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Summary of Radical Reactions Mechanisms

May 18, 2025

Radical Reactions Lecture Summary

Overview

  • Presenter: Leah from leah4sci.com
  • Topic: Radical reactions, focusing on initiation, propagation, and termination
  • Additional Resources: More information available at leah4sci.com/radical

What is a Radical?

  • A radical is a single or unpaired electron.
  • Electrons typically exist in pairs (e.g., in water, H2O, oxygen is bonded to hydrogen and has lone pairs).
  • Free radicals are highly reactive due to having unpaired electrons.
  • Free radicals can cause damage in biological systems by attacking cells or DNA.

Reaction Mechanisms

  • Heterolytic cleavage: Electrons move together as a pair to one atom.
    • Represented by a double-headed arrow.
  • Homolytic cleavage: Electrons split with one going to each atom.
    • Represented by a single-headed or fish hook arrow.
    • Both atoms become radicals.

Steps of a Radical Reaction

1. Initiation

  • Purpose: Create radicals.
  • Example: Cl2 (chlorine gas) can be split by heat or light.
  • Mechanism: Homolytic cleavage where each chlorine atom gets one electron, forming two chlorine radicals.
  • Recognition: No radicals on the reactant side, radicals appear only in the products.

2. Propagation

  • Purpose: Radicals react with stable molecules to create new radicals, propagating the chain reaction.
  • Example: Chlorine radical reacts with methane, forming methyl radicals and HCl.
  • Mechanism: Radical reacts with a stable molecule, forming a new radical in the products.
  • Recognition: One radical in the reactants, one radical in the products.

3. Termination

  • Purpose: Two radicals combine to form a stable molecule, ending the reaction.
  • Example: Two chlorine radicals form Cl2, or two methyl radicals form ethane.
  • Mechanism: Radicals meet and form a stable bond.
  • Recognition: Two radicals in reactants, none in products.

Example: Radical Chlorination of Methane

  • Initiation: Cl2 breaks into two Cl radicals with heat/light.
  • Propagation Step 1: Chlorine radical forms HCl and methyl radical.
  • Propagation Step 2: Methyl radical reacts with another Cl2 to form chloromethane and a new Cl radical.
  • Termination: Unlikely as radicals typically propagate rather than terminate.

Conclusion

  • Radical reactions are characterized by initiation, propagation, and less frequently, termination.
  • Understanding radical reactions is crucial for chemistry, especially in organic synthesis and biochemical processes.
  • More resources are available on Leah's website for further study.