Heterogeneous reaction of NO2 on diesel soot particles

Soot particles were collected from a diesel engine using a procedure that realistically mimics exhaust gas conditions in tailpipes and during dilution at room temperature. After being sampled, the particles were exposed to NO2 concentrations and relative humidity in ranges relevant for the troposphere using N-13 as tracer. Gas-phase nitrous acid (HONO) and irreversibly bound (i.e., chemisorbed)species were the main reaction products with initial yields of 80-90% and about 10%, respectively. Neither NO nor HNO3 were detectable. The HONO formation increased with increasing engine load(i.e., with a decreasing air to fuel ratio, lambda). The reaction rates of HONO and chemisorbed NO;! increased with increasing NO2 concentration and did not depend on relative humidity. At the beginning of reaction, the uptake coefficient averaged over 3 min ranged from 5 x 10(-6) to 10(-5) for NO2 concentrations between 2 and 40 ppb. The HONO formation rates decreased with time, indicating consumption of reactive surface species, while the chemisorption rates remained almost constant. The total HONO formation potential of the particles was estimated to about 1.3 x 10(17) molecules/mg of diesel soot dr to about 4.7 mg/kg of diesel fuel, indicating that the reaction between NO2 and diesel soot particles does not provide a significant secondary HONO source in the atmosphere. A Langmuir-Hinshelwood type reaction mechanism was proposed that adequately describes the observed results and also allows discussing important general features of reactions on soot.