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Application of complex reaction kinetic models in thermal analysis

The least squares evaluation of series of experiments

Journal of Thermal Analysis and Calorimetry
Authors: G. Várhegyi, M. J. Antal, Piroska Szabó, Emma Jakab, and F. Till

The complexity of the phenomena which arise during the heating of the various substances seldom can be described by a single reaction kinetic equation. As a consequence, sophisticated models with several unknown parameters have to be developed. The determination of the unknown parameters and the validation of the models requires the simultaneous evaluation of whole series of experiments. We can accept a model and its parameters if, and only if we get a reasonable fit to several experiments carried out at different experimental conditions. In the field of the thermal analysis the method of least squares alone seldom can select abest model or abest set of parameter values. Nevertheless, the careful evaluation of the experiments may help in the discerning between various chemical or physical assumptions by the quality of the corresponding fit between the experimental and the simulated date. The problem is illustrated by the thermal de-composition of cellulose under various experimental conditions.

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Abstract  

It has been demonstrated that a single plot of the values of Δlnα1/2/Δln(1-α) (taken from a single α−T curve obtained under a controlled linear increase of the reaction rate) as a function of the corresponding values of Δ(1/T)/Δln(1−α) permits the simultaneous determination of both the activation energy and the kinetic model in accordance with a solid state reaction.

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In recent years there has been increasing research interest in the removal of nitrogen-oxides from exhaust gases using a pulsed corona discharge reactor. The pulsed streamer corona produces energetic electrons that excite, ionize and dissociate gas molecules, and by forming radicals that enhance the gas-phase chemical reactions which reduce the pollutant’s concentration.In this paper a method is presented, where the reaction rates of the electron-molecule collision are determined. The model is based on calculation of the energy of free electrons in the time and space varying field, considering the mean free path and the energy-dependent reaction cross sections of molecules. Knowing the rates, it is possible to solve the reaction kinetic equations, and to get the time-evolution of by-products, and the decomposition ratio of the pollutant gases.

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Journal of Thermal Analysis and Calorimetry
Authors: Blaž Likozar, Romana Cerc Korošec, Ida Poljanšek, Primož Ogorelec, and Peter Bukovec

components (melamine and phenol) at elevated temperatures in the melt. Only recently, two quantitative kinetic modelling studies were presented by Kim et al. [ 6 ] and Cai et al. [ 7 ] both utilizing n th-order reaction kinetic models. Kim et al. [ 6

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Summary The SCTA methods for the kinetic analysis of solid-state reactions have been reviewed. It has been shown that these methods present two important advantages with regards to the more conventional rising temperature experiments. Firstly, they have a higher resolution power for discriminating among the reaction kinetic models and, secondly, SCTA is a powerful tool for minimizing the influence of the experimental conditions on the forward reaction.

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Abstract  

Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) is a typical highly energetic material that has been widely used in national defense industries since the 1940s. The aim of this study was to establish a reaction kinetic model on thermal decomposition properties via differential scanning calorimetry (DSC) by well-known kinetic equations and kinetic model simulation. Furthermore, the aim also was to compare kinetic algorithms for thermal decomposition energy parameters under various conditions. Experimental results highly depended on the reliability of the kinetic concept applied, which is essentially defined by the proper choice of a mathematical model of a reaction. In addition, the correctness of the methods is used for kinetics evaluation.

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Abstract  

The kinetics of complexation (C) and decomplexation (D) reactions between Eu(III) and Aldrich humic acid (HA) was investigated as a function of pH (pH 4, 5, 6, 7 and 8) in the system Eu(III) - HA - Amberlite IR-120(Na) (I = 0.1). The derivation of the kinetic differential equations was based on the reactions of Eu3+ with, so called, strong (HAS) and weak (HAW) carboxylic groups of HA formulated in accordance with the new complexation model.1 The differential equations determining d[EuaHAS]/dt and d[EubHAW]/dt have the classical form applicable for reversible reactions where the forward reaction is the C-reaction and the reverse one is the D-reaction. Kinetic model used for the evaluation of experimental data includes these differential equations and the film diffusion model of sorption of Eu3+ on Amberlite IR-120(Na).

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Abstract  

The curing of the neat unsaturated polyester resin (UP) with benzoyl peroxide (initiator) as well as the curing of UP modified with two poly(ε-caprolactone) PCL samples (PCL2 and PCL50) of different molecular masses (M n=2⋅103 and M n=5⋅104, respectively), were investigated by non-isothermal differential scanning calorimetry (DSC), at different heating rates. The activation energy was determined from the variation of the peak exotherm temperature, T peak, upon heating rate. Besides, the degree of conversion (α) was obtained from isothermal DSC measurements at 80°C at different curing times for neat UP, UP+ PCL2 and UP+PCL50. Kinetic parameters were deduced assuming the n th order reaction kinetic model for neat UP, UP+PCL2 and UP+PCL50 systems.

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Abstract

In our previous research (Liu et al., J Anal Appl Pyrol 63:303–325, 2002), the pseudo bi-component separated-stage model (PBSM) was suggested for the kinetic analysis on the decomposition of lignocellulosic materials in air at relatively lower heating rates. As a continuing work, this paper is intended to investigate the applicability of PBSM at different heating rates by experimental analyses. Decomposition of oil tea wood has been studied by means of non-isothermal thermogravimetric analysis in air atmosphere at 10–25 K min−1 heating rates. A two-step parallel reaction kinetic model is used to optimize the kinetic parameters of these materials in air. Meanwhile, an improved PBSM is developed to describe the thermal degradation process of oil tea wood. Furthermore, a comparison between the kinetic results of parallel model and PBSM reveals realistic applicability of PBSM. It is concluded that the PBSM has relatively high accuracy for the first decomposition step in the lower temperature range, while fails to predict the thermal decomposition behavior in the char oxidative process which occurs in the higher temperature range.

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transformation. From the analysis of the experimental results of a thermal degradation, one can construct a reaction kinetic model of the chemical processes leading from the precursor(s) to the product(s) of a reaction [ 1 ]. One well-known ligand—oxalate can be

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