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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：混合蒸气压数据分析：过氧化氢/水系统及其过量的热力学函数

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摘要

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 H_2O_2-H_2O mixture vapor pressure measurements reported by Scatchard,Kavanagh,and Tickner(G.Scatchard,G.M.Kavanagh,L.B.Tick-nor,J.Am.Chem.Soc.1952,74,3715-3720;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 H_2O_2-H_2O mixtures not evident in the original analyses of this suite of experimental results.
机译：此处报告的是迄今尚未认识到的使用无模型Redlich-Kister方法进行的混合蒸气压数据分析的某些方面，这些方面是一种或多种组分的纯蒸气压以及所用复杂设备的平均温度在这种研究中可以从混合蒸气压力获得。这里报告的发现提出了有关分析混合蒸气压力数据的当前和过去方法的疑问。作为此分析方法的测试案例，Scatchard报告了H_2O_2-H_2O混合蒸气压力的测量结果。 ，卡瓦那和蒂克纳（G.Scatchard，GMKavanagh，LBTick-nor，J.Am.Chem.Soc.1952,74,3715-3720; GMKavanagh，Ph.Thesis，Massachusetts Institute of Technology（USA），1949） ）;已经对该系统产生了极大的兴趣，发现原始数据在四参数Redlich-Kister过量能量膨胀（包括纯过氧化氢蒸气压）的情况下拟合得更好目前的结果与之前对这组数据的分析结果的比较显示出明显的偏差.Uchida，Ogawa和Yamaguchi（S.Uchida）的鲜为人知的工作存在考虑温度迭代的先例。 ，M。小川日本山口科学技术大学（Sci.Eng.Sci.1950,1,41-49）观察到，在传统上用于混合物蒸气压测量的那种小心绝缘的设备中，温度随位置的变化很大。对于过氧化氢，新的临界常数导出了上述分析方法所需的蒸汽压力-温度方程式。还导出了四个Redlich-Kister参数的温度函数，从而可以计算出在不同温度下其值的过量Gibbs能量，过量熵和过量焓。指出在这组实验结果的原始分析中没有发现H_2O_2-H_2O混合物的复杂性。

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