Abstract
Pulsed-laser photolysis of hydrazine (N2H4) in the gas phase has been studied at 222 nm relative to 248 nm. The major primary process in the photolysis is believed to be cleavage of the N-H bond, N2H4 + hv → H + N2H3. Direct measurement of hydrogen atom yield in the experiments by vacuum-uv cw-resonance fluorescence detection of H(2S) showed that the H-atom quantum yield was unity at 296 K. Laser photodissociation of N2H4 is thus used as a "clean" source of H-atoms in excess N2H4 and He buffer gas to study the reaction, H + N2H4 → products; (k1). The pseudo-first-order temporal profiles of [H] decay immediately after the photolysis were determined for a range of different hydrazine concentrations employed in the experiments to calculate the absolute second-order reaction rate coefficient, k1, in the temperature range 222−296 K. The Arrhenius activation energy for the reaction was determined to be 2.3 ± 0.1 kcal mol−1, and the pre-exponential factor to be (7.57 ± 1.55) × 10−12 cm3 molec−1 s−1.
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