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In this laboratory study a multidiagnostic experimental approach includingFourier transform infrared (FTIR) absorption of 1 to 2 μm thickpolycrystalline ice films, residual gas mass spectrometry (MS) and totalpressure measurement were employed. Both amorphous HCl–H2O andcrystalline HCl hexahydrate (HCl · 6H2O) have beeninvestigated. After controlled doping with HCl and evaporation of excessH2O from the ice film, transmission FTIR of pureHCl · 6H2O films and use of calibrated mass spectrometryenabled the measurement of differential (peak) IR cross sections at severalmid-IR frequencies, for example σ = (6.5 ± 1.9)× 10−19 cm2 molec−1 at 1635 cm−1. Two types ofkinetic experiments on pure HCl · 6H2O have been performedunder SFR conditions: (a) evaporation of pure HCl · 6H2O overa narrow T range after evaporation of excess H2O, and (b) observationof the phase transition from crystalline HCl · 6H2O toamorphous HCl–H2O under H2O-rich conditions at increasing T. Thetemperature dependence of the zero-order evaporation flux of HCl in pureHCl · 6H2O led tologJev molec cm−2 s−1 = (36.34 ± 3.20) –(80 810 ± 5800)/2.303 RT withR = 8.314 JK−1 mol−1, which turned out to be rate-limitingfor evaporation. HCl · 6H2O has a significant intrinsickinetic barrier to HCl evaporation of 15.1 kJ mol−1 in excess of theHCl sublimation enthalpy of 65.8 kJ mol−1 at 200 K but is kineticallyunstable (metastable) at T ≥ 173 K. The atmospheric importance ofHCl · 6H2O is questioned in view of its large nucleationbarrier and its dependence on T and P(HCl) compared to the amorphousHCl–H2O phase at upper tropospheric–lower stratospheric (UT/LS)conditions

atmospheric chemistry and physics

The metastable HCl · 6H&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;O phase – IR spectroscopy, phase transitions and kinetic/thermodynamic properties in the range 170–205 K