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Thermodynamic Potentials01:26

Thermodynamic Potentials

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Thermodynamic potentials are state functions that are extremely useful in analyzing a thermodynamic system. They have dimensions of energy. The four important thermodynamic potentials are internal energy, enthalpy, Helmholtz free energy, and Gibbs free energy. These thermodynamic potentials can be expressed using two of the following variables: pressure, volume, temperature, and entropy. These two variables are expressed as the rate of change of the thermodynamic potential with respect to other...
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A thermodynamic system is a set of objects whose thermodynamic properties are of interest. The system is considered to be embedded in its surroundings or the environment. The system and its environment can exchange heat and do work on each other through a boundary that separates them. However, the immediate surroundings of the system interact with it directly and therefore have a much stronger influence on its behavior and properties.
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The spontaneity of a process depends upon the temperature of the system. Phase transitions, for example, will proceed spontaneously in one direction or the other depending upon the temperature of the substance in question. Likewise, some chemical reactions can also exhibit temperature-dependent spontaneities. To illustrate this concept, the equation relating free energy change to the enthalpy and entropy changes for the process is considered:
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Maxwell's thermodynamic relations are very useful in solving problems in thermodynamics. Each of Maxwell's relations relates a partial differential between quantities that can be hard to measure experimentally to a partial differential between quantities that can be easily measured. These relations are a set of equations derivable from the symmetry of the second derivatives and the thermodynamic potentials.
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A thermodynamic process is a path through a sequence of states that takes a system from an initial state to a final state. In a cyclic process, the system returns to its initial state, so the changes in state properties and state functions (ΔT, Δp, ΔV, ΔU, ΔH) over one complete cycle are zero. However, heat and work transfers can still occur during the cycle, and the net heat and net work over the cycle need not be zero.A reversible process occurs when the system is...
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Implications of interface conventions for morphometric thermodynamics.

Andreas Reindl1, Markus Bier1, S Dietrich1

  • 1Max-Planck-Institut für Intelligente Systeme, Heisenbergstr. 3, 70569 Stuttgart, Germany and IV. Institut für Theoretische Physik, Universität Stuttgart, Pfaffenwaldring 57, 70569 Stuttgart, Germany.

Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics
|March 14, 2015
PubMed
Summary
This summary is machine-generated.

Density functional theory reveals that morphometric thermodynamics is an approximation for solid-fluid interfacial tension, not exact. Its accuracy for curved surfaces depends on interface location choice.

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Area of Science:

  • Statistical Mechanics
  • Physical Chemistry

Background:

  • Density functional theory (DFT) is a powerful tool for studying fluid behavior at interfaces.
  • Understanding solid-fluid interfacial tension is crucial for various applications, including materials science and nanotechnology.
  • Morphometric thermodynamics offers a framework for analyzing interfacial properties, but its applicability to curved surfaces requires scrutiny.

Purpose of the Study:

  • To investigate the accuracy of morphometric thermodynamics for solid-fluid interfacial tension.
  • To examine the influence of wall curvature (planar, spherical, cylindrical) on interfacial tension.
  • To analyze the impact of interface location definition on calculated interfacial tension.

Main Methods:

  • Utilizing density functional theory (DFT) for small number density systems.
  • Comparing DFT results with predictions from morphometric thermodynamics.
  • Systematically varying wall curvature and interface location.

Main Results:

  • Morphometric thermodynamics was found to be an approximation, not an exact theory, for the studied model fluids and geometries.
  • The accuracy of morphometric thermodynamics was highly sensitive to the chosen interface location.
  • Interfacial tension showed dependence on wall curvature for spherical and cylindrical surfaces.

Conclusions:

  • Morphometric thermodynamics provides a useful, albeit approximate, framework for interfacial tension calculations.
  • Careful consideration of interface location is essential for accurate interfacial tension determination, especially for curved interfaces.
  • DFT offers a robust method for evaluating interfacial properties and the validity of thermodynamic approximations.