SURFACE-REACTION AND PORE DIFFUSION IN FLOW-TUBE REACTORS

The interaction of gas diffusion with surface reaction in porous solids is discussed and applied specifically to heterogeneous rate measurements in flow-tube reactors. External diffusion to the outer surface of a reactive solid, internal diffusion within the pores, surface reaction, and laminar flow are considered. A procedure is developed to correct observed surface rate constants for the interaction of these processes. Measured surface areas and bulk densities are used to construct a semiempirical model for porous diffusion in vapor-formed HNO3-H2O ices which are used to simulate polar stratospheric cloud surfaces. The model is tested experimentally by varying the thickness of these ices from about 15 to 120-mu-m. The results are consistent with the model predictions and show that the HNO3-H2O ices used are highly porous, and the internal surface must be considered in calculating kinetic parameters from observed loss rates. The best fit of the data yields a tortuosity factor of 3.3 +/- 1.1 for the ice substrates.