Variational transition state theory based surface chemistry for the C2H6/H2/O2/Pt system
File(s)paper.pdf (1.09 MB)
Accepted version
Author(s)
Kraus, P
Lindstedt, RP
Type
Journal Article
Abstract
A reaction class-based framework for the development of heterogeneous mechanisms is applied to study the (partial) oxidation of ethane over platinum. The rate parameters for the surface chemistry were derived using a systematic application of variational transition state theory (VTST) for adsorption, desorption, and Eley–Rideal reactions coupled with two-dimensional (2D) collision theory for reactions occurring on the surface. The approach removes the need for the experimental determination of surface sticking coefficients and the associated major uncertainties. The barrier heights were determined using the unity bond index–quadratic exponential potential (UBI–QEP) method. The combined gas- and surface-phase chemistry was evaluated against independent data sets obtained from three experimental configurations. The associated 18 cases cover a wide range of residence times, stoichiometries (0.1 < ϕ < 10.4), and inlet pressures (1–12 bar). The work highlights the generality of the VTST approach that is shown to outperform the customary sticking coefficient-based methods for key aspects. A sensitivity analysis highlights the importance of the O2 and CO adsorption pathways.
Date Issued
2016-11-27
Date Acceptance
2016-11-27
Citation
Energy & Fuels, 2016, 31 (3), pp.2217-2227
ISSN
1520-5029
Publisher
American Chemical Society
Start Page
2217
End Page
2227
Journal / Book Title
Energy & Fuels
Volume
31
Issue
3
Copyright Statement
© 2016 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Energy & Fuels, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/acs.energyfuels.6b02189
Subjects
Science & Technology
Technology
Energy & Fuels
Engineering, Chemical
Engineering
DENSITY-FUNCTIONAL THEORY
PARTIAL OXIDATION
ETHANE HYDROGENOLYSIS
AB-INITIO
PLATINUM
KINETICS
ETHYLENE
METHANE
DEHYDROGENATION
HYDROGENATION
Energy
03 Chemical Sciences
09 Engineering
Publication Status
Published