FTIR spectroscopic investigations of supersaturated NaClO4 aerosols

Supersaturated NaClO4 aerosols have been studied using a Fourier transform infrared (FTIR) spectrometer coupled with an aerosol flow tube (AFT). Compared with previous Raman results, the water O-H stretching envelope in the supersaturated solutions of NaClO4 aerosols was more structured in response to changing RH, revealing at the same time the existence of water monomers weakly hydrogen-bonded with ClO4- at extremely high concentrations. Due to enhanced ion interactions in the supersaturated solutions of NaClO4 aerosols, the formation of contact ion pairs (CIPs) could be observed without component decomposition for the nondegenerate nu1 band of ClO4-, and the degenerate nu3 band of ClO4- was successfully related to the formation of CIPs in NaClO4 solutions. Based on these observations, a new mechanism featured by the attack of ClO4- upon hydrated Na+ for CIPs formation in the supersaturated solutions of NaClO4 aerosols was further proposed. The anhydrous NaClO4, characterized by the upper limit deliquescence relative humidity (DRH) of approximately 43% and the disappearance of the nu1 band of ClO4- in the infrared spectra, was observed to form on the silicon windows at low RHs.