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Related Concept Videos

States of Water01:23

States of Water

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.
Water freezes when the intermolecular forces are greater than the kinetic energy. Unlike most other substances, water is less dense in its solid state than in its liquid state. This is because each water molecule can form...
Cohesion01:07

Cohesion

Cohesion is the attraction between molecules of the same type, such as water molecules. Water molecules have an overall neutral charge but are polar molecule. An oxygen atom in one water molecule has a partial negative charge that can bind to a hydrogen atom with a partial positive charge in a second water molecule, forming a hydrogen bond. Each water molecule can form up to four hydrogen bonds with other water molecules. Hydrogen bonds are responsible for water's cohesive nature.
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Entropy02:39

Entropy

Salt particles that have dissolved in water never spontaneously come back together in solution to reform solid particles. Moreover, a gas that has expanded in a vacuum remains dispersed and never spontaneously reassembles. The unidirectional nature of these phenomena is the result of a thermodynamic state function called entropy (S). Entropy is the measure of the extent to which the energy is dispersed throughout a system, or in other words, it is proportional to the degree of disorder of a...
Second Law of Thermodynamics02:49

Second Law of Thermodynamics

In the quest to identify a property that may reliably predict the spontaneity of a process, a promising candidate has been identified: entropy. Processes that involve an increase in entropy of the system (ΔS > 0) are very often spontaneous; however, examples to the contrary are plentiful. By expanding consideration of entropy changes to include the surroundings, a significant conclusion regarding the relation between this property and spontaneity may be reached. In thermodynamic models, the...
Thermal Expansion01:22

Thermal Expansion

The expansion of alcohol in a thermometer is one of many commonly encountered examples of thermal expansion, which is the change in size or volume of a given system as its temperature changes. The most visible example is the expansion of hot air. When air is heated, it expands and becomes less dense than the surrounding air, which then exerts an upward force on the hot air to, for example, make steam and smoke rise, and hot air balloons float. The same behavior happens in all liquids and gases,...
Role of Water in Human Biology01:27

Role of Water in Human Biology

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An Analog Macroscopic Technique for Studying Molecular Hydrodynamic Processes in Dense Gases and Liquids
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Common microscopic structural origin for water's thermodynamic and dynamic anomalies.

Rui Shi1, John Russo1, Hajime Tanaka1

  • 1Department of Fundamental Engineering, Institute of Industrial Science, University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505, Japan.

The Journal of Chemical Physics
|December 17, 2018
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Summary

This study unifies the understanding of water's anomalies using locally favored structures. A novel hierarchical model explains thermodynamic and dynamic properties, predicting unique behaviors in supercooled water.

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Area of Science:

  • Physical Chemistry
  • Condensed Matter Physics
  • Materials Science

Background:

  • Water exhibits numerous anomalies, properties deviating from typical liquid behavior, with origins debated.
  • Current explanations for thermodynamic and dynamic anomalies often differ, lacking a unified microscopic perspective.

Purpose of the Study:

  • To provide a unified microscopic physical picture of water's anomalies.
  • To explain both thermodynamic and dynamic anomalies using the concept of locally favored structures.
  • To develop and validate a hierarchical model for water's anomalous behavior.

Main Methods:

  • Identification of locally favored structures using a microscopic structural descriptor measuring local translational order.
  • Development of a novel hierarchical two-state model.
  • Extensive simulations of two popular water models.

Main Results:

  • Thermodynamic anomaly strength is directly proportional to the amount of locally favored structures.
  • Dynamic properties depend on local and nearest-neighbor structures.
  • The hierarchical two-state model accurately explains thermodynamic and kinetic anomalies based on temperature and pressure dependence of the structural descriptor.
  • Three unique predictions for supercooled water were made and verified: an Arrhenius-to-Arrhenius crossover, a maximum in dynamic heterogeneity, and a violation of the Stokes-Einstein-Debye relation at ~2Tg.

Conclusions:

  • Locally favored structures provide a unified explanation for water's thermodynamic and dynamic anomalies.
  • The hierarchical two-state model successfully captures water's complex behavior.
  • The findings suggest that similar scenarios may explain anomalies in other liquids that form locally favored structures, including silicon, germanium, silica, and certain metallic and chalcogenide liquids.