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Radical Reactivity: Overview

Radical Reactivity: Overview

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 molecule. These three...

Radical Formation: Overview

Radical Formation: Overview

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:
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the latter, also known...

Radical Formation: Homolysis

Radical Formation: Homolysis

A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up by one atom forming ions by the cleavage called heterolysis, or the two electrons are shared by two atoms, with one each creating radicals by the cleavage called homolysis.

Mass Spectrometry: Molecular Fragmentation Overview

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The ionization of a molecule into a molecular ion inside the mass spectrometer causes instability in the molecule's structure due to the loss of an electron. This eventually leads to the fragmentation or breaking of some bonds in the molecule. The fragmentation occurs predominantly at specific bonds to yield relatively stable fragments.
One type of fragmentation pattern is the cleavage of a single bond in the molecular ion. The cleavage leads to a radical and a cation. The cleavage can occur at...

Radical Formation: Addition

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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.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an unpaired...

Radical Formation: Abstraction

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The electron of an atom can be abstracted from a compound by a relatively unstable radical to generate a new radical of relatively greater stability. For example, an initiator which forms radicals by homolysis can abstract a suitable species like a hydrogen atom or a halogen atom from a compound to generate a new radical. This ability of radicals to propagate by abstraction is a crucial feature of radical chain reactions.
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Related Experiment Video

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Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F⁻

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Dissociative electron attachment to C2F5 radicals.

Sean A Haughey¹, Thomas A Field, Judith Langer

¹Centre for Plasma Physics, School of Mathematics and Physics, Queen's University Belfast, Belfast BT7 1NN, United Kingdom.

The Journal of Chemical Physics

|August 17, 2012

Summary

This summary is machine-generated.

Dissociative electron attachment to pentafluoroethane (C2F5) primarily forms fluoride ions (F-) near zero electron energy. Rate constants for this process range from 3.7-4.7 × 10(-9) cm(3) s(-1) across tested temperatures.

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Area of Science:

Physical Chemistry
Chemical Physics
Molecular Physics

Background:

The reactive pentafluoroethane (C2F5) radical is relevant in various chemical processes.
Understanding electron-molecule interactions is crucial for predicting chemical reactivity and reaction pathways.

Purpose of the Study:

To investigate the mechanism of dissociative electron attachment (DEA) to the C2F5 radical.
To quantify the formation of F- ions and determine reaction rate constants.

Main Methods:

Utilized a single collision beam experiment to study DEA.
Employed a novel flowing afterglow Langmuir probe technique for measurements.

Main Results:

DEA to C2F5 predominantly forms F- ions at near-zero electron energies.
Measured rate constants for F- formation between 3.7 × 10(-9) and 4.7 × 10(-9) cm(3) s(-1) for temperatures ranging from 300 K to 600 K.
Observed a slow, statistically insignificant increase in the rate constant with increasing temperature.

Conclusions:

F- ion formation via DEA is a significant reaction pathway for C2F5.
The temperature dependence of the rate constant is minimal within the studied range.
The findings provide valuable data for modeling chemical reactions involving C2F5 radicals.