Using a coated-wall flow tube connected to a mass spectrometer, the heterogeneous conversion of NO2 to HONO on dry hydrocarbon soot surfaces has been studied at room temperature and 243 K. Particular attention was given to the measurement of the HONO yield as a function of hydrocarbon fuel, NO2 partial pressure, extent of uptake, and surface oxidation state. In all cases, the yield is invariant of these parameters and close to unity, indicative of an irreversible oxidation mechanism by which the NO2 abstracts an H atom from the surface. XPS analysis shows that the surface N content does not measurably increase with NO2 exposure. There is minimal surface reactivity regeneration with time or via exposure to high relative humidity. A BET surface area measurement of the entire soot film exposed to NO2 was used to determine the amount of HONO that can be generated from the soot surface per unit surface area, prior to its deactivation. The reduction of NO2 to HONO on soot is unlikely to account for the observed nighttime buildup of HONO in polluted urban environments.

The adsorption of gas-phase nitric acid on n-hexane soot was measured as a function of temperature, relative humidity (RH), and nitric acid partial pressure in a coated-wall flow tube coupled to an electron-impact mass spectrometer. The specific surface area (SSA) of the soot, determined from the BET isotherm of Kr at 77 K for each sample, was 88-372 times larger than the geometric surface area. The SSA increased linearly with soot mass for thin samples but saturated at high mass. For the most part, the nitric acid adsorption was reversible in the submonolayer regime, and no indication of HONO formation was observed. The uptake increased with decreasing temperature and, for surface coverages between 10 12 and 10 13 molecules cm -2 , the average enthalpy of adsorption was -55.8 ( 7.7 kJ mol -1 . A Langmuir-Freundlich model with the heterogeneity parameter equal to 0.5 closely describes the uptake data, implying either that the surface sites are energetically heterogeneous or that nitric acid is dissociating on the surface. The nitric acid adsorption isotherms were independent of relative humidity up to 80% RH at 243 K. Exposure to ppm levels of ozone for about 1 h had no effect on the adsorption. The atmospheric implications of this work are discussed.

The adsorption isotherms of a series of aromatic hydrocarbons on n-hexane soot were measured as a function of temperature and partial pressure in a coated-wall flow tube coupled to an electron-impact mass spectrometer. The specific surface area was determined for each of the samples by measuring the BET isotherm of Kr at 77 K. The gas-to-surface uptakes were fully reversible with the extent of adsorption increasing with decreasing temperature and increasing partial pressures. At low partial pressures, the isotherms were well modeled by the Langmuir isotherm for all experimental conditions, and the adsorption was found to saturate at one monolayer of coverage at approximately 2 x 10(14) molecule cm(-2). For the less volatile species, evidence for multilayer adsorption was observed and the BET isotherm was used instead. The experimental enthalpies of adsorption were consistently higher than the enthalpies of vaporization for all compounds. A linear free-energy relationship was developed between the Langmuir equilibrium constant for adsorption and the compound's (sub-cooled) liquid vapor pressure, providing validation for the use of such relationships in assessing gas-particle partitioning of aromatic hydrocarbons to soot aerosols in the environment. The experimental results were compared to the Junge-Pankow gas-to-aerosol partitioning model.

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