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Knudsen effusion mass spectrometry (KEMS) has long been a key technique to obtain thermodynamic data based on vapor pressures. A Knudsen cell is a small enclosure, typically 1 cm diameter × 1 cm long, with a well-defined orifice which is generally 1 mm diameter. Equilibrium, or near equilibrium, is attained in the cell and the ensuing vapor is sampled from the orifice. Mass spectrometry is an ideal tool for probing the resulting vapor, as the vapor composition can be determined from the mass-to-charge ratio of the generated ions and the signal intensity can be related to the absolute vapor pressure. The temperature dependence of this vapor pressure yields heats of vaporization, which in turn can be related to heats of formation for pure compounds. For solution phases, a variety of thermodynamic parameters of the solutions can be generated such as component activities and partial molar quantities.
机译:努森渗流质谱法(KEMS)长期以来一直是一项基于蒸汽压获得热力学数据的关键技术。克努森(Knudsen)电池是一个小外壳,通常直径1厘米×长1厘米,并有一个直径通常为1毫米的孔口。在样品池中达到平衡或接近平衡,随后从孔中取样蒸气。质谱法是探测所得蒸气的理想工具,因为可以根据产生的离子的质荷比确定蒸气成分,并且信号强度可以与绝对蒸气压相关。该蒸气压的温度依赖性产生汽化热,其又可以与纯化合物的形成热有关。对于溶液阶段,可以生成溶液的各种热力学参数,例如组分活度和部分摩尔量。

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