87321-27-5Relevant articles and documents
Reactions of NH Radicals. II. Photolysis of HN3 in the Presence of C2H6 at 313 nm
Kodama, Sukeya
, p. 2355 - 2362 (1983)
Photolysis of HN3 vapor with C2H6 was studied at 313 nm and 30 deg 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 + hv(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 deg 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.
Reactions of NH Radicals. V. Photolysis of HN3 in the Presence of C3H8 at 313 nm
Kodama, Sukeya
, p. 2900 - 2910 (2007/10/02)
The photolysis of HN3 vapor in the presence of C3H8 was studied at 313 nm and 30 deg C.The main products were N2, H2, CH4, C2H6, C3H6, NH4N3, CH3NH2*HN3, C2H5NH2*HN3, and n- and i-C3H7NH2*HN3.The quantum yields of these products were measured as a function of the pressure of HN3 or C3H8.The following mechanisms for the main reactions were proposed: HN3 + hν(313 nm) -> N2 + NH(a1Δ); NH(a1Δ) + HN3 -> 2N2 + 2H, NH2 + N3, and N2 + N2H2* (2); NH(a1Δ) + C3H8 -> C3H7NH2*(n- and i-propylamine) (3); NH(a1Δ) + C3H8 -> NH(X3Σ) + C3H8 (4); C3H7NH2* -> CH3 + C2H4NH2 (5); CH4 + C2H4NH (6), C2H4 + CH3NH2 (7), C2H5 + CH2NH2 (8), C2H6 + CH2NH (9), H2 + C3H6NH (10), and NH3 + C3H6 (11); C3H7NH2* + HN3 -> C3H7NH2 + HN3 (12); C3H7NH2* + C3H8 -> C3H7NH2 + C3H8 (13).The rate constant ratios are: k3/k2 = 1.28; k4/k2 = 0.262; k6/k5 = 0.109; k7/k5 = 0.050; k8/k5 = 1.39; k9/k5 = 0.040; k10/k5 = 1.20; k11/k5 = 4.72; k12/k5 = 666 dm3mol-1; k13/k5 = 860 dm3mol-1.The formation ratio of n-C3H7NH2/i-C3H7NH2 was 1.55, regardless of the total pressure.The half-life of 1.78E-10 s for C3H7NH2* was obtained by using the collision theory.The relative and absolute rate constants were compared for the reactions of NH(a1Δ) with CH4, C2H6, and C3H8; it was found that the relative yield for the insertion of NH(a1Δ) into a C-H bond increases with a decrease in the C-H bond dissociation energy.
