TY - GEN
T1 - Dft study of trichloroethylene chemisorption to iron surfaces using density functional theory
AU - Blowers, Paul
AU - Zhang, Nianliu
AU - Farrell, James
PY - 2005
Y1 - 2005
N2 - The mechanisms for chemical adsorption of trichloroethylene (TCE) to iron surfaces were studied using periodic density functional theory (DFT). DFT modeling of adsorbed species was performed using the generalized gradient approximation with the Perdew-Burke-Enzerhof (PBE) functional. Chemisorption structures were obtained for four adsorbed initial configurations. Di-sigma C-Fe and Cl-Fe complexes were formed by initial configurations with two carbon (C-bridge) or two chlorine atoms (Cl-bridge) adsorbed at bridge sites between adjacent iron atoms, respectively. Calculated binding energies indicated that chemisorption was highly exothermic, with the complex formed at the C-bridge site being the most energetically favorable. Chemisorption at the C-bridge site had an early transition state in which all three C-Cl bonds were activated from ∼ 1.7 to ∼ 2.2 Å, with an activation energy of 50 kJ/mole. The early transition state and the loss of all three Cl atoms upon chemisorption were consistent with most experimental observations that TCE undergoes complete dechlorination in one interaction with the iron surface. This is an abstract of a paper presented at the AIChE Annual Meeting and Fall Showcase (Cincinnati, OH 1/04/2005).
AB - The mechanisms for chemical adsorption of trichloroethylene (TCE) to iron surfaces were studied using periodic density functional theory (DFT). DFT modeling of adsorbed species was performed using the generalized gradient approximation with the Perdew-Burke-Enzerhof (PBE) functional. Chemisorption structures were obtained for four adsorbed initial configurations. Di-sigma C-Fe and Cl-Fe complexes were formed by initial configurations with two carbon (C-bridge) or two chlorine atoms (Cl-bridge) adsorbed at bridge sites between adjacent iron atoms, respectively. Calculated binding energies indicated that chemisorption was highly exothermic, with the complex formed at the C-bridge site being the most energetically favorable. Chemisorption at the C-bridge site had an early transition state in which all three C-Cl bonds were activated from ∼ 1.7 to ∼ 2.2 Å, with an activation energy of 50 kJ/mole. The early transition state and the loss of all three Cl atoms upon chemisorption were consistent with most experimental observations that TCE undergoes complete dechlorination in one interaction with the iron surface. This is an abstract of a paper presented at the AIChE Annual Meeting and Fall Showcase (Cincinnati, OH 1/04/2005).
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M3 - Conference contribution
AN - SCOPUS:33646743785
SN - 0816909962
SN - 9780816909964
T3 - AIChE Annual Meeting Conference Proceedings
BT - 05AIChE
PB - American Institute of Chemical Engineers
T2 - 05AIChE: 2005 AIChE Annual Meeting and Fall Showcase
Y2 - 30 October 2005 through 4 November 2005
ER -