The kinetics of the dissociation of CF3I behind shock waves was experimentally investigated. The reaction CF3I + Ar → CF3 + I + Ar was studied at temperatures between 900 and 1250 K and pressures of 2–3 bar. For this purpose, the time profiles of the concentration of atomic iodine were measured using a highly sensitive atomic resonance absorption spectroscopy method at a wavelength of 183.04 nm. From these data, the experimental value of the dissociation rate constant of CF3I was obtained: . We found that the investigated range of pressures and temperatures for the CF3I dissociation lies in the pressure transition region. Based on the Rice-Ramsperger–Kassel–Marcus theory, the threshold high and low-pressure rate constants ( and k0) and falloff curves are calculated for the temperatures of 950–1200 K. As a result of this calculation, the threshold rate constants could be evaluated in the forms: and , and the center broadening factor, which takes into account the contribution of strong and weak collisions in the transition region, is .
The influence of the kind of bath gas and its pressure on the iron nanoparticle formation and growth was investigated experimentally. Iron nanoparticles were synthesized from supersaturated iron vapour generated by ArF excimer laser pulse photolysis of gaseous Fe(CO)5 at room temperature. The particle size was determined by time-resolved laser-induced incandescence (TiRe-LII) as a function of time after photolysis at different experimental conditions. Additionally, final particles were sampled and analysed by transmission electron microscopy and by energy-dispersive x-ray analysis. The particle growth rate and the final particle size depended on the bath-gas composition and pressure. Increasing the argon bath-gas pressure accelerated the iron nanoparticle growth rate. In contrast to argon, no influence of helium on the particle growth rate was observed. The experimental results are compared with numerical simulations of particle surface growth, based on the model developed in previous investigations. The simulations indicate that the observed differences in the influence of the bath gas on the particle formation are caused by the species-dependent quenching probability of the active atom-particle complexes by the bath gas.
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