Reaction of fluorine atoms with alkyl iodides: a possible observation of the Walden inversion in the gas phase

Journal Article · Wed Dec 14 04:00:00 EST 1983 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00363a046· OSTI ID:6856537

Venkitachalam, T V; Das, P; Bersohn, R

Evidence is presented to show that The Walden Inversion does take place in these gaseous reactions. CO/sub 2/ laser radiation of a mixture of SF/sub 6/ and alkyl iodides at equal pressures dissociated the SF/sup 6/ to F and SF/sup 5/. One ..mu..s later, the alkyl iodides were dissociated by a pulse from a dye laser. The experiment was repeated at 5 Hz. The resulting fluorescence intensities at 304.7 nm and 306.7 nm for I/sup */ atoms and excited I atoms are shown for methyl, ethyl, isopropyl, and tert-butyl iodide. From the relative intensities produced, conclusions can be drawn that a tertiary iodide does not produce any iodine atoms, while a primary iodide produces many more. Tests were performed to show that the iodine atoms were not photodissociated from the alkyl iodide cy the CO/sub 2/ laser or by 2-photon dissociation by the dye laser of the radical products of competing reactions. In the absence of SF/sub 6/, CO/sub 2/ laser pulses did not produce additional I atoms. 1 figure.

• Research Organization: Columbia Univ., New York, NY
• OSTI ID: 6856537
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 105:25; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400104 -- Spectral Procedures-- (-1987)
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500 -- Photochemistry
ATOMS
CARBON DIOXIDE LASERS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMPARATIVE EVALUATIONS
DECOMPOSITION
DYE LASERS
ELEMENTS
EMISSION SPECTROSCOPY
FLUIDS
FLUORESCENCE
FLUORESCENCE SPECTROSCOPY
FLUORIDES
FLUORINATED ALIPHATIC HYDROCARBONS
FLUORINE
FLUORINE COMPOUNDS
GAS LASERS
GASES
HALIDES
HALOGEN COMPOUNDS
HALOGENATED ALIPHATIC HYDROCARBONS
HALOGENS
IODINATED ALIPHATIC HYDROCARBONS
IODINE
LASERS
LIQUID LASERS
LOW PRESSURE
LUMINESCENCE
NONMETALS
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC IODINE COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PRESSURE DEPENDENCE
SPECTROSCOPY
SULFUR COMPOUNDS
SULFUR FLUORIDES
YIELDS