Reactions of NH Radicals. II. Photolysis of HN3 in the Presence of C2H6 at 313 nm

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Abstract
Photolysis of HN3 vapor with C2H6 was studied at 313 nm and 30 °C. The products are N2, H2, CH4, NH4N3, CH3NH2·HN3, C2H5NH2·HN3, CH3N3, and CH3CN. The quantum yields of these products were measured as a function of pressures of HN3 and C2H6, and the light intensity. The following mechanism for the main reactions was proposed: HN3+hν(313 nm)→N2+NH(a1Δ); NH(a1Δ)+HN3→2N2+2H (2a); NH(a1Δ)+HN3→NH2+N3 (2b); NH(a1Δ)+HN3→N2+N2H2* (2c); NH(a1Δ)+C2H6→C2H5NH2* (3); NH(a1Δ)+C2H6→NH(X3Σ−)+C2H6 (4); C2H5NH2*→CH3+CH2NH2 (5); C2H5NH2*→CH3CN+2H2 (6); C2H5NH2*+M→C2H5NH2+M (7). The rate constant ratios at 30 °C are: k3⁄k2=0.334; k4⁄k2=0.217; k6⁄k5=0.038. The values of k7⁄k5 for C2H6, HN3, CO2, and Xe are 36.5, 30.3, 29.0, and 14.5 dm3 mol−1, respectively. The values of k5=9.8×109 s−1, k6=3.7×108 s−1, τ (half life of C2H5NH2*)=6.8×10−11 s, η (collisional deactivation efficiency of C2H5NH2*)=1 for C2H6, HN3, and CO2, and η=0.60 for Xe were obtained by using the collision theory.

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