Conversion of Carbon Dioxide to Acetylene on a Micro Scale
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And C,N-Chelated Organocopper Compounds†
Preprints (www.preprints.org) | NOT PEER-REVIEWED | Posted: 2 September 2021 Review C,C- and C,N-Chelated Organocopper Compounds† Liang Liu1, Hui Chen2, Zhenqiang Yang2, Junnian Wei1* and Zhenfeng Xi1,3* 1 Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China; [email protected] (L.L.), [email protected] (J.W.), [email protected] (Z.X.) 2 Henan Institute of Chemistry Co. Ltd., Henan Academy of Sciences, Zhengzhou 450002, China; [email protected] (H.C.), [email protected] (Z.Y.) 3 State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry (SIOC), Shanghai 200032, China; [email protected] (Z.X.) * Correspondence: [email protected] (J.W.), [email protected] (Z.X.) † Dedicated to Professor Gerard van Koten on the occasion of his 80th birthday Abstract: Copper-catalyzed and organocopper-involved reactions are of great significance in organic synthesis. To have a deep understanding of the reaction mechanisms, the structural characterizations of organocopper intermediates become indispensable. Meanwhile, the structure- function relationship of organocopper compounds would advance rational design and development of new Cu-based reactions and organocopper reagents. Compared to the mono- carbonic ligand, the C,N- and C,C-bidentate ligands better stabilize the unstable organocopper compounds. The bidentate ligands can chelate to the same copper atom via 휂2-mode, forming a mono-cupra-cyclic compounds with at least one acute C-Cu-C angle. When the bidentate ligands bind to two copper atoms via 휂1-mode at each coordinating site, the bimetallic macrocyclic compounds will form nearly linear C-Cu-C angles. -
Cylinder Valve Selection Quick Reference for Valve Abbreviations
SHERWOOD VALVE COMPRESSED GAS PRODUCTS Appendix Cylinder Valve Selection Quick Reference for Valve Abbreviations Use the Sherwood Cylinder Valve Series Abbreviation Chart on this page with the Sherwood Cylinder Valve Selection Charts found on pages 73–80. The Sherwood Cylinder Valve Selection Chart are for reference only and list: • The most commonly used gases • The Compressed Gas Association primary outlet to be used with each gas • The Sherwood valves designated for use with this gas • The Pressure Relief Device styles that are authorized by the DOT for use with these gases PLEASE NOTE: The Sherwood Cylinder Valve Selection Charts are partial lists extracted from the CGA V-1 and S-1.1 pamphlets. They can change without notice as the CGA V-1 and S-1.1 pamphlets are amended. Sherwood will issue periodic changes to the catalog. If there is any discrepancy or question between these lists and the CGA V-1 and S-1.1 pamphlets, the CGA V-1 and S-1.1 pamphlets take precedence. Sherwood Cylinder Valve Series Abbreviation Chart Abbreviation Sherwood Valve Series AVB Small Cylinder Acetylene Wrench-Operated Valves AVBHW Small Cylinder Acetylene Handwheel-Operated Valves AVMC Small Cylinder Acetylene Wrench-Operated Valves AVMCHW Small Cylinder Acetylene Handwheel-Operated Valves AVWB Small Cylinder Acetylene Wrench-Operated Valves — WB Style BV Hi/Lo Valves with Built-in Regulator DF* Alternative Energy Valves GRPV Residual Pressure Valves GV Large Cylinder Acetylene Valves GVT** Vertical Outlet Acetylene Valves KVAB Post Medical Valves KVMB Post Medical Valves NGV Industrial and Chrome-Plated Valves YVB† Vertical Outlet Oxygen Valves 1 * DF Valves can be used with all gases; however, the outlet will always be ⁄4"–18 NPT female. -
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— Studies on Lithium Acetylide Kenneth N. Campbell and Barbara K. Campbell, The University of Notre Dame In contrast to the large amount of work done on the acetylene derivatives of sodium, potassium and calcium, little attention has been paid to the analogous compounds of lithium. In 1898 Moissani prepared lithium acetylide on a small scale, by the action of acetylene on a liquid ammonia solution of lithium. He reported that lithium acetylide was less soluble in liquid ammonia than sodium acetylide, and that when isolated from the solvent, it was less stable, undergoing decomposition with evolu- tion of acetylene. On the basis of the weight of lithium acetylide obtained from a given weight of lithium, and from the amount of acetylene liberated on hydrolysis, he assigned to lithium acetylide the formula C2Li2.C2H2.2NH3. Since that time no references to lithium acetylide or lithium alkylacetylides have appeared in the literature. It was the pur- pose of the present work, therefore, to prepare and analyze lithium acetylide and a lithium alkylacetylide, and to compare their reactions with those of the better known sodium derivatives. Experimental Procedure Preparation of Lithium and Sodium Acetylides.—Acetylene gas, washed by bubbling through concentrated sulfuric acid, was passed into two liters of liquid ammonia, while 7 g. (1 mole) of metallic lithium, cut in small pieces, was added gradually, with stirring, at a rate such that the solution did not develop a permanent deep blue color. When the solution became colorless after the addition of the last piece of lithium, the flow of acetylene was stopped. -
Kinetic Study of the Selective Hydrogenation of Acetylene Over Supported Palladium Under Tail-End Conditions
catalysts Article Kinetic Study of the Selective Hydrogenation of Acetylene over Supported Palladium under Tail-End Conditions Caroline Urmès 1,2, Jean-Marc Schweitzer 2, Amandine Cabiac 2 and Yves Schuurman 1,* 1 IRCELYON CNRS, UMR 5256, Univ Lyon, Université Claude Bernard Lyon 1, 2 avenue Albert Einstein, 69626 Villeurbanne Cedex, France; [email protected] 2 IFP Energies nouvelles, Etablissement de Lyon, Rond-point de l’échangeur de Solaize, BP3, 69360 Solaize, France; [email protected] (J.-M.S.); [email protected] (A.C.) * Correspondence: [email protected]; Tel.: +33-472445482 Received: 9 January 2019; Accepted: 31 January 2019; Published: 14 February 2019 Abstract: The kinetics of the selective hydrogenation of acetylene in the presence of an excess of ethylene has been studied over a 0.05 wt. % Pd/α-Al2O3 catalyst. The experimental reaction conditions were chosen to operate under intrinsic kinetic conditions, free from heat and mass transfer limitations. The data could be described adequately by a Langmuir–Hinshelwood rate-equation based on a series of sequential hydrogen additions according to the Horiuti–Polanyi mechanism. The mechanism involves a single active site on which both the conversion of acetylene and ethylene take place. Keywords: power-law; Langmuir–Hinshelwood; kinetic modeling; Pd/α-Al2O3 1. Introduction Ethylene is the largest of the basic chemical building blocks with a global market estimated at more than 140 million tons per year with an increasing growth rate. It is used mainly as precursor for polymers production, for instance polyethylene, vinyl chloride, ethylbenzene, or even ethylene oxide synthesis. -
United States Patent Office Patented Nov
3,111,372 United States Patent Office Patented Nov. 19, 1963 1. 2 earth metal borohydrides, which comprises reacting an 3,111,372 PROCESS FOR THE PRODUCTION OF ALKALI N-trialkyl borazane with an alkali metal acetylide or METAL AND ALKALINE EARTH METAL BORO alkaline earth metal acetylide in the presence of hydrogen HYDRIDES under pressure. For example, N-triethyl borazane can Roland Köster, Mulheim (Ruhr), Germany, assignor to 5 be split up at temperatures higher than 140 C., prefer Studiengesellschaft Kohle m.b.H., Mulheim (Ruhr), ably between 200 and 300° C. by calcium carbide, the Germany acetylide fraction of the calcium carbide becoming free No Drawing. Filed Apr. 28, 1958, Ser. No. 731,125 mostly in the form of ethane. The temperatures used are Claims priority, application Germany Apr. 30, 1957 so low that the initial formation of calcium hydride from 7 Claims. (C. 23-14) O calcium carbide must be considered as not occurring in This invention relates to a process for the production of practice, since the temperatures at which calcium carbide alkali metal and alkaline earth metal borohydrides. reacts with hydrogen alone to form calcium hydride are Belgian patent specification No. 559,053 discloses a substantially higher. Moreover, calcium carbide only process for the production of alkali metal and alkaline reacts easily with hydrogen to form calcium hydride if earth metal borohydrides from borazanes having 3 hydro certain catalysts are present, and in addition the calcium carbon radicals, especially N-trialkyl borazanes, by re hydride formation requires a substantially higher tem action with an alkali metal or alkaline earth metal hy perature than is necessary in the process of the inven dride, with a metal compound of the general formulae tion. -
Common Name: METHYL ACETYLENE HAZARD SUMMARY
Common Name: METHYL ACETYLENE CAS Number: 74-99-7 RTK Substance number: 1218 DOT Number: UN 1954 Date: May 1999 ----------------------------------------------------------------------- ----------------------------------------------------------------------- HAZARD SUMMARY * Methyl Acetylene can affect you when breathed in. * Exposure to hazardous substances should be routinely * Breathing Methyl Acetylene can irritate the nose and evaluated. This may include collecting personal and area throat. air samples. You can obtain copies of sampling results * Breathing Methyl Acetylene can irritate the lungs causing from your employer. You have a legal right to this coughing and/or shortness of breath. Higher exposures information under OSHA 1910.1020. can cause a build-up of fluid in the lungs (pulmonary * If you think you are experiencing any work-related health edema), a medical emergency, with severe shortness of problems, see a doctor trained to recognize occupational breath. diseases. Take this Fact Sheet with you. * Exposure to Methyl Acetylene can cause headache, dizziness, convulsions (fits) and unconsciousness. WORKPLACE EXPOSURE LIMITS * Liquified Methyl Acetylene can cause frostbite. OSHA: The legal airborne permissible exposure limit * Methyl Acetylene is a HIGHLY FLAMMABLE and (PEL) is 1,000 ppm averaged over an 8-hour REACTIVE chemical and is a DANGEROUS FIRE and workshift. EXPLOSION HAZARD. NIOSH: The recommended airborne exposure limit is IDENTIFICATION 1,000 ppm averaged over a 10-hour workshift. Methyl Acetylene is a colorless gas, which is shipped as a liquid, with a sweet odor. It is used as a simple anesthetic and ACGIH: The recommended airborne exposure limit is in the manufacture of other chemicals, and as a welding torch 1,000 ppm averaged over an 8-hour workshift. -
Mixed Metal Acetylides: the Ptii Aryl Acetylide "[Ptc6h2(Ch2nme2)22,6
FULL PAPER II Mixed Metal Acetylides: The Pt Aryl Acetylide ‘‘[PtC6H2(CH2NMe2)2- 2,6-(C;C)-4]’’ as a Connective Fragment Stephan Back,[a] Robert A. Gossage,[b] Heinrich Lang,*[a] and Gerard van Koten*[b] Keywords: Alkynes / Cyclic voltammetry / Metal-metal interactions / Conjugation / Platinum Using Me3SiC;C{Pt}Cl (1;Me3SiC;C{Pt} = [Pt(C6H2- successful attachment of 1 toaPh3PAu unit leads to linear + {CH2NMe2}2-2,6-{C;CSiMe3}-4] ) a series of platinum Ph3PAuC;C{Pt}Cl (11). Treatment of 11 with FcC;CSnMe3 monoacetylides of the type XC;C{Pt}C;CR [X = SiMe3: 2, produces the heterotrimetallic rigid-rod shaped complex 5 5 R = Ph; 3,R=(η -C5H4)Fe(η -C5H5) (abbreviated as Fc); 4, Ph3PAuC;C{Pt}C;CFc (13). Cyclic voltammetric studies R=C6H4CN-4; 5,R=C6H4(C;CSnMe3)-4;X=H:7,R=Ph; carried out on these Ph3PAu-capped molecules show that the 8,R=Fc;9,R=C6H4CN-4] have been prepared. Studies attachment of an organometallic entity on either side of the II IV directed towards the coordinative properties of the C2 unit of C;C{Pt} fragment leads to a facilitation of the Pt /Pt oxida- 1 have been carried out and heterotrimetallic [µ- tion. (Me3SiC;C{Pt}Cl][Co2(CO)6](10) could be synthesised. The Introduction The growing interest in the application of organometallic Scheme 1. Precursor complex 1 compounds as building blocks for new materials has led to a large number of publications on their synthesis,[1] and the evaluation of theoretical aspects.[2] In particular, the assem- A useful property of 1 is that it possesses two chemically bly, chemistry, and the physical properties of a number of unique reactive sites. -
Benzene⋯Acetylene: a Structural Investigation of the Prototypical CH
Physical Chemistry Chemical Physics Benzene ⋯⋯⋯Acetylene: A structural investigation of the prototypical CH ⋯⋯⋯π interaction Journal: Physical Chemistry Chemical Physics Manuscript ID: CP-ART-02-2014-000845.R1 Article Type: Paper Date Submitted by the Author: 20-Mar-2014 Complete List of Authors: Ulrich, Nathan; Eastern Illinois University, Chemistry Seifert, Nathan; University of Virginia, Chemistry Dorris, Rachel; Eastern Illinois University, Chemistry Peebles, Rebecca; Eastern Illinois University, Chemistry Pate, Brookes; University of Virginia, Chemistry Peebles, Sean; Eastern Illinois University, Chemistry Page 1 of 30 Physical Chemistry Chemical Physics 3/20/2014 10:13:21 AM Benzene ⋯⋯⋯A⋯AAAcetylene: A structural investigation of the prototypical CH ⋯⋯⋯π interaction Nathan W. Ulrich, a Nathan A. Seifert, b Rachel E. Dorris, a Rebecca A. Peebles, a Brooks H. Pate, b Sean A. Peebles a, * a Eastern Illinois University, Department of Chemistry, 600 Lincoln Ave., Charleston, IL 61920 b University of Virginia, Department of Chemistry and Biochemistry, McCormick Rd., PO Box 400319, Charlottesville, VA 22904 *To whom correspondence should be addressed: email: [email protected] phone: (217) 581-2679 1 Physical Chemistry Chemical Physics Page 2 of 30 3/20/2014 10:13:21 AM Abstract The structure of a prototype CH ⋯π system, benzene ⋯acetylene, has been determined in the gas phase using Fourier-transform microwave spectroscopy. The spectrum is consistent with an effective C6v structure with an H ⋯π distance of 2.4921(1) Å. The HCCH subunit likely tilts by ~5º from the benzene symmetry axis. The dipole moment was determined to be 0.438(11) D from Stark effect measurements. The observed intermolecular distance is longer than in similar benzene ⋯HX complexes and than the distances observed in the benzene ⋯HCCH cocrystal and predicted by many high level ab initio calculations; however, the experimentally estimated –1 binding energy of 7.1(7) kJ mol is similar to previously studied benzene ⋯HX complexes. -
Acetylene Fact Sheet
Occupational Safety Fact Sheet Compressed Acetylene Gas DESCRIPTION ACETYLENE STORAGE Acetylene is a compressed gas that is commonly Acetylene cylinders must always be transported, used in conjunction with compressed oxygen to fuel stored and used in the upright position. torches used for various tasks. Acetylene cylinders must be stored with the valve HAZARDS caps installed and in a well-ventilated area. Particular care must be taken with small cylinders that do not have valve protection caps. Keep cylinders away from external sources of heat. Cylinders are not designed for temperatures in excess of 125F (52C). Acetylene must be stored at least 20-feet away from oxygen or separated by a five foot high fire-rated wall. MSHA Photo Acetylene poses unique hazards based on its high flammability, instability and unique storage and transportation requirements. Acetylene is highly unstable. High pressure or temperatures can result in decomposition that can result in fire or explosion. Acetylene cylinders must never be transported or stored in a closed vehicle. There are several documented explosions that have occurred due to the buildup of acetylene vapors inside of a vehicle that were triggered by a spark from the vehicle’s Canadian Center for Occupation Health & Safety electrical system. ACETYLENE USE THE UNIQUE ACETYLENE CYLINDER Regulator Connection - Always carefully inspect Acetylene cylinders do not the CGA connection on the cylinder and remove any contain compressed or visible contamination before connecting the liquefied acetylene; instead regulator. they contain acetylene gas dissolved in acetone that is Leak Test - Once all components are connected, absorbed onto a porous mass perform a leak test with a soap and water solution. -
(Pahs) Coming from Pyrolysis in Low-Pressure Gas Carburizing Conditions Tsilla Bensabath, Hubert Monnier, Pierre-Alexandre Glaude
View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Archive Ouverte en Sciences de l'Information et de la Communication Detailed kinetic modeling of the formation of toxic polycyclic aromatic hydrocarbons (PAHs) coming from pyrolysis in low-pressure gas carburizing conditions Tsilla Bensabath, Hubert Monnier, Pierre-Alexandre Glaude To cite this version: Tsilla Bensabath, Hubert Monnier, Pierre-Alexandre Glaude. Detailed kinetic modeling of the for- mation of toxic polycyclic aromatic hydrocarbons (PAHs) coming from pyrolysis in low-pressure gas carburizing conditions. Journal of Analytical and Applied Pyrolysis, Elsevier, 2016, 122, pp.342-354. 10.1016/j.jaap.2016.09.007. hal-01510237 HAL Id: hal-01510237 https://hal.archives-ouvertes.fr/hal-01510237 Submitted on 19 Apr 2017 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Title: Detailed kinetic modeling of the formation of toxic polycyclic aromatic hydrocarbons (PAHs) coming from pyrolysis in low-pressure gas carburizing conditions Authors: Tsilla Bensabatha,b -
On Reversible H2 Loss Upon N2 Binding to Femo-Cofactor of Nitrogenase
On reversible H2 loss upon N2 binding to FeMo-cofactor of nitrogenase Zhi-Yong Yanga, Nimesh Khadkaa, Dmitriy Lukoyanovb, Brian M. Hoffmanb,1, Dennis R. Deanc,1, and Lance C. Seefeldta,1 aDepartment of Chemistry and Biochemistry, Utah State University, Logan, UT 84322; bDepartments of Chemistry and Molecular Biosciences, Northwestern University, Evanston, IL 60208; and cDepartment of Biochemistry, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061 Contributed by Brian M. Hoffman, August 23, 2013 (sent for review July 15, 2013) Nitrogenase is activated for N2 reduction by the accumulation of obligatory, reversible H2 loss upon N2 binding (5). We consid- four electrons/protons on its active site FeMo-cofactor, yielding ered two models for this process, both built on our character- a state, designated as E4, which contains two iron-bridging hydrides ization of the key E4 state, and tested them against the numerous – – [Fe H Fe]. A central puzzle of nitrogenase function is an apparently constraints imposed by turnover under N2 plus D2 or T2 (5, 9– obligatory formation of one H2 per N2 reduced, which would “waste” 16). In particular, these constraints include the key findings that two reducing equivalents and four ATP. We recently presented during catalytic reduction of N2 (see Scheme S1), a molecule of a draft mechanism for nitrogenase that provides an explanation D2 or T2 will reduce two protons to form two HD or HT without + + for obligatory H2 production. In this model, H2 is produced by re- D /T exchange with solvent, even though neither D2 nor T2 by ductive elimination of the two bridging hydrides of E4 during N2 themselves reacts with nitrogenase during turnover under Ar (5). -
Approach and Synthesis of Strychnos Alkaloids
N° d'ordre : 4155 THÈSE Présentée à L'UNIVERSITÉ BORDEAUX I ÉCOLE DOCTORALE DES SCIENCES CHIMIQUES par Dawood Hosni DAWOOD POUR OBTENIR LE GRADE DE DOCTEUR SPÉCIALITÉ : CHIMIE ORGANIQUE ********************* TOWARDS THE SYNTHESIS OF MONOTERPENOIDS INDOLE ALKALOIDS OF THE ASPIDOSPERMATAN AND STRYCHNAN TYPE ********************* Soutenue le: 17 décembre 2010 Après avis de: MM. PIVA Olivier Professeur, Claude Bernard Lyon 1 Rapporteur PALE Patrick Professeur, Louis Pasteur Strasbourg 1 Rapporteur Devant la commission d'examen formée de : MM. PIVA Olivier Professeur, Claude Bernard Lyon 1 Rapporteur PALE Patrick Professeur, Louis Pasteur Strasbourg 1 Rapporteur POISSON Jean-François Chargé de recherche, CNRS Examinateur VINCENT Jean-Marc Directeur de recherche, CNRS Examinateur LANDAIS Yannick Professeur, Bordeaux 1 Directeur de thèse ROBERT Frédéric Chargé de recherche, CNRS Codirecteur de thèse - 2010 - Abbreviations ∆: reflux °C: celsius degrees Ac: acetyle ALB Aluminium Lithium bis(binaphthoxide) complex AIBN : azobis(isobutyronitrile) aq.: aqueous Ar : aromatic BINAP : 2,2'-bis(diphenylphosphino)-1,1'-binaphthyle BINAPO : 2-diphenylphosphino-2'-diphenylphosphinyl-1,1'-binaphthalene BINOL: 1,1’-bi-2-naphthol Boc: tert-butyloxycarbonyle BOX: Bisoxazoline Bz : benzoyle Bn: benzyle cat. : catalytic DBU: 1,8-diazabicyclo[5.4.0]undec-7-ene DCM: dichloromethane DCC: dicyclohexacarbodiimide dr.: diastereomeric ratio DIBAL-H: diisobutylaluminium hydride DIPEA: diisopropyléthylamine (Hünig Base) DMAP: dimethylaminopyridine DME: dimethoxyethane