TY - JOUR
T1 - Study of the hydrolysis of acetonitrile using different brønsted acid models : zeolite-type and HCl(H2O)x clusters
AU - Barbosa, Louis
AU - Santen, van, R.A.
PY - 2000
Y1 - 2000
N2 - The hydrolysis of acetonitrile has been studied theoretically by different ab initio methods (RHF, DFT, and MP2). Two Brønsted acid catalysts have been compared: zeolite and HCl(H2O)x=2,1 clusters. Some interesting analogies have been found for the reaction path catalyzed by these different acids, especially in the hydration transition state. The size and the configuration of a zeolite cluster model have an important influence on predicting the reaction mechanism. The van der Waals interactions also play an important role in this reaction. Due to these interactions, oxygen atoms of the zeolite cavity can stabilize charged species as N- and O-protonated acetamide configurations. For the zeolite catalyst, the rate-limiting step of the overall reaction is the hydration of acetonitrile. On the other hand, in the hydrochloric acid catalysis, the rate-limiting step is either the hydration or the isomerization step. Acetamide appears to be the most stable species adsorbed on zeolite and it is responsible for poisoning the reaction.
AB - The hydrolysis of acetonitrile has been studied theoretically by different ab initio methods (RHF, DFT, and MP2). Two Brønsted acid catalysts have been compared: zeolite and HCl(H2O)x=2,1 clusters. Some interesting analogies have been found for the reaction path catalyzed by these different acids, especially in the hydration transition state. The size and the configuration of a zeolite cluster model have an important influence on predicting the reaction mechanism. The van der Waals interactions also play an important role in this reaction. Due to these interactions, oxygen atoms of the zeolite cavity can stabilize charged species as N- and O-protonated acetamide configurations. For the zeolite catalyst, the rate-limiting step of the overall reaction is the hydration of acetonitrile. On the other hand, in the hydrochloric acid catalysis, the rate-limiting step is either the hydration or the isomerization step. Acetamide appears to be the most stable species adsorbed on zeolite and it is responsible for poisoning the reaction.
U2 - 10.1006/jcat.1999.2789
DO - 10.1006/jcat.1999.2789
M3 - Article
SN - 0021-9517
VL - 191
SP - 200
EP - 217
JO - Journal of Catalysis
JF - Journal of Catalysis
IS - 1
ER -