Deutsch

Es wurden Geschwindigkeitskostanten (in cm³ / (Molekül · s)) für die Reaktionen von OH Radikalen und Cl Atomen mit 1-Butanol, 1-Pentanol, Propionsäuremethylester (MPR), Bernsteinsäuredimethylester (DBE-4), Glutarsäuredimethylester (DBE-5), Adipinsäuredimethylester (DBE-6), Ameisensäurepropionsäureanhydrid (PRFA), Propionsäure (PRA) und Brenztraubensäuremethylester (MPYR) bei 298 K und 1 bar gemessen: k(OH+1-butanol) = (8,28 ± 0,85) 10-12 k(OH+1-pentanol) = (1,11 ± 0,11) 10-12 k(OH+MPR) = (9,29 ± 1,13) 10-13 k(OH+DBE-4) = (1,95 ± 0,27) 10-12 k(OH+DBE-5) = (2,18 ± 0,30) 10-12 k(OH+DBE-6) = (3,73 ± 0,59) 10-12 k(Cl+MPR) = (1,51 ± 0,22) 10-11 k(Cl+DBE-4) = (6,79 ± 0,93) 10-12 k(Cl+DBE-5) = (1,90 ± 0,33) 10-11 k(Cl+DBE-6) = (6,08 ± 0,86) 10-11 k(Cl+PRFA) = (2,89 ± 0,35) 10-12 k(Cl+PRA) = (4,72 ± 0,62) 10-12 k(Cl+MPYR) = (4,99 ± 0,96) 10-13 Die Produktstudien der OH-initiierten Oxidation in Gegenwart von NO ergaben folgende Produkte (molare Ausbeuten) für 1-Butanol: Butyraldehyd (BAL) 0,518 ± 0,071; Propionaldehyd (PAL) 0,234 ± 0,035; Acetaldeyd (AAL) 0,127 ± 0,022; HCHO 0,434 ± 0,024 und 4-Hydroxy-2-butanon 0,050 ± 0,010. Für 1-Pentanol: Valeraldehyd 0,405 ± 0,082; BAL 0,161 ± 0,037; PAL 0,081 ± 0,019; AAL 0,181 ± 0,042 und HCHO 0,251 ± 0,013. Die Produktstudien der Cl-initiierten Oxidation in Gegenwart von NO ergaben folgende Produkten für MPR: PRFA 0,099 ± 0,019; PRA 0,139 ± 0,027; CO 0,132 ± 0,026; MPYR 0,289 ± 0,057; AAL 0,077 ± 0,015; Methoxyformylperoxynitrat 0,083 ± 0,016; Methylglyoxylat 0,111 ± 0,022 and HCHO. Für DBE-4: Ameisensäurebersteinsäureanhydrid 0,341 ± 0,068; Bernsteinsäuremonomethylester 0,447 ± 0,111; CO 0,307 ± 0,061; Dimethyloxalacetat 0,176 ± 0,044 und Methoxyformylperoxynitrat 0,032-0,084.

Relative rate coefficients (in cm³/ (molecule · s) units) were measured, at 298 K and 1 bar, for the gas-phase reactions of OH radicals and Cl atoms with 1-butanol, 1-pentanol, methyl propionate (MPR), dimethyl succinate (DBE-4), dimethyl glutarate (DBE-5), dimethyl adipate (DBE-6), formic propionic anhydride (PRFA), propionic acid (PRA) and methyl pyruvate (MPYR): k(OH+1-butanol) = (8.28 ± 0.85) 10-12 k(OH+1-pentanol) = (1.11 ± 0.11) 10-12 k(OH+MPR) = (9.29 ± 1.13) 10-13 k(OH+DBE-4) = (1.95 ± 0.27) 10-12 k(OH+DBE-5) = (2.18 ± 0.30) 10-12 k(OH+DBE-6) = (3.73 ± 0.59) 10-12 k(Cl+MPR) = (1.51 ± 0.22) 10-11 k(Cl+DBE-4) = (6.79 ± 0.93) 10-12> k(Cl+DBE-5) = (1.90 ± 0.33) 10-11 k(Cl+DBE-6) = (6.08 ± 0.86) 10-11 k(Cl+PRFA) = (2.89 ± 0.35) 10-12 k(Cl+PRA) = (4.72 ± 0.62) 10-12 k(Cl+MPYR) = (4.99 ± 0.96) 10-13 Product studies were performed on the OH initiated oxidation of the two alcohols, in the presence of NO. The products and the molar yield observed for 1-butanol + OH were: butanal 0.518 ± 0.071, propanal 0.234 ± 0.035, ethanal 0.127 ± 0.022, HCHO 0.434 ± 0.024 and 4-hydroxy-2-butanone 0.050 ± 0.010; for 1-pentanol + OH: pentanal 0.405 ± 0.082, butanal 0.161 ± 0.037, propanal 0.081 ± 0.019, ethanal 0.181 ± 0.042 and HCHO 0.251 ± 0.013. Cl atom initiated product studies were performed on methyl propionate and dimethyl succinate, in the presence of NO. The products and the molar yield observed for MPR + Cl were: PRFA 0.099 ± 0.019, PRA 0.139 ± 0.027, CO 0.132 ± 0.026, MPYR 0.289 ± 0.057, ethanal 0.077 ± 0.015, methoxy formyl peroxy nitrate 0.083 ± 0.016, methyl glyoxylate 0.111 ± 0.022 and HCHO; for DBE-4 + Cl: succinic formic anhydride 0.341 ± 0.068, mono-methyl succinate 0.447 ± 0.111, CO 0.307 ± 0.061, dimethyl oxaloacetate 0.176 ± 0.044, and methoxy formyl peroxy nitrate 0.032-0.084.