N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMA) reactions with NO , OH and Cl: A theoretical study of the kinetics and mechanisms 3
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Date
2016-11-09
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Abstract
Abstract A theoretical study of the kinetics and the mechanism of the hydrogen abstraction by
OH, Cl and NO
radicals from two amides (DMF and DMA) has been investigated. Calculations
were carried out using DFT B3LYP/6-311++G(2d,pd)/CBS-QB3 and transition-state theory. This
work provides the first theoretical determination of the rate coefficients and detailed mechanism for
the reactions of OH, NO
3
radicals and chlorine atoms with DMF/DMA, over a temperature range
273–380 K and at atmospheric pressure. The obtained rate coefficients are in reasonable agreement
with experiments. Results indicate that the mechanism of the Cl and NO
3
reactions with amides
goes preferentially through H-abstraction from (C(O)H) and (C(O)CH
3
3
) groups. Meanwhile the
mechanism of the OH with amides (DMF, DMA) is dominated by H-abstraction from the
N-methyl groups.