Autor: |
Lewis TWR; Air Force Research Laboratory, Space Vehicles Directorate, Kirtland Air Force Base, New Mexico 87117, United States., Long BA; Air Force Research Laboratory, Space Vehicles Directorate, Kirtland Air Force Base, New Mexico 87117, United States., Eyet N; Chemistry Department, Saint Anselm College, Manchester, New Hampshire 03102, United States., Shuman NS; Air Force Research Laboratory, Space Vehicles Directorate, Kirtland Air Force Base, New Mexico 87117, United States., Ard SG; Air Force Research Laboratory, Space Vehicles Directorate, Kirtland Air Force Base, New Mexico 87117, United States., Viggiano AA; Air Force Research Laboratory, Space Vehicles Directorate, Kirtland Air Force Base, New Mexico 87117, United States. |
Abstrakt: |
Rate constants and product branching fractions were measured for reactions of Ar + , O 2 + , and NO + with isoprene (2-methyl-1,3-butadiene C 5 H 8 ) as a function of temperature. The rate constants are large (∼2 × 10 -9 cm 3 s -1 ) and increase with temperature, exceeding the ion-dipole/induced dipole capture rate. Adding a hard sphere term to the collision rate provides a more useful upper limit and predicts the positive temperature dependences. Previous kinetic energy-dependent rate constants show a similar trend. NO + reacts only by non-dissociative charge transfer. The more energetic O 2 + reaction has products formed through both non-dissociative and dissociative charge transfer, or possibly through an H atom transfer. The very energetic Ar + has essentially only dissociative products; assumption of statistical behavior in the dissociation reasonably reproduces the product branching fractions. |