Mechanistic and kinetics study on the reaction of methylallyl alcohol with Cl: A theoretical study

Abstract

The Cl-initiated degradation mechanism of methylallyl alcohol (MA) has been investigated by performing quantum chemical calculations. The reactants, transition states, intermediates and products are optimized at the MP2/6-311G(d,p) level. A detailed degradation mechanism is presented and discussed in this paper. The possible reactions of MA include two Cl-addition channels and eight H-abstraction reactions. Present results show that Cl-addition reactions are more favorable than H-abstraction processes, and the most energetically favorable pathway is the Cl-addition to the terminal carbon C1 atom. Main products detected in experiments and obtained in our study have been determined. The rate constants of dominant paths over a temperature range of 180–380 K are estimated. The total rate coefficients show a negative temperature dependence, and the Arrhenius equation is fitted as ktotal = (1.81 × 10−11)exp(511.21/T). At 298 K, the atmospheric lifetime of MA with respect to Cl is estimated to be 1.11 days.