Condensation in CO2 free jet expansions. II - Growth of small clusters.
An investigation into the kinetics of molecular clustering processes which occur in the highly supersaturated vapor of a CO2 free jet is described. Terminal cluster concentrations in expansions from room temperature and reservoir pressures in the range from 400 to 900 torr were determined for trimeric CO2 for nozzle diameters of .0076 cm, .015 cm, and .023 cm and in the case of CO2 tetramer and pentamer for .015 cm nozzle diameter. The measurements were made mass spectrometrically in a supersonic molecular beam apparatus. A kinetic analysis was developed from an extension of the critical nucleus concept of nucleation theory and rate equations based on intermolecular collisions. The observed cluster populations could be accounted for by the theory by adopting sticking probabilities of approximately .03 for monomer impinging on dimer, trimer, and tetramer.