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Impact of Zeolite Structure on Entropic–Enthalpic Contributions to Alkane Monomolecular Cracking: An IR Operando Study
Author(s) -
Kadam Shashikant A.,
Li Haoguang,
Wormsbecher Richard F.,
Travert Arnaud
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201800793
Subject(s) - zeolite , alkane , propane , butane , cracking , enthalpy , adsorption , thermodynamics , chemistry , activation energy , entropy of activation , hydrocarbon , organic chemistry , catalysis , reaction rate constant , kinetics , physics , quantum mechanics
Abstract The monomolecular cracking rates of propane and n ‐butane over MFI, CHA, FER and TON zeolites were determined simultaneously with the coverage of active sites at reaction condition using IR operando spectroscopy. This allowed direct determination of adsorption thermodynamics and intrinsic rate parameters. The results show that the zeolite confinement mediates enthalpy–entropy trade‐offs only at the adsorbed state, leaving the true activation energy insensitive to the zeolite or alkane structure while the activation entropy was found to increase with the confinement. Hence, relative cracking rates of alkanes within zeolite pores are mostly governed by activation entropy.