DOCSLIB.ORG

(12) Patent Application Publication (10) Pub. No.: US 2008/0302728A1 Wang Et Al

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
(12) Patent Application Publication (10) Pub. No.: US 2008/0302728A1 Wang Et Al US 20080302728A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2008/0302728A1 Wang et al. (43) Pub. Date: Dec. 11, 2008 (54) SULFUR-IMPREGNATED ORGANOCLAY (22) Filed: Jun. 5, 2007 MERCURY AND/OR ARSENC ON REMOVAL MEDIA Publication Classification (51) Int. Cl. (75) Inventors: Zhen Wang, Hoffman Estates, IL CO2F I/28 (2006.01) (US); Robert Abraham, BOLD IS/00 (2006.01) Bolingbrook, IL (US) BOI 20/2 (2006.01) Correspondence Address: (52) U.S. Cl. ............................ 210/688; 210/690: 502/80 MARSHALL, GERSTEIN & BORUN LLP 233 S. WACKER DRIVE, SUITE 6300, SEARS (57) ABSTRACT TOWER The use of a Sulfur-impregnated organoclay provides a mer CHICAGO, IL 60606 (US) cury or arsenic removal media having increased reactivity, stability, and mercury removal ability. The Hg/AS removal (73) Assignee: AMCOL International media described herein is prepared by impregnating an orga Corporation, Arlington Heights, IL nophilic clay with elemental (free state) sulfur. Alternatively, (US) the clay can be made organophilic by onium ion reaction prior to or simultaneously with impregnating the organoclay with (21) Appl. No.: 11/810,363 sulfur. Patent Application Publication Dec. 11, 2008 Sheet 1 of 8 US 2008/0302728A1 £GZ0Z990 seuunioApeg 0 | (udd) uoleiueauoo () fi Patent Application Publication Dec. 11, 2008 Sheet 2 of 8 US 2008/0302728A1 'Zaun6!-- sauun?oApag 090/09090?7090Z0||0 9| (Ludd) uoeueouoso () 5H Patent Application Publication Dec. 11, 2008 Sheet 3 of 8 US 2008/0302728A1 €3.Infil-H Patent Application Publication Dec. 11, 2008 Sheet 4 of 8 US 2008/0302728A1 Patent Application Publication Dec. 11, 2008 Sheet 5 of 8 US 2008/0302728A1 SNS.SriSri SSSt F s N SS 63 N 61 56C 59 111 a 5B 11g - - - - - FIG. 5 Patent Application Publication Dec. 11, 2008 Sheet 6 of 8 US 2008/0302728A1 Patent Application Publication Dec. 11, 2008 Sheet 7 of 8 US 2008/0302728A1 FIG. 8 44 N 57 55 76 . ... 76 US 2008/0302728A1 Dec. 11, 2008 SULFUR-IMPREGNATED ORGANOCLAY types of mercury and arsenic, including organic mercury and MERCURY AND/OR ARSENC ON arsenic compounds, mercury metal (Zero Valent); arsenite and REMOVAL MEDIA arsenate compounds; arsenic ions (both III and V valent); and mercury ions (both I and II valent). When the organic-based FIELD OF THE INVENTION mercury and/or arsenic is involved, the adsorption mecha nism of partition could be involved in addition to chemical 0001. The present invention is directed to compositions: bonding. In addition, the Hg/AS removal media described methods of manufacturing the compositions; and methods of herein also is effective to remove oil, grease and other organic using the compositions for removing mercury (organic mer contaminant molecules. The media will be spent eventually cury, Hg, Hg"; and/or Hg") and/or arsenic (As and/or when all of the adsorption sites are saturated. The actual As") from water. The compositions, also identified hereinas media life will depend on the contaminated water composi “media', or “mercury removal media', or “arsenic removal tions and the field operation conditions. media', or “Hg/AS removal media', can be used to remove 0005 Greco U.S. Pat. No. 5,512,526 describes a clay mercury and/or arsenic from any water source and is particu based heavy metal removal media prepared by reacting a fatty larly useful for removal of mercury and/or arsenic from drink mercaptan, e.g., dodecylmercaptan, with a fatty alkyl-con ing water, industrial wastewater, contaminated groundwater, taining quaternary ammonium compound. As described, the contaminated sediment; offshore produced water, so that the mercaptan's hydrophobic fatty alkyl group associates in some produced water can be returned to the ocean; and for removal of mercury and/or arsenic from aqueous mining wastes. The manner with the fatty alkyl group of the quaternary ammo Hg/AS removal media comprises a homogeneous, preferably nium compound. extruded composition comprising a layered phyllosilicate, elemental Sulfur (free state Sulfur), and an organic phyllosili SUMMARY cate surface treating agent, preferably an onium cation, 0006. It has been found in accordance with the present resulting in an organoclay containing Sulfur. The Sulfur is invention that the use of a Sulfur-impregnated organoclay bonded to the phyllosilicate covalently, ionically, physically, provides a mercury and arsenic removal media having or by a combination of mechanisms. increased reactivity, stability, and mercury and arsenic removal ability. The Hg/AS removal media described herein is BACKGROUND AND PRIOR ART prepared by impregnating an organophilic clay with elemen 0002 The technologies available for mercury and arsenic tal (free state) Sulfur. Alternatively, a clay can be made orga removal. Such as precipitation, coagulation/co-precipitation, nophilic by treating the clay with a Surface-treating agent, activated carbon adsorption, ion-exchange and the like, are Such as a polymer capable of increasing the d-spacing of the not sufficiently effective for mercury and arsenic (arsenite clay platelets, or preferably, withonium ions prior to or simul and arsenate compounds) removal. This assignee's organo taneously with impregnating the resulting organoclay with clay has been proven effective on a variety of organic con sulfur. taminants in the last decade. See, for example, this assignee's U.S. Pat. Nos. 6,398,951; 6,398,966; 6,409,924; and 6,749, BRIEF DESCRIPTIONS OF THE DRAWINGS 757, incorporated herein by reference. A new Hg/AS filtration 0007 FIGS. 1 and 2 are graphs showing the mercury media, described herein, can be operated in a similar fashion, removal efficacy of the Hg/AS removal media described in the or together with the organoclay media, but is much more examples; effective for mercury or arsenic removal. 0003. The Hg/AS removal media described herein has a 0008 FIG. 3 is a graph showing the arsenic removal similar physical form to the organoclays used for organic results for the Hg/AS removal media of Example 6: contaminant removal and can be similarly packed in a canis 0009 FIG. 4 is a side view of an offshore oil well drilling ter or cartridge, as described in the above-listed patents. In platform generally showing the Hg/AS removal media held addition, the Hg/AS removal media described herein can be within a canister attached to an offshore oil well drilling deployed in single layer or multi-layer water-permeable mats, platform Support structure with an alternative placement of a as described in this assignee's published applications, Ser. Sump tank; Nos.10/718,128, filed Nov. 19, 2003 (Publication No. 2005 0010 FIG. 5 is a sectional view of an embodiment of a 01.013707 A1), Ser. No. 1 1/221,019, filed Sep. 7, 2005 (Pub vessel containing a plurality of Hg/AS removal media-con lication No. 2006/0000767 A1), Ser. No. 1 1/489,383, filed taining cartridges or canisters for efficient removal of mer Jul. 19, 2006, (Publication No. 2006-0286888A1), Ser. No. cury and arsenic contained in water; 1 1/599,080, filed Nov. 14, 2006 (Publication No. 2007 0011 FIG. 6 is an elevational view of a preferred embodi 0059542 A1); and Ser. No. 1 1/741,376, filed Apr. 27, 2007, all ment of a vessel containing a plurality of Hg/AS removal of which are hereby incorporated by reference. Fundamen media-containing cartridges or canisters; tally, the Hg/AS removal media is based on organoclay tech (0012 FIG. 7 is a top plan view of the header of the vessel nology but it has been Substantially modified using several shown in FIG. 6 and openings within the header for receiving unique chemistries to enhance adsorption of mercury and permeable conduits each of which can extend through a stack arsenic-containing compounds. The mechanism of mercury of cartridges or canisters as shown in FIGS. 5 and 6: adsorption is based upon chemical bonding, ionic bonding, 0013 FIG. 8 is a partially broken-away side view of an mechanical bonding, or a combination thereof. The mercury embodiment of a Hg/AS removal media-containing vessel, and/or arsenic will be bonded to the media's external and containing multiple, stacked cartridges (FIGS. 5 and 6); and internal Surfaces and the bonding process is non-reversible. 0014 FIG. 9 is an elevational view of a preferred embodi 0004. The Hg/AS removal media described herein is effec ment of a mercury removal media-containing cartridge tive on all sources of mercury and arsenic including organic shown in FIGS. 5 and 6. US 2008/0302728A1 Dec. 11, 2008 0015. It should be understood that the drawings are not since the clay is now hydrophobic, and dried in an oven to less necessarily to Scale and that the embodiments are sometimes than about 5% water, preferably bone dry. The onium ion illustrated by graphic symbols, phantom lines, diagrammatic Surface modification agent compound or polymer can be representations and fragmentary views. In certain instances, added as a solid with the addition to the layered material details which are not necessary for an understanding of the surface modification agent blend of preferably about 20% to present invention or which render other details difficult to about 40% water and/or organic solvent, more preferably at perceive may have been omitted. It should be understood, of least about 30% water or more, based on the dry weight of course, that the invention is not necessarily limited to the layered material. Preferably about 30% to about 40% water, particular embodiments illustrated herein. more preferably about 25-35% water, based on the dry weight of the layered material, is included in the onium ion interca DETAILED DESCRIPTION OF THE PREFERRED lating composition, so that less water is sorbed by the inter EMBODIMENT calate, thereby necessitating less drying energy after onium ion intercalation.
Load more

Recommended publications
  • Preparation of Inorganic–Organic Composites As Acid–Base Catalysts Using Hca2nb3−Xta Xo10 and Quaternary JCS-Japan Onium Salts
    Journal of the Ceramic Society of Japan 128 [1] 51-55 2020 -Japan DOI http://doi.org/10.2109/jcersj2.19119 JCS NOTE Preparation of inorganic­organic composites as acid­base catalysts using HCa2Nb3¹xTaxO10 and quaternary onium salts Masataka OGASAWARA1,³, Takuto BAN2, Kanji SAITO1,3 and Sumio KATO1 1 Graduate School of Engineering Science, Department of Materials Science, Akita University, 1–1 Tegata gakuen-machi, Akita 010–8502, Japan 2 Graduate School of Engineering and Resource Science, Department of Applied Chemistry, Akita University, 1–1 Tegatagakuen-machi, Akita 010–8502, Japan 3 Kagami Memorial Research Institute for Materials Science and Technology, Waseda University, 2–8–26 Nishiwaseda, Shinjuku-ku, Tokyo 169–0054, Japan Inorganic­organic composites have been prepared using Dion­Jacobson-type layered perovskite compounds as base catalysts. Dodecyltributylphosphonium bromide (C12TBPBr), dodecyltriphenylphosphonium bromide (C12TPPBr), or dodecyltrimethylammonium chloride (C12TMACl) were used as the organic species of the + + + inorganic­organic composite. It was suggested that C12TBP ,C12TPP ,orC12TMA were intercalated by ion- + exchange with interlayer H of HCa2Nb3O10. The acid­base reaction was evaluated by consecutive deacetalization­Knoevenagel reactions. The product of the second-step reaction of the inorganic­organic composite catalysts was obtained, which suggested that the composites were acid­base bifunctional materials. For composites prepared using HCa2Nb3¹xTaxO10 (x = 1, 2, and 3) as inorganic species, the base catalytic activity decreased with decreasing fraction of organic species. Therefore, the hydrophobicity of the layered compounds affected the catalytic activity of the composite. Various catalysts should be prepared using reported layered perovskite-type compounds having various compositions. ©2020 The Ceramic Society of Japan.
    [Show full text]
  • Pdf 290.76 K
    Iranica, Vol. 14, No. 4, pp 297{302 Scientia c Sharif University of Technology, August 2007 y-Supp orted Quaternary Ammonium and Cla Cations in Triphase Catalysis and Phosphonium E ect of Cosolvent in Catalytic Activity the 1 1 1 B.L. Cutts D. Dutko and S. Khazaeli , Shab estary , N. this research, a naturally o ccurring clay mineral, hectorite, was used as the supp ort for several In ry ammonium and phosphonium cations to measure and compare their catalytic activity quaterna a triphase catalytic system. The intercalation of the catalysts in the clay has the advantage in easy catalyst recovery; the catalyst can b e removed by a simple separation technique, such of ltration or centrifugation, up on completion of the reaction. The rate of conversion of n- as yl bromide to n-butyl chloride was measured in the presence of two classes of phase transfer but Quaternary ammonium and quaternary phosphonium cations. The rate of the reaction catalyst: as measured for the biphase reactions (no supp orting clay) and for the triphase catalytic system w supp orting clay). The results have shown that quaternary phosphonium catalysts ar e (with more reactive than the corresponding quaternary ammonium catalysts. It wa s also somewhat that the intercalated catalysts could be used several times b efore losing their catalytic found y. Also, a remarkable increase in catalytic activity has b een observed using a co-solvent. activit wever, it app ears that there is a limit for the co-solvent concentration to b e e ective. Ho Based on this technique, synthetic metho ds phases.
    [Show full text]
  • Onium Method for Extraction and Spectrophotometric Determination of Zn (Ii) and Co (Ii)
    IMPACT: Journal of Research in Applied, Natural and Social Sciences (IMPACT: JRANSS) ISSN(E): Applied; ISSN(P): Applied Vol. 1, Issue 2, Dec 2015, 41-54 © Impact Journals ONIUM METHOD FOR EXTRACTION AND SPECTROPHOTOMETRIC DETERMINATION OF ZN (II) AND CO (II) SHAWKET KADHIM JAWAD & JIHAN RAZZAQ MUSLIM Department of Chemistry, College of Education for Girls, Iraq ABSTRACT UV-Vis. spectrum for complexes of Zn (II) and Co (II) extracted according to onium system from acidic HCL solution by use 2,4-dimethylpentan-3-one (2,4-DMP) as onium complex was (262nm) for Zn(II) but onium complex for Co(II) was (243nm), this method show need 0.5M HCL for extraction Zn 2+ and 0.8M HCL for Co 2+ , as well giving obey to Beer-Lambert relation at the (1-20µg) for Zn 2+ and (1-50µg) for Co 2+ . The onium complex extracted have structure + - + - H(H 2O)(2,4-DMP) 3 ;HZnCl 4 , H(H 2O)(2,4-DMP) 3 ;HCoCl 4 . This method obey to Beer-Lambert relation at the range (1-20µg) for Zn 2+ ε=16893.56L.mol -1.cm -1, D.L=6.33×10 -6µg/Ml, RSD%=0.0069µg/Ml, Sandell’s sensitivity=3.87×10 - 9µg/cm 2 and (5-50µg) for Co 2+ , ε=8918.77L.mol -1.cm -1, D.L=3.38×10 -5 µg/Ml, RSD%=0.00664µg/Ml, Sandell’s sensitivity=7.33×10 -9µg/cm 2. As well as this research involved many studies and apply for determination Zn 2+ and Co 2+ in different samples.
    [Show full text]
  • Inorganic Seminar Abstracts
    C 1 « « « • .... * . i - : \ ! -M. • ~ . • ' •» »» IB .< L I B RA FLY OF THE. UN IVERSITY Of 1LLI NOIS 546 1^52-53 Return this book on or before the Latest Date stamped below. University of Illinois Library «r L161— H41 Digitized by the Internet Archive in 2012 with funding from University of Illinois Urbana-Champaign http://archive.org/details/inorganicsemi195253univ INORGANIC SEMINARS 1952 - 1953 TABLE OF CONTENTS 1952 - 1953 Page COMPOUNDS CONTAINING THE SILICON-SULFUR LINKAGE 1 Stanley Kirschner ANALYTICAL PROCEDURES USING ACETIC ACID AS A SOLVENT 5 Donald H . Wilkins THE SOLVENT PHOSPHORYL CHLORIDE, POCl 3 12 S.J. Gill METHODS FOR PREPARATION OF PURE SILICON 17 Alex Beresniewicz IMIDODISULFINAMIDE 21 G.R. Johnston FORCE CONSTANTS IN POLYATOMIC MOLECILES 28 Donn D. Darsow METATHESIS IN LIQUID ARSENIC TRICHLORIDE 32 Harold H. Matsuguma THE RHENI DE OXIDATION STATE 40 Robert L. Rebertus HALOGEN CATIONS 45 L.H. Diamond REACTIONS OF THE NITROSYL ION 50 M.K. Snyder THE OCCURRENCE OF MAXIMUM OXIDATION STATES AMONG THE FLUOROCOMPLEXES OF THE FIRST TRANSITION SERIES 56 D.H. Busch POLY- and METAPHOSPHATES 62 V.D. Aftandilian PRODUCTION OF SILICON CHLORIDES BY ELECTRICAL DISCHARGE AND HIGH TEMPERATURE TECHNIQUES 67 VI. £, Cooley FLUORINE CONTAINING OXYHALIDES OF SULFUR 72 E.H. Grahn PREPARATION AND PROPERTIES OF URANYL CARBONATES 76 Richard *• Rowe THE NATURE OF IODINE SOLUTIONS 80 Ervin c olton SOME REACTIONS OF OZONE 84 Barbara H. Weil ' HYDRAZINE BY ELECTROLYSIS IN LIQUID AMMONIA 89 Robert N. Hammer NAPHTHAZARIN COMPLEXES OF THORIUM AND RARE EARTH METAL IONS 93 Melvin Tecotzky THESIS REPORT 97 Perry Kippur ION-PAIR FORMATION IN ACETIC ACID 101 M.M.
    [Show full text]
  • United States Patent (19) 11 Patent Number: 5,654,374 Arren Et Al
    US005654374A United States Patent (19) 11 Patent Number: 5,654,374 Arren et al. 45 Date of Patent: Aug. 5, 1997 54 CURABLE COMPOSITIONS CONTAINING Corbridge, “Phosphonium Salts.” Phosphorus, pp. 176-179, SLYL-FUNCTIONAL ONUM CURE Elsevier Scientific Publishing Company (1978). ACCELERATORS AND METHOD OF Carey et al., Advanced Organic Chemistry, Part B, 3rd ed., CURING USING SAME pp. 96-97, Plenum Press (1990). 75) Inventors: Dirk H. C. Arren, Borsbeek, Belgium; Rauhut et al., “The Free Radical Addition of Phosphines to William D. Coggio, Woodbury; Unsaturated Compounds”, Journal of Organic Chemistry, Douglas S. Parker, Afton, both of vol. 26, pp. 5138-5145 (1961). Minn. Pellon, "Reversibility in the Reaction of Phosphinyl Radi cals with Olefins", Journal of American Chemistry Society, 73) Assignee: Minnesota Mining and vol. 83, pp. 1915-1916 (1961). Manufacturing Company, St. Paul, Buckler et al., "Reactions of Phosphine with Aliphatic Minn. Aldehydes”, Journal of American Chemistry Society, vol. 83, pp. 168-173 (1961). (21) Appl. No.: 520,129 Langhans et al., "Synthese Primarer und Sekundarer Phos 22 Filed: Aug. 28, 1995 phane Durch Selektive Alkylierung von PH. Unter Phasen transferbedingungen”.Z. Naturforsch, vol. 45b, pp. 203-211 (51 int. C. m. C08F 8/100 (1990). 52 U.S. Cl. ....................... 525/326.3; 524/154; 524/186; Horváth et al., "Facile Catalyst Separation Without Water: 524/188: 524/236; 525/326.2 Fluorous Biphase Hydroformylation of Olefins' Science, 58. Field of Search ............................ 525/326.3, 326.2: vol. 266, pp. 72-75 (1994). 524/186, 188, 236, 154 Colvin, "Silanes as Reducing Agents' Silicon in Organic (56) References Cited Synthesis, pp.
    [Show full text]
  • Polymer-Supported Quaternary Onium Salts Catalysts Prepared Via Concentrated Emulsion Polymerization
    Polymer-supported quaternary onium salts catalysts prepared via concentrated emulsion polymerization L. Hong and E. Ruckenstein* Department of Chemical Engineering, State University of New York at Buffalo, Buffalo, NY 14260, USA (Received 2 7 December 1990; accepted 24 July 7991) A concentrated emulsion has a very large volume fraction of dispersed phase (0.74-0.95 in this case) and the appearance of a gel. Three procedures based on concentrated emulsion polymerization are suggested for the preparation of polymer-supported quaternary onium salts. ( 1) Concentrated emulsions of vinylbenzyl chloride (VBC) in water are subjected to polymerization. The polymer resins thus obtained are composed of particles in the micrometre range. A large fraction of the pendant benzyl-chloride groups present in the poly(VBC) particles are converted to onium chloride by a quaternization reaction. (2) A small amount of VBC is added to a partially polymerized concentrated emulsion of styrene (containing a crosslinking agent) in water under vigorous stirring. The system is subsequently subjected to complete polymerization. The obtained polystyrene-poly(VBC) is found to consist of particles having a non-uniform poly (VBC) shell that covers a crosslinked polystyrene core. This polymer is then subjected to a quaternization reaction in order to generate a polymer substrate with bound quaternary onium chloride. (3) A concentrated emulsion of styrene in an aqueous solution of a quaternary onium chloride monomer is prepared. The onium chloride adsorbed on the surface of the dispersed phase polymerizes simultaneously with styrene when the concentrated emulsion is subjected to polymerization. The polymer-supported onium salts thus prepared were used as phase transfer catalysts in the alkylation of isopropylidene malonates.
    [Show full text]
  • Electrophilic and Free Radical Nitration of Benzene and Toluene with Various Nitrating Agents* (Aromatic Compounds/Selectivity) GEORGE A
    Proc. Natl. Acad. Sci. USA yol. 75, No. 3, pp. 1045-1049, March 1978 Chemistry Electrophilic and free radical nitration of benzene and toluene with various nitrating agents* (aromatic compounds/selectivity) GEORGE A. OLAH, HENRY C. LIN, JUDITH A. OLAH, AND SUBHASH C. NARANG Institute of Hydrocarbon Chemistry, Department of Chemistry, University of Southern California, Los Angeles, California 90007 Contributed by George A. Olah, September 29, 1977 ABSTRACT Electrophilic nitration of toluene and benzene RESULTS AND DISCUSSION was studied under various conditions with several nitrating systems. It was found that high ortlopara regioselectivity is With Nitronium Salts. Although we had previously exam- prevalent in all reactions and is independent of the reactivity ined competitive nitration using high-speed mixing (7), it was of the nitrating agent. The methyl group of toluene is predom- considered of interest to extend the studies by using more ad- inantly ortho-para directing under all reaction conditions. Steric vanced methods such as the mixing chamber of an efficient factors are considered to be important but not the sole reason Durrum-Gibson stopped-flow apparatus. Competitive nitra- for the variation in the ortho/para ratio. The results reinforce our earlier views that, in electrophilic aromatic nitrations with tions, with nitronium hexafluorophosphate in nitromethane, reactive nitrating agents, substrate and positional selectivities provided the data in Table 1. Whereas mixing still can be in- are determined in two separate steps. The first step involves a complete before reaction, with the nitration rates being very ir-aromatic-NO2 ion complex or encounter pair, whereas the fast (or reaching the encounter-controlled limit), the data seem subsequent step is of arenium ion nature (separate for the oftho, to indicate that, in the present system, both toluene and benzene meta, and para positions).
    [Show full text]
  • Chapter 2 – Acids & Bases Dr.Gergens
    Chapter 2 - Acids & Bases Dr. Gergens – SD Mesa College Mantra – We say ACID, and as Citizens of Science we say … Ammork & HClindy: Nano, Nano … Particle Demonstration A. “I am Ammork from Ammonium Hydroxide. I smell like fish. I am a little unstable. Greetings, I leave in pieces." 1 NH4OH (aq) ------> NH3 (g) + H2O (l) NH4OH aqueous aqueous solution Ammork solution B. “Hi, I am HClindy. I am bubbly …. out of a solution of HCl (aq) I turn blue litmus paper red, acid 1 HCl (aq) ------> HCl (g) + H O (l) 2 HCl aqueous solution HClindy aqueous solution C. “And together, we are Ammork & HClindy” Nano, Nano 1 NH3 (g) + 1 HCl (g) ------> particles NH4OH HCl aqueous aqueous solution solution Ammork & HClindy: Nano, Nano … Particle Demonstration A. “I am Ammork from Ammonium Hydroxide. Greetings, I leave in peaces." B. Nano Particle Demonstration - What are those particles forming in mid-air ???? 1 NH3 (g) + 1 HCl (g) ------> C. Draw the Lewis Dot for each substance • ICAO on each substance • follow all rules for drawing Lewis Dot structure • indicated full and partial charges D. Law of Electrostatics, Opposites Attract & FONClBrISCH E. Complete the reaction: • atoms • electrons • formal charges • ALL must balance • opposites attract F. Draw an electron arrow push between substances to show chemical reactivity. 2 Acid-Base Trends, Conjugates, and Reactions Dr. Gergens - SD Mesa College Periodic Trend ACIDS conjugate bases acidity increases basicity increases – – - - CH4 NH3 H2O H-F CH3 NH2 OH F – - - PH3 H2S H-Cl PH2 SH Cl acidity basicity increases
    [Show full text]
  • Synthetic Methods and Reactions*
    Proc. Indian Acad. Sci. (Chem. Sci.), Vol. 100, Nos 2 & 3, April 1988, pp. 143-185. t~ Printed in India. Synthetic methods and reactions* G K SURYA PRAKASH and GEORGE A OLAH* Donald P and Katherine B Loker Hydrocarbon Research Institute, and Department of Chemistry, University of Southern California, Los Angeles, California 90089, USA Abstract. This review deals with the development of a series of reagents and reactions for organic synthesis using simple starting materials. A wide array of carbocationic and onium ion reagents, haiogenating agents, FriedeI-Crafts catalysts, metal-induced oxidation- reductions and silicon reagents were utilized in basic (unit) reactions, which serve as building blocks for general synthetic transformations. Keywords. Carbocations; onium ions; halogenating agents; Friedel-Crafts reactions; oxidizing agents; reducing agents; silicon reagents. Introduction Synthetic chemistry in general is directed either towards the preparation of specific molecules or towards the development of new reactions and reagents as well as improvement of existing methods. Over the years our group has been involved in developing selective reagents and methods for organic synthetic transformations using simple and inexpensive starting materials. The development of basic (unit) reactions are important as they serve as building blocks for all syntheses including those of complex target molecules such as natural products. In this review we give an account of our synthetic studies of recent years. In a short review it is not possible to give sufficient background for such a diverse and broad field or comparison with other existing methods and reactions. The reader should be aware of the large diversity of existing synthetic methods to which we hope to have made some useful contributions.
    [Show full text]
  • Fluoronium Ion in Solution
    Article Cite This: Acc. Chem. Res. XXXX, XXX, XXX−XXX pubs.acs.org/accounts Quest for a Symmetric [C−F−C]+ Fluoronium Ion in Solution: A Winding Path to Ultimate Success Maxwell Gargiulo Holl, Cody Ross Pitts, and Thomas Lectka* Department of Chemistry, Johns Hopkins University, 3400 N. Charles Street, Baltimore, Maryland 21218, United States CONSPECTUS: In this Account, we chronicle our tortuous but ultimately fruitful quest to synthesize a [C−F−C]+ fluoronium ion in solution, thus providing the last piece of the organic halonium ion puzzle. Inspiration for the project can be traced all the way back to the graduate career of the corresponding author, wherein the analogy between a [C−H− C]+ “hydrido” bridge and a hypothetical [C−F−C]+ bridge was first noted. The earliest attempt to construct a bicyclo[5.3.3]tridecane-based fluoronium ion (based on the analogous hydrido bridged cation) proved to be synthetically difficult. A subsequent ̈ attempt involving a 1,8-substituted naphthalene ring was theoretically naive in retrospect, and it resulted in a classical benzylic carbocation instead. A biphenyl-based substrate, although computationally sound, proved to be kinetically untenable. At last, after some tweaking (including a dead-end detour into a fluoraadamantane skeleton), we finally achieved success with a highly rigid, semicage precursor based on the decahydro-1,4:5,8- dimethanonaphthalene system. This strained substrate possessed a triflate leaving group to enhance its solvolytic reactivity. Detailed isotopic labeling and kinetic studies supported the generation of a symmetrical [C−F− C]+ bridge; interesting solution behavior allowed the manipulation of the rate-determining step for solvolysis depending on solvent nucleophilicity.
    [Show full text]
  • Solution Viscosity Behavior and Swelling Behavior of Polystyrene-Based Cationic Ionomers
    Polymer Journal, Vol. 28, No. I, pp 11-15 (1996) Solution Viscosity Behavior and Swelling Behavior of Polystyrene-Based Cationic Ionomers. Effects of Added Salts and Counterion Noritaka OHTANI,* Yukihiko INOUE, Yasumasa KANEKO, Akiko SAKAKIDA, Ichiro TAKEISHI, and Hiroshi FURUTANI Department of Materials Engineering & Applied Chemistry, Akita University, Akita 010, Japan (Received June 21, 1995) ABSTRACT: Dilute-solution viscosity was investigated for several polystyrene-based cationic ionomers in the presence of small salts. The results were compared with the swellability of the corresponding crosslinked ionomers. It was found that intra- and intermolecular aggregation among the ionic groups in nonpolar solvents was eliminated by the addition of the low-molecular quaternary salts, leading to increases in the solubility and the reduced viscosity of the linear ionomers as well as an increased swelling of the crosslinked ionomers. Polyelectrolyte behavior in polar organic solvents was suppressed by the minute addition of soluble salts, resulting in a decreased reduced viscosity of linear ionomers and a decreased swelling of crosslinked ionomers. These results are discussed in terms of the change in the intra- and intermolecular aggregation of quaternary salts of the ionomers. KEY WORDS Cationic Ionomers / Polystyrene-Based Ionomers / Solution Viscosity/ Quaternary Salts / Solvation / Aggregation of Ionic Groups / lonomers are a class of linear polymers containing a strongly influence the ionic aggregation even in polar relatively low level of ionic groups. The solution viscosi­ solvents. There are some quaternary salts that are soluble ty behavior of anionic ionomers has been extensive­ in nonpolar solvents. Therefore, it is very interesting to ly studied because of their importance as industrial investigate the influence of such salts on the ionic ag­ materials.
    [Show full text]
  • The Institute of Paper Chemistry
    The Institute of Paper Chemistry Appleton, Wisconsin Doctor's Dissertation Anodic Reactions of Simple Phenolic Compounds Frederick J. Vermillion, Jr. June, 1963 ANODIC REACTIONS OF SIMPLE PHENOLIC COMPOUNDS A thesis submitted by Frederick J. Vermillion, Jr. B.S. 1957, University of Maine M.S. 1958, University of Maine M.S. 1960, Lawrence College in partial fulfillment of the requirements of The Institute of Paper Chemistry for the degree of Doctor of Philosophy from Lawrence College, Appleton, Wisconsin June, 1963 TABLE OF CONTENTS Page INTRODUCTION 1 LITERATURE REVIEW 3 Previous Electrochemical Studies of Phenols 3 Acetonitrile as a Solvent for Electrochemical Studies 7 EXPERIMENTAL 9 Equipment 9 Voltammetry 9 Electrolysis 15 Millicoulometry 18 Chemicals 20 Acetonitrile 20 Supporting Electrolyte 22 Additives for Voltammetric Studies 23 Phenols and Other Electroactive Compounds 25 Electrode Pretreatment for Voltammetry 27 Voltammetric Procedure 29 Electrolysis of 2,6-Di-tert-butyl-p-cresol 31 Electrolysis of the Vanillinate Anion 33 VOLTAMMETRY: THEORY, AND ANALYSIS OF DATA 37 PHENOXONIUM ION MECHANISM IN ACETONITRILE 43 Detailed Studies on 2,6-Di-tert-butyl-p-cresol 43 Effect of Concentration 44 Effect of Hydrogen Ion Concentration 52 Buffered Solutions 55 Effect of Water and Methanol 57 Electrolysis 60 iii Discussion 67 Other Hindered Phenols 70 Correlation of Half-Wave Potentials 72 Mechanism of the Electrode Reaction 79 FREE RADICAL MECHANISM OF PHENOXIDE ANIONS IN ACETONITRILE 81 Hindered Phenols 81 Vanillinate Anion 83 Voltammetry
    [Show full text]