth model) and model-free (integral isoconversional) methods. The results demonstrate the utility of the isoconversional approach for identifying when fitting to a single model is not appropriate, particularly for characterizing the temperature dependence of the reaction kinetics. 相似文献
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