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Vapor-liquid Equilibria Pertaining to the Study of Alternative Fuels and the Forensic Analysis of Chemical Evidence

机译：替代燃料研究的汽液平衡和化学证据的法医学分析

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摘要

Measurement of the vapor-liquid equilibrium (VLE) of fluid mixtures with many components presents a challenge. Data describing such mixtures, like fuels, are important for the development of alternative energy sources and to support forensic science, but there is a lack of suitable instrumentation to provide data with reasonable uncertainty for mixtures with many components. In this thesis, three different techniques for fluid characterization are explored: the advanced distillation curve (ADC), the advanced distillation curve with reflux (ADCR), and PLOT-cryoadsorption. Two pyrolysis fuels similar to gasoline and diesel fuel made from polypropylene were studied with respect to volatility, composition, and energy content using the advanced distillation curve. The diesel fuel demonstrated volatility very similar to previously measured diesel fuels. The gasoline was less volatile than petroleum-derived counterparts and did not meet specifications.;Two pyrolysis crude oils made from ponderosa pine and dairy manure were assessed using the ADC coupled to an approach for characterizing fluids with multiple, immiscible liquid phases. Both oils contained high water levels and would require further refinement before use. The organic phases of each oil contained components indicative of the feedstock used.;A modification of the ADC method, the advanced distillation curve with reflux, was introduced as an approach to measuring the VLE of fluids with many components. The ADCR additionally approximates the weathering of an ignitable liquid that occurs during an arson fire and measures VLE across a range of weathered conditions. The method was demonstrated using two simple mixtures. The measurements agreed well with models, indicating that ADCR is a suitable VLE metrology.;Vapor-liquid equilibrium data are crucial for interpreting the results of headspace characterization used often in forensic science. One headspace method, portable PLOT-cryoadsorption, was tested in a series of experiments in the laboratory and then deployed for the first time in a field environment that simulated a cargo container. The technology was found to be rapid and sensitive to a variety of compounds of interest to forensic science. Each of the three techniques described in this thesis contribute valuable property data for multicomponent mixtures, towards the development of high-quality predictive models.
机译：具有许多成分的流体混合物的气液平衡（VLE）的测量提出了挑战。描述此类混合物（如燃料）的数据对于开发替代能源和支持法医学很重要，但是缺乏合适的仪器来为具有多种成分的混合物提供具有合理不确定性的数据。本文探讨了三种不同的流体表征技术：高级蒸馏曲线（ADC），带回流的高级蒸馏曲线（ADCR）和PLOT低温吸附。使用先进的蒸馏曲线，研究了两种与聚丙烯制汽油和柴油燃料相似的热解燃料的挥发性，组成和能量含量。柴油显示出的挥发性非常类似于先前测得的柴油。汽油的挥发性比石油衍生的挥发性小，并且不符合规格。使用ADC结合一种表征具有多种不混溶液相的流体的方法，评估了由黄松和乳牛粪制得的两种热解原油。两种油均含高水，使用前需要进一步精制。每种油的有机相均含有指示所用原料的组分。引入了ADC方法的一种改进，即带有回流的先进蒸馏曲线，作为一种测量具有多种组分的流体的VLE的方法。 ADCR还可以近似估算纵火火灾期间发生的可燃液体的风化程度，并在一系列风化条件下测量VLE。使用两种简单的混合物演示了该方法。测量结果与模型非常吻合，表明ADCR是一种合适的VLE度量衡。汽液平衡数据对于解释法医学中经常使用的顶空表征结果至关重要。在实验室的一系列实验中测试了一种顶空方法，即便携式PLOT低温吸附法，然后首次在模拟货物集装箱的现场环境中进行了部署。发现该技术是快速且对法医学感兴趣的多种化合物敏感的。本文描述的三种技术中的每一种都为多组分混合物提供了有价值的性能数据，有助于开发高质量的预测模型。

著录项

  • 作者

    Harries, Megan Elizabeth.;

  • 作者单位

    University of Colorado at Boulder.;

  • 授予单位 University of Colorado at Boulder.;
  • 学科 Analytical chemistry.;Alternative Energy.;Environmental science.
  • 学位 Ph.D.
  • 年度 2018
  • 页码 194 p.
  • 总页数 194
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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