FY 1985 Research in the Chemical Sciences
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Depa1'tment of Physical Chemistry Isl'ael
.. ANNUAL PROGRESS REPORT C00-3221-67 (For the period September 79 - July 80) Under Contract No. DOE/EV/03221 on THE NATURE OF OXYGEN CONTAINING RADICALS IN RADIATION CHEMISTRY AND PHOTOCHEMISTRY OF AQUEOUS SOLUTIONS Submitted by PROFESSOR GIDON CZAPSKI Depa1'tment of Physical Chemistry The Hebl'eW Univel'sity~ Jerusalem~ Isl'ael IJISTRIBUTIOJI OF THIS DOCUMENT IS UNUMITEJJ DISCLAIMER This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency Thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. DISCLAIMER Portions of this document may be illegible in electronic image products. Images are produced from the best available original document. ANNUAL PROGRESS REPORT C00-3221-67 (For the period September 79 - July 80) Und~r Contract No. DOE/EV/03221·· on THE NATURE OF OXYGEN CONTAINING RADICALS IN RADIATION CHEMISTRY AND PHOTOCHEMISTRY OF AQUEOUS SOLUTIONS Submitted by PROFESSOR GIDON CZAPSKI lh~s book was ~repared as an account of work sponsored by an agency of the United States Government :!:~; the ~~•ted Stat~ ~nment nor any agency thereof, nor any of their employees, makes an~ v. -
Appendix 1 Some Astrophysical Reminders
Appendix 1 Some Astrophysical Reminders Marc Ollivier 1.1 A Physics and Astrophysics Overview 1.1.1 Star or Planet? Roughly speaking, we can say that the physics of stars and planets is mainly governed by their mass and thus by two effects: 1. Gravitation that tends to compress the object, thus releasing gravitational energy 2. Nuclear processes that start as the core temperature of the object increases The mass is thus a good parameter for classifying the different astrophysical objects, the adapted mass unit being the solar mass (written Ma). As the mass decreases, three categories of objects can be distinguished: ∼ 1. if M>0.08 Ma ( 80MJ where MJ is the Jupiter mass) the mass is sufficient and, as a consequence, the gravitational contraction in the core of the object is strong enough to start hydrogen fusion reactions. The object is then called a “star” and its radius is proportional to its mass. 2. If 0.013 Ma <M<0.08 Ma (13 MJ <M<80 MJ), the core temperature is not high enough for hydrogen fusion reactions, but does allow deuterium fu- sion reactions. The object is called a “brown dwarf” and its radius is inversely proportional to the cube root of its mass. 3. If M<0.013 Ma (M<13 MJ) the temperature a the center of the object does not permit any nuclear fusion reactions. The object is called a “planet”. In this category one distinguishes giant gaseous and telluric planets. This latter is not massive enough to accrete gas. The mass limit between giant and telluric planets is about 10 terrestrial masses. -
EPA Method 8315A (SW-846): Determination of Carbonyl Compounds by High Performance Liquid Chromatography (HPLC)
METHOD 8315A DETERMINATION OF CARBONYL COMPOUNDS BY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY (HPLC) 1.0 SCOPE AND APPLICATION 1.1 This method provides procedures for the determination of free carbonyl compounds in various matrices by derivatization with 2,4-dinitrophenylhydrazine (DNPH). The method utilizes high performance liquid chromatography (HPLC) with ultraviolet/visible (UV/vis) detection to identify and quantitate the target analytes. This method includes two procedures encompassing all aspects of the analysis (extraction to determination of concentration). Procedure 1 is appropriate for the analysis of aqueous, soil and waste samples and stack samples collected by Method 0011. Procedure 2 is appropriate for the analysis of indoor air samples collected by Method 0100. The list of target analytes differs by procedure. The appropriate procedure for each target analyte is listed in the table below. Compound CAS No. a Proc. 1b Proc. 2 b Acetaldehyde 75-07-0 X X Acetone 67-64-1 X Acrolein 107-02-8 X Benzaldehyde 100-52-7 X Butanal (Butyraldehyde) 123-72-8 X X Crotonaldehyde 123-73-9 X X Cyclohexanone 108-94-1 X Decanal 112-31-2 X 2,5-Dimethylbenzaldehyde 5779-94-2 X Formaldehyde 50-00-0 X X Heptanal 111-71-7 X Hexanal (Hexaldehyde) 66-25-1 X X Isovaleraldehyde 590-86-3 X Nonanal 124-19-6 X Octanal 124-13-0 X Pentanal (Valeraldehyde) 110-62-3 X X Propanal (Propionaldehyde) 123-38-6 X X m-Tolualdehyde 620-23-5 X X o-Tolualdehyde 529-20-4 X p-Tolualdehyde 104-87-0 X a Chemical Abstract Service Registry Number. -
Toxicological Profile for Formaldehyde
TOXICOLOGICAL PROFILE FOR FORMALDEHYDE U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES Public Health Service Agency for Toxic Substances and Disease Registry July 1999 FORMALDEHYDE ii DISCLAIMER The use of company or product name(s) is for identification only and does not imply endorsement by the Agency for Toxic Substances and Disease Registry. FORMALDEHYDE iii UPDATE STATEMENT Toxicological profiles are revised and republished as necessary, but no less than once every three years. For information regarding the update status of previously released profiles, contact ATSDR at: Agency for Toxic Substances and Disease Registry Division of Toxicology/Toxicology Information Branch 1600 Clifton Road NE, E-29 Atlanta, Georgia 30333 FORMALDEHYDE vii QUICK REFERENCE FOR HEALTH CARE PROVIDERS Toxicological Profiles are a unique compilation of toxicological information on a given hazardous substance. Each profile reflects a comprehensive and extensive evaluation, summary, and interpretation of available toxicologic and epidemiologic information on a substance. Health care providers treating patients potentially exposed to hazardous substances will find the following information helpful for fast answers to often-asked questions. Primary Chapters/Sections of Interest Chapter 1: Public Health Statement: The Public Health Statement can be a useful tool for educating patients about possible exposure to a hazardous substance. It explains a substance’s relevant toxicologic properties in a nontechnical, question-and-answer format, and it includes a review of the general health effects observed following exposure. Chapter 2: Health Effects: Specific health effects of a given hazardous compound are reported by route of exposure, by type of health effect (death, systemic, immunologic, reproductive), and by length of exposure (acute, intermediate, and chronic). -
A Study of Organosilicon Free Radicals Jay Stephen Curtice Iowa State College
Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1954 A study of organosilicon free radicals Jay Stephen Curtice Iowa State College Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons, and the Physical Chemistry Commons Recommended Citation Curtice, Jay Stephen, "A study of organosilicon free radicals " (1954). Retrospective Theses and Dissertations. 13411. https://lib.dr.iastate.edu/rtd/13411 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. A STUDY OF ORGANOSILICON FREE RADICALS by Jay Stephen Curtice A Dissertation Sul»nitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Major Subject: Physical Organic Chemistry Approved; Signature was redacted for privacy. Signature was redacted for privacy. In CJiiarge of Major Work Signature was redacted for privacy. Head of Major DepartMnt Signature was redacted for privacy. Dean of Graduate College Iowa State College 195^ UMI Number: DP12662 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. -
Influence of Impurities in a Methanol Solvent on the Epoxidation of Propylene with Hydrogen Peroxide Over Titanium Silicalite‐1
Supplementary Materials Influence of Impurities in a Methanol Solvent on the Epoxidation of Propylene with Hydrogen Peroxide over Titanium Silicalite‐1 Gang Wang, Yue Li, Quanren Zhu, Gang Li, Chao Zhang, and Hongchen Guo* State Key Laboratory of Fine Chemicals and School of Chemical Engineering, Dalian University of Technology, No. 2 Linggong Road, Dalian 116024, PR China; [email protected] (G.W.); [email protected] (Y.L.); [email protected] (Q.Z.); [email protected] (G.L.); [email protected] (C.Z.) * Correspondence: [email protected]; Tel./Fax: +86‐411‐84986120 Received: 23 November 2019; Accepted: 18 December 2019; Published: date Table S1. Influence of fusel alcohol content on the product distribution and turnover numbers in epoxidation of propylene with H2O2a Conten Selectivity, % Impurity TONb t, wt.% 1M2Pc 2M1Pc PGc DGMEc PGMEc AAc PAc ATc noned 0.00 314.5 0.50 0.52 0.17 0.08 0.00 0.23 0.06 0.00 ethanol 1.00 296.8 0.48 0.46 0.17 0.06 0.01 0.22 0.06 0.00 1.50 286.8 0.45 0.45 0.15 0.05 0.02 0.26 0.06 0.01 2.00 282.9 0.38 0.42 0.14 0.04 0.02 0.28 0.07 0.01 2.50 267.9 0.38 0.41 0.14 0.03 0.03 0.29 0.07 0.01 2‐propanol 0.50 296.8 0.45 0.49 0.17 0.06 0.00 0.21 0.07 0.03 0.75 286.8 0.43 0.47 0.15 0.06 0.00 0.22 0.07 0.05 1.00 282.9 0.41 0.47 0.15 0.04 0.00 0.25 0.08 0.07 1.25 267.9 0.37 0.38 0.14 0.03 0.00 0.26 0.09 0.08 1‐propanol 0.50 297.7 0.51 0.55 0.18 0.06 0.00 0.21 0.11 0.00 0.75 289.0 0.45 0.49 0.18 0.05 0.00 0.22 0.11 0.00 1.00 282.5 0.44 0.49 0.17 0.05 0.00 0.24 0.14 0.01 1.25 266.0 0.43 0.48 0.16 0.05 0.00 0.26 0.14 0.01 Note: a Reaction conditions: pre‐adsorbed TS‐1 powder 0.4 g, fresh methanol or simulated methanol solvents containing ethanol, 2‐propanol and 1‐propanol 35.5 mL, H2O2 (50 wt.%) 4.5 mL, NH3∙H2O (0.32 mol/L) 0.2 mL, propylene pressure 0.6 MPa, 50 ℃, 1 h. -
"High Accuracy Rotation--Vibration Calculations on Small Molecules" In
High Accuracy Rotation–Vibration Calculations on Small Molecules Jonathan Tennyson Department of Physics and Astronomy, University College London, London, UK 1 INTRODUCTION comprehensive understanding requires the knowledge of many millions, perhaps even billions, of individual transi- High-resolution spectroscopy measures the transitions bet- tions (Tennyson et al. 2007). It is not practical to measure ween energy levels with high accuracy; typically, uncer- this much data in the laboratory and therefore a more real- tainties are in the region of 1 part in 108. Although it is istic approach is the development of an accurate theoretical possible, under favorable circumstances, to obtain this sort model, benchmarked against experiment. of accuracy by fitting effective Hamiltonians to observed The incompleteness of most experimental datasets means spectra (see Bauder 2011: Fundamentals of Rotational that calculations are useful for computing other properties Spectroscopy, this handbook), such ultrahigh accuracy is that can be associated with spectra. The partition functions largely beyond the capabilities of purely ab initio proce- and the variety of thermodynamic properties that are linked dures. Given this, it is appropriate to address the question to this (Martin et al. 1991) are notable among these. Again, of why it is useful to calculate the spectra of molecules ab calculations are particularly useful for estimating these initio (Tennyson 1992). quantities at high temperature (e.g., Neale and Tennyson The concept of the potential energy surfaces, which in 1995). turn is based on the Born–Oppenheimer approximation, Other more fundamental reasons for calculating spectra underpins nearly all of gas-phase chemical physics. The include the search for unusual features, such as clustering of original motivation for calculating spectra was to provide energy levels (Jensen 2000) or quantum monodromy (Child stringent tests of potential energy surfaces. -
Propionaldehyde Pad
PROPIONALDEHYDE PAD CAUTIONARY RESPONSE INFORMATION 4. FIRE HAZARDS 7. SHIPPING INFORMATION 4.1 Flash Point: 7.1 Grades of Purity: 97-99+% Common Synonyms Liquid Colorless Suffocating, –22°F O.C. 7.2 Storage Temperature: Ambient Methyl acetaldehyde unpleasant odor 4.2 Flammable Limits in Air: 2.6%-16.1% Propanal 7.3 Inert Atmosphere: No requirement 4.3 Fire Extinguishing Agents: Carbon Propionic aldehyde 7.4 Venting: Open (flame arrester) or pressure- dioxide or dry chemical for small fires, Propyl aldehyde Floats and mixes slowly with water. Flammable, irritating vapor is vacuum Propylic aldehyde produced. alcohol-type foam for large fires. 4.4 Fire Extinguishing Agents Not to Be 7.5 IMO Pollution Category: C Used: Water may be ineffective. 7.6 Ship Type: 3 Keep people away. Avoid contact with liquid and vapor. Wear goggles, self-contained breathing apparatus, and rubber overclothing 4.5 Special Hazards of Combustion 7.7 Barge Hull Type: Currently not available (including gloves). Products: Not pertinent Shut off ignition sources and call fire department. 4.6 Behavior in Fire: Vapor is heavier than 8. HAZARD CLASSIFICATIONS Stay upwind and use water spray to ``knock down'' vapor. air and may travel considerable distance Notify local health and pollution control agencies. to a source of ignition and flash back. 8.1 49 CFR Category: Flammable liquid Protect water intakes. 4.7 Auto Ignition Temperature: 405°F 8.2 49 CFR Class: 3 4.8 Electrical Hazards: Not pertinent 8.3 49 CFR Package Group: II FLAMMABLE. Fire Flashback along vapor trail may occur. 4.9 Burning Rate: 4.4 mm/min. -
Synthesis of Phosphine-Functionalized Metal
DISS. ETH NO. 23507 Understanding and improving gold-catalyzed formic acid decomposition for application in the SCR process A thesis submitted to attain the degree of DOCTOR OF SCIENCES of ETH ZURICH (Dr. sc. ETH Zurich) presented by MANASA SRIDHAR M. Sc. in Chemical Engineering, University of Cincinnati born on 12.12.1987 citizen of India accepted on the recommendation of Prof. Dr. Jeroen A. van Bokhoven, examiner Prof. Dr. Oliver Kröcher, co-examiner Prof. Dr. Christoph Müller, co-examiner 2016 “anything can happen, in spite of what you’re pretty sure should happen.” Richard Feynman Table of content Abstract .............................................................................................................................. II die Zusammenfassung ..................................................................................................... VI Chapter 1 Introduction .......................................................................................................... 1 Chapter 2 Methods ............................................................................................................ 15 Chapter 3 Unique selectivity of Au/TiO2 for ammonium formate decomposition under SCR- relevant conditions ............................................................................................................. 25 Chapter 4 Effect of ammonia on the decomposition of ammonium formate and formic acid on Au/TiO2 ............................................................................................................................. -
Lowtemperature Chemoselective Goldsurfacemediated
DOI: 10.1002/cctc.201200311 Low-Temperature Chemoselective Gold-Surface-Mediated Hydrogenation of Acetone and Propionaldehyde Ming Pan,[a] Zachary D. Pozun,[b] Adrian J. Brush,[a] Graeme Henkelman,[b] and C. Buddie Mullins*[a] Since nanoscale gold was first discovered to be catalytically First, the hydrogenation of acetone was investigated on active,[1] gold-based catalysts have been studied both theoreti- a Au(111) surface. In a control experiment (Figure 1a), 1.62 ML cally[2] and experimentally[3] in a wide range of reactions.[4] (ML= monolayer) of acetone (m/z=43, the most-abundant These catalysts exhibit high activity for hydrogenation process- mass fragment of acetone) was adsorbed onto a clean Au(111) es,[5] in particular showing enhanced selectivity.[6] However, there is a lack of relevant fundamental studies into these pro- cesses. Conducting hydrogenation reactions on model gold surfaces is useful for obtaining mechanistic insight and for fur- ther enhancing our understanding of the catalytic properties of supported-gold catalysts. Herein, we report the chemoselec- tive hydrogenation of aldehydes over ketones on gold surfaces. The hydrogenation chemistry of oxygenated hydrocarbons has been studied on transition-metal surfaces for a variety of reactions that are important to the pharmaceutical- and chemi- cal industries.[7] For example, C=O bond hydrogenation is a key step in the catalytic conversion of cellulosic biomass.[8] In addi- tion, gold-based catalysts have also shown exceptional activity for the selective hydrogenation of a,b-unsaturated carbonyl compounds.[9] Claus found that, in the production of allyl alco- hol from the hydrogenation of acrolein, gold catalysts yielded about 10-times-higher selectivity for C=O bond hydrogenation than traditional platinum-based catalysts.[10] Therefore, explor- ing the individual reactivity of carbonyl-hydrogenation could provide useful information for a better holistic understanding of these important catalytic reactions. -
Basis for Listing Hazardous Waste
NEBRASKA ADMINISTRATIVE CODE Title 128 - Department of Environmental Quality Appendix II - BASIS FOR LISTING HAZARDOUS WASTE EPA Hazardous Hazardous Constituents For Which Listed Waste No. F001 Tetrachloroethylene; methylene chloride; trichloroethylene; 1,1,1-trichloroethane; carbon tetrachloride; chlorinated fluorocarbons. F002 Tetrachloroethylene; methylene chloride; trichloroethylene; 1,1,1-trichloroethane; 1,1,2-trichloroethane; chlorobenzene; 1,1,2-trichloro-1,2,2-trichfluoroethane; ortho- dichlorobenzene; trichlorofluoromethane. F003 N.A. F004 Cresols and cresylic acid, nitrobenzene. F005 Toluene, methyl ethyl ketone, carbon disulfide, isobutanol, pyridine, 2-ethoxyethanol, benzene, 2-nitropropane. F006 Cadmium, hexavalent chromium, nickel, cyanide (complexed). F007 Cyanide (salts). F008 Cyanide (salts). F009 Cyanide (salts). F010 Cyanide (salts). F011 Cyanide (salts). F012 Cyanide (complexed). F019 Hexavalent chromium, cyanide (complexed). F020 Tetra- and pentachlorodibenzo-p-dioxins; tetra- and pentachlorodibenzofurans; tri- and tetrachlorophenols and their chlorophenoxy derivative acids, esters, ethers, amine and other salts. Effective Date: 01/03/07 II-1 Title 128 Appendix II EPA Hazardous Hazardous Constituents For Which Listed Waste No. F021 Penta- and hexachlorodibenzo-p-dioxins; penta- and hexachlorodibenzofurans; pentachlorophenol and its derivatives. F022 Tetra-, penta-, and hexachlorodibenzo-p-dioxins; tetra-, penta-, and hexachlorodibenzofurans. F023 Tetra-, and pentachlorodibenzo-p-dioxins; tetra- and pentachlorodibenzofurans; -
Radical-Radical Reactions, Pyrene Nucleation, and Incipient Soot
Available online at www.sciencedirect.com Proceedings of the Combustion Institute 36 (2017) 799–806 www.elsevier.com/locate/proci Radical–radical reactions, pyrene nucleation, and incipient soot formation in combustion a b b K. Olof Johansson , Tyler Dillstrom , Paolo Elvati , a a c ,d Matthew F. Campbell , Paul E. Schrader , Denisia M. Popolan-Vaida , c c b ,e Nicole K. Richards-Henderson , Kevin R. Wilson , Angela Violi , a , ∗ Hope A. Michelsen a Combustion Research Facility, Sandia National Laboratories, P. O. Box 969, MS 9055, Livermore, CA 94551, USA b Department of Mechanical Engineering, University of Michigan, Ann Arbor, MI 48109, USA c Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA d Department of Chemistry, University of California, Berkeley, CA 94720, USA e Departments of Chemical Engineering, Biomedical Engineering, Macromolecular Science and Engineering, Biophysics Program, University of Michigan, Ann Arbor, MI 48109, USA Received 3 December 2015; accepted 31 July 2016 Available online 12 October 2016 Abstract We present a combined experimental and probabilistic simulation study of soot-precursor. The experi- ments were conducted using aerosol mass spectrometry coupled with tunable vacuum ultraviolet radiation from the Advanced Light Source at Lawrence Berkeley National Laboratory. Mass spectra and photoion- ization efficiency (PIE) curves of soot precursor species were measured at different heights in a premixed flat flame and in a counter-flow diffusion flame fueled by ethylene and oxygen. The PIE curves at the pyrene mass from these flames were compared with reference PIE scans recorded for pyrene. The results demonstrate that other C 16 H 10 isomers than pyrene are major components among species condensed onto incipient soot in this study, which is in agreement with the simulations.