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Pressure and Volume in an Adiabatic Process01:27

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Free expansion of a gas is an adiabatic process. However, there are few differences between free expansion and adiabatic expansion. During free expansion, no work is done, and there is no change in internal energy. But, for an adiabatic expansion, work is done, and there is a change in internal energy. During an adiabatic process, the relation between the pressure and volume is obtained from the condition for the adiabatic process, that is, 
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In certain chromatographic separations, solutes transfer between the mobile phase and the stationary phase via sorption, which typically refers to the process of adsorption. For many chromatographic systems, the sorption process often depends on the polarity of the compounds—an expression of the overall dipole moment within the molecule. During the separation process, there is competition between the solute and solvent for adsorption to the stationary phase. Highly polar compounds and...
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Adiabatic Processes for an Ideal Gas01:18

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When an ideal gas is compressed adiabatically, that is, without adding heat, work is done on it, and its temperature increases. In an adiabatic expansion, the gas does work, and its temperature drops. Adiabatic compressions actually occur in the cylinders of a car, where the compressions of the gas-air mixture take place so quickly that there is no time for the mixture to exchange heat with its environment. Nevertheless, because work is done on the mixture during the compression, its...
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Double resonance techniques in Nuclear Magnetic Resonance (NMR) spectroscopy involve the simultaneous application of two different frequencies or radiofrequency pulses to manipulate and observe two distinct nuclear spins. One important application of double resonance is spin decoupling, which selectively suppresses coupling with one type of nucleus while observing the NMR signal from another nucleus, simplifying the spectrum and enhancing resolution.
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Atomic Absorption Spectroscopy: Atomization Methods01:25

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Atomic Absorption Spectroscopy (AAS) atomizes samples through flame atomization or electrothermal atomization. Flame atomization typically involves a nebulizer and spray chamber assembly to combine the sample with a fuel–oxidant mixture, creating a fine aerosol mist that enters a burner. Typically, the fuel and oxidant are combined in an approximately stoichiometric ratio. However, for atoms that are easily oxidized, a fuel-rich mixture may be more advantageous. Only about 5% of the...
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Sublimation is the direct transformation of a solid to a gaseous state. For instance, at standard pressure and room temperature, solid carbon dioxide sublimes to gaseous carbon dioxide. The phase diagram depicts the conditions required for sublimation. This process occurs at the solid-gas phase boundary and is not observed above the triple point of the substance. The reverse of sublimation is called deposition, where a gaseous substance condenses directly into a solid. Sublimation and...
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Related Experiment Video

Updated: Jun 13, 2025

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
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Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

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Accelerated convergence via adiabatic sampling for adsorption and desorption processes.

Caroline Desgranges1, Jerome Delhommelle2

  • 1Department of Physics and Applied Physics, University of Massachusetts, Lowell, Massachusetts 01854, USA.

The Journal of Chemical Physics
|September 9, 2024
PubMed
Summary
This summary is machine-generated.

Adiabatic simulations accelerate phase transition equilibrium discovery, overcoming slow kinetics and hysteresis observed in isothermal simulations for bulk and nanoporous materials. This enhances predictions for phase diagrams and gas storage.

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Last Updated: Jun 13, 2025

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Area of Science:

  • Computational chemistry and materials science
  • Statistical mechanics and thermodynamics

Background:

  • Phase transitions under isothermal conditions are hindered by nucleation barriers and slow kinetics, leading to hysteresis.
  • This phenomenon impacts predicting phase diagrams and screening porous materials for gas storage.
  • Current simulation methods, like the grand-canonical ensemble, can be inefficient for reaching equilibrium.

Purpose of the Study:

  • To introduce and validate the adiabatic grand-isochoric ensemble (μ, V, L) for efficient equilibrium state discovery.
  • To compare the convergence rates of adiabatic and isothermal simulations for bulk and confined systems.
  • To demonstrate the utility of adiabatic simulations for systems exhibiting hysteresis, such as gas adsorption in nanoporous materials.

Main Methods:

  • Utilized adiabatic grand-isochoric ensemble (μ, V, L) simulations.
  • Compared convergence rates with isothermal grand-canonical ensemble simulations.
  • Applied simulations to bulk systems and argon adsorption/desorption in nanoporous materials (IRMOF-1, MCM-41).

Main Results:

  • Adiabatic simulations show significantly faster convergence than isothermal simulations, especially at low supersaturation.
  • The (μ, V, L) ensemble reliably predicts equilibrium loading for argon adsorption/desorption in MCM-41, a system with hysteresis.
  • Quantitative measures confirm the increased rate of convergence and wider temperature exploration offered by adiabatic simulations.

Conclusions:

  • Adiabatic simulations provide a more efficient route to equilibrium compared to isothermal methods, particularly for systems with slow kinetics.
  • The adiabatic grand-isochoric ensemble is a powerful tool for accurately predicting phase behavior and adsorption in nanoporous materials.
  • This approach enhances the efficiency of simulations for phase diagram prediction and materials screening applications.