We present an analysis of partial heterogeneous condensation phenomena in multicomponent reacting systems, including previously neglected chemical element transport considerations. These phenomena, associated with the tendency of the chemical elements to preferentially “segregate” (according to the local temperature and the transport properties of the chemical species containing each element), are found to: (a) systematically “shift” the prevailing dew-point from that predicted purely thermodynamically, (b) systematically alter concentrations in the incipient condensate and (c) even influence the identity of a resulting single component condensate. Several distinct dew-points are shown to exist in such systems (depending upon one's operational definition or method of detection), and, as a result of transport constraints, the “sharp” locus between two chemically distinct condensates is systematically moved to a difference mainstream composition. These novel aspects of partial condensation-chemical vapor deposition (CVD) phenomena in multicomponent, chemically reacting systems are demonstrated using representative calculations and recent experiments on alkali compound condensation from the gaseous products of fossil fuel combustion. However, the phenomena illustrated here are rather general, and can be anticipated in other CVD-systems of technological importance (e.g. in semiconductor processing) by applying the concepts and methods outlined below.
Read full abstract