Reaction Kinetics in Differential Thermal Analysis
About: This article is published in Analytical Chemistry.The article was published on 1957-11-01. It has received 10842 citations till now. The article focuses on the topics: Reaction rate constant & Chemical kinetics.
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TL;DR: In this article, the authors have developed recommendations for reliable evaluation of kinetic parameters (the activation energy, the preexponential factor, and the reaction model) from the data obtained by means of thermal analysis methods such as TGA, differential scanning calorimetry (DSC), and differential thermal analysis (DTA).
Abstract: The present recommendations have been developed by the Kinetics Committee of the International Confederation for Thermal Analysis and Calorimetry (ICTAC). The recommendations offer guidance for reliable evaluation of kinetic parameters (the activation energy, the pre-exponential factor, and the reaction model) from the data obtained by means of thermal analysis methods such as thermogravimetry (TGA), differential scanning calorimetry (DSC), and differential thermal analysis (DTA). The recommendations cover the most common kinetic methods, model-free (isoconversional) as well as model-fitting. The focus is on the problems faced by various kinetic methods and on the ways how these problems can be resolved. Recommendations on making reliable kinetic predictions are also provided. The objective of these recommendations is to help a non-expert with efficiently performing analysis and interpreting its results.
4,112 citations
Cites methods from "Reaction Kinetics in Differential T..."
...Because of its easy use the Kissinger method [34] has been applied for determining the activation energies more extensively than any other multiple-heating rate method....
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Abstract: A review article is presented of the research results obtained by the author on the properties of amorphous silica surface. It has been shown that in any description of the surface silica the hydroxylation of the surface is of critical importance. An analysis was made of the processes of dehydration (the removal of physically adsorbed water), dehydroxylation (the removal of silanol groups from the silica surface), and rehydroxylation (the restoration of the hydroxyl covering). For each of these processes a probable mechanism is suggested. The results of experimental and theoretical studies permitted to construct the original model (Zhuravlev model-1 and model-2) for describing the surface chemistry of amorphous silica. The main advantage of this physico-chemical model lies in the possibility to determine the concentration and the distribution of different types of silanol and siloxane groups and to characterize the energetic heterogeneity of the silica surface as a function of the pretreatment temperature of SiO2 samples. The model makes it possible to determine the kind of the chemisorption of water (rapid, weakly activated or slow, strongly activated) under the restoration of the hydroxyl covering and also to assess of OH groups inside the SiO2 skeleton. The magnitude of the silanol number, that is, the number of OH groups per unit surface area, αOH, when the surface is hydroxylated to the maximum degree, is considered to be a physico-chemical constant. This constant has a numerical value: αOH,AVER=4.6 (least-squares method) and αOH,AVER=4.9 OH nm−2 (arithmetical mean) and is known in literature as the Kiselev–Zhuravlev constant. It has been established that adsorption and other surface properties per unit surface area of silica are identical (except for very fine pores). On the basis of data published in the literature, this model has been found to be useful in solving various applied and theoretical problems in the field of adsorption, catalysis, chromatography, chemical modification, etc. It has been shown that the Brunauer–Emmett–Teller (BET) method is the correct method and gives the opportunity to measure the real physical magnitude of the specific surface area, SKr (by using low temperature adsorption of krypton), for silicas and other oxide dispersed solids.
1,992 citations
TL;DR: In this article, two methods of obtaining kinetic parameters from derivative thermoanalytical curves are proposed based on the general form of kinetic formulae and are applicable to general types of reactions governed by a single activation energy.
Abstract: Two methods of obtaining kinetic parameters from derivative thermoanalytical curves are proposed The methods are based on the general form of kinetic formulae and are applicable to general types of reactions governed by a single activation energy One method utilizes the linear relation between peak temperature and heating rate in order to estimate the activation energy, and only the information of the rate of conversion versus the temperature is necessary The other method needs the information of both the conversion and the rate of conversion versus the temperature, and the Arrhenius plot is made for an assumed kinetic mechanism
1,974 citations
TL;DR: A broad review of the state-of-the-art biomass pyrolysis research can be found in this article, where three major components (cellulose, hemicellulose and lignin) are discussed in detail.
Abstract: The past decades have seen increasing interest in developing pyrolysis pathways to produce biofuels and bio-based chemicals from lignocellulosic biomass. Pyrolysis is a key stage in other thermochemical conversion processes, such as combustion and gasification. Understanding the reaction mechanisms of biomass pyrolysis will facilitate the process optimization and reactor design of commercial-scale biorefineries. However, the multiscale complexity of the biomass structures and reactions involved in pyrolysis make it challenging to elucidate the mechanism. This article provides a broad review of the state-of-art biomass pyrolysis research. Considering the complexity of the biomass structure, the pyrolysis characteristics of its three major individual components (cellulose, hemicellulose and lignin) are discussed in detail. Recently developed experimental technologies, such as Py-GC–MS/FID, TG-MS/TG-FTIR, in situ spectroscopy, 2D-PCIS, isotopic labeling method, in situ EPR and PIMS have been employed for biomass pyrolysis research, including online monitoring of the evolution of key intermediate products and the qualitative and quantitative measurement of the pyrolysis products. Based on experimental results, many macroscopic kinetic modeling methods with comprehensive mechanism schemes, such as the distributed activation energy model (DAEM), isoconversional method, detailed lumped kinetic model, kinetic Monte Carlo model, have been developed to simulate the mass loss behavior during biomass pyrolysis and to predict the resulting product distribution. Combined with molecular simulations of the elemental reaction routes, an in-depth understanding of the biomass pyrolysis mechanism may be obtained. Aiming to further improve the quality of pyrolysis products, the effects of various catalytic methods and feedstock pretreatment technologies on the pyrolysis behavior are also reviewed. At last, a brief conclusion for the challenge and perspectives of biomass pyrolysis is provided.
1,613 citations
TL;DR: In this paper, the polycondensation of resorcinol with formaldehyde under alkaline conditions results in the formation of surface functionalized polymer "clusters" which are processed under supercritical conditions to obtain low density, organic aerogels.
Abstract: The polycondensation of resorcinol with formaldehyde under alkaline conditions results in the formation of surface functionalized polymer “clusters”. The covalent crosslinking of these “clusters” produces gels which are processed under supercritical conditions to obtain low density, organic aerogels ( ⩽ 0.1 g cm−3). The aerogels are transparent, dark red in colour, and consist of interconnected colloidal-like particles with diameters of approximately 10 nm. The polymerization mechanism, structure and properties of the resorcinol-formaldehyde aerogels are similar to the sol-gel processing of silica.
1,603 citations
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TL;DR: In this article, the temperature at which the maximum deflection is observed varies with heating rate for certain types of reactions, and an expression can be derived relating this variation with the kinetics of the reaction.
Abstract: In differential thermal analysis, the temperature at which the maximum deflection is observed varies with heating rate for certain types of reactions. An expression can be derived relating this variation with the kinetics of the reaction. By making a number of differential thermal patterns at different heating rates, the kinetic constants can be obtained directly from the differential thermal data. Measurements of the variation of peak temperature with heating rate have been made for several minerals of the kaolin group, the values of the kinetic constants determined, and these values compared with corresponding values obtained for both the same samples and similar material by conventional isothermal techniques. Some factors affecting the results are discussed. The method of differential thermal analysis (DTA) has been universally accepted by mineralogical laboratories as a rapid and convenient means for recording the thermal effects that occur as a sample is heated. Changes in heat content of the active sample are indicated by deflections shown by a line representing the differential temperature. It is conventional to represent an endothermic effect by a negative deflection and an exothermic effect by a positive deflection. The deflections, whether positive or negative, are called peaks.
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