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A Fairly Common Error in Processing the Results of Knudsen Effusion Mass Spectrometry. Sublimation Enthalpy of Vanadium as an Example

机译:处理Chaudsen积分质谱法的结果时相当常见的误差。钒的升华焓为例

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It has been shown in this paper, that a fairly common approach of Knudsen effusion mass spectrometry based on the so called "self-calibration" for the instrument sensitivity (combination of single measurement for absolute vapor pressure by Knudsen method with the mass spectrometry for its temperature dependence) leads to a very large uncertainty for the enthalpy of sublimation for the substance under investigation. The uncertainty may not be less than the uncertainty of initial single measurement for vapor pressure, and so, the array of data obtained by its combination with the mass spectral data is not the array of independent measurements. The difference between the uncertainties for two approaches (considered and criticized) may be near one order of magnitude for vapor pressure. There are presented the results of 13 measurements of vapor pressure for vanadium in the paper (1). Formal statistical treating of these results leads to sublimation enthalpy with the uncertainty less than ±1 kJ·mol~(-1), although the uncertainty of the calibration experiments (2 experiments) amounts near ±13 kJ·mol~(-1).
机译:本文已被证明,基于所谓的“自校准”的knudsen积分质谱法的相当常见的方法,用于仪器敏感性(通过Knudsen方法用knudsen方法与质谱法为其的单次测量的组合温度依赖)导致对正在调查的物质的升华焓的非常大的不确定性。不确定性可能不会小于蒸汽压力初始单个测量的不确定性,因此,通过其与质谱数据组合获得的数据阵列不是独立测量的阵列。两种方法(考虑和批评)之间的不确定性之间的差异可能是蒸气压的一个级别。介绍了纸中钒蒸气压测量的结果(1)。这些结果的正式统计处理导致升华焓,不确定度小于±1 kJ·mol〜(-1),尽管校准实验(2实验)的不确定性差±13 kJ·mol〜(-1)。

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