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Whether solid, liquid, or gas, a substance's state depends on the order and arrangement of its particles (atoms, molecules, or ions). Particles in the solid pack closely together, generally in a pattern. The particles vibrate about their fixed positions but do not move or squeeze past their neighbors. In liquids, although the particles are closely spaced, they are randomly arranged. The position of the particles are not fixed—that is, they are free to move past their neighbors to...
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The internal energy of a substance—the total kinetic energy of all its molecules and the potential energy of their associated forces—depends on the strength of the intermolecular forces in the condensed phases and the pressure exerted on the substance. The internal energy of a substance is the highest in the gaseous state, the lowest in the solid state, and intermediate in the liquid state. Phase transitions are caused by changes in physical conditions, such as temperature and...
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In Ultraviolet–Visible (UV–Vis) spectroscopy, the absorption of electromagnetic radiation is used to probe the electronic structure of molecules. This technique provides insights into molecular electronic transitions, particularly the movement of electrons between different molecular orbitals. Radiation is absorbed if the energy of the electromagnetic radiation passing through the molecule is precisely equal to the energy difference between the excited and ground states. During this...
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Heating a crystalline solid increases the average energy of its atoms, molecules, or ions, and the solid gets hotter. At some point, the added energy becomes large enough to partially overcome the forces holding the molecules or ions of the solid in their fixed positions, and the solid begins the process of transitioning to the liquid state or melting. At this point, the temperature of the solid stops rising, despite the continual input of heat, and it remains constant until all of the solid is...
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Phase transitions play an important theoretical and practical role in the study of heat flow. In melting or fusion, a solid turns into a liquid; the opposite process is freezing. In evaporation, a liquid turns into a gas; the opposite process is condensation.
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Erratum: "Thermodynamics of supercooled and stretched water: Unifying two-structure description and liquid-vapor spinodal" [J. Chem. Phys. 151, 034503 (2019)].

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Phase transitions affected by natural and forceful molecular interconversion.

Thomas J Longo1, Mikhail A Anisimov1

  • 1Institute for Physical Science and Technology, University of Maryland, College Park, Maryland 20742, USA.

The Journal of Chemical Physics
|March 2, 2022
PubMed
Summary

Molecular interconversion in binary liquid mixtures can lead to phase amplification or microphase separation, altering standard spinodal decomposition. This study generalizes Cahn-Hilliard theory to explain these phenomena.

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Area of Science:

  • Physical Chemistry
  • Materials Science
  • Chemical Engineering

Background:

  • Binary liquid mixtures can undergo spinodal decomposition when quenched below their critical point.
  • Molecular interconversion between species can significantly alter phase separation dynamics.

Purpose of the Study:

  • To generalize the Cahn-Hilliard theory for spinodal decomposition to include molecular interconversion.
  • To describe the physical properties of systems exhibiting phase amplification or microphase separation.
  • To apply the developed theory to atomistic models and polyamorphic liquids.

Main Methods:

  • Phenomenological generalization of the Cahn-Hilliard theory.
  • Application to simulation results from three atomistic models.
  • Analysis of fluctuations in the critical region.

Main Results:

  • The generalized theory accurately describes phase amplification and microphase separation.
  • Phase amplification involves the growth of one phase at the expense of another.
  • Microphase separation results in nongrowing, steady-state microdomains.

Conclusions:

  • Molecular interconversion is a critical factor influencing phase separation in binary mixtures.
  • The developed framework provides a robust tool for understanding complex phase transitions.
  • The approach is applicable to diverse systems, including polyamorphic liquids.