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Phase Diagrams02:39

Phase Diagrams

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A phase diagram combines plots of pressure versus temperature for the liquid-gas, solid-liquid, and solid-gas phase-transition equilibria of a substance. These diagrams indicate the physical states that exist under specific conditions of pressure and temperature and also provide the pressure dependence of the phase-transition temperatures (melting points, sublimation points, boiling points). Regions or areas labeled solid, liquid, and gas represent single phases, while lines or curves represent...
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The phase of a given substance depends on the pressure and temperature. Thus, plots of pressure versus temperature showing the phase in each region provide considerable insights into the thermal properties of substances. Such plots are known as phase diagrams. For instance, in the phase diagram for water (Figure 1), the solid curve boundaries between the phases indicate phase transitions (i.e., temperatures and pressures at which the phases coexist).
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Molecular Comparison of Gases, Liquids, and Solids02:26

Molecular Comparison of Gases, Liquids, and Solids

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Particles in a solid are tightly packed together (fixed shape) and often arranged in a regular pattern; in a liquid, they are close together with no regular arrangement (no fixed shape); in a gas, they are far apart with no regular arrangement (no fixed shape). Particles in a solid vibrate about fixed positions (cannot flow) and do not generally move in relation to one another; in a liquid, they move past each other (can flow) but remain in essentially constant contact; in a gas, they move...
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Distillation: Vapor–Liquid Equilibria01:01

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Distillation is a separation technique that takes advantage of the boiling point properties of disparate elements in a mixture. To perform distillation, we begin by heating a miscible mixture of two liquids with a significant difference in boiling points (at least 20°C). As the solution heats up and reaches the bubble point of the more volatile component, some molecules of the more volatile component transition into the gas phase and travel upward into the condenser, which is a glass tube...
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States of Water01:23

States of Water

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Water exists in any one of the three classical states: solid (ice), liquid (water), and gas (steam or water vapor). The state of water depends on i) the intermolecular forces that draw molecules together and ii) the kinetic energy that leads to movements that pull them apart.
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Phase Transitions: Vaporization and Condensation02:39

Phase Transitions: Vaporization and Condensation

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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 molecules...
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Rethinking the evidence for a liquid-liquid transition in water: What decompression experiments reveal.

Rajat Kumar1, Ingrid de Almeida Ribeiro1, Debdas Dhabal2

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The liquid-liquid transition in water shows a single peak in structure factor S(q) due to nanoscopic domains. The key signature is the apparent correlation length ξ, not peak splitting, resolving experimental contradictions.

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Area of Science:

  • Physical Chemistry
  • Condensed Matter Physics
  • Materials Science

Background:

  • The existence of a liquid-liquid transition (LLT) in supercooled water is a long-standing debate.
  • Experimental studies suggest liquid-liquid coexistence based on two peaks in the structure factor S(q) during decompression.
  • This interpretation conflicts with theoretical predictions of coexistence only above the liquid-liquid critical point (LLCP).

Purpose of the Study:

  • To reconcile the apparent contradiction between experimental observations and theoretical predictions of the LLT in water.
  • To identify the definitive structural signature of the LLT in supercooled water.
  • To explain the origin of the two-peak S(q) observed in experiments.

Main Methods:

  • Decompression simulations using ML-BOP (Machine Learning-based Bond Order Potentials).
  • Analysis of the structure factor S(q) and apparent correlation length ξ at low momentum transfer (q).
  • Comparison of simulation results with experimental pump-probe data.

Main Results:

  • Simulations show S(q) retains a single peak even during LLT due to nanoscopic high-density liquid (HDL) and low-density liquid (LDL) domains.
  • The experimental two-peak S(q) is explained by an evolving liquid peak superimposed on a slower-responding, colder HDL from a temperature gradient.
  • A transient growth and decay of the apparent correlation length ξ at low q is identified as the decisive LLT signature, peaking near the LLCP.

Conclusions:

  • The apparent correlation length ξ evolution at low q, not S(q) peak splitting, is the key structural marker for the LLT in water.
  • Experimental signatures can be explained by a specific pressure drop profile and the subsequent growth and decay of ξ.
  • The study resolves the contradiction between LLCP location and observed structural signatures, clarifying the nature of the LLT in water.