scholarly journals A Study on the Numerical Integration of Reaction Rate Laws

1998 ◽  
Vol 43 (Supplement) ◽  
pp. S1-S8
Author(s):  
塚田 雅夫 ◽  
西村 英俊
1992 ◽  
Vol 296 ◽  
Author(s):  
M. D. Fayer ◽  
Andrei Tokmakoff ◽  
Dana D. Dlott

AbstractA theoretical model is developed to describe multiphonon up-pumping of internal vibrations. The dominant mechanism for up-pumping is anharmonic coupling of excited phonon modes with low frequency molecular vibrations, termed doorway modes. Quantitative calculations were performed which show the extent and rate of multiphonon up-pumping caused by shock excitation. The time dependence of chemical reactivity behind the front is calculated using reaction rate laws for the decomposition of nitramine explosives. A mechanism for hot spot formation, based on defect induced local increases in anharmonic coupling, is discussed.


2021 ◽  
pp. 17-35
Author(s):  
Luis Arnaut
Keyword(s):  

2011 ◽  
Vol 312-315 ◽  
pp. 7-12 ◽  
Author(s):  
Mohammad Ebrahim Zeynali

The diffusion coefficients of DEB and EVB into a synthesized and a commercial catalyst pellet were determined by numerical integration of the Stewart-Johanson equation at the reaction condition. The continuity equation was solved by the orthogonal collocation method. DVB was prepared by a commercial catalyst. The production rate and effectiveness factor were determined experimentally and compared with the predicted value. It was seen that the diffusion into the catalyst pellet is strongly limiting the process of DVB production.


1982 ◽  
Vol 60 (6) ◽  
pp. 765-771 ◽  
Author(s):  
J. Peter Guthrie

Two methods for deriving rate constants from absorbance–time data when the rate laws cannot be integrated in closed form are presented, and their use illustrated. One method uses least-squares fitting to the curve obtained by numerical integration of the rate law. The other involves analysis of the numerically evaluated derivative with respect to time of the absorbance–time curve. This allows calculation of rate constants in a direct fashion, either from the initial and minimum values of a function of the derivative or by fitting the decrease in the value of this function to a first-order rate equation when this is suitable. The advantages and disadvantages of the methods are discussed. The illustrations are from recent studies of the reactions of steroidal imidazoles with aryl esters. The derivative method appears to be superior, and of potentially wide utility.


The conductive theory of thermal explosion in its original form (Frank-Kamenetskii, Acta phys. -chim . URSS (1939)) expresses the balance between heat generation and heat conduction in terms of the dimensionless parameter δ = [QEA a 2 0 c n 0 exp ( - E/RT a )]/ K RT 2 a Stability is lost when δ exceeds a critical value which, in this approximation, depends only on the geometry of the system. Matters are usually more complicated than this. First, heat transfer is often impeded both in the interior (by conduction) and at the surface; the relative importance of these impedances is expressed by the Biot number B i = X a o / K - Second, the temperature dependence of reaction rate may not be well enough represented by the 'exponential approximation’ (which simply implies a doubling of rate every so many degrees). The natural and convenient dimensionless measure here is the parameter ϵ = RT a /E. In the present paper, critical values for the parameter δ and for the dimensionless central-temperature excess Ɵ o have been evaluated for the whole range of Biot number from the uniform case (Semenov extreme, B i → 0) to the Frank-Kamenetskii extreme (B i →∞). The procedures can handle any temperature-dependence of rate and are illustrated here for the Arrhenius and 'bimolecular’ forms for which, k∝ exp ( — E /RT ) and k ∝T ½ exp ( - E /R T ) respectively. When E /RT a is not large, criticality is lost at ϵ = ϵ tr ≤ ¼. Such transitional values for the reduced ambient temperature ϵ, for the critical value of δ, and for the dimensionless central temperature excess Ɵ 0 have also been obtained. They are represented both graphically and numerically. The present results are also compared with earlier work.


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