Dinámica de reacciones unimoleculares en fase gas: Desviaciones del comportamiento estadístico

Martı́nez-Núñez, Emilio; Vázquez, Saulo A.

doi:10.1590/s0100-40422002000400013

Cited by 5 publications

(1 citation statement)

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“…Unimolecular decompositions are commonly the first step in the conversion of a fuel in combustion systems. Correspondingly, the accurate determination of rate coefficients for unimolecular reactions has attracted a great deal of attention from combustion kinetics researchers [1][2][3][4][5][6][7][8][9]. The RRKM/master equation (ME) method is the preferred approach for computing the temperature-and pressure-dependent rate coefficients for unimolecular reactions [10][11][12][13].…”

Section: Introductionmentioning

confidence: 99%

Global uncertainty analysis for RRKM/master equation based kinetic predictions: A case study of ethanol decomposition

Xing

Wang

et al. 2015

Combustion and Flame

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A precise understanding of the accuracy of reaction rate constants, whether determined experimentally or theoretically, is of considerable importance to kinetic modelers. While the uncertainties of experimentally measured rate constants are commonly provided, the "error bars" of computed (temperature-and pressure-dependent) rate constants are rarely evaluated rigorously. In this work, global uncertainty and sensitivity analysis is applied to the propagation of the uncertainties in the input parameters (e.g. barrier heights, frequencies and collisional energy transfer parameters et al.) to those in the rate constants computed by the RRKM/master equation method for the decomposition of ethanol. This case study provides a systematic exploration of the effect of temperature and pressure on the parametric uncertainties in RRKM/master equation calculations for a prototypical single-well multiple-channel dissociation. In the high pressure limit, the uncertainties in the theoretical predictions are controlled by the uncertainties in the input parameters involved in the transition state theory calculations, with the most important ones being those describing the energetics of the decomposition. At lower pressures, where fall-off is important, the uncertainties in the collisional energy transfer parameters play a significant role, particularly for the higher energy of

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