Journal of Physical Chemistry A, Vol.104, No.10, 2038-2047, 2000
Infrared observations of the response of NaCl, MgCl2, NH4HSO4, and NH4NO3 aerosols to changes in relative humidity from 298 to 238 K
Infrared extinction spectroscopy has been used to monitor liquid-to-solid and solid-to-liquid phase transitions of a variety of model tropospheric aerosols over a temperature range from 298 to 238 K. Uptake and loss of water were induced by controlling the relative humidity (RH) as submicron-sized aerosols passed through a low-temperature, atmospheric pressure flow tube on a time scale of tens of seconds. Observation of the absorption features of condensed-phase liquid water showed that NaCl aerosols deliquesced at a RH within +/-2% of the thermodynamic value from 298 to 253 K, whereas efflorescence did not occur until 40 +/- 5% RH. No hydrate formation was observed. By contrast, aerosols composed of species with considerably lower deliquescence points, including MgCl2, NH4HSO4, and NH4NO3, exhibited a strong inhibition to efflorescence down to 2% RH. As aerosols, the only one of these three which began to effloresce was MgCl2, and only at relative humidities below 2%. MgCl2. 6H(2)O is the likely product. NH4HSO4 aerosols were induced to effloresce when sprayed onto an infrared window and subjected to relative humidities of less than 1 % fur periods of hours. These findings strongly suggest that, in the absence of heterogeneous nuclei, a wide variety of inorganic aerosols will exist as liquid solutions in the atmosphere regardless of relative humidity and temperature conditions.
Keywords:METASTABILITY PHASE-DIAGRAMS;AMMONIUM-SULFATE;DELIQUESCENCE;TEMPERATURE;EQUILIBRIUM;MODEL;N2O5