Compensation between activation entropy and enthalpy in reactions of aromatic hydrocarbons catalyzed by solid acids
Compensation between activation entropy and enthalpy in reactions of aromatic hydrocarbons catalyzed by solid acids
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固体酸催化芳烃反应活化熵与热函的补偿
DOI：
10.1016/j.catcom.2017.08.033
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
Etsushi Tsuji and Naonobu Katada
中科院分区：
文献类型：
--
作者：
Koshiro Nakamura;Ryo Mizuta;Satoshi Suganuma;Etsushi Tsuji and Naonobu Katada
分析了铝硅酸盐上甲苯净化（A）和枯烯裂解（B）的反应速率，其通过布朗斯台德酸位点的数量进行归一化。活化熵与活化焓呈线性补偿关系。熵-焓图的斜率为（B）>（A）>小分子烷烃裂解，横轴截距为丙烷和异丁烷裂解>直链C4 - 8烷烃和异戊烷裂解>（A）>（B）。前者与反应物的体积一致，而后者与中间体阳离子形成的内在困难一致。
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.