کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
240720 1427929 2007 8 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Oxidation pathways in the reaction of diacetylene with OH radicals
موضوعات مرتبط
مهندسی و علوم پایه مهندسی شیمی مهندسی شیمی (عمومی)
پیش نمایش صفحه اول مقاله
Oxidation pathways in the reaction of diacetylene with OH radicals
چکیده انگلیسی

We present a portion of the potential energy surface of the reaction of diacetylene with OH radicals, calculated using RQCISD(T) and two basis set extrapolation schemes. Based on this surface, we performed calculations of the rate coefficients using an RRKM/master-equation formalism. After a small (1 kcal/mol) adjustment to the energy barrier of the association reaction, our calculated rate coefficients of the high-pressure limit agree very well with previous direct measurements. However, our calculations at high temperatures are considerably smaller than the values inferred in previous studies. The non-Arrhenius behavior and significant pressure dependence of the rate coefficients above 800 K is due to the competition between stabilization, abstraction and addition–elimination channels. At low temperatures, the reaction proceeds mostly to the addition products, as well as to CO and propargyl. Above 1200 K, direct hydrogen abstraction and production of H atoms become important.

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Proceedings of the Combustion Institute - Volume 31, Issue 1, January 2007, Pages 185–192
نویسندگان
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