Paper I: Design and construction of a Knudsen-cell reactor for the study of heterogeneous reactions over the temperature range 130–750 K: Performances and limitations

A new low-pressure flow reactor operated as a Knudsen cell and intended for chemical kinetic studies is described. The reactor is specifically designed to study the kinetics of heterogeneous reactions. Gas-phase species are detected either by mass-spectrometric sampling or by in situ optical techniques, e.g., laser-induced fluorescence, resonantly enhanced multiphoton ionization. A feature of the reactor is its modular design, allowing full interchangeability of several sample holders at minimal effort, allowing the measurement of uptake coefficients ranging from ${10}^{\text{−7}}$ to 1.0. Sample supports operating at low and high temperatures have been developed which cover the stated temperature range. Several experimental examples of the utility of the reactor are detailed. The reliability and error bars of the kinetic results due to the errors and uncertainties associated with the experimental procedures are discussed, in particular for fast heterogeneous processes. It is found that even in the molecular flow regime, for fast reaction, the effects of diffusion limitations within the cell must be taken into account. This fact has been shown here from an experimental point of view. In a companion article the phenomena are studied using Monte Carlo simulation of the gas dynamics under molecular flow conditions.