PNNL

Abstract

Heterogeneous reaction kinetics of gaseous nitric acid (HNO3) with calcium carbonate (CaCO3) particles was investigated using the Particle-on-Substrate Stagnation Flow Reactor (PS-SFR). The technique utilizes the exposure of substrate deposited, isolated, and narrowly dispersed particles to a gas mixture of HNO3/H2O/N2 followed by microanalysis of individual reacted particles using computer-controlled scanning electron microscopy with energy-dispersive X-ray analysis (CCSEM/EDX). The first series of experiment was conducted at atmospheric pressure, room temperature and constant relative humidity (40%) with a median dry particle diameter pD = 0.85 µm, particle loading densities 2×104 = Ns = 6×106 cm–2 and free stream HNO3 concentrations of 7, 14 and 25 ppb. The apparent, pseudo first-order rate constant for the reaction was determined from oxygen enrichment in individual particles as a function of particle loading. Quantitative treatment of the data using a diffusion-kinetic model yields lower limit to the net reaction probability ?net = 0.06 (×3/÷2). In the second series of experiments, HNO3 uptake on CaCO3 of the same particle size was examined over a wide range of relative humidity, from 10 to 80%. The lower limit for the net reaction probability was found to increase with an increase in the relative humidity, from ?net = 0.003 at RH = 10% to 0.21 at 80%.