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Solid–Solid Solutions01:24

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The temperature-composition phase diagram of two solids, A and B, which are immiscible in the solid phase but form miscible liquids, shows that when the temperature is low, these two exist as separate, pure solids (A and B). As the temperature increases, they transition into a single-phase liquid solution where A and B coexist. Moving from point a1 to a2 in the phase diagram, the composition changes such that solid B begins to separate from the solution, enriching the remaining liquid with A.
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Intermolecular forces are attractive forces that exist between molecules. They dictate several bulk properties, such as melting points, boiling points, and solubilities (miscibilities) of substances. Molar mass, molecular shape, and polarity affect the strength of different intermolecular forces, which influence the magnitude of physical properties across a family of molecules.
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A pressure-composition phase diagram explicitly describes the behavior of an ideal solution of two volatile liquids under varying pressures and compositions. A pressure-composition diagram has two main curves. The bubble point curve represents the plot of pressure versus liquid mole fraction. It indicates the pressure at which the first bubble of vapor forms from the liquid phase as the system pressure decreases.The dew point curve is the pressure versus vapor mole fraction. It indicates the...
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Atoms and molecules interact through bonds (or forces): intramolecular and intermolecular. The forces are electrostatic as they arise from interactions (attractive or repulsive) between charged species (permanent, partial, or temporary charges) and exist with varying strengths between ions, polar, nonpolar, and neutral molecules. The different types of intermolecular forces are ion–dipole, dipole–dipole, hydrogen bonds, and dispersion; among these, dipole–dipole, hydrogen...
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Many common substances around us exist as a solution, such as ocean water, air, and gasoline. All solutions are mixtures of substances that are composed of varying amounts of two or more types of atoms or molecules. A mixture with a non-uniform composition is a heterogeneous mixture, whereas a mixture with a uniform composition is a homogeneous mixture. The components that make the homogeneous mixture are evenly spread out and thoroughly mixed. 
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A continuous mixture of two different dimers in liquid water.

L C Pardo1, A Henao, S Busch

  • 1Grup de Caracterització de Materials, Departament de Física i Enginyeria Nuclear, ETSEIB, Universitat Politècnica de Catalunya, Diagonal 647, E-08028 Barcelona, Catalonia, Spain. luis.carlos.pardo@upc.edu.

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Area of Science:

  • Physical Chemistry
  • Chemical Physics
  • Materials Science

Background:

  • Liquid water is thought to have tetrahedrally coordinated molecules with asymmetric interactions.
  • Previous work suggested this asymmetry reconciles homogeneous and inhomogeneous viewpoints of liquid water.

Purpose of the Study:

  • To investigate the geometric origin of asymmetry in liquid water's molecular interactions.
  • To analyze the role of molecular orientations in water structure.

Main Methods:

  • Utilized Molecular Dynamics (MD) simulations of water.
  • Analyzed the five-dimensional probability distribution function of Euler angles to determine molecular positions and orientations.

Main Results:

  • Identified a series of molecular orientations beyond the typical tetrahedral structure.
  • Discovered two prevalent dimer orientations: one with perpendicular dipole alignment (lower energy) and another with parallel alignment (less bound).
  • Observed that these dimer orientations influence the orientation of other water dipoles up to approximately 6 Å.

Conclusions:

  • Liquid water is a mixture of two dimer types with identical hydrogen bond geometry but differing interaction energies due to dipole orientation.
  • Molecular orientation, not just geometry, is crucial for understanding liquid water's structure and properties.