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Systems in mechanical equilibrium exert equal pressure on the separating wall. Similarly, systems in thermal equilibrium share a common thermodynamic property: temperature.Temperature is a measure of the average kinetic energy of particles within a system. More generally, it reflects the internal energy state of the system. The higher the temperature, the more energy a system has, given that other variables, such as volume and pressure, remain constant. However, temperature is not a form of...
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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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Consider an arbitrary process that moves between two specific states (A and B) in a cyclic manner. This process is reversible and broken down into smaller parts that each follow a Carnot cycle. A Carnot cycle has two isothermal (constant temperature) processes. During these processes, the ratio of the amount of heat transferred to their respective temperature remains constant. The other two processes in the Carnot cycle are also reversible but adiabatic, which means they occur without any heat...
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Nonequilibrium thermodynamics of an interface.

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We developed a new model for interfacial thermodynamics applicable to nonequilibrium processes like evaporation. Our findings show interfacial temperature can differ from bulk phases, verified by molecular dynamics simulations.

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Area of Science:

  • Physical Chemistry
  • Thermodynamics
  • Fluid Dynamics

Background:

  • Interfacial thermodynamics is crucial for transport theories.
  • Understanding interfaces under nonequilibrium conditions is challenging.

Purpose of the Study:

  • To extend Gibbs' dividing surface concept to nonequilibrium interfaces.
  • To develop a consistent thermodynamic framework for interfaces in dynamic processes.

Main Methods:

  • Formulation of local equilibrium for interfaces.
  • Utilizing gauge-invariance for defining interfacial variables.
  • High-precision nonequilibrium molecular-dynamics simulations.

Main Results:

  • A consistent definition of intensive variables for interfaces.
  • Demonstration that interfacial temperature can differ from bulk phases.
  • Validation of the model with Lennard-Jones fluid simulations.

Conclusions:

  • The proposed model provides a foundation for nonequilibrium interfacial thermodynamics.
  • Surface tension can serve as a thermometer for interfacial temperature.
  • The findings are critical for modeling phase transitions and transport phenomena.