IONIC AND FREE RADICAL PROCESSES IN THE RADIOLYSIS OF LIQUID METHYL AND ETHYL IODIDES

Journal Article · Sun Jan 01 04:00:00 EST 1961 · Journal of the American Chemical Society (U.S.)

DOI:https://doi.org/10.1021/ja01462a003· OSTI ID:4117659

Gillis, H A; Williams, Jr, R R; Hamill, W H

Liquid methyl and ethyl iodides were irradiated at room temperature with Co/sup 60/ source at dose rates approximating 10/sup 19/ ev hr-/sup 1/ ml-/sup 1/ in air-free samples with added HI and I/sub 2/. In ethyl iodide, C/sub 4/H/sub 10/ is a small but significant product; G(C/sub 2/H/sub 4/) decreases at HI or I/ sub 2/ concentrations> 10-/sup 2/ M; G(C/sub 2/H/sub 6/) increases at HI concentrations> 10-/sup 2/ M provided I/sub 2//HI approximately 0; G(C/sub 2/H/ sub 6/) decreases at I/sub 2/ concentrations> 10-/sup 2/ M provided HI/I/sub 2/ approximately 0; and G(C/sub 4/H/sub 10/) decreases at HI or I/sub 2/ con centrations>10-/sup 2/ M. In methyl iodide, G(CH/sub 4/) increases at HI concentrations>10-/sup 2/ M and G(C/sub 2/H/sub 6/) decreases at I/sub 2/ or HI concentrations>10-/sup 2/ M. These results indicate that C/sub 2/>i and CH/sub 3/ are involved in diffusion-controlled reactions as 2C/sub 2/H/sub 5/ - C/sub 4/H/ sub 10/; C/sub 2/H/sub 5/ + I - C/sub 2/H/sub 4/ + HI; 2CH/sub 3/ i - C/sub 2/H/ sub 6/, etc. Disposition of radicals favorable to diffusion-controlled reencounters may arise from track effects in general. In particular they would be favored by the pairing of alkyl radicals following charge neutralization of the products of ion-molecule reactions, as CH/sub 3/I/sup +/ + CH/sub 3/I - C/sub 2/H/sub 6/I/sup +/ + I and C/sub 2/H/sub 5/I/sup +/ + C/sub 2/H/sub 5/I - C/sub 4/ H/sub 10/I/sup +/ + I, which were obs erved in the mass spectrometer. The reaction products are qualitatively and quantitatively consistent with electron impact cracking patterns as determined by mass spectrometry. (auth)

• Research Organization: Univ. of Notre Dame, Ind.
• Sponsoring Organization: USDOE
• NSA Number: NSA-15-007369
• OSTI ID: 4117659
• Journal Information: Journal of the American Chemical Society (U.S.), Journal Name: Journal of the American Chemical Society (U.S.) Vol. Vol: 83; ISSN JACSA
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

ALKYL RADICALS
BUTANE
CHEMICAL REACTIONS
CHEMISTRY
COBALT 60
CONFIGURATION
DECOMPOSITION
DIAGRAMS
DOSE RATES
ELECTRON BEAMS
FREE RADICALS
HYDROGEN IODIDES
IODIDES
IODINE
IONS
IRRADIATION
LIQUIDS
MASS SPECTROMETERS
RADIATION DOSES
RADIATIONS
TEMPERATURE