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Related Concept Videos

Radical Reactivity: Overview01:11

Radical Reactivity: Overview

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Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
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Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
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A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to represent the motion of a single electron in homolytic bond cleavage. There are two main sources from which radicals can be formed:
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Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
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Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
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Separation of Aldehydes and Reactive Ketones from Mixtures Using a Bisulfite Extraction Protocol
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Spinodal decomposition of chemically reactive binary mixtures.

A Lamorgese1, R Mauri1

  • 1Department of Civil and Industrial Engineering, University of Pisa, Largo Lazzarino 1, 56122 Pisa, Italy.

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This study simulates how reversible reactions affect phase separation in binary mixtures. Results show that reactions can drive mixtures towards a single-phase equilibrium state, influenced by concentration and reaction rates.

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Area of Science:

  • Thermodynamics
  • Chemical Kinetics
  • Materials Science

Background:

  • Phase segregation is crucial in materials science, influencing material properties.
  • Spinodal decomposition is a key mechanism for phase segregation in binary mixtures.
  • The interplay between reaction kinetics and diffusion dynamics is not fully understood in phase-separating systems.

Purpose of the Study:

  • To investigate the influence of reversible isomerization reactions on phase segregation.
  • To understand the coupling between reaction and diffusion in binary mixtures.
  • To quantify the competition between segregation and reaction using the Damköhler number.

Main Methods:

  • Utilized a diffuse-interface model for partially miscible binary mixtures.
  • Employed nonequilibrium thermodynamics to couple reaction and diffusion.
  • Conducted two-dimensional simulations to analyze phase segregation dynamics.
  • Investigated the dependence of reaction rate on local chemical potential difference.

Main Results:

  • Reaction rates exhibit a linear dependence on chemical affinity.
  • The Damköhler number characterizes the competition between segregation and reaction.
  • Skewed phase diagrams in asymmetric mixtures lead to convergence towards a single-phase equilibrium state.
  • Symmetric mixtures also converge to equilibrium, with the final state dependent on initial concentration relative to critical concentration.

Conclusions:

  • Reversible reactions can significantly alter phase segregation pathways in binary mixtures.
  • The interplay of diffusion, reaction, and initial composition dictates the final equilibrium state.
  • This research provides insights into controlling phase behavior through chemical reactions.