Sulphuryl Fluoride Research Articles

Electrolyte Solvation and Ionic Association: Part IX. Structures and Raman Spectroscopic Characterization of LiFSI Solvates

The bis(fluorosulfonyl)imide anion N(SO2F)2 − (i.e., FSI−) (also referred to as bis(fluorosulfonyl)amide (i.e., FSA−) and imidodi(sulphuryl fluoride)) has attracted tremendous interest in recent years for its utility in both lithium salts and ionic liquids for battery electrolyte applications. To facilitate the understanding of the characteristics of this anion, crystal structures are reported here for the uncoordinated anion in LiFSI-based solvates with cryptand CRYPT-222 and tetraglyme (G4). These crystalline solvates were analyzed by Raman spectroscopy to aid in assigning the Raman bands to the modes of ion coordination found in liquid electrolytes. These structures, as well as a thorough review of other relevant crystallographic data, provide insights into the rather remarkable properties of the FSI− anion with regard to solvate formation and electrolyte properties.

First detection and eradication of a structural infestation by western drywood termite, Incisitermes minor (Hagen) (Isoptera: Kalotermitidae), in Australia

AbstractThe western drywood termite, Incisitermes minor, is one of the most economically damaging termites in the United States of America. Although native to the southwestern USA and northwestern Mexico, it has spread widely across the USA and to other countries including China and Japan. The first structural infestation by I. minor in Australia was detected in the timber roofing of a house in Sydney, NSW, in July 2019. Imported exotic timbers, including Douglas fir from the USA, installed approximately 20 years prior to the detection, were the likely source of the infestation. Measures undertaken to eradicate I. minor were (1) ‘tent’ fumigation of the house with sulphuryl fluoride; (2) trap deployment for termite alates; and (3) delimiting surveillance in nearby homes. No I. minor termites were detected outside the infested premises. The haplotype observed by way of DNA sequencing was similar to those of I. minor specimens collected from Louisiana, USA, and Japan. Given the potential economic impacts of I. minor, should it establish in Australia, along with other drywood termites, especially West Indian drywood termite, Cryptotermes brevis, government biosecurity organisations should devote more resources to the design and implementation of drywood termite management systems for new and existing buildings.

Environmental evaluation of alternative chemicals to methyl bromide for fumigation of quarantine pests in transit

The majority of recent quarantine schedules have relied on methyl bromide fumigation. However, due to the phase-out of this fumigant in January 2005 alternative treatments are needed. Four alternative chemical fumigants were tested for their potential to replace methyl bromide as a control agent for Bemisia tabaci, Liriomyza huidobrensis and Frankliniella occidentalis. Phosphine at 2 g/m3 gave promising results at 15 °C with complete mortality of all insects after 24 h exposure. Sulphuryl fluoride, ethyl formate and acetaldehyde caused severe damage to plant foliage after only 4 h exposure. However, sulphuryl fluoride produced 100 % mortality of L. huidobrensis pupae after only 2 h exposure. In a large scale test using phosphine 2 g/m3 at 15 °C complete mortality of L. huidobrensis eggs and pupae was recorded after a 24 h exposure. However, only 98.5 and 86 % mortality of B. tabaci eggs and F. occidentalis eggs, respectively, was recorded after this treatment. Treatments with phosphine produced no significant detrimental effects on subsequent plant growth. The potential of these chemicals to act as alternatives to methyl bromide as quarantine fumigants is discussed.

Stabilities and properties of ozone–sulphuryl fluoride (O3–SO2F2) complexes:a computational study

MP2, M05-2x and CCSD(T) calculations with aug-cc-pVDZ basis sets were used to analyse the interaction between sulphuryl fluoride (SO2F2) and ozone (O3). Four minima were located on the potential energy surface of SO2F2…O3 complexes at these computational levels. The basis set superposition error-corrected interaction energies were in a range between 3.2 and 7.5 kJ mol− 1 at the MP2/aug-cc-pVDZ computational level. The atoms in molecules theory was also applied to explain the nature of the complexes. The interaction energies were partitioned with the natural energy decomposition analysis showing that the most important attractive term corresponds to the polarisation one.

Quo Vadis the fumigants

Fumigation is the most widely used procedure to control stored product pests to prevent economic and quality losses by providing various application methods and penetration capability into the treated commodity. However, most of the available fumigants have limitations in use due to various reasons. Methyl bromide (MB), according to Montreal Protocol, is scheduled to be phased out worldwide by 2015. Sulphuryl fluoride (SF) is known to have limited efficiency on egg stages of insects. Reportedly, it also contributes to the greenhouse effects, which may jeopardize its future use. Currently, phosphine (PH 3 ) is the most widely used fumigant worldwide due to its low cost and ease of application, though resistance observed in major pest species threatens the continued use of PH 3 . Recent studies in beetles reveal that phosphine resistance is governed through two genes on separate autosomal chromosomes. Research on new fumigants continue to be restricted due to concerns over the adverse effects of fumigant residues in food and the environment that led regulatory agencies to take actions by imposing strict limitations on fumigant registration. On the other hand the phase out of MB and resistance to PH 3 has stimulated significant interest on development of alternatives like modified atmospheres (MAs), thermal disinfestation and irradiation. In Turkey, MAs applications are preferred for the treatment of organic food products and are performed mostly in transportable PVC structures (Cocoons or Volcani Cubes). In museums high nitrogen or SF applications are the only procedures to eradicate structural pests. Under the given constraints of registration of new fumigants, it is anticipated that more attention will be devoted to develop novel alternative treatments that are economically feasible, sustainable, user friendly and environmentally benign. Keywords : Fumigants, Modified atmospheres, Insect resistance, Stored products pests, Fumigant alternatives

Sulfuryl fluoride fumigation of dried fruits and nuts to control various stored product insects

EPPO BulletinVolume 39, Issue 1 p. 29-30 Free Access Sulfuryl fluoride fumigation of dried fruits and nuts to control various stored product insects First published: 11 March 2009 https://doi.org/10.1111/j.1365-2338.2009.02226.x European and Mediterranean Plant Protection Organization Organisation Européenne et Méditerranéenne pour la Protection des Plantes AboutSectionsPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat PM 10/4 (1) Specific scope This standard describes the sulfuryl fluoride fumigation of dried fruits and nuts to control various stored product insects. It is an alternative to the standard PM 10/5 Methyl Bromide fumigation of dried fruits and nuts (previously PM 3/9), which may still be used for critical uses. The use of phosphine fumigation of dried fruits and nuts to control various stored product insects is described in the standard PM 10 (in preparation). Specific approval and amendment First approved 2008-09. Introduction Dried fruits and nuts may be often infested by insect pests which affect the quality of the product by feeding and excrements. Most of the insects listed below are cosmopolitan and their spread should be avoided. Commodities/regulated articles Post-harvest commodities such as dried fruits, e.g. raisins, prunes, apricots, walnuts and pistachios. Pests Stored product insects, beetles e.g. Oryzaephilus surinamensis (ORYZSU), Trogoderma variabile (TROGPA) and others and Lepidoptera pests such as Ephestia kuehniella (EPHEKU) and Plodia interpunctella (PLODIN). Treatment schedule Treatment name: sulfuryl fluoride (F2O2S) fumigation of dried fruits and nuts to control various stored product insects Treatment type: chemical Formulation: fumigant gas, packed as a liquid under pressure Concentration: 99.8% Schedule Mode of action: fumigation Growth stage: Post harvest pest control Number of applications: 1–4 (depends on length of commodity storage) Interval between applications: Not applicable, re-application depends on re-infestation of the commodity. Application rate per treatment under atmospheric pressure Temperature, initial dosage and exposure time without vacuum (under atmospheric pressure) Temperature (°C) Initial dose (g/m3) Exposure time (h) 10–20 50–75 24–48 >20 35–60 24–48 Correct dose and time should be calculated with the Fumiguide Calculator provided by the company selling the product. Waiting period Consumption is allowed after product (sulfuryl fluoride) has completely dissipated. Efficacy of treatment Product recently registered in Austria and Germany. Notes The dose depends on the temperature. CTP for stored product insects should not exceed 1500 g h/m3. Representative fumigation is conducted with a 24-h fumigation at about 25°C. References Derrick MR, Burgess HD, Baker MT & Binni NE (1990) Sulfuryl fluoride (Vikane®): a review of its use as a fumigant. Journal of the American Institute for Conservation 29, 77– 90 http://aic.stanford.edu/jaic/articles/jaic29-01-005.html Kenaga EE (1957) Some biological, chemical and physical properties of sulfuryl fluoride as an insecticidal fumigant. Journal of Economic Entomology 50, 1– 6. Xu G (1998) Development of Sulfuryl fluoride (SO2F2), techniques, and equipment of fumigation, a comprehensive study. Plant quarantine, 12 (1), 38– 46. Xu G, Zhongmei C, Zhao S & Nengzhi Q (1999) The development of sulphuryl fluoride (SO2F2), in China – a brief introduction. Proceedings of the 7th International Working Conference on Stored product Protection, 562– 566. Volume39, Issue1April 2009Pages 29-30 ReferencesRelatedInformation

The atmospheric chemistry of sulphuryl fluoride, SO<sub>2</sub>F<sub>2</sub>

Abstract. The atmospheric chemistry of sulphuryl fluoride, SO2F2, was investigated in a series of laboratory studies. A competitive rate method, using pulsed laser photolysis (PLP) to generate O(1D) coupled to detection of OH by laser induced fluorescence (LIF), was used to determine the overall rate coefficient for the reaction O(1D) + SO2F2 → products (R1) of k1 (220–300 K) = (1.3 ± 0.2) × 10−10 cm3 molecule−1 s−1. Monitoring the O(3P) product (R1a) enabled the contribution (α) of the physical quenching process (in which SO2F2 is not consumed) to be determined as α (225–296 K)=(0.55 ± 0.04). Separate, relative rate measurements at 298 K provided a rate coefficient for reactive loss of O(1D), k1b, of (5.8 ± 0.8) × 10−11 cm3 molecule−1 s−1 in good agreement with the value calculated from (1−α) × k1=(5.9 ± 1.0) × 10−11 cm3 molecule−1 s−1. Upper limits for the rate coefficients for reaction of SO2F2 with OH (R2, using PLP-LIF), and with O3 (R3, static reactor) were determined as k2 (294 K)<1 × 10−15 cm3 molecule−1 s−1 and k3 (294 K)<1 × 10−23 cm3 molecule−1 s−1. In experiments using the wetted-wall flow tube technique, no loss of SO2F2 onto aqueous surfaces was observed, allowing an upper limit for the uptake coefficient of γ(pH 2–12)<1 × 10−7 to be determined. These results indicate that SO2F2 has no significant loss processes in the troposphere, and a very long stratospheric lifetime. Integrated band intensities for SO2F2 infrared absorption features between 6 and 19 μm were obtained, and indicate a significant global warming potential for this molecule. In the course of this work, ambient temperature rate coefficients for the reactions O(1D) with several important atmospheric species were determined. The results (in units of 10−10 cm3 molecule−1 s−1, k(O1D + N2)=(0.33 ± 0.06); k(O1D + N2O)=(1.47 ± 0.2) and k(O1D + H2O)=(1.94 ± 0.5) were in good agreement with other recent determinations.

Estimating Outside Air Concentrations surrounding Fumigated Grain Mills

Fumigation is often performed in grain-milling facilities and warehouses to control unwanted insect pests. Fumigants are typically gases or liquids having a high vapour pressure such that the fumigant permeates throughout the facility. Multiple fumigant field studies using commercial mill structures were performed using sulphuryl fluoride (SF). Internal building concentrations, SF leakage rates, and external air concentrations at specific setback distances from the treated structure were quantified. However, field studies are limited to the parametric combinations of management practices, mill geometry, and meteorological conditions that occurred during the experiment. The use of two existing US Environmental Protection Agency air dispersion models [Building Profile Input Program (BPIP) and the Industrial Source Complex dispersion model (ISCST3)], with custom applications of Visual Basic and Monte Carlo algorithms were employed to calculate different exposure scenarios and to extrapolate external SF air concentrations for parameter ranges not used/observed in the field trials. Different inputs included application rate, application date, application timing, meteorological variability, and parameters quantifying building leakage and aeration processes. Results from the numerical system were validated against observations from three US mill field studies located in Kansas, Texas, and Indiana with excellent agreement (average difference from 32·9% to 42·7%), giving credence that the modelling can expand field observations to other diverse situations where mill fumigation may be used. Sensitive input parameters were allowed to vary by Monte Carlo techniques to quantify parametric uncertainty. It was found that the orientation of wind speed and direction surrounding a fumigated mill can influence external air concentrations due to the effect of neighbouring buildings and silos.

Sulphuryl fluoride fumigation: effect on DNA extraction and amplification from herbarium specimens

SummaryWhitten, W. M., Williams, N. H. & Glover, K. V.: Sulphuryl fluoride fumigation: effect on DNA extraction and amplification from herbarium specimens. – Taxon 48: 507‐510. 1999. – ISSN 0040‐0262.Dried leaf samples were exposed to sulphuryl fluoride (Vikane) during herbarium fumigation. DNA was extracted from fumigated leaf samples and from unfumigated controls. Both fumigated and control samples yielded good quality DNA; DNA amplification yielded similar products from both sets of samples. Vikane does not appear to degrade DNA present in herbarium specimens, and appears to be a non‐destructive fumigant for pest control in herbaria.

Effects of two fumigants and a fungicide formulation on the development of kiln brown stain in radiata pine lumber

Two fumigants (methyl bromide and sulphuryl fluoride) were used to treat freshly sawn radiata pine (Pinus radiata D. Don) lumber and log sections to evaluate their influence on development of kiln brown stain. Both treatments reduced severity of stain when compared with controls. The sulphuryl fluoride treatment was notably better than methyl bromide at the highest fumigant dosage, but levels of overall stain were still considered unacceptable with only 20–30% of lumber having either no or slight stain beneath the surface. Sulphuryl fluoride showed superior penetration into sapwood compared to methyl bromide as determined by a colour assay of parenchyma cell viability. A fungicide formulation which was successful in preventing brown stain in kiln dried eastern white pine was ineffective against kiln brown stain in radiata pine. The results of the present study indicates that the mechanism for kiln brown stain in radiata pine differs from that in eastern white pine.

Mass Spectrometric Study of the Dissociative Ionization of Sulphuryl Fluoride by Monoenergetic Electron Impact. Part I. Heteronuclear Fragment Ions

Mass Spectrometric Study of the Dissociative Ionization of Sulphuryl Fluoride by Monoenergetic Electron Impact. Part I. Heteronuclear Fragment Ions

Mass Spectrometric Study of the Dissociative Ionization of Sulphuryl Fluoride by Monoenergetic Electron Impact. Part I. Heteronuclear Fragment Ions

The dissociative ionization of sulphuryl fluoride (SO2F2) under electron impact has been examined by using a trochoidal electron velocity selector and a magnetic sector mass spectrometer. The ionization efficiency curves of SO2F

Structure of the silver imidodi(sulphuryl fluoride)-benzene solvate AgN(SO 2F) 2·C 6H 6

The structure of the monobenzene solvate of silver imidodi(sulphuryl fluoride), AgN(SO 2F) 2 · C 6H 6, was determined from single crystal X-ray data. The asymmetric unit contains one quarter of the formula unit with the silver and nitrogen atoms lying at the intersection of two mirror planes; the sulphur and one of the oxygen atoms, O(2), lie on the same mirror plane. The remaining substituent at sulphur is in a general position that must be occupied equally by oxygen and fluorine and is designated as O/F (1). The bonding between silver and benzene is of a new type, in which each benzene is symmetrically η 2-coordinated (Ag-C 2.490(7) Å) to each of two silver atoms to give infinite chains parallel to the c axis. A weak C(1)-H(1) ṫ O/F(1) hydrogen bond (C ṫ O/F 3.47 Å) was located, which cross-links these chains in the b direction, and probably accounts for the fact that the more electronegative fluorine atom predominantly occupies the general position.

The Effect of VikaneTm on the Stability of Cellulosic and Ligneous Materials -- Measurement of Deterioration by Chemical and Physical Methods

AbstractVikaneTM (sulphuryl fluoride) is a commercial fumigant[1] which is used for the control of pests in museum collections. This paper summarizes the results obtained through an investigation of the effect of VikaneTM on twenty-five paper and textile samples. Samples chosen were representative of artifacts present in North American collections (cotton, linen, jute, and wood pulp fibres, from 1622 to present).The effect of the fumigation treatment has been evaluated by chemical and physical analyses: (1) Acidity -- surface pH, cold extracted pH, total acid (iodometric titration), (2) Oxidative and Hydrolytic Degradation - viscometric average degree of polymerization, carbonyl content (hydrazone derivatization), (3) and Fumigant Residues (specific ion electrode). Analysis of unfumigated and fumigated samples was carried out before and after accelerated ageing (70°C and 50% relative humidity) in order to estimate the long term stability of fumigated samples.The data obtained show that commercial grade VikaneTM degrades cellulosic and ligneous fibres. A second set of experiments on two fibre types using a new experimental grade of VikaneTM gave significantly less degradation. The presentation of this work will concentrate upon a general scientific interpretation of results.It is anticipated that the conclusions will be applicable to a broad range of artifacts.

The Development of a Research Approach to the Scientific Study of Cellulosic and Ligneous Materials

AbstractThis article presents details of the rationale used in setting up a research project, describes the characterization of the 25 different papers and textiles selected for study, and gives an in-depth discussion of the purpose, advantages, and disadvantages of the 10 different analytical procedures used. The project investigated the effects of a fumigant, sulphuryl fluoride (Vikane), on cellulosic and ligneous materials. The data gathered by this project will be presented at a later date.

The feasibility of detecting partial discharges in metalclad equipment by tunable diode laser spectrometry of SF 6 breakdown products

Passage of electricity through SF 6 under arcing or partial discharge conditions causes decomposition of the SF 6 and the eventual production of breakdown products, two of the principal of which are thionyl fluoride and sulphuryl fluoride. Analysis of samples of SF 6 from the gas-zones of metalclad substations to monitor the build-up of breakdown products could in principle be used to give early warning of the development of a fault in the gas-zone. However, no analytical method is at present available which is capable of measuring the low concentrations of the breakdown products necessary to give adequate warning of a fault. It is estimated that detection of the breakdown products at ppb levels or below in SF 6 would be required. Tunable diode laser spectrometry is one technique which is potentially capable of achieving the sensitivity and selectivity required for breakdown product monitoring. To investigate the possibility of applying the technique, high-resolution spectra of sulphur hexafluoride, thionyl fluoride and sulphuryl fluoride were measured using a Fourier transform spectrometer. It was established that, though the choice is limited by the proximity of SF 6 absorption bands, suitable spectral regions do exist for determination of traces of either of these breakdown products in SF 6, and that detection at ppb levels should be possible. Using recently published data for the production rates of discharge-generated decomposition products of SF 6, it is estimated that this would enable discharge levels as low as 3 pC/cycle to be detected in a gas-zone containing 100 kg of SF 6, assuming that the zone was sampled at 6-monthly intervals. Application of the technique would, however, require that the practice of including canisters of alumina or molecular sieve in the gas-zones be stopped, as both sulphuryl and thionyl fluorides are irreversibly absorbed. Of the two decomposition products, sulphuryl fluoride has a simpler spectrum than thionyl fluoride, with stronger absorption lines. The predicted detection limit for sulphuryl fluoride is therefore lower, and if only one breakdown product were to be monitored, sulphuryl fluoride would be preferable for tunable diode laser measurements even though rather higher concentrations of thionyl fluoride are produced in the discharge.

Reactions of sulphuryl fluoride, sulphuryl chlorofluoride and sulphuryl chloride with amines

The reactions of sulphuryl fluoride, sulphuryl chlorofluoride and sulphuryl chloride with the amines tert-butylamine, benzylamine, piperidine, pyridine and quinoline have been investigated. The primary and secondary amines react with the elimination of hydrogen halides and formation of SN bonds whereas tertiary amines form 1:2 adducts.

Reaction of sulphuryl chlorofluoride with a few metals and metal oxides

Sulphuryl chlorofluoride has no observable reaction with metals and metal oxides at room temperature. Metals like copper, silver, iron, and zinc react with the chlorofluoride in the temperature range 200–400°C. Metal chlorides, metal fluorides and sulphur dioxide are the main products of these reactions. With the corresponding metal oxides, on the other hand, the respective metal sulphates are formed in addition to the metal chlorides and fluorides. In the case of lead and lead oxide, lead chlorofluoride is formed instead of lead chloride and lead fluoride. Sulphuryl fluoride is formed in small quantities in all these reactions by the decomposition of the chlorofluoride. Glass is not attacked by sulphuryl chlorofluoride below 500°C.During the course of our investigations on the reactivity of sulphuryl chlorofluoride, it is observed that sulphuryl chlorofluoride does not react with glass up to 500° C. However, it reacts with metals and metal oxides between 200° to 400° C. The reaction products with metals are the corresponding metal chlorides, metal fluorides and sulphur dioxide. With the oxides, in addition to the metal chlorides and metal fluorides, metal sulphates are formed. The results of these investigations are presented in this communication.

Stepwise bond dissociation energies for the removal of fluorine from thionyl fluoride and sulphuryl fluoride

Detailed energy balance studies of the single-collision chemiluminescent reactions of metastable strontium atoms with thionyl fluoride and sulphuryl fluoride yield the bond dissociation energies: D0⊖(FSO–F) 362 ± 19, D0⊖(SO–F) 337 ± 106, D0⊖(FSO2–F) 379 ± 18, and D0⊖(SO2–F) 229 ± 20 kJ mol–1.

Identification by Raman spectroscopy of various weak oxygen-bridged donor–acceptor adducts of arsenic and antimony pentafluorides; a reversal of the usual Lewis acidities of these pentafluorides towards sulphuryl fluoride

The compounds POF3, SO2, SOF2, and COF2 form 1 : 1 oxygen-bridged adducts with AsF5 and SbF5 as shown from their Raman spectra obtained at various temperatures. The base strength of the donors appears to decrease in the given order. Sulphuryl fluoride behaves as a still weaker base; however, Raman spectra show the formation of an oxygen-bridged 1 : 1 adduct with AsF5, but not SbF5, a reversal of the usual Lewis acidities.