Mechanism Studies of the Conversion of 13C-Labeled n-Butane on Zeolite H-ZSM-5 by Using 13C Magic Angle Spinning NMR Spectroscopy and GC–MS Analysis Full article
| Journal |
Chemistry - A European Journal
ISSN: 0947-6539 , E-ISSN: 1521-3765 |
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| Output data | Year: 2006, Volume: 12, Number: 2, Pages: 457-465 Pages count : 9 DOI: 10.1002/chem.200500382 | ||||||
| Tags | Butane, GC-MS analysis, NMR spectroscopy, Reaction mechanisms, Zeolites | ||||||
| Authors |
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| Affiliations |
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Funding (6)
| 1 | North Atlantic Treaty Organization | PST.CLG.979335 |
| 2 | Russian Foundation for Basic Research | 04-03-32372 |
| 3 | International Association for the Promotion of Co-operation with Scientists from the New Independent States of the Former Soviet Union | 03-51-5286 |
| 4 | German Research Foundation | FR 902/15 |
| 5 | Siberian Branch of the Russian Academy of Sciences | |
| 6 | Russian Science Support Foundation |
Abstract:
By using 13C MAS NMR spectroscopy (MAS=magic angle spinning), the conversion of selectively 13C-labeled n-butane on zeolite H-ZSM-5 at 430–470 K has been demonstrated to proceed through two pathways: 1) scrambling of the selective 13C-label in the n-butane molecule, and 2) oligomerization–cracking and conjunct polymerization. The latter processes (2) produce isobutane and propane simultaneously with alkyl-substituted cyclopentenyl cations and condensed aromatic compounds. In situ 13C MAS NMR and complementary ex situ GC–MS data provided evidence for a monomolecular mechanism of the 13C-label scrambling, whereas both isobutane and propane are formed through intermolecular pathways. According to 13C MAS NMR kinetic measurements, both pathways proceed with nearly the same activation energies (Ea=75 kJ mol−1 for the scrambling and 71 kJ mol−1 for isobutane and propane formation). This can be rationalized by considering the intermolecular hydride transfer between a primarily initiated carbenium ion and n-butane as being the rate-determining stage of the n-butane conversion on zeolite H-ZSM-5.
Cite:
Luzgin M.V.
, Stepanov A.G.
, Arzumanov S.S.
, Rogov V.A.
, Parmon V.N.
, Wang W.
, Hunger M.
, Freude D.
Mechanism Studies of the Conversion of 13C-Labeled n-Butane on Zeolite H-ZSM-5 by Using 13C Magic Angle Spinning NMR Spectroscopy and GC–MS Analysis
Chemistry - A European Journal. 2006. V.12. N2. P.457-465. DOI: 10.1002/chem.200500382 WOS Scopus РИНЦ ANCAN PMID OpenAlex
Mechanism Studies of the Conversion of 13C-Labeled n-Butane on Zeolite H-ZSM-5 by Using 13C Magic Angle Spinning NMR Spectroscopy and GC–MS Analysis
Chemistry - A European Journal. 2006. V.12. N2. P.457-465. DOI: 10.1002/chem.200500382 WOS Scopus РИНЦ ANCAN PMID OpenAlex
Dates:
| Submitted: | Apr 5, 2005 |
| Published online: | Sep 15, 2005 |
| Published print: | Dec 23, 2005 |
Identifiers:
| Web of science: | WOS:000234453300013 |
| Scopus: | 2-s2.0-29544437228 |
| Elibrary: | 13489769 |
| Chemical Abstracts: | 2006:57772 |
| Chemical Abstracts (print): | 144:273875 |
| PMID: | 16163765 |
| OpenAlex: | W2171329660 |