Enhanced Surface Partitioning of Nitrate Anion in Aqueous Bromide Solutions.

ABSTRACT

The proximity of nitrate anions to the air-water interface is thought to strongly influence their photodissociation quantum yield, due to a reduced solvent cage effect at the water surface. Although nitrate in aqueous solution exhibits little or no surface affinity, the release of gas phase NO2 (nitrate's primary photodissociation product) has been reported to be enhanced when halides, in particular bromide, are also present in solution. Here, we use glancing-angle Raman spectroscopy to investigate whether solutions containing both nitrate and halides show different propensities for nitrate at the air-water interface. We find that bromide enhances, and chloride has little effect on (or perhaps suppresses) the surface partitioning of nitrate anions.