Gas-phase reactions in plasmas of SF6 with O2 in He

Processes which occur in microwave discharges of dilute mixtures of SF₆ and O₂ in He have been examined using a flow reactor sampled by a mass spectrometer. Two classes of experiments were performed. In the first set of experiments, mixtures containing 6×10¹¹ cm^–3 SF₆, 6×10¹⁶ cm^–3 He, and O₂ in the range (0–3.6)×10¹³ cm^–3 were passed through a 20-W 2450-MHz microwave discharge. The gas mixtures arriving at a sample point downstream from the discharge were examined for SF₆, SF₄, SOF₂, SOF₄, SO₂F₂, SO₂, F, and O. In the second class of experiments, rate coefficients were measured for the reactions of SF₄ with O and O₂ and for the reaction of SF with O. The rate coefficient for the reaction of SF with O was found to be (4.2±1.5)×10^–11 cm^–3 s^–1. SF₄ was found to react so slowly with both oxygen atoms and oxygen molecules that only upper limits could be placed on the rate coefficients for these reactions. These values were 2×10^–14 cm³ s^–1 and 5×10^–15 cm³ s^–1 for reactions with O and O₂ respectively. The observed distribution of products from the discharged mixtures is discussed in terms of the measured rate coefficients.     

Gas-phase reactions of SF5, SF2, and SOF with O(3 P): Their significance in plasma processing

Reactions of both SF₅ and SF₂ with O(³ P) and molecular oxygen have been studied at 295 K in a gas flow reactor sampled by a mass spectrometer. For reactions with O(³ P), rate coefficients of (2.0±0.5)×10^–11 cm³ s^–1 and (10.8±2.0)×10^–11 cm³ s^–1 were obtained for SF₅ and SF₂ respectively. The rate coefficients for reactions with O₂ are orders of magnitude lower, with an estimated upper limit of 5×10^–16 cm³ s^–1 for both SF₅ and SF₂. Reaction of SF₂ with O(³ P) leads to the production of SOF which then reacts with O(³ P) with a rate coefficient of (7.9±2.0)×10^–11 cm³ s^–1. Both SO and SO₂ are products in the reaction sequence initiated by reaction between SF₂ and O(³ P). Although considerable uncertainty exists for the heat of formation of SOF, it appears that SO arises only from reaction between SOF and O atoms which is also the source of SO₂. These results are discussed in terms of a reaction scheme proposed earlier to explain processes occurring during the plasma etching of Si in SF₆/O₂ plasmas. A comparison between the results obtained here and those reported earlier for reactions of both CF₃ and CF₂ with O and O₂ shows that there is a marked similarity in the free radical chemistry which occurs in SF₆/O₂ and CF₄/O₂ plasmas.     

Gas-phase combination reactions of SF4 and SF5 with F in plasmas of SF6

Reactions of both SF₄ and SF₅ with F have been studied at 295 K in a gas-flow reactor sampled by a mass spectrometer. The rate coefficient for the combination reaction of F with SF₄ to produce SF₅ was found to increase from (0.9 to 3.0)×10^–12 cm³ s^–1 when the helium bath gas number density was increased from (2 to 26)×10¹⁶ cm^–3. The values obtained here are three orders of magnitude higher than a recent estimate of the high-pressure value based on the modelling of photochemical studies. The experimental results have been compared with RRKM and master equation calculations in which a simplified Gorin model has been used to determine the structure of the transition state. These calculations show that reasonable agreement can be obtained between the experimental data and the calculation if a small (2 KJ/mol) activation energy is assumed. The rate coefficient for the reaction between SF₅ and F to produce SF₆ was found to be independent of helium bath gas number density within the range given above. The value obtained for the rate coefficient was 9×10^–12 cm³ s^–1 with an uncertainty of a factor of 2. This value is close to that of 1×10^–11 cm³ s^–1 computed from the simplified Gorin model and to the value of 1.7×10^–11 cm³ s^–1 deduced from modelling of photochemical experiments.     

Ozone synthesis in charged particle induced noble gas-oxygen and noble gas-oxygen-sulfur hexafluoride discharges

A series of experimental measurements of ozone concentration produced by irradiation of noble gas (He, Ne, and Ar)-O₂ and noble gas-O₂-SF₆ mixtures with energetic (MeV) helium and lithium ions are reported. Continuous irradiations at dose rates of 10¹⁵–10¹⁷ eV cm ^–3 s ^–1 for a few hundred milliseconds were used. The resulting ozone concentration was found to be nonlinear with dose rate for a given irradiation time. This nonlinearity was effectively reduced by an increase in noble gas pressure. Few mole percent addition of SF₆ generally resulted in an increase in the ozone concentration. This increase was highest for lower noble gas pressures and longer irradiation times. Further SF₆ addition, however, caused a reduction in the ozone concentration. Results are explained by considering the relevant reactions responsible for ozone production and loss.     

Features of sulfur hexafluoride adsorption on carbon adsorbents

The isotherms describing excess adsorption of SF₆ and N₆I₆ on carbon adsorbents with different pore structures were measured at pressures of 0.001—2.4 and 0.0001—0.1 MPa, respectively, and temperatures of 298—408 E. A linear dependence of Henry"s constant on temperature in the lnK—10³/O coordinates was found for all the samples. The specific surface areas of the samples determined by the BET method from the SF₆ adsorption are lower than those derived from benzene adsorption. The most pronounced difference was found for the grafitized carbon black. When SF₆ was adsorbed on supermicroporous carbon AC-71 and on microporous carbons PAC and CMS, a hysteresis was found, which, unlike that on mesoporous carbon adsorbents, is observed in the initial region of the equilibrium pressures.     

By-product formation in spark breakdown of SF6/O2 mixtures

The yields of SOF₄, SO₂F₂, SOF₂, and SO₂ have been measured as a function of O₂ content in SF₆/O₂ mixtures, following spark discharges. All experiments were made at a spark energy of 8.7 J/spark, a total pressure of 133 kPa, and for O₂ additions of 0, 1, 2, 5, 10, and 20% to SF₆. Even for the case of no added O₂, trace amounts of O₂ and H₂O result in the formation of the above by-products. However, addition of O₂ significantly increases the yields of SOF₄ and SO₂F₂, while SOF₂ is only slightly affected. The net yields for SOF₄ and SO₂F₂ formation range from 0.18×10^–9 and 0.64×10^–10 mol·J^–1, respectively, at 1% O₂ content to 10.45×10^–9 and 7.15×10^–10 mol·J^–1, respectively, at 20% O₂ content. The mechanism for SOF₄ production appears to involve SF₄, an important initial product of SF₆, as a precursor. Comparison of the SOF₄ and SO₂F₂ yield from spark discharges (arc and corona) shows that the yields from other discharges (arc and corona) shows that the yields can vary by at least three orders of magnitude, depending on the type of discharge and on other discharge parameters.     

Structures, vibrational frequencies, and electron affinities of SF5On/SF5On (n = 1–3)

The molecular structures, vibrational frequencies, and electron affinities of the SF₅O_n/SF₅O_n⁻ (n = 1–3) species have been examined with four hybrid density functional theory (DFT) methods. The basis set used in this work is of double-ζ plus polarization quality with additional diffuse s- and p-type functions, denoted DZP++. The geometries are fully optimized with each DFT method independently. The SF₅O_n (n = 1–3) species should be potential greenhouse gases. The anion SF₅O₂⁻ with C_s symmetry has a ³A″ electronic state, and the neutral SF₅O₃ with ²A″ electronic state has C_s symmetry. The anions SF₅O₂⁻ and SF₅O₃⁻ should be regarded as SF₅⁻·O₂ and SF₅O⁻·O₂ complexes, respectively. Three different types of the neutral–anion energy separation presented in this work are the adiabatic electron affinity (EA_ad), the vertical electron affinity (EA_vert), and the vertical detachment energy (VDE). The EA_ad values predicted by the B3PW91 method are 5.22 (SF₅O), 4.38 (SF₅O₂), and 3.61 eV (SF₅O₃). Compared with the experimental vibrational frequencies, the BHLYP method overestimates the frequencies, and the other three methods underestimate the frequencies. The bond dissociation energies D_e (SF₅O_n → SF₅O_n−m + O_m) for the neutrals SF₅O_n and D_e (SF₅O_n⁻ → SF₅O_n−m⁻ + O_m and SF₅O_n⁻ → SF₅O_n−m + O_m⁻) for the anions SF₅O_n⁻ are reported.     

Negative ion formation in compounds relevant to SF6 decomposition in electrical discharges

Dissociative and nondissociative electron attachment in the electron impact energy range 0–14 eV are reported for SOF₂ SOF₄, SO₂F₂, SF₄, SO₂, and SiF₄ compounds which can be formed by electrical discharges in SF₆. The electron energy dependences of the mass-identified negative ions were determined in a time-of-flight mass spectrometer. The ions studied include F^– and SOF ₂ ^–* from SOF₂; SOF ₃ ^– and F^– from SOF₄; SO₂F ₂ ^–* , SO₂F^–, F ₂ ^– , and F^– from SO₂F₂; SF ₄ ^–* and F^– from SF₄; O^–, SO^–, and S^– from SO₂; and SiF ₃ ^– and F^– from SiF₄. Thermochemical data have been determined from the threshold energies of some of the fragment negative ions. Lifetimes of the anions SOF ₂ ^–* , SO₂F ₂ ^–* , and SF ₄ ^–* are also reported.     

Preparation of high-permeance MFI membrane with the modified secondary growth method on the macroporous α-alumina tubular support

MFI membrane with high permeance was successfully synthesized on the macroporous (pore size of 3–4 μm) α-Al₂O₃ tubular support with a novel modified secondary growth method. Before the crystallization, the seeded support was wrapped with Teflon tape in order to focalize the growth of crystals in the region of seed layer. The as-synthesized membrane was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and single-gas permeation testing. The results indicated that the as-synthesized membrane had a thickness of 6–8 μm similar to the thickness of the seed layer and exhibited high gas permeance. At room temperature, the permeance of H₂ and the ideal separation factor of H₂/SF₆ reached 1.64 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ and 71, respectively. The permeance of single-gas increased with the increasing of temperature. The ideal separation factors of H₂/i-C₄H₁₀ and H₂/SF₆ decreased with the increasing of temperature from 298 to 473 K. At 473 K, the ideal separation factors of H₂/i-C₄H₁₀ and H₂/SF₆ were 12.16 and 11.08, which were still higher than their Knudsen ratios of 5.39 and 8.54, respectively.     

Kinetics of Sulfur Oxide, Sulfur Fluoride, and Sulfur Oxyfluoride Anions with Ozone

Rate constants and product branching ratios were measured for eleven sulfur oxide, sulfur fluoride, and sulfur oxyfluoride anions reacting with O₃. The SO^– ₂ ion reacts rapidly to form –O^– ₃, SO^– ₃, and e^–. The temperature dependence of the branching ratio shows more reactive detachment and less SO^– ₃ formation at higher temperature. SO^– ₃ reacts with O₃, forming SO^– ₄ at 1/3 to 1/4 of the collisional rate from 200 to 500 K, respectively. At 300 K, SF^– ₆ charge transfers to O₃ at 20% of the collisional rate. F₂SO^– ₂ reacts with O₃ at a few percent of the collision rate, forming both O^– ₃ and FSO^– ₃; The ion F₃SO^– reacts slowly with O₃ to form F₃SO^– ₂. The ions SO^– ₄, SF^– ₅, FSO^– ₂, FSO^– ₃, F₃SO^–, and F₅SO^– are unreactive with O₃. A trend is noted relating the ion reactivity with the coordination of the central sulfur atom, i.e., the number of S–F bonds plus two times the number of S=O bonds. Only ions with a sulfur coordination of 4 or 6 are reactive, although the reaction rate constants are generally small. The reactivity trends appear to be partially explained by spin conservation. These reactions are all sufficiently slow, so O₃ reactions should not play a major role in SF₆/O₂ discharges. All ions studied have been found to be unreactive with O₂.     

Conversion of sulphur dioxide in the atmosphere

Summary Pertinent, previous studies of the oxidation of SO₂ in the atmosphere are briefly reviewed. A project dealing with the conversion in the plume from an oil-fired power station is described in greater detail. Measurements were performed from an aircraft and included continuous registration of NO_x, SO₂ and ozone concentrations. The possibility of using NO_x as an internal tracer is discussed; also the use of the inert tracer SF₆ is treated and a special detector for the continuous registration of SF₆ in relative concentrations down to 10^–6 ppm is described. Preliminary results indicate a half-life for SO₂ in the plume of about half an hour.

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Umsetzung von Schwefeldioxid in der Atmosphäre

Zusammenfassung Einschlägige frühere Studien über die Oxidation von SO₂ in der Atmosphäre werden kurz diskutiert. Ein Projekt zum Studium der Umwandlung im Abrauch eines ölbefeuerten Kraftwerkes wird im Detail beschrieben. Die Messungen wurden mit Hilfe eines Flugzeuges vorgenommen und schließen die kontinuierliche Aufzeichnung von NO_x-, SO₂- und Ozon-Konzentrationen ein. Die Möglichkeit der Verwendung von NO_x als interner Indicator wird diskutiert. Außerdem wird der Gebrauch des inerten Indicators SF₆ behandelt und ein spezieller Detektor für die kontinuierliche Aufzeichnung von SF₆ mit relativen Konzentrationen bis herunter auf 10^–6 ppm beschrieben. Vorläufige Ergebnisse deuten auf eine Halbwertszeit von SO₂ im Abrauch von etwa 30 min hin.

Presented at the 6th Annual Symposium on Recent Advances in the Analytical Chemistry of Pollutants, April 21–23, 1976; Vienna, Austria     

Calculation of thermodynamic properties and transport coefficients for SF6-N2 mixtures in the temperature range 1,000–30,000 K

We have computed the equilibrium composition, the transport coefficients (viscosity, electrical and thermal conductivities), the thermodynamic properties (Gibbs and Helmholtz potentials, entropy, enthalpy, specific heats), and the derived quantities (mass density, sound velocity) for SF₆-N₂ mixtures in conditions relevant to circuit-breaker arcs: temperatures between 1000 and 30,000 K, pressures in the range 1–10 atm. The validity of our computation has been checked by a detailed comparison of our results with those available in the literature concerning pure SF₆ and pure N₂. In SF₆-N₂ mixtures the chemical reactions (dissociation, ionization) have a strong influence on thermal conduction and heat capacities. The effect of SF₆ on the properties of such mixtures is elucidated: in a mixture containing 40% SF₆, the amplitude of the thermal conduction peak appearing around 7500 K is reduced by a factor of 4 relative to that of pure N₂. The influence of pressure on the properties of the plasma between 1 and 10 atm is relatively low.     

Gas-phase reactions in plasmas of SF6 with O2: Reactions of F with SOF2 and SO2 and reactions of O with SOF2

The plasma chemistry of SF₆/O₂ mixtures is particularly complicated because of the large number of possible reactions. Over a wide range of conditions, products including SF₄, SOF₄, SOF₂, and SO₂F₂ can be formed but thre is considerable uncertainty about the major reactions which contribute to the formation of these species. In this work reactions of oxygen atoms with SOF₂ and fluorine atoms with SOF₂ and SO₂ have been studied in order to determine the principal sources of SO₂F₂ in these plasmas. Reactions were studied at 295 K in a gas flow reactor sampled by a mass spectrometer. No reaction could be detected between oxygen atoms and SOF₂, which for the conditions employed, means that the upper limit for the reaction rate coefficient is 1×10^–14 cm³ sec^–1. The reaction of fluorine atoms with SOF₂ was studied with the helium bath gas number density ranging from 3.1×10¹⁶ to 2.0×10¹⁷ cm^–3. Within this range the rate coefficient increased with increasing [He] from (4.1 to 10.8)×10^–14 cm³ sec^–1. SO₂ was found to react with fluorine atoms with a rate coefficient which appeared to be independent of the helium bath gas number density over the range given above. The possibility that this reaction occurred entirely on the walls of the reactor is discussed.     

Aspects of the chemistry of SF6/O2 plasmas

The production ofSOF ₄ initiated by the reaction of F atoms withSOF ₂ has been studied in a gas-flow reactor at 295 K for helium bath gas number densities in the range (3.0–27.0)×10¹⁶ cm^–3. The effect of O atoms on the formation ofSOF ₄ has been analyzed in terms of the competing reactionsSOF ₃+FSOF₄ andSOF ₃+OSO ₂ F ₂+F. This analysis leads to the conclusion that the rate coefficients for these two processes are equal within an uncertainty of about 50%. Furthermore, both experiment and calculations indicate that the rate coefficient for reactions between F atoms andSOF ₃ is close to its high-pressure limit under the conditions employed. The experiments set a lower limit on this rate coefficient of 5×10^–11 cm³ s^–1, while calculations based on unimolecular rate theory suggest that it may be greater than 1×10^–10 cm³ s^–1. These results make it clear that the two reactions shown above cannot explain the relative abundances ofSOF ₄ andSO ₂ F ₂ which are observed inSF ₆/O ₂ plasmas. This suggests thatSF ₂ is a major precursor in the sequence of reactions following the dissociation ofSF ₆.     

Structures, electron affinities, and vibrational frequencies of the mono-, di-substituted SF6 radicals

Optimized molecular structures, electron affinities, and IR-active vibrational frequencies have been predicted using five different hybrid Hartree–Fock/density functional theory (DFT) methods for a series of mono-, di-substituted SF₆ compounds. The basis set used in this work is of double-ζ plus polarization quality with additional diffuse s- and p-type functions, denoted DZP++. These methods have been carefully calibrated [J.C. Rienstra-Kiracofe, G.S. Tschumper, H.F. Schaefer, S. Nandi, G.B. Ellison, Chem. Rev. 102 (2002) 231]. The equilibrium configurations of the anions and are found to be a zigzag geometry with ²A electronic state. Three different types of the neutral-anion energy separation reported in this work are the adiabatic electron affinity (EA_ad), the vertical electron affinity (EA_vert), and the vertical detachment energy (VDE). The most reliable adiabatic electron affinities of the mono-, di-substituted SF₆ compounds obtained at the KMLYP function are 1.48 eV (SF₆), 3.20 eV (SF₅Cl), 3.49 eV (SF₅Br), 1.59 eV (SF₅CF₃), 3.21 eV (CF₃SF₄Cl), 3.59 eV (CF₃SF₄Br), 1.36 eV (CF₃SF₄CH₃), 2.32 eV (CF₃SF₄CF₃), respectively.     

Cluster-assisted decomposition reactions of the molecular anions of SF6 and C7F14

The cluster ions formed by the attachment of dimethylsulfoxide (DMSO) and methanol to the molecular negative ions of C₇F₁₄ and SF₆ have been studied by a pulsed e-beam high pressure mass spectrometer (PHPMS) and by an atmospheric pressure ionization mass spectrometer (APIMS). The free energy change (ΔG°) for the clustering equilibria reaction, M⁻ + S M⁻S, at 35 °C are found to be −7.7 and −7.s kcal/mol for S = DMSO and M⁻ = C₇F⁻₁₄ and SF⁻₆, respectively, and −6.4 and −4.5 kcal/mol for S = methanol and M⁻ = C₇F⁻₁₄ and SF⁻₆, respectively. While the cluster ions formed by DMSO are found to be stable against side reactions, those formed by methanol undergo decomposition processes in which the central core ion is fragmented. At 35 °C, the rate law for the decomposition of the SF⁻₆ (CH₃OH)₁ ion is second-order, involving the M⁻ (CH₃OH)₁ cluster ion and another methanol molecule. While the C₇F⁻₁₄(CH₃OH)₁ ion also decomposes through this second-order process, a competing unimolecular mechanism is also operative at 35 °C. With increases in the PHPMS ion source temperature to 150 °C, the unimolecular decomposition process becomes progressively dominant for both of the M⁻(CH₃OH)₁ cluster ions of C₇F₁₄ and SF₆. Methanol cluster ions of the type M⁻S₂ are not observed under any of the conditions examined here. When methanol or water partial pressures of a few torr or higher are present in the buffer gas of the APIMS ion source, the decomposition reactions are very fast and only the fragment ions produced by these reactions are observed in the electron-capture (EC)-APIMS spectra of C₇F₁₄ and SF₆. Also, in the methanol-containing APIMS ion source, the course of the SF⁻₆ decomposition reaction is altered so that fragment ions of the type F⁻(S)_n dominate the EC-APIMS spectrum of SF₆ at all ion source temperatures. For C₇F₁₄, fragment ions of the type F⁻(S)_n become dominant at lower ion source temperatures. These previously unknown reactions are expected to be important in the analysis of perfluorinated compounds by mass spectrometric methods that utilize ionization by electron capture or negative chemical ionization. The nature of the fragment ions produced in these cluster-assisted reactions may also provide a new source of information concerning the structures of the molecular negative ions of SF₆ and C₇F₁₄.     

Photometrisch-potentiometrische Bestimmung der Hydrolysenkonstanten vonN-Bromverbindungen

The equilibrium concentrations of all reaction products emerging from the hydrolysis ofN-bromo compounds in the presence of bromide and thereby also the hydrolysis constants (K ₁) have been calculated from the absorbance at 392.8 nm, thepH-value and the initial concentrations of theN-bromo compound and the bromide. The following compounds have been investigated:N-bromo-succinimide:K ₁=2.2·10^–6, 1,3-dibromo-5,5-dimethylhydantoin:K ₁=1.7·10^–5,N-bromoacetamide:K ₁=1.8·10^–6,N-bromo-monochloroacetamide: 5.2·10^–6,N-bromo-dichloroacetamide:K ₁=8.9·10^–6 andN-bromo-trichloroacetamide:K ₁=1.8·10^–5. The precision of the method, which is mainly suited for weak hydrolizingN-bromocompounds (K ₁<10^–4) are discussed and the overall error of the calculated values was found to be in the range of ±5–12%. The reactivities in aqueous solution of the most frequently usedN-bromo compounds are compared by means of the calculated HOBr equilibrium concentrations. The differences to be expected on the basis of the latters are at concentrations >10^–5 mol/l rather great, while they can be neglected in very dilute solutions (-10^–6 mol/l).

     

Ion pair formation in alkali-SF6 collisions: Dependence on collisional and vibrational energy

The dependence of ion pair formation in collisions of fast alkali atoms (K, Na and Li) with SF₆ on the initial relative kinetic energy and the internal energy of the target molecule has been studied by the crossed molecular beam method. Using a mass spectrometer we have measured total cross sections for negative ion formation as a function of translational and internal energy. Collision energies ranged from threshold up to 35 eV and SF₆ source temperatures were varied from 300 K to 850 K.By means of an inverse Laplace transform of the measured cross sections, we have determined total specific cross sections for each negative ion depending on the SF₆ vibrational energy and at fixed relative kinetic energy.The relative importance of both collisional and internal energy in promoting the electron transfer process is discussed for the various reaction channels in terms of a collision model. An essential feature of this model is the stretching of the S-F molecular ion bond during the collision. The product show complete relaxation in the threshold region, i.e., vibrational and collisional energy are equivalent: This holds for the SF⁻₆ formation only near threshold and for the SF⁻₅ and F⁻ formation up to about 2 eV above threshold. In the post-threshold region the effect of the internal energy on the cross section dominates over that of the translational energy.From these measurements the adiabatic electron affinity of SF₆ is inferred to be 0.32 ± 0.15 eV, T = 0 K. Some other thermodynamic data are deduced: EA(SF₅) > 2.9 ± 0.1 eV (T = 300 K) and D₀(SF⁻₅-F) = 1.0 ± 0.1 eV.     

Transfer of F− in the reaction of SF 6 − with SOF4: Implications for SOF4 production in corona discharges

The temperature (T) and electric field-to-gas pressure (E/P) dependences of the rate coefficientk for the reaction SF ₆ ^– +SOF₄SOF ₅ ^– +SF₅ have been measured. ForT<270 K,k approaches a constant of 2.1×10^–9 cm³/s, and for 433>T>270 K,k decreases withT according tok (cm³/s)=0.124 exp [–3.3 lnT(K)]. ForE/Pk has a constant value of about 2.5×10^–10 cm³/s, and for 130 V/cm·torr>E/P>60 V/cm·torr, the rate is approximately given byk (cm³/s)7.0×10^–10 exp (–0.022E/P). The measured rate coefficient is used to estimate the influence of this reaction on SOF₄ production from negative, point-plane, glow-type corona discharges in gas mixtures containing SF₆ and at least trace amounts of O₂ and H₂O. A chemical kinetics model of the ion-drift region in the discharge gap is used to fit experimental data on SOF₄ yields assuming that the SF ₆ ^– +SOF₄ reaction is the predominant SOF₄ loss mechanism. It is found that the contribution of this reaction to SOF₄ destruction falls considerably below the estimated maximum effect assuming that SF ₆ ^– is the predominant charge carrier which reacts only with SOF₄. The results of this analysis suggest that SF ₆ ^– is efficiently deactivated by other reactions, and the influence of SF ₆ ^– +SOF₄ on SOF₄ production is not necessarily more significant than that of other slower secondary processes such as gas-phase hydrolysis.     

CEPA calculations on open-shell molecules. V. The vibration frequencies of SF and SCl

Ab initio calculations for the ² ground states of SF and SCl have been performed on Hartree-Fock level and with inclusion of valence shell correlation effects by means of the CI and CEPA approaches. The calculated properties are: Equilibrium distances, vibration frequencies, and dipole moment curves in the vicinity of the respective equilibrium geometries. Our best estimates for the 0 1 infrared absorption frequencies _o for SF and SCl are 786 cm^–1 and 520 cm^–1, respectively, both with an uncertainty of about 10 cm^–1. This confirms a recent experimental value obtained by Willner for SF (791 cm^–1), but indicates that for SCl both experimental values reported previously in the literature (617 cm^–1 and 574 cm^–1) are wrong. The S—F and S—Cl bonds in SF and SCl are very similar to the ones in SF₂ and SCl₂, being essentially single p-bonds in either case. In the analogous oxygen-halogen molecules the situation is different, the O—F and O—Cl bonds in the diatomic radicals OF and OCl have partial double bond character and are much stronger than those in OF₂ and OCl₂ or in HOF and HOCl.