کد مقاله کد نشریه سال انتشار مقاله انگلیسی ترجمه فارسی نسخه تمام متن
6455901 1419765 2016 17 صفحه PDF سفارش دهید دانلود رایگان
عنوان انگلیسی مقاله ISI
Microkinetic analysis of ring opening and decarboxylation of γ-valerolactone over silica alumina
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موضوعات مرتبط
مهندسی و علوم پایه مهندسی شیمی کاتالیزور
پیش نمایش صفحه اول مقاله
Microkinetic analysis of ring opening and decarboxylation of γ-valerolactone over silica alumina
چکیده انگلیسی


- Thermochemical analysis of γ-valerolactone and pentenoic acid interconversion.
- Apparent kinetic trends in γ-valerolactone and pentenoic acid interconversion.
- Apparent kinetic trends in γ-valerolactone and pentenoic acid decarboxylation.
- Reconciliation of apparent kinetic trends with detailed microkinetic model.
- Study provides a framework for analysis of system chemistry over any solid acid.

This study considers the thermochemistry and kinetics of γ-valerolactone and pentenoic acid interconversion as well as the decarboxylation of both molecules over amorphous silica alumina. Through microkinetic analysis, macroscopically observed production rates and product distributions are reconciled with a mechanistic description of all chemistries. Ring opening of γ-valerolactone, cyclization of pentenoic acids, and decarboxylation of either molecule occur in parallel at surface Brønsted sites through a sequence of proton-mediated elementary steps. Conceptually, this is illustrated as proceeding through gas-phase oxonium and carbenium ions that are stabilized through interactions with deprotonated Brønsted sites and/or the solid oxide lattice. This interpretation provides a rigorous thermochemical foundation for detailed microkinetic analysis, which we employ to regress elementary interaction energies and kinetic parameters-moving the field toward a fundamental description of reactivity in acid-catalyzed upgrading of γ-valerolactone.

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ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Catalysis - Volume 344, December 2016, Pages 640-656
نویسندگان
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