Modeling the Reaction of Fe Atoms with CCl4

Journal Article · Mon Jan 05 04:00:00 EST 2009 · Journal of Physical Chemistry C, 113(5):1830-1836

DOI:https://doi.org/10.1021/jp807604f· OSTI ID:949065

Camaioni, Donald M; Ginovska, Bojana; Dupuis, Michel

The reaction of zero-valent iron with carbon tetrachloride (CCl4) in gas phase was studied using density functional theory. Temperature programmed desorption experiments over a range of Fe and CCl4 coverages on a FeO(111) surface, demonstrate a rich surface chemistry with several reaction products (C2Cl4, C2Cl6, OCCl2, CO, FeCl2, FeCl3) observed. The reactivity of Fe and CCl4 was studied under three stoichiometries, one Fe with one CCl4, one Fe with two CCl4 molecules and two Fe with one CCl4, modeling the environment of the experimental work. The electronic structure calculations give insight into the reactions leading to the experimentally observed products and suggest that novel Fe-C-Cl containing species are important intermediates in these reactions. The intermediate complexes are formed in highly exothermic reactions, in agreement with the experimentally observed reactivity with the surface at low temperature (30 K). This initial survey of the reactivity of Fe with CCl4 identifies some potential reaction pathways that are important in the effort to use Fe nano-particles to differentiate harmful pathways that lead to the formation of contaminants like chloroform (CHCl3) from harmless pathways that lead to products such as formate (HCO2-) or carbon oxides in water and soil. The Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 949065
• Report Number(s): PNNL-SA-61537; KP1504010
• Journal Information: Journal of Physical Chemistry C, 113(5):1830-1836, Journal Name: Journal of Physical Chemistry C, 113(5):1830-1836 Journal Issue: 5 Vol. 113; ISSN 1932-7447
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
54 ENVIRONMENTAL SCIENCES
ACTIVATION ENERGY
CARBON TETRACHLORIDE
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DENSITY FUNCTIONAL METHOD
ELECTRONIC STRUCTURE
IRON
REACTION INTERMEDIATES
carbon tetrachloride
iron nano-particles
remediation technologies