Isotope exchange and collisional association in the reactions of CH3/+/ and its deuterated analogs with H2, HD, and D2.

Details Isotope exchange and collisional association in the reactions of CH3/+/ and its deuterated analogs with H2, HD, and D2. Isotope exchange and collisional association in the reactions of CH3/+/ and its deuterated analogs with H2, HD, and D2.

Aug 1982

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1982jchph..77.1261s&link_type=abstract

Journal of Chemical Physics, vol. 77, Aug. 1, 1982, p. 1261-1268. Research supported by the Science and Engineering Research Co

Physics

Chemical Physics

36

Association Reactions, Deuterium, Hydrogen, Interstellar Chemistry, Methyl Compounds, Molecular Clouds, Gas-Ion Interactions, Ionic Collisions, Isotope Effect, Molecular Interactions, Temperature Effects

Scientific paper

Two types of reaction, characterized by isotope (H/D) exchange and by ion-molecule collisionally stabilized association, are distinguished by a selected ion flow tube apparatus which determined the rate coefficients and product ion distributions at 80, 205, and 295 K for the reactions of CH3(+), CH2D(+), CHD2(+), and CD3(+) with H2, HD, and D2. Both exoergic and endoergic isotope exchange occurred, and more than one product was often observed. From the endoergic and exoergic rate coefficients of some of the reactions, van't Hoff plots are constructed for the derivation of enthalpy and entropy changes. It is noted that association channels occur in parallel with endoergic, but not exoergic, isotope exchange channels. It is suggested that this is due to internal rearrangement of the H and D atoms in the excited intermediate complexes, resulting in adiabatic cooling of the complex when endoergic isotope exchange channels are available.

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