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Journal ArticleDOI

Rational approximations of the integral of the Arrhenius function

01 Jun 1977-Journal of Thermal Analysis and Calorimetry (Akadémiai Kiadó, co-published with Springer Science+Business Media B.V., Formerly Kluwer Academic Publishers B.V.)-Vol. 11, Iss: 3, pp 445-447
TL;DR: Rational approximations have been derived for the integral of the Arrhenius function dT which is important in the kinetic analysis of thermogravimetric data and is found to be equivalent to the Gorbachev approximation.
Abstract: Rational approximations have been derived for the integral of the Arrhenius function $$\int\limits_0^T {\exp ( - E/RT)}$$ dT which is important in the kinetic analysis of thermogravimetric data. The first degree rational approximation is found to be equivalent to the Gorbachev approximation, i.e., RT2 exp (−E/RT)/(E+2RT). The second degree rational approximation is more accurate than the Zsako empirical approximation when E/RT 5. The third and higher degree rational approximations are found to be more accurate than any other previous approximation.
Citations
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TL;DR: In this article, a simple method of kinetic analysis of thermal analysis (TA) data is described, which allows one to find the appropriate model characterizing the process studied as well as the calculation of the kinetic parameters.

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Journal ArticleDOI
TL;DR: In this paper, the authors proposed a method to take into account the effect of temperature deviations on kinetic evaluations by combining the isoconversional principle of evaluating the activation energy with numerical integration of the equation.
Abstract: The thermal effect of a reaction makes the temperature inside the reaction system deviate from a prescribed heating program. To take into account the effect of such temperature deviations on kinetic evaluations, a computational method applicable to an arbitrary variation in temperature has been developed. The method combines the isoconversional principle of evaluating the activation energy with numerical integration of the equation, dα/dt = k[T(t)]f(α), over the actual variation of the temperature with the time, T(t). Details of the numerical algorithm are reported. A model example has been used to verify the reliability of this method as compared to an analogous method which does not account for the deviations of the temperature from a prescribed program. The method has been tested for tolerance for noise in the temperature. © 1997 by John Wiley & Sons, Inc.

666 citations

Journal ArticleDOI
TL;DR: In this paper, the concept of generalized time, introduced by Ozawa, has been used to define master plots for the analysis of solid-state reactions, regardless of the type of temperature program used for recording the experimental data.
Abstract: Master plot methods based on the integral and/or the differential forms of the kinetic equation describing solid-state reactions have been redefined by using the concept of the generalized time, θ, introduced by Ozawa. This redefinition permits the application of these master plots to the kinetic analysis of solid-state reactions, whatever the type of temperature program used for recording the experimental data. In isothermal conditions, a single curve is enough to construct the experimental master plots. In nonisothermal conditions, the knowledge of both α as a function of temperature and activation energy is required for calculating the master plot curves from the experimental data. Practical usefulness of the present master plot methods is examined, and exemplified by being applied to the thermal decomposition of ZnCO3 under isothermal, linear nonisothermal, and nonlinear nonisothermal conditions.

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References
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Journal ArticleDOI
01 Jan 1964-Nature
TL;DR: In this article, a thermocouple is used to measure the sample temperature in a Stanton HT-D thermobalance, the bead of which is positioned in or near the sample, depending on crucible design.
Abstract: THE use of thermogravimetric data to evaluate kinetic parameters of solid-state reactions involving weight loss (or gain) has been investigated by a number of workers1–4. Freeman and Carroll2 have stated some of the advantages of this method over conventional isothermal studies. To these reasons may be added the advantage of using one single sample for investigation. However, the importance of procedural details, such as crucible geometry, heating rate, pre-history of sample, and particle size, on the parameters has yet to be fully investigated. It is also necessary to ensure accurate temperature measurement, both for precision and also to detect any departure from a linear heating rate due to endo- or exo-thermic reactions. (The effect of these may be largely eliminated by the use of small samples.) In our present work (using a Stanton HT–D thermobalance) the sample temperature is measured directly by means of a thermocouple the bead of which is positioned in or near the sample, depending on crucible design, the wires of which run down a twin-bore rise rod. The connexion between the end of the thermocouple wires on the balance arm and the terminal block is made by 0.001 in. platinum and platinum/rhodium wires5. It has been shown that these wires do not affect the performance of the balance but act merely as a subsidiary damping. From the terminal block compensated cable leads to the cold junction and a potentiometric arrangement for direct measurement of the thermocouple output.

5,770 citations

Book
01 Jan 1975

576 citations


"Rational approximations of the inte..." refers background or methods in this paper

  • ...Rational approximations for f(x) can be derived knowing Eq. (2) and thus simply using the exponential integral rational approximation already given by Luke [ 6 ]....

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  • ...The rational approximations f~(x) are given in Table 1. Higher degree approximations may be found by consulting Luke [ 6 ]....

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  • ...Most often, rational approximations are derived from the power series expansion of the function, such as the methods given by Luke [ 6 ]....

    [...]

Journal ArticleDOI
TL;DR: The exponential integral of the exponential integral can be approximated by means of the empirical formula, e.g. as mentioned in this paper, which approximates p(x) = - \int\limits_\infty ^x {\frac{{e^{ - u} }}{{u^2 }}} \cdot du\).
Abstract: The exponential integral\(p(x) = - \int\limits_\infty ^x {\frac{{e^{ - u} }}{{u^2 }}} \cdot du\) can be approximated by means of the empirical formula\(p(x) \approx \frac{{e^{ - x} }}{{(x - d)(x + 2)}}\) with\(d = \frac{{16}}{{(x^2 - 4x + 84)}}\). Ifx> 1.6, errors are less than 0.5%.

54 citations

Journal ArticleDOI
TL;DR: In this paper, the relationship between chemical kinetics and differential thermal analysis (DTA) curves is studied for the reactions which follow the general rate expression: r = r/sub 0/e/sup -E/RT/(1 - x).
Abstract: Quantitative relationships between chemical kinetics and differential thermal analysis (DTA) curves are studied for the reactions which follow the general rate expression: r = r/sub 0/e/sup -E/RT/(1 - x). Both the frequency factor and the activation energy can be derived from a single DTA curve. From the known kinetic parameters, the DTA curve can also be predicted. The rather simple models developed in this work have been tested by the oxidation reaction of nuclear graphite with CO/sub 2/ and by data in the literature on the thermal dehydration of clays. The results are satisfactory considering the complexities involved in DTA.

51 citations