The photolysis of azomethane in the presence of HN<sub>3</sub>

Konar, R. S.; Darwent, B. deB.

doi:10.1139/v70-379

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1976

1985

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Cited by 5 publications

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Chapter 2 Metathetical Reactions of Atoms and Radicals

Kerr¹

1976

Selected Elementary Reactions

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Chapter 2 Metathetical Reactions of Atoms and Radicals

Kerr¹

1976

Selected Elementary Reactions

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Reactions of NH Radicals. I. Photolysis of HN3 Vapor at 313 nm

Kodama¹

1983

Bulletin of the Chemical Society of Japan

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Photolysis of HN3 vapor was studied at 313 nm as a function of HN3 and Xe pressures, light intensity, and temperature. The photolysis of hydrazoic acid labeled with 15N was also studied. The quantum yields of N2, H2, and NH4N3 as a product were 4.85, 0.494, and 0.842 at 30 °C and 6.7 kPa of HN3, respectively. The mechanism for the main reactions was postulated as follows: HN3+hν(313 nm)→N2+NH(a1Δ); NH(a1Δ)+HN3→2N2+2H (2); NH(a1Δ)+HN3→N3+NH2 (3); NH(a1Δ)+HN3→N2+N2H2* (4). The rate constant ratios of k3⁄k2=0.746 and k4⁄k2=1.23 were obtained at 30°C. (k3+k4)⁄k2 decrease drastically with rising temperature. Xe is effective for the collisional deactivation, NH(a1Δ)+Xe→NH(X3Σ−)+Xe (15), and k15⁄(k2+k3+k4)=0.187 was obtained at 30 °C.

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

Kodama

1983

Bulletin of the Chemical Society of Japan

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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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The photolysis of azomethane in the presence of HN₃

Cited by 5 publications

References 4 publications

Chapter 2 Metathetical Reactions of Atoms and Radicals

Chapter 2 Metathetical Reactions of Atoms and Radicals

Reactions of NH Radicals. I. Photolysis of HN3 Vapor at 313 nm

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

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The photolysis of azomethane in the presence of HN3

Cited by 5 publications

References 4 publications

Chapter 2 Metathetical Reactions of Atoms and Radicals

Chapter 2 Metathetical Reactions of Atoms and Radicals

Reactions of NH Radicals. I. Photolysis of HN3 Vapor at 313 nm

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

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The photolysis of azomethane in the presence of HN₃