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Geometric analysis of thermodynamic equilibrium processes.

机译:热力学平衡过程的几何分析。

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摘要

We introduce a method for the analysis of the asymptotic behavior of thermodynamic equilibrium processes from a geometric viewpoint. In many of the previous studies the thermodynamic equilibrium conditions were enforced approximately or incorrectly. In this work, a geometric interpretation is given for the thermodynamics equilibrium conditions by proving that the global minimum of the Gibbs free energy is located on the convex hull of the molar Gibbs energy function. This geometric equivalence is extended to the general equilibrium defined by the maximization of entropy and the chemical phase equilibrium. The convex hulls for the thermodynamic functions are shown to be C1-smooth. As a result, the boundary between the single phase region and the multiple ones is also smooth. This property can be used to check the phase diagrams generated from numerical calculation. A phase number function defined on the domain of the convex hull is shown to be lower semi-continuous and is used to investigate the properties of the phase regions. In particular, the properties of the two phase regions are used in the stability analysis of the isothermal isobaric flash. Its dynamics are given a clear geometric explanation and it is shown to converge to a steady state. This analysis method is extended to the adiabatic flash and the reactive flash with equimolar reactions. Finally, the uniqueness of the steady state is analyzed for different flash processes.
机译:我们介绍了一种从几何角度分析热力学平衡过程的渐近行为的方法。在许多先前的研究中,热力学平衡条件近似或不正确地实施。在这项工作中,通过证明吉布斯自由能的整体最小值位于摩尔吉布斯能函数的凸包上,给出了热力学平衡条件的几何解释。这种几何等价关系扩展到了由熵的最大化和化学相平衡所定义的一般平衡。热力学函数的凸包显示为C1光滑。结果,单相区域和多相区域之间的边界也很平滑。此属性可用于检查由数值计算生成的相图。在凸包的域上定义的相数函数显示为较低的半连续,并用于研究相区域的属性。特别地,在等温等压闪蒸的稳定性分析中使用了两个相区域的特性。对其动力学进行了清晰的几何解释,并显示收敛到稳态。该分析方法扩展到了具有等摩尔反应的绝热闪蒸和反应闪蒸。最后,针对不同的闪光过程分析了稳态的唯一性。

著录项

  • 作者

    Xu, Yuan.;

  • 作者单位

    Carnegie Mellon University.;

  • 授予单位 Carnegie Mellon University.;
  • 学科 Mathematics.; Engineering Chemical.; Engineering Mechanical.
  • 学位 Ph.D.
  • 年度 2008
  • 页码 149 p.
  • 总页数 149
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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