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Abstract  

The non-parametric kinetics (NPK) method has been recently developed for the kinetic treatment of thermoanalytical data. The most significant feature of this method is its ability to provide information about the reaction kinetics without any assumptions either about the functionality of the reaction rate with the degree of conversion or the temperature. This paper presents the results of the application of the method to adiabatic calorimetry. Some data have been obtained by numerical simulation, but also the thermal decomposition of DTBP, a well known first order reaction, has been studied, being the obtained results in good agreement with literature.

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-007-7936-8 . 13. Serra , R , Nomen , R , Sempere , J . The non-parametric kinetics a new method for the kinetic study of thermoanalytical data . J Therm Anal Calorim . 1998 ; 52 : 933 – 943 . 10.1023/A:1010120203389

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Summary Due to the criticism of the non-isothermal kinetic at a single heating rate, in the last period, data obtained at different heating rates are processed by means of elevated methods like Friedman’s (FD) differential-isoconversional method or the one suggested by Budrugeac and Segal (BS). The non-parametric kinetics (NPK) method, suggested by Serra, Nomen and Sempere offers two major advantages: the possibility of separation of two or more steps of a complex decomposition reaction; and the possibility of discrimination between the conversion, with regard to the temperature functions of a rate equation. Comparative data of FD, BS and modified version of NPK method are presented for decomposition of three compounds used as polyisocyanate stabilizer.

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Abstract  

The topic of the present work is to study the thermal behavior of phenitoine and pharmaceuticals by means of kinetic parameters determined in non-isothermal conditions. The TG/DTG data were obtained at four heating rates. These data were processed by the following methods: Friedman (FR), Budrugeac-Segal (BS) and the modified non-parametric kinetics (Sempere-Nomen). The main conclusions of the kinetic study are The FR method is versatile, but the values of the kinetic parameters are not certain, especially by multistep processes. The BS method offer a non-variant part of the activation energy, but the kinetic description is only formal. The NPK method is able to discriminate between two or more steps of a complex process. In our case, there are a preponderant process (more than 70% of the explained variance). By the NPK method there is a non-speculative separation of the temperature, respective conversion degree dependence of the reaction rate.

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Summary The thermal behavior of KH2PO4, NaH2PO4 and Na2HPO4 under non-isothermal conditions using TG method with different heating rates was studied. The values of the reaction rate were processed by means of Friedman’s differential-isoconversional method. A dependence of the activation energy vs. conversion was observed. Therefore a procedure based on the compensation effect (suggested by Budrugeac and Segal) was applied. A less speculative data processing protocol was offered by the non-parametric kinetics method suggested by Serra, Nomen and Sempere. Three steps were observed by non-isothermal heating: a dehydration, a dimerization and a polycondensation. The differences in the intimate reaction mechanism are determined by the initial number of water molecules.

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Abstract  

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.

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In the case of TiN, other methods non-requiring the assumption of a kinetic model, such as non-parametric kinetics (NPK) [ 30 , 31 ], does not give accurate results due to the crossing of the curves at low conversions. Usual literature

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imperative condition of the separability of both temperature and conversion functions. To check the separability of these functions, the Non-Parametric Kinetics method (NPK), developed by Serra et al. [ 2 ], could be very suitable. The NPK method is based on

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, α ) with extent of conversion (isoconversional method) [ 12 – 14 , 24 – 29 ] and temperature (non-parametric kinetics method) [ 30 , 31 ]. Further, Arrhenius parameters evaluated using model-free techniques facilitate modeling of a degradation

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