title: Kinetics of gas-phase reaction of OH with morpholine: an experimental and theoretical study.
abstract: Kinetics of reaction of OH radical with morpholine, a heterocyclic molecule with both oxygen and nitrogen atoms, has been investigated using laser photolysis-laser-induced fluorescence technique, in the temperature range of 298-363 K. The rate constant at room temperature (k(298)) is (8.0 +/- 0.1) x 10(-11) molecule(-1) cm(3) s(-1). The rate constant decreases with temperature in the range studied, with the approximate dependence given by k(T) = (1.1 +/- 0.1) x 10(-11) exp[(590 +/- 20)/T] cm(3) molecule(-1) s(-1). The rate constants are high compared with those of similar heterocyclic molecules with oxygen atom but comparable to those reported for aliphatic amines. Ab initio molecular orbital calculations show that prereactive complexes, 5-7 kcal mol(-1) lower in energy as compared with the reactants, are formed because of hydrogen bond interaction between OH and the N/O atom of morpholine. The stability of the complex involving the nitrogen atom is found to be more than that involving the oxygen atom. The optimized transition-state structures and energies for the different pathways of hydrogen abstraction from these prereactive complexes explain the observation of negative activation energy.
authors.affiliation: Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai, India 400 085.
authors.forename: Sumana
authors.initials: S
authors.lastname: SenGupta
authors.forename: Yogesh
authors.initials: Y
authors.lastname: Indulkar
authors.forename: Awadhesh
authors.initials: A
authors.lastname: Kumar
authors.forename: Suresh
authors.initials: S
authors.lastname: Dhanya
authors.forename: Prakash Dattatray
authors.initials: PD
authors.lastname: Naik
authors.forename: Parma Nand
authors.initials: PN
authors.lastname: Bajaj