DOCSLIB.ORG

INTRODUCTION to PFAS November 8, 2019

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
INTRODUCTION to PFAS November 8, 2019 INTRODUCTION TO PFAS November 8, 2019 trcsolutions.com | PFAS in the News https://pfasproject.com trcsolutions.com 2 Today’s Topics • PFAS Naming Conventions • Physical/Chemical Properties of PFAS • Sources of PFAS and Potentially- affected Sites • Replacement PFAS Chemistry • AFFF • Toxicology 3 PFAS Naming Conventions 4 Acronyms • PFC = Per-fluorinated chemical PFCA • PFAS = Per- and Poly-fluoroalkyl substances Perfluoroalkyl Substances PFAA • PFAA = Perfluoroalkyl acids PFSA • PFOA = Perfluorooctanoic acid (perfluorooctanoate) • PFOS = Perfluorooctane sulfonic acid (perfluorooctane sulfonate) • PFCA = Perfluorocarboxylic acids • PFSA = Perfluorosulfonic acids trcsolutions.com 5 Perfluorinated Compounds (PFCs) PFCs: Do not use this acronym anymore! • PFCs previously used to describe greenhouse gases • PFCs do not include polyfluorinated compounds 6 Quick Chemistry Lesson #1 • Remember: PFAS are Per and Polyfluoroalkyl substances • Per-fluoroalkyl substances: fully fluorinated alkyl tail • Perfluoroalkane carboxylates (or carboxylic acids): PFCAs FFF F F F O COOH = Head F C C C C (PFOA) C C C C OH F PFAAs F FFFFFF Alkyl tail, fully fluorinated • Perfluoroalkane sulfonates (or sulfonic acids): PFSAs FFF F F F F F F C C C C (PFOS) C C C C SO3H SO3H= Head F F FFFFFF 7 Quick Chemistry Lesson #2 • Remember: PFAS are Per and Polyfluoroalkyl substances • Poly-fluoroalkyl substances: non-fluorine atom (typically hydrogen or oxygen) attached to at least one carbon atom in the alkane chain Fluorotelomer Alcohol (8:2 FTOH) FFF F F F F F HH C C C C C C C C C C OH F FFFFFFFFHH Non-fluorine atom on one or more carbons. Polyfluoroalkyl substances may also be degraded to perfluoroalkyl substances (e.g., PFOS or PFOA): PRECURSORS 8 Nomenclature • Remember: PFAS are Per and Polyfluoroalkyl substances • Per-fluoroalkyl substances: fully fluorinated alkyl tail Acronym Compound Name Carbon Chain Length PFOA Perfluorooctanoic acid C8 PFOS Perfluorooctanesulfonic acid C8 PFBA Perfluorobutanoic acid C4 PFBS Perfluorobutane sulfonic acid C4 PFHxA Perfluorohexanoic acid C6 PFHxS Perfluorohexane sulfonic acid C6 • Poly-fluoroalkyl substances: partially fluorinated alkyl tail ‒ Fluorotelomers TRCcompanies.com Polyfluoroalkyl substances can also be precursors. 9 Summary of PFAS Families PFAS Non-polymer Polymer Potential Precursors Perfluorinated Polyfluorinated Precursors PFAAs FTSAs PFCAs FTCAs FTOHs PFSAs FASEs FASAs FASAAs trcsolutions.com 10 What is a Precursor? FTSAs: . Stable under anoxic conditions . Likely degrade to PFCAs in aerobic surface waters • Polyfluoroalkyl substances transformed to PFAAs • Transformation • Precursors are a concern • 1000s of these trcsolutions.com 11 PFAS Families PFCA Fluorotelomer-based Substances FOSE ECF-based PFAA FTOH FTSA FTCA Substances PFSA FOSAA • FOSE: raw material in ECF • Directly released to • From telomerization process process environment • Can biotransform into PFCAs • FOSAA: degradation • Produced by precursor intermediate degradation • FTOH far more volatile • Can biotransform into PFCAs and PFSAs trcsolutions.com 12 Polyfluorinated Substances Producing PFAAs 13 PFOS: Linear and Branched Isomers Linear Isomers 3M AFFF: Branched and linear isomers (30:70) If exclude branched isomers, concentrations underestimated and biased low. Branched Isomers trcsolutions.com 14 PFOS: Linear and Branched Isomers trcsolutions.com 15 PFOA: Branched and Linear Isomers: Lab Quantitation Correct integration of PFOA Incorrect integration of PFOA trcsolutions.com 16 Long Chain Versus Short Chain Why does it matter? • Short chain: • Long chain: – PFCAs with seven or fewer carbons – PFCAs with 8 or more carbons – PFSAs with five carbons or less – PFSAs with six or more carbons Perfluorohexanoic acid (PFHxA) is short chain PFCA. Perfluorohexane sulfonic acid (PFHxS) is long chain PFSA. Short-chain PFCAs Long-chain PFCAs PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFBS PFPeS PFHxS PFHpS PFOS PFNS PFDS PFUnS PFDoS Short-chain PFSAs Long-chain PFSAs trcsolutions.com Source: March 2018 ITRC Factsheet 17 What Are PFAS? • Poly- and per-fluoroalkyl substances ─ Generic family of chemicals ─ Manmade and do not occur naturally ─ Used since 1940 (Critical for the Manhattan Project) ─ Can be branched or linear ─ Used to make products that resist heat, oils, grease, stains, and water • Most prevalent and researched: PFOA and PFOS • PFAS: Acid or anion? PFOS is present in the environment in the anionic form: perfluorooctane sulfonate. Perfluorobutanoic acid Perfluorobutanoate (+ dissociated proton) trcsolutions.com 18 CAS Numbers and PFAS State PFAS State Structure CAS No. - Anion Perfluorooctanoate C7F15CO2 45285-51-6 PFOA Acid Perfluorooctanoic acid C7F15COOH 335-67-1 - Anion Perfluorooctane sulfonate C8F17SO3 45298-90-6 PFOS Acid Perfluorooctane sulfonic acid C8F17SO3H 1763-23-1 trcsolutions.com Why is this important? 19 Chemical Properties of Perfluoroalkyl Substances A PFAS Micelle • C-F: Strong bond • Chemically and thermally stable • Water soluble and mobile in groundwater • Surfactant properties • Recalcitrant in environment trcsolutions.com 20 Properties: Acid vs Cation vs Anion Form PROPERTY AVAILABILITY • Physical description • White powder or waxy substance • Molecular weight • Known • Solubility in water • Known for acid and cation; N/A for Anion • Vapor Pressure • Known for acid; N/A for anion and cation (*) • Henry’s Law constant • Estimated for acid; N/A for anion and cation (*) • Kow • Typically see values for acid form • pKa • Half-life • Generally not available (some modeled values available) • BCF and/or BAF • Known for anion; N/A for acid & cation trcsolutions.com 21 Sources of PFAS and Potentially Affected Sites trcsolutions.com 22 Where Are PFAS Used? trcsolutions.com 23 What Types of Sites Can Be Sources of PFAS? • Fire training facilities • Fire stations • Refineries • DoD sites/Military bases • Commercial and private airports • Landfills (leaching from consumer products) • Biosolids land application • Rail yards • Chemical facilities • Plating facilities • Textile/carpet manufacturers • Residential areas with septic systems trcsolutions.com 24 Timeline of PFAS 1938 1949 1956 1968 1978 •PTFE •PTFE used in • Stain-resistant •Navy •Detected in discovered products products developed blood of (PFOS) AFFF manufacturing workers 2016 2002 2006 2009 2013-2015 •EPA Health •PFOS • PFOA phased out •Stockholm • PFOA phase-out Advisory manufacturing •EPA PFOA Convention complete announced for phased out Stewardship classifies PFOA/PFOS Program PFOS as POP • Sampling of public (70 ppt) drinking water wells for PFAAs (UCMR3) trcsolutions.com 25 Global Manufacture and Use of PFAS Banned Sale, Prohibits Import, Use and Import Manufacture, of PFOA: Use & Sale of PFOS/PFOA: European Union Canada Restrict Manufacture, PFOA & PFOS No Import, Export, and Use of Longer PFOS: Japan Produced: US, Increased Europe, Japan Production of PFOA: China, India, EtFOSA Produced on Industrial Scale: Brazil Russia Class B AFFF with PFAS Banned: PFAS Manufactured Globally South Australia trcsolutions.com 26 Replacement Chemistry • GenX replaces PFOA • ADONA replaces PFOA • 6:2 Fluorotelomers replace PFOS in metals plating • Telomers replace PFOS and PFHxS in AFFF • Shorter chain PFAAs replace PFOA: PFBA, PFPeA trcsolutions.com 27 Four New PFAS in Revised EPA 537 Method Analyte Acronym CAS Number Hexafluoropropylene oxide dimer acid HFPO-DA 13252-13-6 11-chloroeicosafluoro-3-oxaundecane-1-sulfonic acid 11Cl-PF3OUdS 763051-92-9 9-chlorohexadecafluoro-3-oxanone-1-sulfonic acid * 9Cl-PF3ONS 756426-58-1 4,8-dioxa-3H-perfluorononanoic acid * ADONA 919005-14-4 *F53B compounds All new compounds have an oxygen molecule in the carbon chain. 28 Hexafluoropropylene oxide dimer acid (HFPO-DA) • Perfluoroether carboxylate surfactant • Dupont/Chemours • Is not Gen-X – one component of the Gen-X processing aid technology – is a Gen-X chemical • Shorter-chain PFAS: 6 carbons; 5 fluorinated • Replacement for PFOA as a surfactant and polymerization aid in production of PTFE product 29 ADONA • Polyfluoroether carboxylate surfactant • 3M/Dyneon ADONA • Shorter-chain PFAS (7 carbons; 6 are fluorinated) • Replacement for PFOA as a polymerization aid in production of PTFE product 30 F-53B • Chlorinated polyfluorinated ether sulfonate • Used in metal plating as alternatives to PFOS for mist suppression • F-53 salts likely derived from fluorotelomer raw material • Used as mist suppressant in chrome plating industry for over 30 years in China • F-53 vs F-53B 11Cl-PF3OUdS 9Cl-PF3ONS F53B: minor component F-53B: major component 31 Aqueous Film Forming Foam (AFFF) trcsolutions.com What is AFFF? • Highly effective fire-fighting foam • Used for hydrocarbon fuel fires • AFFF acts as: – An aqueous foam: primary fire extinguishing agent – An aqueous film former: a fuel vapor suppressor TRCcompanies.com 33 Where is AFFF Used? • Airports (military/domestic) • Petrochemical Facilities • Municipal Fire Dept. • Industrial Fixed Systems • Military / Government • Marine – Off Shore Fire Protection • Where: – Historical Use (where used to fight a fire) – Fire Training Areas – Nozzle Testing Areas –Storage Areas TRCcompanies.com 34 Types of Fluorine-Based AFFF nd Modern Legacy 1st 2 Generation Fluorotelomer & Fluorotelomer Generation AFFF Precursors AFFF AFFF . PFOS based (80%) . Sold from 1970s - 2016 . Most foam mfrs transitioned to this . Telomer based (20%) . Telomers . No PFOS and no . Developed in 1960s . PFOR compounds (R= cationic and anionic heads) breakdown to PFOS .
Load more

Recommended publications
  • United States Patent Office
    Patented Mar. 30, 1948 2,438,754 UNITED STATES PATENT OFFICE 2,438,754 COPPER, CONTAINING DSAZO, DYESTUFFS Adolf Krebser, Riehen, near Basel, and Werner Bossard, Basel, Switzerland, assignors to the firm J. R. Geigy A. G., Basel, Switzerland No Drawing. Application March 1, 1943, Serial : No. 477,630. In Switzerland April 28, 1942 1. Claims. (C. 260-148) 2 - It has been found that valuable new Copper For the dyestuffs of the type (a): 2-amino containing disazo dyestuffs are obtained by 1-hydroxy-, -methoxy- or -benzyloxybenzene coupling a diazotised amino Sulfonic acid of the 4-Sulfonic acid, 4- or 6-methyl-2-amino-1-hy benzene or naphthalene series, which contains, in droxy- or ethoxybenzene sulfonic acid, 4- or o-position to the amino group, a hydroxy group 5 6-chloro-2-amino-1-hydroxy- or -methoxyben or a Substituent convertible into a hydroxy group Zene Sulfonic acid, 4- or 6-nitro-2-amino-1-hy. by coppering, with a 1:3-dihydroxy-benzene, droxy- or -methoxybenzene sulfonic acid, then causing a diazonium compound which is 1-amino-2-hydroxynaphthalene-4-sulfonic acid, free from sulfonic acid groups to react with the 6-nitro-2-amino-1-hydroxynaphthalene - 4 -sul said monoazo dyestuff and after-treating the 0. fonic acid. so-obtained disazo dyestuff with copper-yielding For the dyestuffs of the type (b) and (c) : agents, with the condition that at least one of 3-amino-4-hydroxy-, -methoxy- or -chloro-1:1'- the diazo components is substituted by a phenyl diphenylsulfone-5- or -3'-sulfonic acid, 3-amino nucleus bound by a non-basic bridge.
    [Show full text]
  • Cofactor Binding Protects Flavodoxin Against Oxidative Stress
    Cofactor Binding Protects Flavodoxin against Oxidative Stress Simon Lindhoud1., Willy A. M. van den Berg1., Robert H. H. van den Heuvel2¤, Albert J. R. Heck2, Carlo P. M. van Mierlo1, Willem J. H. van Berkel1* 1 Laboratory of Biochemistry, Wageningen University, Wageningen, The Netherlands, 2 Biomolecular Mass Spectrometry and Proteomics, Bijvoet Center for Biomolecular Research and Utrecht Institute for Pharmaceutical Sciences, Utrecht University, Utrecht, The Netherlands Abstract In organisms, various protective mechanisms against oxidative damaging of proteins exist. Here, we show that cofactor binding is among these mechanisms, because flavin mononucleotide (FMN) protects Azotobacter vinelandii flavodoxin against hydrogen peroxide-induced oxidation. We identify an oxidation sensitive cysteine residue in a functionally important loop close to the cofactor, i.e., Cys69. Oxidative stress causes dimerization of apoflavodoxin (i.e., flavodoxin without cofactor), and leads to consecutive formation of sulfinate and sulfonate states of Cys69. Use of 7-chloro-4- nitrobenzo-2-oxa-1,3-diazole (NBD-Cl) reveals that Cys69 modification to a sulfenic acid is a transient intermediate during oxidation. Dithiothreitol converts sulfenic acid and disulfide into thiols, whereas the sulfinate and sulfonate forms of Cys69 are irreversible with respect to this reagent. A variable fraction of Cys69 in freshly isolated flavodoxin is in the sulfenic acid state, but neither oxidation to sulfinic and sulfonic acid nor formation of intermolecular disulfides is observed under oxidising conditions. Furthermore, flavodoxin does not react appreciably with NBD-Cl. Besides its primary role as redox- active moiety, binding of flavin leads to considerably improved stability against protein unfolding and to strong protection against irreversible oxidation and other covalent thiol modifications.
    [Show full text]
  • Secondary Alkane Sulfonate (SAS) (CAS 68037-49-0)
    Human & Environmental Risk Assessment on ingredients of household cleaning products - Version 1 – April 2005 Secondary Alkane Sulfonate (SAS) (CAS 68037-49-0) All rights reserved. No part of this publication may be used, reproduced, copied, stored or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise without the prior written permission of the HERA Substance Team or the involved company. The content of this document has been prepared and reviewed by experts on behalf of HERA with all possible care and from the available scientific information. It is provided for information only. Much of the original underlying data which has helped to develop the risk assessment is in the ownership of individual companies. HERA cannot accept any responsibility or liability and does not provide a warranty for any use or interpretation of the material contained in this publication. 1. Executive Summary General Secondary Alkane Sulfonate (SAS) is an anionic surfactant, also called paraffine sulfonate. It was synthesized for the first time in 1940 and has been used as surfactant since the 1960ies. SAS is one of the major anionic surfactants used in the market of dishwashing, laundry and cleaning products. The European consumption of SAS in detergent application covered by HERA was about 66.000 tons/year in 2001. Environment This Environmental Risk Assessment of SAS is based on the methodology of the EU Technical Guidance Document for Risk Assessment of Chemicals (TGD Exposure Scenario) and the HERA Exposure Scenario. SAS is removed readily in sewage treatment plants (STP) mostly by biodegradation (ca. 83%) and by sorption to sewage sludge (ca.
    [Show full text]
  • Reactivity of Benzenesulfonic Acids in the Hydrogen-Isotope Exchange Reaction
    RADIOISOTOPES,52,57-64(2003) Original Reactivity of Benzenesulfonic Acids in the Hydrogen-Isotope Exchange Reaction Dongyu ZHAO, Hiroshi IMAIZUMI* and Naoki KANO* Graduate School of Science and Technology, Niigata University *Department of Chemistry and Chemical Engineering , Faculty of Engineering, Niigata University 8050 Ikarashi 2-Nocho, Niigata-shi, Niigata Pref. 950-2181, Japan Received September 2, 2002 In order to reveal the reactivity of a functional group in an aromatic compound having two substituents in the aromatic ring, the hydrogen-isotope exchange reaction (T for-H exchange reaction) between tritiated water vapor (HTO vapor) and 3-amino-4-methoxybenzenesulfonic acid (and 2-aminotoluene-5-sulfonic acid) was dynamically observed at 50•Ž (and 70•Ž) in a gas-solid system. Consequently, the specific activity of the acid increased with time, and it showed that the T for-H exchange reaction occurred. Applying the A•h-McKay plot method to the data observed, the rate constant of each functional group for the reaction was obtained. After the additive property of the Hammett's rule was applied to this work; the new substituent constants were obtained. From the above-mentioned, the following four items have been confirmed. (1) The reactivity of the functional groups can be dynamically analyzed, and the A•h-McKay plot method is useful to analyze the reactivity. (2) The additive property of the Hammett's rule is applicable to quantitative comparison of the reactivity of the functional groups. (3) The reactivity of the functional groups can be simultaneously analyzed by using the A•h-McKay plot method in the T-for-H exchange reaction.
    [Show full text]
  • PDF (ELM-03-Chapter3.Pdf)
    46 Chapter 3 THIOL/ARYLSULFONIC ACID-PAIRED CATALYSTS FOR THE SYNTHESIS OF BISPHENOLS Abstract We recently demonstrated that mesoporous silica materials functionalized with pairs of alkylsulfonic acid and thiol groups are excellent catalysts for the synthesis of bisphenols from the condensation of phenol and various ketones, with activity and selectivity highly dependent on the thiol/acid distance. Here, we report the synthesis and catalytic properties of a mesoporous silica bearing thiol groups paired with stronger arylsulfonic acid groups. This catalyst was generated by grafting a bissilane precursor molecule containing both a disulfide and a sulfonate ester bond onto SBA-15, followed by simultaneous disulfide reduction and sulfonate ester hydrolysis. The resulting catalyst significantly outperformed the alkylsulfonic acid/thiol paired catalyst in bisphenol A and Z synthesis, while maintaining a very high selectivity to the desired isomer p,p’ isomer. The paired catalyst had similar activity to a randomly-bifunctionalized arylsulfonic acid/thiol catalyst in the bisphenol A reaction, but exhibited greater activity and selectivity than the randomly-bifunctionalized catalyst in the bisphenol Z reaction. 47 Introduction Bisphenols, such as bisphenol A and bisphenol Z, are important industrial feedstocks, especially as monomers in polycarbonate polymers and resins. They are synthesized in the acid-catalyzed condensation between a ketone and phenol, yielding the desired p,p’ isomer and a byproduct, the o,p’ isomer (Scheme 3.1). The addition of thiols as a cocatalyst is known to improve both the rate of reaction and the selectivity to the desired isomer. Mineral acids can be used to catalyze the bisphenol condensation reaction, but solid acid catalysts such as polymeric ion-exchange resins are typically used for commercial bisphenol production due to their non-corrosive nature and reusability.
    [Show full text]
  • United States Patent (19) 11 4,395,569 Lewis Et Al
    United States Patent (19) 11 4,395,569 Lewis et al. (45) "Jul. 26, 1983 (54) METHOD OF PREPARNG SULFONCACD 58) Field of Search ................... 560/87, 88, 193, 196, SALTS OF ACYLOXYALKYLAMINES AND 560/220, 221, 222, 127, 38, 49, 155, 169, 171, POLYMERS AND COMPOUNDS 74, 80, 153, 154; 54.6/321 THEREFROM (56) References Cited (75) Inventors: Sheldon N. Lewis, Willow Grove; U.S. PATENT DOCUMENTS Jerome F. Levy, Dresher, both of Pa. 2,628,249 2/1953 Bruno . 2,871,258 1/1959 Hidalgo et al. 73) Assignee: Rohm and Haas Company, 3,211,781 10/1965 Taub et al. Philadelphia, Pa. 3,256,318 7/1966 Brotherton et al. 3,459,786 8/1969 Brotherton et al. * Notice: The portion of the term of this patent 3,468,934 9/1969 Emmons et al. subsequent to Mar. 18, 1997, has been 3,729,416 4/1973 Bruning et al. disclaimed. 4,194,052 3/1980 Lewis et al. ........................ 560/222 FOREIGN PATENT DOCUMENTS 21 Appl. No.: 104,256 1351368 2/1964 France . 22 Filed: Dec. 17, 1979 1507036 12/1967 France . Primary Examiner-Natalie Trousof Assistant Examiner-L. Hendriksen Related U.S. Application Data Attorney, Agent, or Firm-Terence P. Strobaugh; (60) Division of Ser. No. 821,068, May 1, 1969, Pat. No. George W. F. Simmons 4,194,052, which is a continuation-in-part of Ser. No. 740,480, Jun. 27, 1968, Pat. No. 4,176,232. 57 ABSTRACT A sulfonic acid salt of an acyloxyalkylamine is prepared (51) Int, C. ..................... C07C 67/08; C07C 101/00 by reaction of an organic acid or amino-acid with a (52) U.S.
    [Show full text]
  • Human Health Toxicity Values for Perfluorobutane Sulfonic Acid (CASRN 375-73-5) and Related Compound Potassium Perfluorobutane Sulfonate (CASRN 29420 49 3)
    EPA-823-R-18-307 Public Comment Draft Human Health Toxicity Values for Perfluorobutane Sulfonic Acid (CASRN 375-73-5) and Related Compound Potassium Perfluorobutane Sulfonate (CASRN 29420-49-3) This document is a Public Comment draft. It has not been formally released by the U.S. Environmental Protection Agency and should not at this stage be construed to represent Agency policy. This information is distributed solely for the purpose of public review. This document is a draft for review purposes only and does not constitute Agency policy. DRAFT FOR PUBLIC COMMENT – DO NOT CITE OR QUOTE NOVEMBER 2018 Human Health Toxicity Values for Perfluorobutane Sulfonic Acid (CASRN 375-73-5) and Related Compound Potassium Perfluorobutane Sulfonate (CASRN 29420 49 3) Prepared by: U.S. Environmental Protection Agency Office of Research and Development (8101R) National Center for Environmental Assessment Washington, DC 20460 EPA Document Number: 823-R-18-307 NOVEMBER 2018 This document is a draft for review purposes only and does not constitute Agency policy. DRAFT FOR PUBLIC COMMENT – DO NOT CITE OR QUOTE NOVEMBER 2018 Disclaimer This document is a public comment draft for review purposes only. This information is distributed solely for the purpose of public comment. It has not been formally disseminated by EPA. It does not represent and should not be construed to represent any Agency determination or policy. Mention of trade names or commercial products does not constitute endorsement or recommendation for use. i This document is a draft for review purposes only and does not constitute Agency policy. DRAFT FOR PUBLIC COMMENT – DO NOT CITE OR QUOTE NOVEMBER 2018 Authors, Contributors, and Reviewers CHEMICAL MANAGERS Jason C.
    [Show full text]
  • Hydroxylamine-O -Sulfonic Acid — a Versatile Synthetic Reagent
    Hydroxylamine-O -sulfonic acid — a versatile synthetic reagent Raymond G. Wallacef School of Chemistry Brunei University Uxbridge, Middlesex UBS 3PH Great Britain imidazoli nones and related derivatives are time to these various modes of reaction. discussed in the review. Many of these The uses of HOSA as a reagent are organiz­ preparations can be carried out in high ed below according to the different syn­ yield, thetic transformations that it can bring about. Hydroxylamine-Osulfonic acid, NHj-OSOjH (abbreviated to HOSA in Probably by far the most well known this article) has become in recent years and explored reactions of HOSA are commercially available. Although much animation reactions, illustrating elec­ fruitful chemistry has been carried out us­ trophilic attack by HOSA, with amination ing HOSA, to this author's knowledge, on nitrogen being the most important, there has been no systematic review in although a significant number of English* of its use as a synthetic reagent. It animations on both carbon and sulfur have is a chemically interesting compound been reported, Amination on phosphorus because of the ability of the nitrogen center also occurs. to act in the role of both nucleophile and AMINATION electrophile, dependent on circumstances, Synopsis (a) At a nitrogen atom and thus it has proved to be a reagent of Hydroxylamine-0-sulfonic acid (0 Preparation of mono- and di- great synthetic versatility. (HOSA) has only recently become widely substituted hydrazines and trisubstituied commercially available despite the fact that H,N-Nu hydrazinium salts it has proved to be a valuable synthetic reagent in preparative organic chemistry.
    [Show full text]
  • Of Operation and Control Ion-Exchange Processes For
    TECHNICAL REPORTS SERIES No. 78 Operation and Control Of Ion-Exchange Processes for Treatment of Radioactive Wastes INTERNATIONAL ATOMIC ENERGY AGENCY,VIENNA, 1967 OPERATION AND CONTROL OF ION-EXCHANGE PROCESSES FOR TREATMENT OF RADIOACTIVE WASTES The following States are Members of the International Atomic Energy Agency: AFGHANISTAN GERMANY, FEDERAL NIGERIA ALBANIA REPUBLIC OF NORWAY ALGERIA GHANA PAKISTAN ARGENTINA GREECE PANAMA AUSTRALIA GUATEMALA PARAGUAY AUSTRIA HAITI PERU BELGIUM HOLY SEE PHILIPPINES BOLIVIA HUNGARY POLAND BRAZIL ICELAND PORTUGAL BULGARIA INDIA ROMANIA BURMA INDONESIA SAUDI ARABIA BYELORUSSIAN SOVIET IRAN SENEGAL SOCIALIST REPUBLIC IRAQ SIERRA LEONE CAMBODIA ISRAEL SINGAPORE CAMEROON ITALY SOUTH AFRICA CANADA IVORY COAST SPAIN CEYLON JAMAICA SUDAN CHILE JAPAN SWEDEN CHINA JORDAN SWITZERLAND COLOMBIA KENYA SYRIAN ARAB REPUBLIC CONGO, DEMOCRATIC KOREA, REPUBLIC OF THAILAND REPUBLIC OF KUWAIT TUNISIA COSTA RICA LEBANON TURKEY CUBA LIBERIA UKRAINIAN SOVIET SOCIALIST CYPRUS LIBYA REPUBLIC CZECHOSLOVAK SOCIALIST LUXEMBOURG UNION OF SOVIET SOCIALIST REPUBLIC MADAGASCAR REPUBLICS DENMARK MALI UNITED ARAB REPUBLIC DOMINICAN REPUBLIC MEXICO UNITED KINGDOM OF GREAT ECUADOR MONACO BRITAIN AND NORTHERN IRELAND EL SALVADOR MOROCCO UNITED STATES OF AMERICA ETHIOPIA NETHERLANDS URUGUAY FINLAND NEW ZEALAND VENEZUELA FRANCE NICARAGUA VIET-NAM GABON YUGOSLAVIA The Agency's Statute was approved on 26 October 1956 by the Conference on the Statute of the IAEA held at United Nations Headquarters, New York; it entered into force on 29 July 1957, The Headquarters of the Agency are situated in Vienna. Its principal objective is "to accelerate and enlarge the contribution of atomic energy to peace, health and prosperity throughout the world". © IAEA, 1967 Permission to reproduce or translate the information contained in this publication may be obtained by writing to the International Atomic Energy Agency, Kamtner Ring 11, A-1010 Vienna I, Austria.
    [Show full text]
  • Preparation of 5-Bromo-2-Naphthol: the Use of a Sulfonic Acid As a Protecting and Activating Group
    Molbank 2009, M602 OPEN ACCESS molbank ISSN 1422-8599 www.mdpi.com/journal/molbank Short Note Preparation of 5-Bromo-2-naphthol: The Use of a Sulfonic Acid as a Protecting and Activating Group Renata Everett, Jillian Hamilton and Christopher Abelt * Department of Chemistry, College of William and Mary, Williamsburg, VA 23187, USA * Author to whom correspondence should be addressed; E-mail: [email protected] Received: 2 June 2009 / Accepted: 25 June 2009 / Published: 29 June 2009 Abstract: The preparation of 5-bromo-2-naphthol (4) in three steps from 5-amino-2- naphthol (1) is described. A sulfonic acid group is introduced at the 1-position as an activating and protecting group for the Sandmeyer reaction. The sulfonate group allows for the use of only water and sulfuric acid as solvents. The sulfonic acid is introduced with three equivalents of sulfuric acid, and it is removed in 20% aq. sulfuric acid. Keywords: Sandmeyer reaction; protecting group; sulfonation; desulfonation 1. Introduction Regioselective synthesis of disubstituted naphthalenes can be challenging especially when the substituents are on different rings. We needed 5-bromo-2-naphthol (4) as a starting material for a multistep synthesis. This simple derivative is virtually unknown [1,2]. The most direct route to 4 is from 5-amino-2-naphthol (1) using the Sandmeyer reaction. Unfortunately, the Sandmeyer reaction fails with 1 because the hydroxyl group is too activating. Even when the hydroxyl group is protected as a methyl ether, the normal solution-phase Sandmeyer reaction employing cuprous salts is still problematic. In their preparation of 5-bromo-2-methoxynaphthalene, Dauben and co-workers resorted to pyrolysis of the diazonium ion double salt with HgBr2, but this procedure gives just a 30% yield of the bromide [3].
    [Show full text]
  • Conductivity, Viscosity, Spectroscopic Properties of Organic Sulfonic Acid Solutions in Ionic Liquids
    chemengineering Article Conductivity, Viscosity, Spectroscopic Properties of Organic Sulfonic Acid solutions in Ionic Liquids Anh T. Tran, Jay Tomlin, Phuoc H. Lam, Brittany L. Stinger, Alexandra D. Miller, Dustin J. Walczyk, Omar Cruz, Timothy D. Vaden * and Lei Yu * Department of Chemistry and Biochemistry, Rowan University, Glassboro, NJ 08028, USA; [email protected] (A.T.T.); [email protected] (J.T.); [email protected] (P.H.L.); [email protected] (B.L.S.); [email protected] (A.D.M.); [email protected] (D.J.W.); [email protected] (O.C.) * Correspondence: [email protected] (T.D.V.); [email protected] (L.Y.) Received: 14 June 2019; Accepted: 25 September 2019; Published: 1 October 2019 Abstract: Sulfonic acids in ionic liquids (ILs) are used as catalysts, electrolytes, and solutions for metal extraction. The sulfonic acid ionization states and the solution acid/base properties are critical for these applications. Methane sulfonic acid (MSA) and camphor sulfonic acid (CSA) are dissolved in several IL solutions with and without bis(trifluoromethanesulfonyl)imine (HTFSI). The solutions demonstrated higher conductivities and lower viscosities. Through calorimetry and temperature-dependent conductivity analysis, we found that adding MSA to the IL solution may change both the ion migration activation energy and the number of “free” charge carriers. However, no significant acid ionization or proton transfer was observed in the IL solutions. Raman and IR spectroscopy with computational simulations suggest that the HTFSI forms dimers in the solutions with an N-H-N “bridged” structure, while MSA does not perturb this hydrogen ion solvation structure in the IL solutions.
    [Show full text]
  • Peroxynitrite Oxidation of Aromatic Thiols: Characterization of the Products Formed Through Oxidation of Thionitrobenzoic Acid and Thionitropyridine by Peroxynitrite
    W&M ScholarWorks Dissertations, Theses, and Masters Projects Theses, Dissertations, & Master Projects 2006 Peroxynitrite Oxidation of Aromatic Thiols: Characterization of the Products Formed through Oxidation of Thionitrobenzoic Acid and Thionitropyridine by Peroxynitrite Catherine Balchunas Mall College of William & Mary - Arts & Sciences Follow this and additional works at: https://scholarworks.wm.edu/etd Part of the Organic Chemistry Commons Recommended Citation Mall, Catherine Balchunas, "Peroxynitrite Oxidation of Aromatic Thiols: Characterization of the Products Formed through Oxidation of Thionitrobenzoic Acid and Thionitropyridine by Peroxynitrite" (2006). Dissertations, Theses, and Masters Projects. Paper 1539626852. https://dx.doi.org/doi:10.21220/s2-td8x-bb97 This Thesis is brought to you for free and open access by the Theses, Dissertations, & Master Projects at W&M ScholarWorks. It has been accepted for inclusion in Dissertations, Theses, and Masters Projects by an authorized administrator of W&M ScholarWorks. For more information, please contact [email protected]. PEROXYNITRITE OXIDATION OF AROMATIC THIOLS Characterization of the Products Formed Through Oxidation of Thionitrobenzoic Acid and Thionitropyridine by Peroxynitrite A Thesis Presented to The Faculty of the Department of Chemistry The College of William and Mary in Virginia In Partial Fulfillment Of the Requirements for the Degree of Master of Science by Catherine Balchunas Mall 2006 APPROVAL SHEET This thesis is submitted in partial fulfillment of the requirements for the degree of Master of Science t * fVkxXA Catherine Balchunas Mall Approved by the Committee, April 2006 Dr. Lisa M. Landino, Advisor and Chair Dr. Dr. Gaw W. Rice 11 DEDICATION This thesis is dedicated to my husband, Matthew Mall, for being the guy I always dreamed I would someday marry.
    [Show full text]