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Investigation of S2fl0 Production and Mitigation in Colllpressed SF6-Insulated Power Systellls

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Investigation of S2fl0 Production and Mitigation in Colllpressed SF6-Insulated Power Systellls Investigation of S2Fl0 Production and Mitigation in COlllpressed SF6-Insulated Power Systellls D. R. James (Editor), 1. Sauers, and G. D. Griffin, Oak Ridge National Laboratory, R. J. Van Brunt, J. K. Olthoff, and K. L. Stricklett, National Institute of Standards and Technology, F. Y. Chu, J. R. Robins, and H. D. Morrison, Ontario Hydro ResearchDivision Introduction Information on SF6 by-products such as S2F10 can be used to assess potential cooperative Research and Development Agree- ment (CRADA) has been established to study hazards and define safe gas handling and A the production and mitigation of S2FlO(disulfur operatingprocedures. decafluoride), one of a number of toxic by-products formed in electrical discharges in the insulating gas SF6. The particular concern for S2FlOis due to its highly toxic Voltage Electric Systems (CIGRE) [5] has reviewed the nature, the Ceiling Limit Value being 10parts per billion literature on SF6decomposition and has recommended (ppb, or 1 part in 108)and the need for development of that the International Electrotechnical Commission sensitive detection techniques down to this level. There are a large number of SF6 gas-insulated electric power (1EC)modify or make new standards or guidelines for utility personnel to handle and dispose of the arc by- systems already in service in North America, particu- larly circuit breakers. SF6 is extensively used as an products using the CIGRE document as a basis. Although much is known about SF6by-products and insulation and current interruption medium in power circuit breakers, compressed gas transmission lines and their formation in typical power system environments, various components in substations. Ensuring the safe recent laboratory research funded by DOE at the Oak operation and maintenance of this equipment is an Ridge National Laboratory (ORNL) and the National important issue for utilities, government agencies, and Institute of Standards and Technology (NIST) has indi- manufacturers. cated that, in addition to the already identified by-prod- ucts, S2FlOis formed under discharge conditions. In the presence of an electrical discharge such as an Because of its highly toxic nature, the issue of whether arc, spark, or corona, a portion of the SF6decomposes or not it is present in actual power equipment war- into lower fluorides of sulphur which can react to form ranted initiation of a comprehensive research project. a number of chemically active by-products including SOF2 and S02F2' During the maintenance or repair of Cooperative Research and Development Agreement SF6insulated equipment, the handling of these gaseous (CRADA) on S2FIO as well as solid by-products is a matter of concern because of their toxic nature. Much effort has been spent The possibility that ~FlO could be present in operat- in identifying the species, the quantities, and some of ing equipment was made apparent when it was de- the properties of the by-products formed under labora- tected in a power arc bum through test by Pettinga in tory and practical operating conditions in power sys- 1985 [6]. The detection of S2FlOin spark discharges at tems. The Electric Power Research Institute (EPRI), the ORNL in 1988 [7] provided evidence that this com- U. S. Department of Energy (DOE) and the Canadian pound contributes significantly to the overall toxicity of Electrical Association (CEA) have carried out several spark-decomposed SF6. These studies suggested that research projects to provide information for the estab- ~FlO might be formed under practical discharge condi- lishment of safe handling procedures for decomposed tions of spark and corona as well as power arc condi- SF6 [1-4]. The International Conference on Large High tions. Therefore, to resolve the questions concerning 0883-7554/93/$1.00@1993 IEEEElectrical Insulation Magazine May/June 1993-VoI.9.No.3 29 *"~""' '_'___ '!.. ~~~~"",,,-,,,"~ ; . 0. .. ~FlO in power equipment, a collaborative research ef- Table I. Decomposition products found following fort was formed among ORNL and NIST, each with a repeated sparking in SF6Ci[16] strong background in basic chemical and physical prop- erties of SF6 and its by-products, and Ontario Hydro Product Approximate Concentration Research Division, who along with considerable expe- (% by volume) rience in the area of by-products has the capability to b perform power arc tests and to sample actual field SOF2, (SF4) 0.5 equipment. A CRADA was then initiated at ORNL as a SOF4 0.085 newly authorized mechanism to allow National Labo- ratories to participate in collaborative research with the SiF4 0.085 private sector. A number of private sector and govern- S2FlO 0.026 ment organizations in the U.S. and Canada joined forces to fund the research effort. Collaborative work began S02F2 0.006 unofficially in 1989 and formal DOE approval of the S02 0.002 CRADA was obtained on October 25,1991. HF 1.0c a 16kJ total energy deposited in 70cm3 SF6gas volume at 133kPa Objectives of the CRADA total pressure The broad objective of this study is to provide utili- b SF4 is quickly hydrolyzed to SOF2 C Estimated concentration based on the molar yield from the reaction ties and other interested parties with adequate informa- SF4 + H20 -> SOF2 + 2 HF [17] tion for prudent and safe operation of gas-insulated the CRADA will be discussed in a later section. systems. Specific objectives include: .Develop or improve detection techniques to permit The formation of ~FlO in corona discharges is sensitive detection of S2FlOdown to the ceiling limit thought to proceed by the reaction [12-15]: value (10 ppb). .SFs+ .SFs-> ~FlO (1) 'e Investigate the formation and destruction rates of S2FlOin SF6under are, spark and corona conditions that where .SFsis formed by electron-impact induced frag- simulate practical operating environments. mentation of SF6in the discharge. Stabilization of the . Determine the stability, toxicity, and ther- ~FlO molecule is achieved via collision with a third mal/ chemical properties of ~F10, body to remove excess energy. For spark and arc dis- . Review existing gas-handling procedures, protec- charges, S2FlOformation probably also arises from reac- tive equipment and field sampling techniques, and rec- tion (1), where the reactant SFs radicals are likely to be ommend changes if required. produced by a number of collisional processes. Table I .Disseminate information for safe gas-insulated sys- gives the concentrations of S2FlOand other by-products tems operation and transfer relevant technology. found in SF6 exposed to sparking [16]. The source of The results from the project will enable realistic esti- oxygen for some by-products is the water impurity mates of ~F10 production for different electrical dis- either in the gas or adsorbed on surfaces. charge conditions in practical systems, and suggest new quantitative chemical analysis procedures that could be Physical/chemical Properties of S2FIO employed to assess ~FlO levels in decomposed SF6. Some confusion on the nomenclature for ~FlO may exist since several different names have been used for Background it. The CAS (Chemical Abstract Service) Registry Num- It is well known that in sparks, corona, and arcs SF6 ber provides a unique number for each chemical com- dissociates into reactive fragments that recombine or pound. The CAS Number for S2FlOis 5714-22-7. The react with impurities present to form new species. The name which is least confusing and should probably be compounds formed include not only gaseous sulfur used in the future is disulfur decafluoride, as given in fluorides and sulfur oxyfluorides but also metal fluo- the 1991-2 CRC Handbook of Chemistry and Physics. rides by reactions with electrode materials and spacers. The Material Safety Data Sheets (MSDS) compiled by The known by-products formed are reviewed in the Martin Marietta Energy Systems (ORNL), American papers by Sauers et al. [8], Chu [9], and Van Brunt (10]. Conference of Governmental Industrial Hygienists CIGRE has also recently published a study of handling (ACGIH), and the Occupational Safety and Health Ad- SF6and its decomposition products with extensive ref- ministration (OSHA) all list ~FlO under sulfur pen- erences [5]. The formation and detection of ~FlO are tafluoride (which may incorrectly imply SFs). discussed in a review by Chu, Sauers, and Griffin which Synonyms also listed in the MSDS are sulfur de- covers work through 1988 [11].More recent work under cafluoride, sulfur fluoride, and TL 70. The latter desig- 30 May/June 1993-VoI.9,No.3 IEEEElectrical Insulation Magazine .. .-- Table II. Properties of S2FI0 use proper reference standards or adequate sampling techniques. Detection of S2FlO'especially in a back- Boiling Point 30.1 °C [18,19] 26.7 °C [20,21] ground of SF6 and other impurities such as discharge by-products, is a difficult challenge. Melting Point -52.7°C [18,19,21] A major difficulty in the detection of S2FlOis the fact Specific Gravity 2.08 [20] that it can not easily be distinguished from SF6 using 90.0 kPa @25°C conventional mass spectrometry. A recent paper by Vapor Pressure [18] Olthoff et aI. [32] examines in detail the relative abun- 31.7 kPa @0 ° C [20,21] dances of the common ions in the mass spectra of SF6 and S2FlOformed as a function of electron-impact en- nation may be a typographical error based on the WWII ergy from 20 to 70 eY. At the standard electron energy Chemical Warfare documents [18] which refer to S2FlO of 70 eV, all of the significant ion peaks in the S2FlO spectrum also appear in the SF6spectrum. There is no as compound 1/1120." evidence of the ions S2FlO+or S2F9+ throughout the . Some of the chemical! physical properties of S2FlOare energy range examined and thus these ions can not be given in Table II for reference. used as indicators for S2FlO'However, at an electron It is known that ~FlO is insoluble in water, but soluble impact energy of 20 eY,there is a substantial difference in a variety oforganic solvents (e.g.,acetone) [18,22].~FlO in the ratios of the relative peak intensities for SF2+and does not react with common laboratory strong alkalis or SF3+which is due in part to differences in their appear- acids.
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