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H2O and HCl trace gas kinetics on crystalline HCl hydrates and amorphous HCl / H2O in the range 170 to 205 K: the HCl / H2O phase diagram revisited

机译:H2O和HCl痕量气体动力学在结晶HCl水合物和170-205k范围内的无定形HCl / H 2 O:HCl / H2O相图再审议

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In this laboratory study, H2O ice films of 1 to 2 μm thickness have been used as surrogates for ice particles at atmospherically relevant conditions in a stirred flow reactor (SFR) to measure the kinetics of evaporation and condensation of HCl and H2O on crystalline and amorphous HCl hydrates. A multidiagnostic approach has been employed using Fourier transform infrared spectroscopy (FTIR) absorption in transmission to monitor the condensed phase and residual gas mass spectrometry (MS) for the gas phase. An average stoichiometric ratio of H2O : HCl = 5.8 ± 0.7 has been measured for HCl 6H2O, and a mass balance ratio between HCl adsorbed onto ice and the quantity of HCl measured using FTIR absorption (Nin – Nesc – Nads) / NFTIR = 1.18 ± 0.12 has been obtained. The rate of evaporation Rev(HCl) for crystalline HCl hexahydrate (HCl 6H2O) films and amorphous HCl / H2O mixtures has been found to be lower by a factor of 10 to 250 compared to Rev(H2O) in the overlapping temperature range 175 to 190 K. Variations of the accommodation coefficient α(HCl) on pure HCl 6H2O up to a factor of 10 at nominally identical conditions have been observed. The kinetics (α, Rev) are thermochemically consistent with the corresponding equilibrium vapour pressure. In addition, we propose an extension of the HCl / H2O phase diagram of crystalline HCl 6H2O based on the analysis of deconvoluted FTIR spectra of samples outside its known existence area. A brief evaluation of the atmospheric importance of both condensed phases – amorphous HCl / H2O and crystalline HCl 6H2O – is performed in favour of the amorphous phase.
机译:在该实验室研究中,1至2μm厚度的H2O冰膜已被用作搅拌的流动反应器(SFR)中的大气相关条件下的冰颗粒的替代物,以测量HCl和H2O在结晶和无定形上的蒸发和缩合的动力学HCl水合物。使用傅里叶变换红外光谱(FTIR)吸收在透射中使用多沟稳态方法,以监测气相的冷凝相和残留气体质谱(MS)。已经测量了HCl 6H 2 O的平均化学计量比例的HCl 6H 2 O,HCl与使用FTIR吸收测量的HCl之间的质量平衡比和使用FTIR吸收测量的HCl的量(nin - nesc - nads)/ nftir = 1.18±已经获得了0.12。与Rev(H2O)在重叠温度范围175至190中,已发现蒸发HCl六水合物(HCl 6H 2 O)膜(HCl 6H 2 O)膜和无定形HCl / H 2 O混合物的蒸发速率(HCl 6H 2 O)膜和无定形HCl / H 2 O混合物的速率降低了10至250倍K.已经观察到纯HCl 6H2O上的容纳系数α(HCl)的变化在名义上相同的条件下达到10倍。动力学(α,Rev)与相应的平衡蒸气压进行热化学均匀。此外,我们提出了基于其已知存在面积之外的样本的去酚醛化FTIR光谱的结晶HCl 6H2O HCl / H2O相图的延伸。简要评价凝聚相 - 无定形HCl / H 2 O和结晶HCl 6H2O - 的大气至关重要的致力于非晶相。

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