Chemical Reductive Transformations of Synthetic Organic Compounds. Probe Compound Studies and Mechanistic Modeling

Abstract

Advanced Oxidation Processes (AOPs) can be used to selectively remove DNT (2,4-dinitrotoluene) from a complex waste stream by adding a precursor compound such as ethanol, which forms a reducing radical upon reaction with hydroxyl radical. A kinetic model that was previously developed to describe the results of batch AOP treatment by H2O2/UV did not give satisfactory predictive results obtained when extended to describe flow experiments. The present study farther investigated the chemistry of this system, including the oxidation by-product acetaldehyde, which was known to have multiple degradation pathways involving the formation of both oxidizing and reducing radicals. During the course of the investigation, the mechanism required to describe the system grew from 8 to over 30 reactions, with several new reactions found and several rate constants measured. The mechanism successfully described subsystems during calibration and upon combination of some subsystems, but the combined model for the entire reaction system did not give satisfactory prediction for some by-products when ethanol was added to the system. This is thought to be partly due to participation of unknown by-products from some of the new reactions, which require further study. The combined model gave better prediction of experimental results from the previous flow experiments than did the simpler model developed earlier. No multistability was found.

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Document Details

Document Type
Technical Report
Publication Date
Dec 01, 2001
Accession Number
ADA397728

Entities

People

  • Gary R. Peyton
  • Mary H. Lefaivre
  • Stephen W. Maloney

Organizations

  • Engineer Research and Development Center

Tags

Communities of Interest

  • Energy and Power Technologies
  • Ground and Sea Platforms

DTIC Thesaurus Topics

  • Advanced Oxidation Processes
  • Aldehydes
  • Chemical Reactants
  • Chemical Reaction Properties
  • Chemical Reactions
  • Chemical Synthesis
  • Chemistry
  • Computational Science
  • Hydroxyl Radical
  • Liquid Chromatography
  • Mathematical Analysis
  • Measurement
  • Organic Chemistry
  • Organic Compounds
  • Oxidation
  • Quantum Yields

Readers

  • Agricultural Chemistry/Soil Science
  • Computational Modeling and Simulation
  • Organic Chemistry