Energy & Fuels, Vol.31, No.3, 2217-2227, 2017
Variational Transition State Theory-Based Surface Chemistry for the C2H6/H-2/O-2/Pt System
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 < phi < 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 O-2 and CO adsorption pathways.