کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
6308724 1618860 2014 8 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Atmospheric oxidation mechanism of chlorobenzene
ترجمه فارسی عنوان
مکانیزم اکسیداسیون اتمسفر کلربرنزن
موضوعات مرتبط
علوم زیستی و بیوفناوری علوم محیط زیست شیمی زیست محیطی
چکیده انگلیسی
The atmospheric oxidation mechanism of chlorobenzene (CB) initiated by the OH radicals is investigated at M06-2X/6-311++G(2df, 2p) and ROCBS-QB3 levels. The oxidation is initiated by OH addition to the ortho (∼50%), para (∼33%) and meta (∼17%) positions, forming CB-OH adducts as R2, R3, and R4; while the ipso-addition is negligible (∼0.2%). The reactions of the CB-OH adducts with the atmospheric oxygen are further investigated in detail by coupling the unimolecular reaction rate theory calculations with master-equation (RRKM-ME). The CB-OH adducts react with O2 either by irreversible H-abstraction to form chlorophenol and HO2 or by reversible additions to form CB-OH-O2 radicals, which subsequently cyclize to bicyclic radicals. RRKM-ME calculations show that the addition reactions of CB-OH and O2 at the atmospheric pressure are close to but not yet reach their high-pressure-limits. The RRKM-ME simulations predict the yields of 93%, 38%, and 74% for ortho-, meta- and para-chlorophenols from the reactions of O2 with R2, R3 and R4, being lower than their high-pressure-limit yields of 95%, 48%, an 80%, respectively. Overall, the yield of chlorophenols is determined as 72% at the atmospheric pressure.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Chemosphere - Volume 111, September 2014, Pages 537-544
نویسندگان
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