Fixation of Nitrogen with Aqueous Atomic Nitrogen.
Abstract
Planned research involved fixation of nitrogen in organic compounds in reactions of potential synthetic utility in which active nitrogen, mostly N(4S), acted on organic solutes dissolved in water or other unreactive polar solvents. A previously reported conversion of aqueous ethanol to acetamide could not be repeated. HCN(10-30 mole percent) and NH3(0-4 mole percent) were the only identified nitrogenous products of the reaction with aqueous or neat liquid methanol or ethanol. Molecular decomposition to H2, (CH2OH)2 and CH2O is the principal process with CH3OH. Product yields, their dependence on concentration of FeCl3, EPR spectra of radicals trapped with phenyl-t-butyl nitrone and isotopic composition of hydrogen produced from CH3OD show that free H atoms and CH2OH radical are only minor precursors of observed products formed from neat MeOH at -79 C. Products are similar whether N(4S) is introduced by rapid bubbling beneath the surface or impinged upon it but dissolved FeCl3 does not affect yields in the latter case. More limited data obtained with ethanol present a similar picture. The data suggest that energy released upon recombination of nitrogen atoms at or near the gas-liquid interface induces decomposition of methanol or ethanol in localized regions similar to 'spur' regions which characterize radiolysis of water. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Feb 28, 1977
- Accession Number
- ADA037091
Entities
People
- Norman N. Lichtin
Organizations
- Boston University