Heterogeneous uptake and reactivity of formic acid on calcium carbonate particles: a Knudsen cell reactor, FTIR and SEM study

The heterogeneous uptake and reactivity of formic acid (HCOOH), a common gas-phase organic acid found in the environment, on calcium carbonate (CaCO3) particles have been investigated using a Knudsen cell reactor, Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). FTIR measurements show that the adsorption of formic acid on the surface of calcium carbonate results in the formation of calcium formate. Besides calcium formate, carbonic acid is also a reaction product under dry conditions (< 1% RH). Under dry conditions and at low pressures, the initial uptake coefficient of formic acid on CaCO3 particles is measured to be 3 +/- 1 x 10(-3) and decreases as the surface saturates with adsorbed products. The maximum surface coverage of formic acid under dry conditions is determined to be (3 +/- 1) x 10(14) molecules cm(-2). Under humidified conditions (RH > 10%), adsorbed water on the surface of the carbonate particles participates in the surface reactivity of these particles, which results in the enhanced uptake kinetics and extent of reaction of this organic acid on CaCO3 as well as opens up several new reaction pathways. These reaction pathways include: (i) the water-assisted dissociation of carbonic acid to CO2 and H2O and (ii) the formation of calcium formate islands and crystallites, as evident by SEM images. The results presented here show that adsorbed water plays a potentially important role in the surface chemistry of gas-phase organic acids on calcium carbonate particles.