Journal of Physical Chemistry, Vol.98, No.35, 8721-8725, 1994
Collisional Stabilization Efficiencies That Control Condensation Flux Rates in Supersaturated Vapors of N-Alcohols and Water
In contrast to classical nucleation theory (CNT), wherein J(S;T) magnitudes are expressed in terms of physical parameters of molecular clusters treated as liquid drops, the kinetic molecular model (KMM) focuses on the dynamics of interaction between clusters and colliding monomers, i.e. the rates of accretion and efficiencies of stabilization of the transient hot adducts. Instead of providing a predictive model, we accept the reported J(S;T) values and derive magnitudes for selected kinetic parameters, in particular, (i) a temperature-dependent stabilization factor (SP), which is strongly correlated with (ii) the size-dependent activation energy for evaporation from stabilized clusters and (iii) size-dependent heats of evaporation. Recently published data on water and six n-alcohols, obtained with the double-piston expansion technique, provided the means to evaluate a self-consistent set of SP values and insights into the proposed mechanism for cluster growth. The results for supersaturated water are of special interest.
Keywords:KINETIC-MOLECULAR-MODEL;HOMOGENEOUS NUCLEATION RATES;CLUSTERS (H2O)N;DISSOCIATION;ENERGETICS;DYNAMICS;ENERGIES;SPECTRA;IONIZATION;VIBRATIONS