Thermal analysis kinetics

J. Sestak, J. Malek Diagnostic limits of phenomenological models of heterogeneous reactions and thermal analysis kinetics Solid State Ionics, 63/65(1993)254... 

Arii, T., and Fujii, N., Controlled Rate Thermal Analysis Kinetic Study in Thermal Dehydration of Calcium Sulfate Dihydrate, J. Anal, and Appl. Pyrolysis, 39 129-143 (1997)... 

Kissinger H E 1957 Reaction kinetics in differential thermal analysis Ana/. Chem. 29 1702... 

Crystallization kinetics have been studied by differential thermal analysis (92,94,95). The heat of fusion of the crystalline phase is approximately 96 kj/kg (23 kcal/mol), and the activation energy for crystallization is 104 kj/mol (25 kcal/mol). The extent of crystallinity may be calculated from the density of amorphous polymer (d = 1.23), and the crystalline density (d = 1.35). Using this method, polymer prepared at —40° C melts at 73°C and is 38% crystalline. Polymer made at +40° C melts at 45°C and is about 12% crystalline. 

Differential thermal analysis (DTA) Onset temperature of exotherms, heat of reaction, Cp, approximate kinetics... 

The techniques referred to above (Sects. 1—3) may be operated for a sample heated in a constant temperature environment or under conditions of programmed temperature change. Very similar equipment can often be used differences normally reside in the temperature control of the reactant cell. Non-isothermal measurements of mass loss are termed thermogravimetry (TG), absorption or evolution of heat is differential scanning calorimetry (DSC), and measurement of the temperature difference between the sample and an inert reference substance is termed differential thermal analysis (DTA). These techniques can be used singly [33,76,174] or in combination and may include provision for EGA. Applications of non-isothermal measurements have ranged from the rapid qualitative estimation of reaction temperature to the quantitative determination of kinetic parameters [175—177]. The evaluation of kinetic parameters from non-isothermal data is dealt with in detail in Chap. 3.6. 

Direct kinetic measurements from the changes in diffracted beam intensities with time during heating of the reactant are illustrated in the work of Haber et al. [255]. Gam [126] has reviewed the apparatus used to obtain X-ray diffraction measurements in thermal analysis. Wiedemann [256] has designed equipment capable of giving simultaneous thermo-gravimetric and X-ray data under high vacuum. X-Ray diffraction studies enable the presence, or absence, of topotactic relationships between reactant and product to be detected [92,102,257—260], Results are sometimes considered with reference to the pseudomorphic shape of residual crystallites. 

The thermal reactions of CaC204 H20 have been very fully investigated and this substance has been used as a thermal analysis reference material [1058], Dehydration, decomposition to the carbonate, and dissociation to CaO are all well separated, though kinetic characteristics are influenced by the presence of C02, 02 and H20 as well as by the reaction conditions, including heating rate, sample size, and sample container. Kinetic parameters for the oxalate decomposition reaction have been summarized by Gurrieri et al. [1059]. Values of E are close to 314 8 kJ mole-1. Decompositions [1057,1060,1061] of Sr (643—743 K) and Ba (663—743 K) oxalates involves some disproportion of CO, yielding residual carbon. 

There is an extensive literature devoted to the preparation and structure determination of coordination compounds. Thermal analysis (Chap. 2, Sect. 4) has been widely and successfully applied in determinations [1113, 1114] of the stoichiometry and thermochemistry of the rate processes which contribute to the decompositions of these compounds. These stages may overlap and may be reversible, making non-isothermal kinetic data of dubious value (Chap. 3, Sect. 6). There is, however, a comparatively small number of detailed isothermal kinetic investigations, together with supporting microscopic and other studies, of the decomposition of coordination compounds which yields valuable mechanistic information. 

Thermal analysis has been widely and usefully applied in the solution of technical problems concerned with the commercial exploitation of natural dolomite including, for example, the composition of material in different deposits, the influence of impurities on calcination temperatures, etc. This approach is not, however, suitable for the reliable determination of kinetic parameters for a reversible reaction (Chap. 3, Sect. 6). 

An Automated Thermal Analysis System for Reaction Kinetics," A.F. Kah, M.E. Koehler, T.H. Grentzer, T.F. Niemann, and T. Provder, Computer Applications... 

GP 11] [R 19] Based on an analysis of the thermal and kinetic explosion limits, inherent safety is ascribed to hydrogen/oxygen mixtures in the explosive regime when guided through channels of sub-millimeter dimensions under ambient-pressure conditions [9], This was confirmed by experiments in a quartz micro reactor [9],... 

Recently, several reports of the flame-retardant properties of boron-containing bisphenol-A resins have appeared from Gao and Liu.89 The synthesis of a boron-containing bisphenol-A formaldehyde resin (64 and 65) (Fig. 42) from a mixture of bisphenol-A, formaldehyde, and boric acid, in the mole ratio 1 2.4 0.5, has been reported.893 The kinetics of the thermal degradation and thermal stability of the resins were determined by thermal analysis. The analysis revealed that the resin had higher heat resistance and oxidative resistance than most common phenol-formaldehyde resins. 

Identification of hazardous chemicals through thermodynamic and kinetic analyses is discussed in Chapter 2. This hazard identification makes use of thermal analysis and reaction calorimetry. In Chapter 2, an overview of the theory of thermodynamics, which determines the reaction (decomposition)... 

Ozawa, T., "Kinetic Analysis of Derivative Curves in Thermal Analysis," /. of Therm. Anal, 2,301 (1979). 

Kissinger, H. E., "Reaction Kinetics in Differential Thermal Analysis," Anal. Chem., 29,1702 (1957). 

Estimation of Polymer Lifetime by TGA Decomposition Kinetics, TA Instruments Thermal Analysis Application Brief TA-125, pp. 1-4. 

K. Galwey, M. E. Brown. Kinetic Background to Thermal Analysis and Calorimetry. In Handbook of Thermal Analysis and Calorimetry, vol 1 Principles and Practice M. E. Brown, Ed. Elsevier Amsterdam, 1998 chapter 3. 

Katz, J. R. and Van Itallie, T. B. (1930). Abhandlugen zur physikalischen chemie der starke und der brotbereitung. Zeitschrift fur physikalische chemie. Abteilung A. A150,90-99. Kissinger, H. E. (1957). Reaction kinetics in differential thermal analysis. Analytical Chemistry. 

Kah, A. F. Koehler, M. E. Grentzer, T. H. Niemann, T. F. Provder, T. "An Automated Thermal Analysis System for Reaction Kinetics" in "Computer Applications in Applied Polymer Science" Provder, T., Ed. ACS SYMPOSIUM SERIES No. 197, American Chemical Society Washington, D.C., 1982 pp. 197-311. 

The criteria by which these resins are evaluated include thermal analysis, cure kinetics and rheological studies of the uncured resin. Mechanical properties including hot/wet sample testing and thermal analysis are then obtained from cured neat resin speciswns. The results from these tests run on the neat resin will give some indication of the suitability of that resin for use as a composite matrix material and future studies to be conducted. 

Irradiation of sulfur by various means yields discoloration of elemental sulfur, but it is doubtful that these forms will ever lead to pure allotropes. Above 92°C, a-sulfur converts into monoclinic sulfur. The kinetics of the transformation depend on various factors. Thermal analysis of single crystals of a-sulfur shows that the conversion is so slow that a-sulfur can be heated to 112°C, where it melts, before j8-sulfur is formed (19). 

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