Compensation between activation entropy and enthalpy in reactions of aromatic hydrocarbons catalyzed by solid acids

Reaction rates of toluene disproportionation (A) and cumene cracking (B) normalized by the number of Brønsted acid sites were analyzed on aluminosilicates. The activation entropy showed linear and compensatory relationship against the activation enthalpy. The slope of entropy-enthalpy plot was in th...

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Published inCatalysis communications Vol. 102; pp. 103 - 107
Main Authors Nakamura, Koshiro, Mizuta, Ryo, Suganuma, Satoshi, Tsuji, Etsushi, Katada, Naonobu
Format Journal Article
LanguageEnglish
Published Elsevier B.V 01.12.2017
Subjects
Activation enthalpy
Activation entropy
Cumene cracking
Silica-alumina
Toluene disproportionation
Zeolite
Activation entropy
Zeolite
Cumene cracking
Toluene disproportionation
Activation enthalpy
Silica-alumina
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Summary:Reaction rates of toluene disproportionation (A) and cumene cracking (B) normalized by the number of Brønsted acid sites were analyzed on aluminosilicates. The activation entropy showed linear and compensatory relationship against the activation enthalpy. The slope of entropy-enthalpy plot was in the order of (B)>(A)>small alkane cracking, whereas the intercept on the horizontal axis was in the order of propane and isobutane cracking>linear C4–8 alkanes and iso-pentane cracking>(A)>(B). The former is consistent with the bulkiness of reactant, while the latter is consistent with intrinsic difficulty of formation of intermediate cations. [Display omitted] •Kinetic parameters in cumene cracking and toluene disproportionation were analyzed.•The activation entropy showed compensatory relationship against the activation enthalpy.•The slope and intercept of entropy-enthalpy plot was related with nature of reaction.
ISSN:1566-7367
1873-3905
DOI:10.1016/j.catcom.2017.08.033