Reactions of Free Radicals with Nitro-Compounds and Nitrates

Abstract

A discharge-flow system has been used to study the reaction of oxygen atoms with methyl nitrate, ethyl nitrate, nitromethane and nitroethane. In each case the initial attack involved abstraction of a hydrogen atom from the alpha- position. The pre-exponential factors were 15 x 10 to the 9th power and 3 x 10 to the 10th power/mol sec for the methyl and ethyl compounds respectively. The activation energies were all within 1 kJ/mol of 22 kJ/mol although the fragment derived from the nitrates but not from the nitro-compounds could undergo exothermic rearrangement. Product analyses and computer modelling were undertaken, these provided a clear explanation of why the nitro-compounds but not the nitrates are readily decomposed by a free-radical chain mechanism.

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Document Details

Document Type
Technical Report
Publication Date
Mar 31, 1981
Accession Number
ADA102286

Entities

People

  • Brian A. Thrush
  • L. F. Salter

Organizations

  • University of Cambridge

Tags

Communities of Interest

  • Energy and Power Technologies

DTIC Thesaurus Topics

  • Alkanes
  • Carbon Monoxide
  • Chain Reactions
  • Chemical Reactions
  • Chemical Synthesis
  • Chemistry
  • Cyanides
  • Dielectric Gases
  • Free Radicals
  • Heat Of Activation
  • Hydrogen Cyanide
  • Hydroxyl Radical
  • Nitro Compounds
  • Nitrogen Oxides
  • Organic Chemistry
  • Oxygen
  • Reaction Time

Readers

  • Organic Chemistry