Neopentane and Solid Acids:  Direct Hydron Exchange before Cracking

The hydrogen/deuterium exchange reaction of 2,2-dimethylpropane (neopentane) over D2O-exchanged zeolites (MOR, FAU, BEA, MFI) using a batch recirculation reactor was studied by means of gas chromatography coupled with mass spectrometer. In the temperature range 473−573 K, H/D exchange proceeds witho...

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Published in:The journal of physical chemistry. B 2006-09, Vol.110 (37), p.18368-18373
Main Authors: Walspurger, Stéphane, Sun, Yinyong, Souna Sido, Abdelkarim Sani, Sommer, Jean
Format: Article
Language:English
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Summary:The hydrogen/deuterium exchange reaction of 2,2-dimethylpropane (neopentane) over D2O-exchanged zeolites (MOR, FAU, BEA, MFI) using a batch recirculation reactor was studied by means of gas chromatography coupled with mass spectrometer. In the temperature range 473−573 K, H/D exchange proceeds without side reaction such as cracking at short contact times. Indeed the C−H bond has appeared favorably involved in the activation of neopentane compared to the less accessible C−C bond. The transition state allowing hydron exchange is most likely a carbonium species (pentacoordinated carbon) as in the case of the H/D exchange between methane and solid acid. The activation energies of the H/D exchange between neopentane and zeolites are the same for all zeolites indicating a common carbonium ion type transition state. On the basis of previous results in the case of the exchange between methane and liquid superacids, the deuterium exchange rates in neopentane were tentatively related to the acidity of the solids. However the order of activity MOR > MFI > BEA > FAU seems to be related to the size of the pores, which may suggest the involvement of a confinement effect in the zeolites cavities. Moreover we found that H/D exchange takes also place between neopentane and deuterated sulfated zirconia (SZ) emphasizing its strong acidity.
ISSN:1520-6106
1520-5207
DOI:10.1021/jp0621676