Thermogravimetric analysis kinetics

When heated, many solids evolve a gas. For example, most carbonates lose carbon dioxide when heated. Because there is a mass loss, it is possible to determine the extent of the reaction by following the mass of the sample. The technique of thermogravimetric analysis involves heating the sample in a pan surrounded by a furnace. The sample pan is suspended from a microbalance so its mass can be monitored continuously as the temperature is raised (usually as a linear function of time). A recorder provides a graph showing the mass as a function of temperature. From the mass loss, it is often possible to establish the stoichiometry of the reaction. Because the extent of the reaction can be followed, kinetic analysis of the data can be performed. Because mass is the property measured, TGA is useful for... 

Thermogravimetric analysis (TGA) measures cellulose pyrolytic mass loss rates and activation parameters. The technique is relatively simple, straightforward and fast, but it does have disadvantages. One disadvantage is that determination of the kinetic rate constants from TGA data is dependent on the interpretation/analysis technique used. Another disadvantage of TGA is that the rate of mass loss is probably not equivalent to the cellulose pyrolysis rate. 

Thermogravimetric analysis (TGA) has often been used to determine pyrolysis rates and activation energies (Ea). The technique is relatively fast, simple and convenient, and many experimental variables can be quickly examined. However for cellulose, as with most polymers, the kinetics of mass loss can be extremely complex (8 ) and isothermal experiments are often needed to separate and identify temperature effects (9. Also, the rate of mass loss should not be assumed to be related to the pyrolysis kinetic rate ( 6 ) since multiple competing reactions which result in different mass losses occur. Finally, kinetic rate values obtained from TGA can be dependent on the technique used to analyze the data. 

TA instruments has developed automated thermogravimetric analysis and related kinetic programs that enable a rapid determination of decomposition rates to be made. The following excerpt from a TA application brief [57] explains the method ... 

Kinetic data on the thermal degradation of ABS and PC/ABS blends are available (130,131). Thermogravimetric analysis suggests that the kinetics of the thermal degradation can be modelled by an auto-catalytic process. 

The common methods of investigating the kinetics of explosive reactions are differential thermal analysis, thermogravimetric analysis and differential scanning calorimetry. 

Early devices fbr thermogravimetric analysis were limited in precision and convenience when compared with DTA or DSC equipment. Now devices for simultaneous DSC and TG are on the market which can operate at high temps in reactive atms permitting the simulation of high temp reactions on a micro scale. The use of TG for the study of reaction kinetics was described in Sect 5.3.3. An exptl study of the sublimation of ammonium perchlorate was published by Jacobs and Jones (Ref 25). Similar techniques should find application in the study of other propint systems. The product gases have been collected for further analysis using gas chromatography and mass spectrometry... 

R.W. Mickelson I.N. Einhom, "Kinetic Interpretation in Thermogravimetric Analysis , Combustn Flame 28 (1) (1977),45-61... 

The thermal behavior of TKX-50 (bis(hydroxylammonium) 5,5 -(tetrazolate-liV-oxide)) and the kinetics of its thermal decomposition were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The thermal decomposition of TKX-50 starts to occur within the range 210-250 °C depending on the heating rate used. 

Application of difiFerential thermal analysis and thermogravimetric analysis techniques to the pyrolysis of cellulose is obviously complicated by the complexity of the reactions involved, and the corrections and simplifying assumptions that are required in calculating the kinetic parameters. Consequently, these methods provide general information, instead of accurate identification and definition of the individual reactions (and their kinetics), which are traditionally conducted under isothermal conditions. The data obtained by dynamic methods are, however, useful for comparing the efiFects of various conditions or treatments on the pyrolysis of cellulose. In this respect, the application of thermal analysis for investigating the effect of salts (and flame retardants in general) on the combustion of cellulosic materials is of special interest and will be discussed later (see p. 467). 

Thermogravimetric analysis can be perfonned with heating rates up to 108 K/min without significant temperature gradients inside small samples. An STA apparatus enabling a temperature calibration under the exact experimental conditions will give reliable process temperatures. This allows kinetic modelling without consideration of the enthalpy balance. 

Thermogravimetric analysis (TGA) has been used to study the kinetics of feedstock pyrolysis. In this work, a Seiko 220 TG/DTA thermal balance system was used. The sample mass was 10.0 0.1 mg. The heating rate was 10 C/min. For each test, the nitrogen gas was first introduced in the furnace to remove the air. Then the pressure in the furnace was lowered by a vacuum pump to 13 kPa absolute. 

Thermogravimetric Analysis (TG). TG involves weighing a sample while it is exposed to heat. The chief use of this technique has been to study the thermal decomposition of polymeric materials and to accumulate kinetic information about such decomposition. A sample is suspended on a sensitive balance that measures the weight (Figure 1) as it is exposed to a furnace. Air, nitrogen, or another gas flows around the sample to remove the pyrolysis or combustion prod-... 

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