The metastable HCl · 6H₂O phase – IR spectroscopy, phase transitions and kinetic/thermodynamic properties in the range 170–205 K

Abstract

Abstract. In this laboratory study, 1 to 2 μm thick polycrystalline ice films have been grown under stirred flow reactor (SFR) conditions and subsequently doped with metered amounts of HCl under static conditions. A multidiagnostic approach including FTIR absorption spectroscopy in transmission, residual gas mass spectrometry (MS) and total pressure measurement was employed. Depending on the growth protocol controlling both temperature and partial pressure of HCl (PHCl), either amorphous HCl/H2O or crystalline HCl hexahydrate (HCl · 6H2O) have been obtained. After controlled doping with HCl and evaporation of excess H2O from the ice film, transmission FTIR of pure HCl · 6H2O films and use of calibrated residual gas MS enabled the measurement of differential (peak) IR cross sections at several mid-IR frequencies (σ = (6.5 ± 1.9) × 10-19 cm2 molec-1 at 1635 cm-1 as an example). Two types of kinetic experiments on pure HCl · 6H2O have been performed under SFR conditions: (a) evaporation of HCl · 6H2O under H2O-poor conditions over a narrow T range, and (b) observation of the phase transition from crystalline HCl · 6H2O to amorphous HCl/H2O under H2O-rich conditions at increasing T. The temperature dependence of the zero-order evaporation flux of HCl in pure HCl · 6H2O monitored at 3426 cm-1 led to log(Jev) molec cm-2s-1= (36.34 ± 3.20) - (80 810 ± 5800)/2.303RT with R=8.312 JK−1 mol-1. HCl · 6H2O has a significant intrinsic kinetic barrier to HCl evaporation of 15.1 kJ mol-1 in excess of the HCl sublimation enthalpy of 65.8 kJ mol-1 at 200 K but is kinetically unstable (metastable) at typical UT/LS conditions of HCl partial pressure (P(HCl)) and temperature. Water-rich HCl · 6H2O undergoes a facile phase transition from crystalline to the amorphous/ supercooled/disordered state easily observable at T≥ 195 K under both static and SFR conditions. This corresponds to low P(HCl) in the neighborhood of 10-7 Torr that also prevails at the Upper Troposphere/Lower Stratosphere (UT/LS). The atmospheric importance of HCl · 6H2O is questioned in view of its nucleation barrier and its dependence on temperature and P(HCl) compared to the amorphous HCl/H2O phase.