Nonlinear vibrational spectroscopic studies of the adsorption and speciation of nitric acid at the vapor/acid solution interface

Nitric acid plays an important role in the heterogeneous chemistry of the atmosphere. Reactions involving HNO(3) at aqueous interfaces in the stratosphere and troposphere depend on the state of nitric acid at these surfaces. The vapor/liquid interface of HNO(3)-H2O binary solutions and HNO(3)-H(2)SO(4)-H2O ternary solutions are examined here using vibrational sum frequency spectroscopy (VSFS). Spectra of the NO2 group at different HNO(3) mole fractions and under different polarization combinations are used to develop a detailed picture of these atmospherically important systems. Consistent with surface tension and spectroscopic measurements from other laboratories, molecular nitric acid is identified at the surface of concentrated solutions. However, the data here reveal the adsorption of two different hydrogen-bonded species of undissociated HNO(3) in the interfacial region that differ in their degree of solvation of the nitro group. The adsorption of these undissociated nitric acid species is shown to be sensitive to the H2O:HNO(3) ratio as well as to the concentration of sulfuric acid.