Coagulation of combustion generated nanoparticles and their measurement behind vehicle engines: can they play a role as atmospheric pollutants?

Based on photoionisation mass spectrometry two types of experiments were carried out. (i) In a fast flow reactor coupled to a low pressure flame as a particle source, rate coefficients for the coagulation of primary nanoparticles were measured through variation of the reactor residence time. The results are kc (350K) = 3.5x10-10cm3/s and kc (573K) = 1.1x10-9cm3/s, i.e. very high rate coefficients. It was also shown that coagulated nanoparticles can have masses beyond 50ku, corresponding to equivalent diameters between 4 to 5nm. These particles are easily fragmented during photoionisation. (ii) Using a second and mobile photoionisation mass spectrometer equipped with a fast flow inlet system, measurements were carried out behind three different vehicle engines, a two-stroke scooter engine, a four-stroke motorbike engine and a DI (direct injection) gasoline research engine. In all cases ion signals around 1000u were found that are clearly dependent on engine conditions. In the case of the DI engine, they correlate with the smoke number. These signals cannot be explained by PAHs due to their low volatility at the respective masses. Major contributions of soot or droplet fragmentation were ruled out through additional experiments using a heated inlet line and a filter. Consequently, these signals are interpreted as fragments of coagulated nanoparticles.

The Reaction of Hydrogen Atoms with Silyl Radicals; the Decomposition Pathways of Chemically Activated Silanes

The reactions of hydrogen atoms with silane and the methylated silanes - with the exception of tetramethylsilane -have been investigated in a fast flow reactor. Under our experimental conditions hydrogen abstraction from the Si-H bond is followed by combination of hydrogen atoms with the corresponding silyl radicals. The molecules formed in this way are activated by about 375 kJ/mol of vibrational energy. Two decomposition channels have been unequivocally identified, namely the elimination of molecular hydrogen and of methane, both with concomittant formation of the respective silylenes. In a subsequent step, silylene inserts into the substrate under formation of disilanes. With increasing degree of methylation. stabilization of the activated molecule competes with decomposition and dominates the kinetics in the case of trimethylsilane. With methyl -and dimethyl-silane, methyl radicals are observed as an additional reaction product. On the basis of RRKM calculations it is unlikely that they originate from a direct decomposition of the activated molecules.Absolute values for the room temperature rate constants of the abstraction reactions are given; for H+CH3SiH3, Arrhenius parameters have been determined.