Hg-sensitized photolysis of diethylamine in the absence and presence of O/sub 2/ or N/sub 2/O
The Hg-sensitized photolysis of diethylamine (DEA) was studied in the absence and presence of O/sub 2/ or N/sub 2/O at room temperature. In the absence of foreign gases, the products were H/sub 2/, CH/sub 3/CH=NC/sub 2/H/sub 5/ and N,N'-diethylbutane-2,3-diamine (III), with respective quantum yields of 1.0, 1.0, and similarly ordered 0.02. Thus CH/sub 3/CHNHC/sub 2/H/sub 5/ radicals are produced exclusively and they are removed by self reaction: 2CH/sub 3/CHNHC/sub 2/H/sub 5/ ..-->.. DEA + CH/sub 3/CH=NC/sub 2/H/sub 5/ (4a) and 2CH/sub 3/CHNHC/sub 2/H/sub 5/ ..-->.. diamine III (4b), with k/sub 4a//k/sub 4b/ = 47.0 +/- 5.6. In the presence of O/sub 2/ the radicals are scavenged exclusively by abstraction of the H atom on the nitrogen to give the imine CH/sub 3/CH=NC/sub 2/H/sub 5/ as the exclusive product: (CH/sub 3/CHNHC/sub 2/H/sub 5/ + O/sub 2/ ..-->.. CH/sub 3/CH=NC/sub 2/H/sub 5/ + HO/sub 2/ (5). The Hg-sensitized photolysis of N/sub 2/O gives O(/sup 3/P) atoms, which in the presence of DEA react to give the imine and (C/sub 2/H/sub 5/)/sub 2/NOH (DEHA) as products in concerted parallel steps: O(/sup 3/P) + (C/sub 2/H/sub 5/)/sub 2/NH ..-->.. CH/sub 3/CH=NC/sub 2/H/sub 5/ + H/sub 2/O (9a) and O(/sup 3/P) + (C/sub 2/H/sub 5/)/sub 2/NH ..-->.. (C/sub 2/H/sub 5/)/sub 2/NOH (9b), with k/sub 9a//k/sub 9b/ similarly ordered 9.5 +/- 1.7.
- Research Organization:
- Pennsylvania State Univ., University Park
- OSTI ID:
- 5240341
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 90:19
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
54 ENVIRONMENTAL SCIENCES
AMINES
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
NITROUS OXIDE
OXYGEN
CHEMICAL REACTION KINETICS
EXPERIMENTAL DATA
MERCURY
CHALCOGENIDES
CHEMICAL REACTIONS
DATA
DECOMPOSITION
ELEMENTS
INFORMATION
KINETICS
METALS
NITROGEN COMPOUNDS
NITROGEN OXIDES
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REACTION KINETICS
400500* - Photochemistry
500200 - Environment
Atmospheric- Chemicals Monitoring & Transport- (-1989)