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Infrared Optical Constants of Crystalline Sodium Chloride Dihydrate: Application To Study the Crystallization of Aqueous Sodium Chloride Solution Droplets at Low Temperatures

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posted on 23.08.2012, 00:00 by Robert Wagner, Ottmar Möhler, Martin Schnaiter
Complex refractive indices of sodium chloride dihydrate, NaCl·2H2O, have been retrieved in the 6000–800 cm–1 wavenumber regime from the infrared extinction spectra of crystallized aqueous NaCl solution droplets. The data set is valid in the temperature range from 235 to 216 K and was inferred from crystallization experiments with airborne particles performed in the large coolable aerosol and cloud chamber AIDA at the Karlsruhe Institute of Technology. The retrieval concept was based on the Kramers–Kronig relationship for a complex function of the optical constants n and k whose imaginary part is proportional to the optical depth of a small particle absorption spectrum in the Rayleigh approximation. The appropriate proportionality factor was inferred from a fitting algorithm applied to the extinction spectra of about 1 μm sized particles, which, apart from absorption, also featured a pronounced scattering contribution. NaCl·2H2O is the thermodynamically stable crystalline solid in the sodium chloride–water system below the peritectic at 273.3 K; above 273.3 K, the anhydrous NaCl is more stable. In contrast to anhydrous NaCl crystals, the dihydrate particles reveal prominent absorption signatures at mid-infrared wavelengths due to the hydration water molecules. Formation of NaCl·2H2O was only detected at temperatures clearly below the peritectic and was first evidenced in a crystallization experiment conducted at 235 K. We have employed the retrieved refractive indices of NaCl·2H2O to quantify the temperature dependent partitioning between anhydrous and dihydrate NaCl particles upon crystallization of aqueous NaCl solution droplets. It was found that the temperature range from 235 to 216 K represents the transition regime where the composition of the crystallized particle ensemble changes from almost only NaCl to almost only NaCl·2H2O particles. Compared to the findings on the NaCl/NaCl·2H2O partitioning from a recent study conducted with micron-sized NaCl particles deposited onto a surface, the transition regime from NaCl to NaCl·2H2O is shifted by about 13 K to lower temperatures in our study. This is obviously related to the different experimental conditions of the two studies. The partitioning between the two solid phases of NaCl is essential for predicting the deliquescence and ice nucleation behavior of a crystalline aerosol population which is subjected to an increasing relative humidity.