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Related Concept Videos

Supercritical Fluid Chromatography01:18

Supercritical Fluid Chromatography

238
Supercritical fluid chromatography (SFC) provides a beneficial substitute for gas chromatography (GC) and liquid chromatography (LC) for certain samples because it merges the top attributes of both techniques. SFC allows the separation and analysis of compounds that GC or LC does not easily manage. These compounds are traditionally nonvolatile or thermally unstable, making GC unsuitable and lacking functional groups required for HPLC analysis.
SFC utilizes a supercritical fluid mobile phase,...
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Path Between Thermodynamics States01:21

Path Between Thermodynamics States

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Consider the two thermodynamic processes involving an ideal gas that are represented by paths AC and ABC in Figure 1:
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Third Law of Thermodynamics02:38

Third Law of Thermodynamics

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A pure, perfectly crystalline solid possessing no kinetic energy (that is, at a temperature of absolute zero, 0 K) may be described by a single microstate, as its purity, perfect crystallinity,and complete lack of motion means there is but one possible location for each identical atom or molecule comprising the crystal (W = 1). According to the Boltzmann equation, the entropy of this system is zero.
18.9K
Phase Diagram01:19

Phase Diagram

5.8K
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).
5.8K
Thermodynamic Systems01:06

Thermodynamic Systems

5.1K
A thermodynamic system is a set of objects whose thermodynamic properties are of interest. The system is considered to be embedded in its surroundings or the environment. The system and its environment can exchange heat and do work on each other through a boundary that separates them. However, the immediate surroundings of the system interact with it directly and therefore have a much stronger influence on its behavior and properties.
Consider an example of  tea boiling in a kettle. The...
5.1K
Thermal Sigmatropic Reactions: Overview01:16

Thermal Sigmatropic Reactions: Overview

2.1K
Sigmatropic rearrangements are a class of pericyclic reactions in which a σ bond migrates from one part of a π system to another. These are intramolecular rearrangements where the total number of σ and π bonds remain unchanged.
Sigmatropic shifts are classified based on an order term [i, j ], where i and j indicate the number of atoms across which each end of the σ bond migrates. Below are examples of a [3,3] sigmatropic shift in...
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Supercritical Nitrogen Processing for the Purification of Reactive Porous Materials
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Thermodynamic crossovers in supercritical fluids.

Xinyang Li1,2, Yuliang Jin1,2,3

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Proceedings of the National Academy of Sciences of the United States of America
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Supercritical fluids exhibit distinct liquid-like and gas-like states, identified by two thermodynamic crossover lines. This finding challenges single-line models and offers a new framework for understanding supercritical phenomena.

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Area of Science:

  • Thermodynamics
  • Statistical Mechanics
  • Condensed Matter Physics

Background:

  • Beyond the critical point, supercritical fluids are conventionally defined as a single phase.
  • Recent studies suggest dynamical crossovers indicating distinct liquid-like and gas-like behaviors in supercritical fluids.
  • Existing theoretical models often propose a single crossover line, which is debated.

Purpose of the Study:

  • To investigate the existence and nature of distinct states within supercritical fluids.
  • To reconcile theoretical inconsistencies regarding supercritical fluid behavior and the Ising model.
  • To propose a new framework defining boundaries of liquid-like, indistinguishable, and gas-like states in supercritical fluids.

Main Methods:

  • Analysis of the supercritical behavior of the Ising model.
  • Theoretical calculations and modeling of thermodynamic properties.
  • Examination of experimental data, including inelastic X-ray scattering and small-angle neutron scattering.

Main Results:

  • Identified two distinct thermodynamic crossover lines in supercritical fluids.
  • Demonstrated that these lines follow critical scalings consistent with the Ising universality class near the critical point.
  • Validated the upper crossover line with experimental data for supercritical argon and carbon dioxide.
  • Verified the lower crossover line using equations of state for the compressibility factor.

Conclusions:

  • The existence of two crossover lines provides a more accurate description of supercritical fluid states.
  • This framework reconciles the Ising model's behavior with experimental observations.
  • Offers a fundamental understanding of supercritical physics and phase transitions.