Reduction of 1,2,3-trichloropropane (TCP): Pathways and mechanisms from computational chemistry calculations

Tifany L. Torralba-Sanchez, Eric J. Bylaska, Alexandra J. Salter-Blanc, Douglas E. Meisenheimer, Molly A. Lyon, Paul G. Tratnyek

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

The characteristic pathway for degradation of halogenated aliphatic compounds in groundwater or other environments with relatively anoxic and/or reducing conditions is reductive dechlorination. For 1,2-dihalocarbons, reductive dechlorination can include hydrogenolysis and dehydrohalogenation, the relative significance of which depends on various structural and energetic factors. To better understand how these factors influence the degradation rates and products of the lesser halogenated hydrocarbons (in contrast to the widely studied per-halogenated hydrocarbons, like trichloroethylene and carbon tetrachloride), density functional theory calculations were performed to compare all of the possible pathways for reduction and elimination of 1,2,3-trichloropropane (TCP). The results showed that free energies of each species and reaction step are similar for all levels of theory, although B3LYP differed from the others. In all cases, the reaction coordinate diagrams suggest that β-elimination of TCP to allyl chloride followed by hydrogenolysis to propene is the thermodynamically favored pathway. This result is consistent with experimental results obtained using TCP, 1,2-dichloropropane, and 1,3-dichloropropane in batch experiments with zerovalent zinc (Zn0, ZVI) as a reductant.

Original languageEnglish (US)
Pages (from-to)606-616
Number of pages11
JournalEnvironmental Science: Processes and Impacts
Volume22
Issue number3
DOIs
StatePublished - Mar 2020

ASJC Scopus subject areas

  • Environmental Chemistry
  • Public Health, Environmental and Occupational Health
  • Management, Monitoring, Policy and Law

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