DOCSLIB.ORG

United States Patent [191 [11] 3,968,155 Gue'rin [451 July 6, 1976

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
United States Patent [191 [11] 3,968,155 Gue'rin [451 July 6, 1976 United States Patent [191 [11] 3,968,155 Gue'rin [451 July 6, 1976 [541 PROCESS FOR PREPARED PERCHLOROMETHYL MERCAPTAN BY Primary Examiner—Lewis Gotts CHLORINATION OF CARBON DISULFIDE Assistant Examiner—D. R. Phillips Attorney, Agent, or Firm—-Pennie & Edmonds [75] Inventor: Jean Guérin, Grenoble, France [73] Assignee: Produits Chimiques Ugine [57] ABSTRACT Kuhlmann, Paris, France Perchloromethyl mercaptan is prepared with about [22] Filed: Apr. 28, 1975 10% saving in raw materials by an improved process [21] Appl. No.: 571,919 comprising (i) chlorinating carbon disul?de in the presence of iodine to produce a ?rst chlorinated li quor, (ii) separating said liquor by distillation into a [30] Foreign Application Priority Data high-boiling fraction of technical-grade per June 21, 1974 France ............................ .. 74.21586 chloromethyl mercaptan and a low-boiling fraction, A, (iii) chlorinating fraction A in the presence of iodine [52] US. Cl. ....................... .. 260/543 H; 260/607 R and absence of any substantial amount of metallic ha [51] Int. Cl.2 .............. .. C07C 145/00; C07C' 149/16 lides to produce a second chlorinated liquor, (iv) sep [58] Field of Search ............. ..'. .............. .;. 260/543 1-1 arating said second liquor by distillation into a high boiling fraction of crude perchloromethyl mercaptan [56] References Cited and a second low-boiling fraction, B, consisting essen UNITED STATES PATENTS tially of sulfur dichloride, and (v)' heating fraction B at about 90°—150°C in presence of a metallic halide to 2,664,442 12/1953 Kamlet .......................... .. 260/543 H form sulfur_monochloride and regenerate chlorine. OTHER PUBLICATIONS Chem. Review vol. 58 pp. 509-512 (1958). 5 Claims, 5 Drawing Figures US. Patent July 6, 1976 Sheet1of2 3,968,155 v IiIilil lllll 1 II I (Tl °°\, >>/ Now_m HWVW IIJII || ON 'WX 1 N9Nowwon I U.S. Patent July 6, 1976 Sheet 2of2 ’ 3,968,155 FIG. 2 35 @ 36 JUL 1 32 i77 33 3,968,155 1 2 In most of the prior processes, the higher boiling PROCESS FOR PREPARED PERCI-ILOROMETI-IYL PCMM and sulfur monochloride are isolated by distil MERCAPTAN BY CHLORINATION OF CARBON lation under reduced pressure being delivered at the DISULFIDE " tail end or foot of the distillation unit while the lower boiling fractions comprising carbon disul?de, sulfur The present invention provides an improved process dichloride and carbon tetrachloride are delivered at the for preparing perchloromethyl mercaptan by chlorina head of the distillation unit and are then transformed tion of carbon disul?de. Perchloromethyl mercaptan, into a mixture of carbon tetrachloride and sulfur mono CCl3SCl, hereinafter abbreviated as PCMM, is known chloride by chlorination according to the overall equa also as trichloromethanesulfenyl chloride. Reduction tion VI, using a metallic chloride as catalyst: of PCMM with stannous chloride or tin and hydrochlo 2.5 SCI; + 0.5 CS2 + 0.25 Clz -> 0.5 CCL, + l.75 ric acid produces thiophosgene or thiocarbonyl chlor SQCIL, (VI) ide CSCI2. Both thiophosgene and PCMM itself are commercially useful as raw materials in the production of many organic sulfur compounds. See KIRIQ SUMMARY OF THE INVENTION OTHMER, ENCYCLOPEDIA OF CHEMICAL Present inventor has now surprisingly established TECHNOLOGY, Second Edition, Volume 4, page 372 that if the above mentioned chlorination of the low (1964); and, for example, US. Pat. Nos. 2,553,771; boiling fraction is, in contrast to the usual practice, 2,653,155; and 2,713,058. 20 carried out in the substantially complete absence of such metallic halide catalyst but in the presence, in BACKGROUND OF THE INVENTION stead, of iodine, the’ chlorine action takes place accord According to the known procedures, PCMM is pro ing to the overall equation (VII) with the formation of duced by chlorination of carbon disul?de in the pres a mixture of PCMM, sulfur monochloride and sulfur ence of small quantities of iodine, about 0.005 to 2% 25 dichloride: ' (based on weight of carbon disul?de) as catalyst, ac 2.5 sci2 + 0.5 cs2 + 1.4 cl2 -» 0.5 CCI,,SC] + 0.1 cording to the overall reaction I: $2012 + 2.8 sci2 _ > (vn) Present inventor has furthermore ascertained that 30 when the (second) liquor, chlorinated according to This reaction theoretically consumes 409 g of carbon equation VII is submitted to distillation under reduced disul?de and 1.145 grams of chlorine per kilogram of pressure i.e., between 50 to 400 torrs, two fractions can PCMM formed, corresponding to a molar ratio Cl2/CS2 be separated, one being crude PCMM containing about equal to 3.0. However, in industrial practice the chlo 10-15% sulfur monochloride, the other being very rich rine is charged in an amount considerably smaller than 35 in sulfur dichloride but substantially free of carbon theoretical, the molar ratio Cl2/CS2 scarcely exceeding disul?de; and that this (“second”) low-boiling fraction 2.50 in order not to risk destruction of part of the (i.e., coming from the “second” distillation) decome‘ formed PCMM in the following well-known side reac poses in the presence of a metallic chloride like molyb ' tions: denum pentachloride at about 90°—l50°C to form sul- ' 40 fur monochloride and regenerate chlorine. A combina CCl_-,SCI + Clz -> CCI. + SCIZ (II) tion of these steps in succession has been found to effect an overall saving of about 10% in the raw materi CCIQSCI + $02 -> CCI, + 82C!2 (III) als required to make a given total weight of technical grade PCMM. Simultaneously reation (IV), forming carbon tetrachlo Brie?y stated, the present invention is an improved ride directly by the action of chlorine and carbon disul process for preparing perchloromethyl mercaptan ?de, can take place, particularly in the presence of light which comprises (i) chlorinating carbon disul?de in the and traces of metallic chlorides: presence of iodine to produce a ?rst chlorinated liquor, (ii) separating said liquor by distillation into a high cs2 + sci2 -> cc], + szcl2 (iv) 50 boiling fraction of technical grade perchloromethyl The extent of this reaction corresponds to at least 5% mercaptan and a low-boiling fraction, A, (iii) chlorinat of the charged carbon disul?de. After separating the ing fraction A in the presence of iodine and absence of low-boiling products by distillation (preferably at re any substantial amount of metallic halides to produce a second chlorinated liquor, (iv) separating said second duced pressure), a minimum of 1.5% of sulfur mono liquor by distillation into a high-boiling fraction of chloride remains, being difficult to remove because-its crude perchloromethyl mercaptan and a second low boiling point (138°C) is so close to that of PCMM boiling fraction, B, comprising sulfur dichloride and (v) (148°C.) heating fraction B at about 90°—l50°C in presence of a In practice, then, equation V represents the overall metallic halide (about 0.5 to 10% of molybdenum pen reaction which takes place with at best 95% yield based 60 tachloride, or ferric chloride, or tungsten chloride...) to on carbon disul?de charged: form sulfur monochloride and regenerate chlorine. This invention also provides for optional steps of acs2 + 7.5012 -> 2.5 cc], — SCI + 2.5 scl2 + 0.5 ‘ CS, (V) processing the crude perchloromethyl mercaptan. Ac cording to one embodiment of the invention, the crude Under these conditions, the consumption of reactants 65 PCMM obtained in step (iv) above is reintroduced into is raised from theoretical to at least 508 grams of car the distillation of step (ii). According to an alternative bon disul?de and 1.188 grams of chlorine per kilogram embodiment of the overall process, the crude PCMM of technical grade of PCMM, 98.5% pure. I from step (iv) is separately puri?ed by chlorination 3,968,155 3 4 under pressure lower than one bar in the presence of ing large capacity, it is advantageous to set up the pro about 100 to 2000 ppm of iodine, based on weight of cess continuously, carrying out in successive steps a PCMM. The sulfur dichloride thus formed is then elim multistage chlorination of carbon disul?de, a distilla inated by distillation to produce a high-purity technical tion under reduced pressure drawing off the technical grade of PCMM containing about 96% to 99% by grade PCMM obtained, the chlorination of the head weight of pure PCMM. ‘ fraction i.e. low-boiling‘ fraction followed by separation by distillation under reduced pressure of 'the PCMM DETAILED DESCRIPTION obtained in this chlorination and recycling this PCMM Thus, the instant invention relates to an improvement in the ?rst distillation column from the second head in the conventional method of preparing PCMM by 0 fraction, and decomposing by heat of the SCl2 in this iodine-catalyzed chlorination of carbon disul?de and second head-fraction with recovery of chlorine and separating the formed PCMM by distilling off a low reintroduction of said chlorine into the ?rst cycle of boiling fraction. In the conventional method, the low chlorination and formation of sulfur monochloride boiling fraction is chlorinated over a metallic chloride S2Cl2. ' catalyst to produce carbon tetrachloride and sulfur The following examples illustrate modi?cations of monochloride. In the improvement of the instant inven the present invention in non-limiting fashion, using tion, metallic chlorides are avoided and the same low equipment described schematically in FIGS. 1 and 2. boiling fraction is chlorinated in the presence of iodine The equipment of FIG. 1 includes three tubular chlo to produce more PCMM. The distillation of this second rinators l, 2 and 3, provided with cooling jackets and a chlorinated product then yields a crude PCMM and a 20 “ripener” or ?nishing-off reactor 4 for the purpose of second low-boiling fraction containing sulfur dichlo effecting the reaction of some 3 or ‘4% with CS2 which ride which is then converted to a sulfur monochloride has not reacted in the three chlorinators as well as by-product and to chlorine which is recycled in the effecting the reaction of SCl2-on the residual CS2 in treatment of fresh carbon disul?de.
Load more

Recommended publications
  • Industry Compliance Programme
    Global Chemical Industry Compliance Programme GC-ICP Chemical Weapons Convention December 2006 Version 1.0 GLOBAL CHEMICAL INDUSTRY COMPLIANCE PROGRAMME FOR IMPLEMENTING THE CHEMICAL WEAPONS CONVENTION The purpose of the handbook is to provide guidance to chemical facilities, traders and trading companies in developing a Global Chemical Industry Compliance Programme (GC-ICP) to comply with the Chemical Weapons Convention (CWC). The GC-ICP focuses first on determining if there is a reporting requirement to your National Authority and second on collecting the relevant support data used to complete the required reports. The GC-ICP is designed to provide a methodology to comply with the CWC and establish systems that facilitate and demonstrate such compliance. Each facility/company should also ensure that it follows its country’s CWC specific laws, regulations and reporting requirements. • Sections 2, 3, and 4 guide you through the process of determining if chemicals at your facility/ company should be reported to your National Authority for compliance with the CWC. • Section 5 provides recommended guidance on information that you may use to determine your reporting requirements under the CWC and administrative tools that your facility/company may use to ensure compliance with the CWC. • Section 6 provides a glossary of terms and associated acronyms. • Section 7 provides a listing of all National Authorities by country. CWC Global Chemical Industry Compliance Programme 1 TABLE OF CONTENTS Section 1 Overview What is the Chemical Weapons Convention?
    [Show full text]
  • New Compositions Containing Carbon and Sulfur
    71 New Compositions Containing Carbon and Sulfur Collin Galloway Final Seminar March 30, 1994 Because binary phases are particularly fundamental to chemistry and materials sci­ ence, most have been rather heavily studied, especially those that might afford molecular species. Nonetheless, compositions of the type CnSm have been overlooked and remain a promising source of new binary molecular and polymeric materials [l]. The known molecu­ lar architectures based on carbon and sulfur are quite varied although they are constructed from only C=C, C=S, and S-S bonds [2]. Using the zinc salt (NBu4)2[Zn(a-C3S5)2], pure [C3Ss]n was prepared via its oxida­ tion with sulfuryl chloride [3]. Raman and reactivity studies indicate that [C3S sln is probably polymeric although it can be converted to the dimer C6S 10 by treatment with CS2 [4]. s SAS / SIS~ s ... s~s s s>= H s=< s ~ sI +s s+n Treatment of the above [Zn(a-C3S5)2]2- with HCl gave the dithiol, C3S5H2. Like cis­ dimercaptoethylene [5], this alkene dithiol is unstable with respect to loss of H2S. Thermoly­ sis of the dithiol afforded the new binary carbon sulfide C6S8 as an insoluble red-brown powder. Both C6S 10 and C6S8 were converted to dicarbonyl derivatives through an Hg2+ pro­ moted 0 for S exchange of the thiocarbonyl groups. For C6S10, this reaction was accompa­ nied by a skeletal rearrangement of the central l,2,5,6-S4C4 ring to a 1,2,3,6 isomer as shown by single crystal X-ray diffraction. When a mixture of the previously reported [6] carbon sulfides C6S12 and C6Ss was subjected to the same 0 for S exchange conditions, only the compound C3S70 was isolated.
    [Show full text]
  • Conflict by the Numbers: the Story of Conflict Through Mathematics
    CHAPTER∏ 1 CONFLICT BY THE NUMBERS: THE STORY OF CONFLICT THROUGH MATHEMATICS Conflict is part of our everyday lives. It is everywhere. When people think of the word conflict, they often think of war. War is indeed a conflict, but it isn’t the only one. Conflicts range from person vs. self to society vs. society. Conflict could be destructive, but it can also be positive. Math and science are subjects that usually have a right or wrong answer. They aren’t anything like English or history where everything is elaborate. Math and science are concise, but they can like history or English, tell stories. Math and science are able to prove theories, make sense out of things and create evidence that can help to tell a story of conflict. ∏SECTION 1 History/Background of Mustard Gas History Uses Mustard gas was possibly discovered first by Cesar-Mansuete Despretez in Mustard gas was used in chemical warfare. It was used as a weapon by 1822. Despretez, however described the reaction of sulfur dichloride and dispensing it into the air as a vapor. It causes ill effects and it is an ethylene, but never described the harmful affects mustard gas has, therefore incapacitating agent. this discovery is not certain. This situation repeated itself in 1854, when Alfred Symptoms Riche didn’t describe the affects of mustard gas, making his Skin: redness and itching of the skin may occur 2 to 48 hours after exposure discovery doubtful as well. and change eventually to yellow blistering of the skin. However in 1860, Frederick Eyes: irritation, pain, swelling, and tearing may occur within 3 to12 hours of a Guthrie noted the irritating mild to moderate exposure.
    [Show full text]
  • Reactions of Sulfur-Dicyanide and Sulfur-Dichlorides with Transition Metal Complexes." (1974)
    Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1974 Reactions of Sulfur-Dicyanide and Sulfur- Dichlorides With Transition Metal Complexes. Diane Singleton Hamilton Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Hamilton, Diane Singleton, "Reactions of Sulfur-Dicyanide and Sulfur-Dichlorides With Transition Metal Complexes." (1974). LSU Historical Dissertations and Theses. 2730. https://digitalcommons.lsu.edu/gradschool_disstheses/2730 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. INFORMATION TO USERS This material was produced from a microfilm copy of the original document. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the original submitted. The following explanation of techniques is provided to help you understand markings or patterns which may appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting thru an image and duplicating adjacent pages to insure you complete continuity. 2. When an image on the film is obliterated with a large round black mark, it is an indication that the photographer suspected that the copy may have moved during exposure and thus cause a blurred image.
    [Show full text]
  • Arsenic and Old Mustard: Chemical Problems in the Destruction of Old Arsenical and 'Mustard' Munitions NATO ASI Series Advanced Science Institute Series
    Arsenic and Old Mustard: Chemical Problems in the Destruction of Old Arsenical and 'Mustard' Munitions NATO ASI Series Advanced Science Institute Series A Series presenting the results of activities sponsored by the NATO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities. The Series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division A Life Sciences Plenum Publishing Corporation B Physics London and New York C Mathematical and Physical Sciences Kluwer Academic Publishers D Behavioural and Social Sciences Dordrecht, Boston and London E Applied Sciences F Computer and Systems Sciences Springer-Verlag G Ecological Sciences Berlin, Heidelberg, New York, London, H Cell Biology Paris and Tokyo I Global Environment Change PARTNERSHIP SUB-SERIES 1. Disarmament Technologies Kluwer Academic Publishers 2. Environment Springer-Verlag / Kluwer Academic Publishers 3. High Technology Kluwer Academic Publishers 4. Science and Technology Policy Kluwer Academic Publishers 5. Computer Networking Kluwer Academic Publishers The Partnership Sub-Series incorporates activities undertaken in collaboration with NATO's Cooperation Partners, the countries of the CIS and Central and Eastern Europe, in Priority Areas of concern to those countries. NATO-PCO-DATA BASE The electronic index to the NATO ASI Series provides full bibliographical references (with keywords and/or abstracts) to about 50,000 contributions from international scientists published in all sections of the NATO ASI Series. Access to the NATO-PCO-DATA BASE is possible via a CD-ROM "NATO Science and Technology Disk" with user-friendly retrieval software in English, French, and German (©WTV GmbH and DATAWARE Technologies, Inc.
    [Show full text]
  • UNITED Sures PATENT“ OFFICE
    Patented Feb. 16,1954 " . 2,669,587 UNITED sures PATENT“ OFFICE PROCESS OF MAKING BIS (BETA CHLOR~ ETHYL) SULFIDE George E. Miller, Edgewood Arsenal, Edgar M. Faber, Baltimore, and Arthur-7M.- Reeves, Havre de Grace, Md, assignors» to the 'United'states of‘ Americaas represented by the Secretary of War - No Drawing. Application June 19, 1937, serial No. 149,233 6 Claims. (Cl. 260--609) (Granted under Title 35, U. 8. Code (1952), see. 266) l a The invention described herein may be manu- not limitedto the precise details herein set forth factured and used by or for the Government for by way of illustration, governmental purposes, without the payment to Theoretically, the formation .of his (beta chlor them of any royalty thereon. ethyl) sul?de from. ethylene and sulfur dichlor This invention relates to an improved process 5 ide is. the ideal method. However, the strong for the manufacture of bis (beta chlorethyl) sul- tendency of the sulfur dichloride to chlorinate ?de commonly known as mustard gas. the mustard gas had not been overcome prior Mustard gas, which is to our invention. These reactions may be ex 610E201}, pressed by the following. equations: 5 1° . ClOHiQEi CICHZCQ modem + set =- ‘5' was used during the World War as a war gas, (31032611! and was manufactured for the German army by women, CICHZCIOH reacting ethylene ch'lorhydrin with sodium sul- 15 g S l _ s S HG] ?de, with subsequent treatment with hydro- ‘ + C “ _ ‘I’ + chloric acid. Later developments showed that 0101520112 0101120112 mustard gas could be produced by the action of Prior to the present invention, sulfur dichlor ethylene upon sulfur monochloride.
    [Show full text]
  • National Chemicals Registers and Inventories: Benefits and Approaches to Development ABSTRACT
    The WHO Regional Oce for Europe The World Health Organization (WHO) is a specialized agency of the United Nations created in 1948 with the primary responsibility for international health matters each with its own programme geared to the particular health conditions of the countries it serves. Member States Albania Andorra Armenia Austria Azerbaijan Belarus Belgium Bosnia and Herzegovina National chemicals Bulgaria Croatia Cyprus registers and inventories: Czechia Denmark Estonia Finland benefits and approaches France Georgia Germany to development Greece Hungary Iceland Ireland Israel Italy Kazakhstan Kyrgyzstan Latvia Lithuania Luxembourg Malta Monaco Montenegro Netherlands Norway Poland Portugal Republic of Moldova Romania Russian Federation San Marino Serbia Slovakia Slovenia Spain Sweden Switzerland Tajikistan The former Yugoslav Republic of Macedonia Turkey Turkmenistan Ukraine UN City, Marmorvej 51, DK-2100 Copenhagen Ø, Denmark United Kingdom Tel.: +45 45 33 70 00 Fax: +45 45 33 70 01 Uzbekistan E-mail: [email protected] Website: www.euro.who.int ACKNOWLEDGEMENT The project “Development of legislative and operational framework for collection and sharing of information on hazardous chemicals in Georgia “ (2015-2017) was funded by the German Federal Environment Ministry’s Advisory Assistance Programme for environmental protection in the countries of central and eastern Europe, the Caucasus and central Asia and other countries neighbouring the European Union. It was supervised by the German Environment Agency. The responsibility
    [Show full text]
  • Federal Register/Vol. 64, No. 95/Tuesday, May 18, 1999/Rules
    27138 Federal Register / Vol. 64, No. 95 / Tuesday, May 18, 1999 / Rules and Regulations DEPARTMENT OF COMMERCE ADDRESSES: Written comments should families of chemicals. The United States be sent to Nancy Crowe, Regulatory is a participant in the Australia Group Bureau of Export Administration Policy Division, Bureau of Export (AG), a 30-nation multilateral chemical Administration, Room 2705, 14th Street and biological weapons non- 15 CFR Parts 734, 736, 738, 740, 742, and Pennsylvania Ave., NW, proliferation regime. All AG 745, 748, 758, 772 and 774 Washington, DC 20230. participants have national export [Docket No. 990416098±9098±01] FOR FURTHER INFORMATION CONTACT: controls on 54 precursor chemicals, Nancy Crowe, Regulatory Policy some of which are listed on the CWC RIN 0694±AB67 Division, Bureau of Export Schedules, and on chemical-related Implementation of the Chemical Administration, at (202) 482±2440. production equipment. Two Schedule 1 Weapons Convention; Revisions to the SUPPLEMENTARY INFORMATION: toxins, ricin and saxitoxin, are subject to Export Administration Regulations the EAR, are listed in Export Control Background Classification Number (ECCN) 1C351 on AGENCY: Bureau of Export As a party to the Convention on the the Commerce Control List (CCL), and Administration, Commerce. Prohibition of the Development, currently require a license for chemical ACTION: Interim rule. Production, Stockpiling, and Use of and biological (CB) non-proliferation Chemical Weapons and on Their reasons for export to all destinations SUMMARY: On
    [Show full text]
  • Chemical Resistance of SIGRATHERM® Foil and Sheets
    Chemical resistance of SIGRATHERM® foil and sheets This technical information is valid for SIGRATHERM flexible graphite foil and sheets, including SIGRATHERM L (lightweight graphite board), which are ● manufactured from expanded natural graphite ● free from additives, e.g. PCM's (Phase Change Material). Chemical properties Graphite is insoluble and infusible. It counts as one of the most chemically resistant materials. Organic chemistry Graphite is resistant to virtually all media in the field of organic chemistry. These typically include, for example, the intermedi- ate and/or final products of the following industries: ● Petrochemistry ● Coal conversion ● Synthetics ● Varnish and paint ● Cosmetics ● Food and stimulants industry ● Photochemicals ● Cooling agents ● Anti-freezing agents Inorganic chemistry Graphite is resistant to almost all inorganic media as well, for example to many acids and bases, as well as probably all ↑ SIGRATHERM flexible graphite foil aqueous salt solutions and to most technical gases. The following media resistance list shall provide an overview. individual cases. It should be noted, that mixtures can be For media which are not included it is generally advised to partly more critical than pure media or vice versa. confer with SGL Carbon. Four different cases can be distinguished: 1. resistant The resistance data apply to operating temperatures of the 2. not resistant medium mentioned which are known to us. However for media 3. limited resistance being operated at above 400 °C or 752 °F, we generally ask for 4. insufficient data – consultation. The third case depends on the stability of operation, operating The information is based on experience, laboratory tests and is temperatures or the concentration.
    [Show full text]
  • The Use of Sulfur Chloride Systems in the Digestion and Purification of Zircaloy Nuclear Fuel Cladding
    University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Masters Theses Graduate School 8-2019 The Use of Sulfur Chloride Systems in the Digestion and Purification of Zircaloy Nuclear Fuel Cladding Jordan Travis University of Tennessee, [email protected] Follow this and additional works at: https://trace.tennessee.edu/utk_gradthes Recommended Citation Travis, Jordan, "The Use of Sulfur Chloride Systems in the Digestion and Purification of Zircaloy Nuclear Fuel Cladding. " Master's Thesis, University of Tennessee, 2019. https://trace.tennessee.edu/utk_gradthes/5502 This Thesis is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Masters Theses by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a thesis written by Jordan Travis entitled "The Use of Sulfur Chloride Systems in the Digestion and Purification of Zircaloy Nuclear Fuel Cladding." I have examined the final electronic copy of this thesis for form and content and recommend that it be accepted in partial fulfillment of the equirr ements for the degree of Master of Science, with a major in Chemistry. Craig Barnes, Major Professor We have read this thesis and recommend its acceptance: David Jenkins, Konstantinos Vogiatzis, Stephen Chmely Accepted for the Council: Dixie L. Thompson Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) The Use of Sulfur Chloride Systems in the Digestion and Purification of Zircaloy® Nuclear Fuel Cladding A Thesis Presented for the Master of Science Degree The University of Tennessee, Knoxville Jordan Robert Travis August 2019 Abstract The overarching goal of this research has been to develop and understand a low temperature protocol for the digestion of zirconium nuclear fuel cladding.
    [Show full text]
  • Structure and Chemistry of Sulfur Tetrafluoride James
    STRUCTURE AND CHEMISTRY OF SULFUR TETRAFLUORIDE JAMES T. GOETTEL B.Sc., University of Alberta, 2011 A Thesis Submitted to the School of Graduate Studies of the University of Lethbridge in Partial Fulfilment of the Requirements for the Degree MASTER OF SCIENCE Department of Chemistry and Biochemistry University of Lethbridge LETHBRIDGE, ALBERTA, CANADA © James T. Goettel, 2013 ABSTRACT Sulfur tetrafluoride was shown to be a useful reagent in preparing salts of VII − V − VII − Re O2F4 , I OF4 , and I O2F4 . Sulfur tetrafluoride reacts with oxo-anions in acetonitrile or anhydrous HF (aHF) via fluoride-oxide exchange reactions to quantitatively form oxide fluoride salts, as observed by Raman and 19F NMR spectroscopy. Pure Ag[ReO2F4] as well as the new CH3CN coordination compounds [Ag(CH3CN)2][ReO2F4] and [Ag(CH3CN)4][ReO2F4]•CH3CN were prepared. The latter was characterized by single-crystal X-ray diffraction. The reaction of [N(CH3)4]IO3 with SF4 in acetonitrile gave the new [N(CH3)4][IOF4] salt. Sulfur tetrafluoride forms Lewis acid-base adducts with pyridine and its derivatives, i.e., 2,6-dimethylpyridine, 4-methylpyridine and 4- dimethylaminopyridine, which have recently been identified in our lab. In the presence of HF, the nitrogen base in the SF4 base reaction systems is protonated, which can formally be viewed as solvolysis of the SF4•base adducts by HF. The resulting salts have been studied by Raman spectroscopy and X-ray crystallography. + − Crystal structures were obtained for pyridinium salts: [HNC5H5 ]F •SF4, + − − + − [HNC5H5 ]F [HF2 ]•2SF4; 4-methylpyridinium salt: [HNC5H4(CH3) ]F •SF4, + − [HNC5H4(CH3) ][HF2 ]; 2,6-dimethylpyridinium salt: + − − [HNC5H3(CH3)2 ]2[SF5 ]F •SF4; 4-dimethylaminopyridinium salts: + − − + − [HNC5H4N(CH3)2 ]2[SF5 ]F •CH2Cl2, [NC5H4N(CH3)2 ][HF2 ]•2SF4; and the 4,4’- + − 2+ − bipyridinium salts: [HNH4C5−C5H4N ]F •2SF4, [HNH4C5−C5H4NH ]2F •4SF4.
    [Show full text]
  • Lok1974 Msc.Pdf
    I it' ï gaiqe consent to this copy of my thesis, when claposited. i¡ tlre University T,ibrarYr being availab].e for loan and. photooopying. q Date . L.t K SignecL 2S REACTI ONS OF AROMATIC ACETYLENIC COMPOUNDS hIITH SULFUR HALIDES A TIIESIS PRNSENTED FOR TIIE DEGREE OF MASTER OF SCIENCE ln the T]NI\TERSITY OF ADELATDE by LOK I,üON NAM, B.Sc. Department of Organl-c ChenistrY L974 CONTENTS Page SUMMARY (i) STATEMENT (ii) ( ACKNOt^lLEDGEMENTS ar-r- / CHAPTER 1. INTRODUCTION 1 CHAPTER 2. REACTIONS OF PHENYLPROPIOLIC ACID AND ITS METHYL ESTER I^JITH SULFUR HALIDES 2.L Thionyl chloríde 10 2.2 Sulfur dichloríde 20 2.3 Sulfur monochloríde 25 2.4 Sulfuryl chloride 32 CHAPTER 3. SYNTHESIS AI\D REACTIONS OF PYRIDYLPROPIOLIC ACIDS AND ESTERS 3.1 Synthesis of pyridylpropiolic acíds and esËers 39 3.2 Reactions with thíonyl chloride 48 CHAPTER 4. EXPERIMENTAL 4.1 Prearnble 54 4.2 tr'lork described in ChaPter 2 58 4.3 tr'lork described in ChaPter 3 7L REFERENCES 86 (i) SUMMARY The react,ions of phenylpropiolic acid and methyl phenylpropiolate with thionyl chloride, sul-fur díchl-oride, sulfur monochl-oride and sul-furyl chloride have been investÍgated. Formation of benzo[b]thlophene products has been observed in some cases. The procedure is not considered to be a particularly useful route to Ëhese systems due to the relatively 1-ow yield and the mu1-tiplícÍty of products formed ín most cases. Compounds derived from the formal addition of chlorine to the triple bond are among the maJor products in rnost of Ëhese react.ions.
    [Show full text]