DOCSLIB.ORG

KINETICS and MECHANICS of the REACTION of HYDRAZOIC ACID with SUBSTITUTED BENZOIC ACIDS DISSERTATION Presented in P Artial Fulfi

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
KINETICS and MECHANICS of the REACTION of HYDRAZOIC ACID with SUBSTITUTED BENZOIC ACIDS DISSERTATION Presented in P Artial Fulfi KINETICS AND MECHANICS OF THE REACTION OF HYDRAZOIC ACID WITH SUBSTITUTED BENZOIC ACIDS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of the Ohio State U n iversity B y MELVILLE ERNEST DOUGLAS HILLMAN, B .A ., M.Sc, ++++++ The Ohio State University 1958 Approved by Department of Chemistry ACKNOWIÆDGMENTS The author wishes to express his appreciation to Dr, Harold Shechter for his suggestion of this problem, for his guidance and encouragement during the course of the investigation, and for his assistance in the preparation of the manuscript. The author is grateful to the Lubrizol Corporation the Socony- Mobile Company and to the Chemistry Department of The Ohio State University for fellowship funds. He also wishes to thank fellow graduate students and members of the staff for their cooperation in innumerable ways. The author is deeply grateful to his wife, Freda, for per­ forming some of the analyses and for taking over the difficult task of organizing and typing the various drafts of the dissertation. 11 CONTENTS Page I. INTRODUCTION................................................................................................ 1 II. HISTORICAL........................................................................................................ 4 The Schmidt Reaction ........................................................................... 4 The Curtins Reaction .........................................................................23 The Hammett Equation .................................................................. 28 Acidity Functions ................... 33 in. DISCUSSION OF RESULTS.................................................................... 41 Kinetic Order of the Schmidt Reaction. ............................41 Leveling of Solvent ................... 42 Decomposition of Hydrazoic Acid............................................ 43 Effect of Acidity on tlie Schmidt Reaction. .......... 48 Proximity Effects. ................... 67 Electrical Effects ................... 72 Activation Param eters. ............ 84 IV. EXPERIMENTAL. ................................................................................... 97 Preparation and Purification of Aromatic A cids,..... 97 o-Isopropylbenzoic Acid............................. 97 o-tert-Butylbenzoic Acid. .................................. 101 2, 6 -Dimethylbenzoic A cid. .......................... 106 2, 3-Dimethylbenzoic Acid. ............ 108 Purification of Substituted Benzoic Acids..................... 109 Determination of the Kinetic Constants................... I l l Constant Temperature Baths .......................................... I l l K in etic P ro ced u re........................................................ 112 Spectrophotometric Techniques................................... 112 Sulfuric Acid Solutions ................................ 115 Sodium Azide and Hydrazoic Acid Solutions 115 Execution of Kinetic Experiments 117 T reatment of Kinetic Data. ..................................... 121 Rate Constants..................................................................... 122 Activation Parameters ................ 125 APPENDIX .................................................................................................. 127 AUT OBIOGRAPH Y................................................................................. 319 iii LIST OF FIGURES Figure Page 1 -2„ Decomposition of Hydrazoic Acid .................. 45-46 3-6, Acidity Correlations for Reaction of £-Toluic A cid ................... 54-57 7. Hammett Plot for Reactions of m- and p- Substituted Benzoic Acids................................................ 76 8 . Enthalpy - Entropy Plot for Reactions of Substituted Benzoic Acids................................................................91 9-12, Activation Energy Plots for Reactions of Substituted Benzoic A cids. ....................... 128-131 13-18. Representative Plots of l/c versus time for Reactions of Substituted Benzoic Acids.................... 132-137 19-36. UV Absorption Spectra of Substituted Benzoic Acids and Substituted Anilines, ............... 138-146 37. Acidity Correlation for Reaction of ^-Toluic A cid .............................................................................. .. 147 IV LIST OF TABLES TEXT Table Page 1. The Schmidt Réaction of Substituted Benzoic Acids .... 9 2. The Schmidt Reaction of QuinolinecaxboxyXic Acids ... 19 3. Acidity Functions and Rate Constants for the Schmidt Reaction of o^-Toluic Acid at 24, 3®............................. 62 4. Rate Constants for Reaction of Hydrazoic Acid with Substituted Benzoic Acids ................................68-69 5. Activation Parameters for Reaction of Hydrazoic Acid with Substituted Benzoic Acids. ................... 74 6 . Physical Constants for the Substituted Benzoic Acids .110 APPENDIX 1-28. Collected Velocity Constants for the Schmidt Reactions of Substituted Benzoic A cids....................... 148-161 ' 29-159. Kinetic Data for the Schmidt Reactions of (O-Substituted Benzoic A cid s........................ 162-231 160-282. Kinetic Data for the Schmidt Reactions of m - and p-Substituted Benzoic A cids ........................ 232-295 283-284. Kinetic Data for the Decomposition of Hydrazoic Acid. ........................296 285-310. Kinetic Data for the Effect of Acidity on the Rate of the Schmidt Reaction of o-Toluic Acid,....... 297-318 I. INTRODUCTION Reaction of hydrazoic acid with a carboxylic acid (the Schmidt reaction) results in formation of the corresponding amine, carbon dioxide, and nitrogen (Equation 1). In order to R-COgH + HNs H2SO4 ^ R-NHz + COg + Ng (l) effect this important general reaction it is necessary to use strong mineral acids as catalysts. Mono-substituted benzenedicarboxylic acids in which the substituent is proximal to one of the carboxylic groups react selectively with one equivalent of hydrazoic acid to give only single mono-substituted amino acids. The novelty and utility of this reaction is that the more #sterically-hindered= carboxyl group is converted to the cor re spending amine. For example, 3-sub stituted phthalic acids or anhydrides in sulfuric acid react at the internal, more hindered, carboxyl group (Equation 2) to OgH CPzH CO2H + HN3 H2SO4 [I I + CO2 + N^ (2) yield exclusively the corresponding 3-substituted anthranilic acids. Upon reaction of 2- or 2,6 -disubstituted terephthalic acids (Equation 3) the more hindered carboxyl group is also 1 COzH m Î 2 (3) G (G) + HNî H2SO4 _ I I + CO2 + Nz COgH CO 2H selectively replaced. Similarly, the sole products obtained from Schmidt reactions of isophthalic acids which contain sub­ stituents in the 4-position (Equation 4) are the corresponding COgH COgH (4) + HNg HgS 0 4 ^ + COg + Ng 4-sub stituted, 3-aminoben.zoic acids. Because of the dramatic accelerative influences associated with proximal groups in Schmidt reactions, a study was initiated of the possible mechanisms of these processes. It was decided to determine the influence of structure on the kinetic order, rates, and kinetic parameters of reaction of hydrazoic acid in sulfuric acid with substituted benzoic acids in the following series: (1 ) ortho-sub stituted benzoic acids, to measure proximity effects on the Schmidt reaction (2 ) meta- and para-substituted benzoic acids, to determine the electrical requirements of the Schmidt reaction (3) di- and trimethyl/benzoic acids, to determine possible buttressing and accumulative electrical and proximity factors in the Schmidt reaction To gain additional insight into fundamental details of the mechanism, a study of the effects of sulfuric acid con­ centration on the rate of the Schmidt reaction of ortho-toluic acid was made. The kinetics of decomposition of hydrazoic acid in concentrated sulfuric acid were also investigated. n. HISTORICAL The Schmidt Reaction Reactions of carbonyl compounds with hydrazoic acid in strong acids have become known as Schmidt reactions. These reactions were first discovered by Schmidt on studying the decom­ position of hydrazoic acid by sulfuric acid (1), Acting on the (1) K, F, Schmidt, Z, angew Chem., 36, 511 (1923). hypothesis that one of the primary decomposition products of hydrazoic acid is imine, NH, which is capable of reacting with an unsaturated group, Schmidt added benzophenone to the reaction mixture. A rapid reaction occurred, and a quantitative yield of benzanilide was obtained (2) (Equation 5). O C> CfiHg-C-C^Hs + HN 3 ------> C6H5-C-NH-C 6H5 + Nz (5) (2) K, F, Schmidt, Acta Acad, Aboensis, Math. etPhys,, 2, 38 1924, C. A ., 19 , 3248 (1925). The Schmidt reaction of carboxylic acids in strong mineral acid (Equation 6 and 7) yields amines having one less carbon atom, carbon dioxide and nitrogen; a presumed 4 R-COzH + HNs > RNCO + Ng ( 6 ) R-NCO + HzO — --------- > RNHz + COg (7) intermediate is the isocyanate which is subsequently hydrolyzed in the aqueous medium. Aldehydes give nitriies and formyl derivatives of amines, and ketones yield amides, AJdehydes and ketones with excess hydrazoic acid (two or more equiva­ lents) form substituted tetrazoles (Equation 8 ), RCOR + 2 HN3 H2SO4 RC = N + H2O + Nz (8 ) A more complete description of the scope of the Schmidt reaction has been given by Wolff (3), (3) H. Wolff in Adams “Organic Reactions, * Vol, III, John Wiley and Sons, Inc,, New York, N, Y ,, 1946, pp, 307-336, The mechanisms of Schmidt reactions of carbonyl com­ pounds have attracted the attention of certain investigators, Schmidt
Load more

Recommended publications
  • Nitrous Acid)
    5. Nitrogen Group Content 5.1 Occurrence 5.2 Group Properties Group 5.3 Physical Properties 15 or VA 5.4 Syntheses 7 1772 5.5 Chemical Behaviour N 15 5.6 Applications 1669 5.7 Chemistry of Elemental Nitrogen P 33 5.8 Compounds Made of Nitrogen and Hydrogen Antique 5.9 Nitrogen Compounds with Oxygen As 51 5.10 Nitrogen Compounds with Halides Antique Sb 5.11 Phosphorus/Hydrogen Compounds 83 1753 5.12 Phosphorus Oxides Bi 5.13 Oxo Acids of Phosphorus 115 2003 5.14 Phosphorus Compounds with Halides Mc 5.15 Arsenic, Antimony and Bismuth 5.16 Biological Aspects „Penteles“ Inorganic Chemistry I Slide 1 Prof. Dr. T. Jüstel 5.1 Occurrence Außer Phosphor kommen alle Pentele auch elementar (gediegen) vor Nitrogen (nitrogenium) N2 (78.1% in the air) NaNO3 Chile saltpetre KNO3 Saltpetre Phosphorus (phosphoros) Ca5(PO4)3(OH,F) Apatite greek: lightbearer Ca3(PO4)2 Phosphorite . Fe3(PO4)2 8H2O Vivianite Arsenic (arsenikos) FeAsS Arsenopyrite greek: mineral name As4S4 Realgar As4S3 Antimony (antimonium) Sb native Stibium = greek mineral name Sb2S3 Bismuth (bismutum) Bi native german: Wismut = Mutung “in the meadows” Bi2S3 Inorganic Chemistry I Slide 2 Prof. Dr. T. Jüstel 5.2 Group Properties Whereas Nitrogen Exhibits the Typical Properties of A Non-Metal, Bismuth Is Solely Metallic N P As Sb Bi Atomic number 7 15 33 51 83 Electronic [He] [Ne] [Ar] [Kr] [Xe]4f14 configuration 2s22p3 3s23p3 3d104s24p3 4d105s25p3 5d106s26p3 Electronegativity 3.0 2.1 2.2 1.8 1.7 Ionisation energy [eV] 14.5 11.0 9.8 8.6 7.3 Electronic affinity [eV] -0.3 0.6 0.7 0.6 > 0.7 Character of oxides acidic acidic amphoteric amphoteric alkaline Oxidation states -3, ...…, +5 With increasing atomic number, the oxidation state +3 becomes more stable, whilst the oxidation state +5 becomes instable.
    [Show full text]
  • United States Patent Office Patented Aug
    3,832,364 United States Patent Office Patented Aug. 27, 1974. 2 zene, o-, m- and p-dichlorobenzene, anisole, methyl. 3,832,364 benzyl ether, n-propyl phenyl ether, m-ethyl-anisole, 4 AMINATION OF AROMATIC COMPOUNDS IN methyldiphenyl ether, di-p-tolyl ether, ethyl 2-cyclohexyl LIQUID HYDROGEN FLUORIDE Dale Robert Coulson, Wilmington, Del assignor to E. I. phenyl ether, n-heptyl phenyl ether, isobutyl phenyl ether, du Pont de Nemours and Company, Wilmington, Del. 5 cyclohexyl phenyl ether, n-octyl phenyl ether, n-octyl p No Drawing. Filed May 25, 1972, Ser. No. 256,770 tolyl ether, n-octyl m-tolyl ether, decyl phenyl ether, 1 Int. C. C07c87/50, 97/12 benzylethylheptyl ether, benzoic acid, p-toluic acid, p U.S. C. 260-378 26 Claims chlorobenzoic acid, phthalic acid, nitrobenzene, m-dinitro benzene, o-, m- and p-nitrotoluene, acetophenone, methyl O benzyl ketone, p-methylacetophenone, 3-phenyl-2-buta ABSTRACT OF THE DISCLOSURE none, propriophenone, 2-methyl-1-tetralone, phenyl. n Disclosed herein is a process for making aromatic butyl ketone, benzophenone, p-methylbenzophenone, di amines from benzene or substituted benzene and an o-tolyl ketone, phenyl isobutyl ketone, phenyl n-hexyl aminating agent via direct amination in liquid hydrogen ketone, phenyl n - undecyl ketone, anthraquinone, 2 - fluoride medium as solvent and catalyst. 15 methylanthraquinone, and 1-methyl-4-isopropylanthra quinone. Preferred aromatic compounds are those containing BACKGROUND OF THE INVENTION two or fewer substituents. Especially preferred com 1. Field of the Invention pounds are those containing two or fewer substituents 20 selected from halogen and alkyl of up to four carbons.
    [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]
  • An Efficient One-Pot Three-Component Synthesis of Novel Sulfanyl Tetrazoles Using Ionic Liquids
    Hindawi Publishing Corporation Journal of Chemistry Volume 2013, Article ID 104690, 6 pages http://dx.doi.org/10.1155/2013/104690 Research Article An Efficient One-Pot Three-Component Synthesis of Novel Sulfanyl Tetrazoles Using Ionic Liquids Sankari Kanakaraju, Bethanamudi Prasanna, and G. V. P. Chandramouli Department of Chemistry, National Institute of Technology, Warangal 506 004, India Correspondence should be addressed to G. V. P. Chandramouli; [email protected] Received 13 June 2012; Accepted 11 August 2012 Academic Editor: Mohamed Afzal Pasha Copyright © 2013 Sankari Kanakaraju et al. is is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. An efficient, simple, and environmentally benign method for the synthesis of novel sulfanyl tetrazoles has been achieved by one- pot three-component reaction of phenacyl bromides/3-(2-bromoacetyl)coumarins with KSCN and NaN using [Bmim]BF ionic liquid. It could be reused and recycled for four runs without signi�cant loss of product yield. 3 4 1. Introduction synthesize the compounds containing coumarin-substituted sulfanyl tetrazoles. Over the years, multicomponent reactions (MCRs) have e most convenient method of synthesizing tetrazoles become increasingly popular tools to ensure sufficient molec- is the addition of azide ions to nitriles. Earlier reported ular diversity and complexity. ey have gained signi�cant methods for the synthesis of 5-substituted tetrazoles suffer popularity in recent years due to their atom-economy and from drawbacks such as the use of strong Lewis acids, straightforward reaction design due to substantial minimiza- or expensive and toxic metals, and the in situ generated tion of waste, labour, time, and cost [1, 2].
    [Show full text]
  • Safe Generation and Synthetic Utilization of Hydrazoic Acid in a Continuous Flow Reactor
    Full Paper Safe Generation and Synthetic Utilization of Hydrazoic Acid in a Continuous Flow Reactor Bernhard Gutmann1, David Obermayer1, Jean-Paul Roduit2, Dominique M. Roberge2* and C. Oliver Kappe1* 1Christian Doppler Laboratory for Microwave Chemistry and Institute of Chemistry, Karl-Franzens-University Graz, Heinrichstrasse 28, A-8010 Graz, Austria 2Microreactor Technology, Lonza AG, CH-3930 Visp, Switzerland Hydrazoic acid (HN3) was used in a safe and reliable way for the synthesis of 5-substitued-1H-tetrazoles and for the preparation of N-(2-azidoethyl)acylamides in a continuous flow format. Hydrazoic acid was generated in situ either from an aqueous feed of sodium azide upon mixing with acetic acid, or from neat trimethylsilyl azide upon mixing with methanol. For both processes, subsequent reaction of the in situ generated hydrazoic acid with either organic nitriles (tetrazole formation) or 2-oxazolines (ring opening to b-azido-carboxamides) was performed in a coil reactor in an elevated temperature/pressure regime. Despite the explosive properties of HN3, the reactions could be performed safely at very high temperatures to yield the desired products in short reaction times and in excellent product yields. The scalability of both protocols was demonstrated for selected examples. Employing a commercially available benchtop flow reactor, productivities of 18.9 g/h of 5-phenyltetrazole and 23.0 g/h of N-(1-azido-2-methylpropan- 2-yl)acetamide were achieved. Keywords: flow chemistry, hydrazoic acid, microreactor, process intensification, tetrazoles 1. Introduction a minimum [6–8]. The characteristics of microreaction technol- ogy (i.e., fast heat and mass transfer, and high pressure resis- Hydrazoic acid (HN ), a gas of “highly peculiar, dreadfully 3 tance of capillaries with small inner diameters) often allow pungent smell,” was discovered by Theodor Curtius in the 1890s temperatures to be used which would be unsafe in traditional by acidification of sodium azide [1].
    [Show full text]
  • The Synthesis and Characterization of Energetic Materials from Sodium Azide
    THE SYNTHESIS AND CHARACTERIZATION OF ENERGETIC MATERIALS FROM SODIUM AZIDE A Thesis Presented to The Academic Faculty By Joshua Aronson In Partial Fulfillment Of the Requirements for the Degree Doctor of Philosophy in the School of Chemistry and Biochemistry Georgia Institute of Technology October 2004 THE SYNTHESIS AND CHARACTERIZATION OF ENERGETIC MATERIALS FROM SODIUM AZIDE Approved by: Charles L. Liotta, Advisor Kent Richman Charles A. Eckert Julia Kubanek David Collard November 17, 2004 ii This thesis is dedicated to M. G. iii ACKNOWLEDGEMENT I would first like to thank Dr. Liotta and Dr. Eckert for their support and encouragement. I will forever envy your enthusiasm and spirit. I would also like to extend my appreciation to everyone at American Pacific. My experiences in Utah and Las Vegas contributed a great deal to my graduate education. In addition, I want to thank the entire Liotta-Eckert research group—especially Kris and Pamela. The two of you made all of this not only bearable, but fun. Finally, I would like to thank my mom and Mary Katherine for their support. I would not have made it without you. iv TABLE OF CONTENTS Acknowledgement iv List of Figures viii List of Tables xii List of Abbreviations xiii Summary xv Chapter I Introduction 1 Chapter II A Novel Approach To The Synthesis Of Tetrazoles 5 Introduction 5 Experimental Methods 10 Materials 10 Apparatus 10 Procedures 11 Results and Discussion 14 Conclusion 37 References 38 Chapter III The Synthesis and Characterization Of Glycidyl 40 Azide Polymer Introduction 40 Experimental
    [Show full text]
  • HHE Report No. HETA-95-0023-2531, American
    ThisThis Heal Healthth Ha Hazzardard E Evvaluaaluationtion ( H(HHHEE) )report report and and any any r ereccoommmmendendaatitonsions m madeade herein herein are are f orfor t hethe s sppeeccifiicfic f afacciliilityty e evvaluaaluatedted and and may may not not b bee un univeriverssaalllyly appappliliccabable.le. A Anyny re reccoommmmendaendatitoionnss m madeade are are n noot tt oto be be c consonsideredidered as as f ifnalinal s statatetemmeenntsts of of N NIOIOSSHH po polilcicyy or or of of any any agen agenccyy or or i ndindivivididuualal i nvoinvolvlved.ed. AdditionalAdditional HHE HHE repor reportsts are are ava availilabablele at at h htttptp:/://ww/wwww.c.cddcc.gov.gov/n/nioiosshh/hhe/hhe/repor/reportsts ThisThis HealHealtthh HaHazzardard EEvvaluaaluattionion ((HHHHEE)) reportreport andand anyany rreeccoommmmendendaattiionsons mmadeade hereinherein areare fforor tthehe ssppeecciifficic ffaacciliilittyy eevvaluaaluatteded andand maymay notnot bbee ununiiververssaallllyy appappapplililicccababablle.e.le. A AAnynyny re rerecccooommmmmmendaendaendattitiooionnnsss m mmadeadeade are areare n nnooott t t totoo be bebe c cconsonsonsiideredderedidered as asas f fifinalnalinal s ssttataatteteemmmeeennnttstss of ofof N NNIIOIOOSSSHHH po popolliilccicyyy or oror of ofof any anyany agen agenagencccyyy or oror i indndindiivviviiddiduuualalal i invonvoinvollvvlved.ed.ed. AdditionalAdditional HHEHHE reporreporttss areare avaavaililabablele atat hhtttpp::///wwwwww..ccddcc..govgov//nnioiosshh//hhehhe//reporreporttss This Health Hazard Evaluation (HHE) report and any recommendations made herein are for the specific facility evaluated and may not be universally applicable. Any recommendations made are not to be considered as final statements of NIOSH policy or of any agency or individual involved. Additional HHE reports are available at http://www.cdc.gov/niosh/hhe/reports HETA 95-0023-2531 AMERICAN AZIDE CORPORATION CEDAR CITY, UTAH Eric Esswein, M.S.P.H.
    [Show full text]
  • Compilation of Chemical Kinetic Data for Combustion Chemistry. Part 2. Non-Aromatic C, H, O, N, and S Containing Compounds
    v NBS PUBLICATIONS r A111D2 TBOmi NAT'L INST OF STANDARDS & TECH R.I.C. All 102730091 Westley, Francls/Compllatlon of chemical 2 QC100 .11573 NO. 73 V2;1987 C.2 NBS-PUB-C NSRDS-NBS 73, Part U.S. DEPARTMENT OF COMMERCE / National Bureau of Standards 1 BB he National Bureau of Standards was established by an act of Congress on March 3, 1901. The Bureau’s overall M goal is to strengthen and advance the nation’s science and technology and facilitate their effective application for public benefit. To this end, the Bureau conducts research to assure international competidveness and leadership of U.S. industry, science arid technology. NBS work involves development and transfer of measurements, standards and related science and technology, in support of continually improving U.S. productivity, product quality and reliability, innovation and underlying science and engineering. The Bureau’s technical work is performed by the National Measurement Laboratory, the National Engineering Laboratory, the Institute for Computer Sciences and Technology, and the Institute for Materials Science and Engineering. The National Measurement Laboratory Provides the national system of physical and chemical measurement; • Basic Standards 2 coordinates the system with measurement systems of other nations and • Radiation Research furnishes essential services leading to accurate and uniform physical and • Chemical Physics chemical measurement throughout the Nation’s scientific community, • Analytical Chemistry industry, and commerce; provides advisory and research
    [Show full text]
  • Chapter 8.0 Chemical and Process Safety. Non-Sensitive Version
    8.0 CHEMICAL AND PROCESS SAFETY 8.1 CONDUCT OF REVIEW This chapter of the revised Draft Safety Evaluation Report (revised DSER) contains the staff’s review of chemical and process safety described by the applicant in Chapter 8 of the revised Construction Authorization Request (revised CAR) (Reference 8.3.19), with supporting process safety information from Chapters 5 and 11 of the revised CAR. The objective of this review is to determine whether the chemical process safety principal structures, systems, and components (PSSCs) and their design bases identified by the applicant provide reasonable assurance of protection against the consequences of potential accidents. The staff evaluated the information provided by the applicant for chemical process safety by reviewing the revised CAR, supplementary information provided by the applicant, and relevant documents available at the applicant’s offices but not submitted by the applicant. The staff also reviewed technical literature as necessary to understand the process and safety requirements. The review of aqueous polishing (AP) and mixed oxide process (MP) safety design bases and strategies was closely coordinated with the review of the radiation and chemical safety aspects of accident sequences described in the Safety Assessment of the Design Bases (see Chapter 5.0 of this revised DSER), the review of fire safety aspects (see Chapter 7.0 of this revised DSER), and the review of plant systems (see Chapter 11.0 of this revised DSER). The staff reviewed the chemical process and safety information in the revised CAR and supporting documents against the following regulations: ! Section 70.23(b) of 10 CFR states, as a prerequisite to construction authorization, that the design bases of the PSSCs and the quality assurance program be found to provide reasonable assurance of protection against natural phenomena and the consequences of potential accidents.
    [Show full text]
  • Non-Metallic Elements; Compounds Thereof; {Metalloids Or Compounds Thereof Not Covered by Subclass C01c}
    CPC - C01B - 2021.08 C01B NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} Definition statement This place covers: The chemical elements of hydrogen, halogen (fluorine, chlorine, bromine, iodine and astatine), oxygen, sulfur, phosphorus, silicon, nitrogen, boron, selenium, tellurium, and noble gases (helium, neon, argon, krypton, xenon and radon). Compounds solely composed of any of the elements listed above. Carbon and compounds of carbon with any of the elements listed above, with the proviso that said compounds cannot contain a carbon atom having direct bonding to another carbon atom, a carbon atom having direct bonding to a hydrogen atom or a halogen atom, or a carbon atom having direct bonding to a nitrogen atom by a single or double bond. Compounds composed solely of one or more metal atoms and hydrogen. Peroxides and salts of peroxyacids. Magnesium, calcium, strontium, or barium sulfides or polysulfides. Alkali metal sulfides or polysulfides. Thiosulfates, dithionites and polythionates. Compounds containing selenium or tellurium. Azides, metal amides and nitrites. Carbamic acid and salts thereof. Binary compounds containing a metal and either N, C or P. Salts of the oxyacids of halogen or phosphorus. Compounds consisting only of carbon atoms, e.g. fullerenes, carbon nanotubes. Phosgene and thiophosgene. Compounds containing silicon such as silicates, silicon oxides or colloidal silica, e.g. dispersions, gels, hydroorganosols, organosols. Compounds containing boron. Substances having molecular sieve properties, but not having base-exchange properties. Substances having a combination of molecular sieve and base-exchange properties, e.g. crystalline zeolites. Synthesis, treatment or modification of any of the elements or compounds above by: • chemical means, i.e.
    [Show full text]
  • Electron-Induced Radiolysis of Astrochemically Relevant Ammonia Ices
    1 Electron-Induced Radiolysis of Astrochemically Relevant Ammonia Ices Katherine E. Shulenberger, Jane L. Zhu, Katherine Tran, Sebiha Abdullahi, Carina Belvin, Julia Lukens, Zoe Peeler, Ella Mullikin, Helen M. Cumberbatch, Jean Huang, Kathleen Regovich, Alice Zhou, Lauren Heller, Milica Markovic, Leslie Gates, Christina Buffo, Rhoda Tano-Menka, a and Christopher R. Arumainayagam Department of Chemistry, Wellesley College, Wellesley, MA 02481 Esther Böhler, Petra Swiderek, Institute of Applied and Physical Chemistry, University of Bremen, D-28334 Bremen, Germany Sasan Esmaili, Andrew D. Bass, Michael Huels, and Léon Sanche Department of Nuclear Medicine and Radiobiology, University of Sherbrooke, Sherbrooke, QC, Canada Abstract We elucidate mechanisms of electron-induced radiolysis in cosmic (interstellar, planetary, and cometary) ice analogs of ammonia (NH3), likely the most abundant nitrogen-containing compound in the interstellar medium (ISM). Astrochemical processes were simulated under ultrahigh vacuum conditions by high-energy (1 keV) and low-energy (7 eV) electron-irradiation of nanoscale thin films of ammonia deposited on cryogenically cooled metal substrates. Irradiated films were analyzed by temperature-programmed desorption (TPD). Experiments with ammonia isotopologues provide convincing evidence for the electron-induced formation of hydrazine (N2H4) and diazene (N2H2) from condensed NH3. To understand the dynamics of ammonia radiolysis, the dependence of hydrazine and diazene yields on incident electron energy, electron flux, electron fluence, film thickness, and ice temperature were investigated. Radiolysis yield measurements versus (1) irradiation time and (2) film thickness are semi-quantitatively consistent with a reaction mechanism that involves a bimolecular step for the formation of hydrazine and diazene from the dimerization of amidogen (NH2) and imine (NH) radicals, respectively.
    [Show full text]
  • United States Patent Office Patented Oct
    3,767,667 United States Patent Office Patented Oct. 23, 1973 1. 2 etc.; "lower alkoxy' means methoxy, ethoxy, propoxy, 3,767,667 isopropoxy, butoxy, isobutoxy, t-butoxy, etc.; "halogen' PROCESS FOR PREPARNG 1H-TETRAZOLE COMPOUNDS means fluorine, chlorine, bromine, iodine; "aryl' means Takashi Kamiya and Yoshihisa Saito, Suita, Japan, as phenyl, tolyl, xylyl, mesityl, naphthyl, biphenylyl, etc. ises to Fujisawa Pharmaceutical Co., Ltd., Osaka, and “ar(lower) alkyl' means benzyl, tolylmethyl, xylyl apan 5 methyl, phenethyl, tolylethyl, or-methylbenzyl, ox-methyl No Drawing. Filed Oct. 7, 1971, Ser. No. 187,561 phenethyl, etc. Int, C. C07d 55/56 The compounds (I) of this invention are known com U.S. C. 260-308 D 7 Claims pounds and there are many known processes for pre paring the same, among which some processes are de O scribed in Chemical Abstract 50, 3418 (1956), Journal ABSTRACT OF THE DISCLOSURE of Organic Chemistry 21, 311-315 (1956) and Canadian A process for preparing 1H-tetrazole compounds of the Journal of Chemistry 47 813-819 (1969). All of the formula: known processes have a disadvantage in that they need multiple steps to produce the compounds (I) and their 5 operation procedures are complex and troublesome. This invention was made in order to overcome this disadvan R l, tage and in addition has advantages, in comparison with the known processes, in that (1) the object Compound I can be obtained in a remarkably good yield, as the proc wherein R1 and R are each hydrogen or a possible sub 20 ess of this invention comprises a single step reaction; stituent, (2) the operation procedure is extremely simple, that is, the object Compound I can be obtained by only heating which comprises reacting an amine compound of the the mixture of the amine Compound II, the orthocar formula: boxylic acid ester (III) and the hydrazoic acid salt, and R-NH2 25 (3) there is no need to use a poisonous gas of hydrazoic wherein R is as defined above, acid which is usually employed in the synthesis of tetra zole compounds.
    [Show full text]