DOCSLIB.ORG

A STUDY OP the EXCHANGE of IODINE BETWEEN ETHYL IODIDE and SODIUM IODIDE in FORMAMIDE by Led Ay CATHARINE ELIZABETH WORSFOLD

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
A STUDY OP the EXCHANGE of IODINE BETWEEN ETHYL IODIDE and SODIUM IODIDE in FORMAMIDE by Led Ay CATHARINE ELIZABETH WORSFOLD Led Ay Ca -I A STUDY OP THE EXCHANGE OF IODINE BETWEEN ETHYL IODIDE AND SODIUM IODIDE IN FORMAMIDE by CATHARINE ELIZABETH WORSFOLD A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF ARTS in the Department of CHEMISTRY We accept this thesis as conforming to the standard required from candidates for the degree of MASTER OF ARTS. Members of the Department of Chemistry THE UNIVERSITY OF.BRITISH COLUMBIA April, 1951 Abstract The exchange system G0H_I — 1* was studied in ethyl alcohol solution. <• 5 The average rate constant for this reaction was 29.9 x 10 ^ moles litre sec at 50.1°C, The exchange of iodine between ethyl iodide and iodide ion was found to be complicated by a reaction of ethyl iodide with the solvent.. The kinetics; of the simultaneous reaction of ethyl iodide with formamide and the exchange reaction were treated theoretically. Experi• mentally the ethyl iodide - formamide reaction was found to be of a complex nature. The measured exchange rate constant was approximately -2 -1 -1 o 1 x 10 mole litre sec at 25 C which is greater than the rate constant of the same reaction in alcohol solution. The exchange system I - IO^ was also studied and k for this reaction was approximately 1 x 10*""* -1 -1 o moles litre sec at 30,8 C. Acknowledgment I wish to express my most sincere gratitude to Dr. Milton Kirsch for his inspiring guidance, patience, and untiring assistance throughout this research project. Thanks are due also to the National Research Council for financial aid and to the Atomic Energy Project at Chalk River for prompt deliveries of radioactive sodium iodide (I ) used in this investigation. April, 1951 Catharine Elizabeth Worsfold TABLE OP CONTENTS INTRODUCTION Exchange Reactions. .... 2 Halogen Exchange Reactions 3 KINETICS OF EXCHANGE REACTIONS Derivation of the Rate Constant Expression 8 EXPERIMENTAL I. Ethyl Iodide-Iodide Ion Exchange in Ethyl Alcohol. ... 11 Preparation of Materials 11 Procedure -. 11 Results ..... 12 II. Ethyl Iodide-Iodide Ion Exchange in Formamide. ..... 14 Preparation of Materials. 14 Preliminary Investigation of the Behaviour of Sodium Iodide, Ethyl Iodide, and Silver Nitrate in Formamide ............... 15 (1) Solubilities . 15 (2) Separation of Ethyl Iodide from Sodium Iodide 16 (a) Distillation 16 (b) Solvent Extraction 17 (c) Oxidation . 19 (3) Precipitation of the Silver Iodides 20 The Use of KIO^ for the Separation of Ethyl Iodide,? from Sodium Iodide 21 Theoretical Consideration of the Kinetics of the Reaction between Ethyl Iodide and Formamide with the Simultaneous Exchange of Ethyl Iodide with Radioactive Iodide Ion ..... 22 The Rate of Reaction of Ethyl Iodide with Formamide. 25 Measurement of the Exchange Rate Constant ...... 26 The Exchange of Iodide Ion with Iodate Ion in Aqueous Formamide. ................ 28 The Exchange between I2 in CCl^ and Ethyl Iodide in Formamide 30 DISCUSSION OF RESULTS AND SUGGESTIONS FOR FURTHER RESEARCH BIBLIOGRAPHY APPENDIX INTRODUCTION Fefore artificially produced radioactive isotopes became readily available there were many processes of interest to the chemist which could not be studied simply because there was no means whereby a particular element could be "tagged." With the possible exception of the lightest elements, where the percentage mass difference between the isotopes of an element is the greatest, there is no chemical means of distinguishing between isotopes. Thus, the isotopic composition remains essentially constant throughout a chemical or biological process. Only Tl, Pb, and Bi (and several other elements in the middle of the periodic table whose radioactive isotopic content is very small) possess both stable and naturally radioactive Isotopes which could be used to investigate reactions. By means of a mass spectrograph it is possible, though often tedious, to follow reactions with stable tracers. Even with the great increase in production of radioactive tracers from nuclear piles there is still a definite limitation on their use since some elements do not possess radioactive isotopes of suitable half-life. Among these are oxygen, nitrogen, helium, lithium, and boron for which the use of separated stable isotopes as tracers is a very valuable technique (1). Deuterium has found many applications as a hydrogen tracer and oxygen and nitrogen enriched with 0^ and N*-5 respectively are essential for many important purposes. However, a great number of elements do possess artificial radioisotopes of suitable half-life for chemical studies and with these it is possible to trace a "marked* atom by the radiations it emits. EVen a brief survey of the literature on tracers and radio chemistry that has accumulated in the space of the few years that radioactive indi• cators have been available is far beyond the scope of this work. (2) This discussion will be concerned only with one phase of tracer appli• cations-—their use in exchange reactions in general and halogen exchanges in particular. References 1 to 9 include general background material on isotopes and their uses. Exchange Reactions An exchange reaction is, as the name implies, a replacement reaction in which the reactants and products are chemically identical. Because of this chemical identity exchange reactions can be studied only by means of tracers. Consider a simple exchange of the type ABV+ B^ ^ AB£ f m Jk where an asterisk indicates a radioactive nuclide. Since the products are the same as the reactants (except for the small mass difference of the added isotope) the rate constants of the forward and reverse reactions are practically equal. Kinetic data may be used to show the mechanism of reactions, to study the character and stability of bonds, and to establish the effect of solvent on reaction rates. The following discussion is not intended to be a complete resume of attempted exchange reactions but is designed to indicate briefly the nature of the experiments which have been done cm exchange systems. In fact, with few exceptions, only halogen exchanges will be considered. One of the earliest exchange experiments was performed by Hevesy in 1920 By means of ThB; (pb2-1-2) he demonstrated the rapid exchange of lead ions between PbCl2 and Pb(1103)2 in aqueous solution. He also showed the rapid exchange of lead atoms between Pb(Ac)2 and Pb(Ac)^ in acetic acid solution. In the first case one would expect exchange since both these salts: give rise to chemically identical Pb ions. In the case of the acetates: the exchange presumably occurs through a reversible interconversion of plumbous and plumbic ions. (3) With the increased production of radionuclides in the 1930"s, very many exchange reactions were studied. In 1935, the mechanism of the Walden inversion was investigated fa*-5). It was shown that the rate of substitution of iodide for the iodine in secondary octyl iodide and the velocity of racemization under similar conditions are the same. This gave direct confirmation that Walden inversion involves substitution. In 1937, Wilson and Dickinson ^) calculated the rate of oxidation and reduction of iodine from the exchange which takes place at equilib• rium between radioactive pentavalent arsenic (As76) and trivalent arsenic. The reaction was carried out in acid solution in the presence of iodide ion and free iodine. Using the assumption that the exchange occurs through the oxidation and reduction of iodine the rates were found to agree with the kinetic expression given by Roebuck for the same reaction remote from equilibrium. While these and many other experiments indicate the utilization of exchange reaction in the study of the mechanisms of other reactions, many exchange reactions have been studied with the hope of reaching a better understanding of the mechanism of the exchange itself. In parti• cular, the exchange of halogens with corresponding halides has been studied in a variety of solvents under different conditions. Halogen Exchange Reactions Hull, Schiflett, and Lind studied exchanges of radioiodine and reported that: l) I2 and I~ exchange freely in aqueous solution presumably by the formation of Lj*", 2') I2 and I0^~ in IN sulphuric acid do not exchange at an appreciable speed, but in 20N hot H2S0^ 10rl5$ of the radioactive iodine appears in the 10^" suggesting oxidation-reduction at a measurable rate, 3) no exchange occurs between C2H5I or CH3I and active I2 even after 15 minutes at 90°C but if active Nal and inactive C2H5I are dissolved in alcohol and heated to 100°C, exchange does occur, L) I2 and iodoform do not exchange in ether solution, and 5) iodoform does not exchange with active Nal in alcohol. Bromine-bromide exchange in aqueous solution was studied by Grosse and Agruss who concluded that the exchange is fairly slow, being governed by the rate of hydrloysis of bromine. Roginski and Gopshtein however, stated that this exchange was rapid. Dodson and Fowler inves• tigated both bromine-bromide and iodine-iodide exchanges and found that both reactions were practically complete in 60 seconds. Long and Olson reported that the exchange between C.I2. and Cl" was immeasurably fast. Juliusberger, Topley, and Weiss showed that appreciable exchange takes place in 1 - 2. minutes between CH3I and active Nal in alcohol solu• tion at room temperature. McKay reported qualitative exchange data for the reaction between several aliphatic and aromatic iodides, and sodium iodide. At room temperature allyl and methyl iodides exchange with active Nal in alcohol or acetone solution. Tinder the same conditions no exchange was found with ethyl, propyl, isopropyl, and methylene iodide, nor does iodoform exchange in acetone solution. However, at 100°C, methylene, propyl, isopropyl, and isoamyl iodides exchange in approxi• mately 15 minutes. Nal*-ethyl iodide exchange was practically complete after 15 minutes at 50 - 55°G. No exchange between active Nal and phenyl iodide, p-nitroiodobenzene, or p-iodoaniline could be detected at 100°C.
Load more

Recommended publications
  • Gas Phase Chemistry and Removal of CH3I During a Severe Accident
    DK0100070 Nordisk kernesikkerhedsforskning Norraenar kjarnoryggisrannsoknir Pohjoismainenydinturvallisuustutkimus Nordiskkjernesikkerhetsforskning Nordisk karnsakerhetsforskning Nordic nuclear safety research NKS-25 ISBN 87-7893-076-6 Gas Phase Chemistry and Removal of CH I during a Severe Accident Anna Karhu VTT Energy, Finland 2/42 January 2001 Abstract The purpose of this literature review was to gather valuable information on the behavior of methyl iodide on the gas phase during a severe accident. The po- tential of transition metals, especially silver and copper, to remove organic io- dides from the gas streams was also studied. Transition metals are one of the most interesting groups in the contex of iodine mitigation. For example silver is known to react intensively with iodine compounds. Silver is also relatively inert material and it is thermally stable. Copper is known to react with some radioio- dine species. However, it is not reactive toward methyl iodide. In addition, it is oxidized to copper oxide under atmospheric conditions. This may limit the in- dustrial use of copper. Key words Methyl iodide, gas phase, severe accident mitigation NKS-25 ISBN 87-7893-076-6 Danka Services International, DSI, 2001 The report can be obtained from NKS Secretariat P.O. Box 30 DK-4000RoskiIde Denmark Phone +45 4677 4045 Fax +45 4677 4046 http://www.nks.org e-mail: [email protected] Gas Phase Chemistry and Removal of CH3I during a Severe Accident VTT Energy, Finland Anna Karhu Abstract The purpose of this literature review was to gather valuable information on the behavior of methyl iodide on the gas phase during a severe accident.
    [Show full text]
  • University Miaorilms International 300 N
    INFORMATION TO USERS This reproduction was made from a copy of a document sent to us for microfilming. While the most advanced technology has been used to photograph and reproduce this document, the quality of the reproduction is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help clarify markings or notations which may appear on this reproduction. 1. The sign or “target” for pages apparently lacking from the document photographed is “Missing Page(s)”. If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure complete continuity. 2. When an image on the film is obliterated with a round black mark, it is an indication of either blurred copy because of movement during exposure, duplicate copy, or copyrighted materials that should not have been filmed. For blurred pages, a good image of the page can be found in the adjacent frame. If copyrighted materials were deleted, a target note will appear listing the pages in the adjacent frame. 3. When a map, drawing or chart, etc., is part of the material being photographed, a definite method of “sectioning” the material has been followed. It is customary to begin filming at the upper left hand comer of a large sheet and to continue from left to right in equal sections with small overlaps. If necessary, sectioning is continued again—beginning below the first row and continuing on until complete.
    [Show full text]
  • Reactions of Tertiary Phosphites with Alkyl Iodides in Acetonitrile
    AN ABSTRACT OF THE THESIS OF LANE JOSEPH GOODELL for the MASTER OF SCIENCE (Name) (Degree) in CHEMISTRY presented on Mcy Q\-\ `j CIL4 (Major) (Dates Title: REACTIONS OF TERTIARY PHOSPHITES WITH ALKYL IODIDES IN ACETONITRILE Abstract approved: Redacted for Privacy Dr. John Thdma Yoke III The Arbuzov reaction is an important method of synthesis of compounds containing a carbon -phosphorus bond. (RO)3P + R'X 1 [(RO)3PR')X],-- (RO)2P(0)R' + RX The intermediate might have a salt -like or a penta- coordinate type of structure, or both in equilibrium. In many systems, the rate determining step of the reaction is not known. A polar solvent might have a significant influence on these points. Although the reaction is normally carried out without a solvent, two groups of workers have studied the kinetics of the reaction in acetonitrile. These two groups published conflicting reports, speci- fically related to the system of tri -n -butyl phosphite with ethyl iodide in acetonitrile at 310 . The possibilities for the reaction to be considered in the present work were (1) olefin elimination from the tertiary phosphite to give a dialkyl hydrogen phosphonate, (2) inadvertent hydrolysis to give a dialkyl hydrogen phosphonate and an alcohol, (3) the Arbuzov reaction to give a dialkyl alkylphosphonate, and (4) no reaction. Assuming that it is the Arbuzov reaction which actually occurs for such reactants in acetonitrile, the previous reports were also in conflict as to the rate determining step. In the present work, it was found by qualitative and quantitative analysis of this system that the Arbuzov reaction occurs, but very slowly, contrary to one of the previous reports.
    [Show full text]
  • 193773 193773.Pdf
    NOTICE: this is the author’s version of a work that was accepted for publication in Science of the Total Environment. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Science of the Total Environment, Vol. 463-464 (2013). DOI: 10.1016/j.scitotenv.2013.05.079 1 Abiotic formation of methyl iodide on synthetic birnessite: A 2 mechanistic study 3 4 5 Sébastien Allarda,b,*, Hervé Gallarda 6 7 a Ecole Nationale Supérieure d'Ingénieurs de Poitiers - Université de Poitiers 8 Institut de Chimie des Milieux et des Matériaux UMR 7285 9 1, rue Marcel Doré 86 022 POITIERS Cedex 10 b ‘Present address’ Curtin Water Quality Research Center, Curtin University, GPO Box 11 U1987, Perth, WA 6845, Australia 12 13 *Corresponding author phone: +61 8 9266 7949, email: [email protected] 14 15 1 1 Abstract 2 Methyl iodide is a well-known volatile halogenated organic compound that contributes to the 3 iodine content in the troposphere, potentially resulting in damage to the ozone layer. Most 4 methyl iodide sources derive from biological activity in oceans and soils with very few abiotic 5 mechanisms proposed in the literature. In this study we report that synthetic manganese oxide 6 (birnessite MnO2) can catalyze the formation of methyl iodide in the presence of natural 7 organic matter (NOM) and iodide.
    [Show full text]
  • New Addition Reactions Op Nitro Compounds with Olefinic Systems
    NEW ADDITION REACTIONS OP NITRO COMPOUNDS WITH OLEFINIC SYSTEMS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By JUNIOR FRANKLIN CONRAD, B.A., M.S. A 9 9 The Ohio State University 1952 Approved byj j f J l f Adviser -i- ACKNOWLEDGMENTS j The author takes this opportunity to express his gratitude to Dr. Harold Shechter for his generous counsel and assistance in this problem. Thanks are also due to Dr. Ralph B. Kaplan, Dr. Harry L. Cates, and Dr. Larry Zeldin for their many helpful suggestions. The author also wishes to express his appreciation to the Office of Naval Research, who generously supplied the funds that made this research possible. S 0 0 4 4 3 -ii- TABLE OP CONTENTS Page ACKNOWLEDGMENTS; i SECTION I: ADDITION OP DINITROGEN TETROXIDE AND NITRYL CHLORIDE TO OLEPINIC SYSTEMS 1 PART I: Addition of Dinitrogen Tetroxide to Methyl Acrylate. 2 A. Background and Purpose 2 B. Results of Present Research 10 C. Discussion of Results 13 D. Conclusions 20 E. Experimental 21 (1) Reaction of Dinitrogen Tetroxide and Methyl Acrylate. 21 (2) Reaction of Methyl 2-Hydroxy-3-nitro- propionate with Acetyl Chloride; Methyl 3-Nitroacrylate. 24 (3) Hydrolysis of Methyl 2-Hydroxy-3- nitropropionate. 24 a. 2-Hydroxy-3-nitropropionic Acid 24 b. Oxalic Acid. 25 (4) Condensation of Glyoxylic Acid and Nitromethane; 2-Hydroxy-3-nitro- propionic Acid. 25 PART II: Addition of Nitryl Chloride to Methyl Acrylate, Acrylic Acid, and Acrylonitrile. 27 A. Background and Purpose 27 B.
    [Show full text]
  • The Preparation of Alkyl Iodides Ernest Milford Parrott University of Massachusetts Amherst
    University of Massachusetts Amherst ScholarWorks@UMass Amherst Masters Theses 1911 - February 2014 1932 The preparation of alkyl iodides Ernest Milford Parrott University of Massachusetts Amherst Follow this and additional works at: https://scholarworks.umass.edu/theses Parrott, Ernest Milford, "The preparation of alkyl iodides" (1932). Masters Theses 1911 - February 2014. 1861. Retrieved from https://scholarworks.umass.edu/theses/1861 This thesis is brought to you for free and open access by ScholarWorks@UMass Amherst. It has been accepted for inclusion in Masters Theses 1911 - February 2014 by an authorized administrator of ScholarWorks@UMass Amherst. For more information, please contact [email protected]. MASSACHUSETTS STATE COLLEGE DATE DUE UNIVERSITY OF MASSACHUSETTS LIBRARY PHYS sell LD ' M268 1932 P26$ PhYS IL?.?'^«2 . ,CE Thes IS TIE PREPARATION OF AUCYL IODIDES Emset Uilford r^rrott Thasis Submitted for The Degree of Master of SeleiK* MASSACHUSSTTS STATE COLLm mj 1932 TABLE OF CONTENTS Page ^ Introduction • Methods of Preparation 10 Experimental Part *3 (1) Preparation of Ethyl Iodide 23 24 (2) Preparation of Methyl Iodide 25 (3) Preparation of Propyl Iodides (a) Using Is ©propyl Alcohol 25 (b) Using Normal Propyl Alcohol 26 27 (4) Preparation of Butyl Iodides (a) Using Normal Butyl Alcohol 27 (b) Using Isobutyl Alcohol 28 28 (e) Using Tertiary Butyl Alcohol 33 Conclusions ..... 34 Bibliography • 36 Acknowledgments . » DfTRODUCTIQH Alkyl faalldttB may be r«gard*d aither as hydrocarbons im which hydrogSB atom ar« rsplaead by halogni at on or as esters of halogen hydraeids and alkyl radicals. By alatalning those two points of view the aode of foraation and the reactions of this class of bodies should be folleved with no difficulty.
    [Show full text]
  • Methods to Prevent the Source Term of Methyl Iodide During a Core Melt Accident
    DK0000090 HIM; Nordisk kemesikkerhedsforskning Norraenar kjarn6ryggisranns6knir Pohjoismainenydinturvallisuustutkimus Nordisk kjernesikkerhetsforskning Nordisk karnsakerhetsforskning Nordic nuclear safety research NKS-13 ISBN 87-7893-063-4 Methods to Prevent the Source Term of Methyl Iodide During a Core Melt Accident Anna Karhu VTT Energy, Finland 31/27 1999-11-26 NKS-13 ISBN 87-7893-063-4 Afd. for Informationsservice, Ris0,2000 The report can be obtained from NKS Secretariat P.O. Box 30 DK-4000Roskilde Denmark Phone +45 4677 4045 Fax +45 4677 4046 http://www.nks.org e-mail: [email protected] Abstract The purpose of this literature review is to gather available information of the methods to prevent a source term of methyl iodide during a core melt accident. The most widely studied methods for nuclear power plants include the impregnated carbon filters and alkaline additives and sprays. It is indicated that some deficiencies of these methods may emerge. More reactive impregnants and additives could make a great improvement. As a new method in the field of nuclear applications, the potential of transition metals to decompose methyl iodide, is introduced in this review. This area would require an additional research, which could elucidate the remaining questions of the reactions. The ionization of the gaseous methyl iodide by corona-discharge reactors is also shortly described. Acknowledgements I am grateful to Dr Jorma Jokiniemi and Mr Ari Auvinen from VTT Energy. They have had patience and enthusiasm to guide me through this work. I wish to thank Prof. Kari Rissanen from University of Jyvaskyla. I thank also Mrs Riitta Zilliacus for the comments.
    [Show full text]
  • A Tandem Mass Spectrometric Investigation of (C <Subscript>2 </Subscript>H <Subscript>5 </Subscript>) &L
    ·A. Tandem Mass Spectrometric Investigation of (C2"S}2X+ Ions (X = CI, Br, I): The Involvement of Classical and Nonclassical Ethyl Structures Therein Dmitri V. Zagorevskii, Sergiu P. Palii," and John L. Holmes Chemistry De p artmen t, Universit y of O llawa, Ottawa, Ontario, Canada The formation of diethyl haloniurn ions (C zHs}zX+ (X = Cl, Br, I) by a variety of ion-mole­ cule reactions is described. The dissociation characteristics (metastable and collision-induced dissociation mass spectra) of these ions and their isomers were studied in detail. Some of the neutral fragmentation products were examined by their collision-induced d issociative ioniza­ tion mass spectra. The participation of classical (1, CH3CHzX+CHzCH3) and nonclassical 2, CH ... H+ ... CHz)II ( 3CHzX CHz forms of the ions was considered. Dissociation reactions for which loss of positional identity of H-D atoms too k place, for example,CZH4 loss (a common fragmentation of metastable ions) and CzH t formation, w ere interpreted as involving nonclassical ions, 2. It was concluded that the ion-molecule reactions produced both ion structures, but in different halogen-d ependent proportions. For (Cz Hs)zCl + ions, 2 is the major species, for (CzHs)zBr+ both 1- and 2-type ions are generated, whereas for (C zH s)zI + the class ical form 1 must be the predominant structure. (JAm Soc Mass Spectrom 1994, 5, 814- 825) cyclic halonium ions R)(+R' (X = halogen; R, whereas (CH))2CI+ and CD3CI+CH) were stable un­ R' = alkyl) are well-known species in the con­ der the exp erimental conditions.
    [Show full text]
  • Table 3: Protective Action Criteria (PAC) Rev. 29 Based on Applicable 60-Minute Aegls, Erpgs, Or Teels
    Table 3: Protective Action Criteria (PAC) Rev. 29 based on applicable 60-minute AEGLs, ERPGs, or TEELs. The chemicals are listed by CASRN. May 2016 Table 3 presents a list of chemicals and associated PAC values in numerical order based on the CASRN1 for each chemical. Chemicals without an identified CASRN number are issued an identification number, preceded by the letter “z” for purposes of identification in the PAC data set. PACs are presented in either ppm or mg/m3. The columns presented in Table 3 provide the following information: Heading Definition No. The ordered numbering of the chemicals as they appear in this listing by CASRN Chemical Name The name of the chemical substance submitted to the PAC development team CASRN The Chemical Abstracts Service Registry Number for this chemical PAC-1 Based on the applicable AEGL-1, ERPG-1, or TEEL-1 value PAC-2 Based on the applicable AEGL-2, ERPG-2, or TEEL-2 value PAC-3 Based on the applicable AEGL-3, ERPG-3, or TEEL-3 value Units The units of the original request (ppm or mg/m3) Chemicals for which AEGLs are available have their chemical name, CASRN, and AEGL values displayed in a bolded and larger font. Chemicals for which ERPGs are available, but no AEGLs, have their chemical name, CASRN, and ERPG values displayed in a bolded font. Chemicals for which TEELs are available, but no AEGLs or ERPGs, have their chemical name, CASRN, and values displayed using a regular font. Additional information on PAC values, TEEL values, and links to other sources of information is provided on the Subcommittee on Consequence Assessment and Protective Actions (SCAPA) webpage at http://orise.orau.gov/emi/scapa/default.htm.
    [Show full text]
  • 134 R. Dunstan
    View Article Online / Journal Homepage / Table of Contents for this issue 134 IX.-On the Alleged Existence of a Second Nitroethane. By WYNDHAMR. DUNSTAN,Professor of Chemistry to the Pharma- ceutical Society, and T. S. DYMOND. IN 1873, Victor Meyer (Annalen, 171, 1-56) found that by the interaction of ethyl iodide and silver nitrite two compounds of the formula C2H,N02were produced. One of these he recognised as the previously known ethyl nitrite (b. p. 16*5"),the other as a new sub- stance (b. p. 113"),to which he gave the name of nitroethane. In this interaction much heat is evolved, and the temperature soon rises far above the boiling point of ethyl nitrite. In order to complete the change, the mixture is heated for some hours with a reflux condenser on a water-bath, when the greater part of the ethyl nitrite will escape unless special means are adopted to condense it ; some, how- ever, remains dissolved in the nitroethane, generally with a little ethyl iodide, and on fractionating the liquid a mixture of these three substances will distil below 100". According to Meyer, the two isomerides are formed in equal quantities. More recently the interaction of ethyl iodide and dry silver nitrite has been studied, under somewhat different conditions, by Kissel" (Journ. Russ. Chcm. Xoc., 1882, 226-230; and 1884, 135-140) ; he adds dry silver nitrite, in small quantities at a time, to the ethyl iodide cooled to O", until no further action ensues. The mixture is kept cool and shaken during one day, great care being taken to avoid Downloaded by University of Rochester on 12/04/2013 22:39:19.
    [Show full text]
  • United States Patent Office Patented Sept
    3,053,910 United States Patent Office Patented Sept. 11, 1962 2 obtained methyl iodide in 50.3% yield by heating meth 3,053,910 anol with iodine and iron, ethyl iodide in 96% yield by METHOD OF MANUEFACTURING ALKYL ODIDES Frederic R. Huber, Mahwah, and Leslie M. Schenck, fusing ethylacetate with iodine in the presence of iron. Mountainside, N.J., assignors to General Aniline & In a later work, Dangyn, J. Gen. Chem. (USSR) 11, Film Corporation, New York, N.Y., a corporation of 314-18; 11, 616-18 (1941), describes the utilization of Delaware aluminum and ethylacetate with iodine at 110-210 C. to No Drawing. Fied Oct. 7, 1960, Ser. No. 61,106 form ethyl iodide, and magnesium, iodine, and methyl 6 Claims. (CI. 260-652) benzoate to synthesize methyl iodide in 70-90% of theo retical yield. Dangyan further teaches that the reaction This invention relates to an improved method for the 0. of aluminum, alcohol, and iodine to form alkyl iodides manufacture of alkyl iodides on a commercial scale in a is an excellent method of preparation, but that extreme practical and most economical manner. caution is required during the heating period of the Syn The synthesis of alkyl iodides is not new to the art. thesis. Dumas and Peligot, Ann. 15, 20 (1835), first reported the Landover and Rydon, J. Chem. Soc. 1953, 2224-34, preparation of methyl iodide by the reaction of an al 5 report the preparation of ethyl iodide in 62% yield by cohol with phosphorus and iodine. A furtherance of the distillation of ethanol from silver iodide.
    [Show full text]
  • Submitted by Andrew Tze Chiu Liu for the Award of Doctor of Philosophy
    A Thesis entitled SOME NOVEL CYANINE DYES submitted by Andrew Tze Chiu Liu for the award of Doctor of Philosophy of the University of London. Imperial College, July, 1961. London, S.W.7. Acknowledgments This work was carried out under the super— vision of Dr. J. A. Tlvidge to whom I am most grateful for his constant and generous help. I am indebted to the staff of the Micro— analytical Laboratory of this Department, under the direction of Miss J. Cuckney also to Mrs. A. I. Boston for the infrared absorption measurements and to Mr. J. Peppercorn for general aid. Finally I wish to express my thanks to Dr. E. B. Knott of Kodak and Co. for testing the photo— graphic sensitivity of some of the cyanine dyes resulting from this work. ABSTRACT The reactions of 1,3-di-iminoisoindoline with various active-methyl-substituted-quaternary-ammonium- salts in boiling butanol, pyridine, and nitroethane have been studied extensively. The products comprise a wide range of new cyanine dyes with absorption maxima from 405 to 735 which have an isoindolenine ring as part of the chromophoric path. These compounds are mostly obtained in high yields. Among pyridine, benzothiazole, quinoline and pyrimidine derivatives, the quinoline compounds gave the longest wave-length absorption maxima and best tinctorial values. The reaction of 3-imino-l-oxoisoindoline with 216-lutidine ethiodide gave a dinuclear cyanine with a terminal amide group. When this product was treated with potassium hydroxide, a merocyanine was obtained. 2-Aminopyridine ethiodide did not react with 1,3-di-iminoisoindoline or with 3-imino-l-oxoiso- indoline in either boiling butanol or pyridine, but 2-amino-6-methylbenzothiazole ethiodide and 2,6-diamino- pyridine ethiodide reacted readily with these hetero- cyclic imines.
    [Show full text]