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Related Concept Videos

Gibbs Free Energy02:39

Gibbs Free Energy

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One of the challenges of using the second law of thermodynamics to determine if a process is spontaneous is that it requires measurements of the entropy change for the system and the entropy change for the surroundings. An alternative approach involving a new thermodynamic property defined in terms of system properties only was introduced in the late nineteenth century by American mathematician Josiah Willard Gibbs. This new property is called the Gibbs free energy (G) (or simply the free...
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Phase Transitions: Vaporization and Condensation02:39

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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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The Phase Rule01:20

The Phase Rule

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The phase rule describes the relationship between the variance (degrees of freedom), the number of components, and the number of phases in a system at equilibrium.Variance is a concept that denotes the number of independent intensive properties (properties are those that do not depend on the amount of material in the system), such as temperature, pressure, and composition, that can be altered without impacting the number of phases in equilibrium.In a single-component system, such as pure water,...
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Phase Diagrams02:39

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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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Phase Transitions: Sublimation and Deposition02:33

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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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Gibbs Free Energy and Thermodynamic Favorability02:23

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The spontaneity of a process depends upon the temperature of the system. Phase transitions, for example, will proceed spontaneously in one direction or the other depending upon the temperature of the substance in question. Likewise, some chemical reactions can also exhibit temperature-dependent spontaneities. To illustrate this concept, the equation relating free energy change to the enthalpy and entropy changes for the process is considered:
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Phase Behavior of Charged Vesicles Under Symmetric and Asymmetric Solution Conditions Monitored with Fluorescence Microscopy
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Unifying hydrotropy under Gibbs phase rule.

Seishi Shimizu1, Nobuyuki Matubayasi

  • 1York Structural Biology Laboratory, Department of Chemistry, University of York, Heslington, York YO10 5DD, UK. seishi.shimizu@york.ac.uk.

Physical Chemistry Chemical Physics : PCCP
|May 12, 2017
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Summary
This summary is machine-generated.

This study presents a unified theory of hydrotropy using statistical thermodynamics. It explains solubility enhancement by focusing on solute-hydrotrope interactions, overcoming hydrotrope self-clustering.

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Area of Science:

  • Thermodynamics and physical chemistry.
  • Solution chemistry and supramolecular chemistry.

Background:

  • Hydrotropy's complex phase behavior complicates understanding solubility enhancement.
  • Existing classification methods for hydrotropes are insufficient.

Purpose of the Study:

  • To develop a unified theory of hydrotropy based on first principles.
  • To rationalize the mechanism of solubility enhancement by hydrotropes.
  • To distinguish diverse molecular scenarios underlying similar experimental solubility curves.

Main Methods:

  • Application of the Gibbs phase rule to classify hydrotropes.
  • Utilizing Kirkwood-Buff integrals to quantify species interactions.
  • Generalizing a previous approach to solutes beyond simple dilution.

Main Results:

  • Demonstrated ability to differentiate molecular scenarios using Gibbs phase rule and Kirkwood-Buff integrals.
  • Identified a unified mechanism for hydrotropy.
  • Showed that strong solute-hydrotrope interactions drive solubilization, overcoming hydrotrope self-clustering.

Conclusions:

  • A unified theoretical framework for hydrotropy is established.
  • Solute-hydrotrope interaction strength is key to solubility enhancement.
  • The approach provides a rational basis for understanding and predicting hydrotropic behavior.