Effects of Rotational, Vibrational, and Translational Energy on the Rate Constants for the Isotope Exchange Reactions of OH(-) + Dsub2 and OD(-) + Hsub2

Abstract

Rate constants for the isotope exchange reactions of OH(-) with D sub 2 and OD(-) with H sub 2 have been measured as a function of average center-of- mass kinetic energy at several temperatures. The reaction of OH(-) with D sub 2 is slightly exothermic, and the rate constant has a negative temperature dependence. The kinetic energy dependences of the rate constants have minima near 0.1 eV. A strong negative dependence on the D sub 2 rotational temperature was found. The reason for this dependence is unclear at present. In contrast, the reaction of OD(-) with H sub 2 is slightly endothermic and shows positive dependences on both temperature and kinetic energy. The negative rotational dependence for the reaction of OD(-) with H sub 2 is not as large as that for OH(-) + D sub 2, presumably because rotational energy can help overcome the endothermicity in the case of OD(-) + H sub 2. Vibrational energy is observed to promote reactivity in both reactions.

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Document Details

Document Type
Technical Report
Publication Date
Feb 15, 1994
Accession Number
ADA277467

Entities

People

  • Albert A Viggiano
  • Robert A. Morris

Organizations

  • Phillips Laboratory

Tags

DTIC Thesaurus Topics

  • Charge Transfer
  • Contrast
  • Curvature
  • Diatomic Molecules
  • Energy
  • Errors
  • Exchange Reactions
  • Flow Rate
  • Ground State
  • Heat Of Activation
  • Isotope Exchange
  • Kinetic Energy
  • Low Temperature
  • Mass Spectrometers
  • Measurement
  • Molecules
  • Potential Energy

Fields of Study

  • Physics

Readers

  • Molecular Photonics/Laser Physics