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Phase Diagrams of Ternary Systems01:28

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Consider a ternary system, which is composed of three components: water (W), ethanoic acid (E), and trichloromethane (T). Here, Ethanoic acid (E) is fully miscible with both water (W) and trichloromethane (T), meaning it can mix entirely with either of them. However, water and trichloromethane have partial miscibility, meaning they can only mix to a certain extent, beyond which two separate phases will form.The phase diagram of a ternary system is represented as an equilateral triangle, where...
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Some solids can transition directly into the gaseous state, bypassing the liquid state, via a process known as sublimation. At room temperature and standard pressure, a piece of dry ice (solid CO2) sublimes, appearing to gradually disappear without ever forming any liquid. Snow and ice sublimate at temperatures below the melting point of water, a slow process that may be accelerated by winds and the reduced atmospheric pressures at high altitudes. When solid iodine is warmed, the solid sublimes...
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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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Recrystallization is a purification technique used to separate impurities from solid compounds. In this technique, no chemical reactions occur. Instead, it exploits physical properties only, specifically, the solubility differences between the desired compound and impurities, either at a single temperature or at different temperatures, and under other selected conditions. The solid-solution equilibrium (solubility equilibrium) of each component in the solution represents a binary phase...
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The physical form of a substance changes on changing its temperature. For example, raising the temperature of a liquid causes the liquid to vaporize (convert into vapor). The process is called vaporization—a surface phenomenon. Vaporization occurs when the thermal motion of the molecules overcome the intermolecular forces, and the molecules (at the surface) escape into the gaseous state. When a liquid vaporizes in a closed container, gas molecules cannot escape. As these gas phase...
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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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Multistage structural evolution in simple monatomic supercritical fluids: superstable tetrahedral local order.

R E Ryltsev1, N M Chtchelkatchev2

  • 1Institute of Metallurgy, Ural Division of Russian Academy of Sciences, 620016 Yekaterinburg, Russia.

Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics
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Supercritical fluids exhibit stable tetrahedral local order at high temperatures and critical densities. Solid-like orders melt at lower temperatures, indicating a two-stage melting process in supercritical states.

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Area of Science:

  • Condensed matter physics
  • Materials science
  • Physical chemistry

Background:

  • Dense simple liquids exhibit three-dimensional (close-packed) local order, including hexagonal close-packed (hcp), face-centered cubic (fcc), and icosahedral clusters.
  • Understanding local atomic arrangements is crucial for characterizing the states of matter, particularly in the complex regime of supercritical fluids.

Purpose of the Study:

  • To investigate the stability and evolution of local order in supercritical fluids.
  • To determine the temperature and density dependence of different local order structures (tetrahedral, hcp, fcc).
  • To elucidate the mechanism of 'melting' in supercritical fluids and its relation to structure relaxation times.

Main Methods:

  • Molecular dynamics simulations were employed to study the local atomic arrangements and dynamics.
  • Analysis of cluster types (tetrahedral, hcp, fcc, icosahedral) as a function of temperature and density.
  • Calculation of structure relaxation times to probe the dynamics of local order evolution.

Main Results:

  • Supercritical fluids maintain superstable tetrahedral local order up to temperatures significantly above the melting point and down to critical density.
  • Solid-like local orders (hcp, fcc) disappear at much lower temperatures and densities compared to tetrahedral order.
  • Structure relaxation times in supercritical fluids are considerably longer than those predicted for weakly interacting gases, even far above the melting line.

Conclusions:

  • Supercritical fluids undergo a two-stage 'melting' of three-dimensional local order, driven by temperature and density.
  • Tetrahedral order exhibits remarkable stability in supercritical fluids, persisting at high temperatures and near-critical densities.
  • The extended structure relaxation times suggest complex dynamics and emergent ordering phenomena in supercritical states.