화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.110, No.9, 3273-3279, 2006
Laser spectroscopic excitation function and reaction threshold studies of the H+DCl -> HCl+D gas-phase isotope exchange reaction
The dynamics of the gas-phase hydrogen atom exchange reaction H + DCI -> HCl + D were studied using the pulsed laser photolysis/laser induced fluorescence "pump-and-probe" method. Laser photolysis of H2S at 222 nm was used to generate nonequilibrium distributions of translationally excited hydrogen atoms at high dilution in a flowing moderator gas (Ar)/reagent (DCl) mixture. H and D atoms were detected with sub-Doppler resolution via Lyman-alpha laser induced fluorescence spectroscopy, which allowed the measurement of the line shapes of the moderated H atom Doppler profiles as well as the concentration of the D atoms produced in the H + DCl -> HCl + D reaction. From the measured H atom Doppler profiles, the time evolution of the initially generated nascent nonequilibrium H atom speed distribution toward its room-temperature thermal equilibrium form was determined. In this way, the excitation function and the reaction threshold (E-0 = 0.65 +/- 0.13 eV) for the H + DCl -> HCl + D reaction could be determined from the measured nonequilibrium D atom formation rates and single collision absolute reaction cross-section values of 0.12 +/- 0.04 angstrom(2) and 0.45 +/- 0.11 angstrom(2) measured at reagent collision energies of 1.0 and 1.4 eV, respectively.