Reduction of 1,2,3-trichloropropane (TCP): pathways and mechanisms from computational chemistry calculations
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.
- Authors:
-
[1];
[2];
[3];
[1];
[1]
- OHSU-PSU School of Public Health; Oregon Health & Science University; Portland; USA
- William R. Wiley Environmental Molecular Sciences Laboratory; Pacific Northwest National Laboratory; Richland; USA
- Jacobs; Portland; USA
- Publication Date:
- Research Org.:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1595844
- Alternate Identifier(s):
- OSTI ID: 1616695
- Report Number(s):
- PNNL-SA-149824
Journal ID: ISSN 2050-7887; ESPICZ
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Published Article
- Journal Name:
- Environmental Science: Processes & Impacts
- Additional Journal Information:
- Journal Name: Environmental Science: Processes & Impacts Journal Volume: 22 Journal Issue: 3; Journal ID: ISSN 2050-7887
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Torralba-Sanchez, Tifany L., Bylaska, Eric J., Salter-Blanc, Alexandra J., Meisenheimer, Douglas E., Lyon, Molly A., and Tratnyek, Paul G. Reduction of 1,2,3-trichloropropane (TCP): pathways and mechanisms from computational chemistry calculations. United Kingdom: N. p., 2020.
Web. doi:10.1039/C9EM00557A.
Torralba-Sanchez, Tifany L., Bylaska, Eric J., Salter-Blanc, Alexandra J., Meisenheimer, Douglas E., Lyon, Molly A., & Tratnyek, Paul G. Reduction of 1,2,3-trichloropropane (TCP): pathways and mechanisms from computational chemistry calculations. United Kingdom. https://doi.org/10.1039/C9EM00557A
Torralba-Sanchez, Tifany L., Bylaska, Eric J., Salter-Blanc, Alexandra J., Meisenheimer, Douglas E., Lyon, Molly A., and Tratnyek, Paul G. Wed .
"Reduction of 1,2,3-trichloropropane (TCP): pathways and mechanisms from computational chemistry calculations". United Kingdom. https://doi.org/10.1039/C9EM00557A.
@article{osti_1595844,
title = {Reduction of 1,2,3-trichloropropane (TCP): pathways and mechanisms from computational chemistry calculations},
author = {Torralba-Sanchez, Tifany L. and Bylaska, Eric J. and Salter-Blanc, Alexandra J. and Meisenheimer, Douglas E. and Lyon, Molly A. and Tratnyek, Paul G.},
abstractNote = {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.},
doi = {10.1039/C9EM00557A},
journal = {Environmental Science: Processes & Impacts},
number = 3,
volume = 22,
place = {United Kingdom},
year = {Wed Jan 01 00:00:00 EST 2020},
month = {Wed Jan 01 00:00:00 EST 2020}
}
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Figures / Tables:
Fig. 1: Summary of the main pathways of alkyl halide transformation under reducing conditions. Nu represents the nucleophiles from water or sulfide, X represents any halide including chlorine, e- represents electrons from any reductant, and R represents any alkyl substituent including -CClH3 for TCP. The abbreviations represent common pathway namesmore »
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