Investigation of reaction steps for the hydrodechlorination of chlorine-containing organic compounds on Pd catalysts

Nan Chen; Robert M. Rioux; Fabio H. Ribeiro

doi:10.1016/S0021-9517(02)93717-6

Investigation of reaction steps for the hydrodechlorination of chlorine-containing organic compounds on Pd catalysts

Nan Chen, Robert M. Rioux, Fabio H. Ribeiro

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Abstract

Reaction steps for the reaction of hydrodechlorination on Pd were investigated by means of isotope-exchange experiments. The reversibility of bond scission for the two C-Cl bonds in CF₃CFCl₂ was investigated by following ³⁷Cl enrichment in the reactant and products. No enrichment of ³⁷Cl was observed in the reactant CF₃CFCl₂ but the product CF₃CHFCl was enriched. Thus, the scission of the first C-Cl bond is irreversible; once the reactant loses the first chlorine it desorbs only as a product. However, after the first C-Cl bond is broken, the second chlorine may be exchanged with the pool of surface chlorine. Isotope exchange experiments between D₂ and HCl during hydrodechlorination of CF₃CFCl₂ showed that the forward rate and reverse rate for the overall reaction H₂ + 2Cl* = 2HCl + 2* were nearly 400 times faster than the overall hydrodechlorination reaction rate. Thus, this experiment confirms that this step is in quasi-equilibrium.

Original language	English (US)
Pages (from-to)	192-197
Number of pages	6
Journal	Journal of Catalysis
Volume	211
Issue number	1
DOIs	https://doi.org/10.1016/S0021-9517(02)93717-6
State	Published - 2002

All Science Journal Classification (ASJC) codes

Catalysis
Physical and Theoretical Chemistry

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10.1016/S0021-9517(02)93717-6

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@article{718924143ec5448f8f3439471d8bdd72,

title = "Investigation of reaction steps for the hydrodechlorination of chlorine-containing organic compounds on Pd catalysts",

abstract = "Reaction steps for the reaction of hydrodechlorination on Pd were investigated by means of isotope-exchange experiments. The reversibility of bond scission for the two C-Cl bonds in CF3CFCl2 was investigated by following 37Cl enrichment in the reactant and products. No enrichment of 37Cl was observed in the reactant CF3CFCl2 but the product CF3CHFCl was enriched. Thus, the scission of the first C-Cl bond is irreversible; once the reactant loses the first chlorine it desorbs only as a product. However, after the first C-Cl bond is broken, the second chlorine may be exchanged with the pool of surface chlorine. Isotope exchange experiments between D2 and HCl during hydrodechlorination of CF3CFCl2 showed that the forward rate and reverse rate for the overall reaction H2 + 2Cl* = 2HCl + 2* were nearly 400 times faster than the overall hydrodechlorination reaction rate. Thus, this experiment confirms that this step is in quasi-equilibrium.",

author = "Nan Chen and Rioux, {Robert M.} and Ribeiro, {Fabio H.}",

note = "Funding Information: We gratefully thank the National Science Foundation for funding through grant CTS-9702699. We thank Degussa for the 5% Pd/C catalyst and DuPont for a sample of CF3CFCl2.",

year = "2002",

doi = "10.1016/S0021-9517(02)93717-6",

language = "English (US)",

volume = "211",

pages = "192--197",

journal = "Journal of Catalysis",

issn = "0021-9517",

publisher = "Academic Press Inc.",

number = "1",

}

TY - JOUR

T1 - Investigation of reaction steps for the hydrodechlorination of chlorine-containing organic compounds on Pd catalysts

AU - Chen, Nan

AU - Rioux, Robert M.

AU - Ribeiro, Fabio H.

N1 - Funding Information: We gratefully thank the National Science Foundation for funding through grant CTS-9702699. We thank Degussa for the 5% Pd/C catalyst and DuPont for a sample of CF3CFCl2.

PY - 2002

Y1 - 2002

N2 - Reaction steps for the reaction of hydrodechlorination on Pd were investigated by means of isotope-exchange experiments. The reversibility of bond scission for the two C-Cl bonds in CF3CFCl2 was investigated by following 37Cl enrichment in the reactant and products. No enrichment of 37Cl was observed in the reactant CF3CFCl2 but the product CF3CHFCl was enriched. Thus, the scission of the first C-Cl bond is irreversible; once the reactant loses the first chlorine it desorbs only as a product. However, after the first C-Cl bond is broken, the second chlorine may be exchanged with the pool of surface chlorine. Isotope exchange experiments between D2 and HCl during hydrodechlorination of CF3CFCl2 showed that the forward rate and reverse rate for the overall reaction H2 + 2Cl* = 2HCl + 2* were nearly 400 times faster than the overall hydrodechlorination reaction rate. Thus, this experiment confirms that this step is in quasi-equilibrium.

AB - Reaction steps for the reaction of hydrodechlorination on Pd were investigated by means of isotope-exchange experiments. The reversibility of bond scission for the two C-Cl bonds in CF3CFCl2 was investigated by following 37Cl enrichment in the reactant and products. No enrichment of 37Cl was observed in the reactant CF3CFCl2 but the product CF3CHFCl was enriched. Thus, the scission of the first C-Cl bond is irreversible; once the reactant loses the first chlorine it desorbs only as a product. However, after the first C-Cl bond is broken, the second chlorine may be exchanged with the pool of surface chlorine. Isotope exchange experiments between D2 and HCl during hydrodechlorination of CF3CFCl2 showed that the forward rate and reverse rate for the overall reaction H2 + 2Cl* = 2HCl + 2* were nearly 400 times faster than the overall hydrodechlorination reaction rate. Thus, this experiment confirms that this step is in quasi-equilibrium.

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U2 - 10.1016/S0021-9517(02)93717-6

DO - 10.1016/S0021-9517(02)93717-6

M3 - Article

AN - SCOPUS:57249087321

SN - 0021-9517

VL - 211

SP - 192

EP - 197

JO - Journal of Catalysis

JF - Journal of Catalysis

IS - 1

ER -

Investigation of reaction steps for the hydrodechlorination of chlorine-containing organic compounds on Pd catalysts

Abstract

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