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Related Concept Videos

Radical Reactivity: Overview01:11

Radical Reactivity: Overview

2.1K
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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Radical Autoxidation01:20

Radical Autoxidation

2.2K
The oxidation of an organic compound in the presence of air or oxygen is called autoxidation. For example, cumene reacts with oxygen to form hydroperoxide. Autoxidation involves initiation, propagation, and termination steps. Many organic compounds are susceptible to autoxidation—especially ethers in the presence of oxygen, which form hydroperoxides. Even though this reaction is slow, old ether bottles contain small amounts of peroxide, which leads to laboratory explosions during ether...
2.2K
Radical Formation: Elimination00:51

Radical Formation: Elimination

1.7K
Another method of radical formation is the elimination process. It is the opposite of the addition route and is driven by the instability of the radical. For example, as depicted in Figure 1, dibenzoyl peroxide yields a pair of unstable radicals upon homolysis. Given its instability, this radical spontaneously undergoes elimination via a C–C bond cleavage to form a relatively more stable phenyl radical. The mechanism involves cleavage of the bond between the α and β positions...
1.7K
Radical Oxidation of Allylic and Benzylic Alcohols01:21

Radical Oxidation of Allylic and Benzylic Alcohols

2.0K
Activated manganese(IV) oxide can selectively oxidize allylic and benzylic alcohols via a radical intermediate mechanism. Primary allylic alcohols are oxidized to aldehydes, while secondary allylic alcohols yield ketones. The redox reaction of potassium permanganate with an Mn(II) salt such as manganese sulfate (under either alkaline or acidic conditions), followed by thorough drying, yields the oxidizing agent: activated MnO2. While MnO2 is insoluble in the solvents used for the reaction, the...
2.0K
Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

1.9K
The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic...
1.9K
Radical Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

2.1K
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...
2.1K

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[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
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Merits and Limitations of Radical vs. Nonradical Pathways in Persulfate-Based Advanced Oxidation Processes.

Yiqi Yan1,2, Zongsu Wei3, Xiaoguang Duan4

  • 1Institute of Environmental Engineering, School of Metallurgy and Environment, Central South University, Changsha, 410083, China.

Environmental Science & Technology
|August 3, 2023
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Summary

Persulfate (PS)-based advanced oxidation processes (AOPs) offer eco-friendly water treatment. Radical-based AOPs excel in speed, while nonradical AOPs suit complex wastewaters, though both have energy considerations.

Keywords:
energy consumptionnonradical pathwaypersulfate activationreactive species

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Resin-Assisted Capture Coupled with Isobaric Tandem Mass Tag Labeling for Multiplexed Quantification of Protein Thiol Oxidation
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Area of Science:

  • Environmental Chemistry
  • Water Treatment Technologies
  • Advanced Oxidation Processes

Background:

  • Urbanization and industrialization degrade water quality, necessitating advanced treatment solutions.
  • Persulfate (PS)-based advanced oxidation processes (AOPs) are promising for industrial wastewater and groundwater remediation.
  • A systematic comparison of radical and nonradical pathways in PS-AOPs is lacking for practical application.

Purpose of the Study:

  • To systematically compare radical and nonradical pathways in PS-based AOPs.
  • To evaluate the efficiency, applicability, and energy requirements of different PS-AOP pathways.
  • To inform the selection and development of PS-AOPs for specific water treatment scenarios.

Main Methods:

  • Comparative analysis of reaction rate constants for radical vs. nonradical species.
  • Evaluation of contaminant degradation efficiency based on chemical structure (electron-donating groups).
  • Consideration of analytical limitations and computational chemistry for byproduct analysis.
  • Estimation of electrical energy per order of reaction (EE/O) for different pathways.

Main Results:

  • Radical-based AOPs offer high organic contaminant removal efficiency with short contact times.
  • Nonradical AOPs demonstrate advantages in complex matrices with minimal interference.
  • Nonradical species effectively degrade contaminants with electron-donating groups.
  • Nonradical pathways exhibit significantly higher energy requirements (EE/O) compared to radical pathways.

Conclusions:

  • PS-based AOPs present viable options for water treatment, with distinct advantages for radical and nonradical pathways.
  • Understanding pathway-specific kinetics and energy demands is crucial for optimizing PS-AOP implementation.
  • Further research should focus on enhancing the efficiency and reducing the energy consumption of nonradical PS-AOPs for broader applicability.