A laboratory study of the heterogeneous reaction of nitric acid on calcium carbonate particles

Abstract

It has been postulated that the reaction of nitric acid with calcium carbonate, namely, CaCO3(s) + 2HNO3(g) → Ca(NO3)2(s) + CO2(g) + H2O(g), plays an important role in the atmosphere. In this study, transmission FTIR spectroscopy, diffuse reflectance UV‐visible spectroscopy, transmission electron microscopy and a Knudsen cell reactor coupled to a quadrupole mass spectrometer have been used to investigate the heterogeneous reactivity of HNO3 on CaCO3 at 295 K as a function of relative humidity. Transmission FTIR spectroscopy was used to probe both gas‐phase and adsorbed products and showed that the reaction of HNO3 and CaCO3 is limited to the surface of the CaCO3 particle in the absence of adsorbed water. However, in the presence of water vapor, the reaction is greatly enhanced and is not limited to the surface of the particle producing both solid calcium nitrate and gaseous carbon dioxide. The enhanced reactivity of the particles is attributed to the presence of a layer of adsorbed water on the particle surface. The amount of adsorbed water on the particle surface is strongly dependent on the extent of the reaction. This can be understood in terms of the increased hydrophilicity of calcium nitrate as compared to calcium carbonate. Data from experiments using a mass‐calibrated Knudsen cell reactor showed the stoichiometry for the reaction determined from gas‐phase species deviated from that expected from the balanced equation. Water adsorption on the particle surface and gases dissolved into the water layer appear to be the cause of this discrepancy. The measured uptake coefficient accounting for the BET area of the sample is determined to be 2.5±0.1×10−4 for HNO3 on CaCO3 under dry conditions and is found to increase in the presence of water vapor. Atmospheric implications of the results presented here are discussed.