%0 Journal Article
%J Journal of Chemical Physics
%D 2011
%T Catalytic conversion reactions mediated by single-file diffusion in linear nanopores: Hydrodynamic versus stochastic behavior
%A Ackerman, D. M.
%A Wang, J.
%A Wendel, J. H.
%A Liu, D. J.
%A Pruski, M.
%A Evans, J. W.
%K kinetics
%K lattice-gas models
%K noninteracting particles
%K systems
%K tracer exchange
%K ZEOLITES
%M ISI:000288597700007
%P 114107
%R 10.1063/1.3563638
%U ://000288597700007http://scitation.aip.org/getpdf/servlet/GetPDFServlet?filetype=pdf&id=JCPSA6000134000011114107000001&idtype=cvips&doi=10.1063/1.3563638&prog=normal
%V 134
%X We analyze the spatiotemporal behavior of species concentrations in a diffusion-mediated conversion reaction which occurs at catalytic sites within linear pores of nanometer diameter. Diffusion within the pores is subject to a strict single-file (no passing) constraint. Both transient and steady-state behavior is precisely characterized by kinetic Monte Carlo simulations of a spatially discrete lattice-gas model for this reaction-diffusion process considering various distributions of catalytic sites. Exact hierarchical master equations can also be developed for this model. Their analysis, after application of mean-field type truncation approximations, produces discrete reaction-diffusion type equations (mf-RDE). For slowly varying concentrations, we further develop coarse-grained continuum hydrodynamic reaction-diffusion equations (h-RDE) incorporating a precise treatment of single-file diffusion in this multispecies system. The h-RDE successfully describe nontrivial aspects of transient behavior, in contrast to the mf-RDE, and also correctly capture unreactive steady-state behavior in the pore interior. However, steady-state reactivity, which is localized near the pore ends when those regions are catalytic, is controlled by fluctuations not incorporated into the hydrodynamic treatment. The mf-RDE partly capture these fluctuation effects, but cannot describe scaling behavior of the reactivity. (C) 2011 American Institute of Physics. [doi:10.1063/1.3563638]
%Z 737VQTimes Cited:0Cited References Count:32
%8 02/21
%@ 0021-9606