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  • Author or Editor: M. Maciejewski x
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The theoretical curves in the coordinates a vs. time for isothermal, and avs. temperature for non-isothermal experiments are calculated as functions of three kinetic parameters: activation energyE, pre-exponentical factorA and theg(α) function describing the mechanism of thermal decomposition of solids. The results show that conclusions not taking into consideration all three parameters can lead to information of little value concerning the mechanism of the decomposition and kinetic calculations. A correlation between non-isothermal and isothermal experiments, important for determination of the thermal stabilities of the compounds, is impossible without a knowledge of theg(α) function.

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Somewhere between fiction and reality

The usefulness of kinetic data of solid-state reactions

Journal of Thermal Analysis and Calorimetry
Author: M. Maciejewski
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Supported catalysts contain often only small amounts of active component(s) which renders their characterization difficult, particularly because they usually contain a substantial amount of water. Thermal analysis (TA) coupled with mass spectrometry (MS) offers an interesting potential for characterizing such material, various steps of catalyst preparation as well as crucial properties of fresh and used catalysts can be investigated. Some examples illustrating the versatility of TA-MS in catalysis research, such as solid-state reactions occurring upon exposure of the precursors or catalysts to reducing, oxidizing or inert atmosphere, are presented in this study. The combined use of TA and MS allows in many cases a much more detailed interpretation of the observed phenomena than could be achieved by one of these methods alone.

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Abstract  

Pulse thermal analysis (PTA) is based on the injection of a specific amount of gaseous reactant into a carrier gas stream. PTA provides the following advantages compared to conventional TA: (i) quantitative calibration of the mass spectrometric signals allows increasing the sensitivity of TA measurements; (ii) monitoring of gas-solid processes with defined extent of reaction i.e. the reaction can be stopped at any point between pulses, enabling elucidation of the relationship between the composition of the solid and the reaction progress; (iii) simultaneous monitoring of changes in mass, thermal effects, composition and amount of gaseous reactants and products under pulse conditions.

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Abstract  

Thermal analysis combined with mass spectrometry was applied to radiocarbon dating procedures (age determination of carbon-containing samples). Experiments carried out under an oxygen atmosphere were used to determine carbon content and combustion range of soil and wood samples. Composition of the shell sample and its decomposition were investigated. The quantification of CO2 formed by the oxidation of carbon was done by the application of pulse thermal analysis. Experiments carried out under an inert atmosphere determined the combustion range of coal with CuO as an oxygen source. To eliminate a possible source of contamination in the radiocarbon dating procedures the adsorption of CO2 by CuO was investigated.

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Abstract  

Simultaneous thermal analysis (TA) and evolved gas analysis by mass spectrometry (MS) and/or Fourier transform infrared spectroscopy (FTIR) is a powerful hyphenated technique combining direct measurement of mass loss and sensitive spectroscopic analysis. In the present study the influence of several experimental parameters which may affect the quantification of FTIR signals have been studied using a combined TA-FTIR-MS system. Parameters studied include: sample mass (1-400 mg), carrier gas flow rate (25-200 mL min-1), resolution of the FTIR spectrometer (1-32 cm-1), and location of injection of the calibrating gas. MS analysis, which was not significantly affected by the experimental conditions, was used as a reference for assessing the accuracy of quantification by FTIR. The quantification of the spectroscopic signals was verified by the decomposition (NaHCO3) or dehydration (CuSO45H2O) of compounds with well-known stoichiometry. The systematic study of the parametric sensitivity revealed that spectral resolution and carrier gas flow rate, which affect the acquisition time in the IR-cell, are key parameters that must be adjusted carefully for reliable quantification. The dependence of the reliability of quantification on these parameters is illustrated and conditions leading to proper quantification are discussed. As an example, for a standard spectral resolution of 4 cm-1 and a FTIR gas cell volume of 8.7 mL, the carrier gas flow must be lower than 100 mL min-1 for warranting accurate results (relative deviation <2%). The concentration range of analyzed species is limited but can be extended by proper selection of the wavenumber regions for molecules giving strong IR signals.

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A new method (based on DTA and TG) for the determination of the eutectic composition is proposed for systems in which one of the components is unstable in the vicinity of the eutectic melting temperature. The eutectic composition established by means of this method for the CaCO3-CaF2 system is in very good agreement with the results obtained in a classical way.

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