Isokinetic behaviour in gas phase catalytic haloarene hydrodehalogenation reactions: Mechanistic considerations
(2006) In Journal of Molecular Catalysis A: Chemical 249(1-2). p.158-165- Abstract
- Compensation behaviour is established for the gas phase hydrodehalogenation of a range of haloarenes over a common Ni/SiO2 catalyst. Analysis of the experimental results delivers an isokinetic temperature (T-iso) at 658 +/- 2K associated with the following reactants: chlorobenzene, 4-chlorotoluene, 3-chlorophenol, 1,3,-dichlorobenzene, 4-chlorophenol, 3,5-dichlorophenol, 1,4-dichlorobenzene, bromobenzene, 2,6-dichlorophenol, 2-chlorophenol, 1,2-dichlorobenzene and 1,3-dibromobenzene. The occurrence of a T-iso is accounted for using the Selective Energy Transfer (SET) model that is based on the premise of resonance between a vibrational mode of the catalyst and a vibrational mode of the reactant with a transferral of resonance energy from... (More)
- Compensation behaviour is established for the gas phase hydrodehalogenation of a range of haloarenes over a common Ni/SiO2 catalyst. Analysis of the experimental results delivers an isokinetic temperature (T-iso) at 658 +/- 2K associated with the following reactants: chlorobenzene, 4-chlorotoluene, 3-chlorophenol, 1,3,-dichlorobenzene, 4-chlorophenol, 3,5-dichlorophenol, 1,4-dichlorobenzene, bromobenzene, 2,6-dichlorophenol, 2-chlorophenol, 1,2-dichlorobenzene and 1,3-dibromobenzene. The occurrence of a T-iso is accounted for using the Selective Energy Transfer (SET) model that is based on the premise of resonance between a vibrational mode of the catalyst and a vibrational mode of the reactant with a transferral of resonance energy from the catalyst to the reactant to generate the "activated complex" with subsequent reaction. In this study of a single catalyst promoting a common (hydrodehalogenation) reaction for a family of haloarene reactants, we establish the complimentary vibrational modes as the out-plane C-H vibrations of substituted benzene and Ni-H vibration at high hydrogen surface coverage. The proposed surface rate-determining step is the C-H "out-of-plane" activation favouring an sp(2) to sp(3) transformation. (c) 2006 Elsevier B.V. All rights reserved. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/410397
- author
- Keane, MA and Larsson, Ragnar LU
- organization
- publishing date
- 2006
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- isokinetic temperature, compensation effect, Ni/SiO2, hydrodehalogenation, haloarenes, selective energy transfer model
- in
- Journal of Molecular Catalysis A: Chemical
- volume
- 249
- issue
- 1-2
- pages
- 158 - 165
- publisher
- Elsevier
- external identifiers
-
- wos:000237173500022
- scopus:33646014795
- ISSN
- 1381-1169
- DOI
- 10.1016/j.molcata.2006.01.017
- language
- English
- LU publication?
- yes
- id
- c0277fda-50ef-417b-9958-d420f2a38937 (old id 410397)
- date added to LUP
- 2016-04-01 16:09:28
- date last changed
- 2023-09-04 13:24:41
@article{c0277fda-50ef-417b-9958-d420f2a38937,
abstract = {{Compensation behaviour is established for the gas phase hydrodehalogenation of a range of haloarenes over a common Ni/SiO2 catalyst. Analysis of the experimental results delivers an isokinetic temperature (T-iso) at 658 +/- 2K associated with the following reactants: chlorobenzene, 4-chlorotoluene, 3-chlorophenol, 1,3,-dichlorobenzene, 4-chlorophenol, 3,5-dichlorophenol, 1,4-dichlorobenzene, bromobenzene, 2,6-dichlorophenol, 2-chlorophenol, 1,2-dichlorobenzene and 1,3-dibromobenzene. The occurrence of a T-iso is accounted for using the Selective Energy Transfer (SET) model that is based on the premise of resonance between a vibrational mode of the catalyst and a vibrational mode of the reactant with a transferral of resonance energy from the catalyst to the reactant to generate the "activated complex" with subsequent reaction. In this study of a single catalyst promoting a common (hydrodehalogenation) reaction for a family of haloarene reactants, we establish the complimentary vibrational modes as the out-plane C-H vibrations of substituted benzene and Ni-H vibration at high hydrogen surface coverage. The proposed surface rate-determining step is the C-H "out-of-plane" activation favouring an sp(2) to sp(3) transformation. (c) 2006 Elsevier B.V. All rights reserved.}},
author = {{Keane, MA and Larsson, Ragnar}},
issn = {{1381-1169}},
keywords = {{isokinetic temperature; compensation effect; Ni/SiO2; hydrodehalogenation; haloarenes; selective energy transfer model}},
language = {{eng}},
number = {{1-2}},
pages = {{158--165}},
publisher = {{Elsevier}},
series = {{Journal of Molecular Catalysis A: Chemical}},
title = {{Isokinetic behaviour in gas phase catalytic haloarene hydrodehalogenation reactions: Mechanistic considerations}},
url = {{http://dx.doi.org/10.1016/j.molcata.2006.01.017}},
doi = {{10.1016/j.molcata.2006.01.017}},
volume = {{249}},
year = {{2006}},
}