A microkinetic chemical reaction mechanism capable of describing both the storage and regeneration processes in a fully formulated lean NO x trap (LNT) is presented. The mechanism includes steps occurring on the precious metal, barium oxide (NO x storage), and cerium oxide (oxygen storage) sites of the catalyst. The complete reaction set is used in conjunction with a transient plug flow reactor code to simulate not only conventional storage/regeneration cycles with a CO/H 2 reductant, but also steady flow temperature sweep experiments that were previously analyzed with just a precious metal mechanism and a steady state code. The results show that NO x storage is not negligible during some of the temperature ramps, necessitating a re-evaluation of the precious metal kinetic parameters. The parameters for the entire mechanism are inferred by finding the best overall fit to the complete set of experiments. Rigorous thermodynamic consistency is enforced for parallel reaction pathways and with respect to known data for all of the gas phase species involved. It is found that, with a few minor exceptions, all of the basic experimental observations can be reproduced with these purely kinetic simulations, i.e., without including mass-transfer limitations. In addition to accounting for normal cycling behavior, the final mechanism should provide a starting point for the description of further LNT phenomena such as desulfation and the role of alternative reductants. 4 ACKNOWLEDGMENTSThe authors thank Dr. Andrew E. Lutz, formerly of Sandia, for initial development of the Chemkin-based transient plug flow reactor code (TPLUG). The efforts at Oak Ridge were sponsored by the U.S.

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A one-dimensional isobaric reactor model is used to simulate hydrogen isotope exchange processes taking place during flow through a powdered palladium bed. This simple model is designed to serve primarily as a platform for the initial development of detailed chemical mechanisms that can then be refined with the aid of more complex reactor descriptions. The onedimensional model is based on the Sandia in-house code TPLUG, which solves a transient set of governing equations including an overall mass balance for the gas phase, material balances for all of the gas-phase and surface species, and an ideal gas equation of state. An energy equation can also be solved if thermodynamic properties for all of the species involved are known. The code is coupled with the Chemkin package to facilitate the incorporation of arbitrary multistep reaction mechanisms into the simulations. This capability is used here to test and optimize a basic mechanism describing the surface chemistry at or near the interface between the gas phase and a palladium particle. The mechanism includes reversible dissociative adsorptions of the three gas-phase species on the particle surface as well as atomic migrations between the surface and the bulk. The migration steps are more general than those used previously in that they do not require simultaneous movement of two atoms in opposite directions; this makes possible the creation and destruction of bulk vacancies and thus allows the model to account for variations in the bulk stoichiometry with isotopic composition. The optimization code APPSPACK is used to adjust the mass-action rate constants so as to achieve the best possible fit to a given set of experimental data, subject to a set of rigorous thermodynamic constraints. When data for nearly isothermal and isobaric deuterium-to-hydrogen (D→H) and hydrogen-to-deuterium (H→D) exchanges are fitted simultaneously, results for the former are excellent, while those for the latter show pronounced deviations at long times. These discrepancies can be overcome by postulating the presence of a surface poison such as carbon monoxide, but this explanation is highly speculative. When the method is applied to D→H exchanges intentionally poisoned by known amounts of CO, the fitting results are noticeably degraded from those for the nominally CO-free system but are still tolerable. When TPLUG is used to simulate a blowdown-type experiment, which is characterized by large and rapid changes in both pressure and temperature, discrepancies are even more apparent. Thus, it can be concluded that the best use of TPLUG is not in simulating realistic exchange scenarios, but in extracting preliminary estimates for the kinetic parameters from experiments in which variations in temperature and pressure are intentionally minimized.5