Dissociative Adsorption of Nitric Acid at the Surface of Amorphous Solid Water Revealed by X-ray Absorption Spectroscopy

A spectral feature unique to the molecularly adsorbed state of HNO3 is found in X-ray absorption spectroscopy. This distinctive signature reveals the extent to which nitric acid is ionically dissociated upon its adsorption on amorphous solid water (ASW) at low coverage and low temperature. Thermal annealing induces irreversible proton transfer from HNO3(ads), demonstrating that it is metastable with respect to ionic dissociation below 100 K at the surface of ASW. The slight decrease in ionic dissociation propensity reported for nitric acid at liquid water surfaces thus appears to be overwhelmed by the strong exothermicity of this reaction as its entropic inhibition becomes increasingly suppressed the lower the temperature. These findings may be relevant for atmospheric chemistry processes involving nitric acid, which should thus, according to thermodynamic considerations, be expected to behave as a strong acid at the surface of supercooled aerosols and of the quasi-liquid layer.