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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Spectroscopic Measurements of Methane Solid-Gas Equilibrium Clapeyron Curve between 40 and 77 K
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Spectroscopic Measurements of Methane Solid-Gas Equilibrium Clapeyron Curve between 40 and 77 K

机译：40至77 k之间的甲烷固体气体平衡蛋白曲线的光谱测量

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摘要

The infrared gas-phase absorption spectrum of methane was used to determine its Clapeyron solid-gas equilibrium curve in the 40-77 K temperature range. For comparative purposes and to obtain more reliable results, two different optical experimental setups were used. At higher temperatures (53-77 K), a single pass cryogenically cooled cell was coupled to a standard low-resolution Fourier transform infrared spectrometer. The second system was a state-of-the-art vertical-external-cavity surface-emitting laser tunable source operating at around 2.3 mu m, combined with a 7 m path Herriott cell, to record methane absorption features down to 40 K. From the measurements, the vapor pressure curve In(p/Pa) = -(1191.92 +/- 8.92)/(T/K) + (22.49 +/- 0.16) was derived in the range 40-77 K. This corresponds to a value of 9910 +/- 75 J mol(-1) for the sublimation enthalpy. The relation was validated down to 40 K, increasing our knowledge of the saturation pressure by 2 orders of magnitude. Data were compared with available pressure measurements from the literature, obtained by manometric or mass spectrometry techniques, and the sublimation enthalpy was compared with a thermodynamic approach based on heat capacity measurements in the solid and gas phases.
机译：甲烷的红外气相吸收光谱用于确定其40-77k温度范围内的蛋白固体气体平衡曲线。对于比较目的，并获得更可靠的结果，使用了两种不同的光学实验设置。在较高温度（53-77 k）处，单通冷冻冷却电池耦合到标准低分辨率傅里叶变换红外光谱仪。第二个系统是最先进的垂直外腔表面发射激光可调源，在约2.3μm，与7米的Herriott电池组合，以将甲烷吸收特征记录为40k。来自测量，（p / pa）= - （1191.92 +/- 8.92）/（t / k）+（22.49 +/- 0.16）的蒸气压曲线均在40-77k范围内得到的。这对应于a升华焓为9910 +/- 75 J mol（-1）的值。的关系进行了验证降至40 K，2个数量级的提高我们的饱和压力的知识。将数据与来自文献的可用压力测量进行比较，通过测量或质谱技术获得，并且将升华焓与基于固体和气相中的热容量测量的热力学方法进行比较。

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