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首页> 外文期刊>Chemistry: A European journal >On the analyses of mixture vapor pressure data: The hydrogen peroxide/water system and its excess thermodynamic functions
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On the analyses of mixture vapor pressure data: The hydrogen peroxide/water system and its excess thermodynamic functions

机译：关于混合物蒸气压数据的分析：过氧化氢/水系统及其过量的热力学功能

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Reported here are some aspects of the analysis of mixture vapor pressure data using the model-free Redlich-Kister approach that have heretofore not been recognized. These are that the pure vapor pressure of one or more components and the average temperature of the complex apparatuses used in such studies can be obtained from the mixture vapor pressures. The findings reported here raise questions regarding current and past approaches for analyses of mixture vapor pressure data. As a test case for this analysis approach the H2O2-H2O mixture vapor pressure measurements reported by Scatchard, Kavanagh, and Tickner (G. Scatchard, G. M. Kavanagh, L. B. Ticknor, J. Am. Chem. Soc. 1952, 74, 37153720; G. M. Kavanagh, PhD. Thesis, Massachusetts Institute of Technology (USA), 1949) have been used; there is significant recent interest in this system. It was found that the original data is fit far better with a four-parameter Redlich-Kister excess energy expansion with inclusion of the pure hydrogen peroxide vapor pressure and the temperature as parameters. Comparisons of the present results with the previous analyses of this suite of data exhibit significant deviations. A precedent for consideration of iteration of temperature exists from the little-known work of Uchida, Ogawa, and Yamaguchi (S. Uchida, S. Ogawa, M. Yamaguchi, Japan Sci. Eng. Sci. 1950, 1, 41-49) who observed significant variations of temperature from place to place within a carefully insulated apparatus of the type traditionally used in mixture vapor pressure measurements. For hydrogen peroxide, new critical constants and vapor pressure-temperature equations needed in the analysis approach described above have been derived. Also temperature functions for the four Redlich-Kister parameters were derived, that allowed calculations of the excess Gibbs energy, excess entropy, and excess enthalpy whose values at various temperatures indicate the complexity of H2O2-H2O mixtures not evident in the original analyses of this suite of experimental results.
机译：此处报告的是使用无模型Redlich-Kister方法进行的混合蒸汽压力数据分析的某些方面，迄今为止尚未得到认可。这些是可以从混合蒸气压中获得一种或多种组分的纯蒸气压以及在这种研究中使用的复杂设备的平均温度。此处报告的发现提出了有关分析混合蒸气压数据的当前和过去方法的疑问。作为此分析方法的测试用例，Scatchard，Kavanagh和Tickner（G.Scatchard，GM Kavanagh，LB Ticknor，J.Am.Chem.Soc.1952、74、37153720; GM所报告的H2O2-H2O混合物蒸气压测量使用了美国麻省理工学院Kavanagh博士论文（1949年）。最近对该系统非常感兴趣。结果发现，原始数据与四参数Redlich-Kister的过量能量膨胀拟合得更好，其中包括纯过氧化氢蒸气压和温度作为参数。当前结果与该组数据的先前分析的比较显示出明显的偏差。内田，小川和山口的鲜为人知的工作是考虑温度迭代的先例（日本内田，小川，山口M，日本科学工程学1950，1，41-49）在传统的混合蒸汽压力测量中使用的这种仔细绝缘的设备中，他观察到了温度随位置的显着变化。对于过氧化氢，推导了上述分析方法中所需的新的临界常数和蒸气压-温度方程式。还导出了四个Redlich-Kister参数的温度函数，从而可以计算出过量的Gibbs能量，过量的熵和过量的焓，其在不同温度下的值表明H2O2-H2O混合物的复杂性在该套件的原始分析中并不明显。实验结果。

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