Studies of the Structure and Reactivity of Soot

Abstract

Vibrational spectroscopy, supplemented with other techniques, is providing a comprehensive picture of the structure and reactivity of soot. Reactions such as soot-NO₂/N₂O₄, soot-O₃, and soot-SO₂, at atmospheric and subatmospheric pressures and at different temperatures, have been studied. Determination of the kinetics and mechanisms of the formation of CO and CO₂ during the soot-O₃ reaction, and the effect of temperatures and the concentrations of soot and ozone on this reaction, have led to further insights about the soot structure. Examination of the identity and role of linkages bonding carbon layers together is underway. Application of the Elovich equation to determine initial rates for the formation of surface species in these reactions indicates that the soot-O₃ reaction is faster than the rapid soot-NO₂/ N₂O₄ reaction which, in turn, is faster than that of soot-SO₂. Oxidation of SO₂ to ionic sulfate, confirmed by isotopic substitution, occurs in the presence of soot, water vapor, and oxygen. The presence of simulated solar radiation results in the formation of both ionic and covalent sulfate species. The substrate, whether it is carbon black, cab-o-sil, or the glass walls of the reaction vessel, seems to play a role in the nonphotochemical oxidation of SO₂ to sulfate. The miscibilities of the reaction products of soot-O₃, soot-NO₂/N₂O₄, soot-SO₂, with water vary greatly and have implications for the depletion of tropospheric ozone in the presence of soot-containing particulates.