Rate constants for F/sup -/ transfer from SF/sub 6//sup -/ to fluorinated gases and SO/sub 2/. Temperature dependence and implications for electrical discharges in SF/sub 6/

Journal Article · Thu Feb 11 00:00:00 EST 1988 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100314a025· OSTI ID:5417074

Sieck, L W; Van Brunt, R J

The reactivity of SF/sub 6//sup -/ toward SO/sub 2/, SOF/sub 2/, SO/sub 2/F/sub 2/, SOF/sub 4/, SF/sub 4/, and SiF/sub 4/ has been investigated by using the technique of pulsed electron beam high-pressure mass spectrometry. These studies were initiated in order to probe the complex anionic chemistry occurring during electrical discharge in SF/sub 6/. Although no reaction of any type was observed with SOF/sub 2/ and SO/sub 2/F/sub 2/, efficient F/sup -/ transfer of the type SF/sub 6//sup -/ + A ..-->.. AF/sup -/ + SF/sub 5/ was found in all of the other systems including the SO/sub 2/F/sup -/ + SOF/sub 4/ pair, which was studied separately. With the exception of the SF/sub 6//sup -/ + SiF/sub 4/ reaction, all of the pairs exhibited a negative temperature coefficient in that the rate constants for F/sup -/ transfer decreased substantially with increasing temperature. The reaction SF/sub 6//sup -/ + SiF/sub 4/ ..-->.. SiF/sub 5//sup -/ + SF/sub 5/ was found to proceed with a rate constant of (5.6 +/- 0.8) x 10/sup -10/ cm/sup 3//(molecule.s) throughout the temperature range studied (298-510 K), which corresponds to a collision efficiency of unity. The other reactions were found to approach unit collision efficiency only at reduced temperatures (<300 K). The reactions studied were used to provide additional information concerning the gas-phase F/sup -/ affinity scale. Some comments are included concerning the stability of the SF/sub 6//sup -/ x SF/sub 6/ dimer ion, and the implications of all of the present data with respect to mobility measurements in SF/sub 6/ are also discussed.

• Research Organization: National Bureau of Standards, Gaithersburg, MD (USA)
• OSTI ID: 5417074
• Journal Information: J. Phys. Chem.; (United States), Vol. 92:3
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
SULFUR FLUORIDES
CHEMICAL REACTIONS
ELECTRIC DISCHARGES
SULFUR OXIDES
ANIONS
CHEMICAL REACTION KINETICS
ELECTRON BEAMS
EXPERIMENTAL DATA
MASS SPECTROSCOPY
TEMPERATURE DEPENDENCE
BEAMS
CHALCOGENIDES
CHARGED PARTICLES
DATA
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
INFORMATION
IONS
KINETICS
LEPTON BEAMS
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
PARTICLE BEAMS
REACTION KINETICS
SPECTROSCOPY
SULFUR COMPOUNDS
400201* - Chemical &amp; Physicochemical Properties