Shadowing effect in catalyst activity : experimental observation

The influence of the spatial distribution of catalyst particles in a fixed bed reactor on the observed reaction rates has historically been of central interest in catalysis and chemical physics. Results from both fields suggest that the apparent catalyst activity is determined by the distance between active particles and transport phenomena, although a universal understanding of their combined influence remains incomplete. In this study, pulse experiments under contrasting transport regimes show that a given amount of catalyst particles exhibits higher activity with increasing degrees of separation. This is attributed to a shadowing effect induced by the competition between closely neighboring active particles, which limits their combined apparent activity. Experimental results also suggest the dependence of this effect on mass transport phenomena within the reactor space

Momentary Equilibrium in Transient Kinetics and Its Application for Estimating the Concentration of Catalytic Sites

We describe the novel concept of momentary equilibrium (ME), a special event during a pulse-response transient experiment in which the non-steady-state rates of adsorption and desorption of a probe molecule are instantaneously balanced. In the absence of other reactions, any system with reversible adsorption will always pass through ME during a pulse-response experiment with effusion. We also suggest a new method for measuring the concentration of adsorption sites on heterogeneous catalysts and the corresponding equilibrium constant by observing momentary equilibrium in thin-zone temporal analysis of products (TZTAP) pulse-response experiments with modulated pulse intensity. The suggested method employs reversible adsorption of probe molecules, contrary to traditional methods of counting adsorption sites which utilize irreversible reactions