Reactions of NH radicals. 6. Reactions of NH(a/sup 1/. delta. ) with C/sub 2/H/sub 2/ and unimolecular decompositions of C/sub 2/H/sub 3/N*
Photolysis of HN/sub 3/ vapor in the presence of C/sub 2/H/sub 2/ was studied at 313 nm and 303 K. The products were N/sub 2/, H/sub 2/, CH/sub 4/, C/sub 2/H/sub 4/, C/sub 2/H/sub 6/, NH/sub 4/N/sub 3/, C/sub 4/H/sub 5/N/times/HN/sub 3/ (salt of C/sub 4/H/sub 5/N with HN/sub 3/), HCN, CH/sub 3/CN, and polymers. From the quantum yields of these products, measured as a function of the pressure of C/sub 2/H/sub 2/ or HN/sub 3/, the following mechanism for the main reactions was inferred: HN/sub 3/ + hv(313 nM) ..-->.. NH(a/sup 1/..delta..) + N/sub 2/; NH(a/sup 1/..delta..) + HN/sub 3/ ..-->.. 2N/sub 2/ + 2H (2a); NH(a/sup 1/..delta..) + HN/sub 3/ ..-->.. NH/sub 2/ + N/sub 3/ (2b); NH(a/sup 1/..delta..) + HN/sub 3/ ..-->.. N/sub 2/ + N/sub 2/H/sub 2/* (2c); NH(a/sup 1/..delta..) + C/sub 2/H/sub 2/ ..-->.. C/sub 2/H/sub 3/N* (CH/double bond/CH-NH (res) and CH/identical to/C-NH/sub 2/) (3); C/sub 2/H/sub 3/N* ..-->.. CH/sub 3/ + CN (4); C/sub 2/H/sub 3/N* ..-->.. H + C/sub 2/H/sub 2/N (5); C/sub 2/H/sub 3/N* ..-->.. C/sub 2/H + NH/sub 2/ (6). The rate constant ratios at 303 K are k/sub 3//k/sub 2/ = 1.2/sub 0/, k/sub 5//k/sub 4/ = 15/sub 7/, and k/sub 6//k/sub 4/ = 0.82. The efficiency of the insertion to give CH/identical to/C-NH/sub 2/ in reaction 3 was about 0.05 of that of the addition to form CH/double bond/CH-NH (res). The spin relaxation of NH(a/sup 1/..delta..) to NH(..xi../sup 3/..sigma../sup -/) by C/sub 2/H/sub 2/ and the collisional deactivation of C/sub 2/H/sub 3/N* were not found. The rearrangement from CH/double bond/CH-NH (res) to CH/sub 3/NH or CH/sub 3/CN and the unimolecular decomposition rates by the RRKM theory for reactions 4 and 6 were discussed. The relative and absolute rate constants were compared for the reactions of NH(a/sup 1/..delta..) with various reactants.
- Research Organization:
- Univ. of Osaka Prefecture (Japan)
- OSTI ID:
- 5992758
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 92:17
- Country of Publication:
- United States
- Language:
- English
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PHYSICAL AND ANALYTICAL CHEMISTRY
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PHOTOLYSIS
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
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ETHYLENE
EXPERIMENTAL DATA
INFRARED SPECTRA
MATHEMATICAL MODELS
MEDIUM TEMPERATURE
RADICALS
ALKENES
CHEMICAL REACTIONS
DATA
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HYDROCARBONS
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NUMERICAL DATA
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400500* - Photochemistry