Formation of Unprecedented Actinide'carbon Triple Bonds in Uranium Methylidyne Molecules

Total Page:16

File Type:pdf, Size:1020Kb

Formation of Unprecedented Actinide'carbon Triple Bonds in Uranium Methylidyne Molecules Formation of unprecedented actinide'carbon triple bonds in uranium methylidyne molecules Jonathan T. Lyon†, Han-Shi Hu‡, Lester Andrews†§, and Jun Li‡§ †Department of Chemistry, University of Virginia, Charlottesville, VA 22904; and ‡Department of Chemistry and Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education, Tsinghua University, Beijing 100084, China Edited by Malcolm H. Chisholm, Ohio State University, Columbus, OH, and approved October 11, 2007 (received for review July 27, 2007) Chemistry of the actinide elements represents a challenging yet vital scientific frontier. Development of actinide chemistry requires 09.0 )i( fundamental understanding of the relative roles of actinide va- )h( lence-region orbitals and the nature of their chemical bonding. We (g) report here an experimental and theoretical investigation of the P ,F, Cl, Br), F2ClU'CH ؍ uranium methylidyne molecules X3U'CH (X and F3U'CF formed through reactions of laser-ablated uranium )f( atoms and trihalomethanes or carbon tetrafluoride in excess ar- )e( gon. By using matrix infrared spectroscopy and relativistic quan- ( )d bsorbance tum chemistry calculations, we have shown that these actinide A complexes possess relatively strong U'C triple bonds between the P U 6d-5f hybrid orbitals and carbon 2s-2p orbitals. Electron-with- UF5 FU 3 drawing ligands are critical in stabilizing the U(VI) oxidation state ( )c and sustaining the formation of uranium multiple bonds. These b( ) 00.0 )a( unique U'C-bearing molecules are examples of the long-sought 580 1- 005 actinide-alkylidynes. This discovery opens the door to the rational W va une bm ers ( cm ) synthesis of triple-bonded actinide–carbon compounds. Fig. 1. Infrared spectra in the 590–490 cmϪ1 region for laser-ablated U atoms codeposited with fluoromethanes in excess argon at 8 K. U and 1% CHF3 ͉ ͉ ͉ actinide multiple bond heavy element laser ablation matrix in argon codeposited for 1 h (a), after Ͼ290 nm irradiation (b), and after Ͼ220 ͉ isolation relativistic quantum chemistry nm irradiation (c). U and 1% CDF3 in argon codeposited for 1 h (d), after Ͼ290 nm irradiation (e), and after Ͼ220 nm irradiation (f). U and 1% CF4 in argon Ͼ Ͼ hemical bonding and bond order are among the most codeposited for 1 h (g), after 290 nm irradiation (h), and after 220 nm irradiation (i). Precursor absorptions are labeled P. Cimportant fundamental concepts in modern chemistry since the birth of the valence theory of Lewis (1). Main-group and CHEMISTRY transition-metal compounds with multiple chemical bonds have L An'CR type of carbyne compounds is not expected to be always been fascinating to chemists because of their pivotal role n highly stable. Well designed ligands that can stabilize the actin- in organic, inorganic, and organometallic chemistry, character- istic chemical and physical properties, and versatile applications ide center at their stable oxidation states are needed to accom- in biological and material science (2–6). Whereas numerous modate the actinide– carbon multiple bonds. organic and inorganic compounds with multiple bonds are High-oxidation state transition metal alkylidene and alkyli- known (7–17), f elements (lanthanides and actinides) with dyne complexes have received increasing attention over the past multiple bonds are relatively rare, except for early actinides. three decades owing to their importance as catalysts in a variety Such bonding has aroused great interest recently in the search for of synthetic organometallic processes (36). Recently, we have actinide complexes with multiple bonds between two actinide prepared simple methylidene and methylidyne molecules metals (18–21) and between actinide (An) and main-group through the reaction of laser-ablated early transition metal ligands (L) (22–28). atoms with methane or methyl halides (37). These studies were Among the actinide complexes with An–L multiple bonds, the extended to the accessible actinide metal atoms Th and U for the importance of first-row elements to bond to actinide metal preparation of the first actinide methylidene species centers has been highlighted by Burns (22), and molecular HXAnϭCH2 (X ϭ H, F, Cl, Br) (38–41). Although Mo and W complexes containing metal-nitride units have been prepared reactions also formed the analogous H2XM'CH methylidynes recently (24–26). Uranium as the leading example forms a (42–46), the H2XU'CH counterparts were energetically too plethora of UϭO bonds and a handful of UϭNR and UϭCR2 high to be produced in these experiments (40). However, very (R ϭ organic groups) bonds. Considerable interest has been recent investigations with the heavy metals Zr, Hf, and Re in developed in recent years in actinide complexes with An–L trihalomethane reactions have demonstrated that the highly double bonds, and most of these investigations have centered on exothermic driving force for halogen transfer from carbon to organometallic systems. Examples include the compounds above heavy metal fosters the formation of the low-energy, very stable ϭ with N–U–N linkages (26) and organoimido (An NR) and trihalo metal carbynes (47, 48). phosphinidene (AnϭPR) groups (29, 30). The matrix isolation technique has revealed several inorganic uranium compounds ϩ with covalent triple bonds, including NUN, CUO, and NUO Author contributions: L.A. and J.L., contributed equally to this work; J.T.L. and H.-S.H. cation (31–33), which are isoelectronic with the ubiquitous performed research; L.A. and J.L. analyzed data; and L.A. and J.L. wrote the paper. uranyl dication. However, An–L multiple bonds are usually The authors declare no conflict of interest. formed between hard-acidic, high-valent actinides and hard This article is a PNAS Direct Submission. Ϫ 2Ϫ 2Ϫ Lewis bases, particularly F ,O , and NR (34, 35), and no §To whom correspondence may be addressed: E-mail: [email protected] or junli@ actinide alkylidyne complexes with An'CR triple bonds are tsinghua.edu.cn. known so far. Because of the high orbital energies of carbon, © 2007 by The National Academy of Sciences of the USA www.pnas.org͞cgi͞doi͞10.1073͞pnas.0707035104 PNAS ͉ November 27, 2007 ͉ vol. 104 ͉ no. 48 ͉ 18919–18924 Downloaded by guest on September 25, 2021 of fluoroform or carbon tetrafluoride reagents with uranium are 0.1 )l( shown in Fig. 1, and the results from reactions with chloroform )k( and bromoform are detailed in Fig. 2. j( ) The geometries, vibrational frequencies, and electronic struc- )i( tures of the potential uranium product complexes were calcu- rBHC 3 )h( lated by using relativistic density functional theory (DFT) with )g( the generalized gradient PW91 approach (51) as implemented in ADF 2006.1 (52). Inasmuch as the 6s and 6p semicore orbitals Absorbance are important for actinide bonding, they are included explicitly ( )f e( ) in the variational space along with the 5f, 6d, 7s, and 7p valence )d( orbitals, whereas frozen-core approximation was applied to the ( )c U[1s2-5d10] atomic core. Slater basis sets with the quality of )b( triple-zeta plus two polarization functions (TZ2P) were used. 0.0 )a( The zero-order regular approximation was used to account for 45 0 -1 24 0 W uneva bm sre ( c )m the relativistic effects (53). We also performed ab initio calcu- Ϫ1 lations at the level of coupled-cluster with single, double, and Fig. 2. Infrared spectra in the 550–410 cm region for laser-ablated U ϭ atoms codeposited with chloroform in excess argon at 8 K. U and 0.5% CHCl3 perturbative triple excitations [CCSD(T)] (54) on X3UCH (X in argon codeposited for 1 h (a), after ␭ Ͼ 290 nm irradiation (b), after ␭ Ͼ 220 H, F) with use of the Stuttgart quasi-relativistic pseudopotential 13 nm irradiation (c), and after annealing to 30 K (d). U and 0.5% CHCl3 in argon and valence basis set for U and 6-31ϩG* basis sets for C, F, and codeposited for 1 h (e), and after ␭ Ͼ 220 nm irradiation (f). U and 0.5% CDCl3 H (55, 56). The optimized CCSD(T) U'C distances (1.926 Å in in argon codeposited for 1 h (g), and after ␭ Ͼ 220 nm irradiation (h). U and H3UCH) lie in the same range as those from DFT calculations, ␭ Ͼ 2% CHBr3 in argon codeposited for 1 h (i), after 290 nm irradiation (j), after indicating that the later are applicable for evaluating these ␭ Ͼ 220 nm irradiation (k), and after annealing to 30 K (l). close-shell triple-bond actinide systems. In the fluoroform spectra stable binary uranium fluorides give Ϫ1 We report here an integrated experimental and theoretical rise to very weak absorptions at 496 and 584 cm for UF3 and UF5, respectively (57), which shows that uranium abstracts study of the actinide-methylidyne species, namely F3U'CH, Cl U'CH, Br U'CH, F ClU'CH, and F U'CF, which ren- fluorine from the precursor molecule. Three new bands marked 3 3 2 3 with arrows in Fig. 1a are observed at 576.2, 540.2, and 527.5 der the long-sought U'C triple bonds in methylidyne com- cmϪ1 in the infrared spectrum recorded after the initial reaction pounds. Detailed bonding analysis based on a variety of relativ- ' of U and CHF3. These bands increase by 30% on UV irradiation istic quantum chemistry calculations indicates that the U C ␭ Ͼ ␭ Ͼ ␴ ␲ ( 290 nm) and another 20% on further UV irradiation ( triple bonds are composed of one (df-sp) bond and two (df-p) 13 220 nm). A more dilute CHF3 sample gave only the most bonds. Interestingly the U'C bond length and bond strength are Ϫ intense absorption shifted to 539.2 cm 1, which demonstrates tunable by changing the electronegativity of the neighboring clearly that carbon is involved in the product species.
Recommended publications
  • Acidity, Basicity, and Pka 8 Connections
    Acidity, basicity, and pKa 8 Connections Building on: Arriving at: Looking forward to: • Conjugation and molecular stability • Why some molecules are acidic and • Acid and base catalysis in carbonyl ch7 others basic reactions ch12 & ch14 • Curly arrows represent delocalization • Why some acids are strong and others • The role of catalysts in organic and mechanisms ch5 weak mechanisms ch13 • How orbitals overlap to form • Why some bases are strong and others • Making reactions selective using conjugated systems ch4 weak acids and bases ch24 • Estimating acidity and basicity using pH and pKa • Structure and equilibria in proton- transfer reactions • Which protons in more complex molecules are more acidic • Which lone pairs in more complex molecules are more basic • Quantitative acid/base ideas affecting reactions and solubility • Effects of quantitative acid/base ideas on medicine design Note from the authors to all readers This chapter contains physical data and mathematical material that some readers may find daunting. Organic chemistry students come from many different backgrounds since organic chemistry occu- pies a middle ground between the physical and the biological sciences. We hope that those from a more physical background will enjoy the material as it is. If you are one of those, you should work your way through the entire chapter. If you come from a more biological background, especially if you have done little maths at school, you may lose the essence of the chapter in a struggle to under- stand the equations. We have therefore picked out the more mathematical parts in boxes and you should abandon these parts if you find them too alien.
    [Show full text]
  • Trifluoromethane)
    SAFETY DATA SHEET Halocarbon R-23 (Trifluoromethane) Section 1. Identification GHS product identifier : Halocarbon R-23 (Trifluoromethane) Chemical name : trifluoromethane Other means of : Fluoroform; Arcton 1; Fluoryl; Freon F-23; Freon 23; Genetron 23; Methyl trifluoride; R identification 23; Trifluoromethane; CHF3; Arcton; Halocarbon 23; UN 1984; Carbon trifluoride; Genetron HFC23; Propellant 23; Refrigerant 23 Product type : Liquefied gas Product use : Synthetic/Analytical chemistry. Synonym : Fluoroform; Arcton 1; Fluoryl; Freon F-23; Freon 23; Genetron 23; Methyl trifluoride; R 23; Trifluoromethane; CHF3; Arcton; Halocarbon 23; UN 1984; Carbon trifluoride; Genetron HFC23; Propellant 23; Refrigerant 23 SDS # : 001078 Supplier's details : Airgas USA, LLC and its affiliates 259 North Radnor-Chester Road Suite 100 Radnor, PA 19087-5283 1-610-687-5253 24-hour telephone : 1-866-734-3438 Section 2. Hazards identification OSHA/HCS status : This material is considered hazardous by the OSHA Hazard Communication Standard (29 CFR 1910.1200). Classification of the : GASES UNDER PRESSURE - Liquefied gas substance or mixture GHS label elements Hazard pictograms : Signal word : Warning Hazard statements : Contains gas under pressure; may explode if heated. May cause frostbite. May displace oxygen and cause rapid suffocation. Precautionary statements General : Read and follow all Safety Data Sheets (SDS’S) before use. Read label before use. Keep out of reach of children. If medical advice is needed, have product container or label at hand. Close valve after each use and when empty. Use equipment rated for cylinder pressure. Do not open valve until connected to equipment prepared for use. Use a back flow preventative device in the piping. Use only equipment of compatible materials of construction.
    [Show full text]
  • New and Improved Infrared Absorption Cross Sections for Chlorodifluoromethane (HCFC-22)
    Atmos. Meas. Tech., 9, 2593–2601, 2016 www.atmos-meas-tech.net/9/2593/2016/ doi:10.5194/amt-9-2593-2016 © Author(s) 2016. CC Attribution 3.0 License. New and improved infrared absorption cross sections for chlorodifluoromethane (HCFC-22) Jeremy J. Harrison1,2 1Department of Physics and Astronomy, University of Leicester, University Road, Leicester, LE1 7RH, UK 2National Centre for Earth Observation, University of Leicester, University Road, Leicester, LE1 7RH, UK Correspondence to: Jeremy J. Harrison ([email protected]) Received: 10 December 2015 – Published in Atmos. Meas. Tech. Discuss.: 18 January 2016 Revised: 3 May 2016 – Accepted: 6 May 2016 – Published: 17 June 2016 Abstract. The most widely used hydrochlorofluorocarbon 1 Introduction (HCFC) commercially since the 1930s has been chloro- difluoromethane, or HCFC-22, which has the undesirable The consumer appetite for safe household refrigeration led effect of depleting stratospheric ozone. As this molecule to the commercialisation in the 1930s of dichlorodifluo- is currently being phased out under the Montreal Pro- romethane, or CFC-12, a non-flammable and non-toxic re- tocol, monitoring its concentration profiles using infrared frigerant (Myers, 2007). Within the next few decades, other sounders crucially requires accurate laboratory spectroscopic chemically related refrigerants were additionally commer- data. This work describes new high-resolution infrared ab- cialised, including chlorodifluoromethane, or a hydrochlo- sorption cross sections of chlorodifluoromethane over the rofluorocarbon known as HCFC-22, which found use in a spectral range 730–1380 cm−1, determined from spectra wide array of applications such as air conditioners, chillers, recorded using a high-resolution Fourier transform spectrom- and refrigeration for food retail and industrial processes.
    [Show full text]
  • Fluoroform (CHF3)
    SYNLETT0936-52141437-2096 © Georg Thieme Verlag Stuttgart · New York 2015, 26, 1911–1912 1911 spotlight Syn lett S. Kyasa Spotlight Fluoroform (CHF3) ShivaKumar Kyasa ShivaKumar Kyasa was born in Telangana state, India, in 1978. After completing a B.Sc. (chemis- try, biology) and a M.Sc. (medicinal chemistry) Department of Chemistry, University of Nebraska-Lincoln, Lincoln, NE 68588-0304, USA from Osmania University, he worked at Dr. Red- [email protected] dy’s Laboratories, Ltd., Hyderabad, India. He is currently pursuing a Ph.D. in chemistry at the Published online: 11.06.2015 University of Nebraska–Lincoln, USA under the DOI: 10.1055/s-0034-1380924; Art ID: st-2015-v0519-v supervision of Prof. Patrick H. Dussault. His re- search focuses on C–O bond formation and syn- thesis of functionalized ethers using peroxide oxygen as an electrophile. Introduction with Lewis bases (most commonly catalytic fluoride) to af- ford pentavalent silicon species as nucleophiles has enabled Fluoroform, which is generated in ~20 kilotons/year trifluoromethylation of a number of electrophiles.4 The tri- as a side product of Teflon manufacture,1,2 is a low-boiling fluoromethyl group has great importance in medicinal, ag- (-82 °C), non-toxic and non-ozone-depleting gas.1,3 Howev- rochemical and materials science.5 This spotlight describes er, fluoroform is a potent greenhouse agent and there is recently reported methods for tri- and difluoromethylation great interest in methods for use of the gas as a synthetic based upon fluoroform. reagent. The direct use of trifluoromethyl anion as a nucleo- phile has been challenging due to facile α-elimination to CF3 CF2 + F fluoride and difluorocarbene (Scheme 1).
    [Show full text]
  • A Van Der Waals Density Functional Study of Chloroform and Other Trihalomethanes on Graphene Joel Åkesson, Oskar Sundborg, Olof Wahlström, and Elsebeth Schröder
    A van der Waals density functional study of chloroform and other trihalomethanes on graphene Joel Åkesson, Oskar Sundborg, Olof Wahlström, and Elsebeth Schröder Citation: J. Chem. Phys. 137, 174702 (2012); doi: 10.1063/1.4764356 View online: http://dx.doi.org/10.1063/1.4764356 View Table of Contents: http://jcp.aip.org/resource/1/JCPSA6/v137/i17 Published by the American Institute of Physics. Additional information on J. Chem. Phys. Journal Homepage: http://jcp.aip.org/ Journal Information: http://jcp.aip.org/about/about_the_journal Top downloads: http://jcp.aip.org/features/most_downloaded Information for Authors: http://jcp.aip.org/authors THE JOURNAL OF CHEMICAL PHYSICS 137, 174702 (2012) A van der Waals density functional study of chloroform and other trihalomethanes on graphene Joel Åkesson,1 Oskar Sundborg,1 Olof Wahlström,1 and Elsebeth Schröder2,a) 1Hulebäcksgymnasiet, Idrottsvägen 2, SE-435 80 Mölnlycke, Sweden 2Microtechnology and Nanoscience, MC2, Chalmers University of Technology, SE-412 96 Göteborg, Sweden (Received 25 July 2012; accepted 14 October 2012; published online 1 November 2012) A computational study of chloroform (CHCl3) and other trihalomethanes (THMs) adsorbed on graphene is presented. The study uses the van der Waals density functional method to obtain ad- sorption energies and adsorption structures for these molecules of environmental concern. In this study, chloroform is found to adsorb with the H atom pointing away from graphene, with adsorption energy 357 meV (34.4 kJ/mol). For the other THMs studied the calculated adsorption energy values vary from 206 meV (19.9 kJ/mol) for fluoroform (CHF3) to 404 meV (39.0 kJ/mol) for bromoform (CHBr3).
    [Show full text]
  • SAFETY DATA SHEET Halocarbon R-503
    SAFETY DATA SHEET Halocarbon R-503 Section 1. Identification GHS product identifier : Halocarbon R-503 Other means of : Not available. identification Product type : Liquefied gas Product use : Synthetic/Analytical chemistry. SDS # : 007306 Supplier's details : Airgas USA, LLC and its affiliates 259 North Radnor-Chester Road Suite 100 Radnor, PA 19087-5283 1-610-687-5253 24-hour telephone : 1-866-734-3438 Section 2. Hazards identification OSHA/HCS status : This material is considered hazardous by the OSHA Hazard Communication Standard (29 CFR 1910.1200). Classification of the : GASES UNDER PRESSURE - Liquefied gas substance or mixture HAZARDOUS TO THE OZONE LAYER - Category 1 GHS label elements Hazard pictograms : Signal word : Warning Hazard statements : Contains gas under pressure; may explode if heated. May cause frostbite. May displace oxygen and cause rapid suffocation. Harms public health and the environment by destroying ozone in the upper atmosphere. Precautionary statements General : Read and follow all Safety Data Sheets (SDS’S) before use. Read label before use. Keep out of reach of children. If medical advice is needed, have product container or label at hand. Close valve after each use and when empty. Use equipment rated for cylinder pressure. Do not open valve until connected to equipment prepared for use. Use a back flow preventative device in the piping. Use only equipment of compatible materials of construction. Always keep container in upright position. Prevention : Not applicable. Response : Not applicable. Storage : Protect from sunlight. Store in a well-ventilated place. Disposal : Refer to manufacturer or supplier for information on recovery or recycling. Hazards not otherwise : Liquid can cause burns similar to frostbite.
    [Show full text]
  • Development of a Solvent Extraction Process for Group Actinide Recovery from Used Nuclear Fuel
    THESIS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY Development of a Solvent Extraction Process for Group Actinide Recovery from Used Nuclear Fuel EMMA H. K. ANEHEIM Department of Chemical and Biological Engineering CHALMERS UNIVERSITY OF TECHNOLOGY Gothenburg, Sweden, 2012 Development of a Solvent Extraction Process for Group Actinide Recovery from Used Nuclear Fuel EMMA H. K. ANEHEIM ISBN 978-91-7385-751-2 © EMMA H. K. ANEHEIM, 2012. Doktorsavhandlingar vid Chalmers tekniska högskola Ny serie Nr 3432 ISSN 0346-718X Department of Chemical and Biological Engineering Chalmers University of Technology SE-412 96 Gothenburg Sweden Telephone + 46 (0)31-772 1000 Cover: Radiotoxicity as a function of time for the once through fuel cycle (left) compared to one P&T cycle using the GANEX process (right) (efficiencies: partitioning from Table 5.5.4, transmutation: 99.9%). Calculations performed using RadTox [HOL12]. Chalmers Reproservice Gothenburg, Sweden 2012 Development of a Solvent Extraction Process for Group Actinide Recovery from Used Nuclear Fuel EMMA H. K. ANEHEIM Department of Chemical and Biological Engineering Chalmers University of Technology Abstract When uranium is used as fuel in nuclear reactors it both undergoes neutron induced fission as well as neutron capture. Through successive neutron capture and beta decay transuranic elements such as neptunium, plutonium, americium and curium are produced in substantial amounts. These radioactive elements are mostly long-lived and contribute to a large portion of the long term radiotoxicity of the used nuclear fuel. This radiotoxicity is what makes it necessary to isolate the used fuel for more than 100,000 years in a final repository in order to avoid harm to the biosphere.
    [Show full text]
  • Use of Chlorofluorocarbons in Hydrology : a Guidebook
    USE OF CHLOROFLUOROCARBONS IN HYDROLOGY A Guidebook USE OF CHLOROFLUOROCARBONS IN HYDROLOGY A GUIDEBOOK 2005 Edition The following States are Members of the International Atomic Energy Agency: AFGHANISTAN GREECE PANAMA ALBANIA GUATEMALA PARAGUAY ALGERIA HAITI PERU ANGOLA HOLY SEE PHILIPPINES ARGENTINA HONDURAS POLAND ARMENIA HUNGARY PORTUGAL AUSTRALIA ICELAND QATAR AUSTRIA INDIA REPUBLIC OF MOLDOVA AZERBAIJAN INDONESIA ROMANIA BANGLADESH IRAN, ISLAMIC REPUBLIC OF RUSSIAN FEDERATION BELARUS IRAQ SAUDI ARABIA BELGIUM IRELAND SENEGAL BENIN ISRAEL SERBIA AND MONTENEGRO BOLIVIA ITALY SEYCHELLES BOSNIA AND HERZEGOVINA JAMAICA SIERRA LEONE BOTSWANA JAPAN BRAZIL JORDAN SINGAPORE BULGARIA KAZAKHSTAN SLOVAKIA BURKINA FASO KENYA SLOVENIA CAMEROON KOREA, REPUBLIC OF SOUTH AFRICA CANADA KUWAIT SPAIN CENTRAL AFRICAN KYRGYZSTAN SRI LANKA REPUBLIC LATVIA SUDAN CHAD LEBANON SWEDEN CHILE LIBERIA SWITZERLAND CHINA LIBYAN ARAB JAMAHIRIYA SYRIAN ARAB REPUBLIC COLOMBIA LIECHTENSTEIN TAJIKISTAN COSTA RICA LITHUANIA THAILAND CÔTE D’IVOIRE LUXEMBOURG THE FORMER YUGOSLAV CROATIA MADAGASCAR REPUBLIC OF MACEDONIA CUBA MALAYSIA TUNISIA CYPRUS MALI TURKEY CZECH REPUBLIC MALTA UGANDA DEMOCRATIC REPUBLIC MARSHALL ISLANDS UKRAINE OF THE CONGO MAURITANIA UNITED ARAB EMIRATES DENMARK MAURITIUS UNITED KINGDOM OF DOMINICAN REPUBLIC MEXICO GREAT BRITAIN AND ECUADOR MONACO NORTHERN IRELAND EGYPT MONGOLIA UNITED REPUBLIC EL SALVADOR MOROCCO ERITREA MYANMAR OF TANZANIA ESTONIA NAMIBIA UNITED STATES OF AMERICA ETHIOPIA NETHERLANDS URUGUAY FINLAND NEW ZEALAND UZBEKISTAN FRANCE NICARAGUA VENEZUELA GABON NIGER VIETNAM GEORGIA NIGERIA YEMEN GERMANY NORWAY ZAMBIA GHANA PAKISTAN ZIMBABWE The Agency’s Statute was approved on 23 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.
    [Show full text]
  • Finding Refrigerant Leaks with the Chempro100i
    Application Note: 108 Finding Refrigerant Leaks with the ChemPro100i The ChemPro100i is a great sniffer for halocarbon refrigerants, often generically referred to as “Freon” because of its multiple sensors and broad sniffing capability. As refrigerant sniffers are only carried by a small subset of first responders, the ChemPro100i can fill the role for those that don’t have a refrigerant sniffer. As a bonus, if someone suspects that it may be a refrigerant leak, and it turns out to be something else, the wide range of detectable gases and vapors seen by the ChemPro100i means that it will most likely find the unexpected gas/vapor too. The ChemPro100i’s Sensors The ChemPro100i uses a suite of seven sensors including an aspirated Ion Mobility Spectroscopy (IMS), five metal oxide sensors and a field effect sensor to detect, characterize, and even identify, some gases and vapors. Using this suite of sensors, the ChemPro100i can find halocarbon refrigerant leaks using its “Trend” or “sniffer” screen. As one gets closer to the refrigerant leak, the trend line will Using other Sniffers for increase. This is a non-quantifiable reading Refrigerants that does not directly correlate with parts per Most dedicated refrigerant detectors use a million (ppm), but the fast response of the Metal Oxide Sensor (MOS) that is doped to ChemPro100i to refrigerants provides one with be relatively specific to the halogenated the means of quickly finding a refrigerant leak. hydrocarbons (halogens) that are the hallmark of most refrigerants. MOS sensors Increase in the Trend line leads you to the leak are non-linear and not suitable for quantification of refrigerants, but they provide sensitive and fast response to halocarbon refrigerants.
    [Show full text]
  • Halocarbon 32 (Difluoromethane) CH 2F2
    Halocarbon 32 (Difluoromethane) CH 2F2 Grade ULSI 4N ULTIMA 4N8 Purity, % 99.99 99.998 Nitrogen ≤40 ppmv ≤5 ppmv Oxygen ≤10 ppmv ≤2 ppmv Carbon Dioxide ≤15 ppmv ≤1 ppmv Methane ≤2 ppmv ≤1 ppmv Water ≤5 ppmv ≤1 ppmv Carbon Tetrafluoride ≤5 ppmv ≤1 ppmv Other Organics ≤100 ppmv ≤10 ppmv Carbon Monoxide ≤1 ppmv Acidity as HF ≤0.1 ppmw • A lot analysis is provided for each order – Individual analysis is also available upon request. • Other Organics = H 12 , H 22 , H 23 , H 134a Internal Volume Liters 43.8 17.1 7.3 R E Cylinder Sizes >> QF GF UF D N I L lbs 64 25 11 Y Content C kg 29.1 11.35 5 Change Point* lbs 4.3 1.7 0.7 *Recommended Cylinder Change Point at NTP, based on Phase Break, or the amount of product left in the cylinder when the liquid phase has completely evaporated and only gaseous product is left (estimate based on ideal gas behavior). DOT Shipping Name Difluoromethane Shipped as P I DOT Classification 2.1 (Flammable Gas) H S Liquefied DOT Label FLAMMABLE GAS Gas UN Number UN 3252 Cylinder Pressure 207 psig Temp, °C 0.0 15.5 21.0 32.2 43.3 A Vapor T A @NTP 15.6 atm Press, psig 102 172 207 279 372 D 3 Pressure L Specific Volume 0.45 m /kg Temp, °F 32 60 70 90 110 A 3 C NTP = 21°C or 70°F and 101.3 kPa or 1 atm I @NTP 7.2 ft /lb N H CAS No 75-10-5 C E T CGA/DISS/JIS 350/724/W22-14L Molecular Weight 52 g/mol Nominal Diameter (OD)xHeight* Material of Construction Cylinder Treatment cm Inches Cylinder Valve ® QF ULTRA-LINE 23x130/134/143 9x51/52.5/56 CS SS ® GF ULTRA-LINE 23x66/70/79 9x26/27.5/31 CS SS ® UF ULTRA-LINE 15x51/55/64 6x19/20.5/24 CS SS *Height is reported as the distance from the bottom of the cylinder to the cylinder neck/ center of the valve outlet/ top of the handwheel CS: Carbon Steel SS: Stainless Steel WARNING: This product can expose you to chemicals including Carbon Monoxide, which is known to the State of California to cause birth defects or other reproductive harm.
    [Show full text]
  • Safety Data Sheet Tetrafluoromethane
    Safety Data Sheet Tetrafluoromethane Section 1: Product and Company Identification Middlesex Gases & Technologies 292 Second Street P.O. Box 490249 Everett, MA 02149 (617) 387-5050 (800) 649-6704 Fax (617) 387-3537 http://www.middlesexgases.com/ Product Code: Tetrafluoromethane Section 2: Hazards Identification Warning Hazard Classification: Gases Under Pressure Hazard Statements: Contains gas under pressure; may explode if heated Precautionary Statements Storage: Protect from sunlight. Store in well-ventilated place. Section 3: Composition/Information on Ingredients CAS # 75-73-0 Middlesex Gases & Technologies page 1 of 5 Generated by the SDS Manager from AsteRisk, LLC. All Rights Reserved Generated: 06/01/2015 Chemical Substance Chemical Trade Names Family TETRAFLUOROMETHANE halogenated, CARBON TETRAFLUORIDE; CARBON FLUORIDE (CF4); CARBON FLUORIDE; FC 14; aliphatic PERFLUOROMETHANE; R 14; R 14 (REFRIGERANT); METHANE, TETRAFLUORO-; FREON 14; TETRAFLUOROCARBON; UN 1982; CF4 Section 4: First Aid Measures Skin Contact Eye Contact Ingestion Inhalation Note to Physicians If frostbite or freezing occur, Wash eyes immediately with If a large If adverse effects occur, remove to For immediately flush with plenty of large amounts of water, amount is uncontaminated area. Give artificial inhalation, lukewarm water (105-115 F; 41-46 occasionally lifting upper and swallowed, get respiration if not breathing. If consider C). DO NOT USE HOT WATER. If lower lids, until no evidence of medical breathing is difficult, oxygen should oxygen. warm water is not available, gently chemical remains. Get attention. be administered by qualified wrap affected parts in blankets. Get medical attention immediately. personnel. Get immediate medical immediate medical attention. attention. Section 5: Fire Fighting Measures Suitable Extinguishing Media Products of Combustion Protection of Firefighters Non-flammable.
    [Show full text]
  • The Actinide Research Quarterly Is Published Quarterly to Highlight Recent Achievements and Ongoing Programs of the Nuclear Materials Technology Division
    1st quarter 2000 TheLos Actinide Alamos National Research Laboratory N u c l e a r M aQuarterly t e r i a l s R e s e a r c h a n d T e c h n o l o g y a U.S. Department of Energy Laboratory Organizers Issue an Invitation to In This Issue Plutonium Futures 1 —The Science Organizers Issue an Invitation to Plutonium Futures —The Science The second of a series of international con- have an exciting collection of some 180 invited ferences on plutonium will be held in Santa Fe, and contributed papers with topics ranging 2 NM, this summer, July 10–13. It follows the very broadly in materials science, transuranic 238Pu Aqueous highly successful 1997 conference, “Plutonium waste forms, nuclear fuels and isotopes, separa- Processing Line Will Futures - The Science,” which attracted over 300 tions, actinides in the environment, detection Provide New NMT participants representing 14 countries. The U.S. and analysis, actinide compounds and com- Capability participants, who made up about 70 percent of plexes, and condensed matter physics of ac- the total participants, came from Department of tinides. These papers, presented in separate 4 Energy national laboratories and a score of uni- oral and poster sessions, will give attendees a Editorial: versities and industries. As in 1997, the confer- chance to learn about current research outside Transactinium ence is sponsored by the Los Alamos National of their particular specialties and provide an Science Needs Laboratory in cooperation with the American opportunity for interdisciplinary discussions Educational Nuclear Society.
    [Show full text]