DOCSLIB.ORG

The Carbon Sulfide Anions (C4S4)2− and Β-(C3S5)

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
The Carbon Sulfide Anions (C4S4)2− and Β-(C3S5) 2− 2− The Carbon Sulfide Anions (C4S4) and β-(C3S5) A Crystallographic Study on the Metal Salts and the Hydrolysis and Oxidation Properties By Younis Omer Ben Amer A thesis submitted for the degree of Doctor of Natural Science in Chemistry The Faculty of Mathematics and Natural Science The University of Bonn 2008 2− 2− The Carbon Sulfide Anions (C4S4) and β-(C3S5) A Crystallographic Study on the Metal Salts and the Hydrolysis and Oxidation Properties D I S S E R T A T I O N zur Erlangung des Doktorgrades (Dr. rer. nat.) der Mathematisch-Naturwissenschaftlichen Fakultät der Rheinischen Friedrich-Wilhelms-Universität Bonn vorgelegt von M. Sc. Chem. Younis O. Ben Amer aus Benghazi, Libyen 2008 Angefertigt mit Genehmigung der Mathematisch-Naturwissenschaftlichen Fakultät der Rheinischen Friedrich-Wilhelms-Universität Bonn 1. Gutachter: Prof. Dr. Johannes Beck 2. Gutachter: Prof. Dr. Robert Glaum Fachnaher Gutachter Prof. Dr. Sigurd Höger Fachfremder Gutachter Prof. Dr. Karl Maier Tag der Promotion: 16.02.2009 Erscheinungsjahr: 2009 Diese Dissertation ist auf dem Hochschulschriftenserver der ULB Bonn http://hss.ulb.uni-bonn.de/diss_online elektronisch publiziert. Acknowledgement First of all, I would like to express my deepest sense of gratitude to my supervisor Prof. Dr. Johannes Beck for his patient guidance, encouragement and excellent advice throughout this study. My sincere thanks go to Dr. Jörg Daniels for his constant support in collecting X-ray diffraction data and in all questions of crystallography. Without his help, this work would not have been possible. I am thankful to Gertrud Dittman for her dedicated help with the synthesis of the sulfur-carbon anions. I would also like to thank the members of my group, especially Rahmat Triandi, Guido and Marcus Zink for their advice, moral and valuable support. Finally, I take this opportunity to express my profound gratitude to my beloved parents, my wife and children for their moral support and patience during my years in the Institute of Inorganic Chemistry, University of Bonn. Younis Ben Amer I Contents Chapter One – Introduction Page 1.1 Binary Compounds of Carbon with Oxygen and Sulfur………………….….. 01 2- 1.2 Thiocarbon Dianions (CnSn) ………………………………………………...… 04 2- 1.2.1 The Tetrathiosquarate Ion (C4S4) …………………..………………..…… 05 2- 1.2.2 The 1,2-Dithiole-3-Thione-4,5-Dithiolate Ion β-(C3S5) ……………..… 09 Chapter Two – Experimental Page 2.1 Materials and Reagents…………………….……………...…………………….. 14 2.2 Preparation of the Potassium Salt of Tetrathiosquarate…............................... 14 2- 2.3 Preparation of the Potassium Salt of β-(C3S5) ……………………………….. 15 2.4 Preparation of Salts of Tetrathiosquarate……………………………….......... 15 2.4.1 Preparation of Earth Alkaline Salts of Tetrathiosquarate........................... 15 2.4.1.1 Preparation of [Mg(H2O) 6](C4S4)………..…………...……………..… 15 2.4.1.2 Preparation of [Ca(H2O) 4](C4S4)…………………….………………... 15 2.4.1.3 Preparation of [Sr(H2O) 4](C4S4)……………….……......................….. 16 2.4.1.4 Preparation of [Ba4K2 (H2O) 16](C4S4)5………….……......................… 16 2.4.2 Preparation of Transition Metal Salts of Tetrathiosquarate……………... 16 2.4.2.1 Preparation of an Iron (II) Salt of Tetrathiosquarate……..... 16 2.4.2.2 Preparation of a Manganese (II) Salt of Tetrathiosquarate…. 17 2- 2.5 Preparation of Salts of 1,2-Dithiole-3-thione-4,5-dithiolate β-(C3S5 ) ……… 17 2+ 2+ 2- 2.5.1 Preparation of Ca and Sr Salts of β-(C3S5 ) ……........................….. 17 2- 2.5.2 Preparation of Tetraphenylarsonium Salts of β-(C3S5) ……………..… 18 2.5.2.1 Preparation in Air……………………….…….……….....................…. 18 2.5.2.2 Preparation under Exclusion of Air……...…...…................................… 18 2.6 Analyses and Physical Measurements….…..…..………………………..………. 19 II 2.7 Crystallography……………………………...………………………………....…. 19 Chapter Three – Results and Discussion Page 3.1 Earth Alkaline Tetrathiosquarate Salts……..………………………..…….… 20 3.1.1 Structure Determination of [Mg(H2O) 6](C4S4)………………………..… 20 3.1.2 Discussion the Structure of [Mg(H2O) 6](C4S4)…….............................… 24 3.1.3 Structure Determination of [Ca(H2O) 4](C4S4)………..……………….… 28 3.1.4 Discussion the Structure of [Ca(H2O) 4](C4S4)…………………….…..… 33 3.1.5 Structure Determination of [Sr(H2O) 4](C4S4)…….………………..….… 35 3.1.6 Discussion the Structure of [Sr(H2O) 4](C4S4)…………………….......… 39 3.1.7 Comparison of the structures of [M(H2O)4](C4S4) with M= Ca and Sr….. 41 3.1.8 Structure Determination of [Ba4K2 (H2O) 16](C4S4)5..............................… 45 3.1.9 Discussion the Structure of [Ba4K2 (H2O) 16](C4S4)5.………………….… 51 3.1.10 IR and Raman Spectroscopy of Earth Alkaline Tetrathiosquarate……... 56 3.1.11 Discussion and Comparison of Earth Alkaline Tetrathiosquarate Salts... 60 3.2 Iron (II) and Manganese (II) Tetrathiosquarates…….......………………….... 61 3.2.1 Structure Determination of [Mn4(OH)4(H2O)2] (C4S4)2 ……………...…. 61 3.2.2 Discussion the Structure of [Mn4(OH)4(H2O)2] (C4S4)2.......................….. 65 3.2.3 Structure Determination of [Fe(H2O)2](C4S4)·4H2O…….......................... 70 3.2.4 Discussion the structure of [Fe(H2O)2](C4S4)·4H2O ………………………. 74 3.2.5 Discussion and Comparison of Transition metal tetrathiosquarate Salts…... 79 2- 3.3 Reactions of β-(C3S5) ……………………………………………………...…….. 81 3.3.1 Oxidation by air…………………………………………………………….. 81 2– 3.3.2 The formation of theC3S6O3 Ion………….……….…………………........ 82 – 3.3.3 The Formation of (HC3S5) Ion…………………...……………………..… 82 – 3.3.4 The formation of the C3S4H Ion………………………..……………….…. 83 2- 3.4 Calcium and Strontium Salts of β-(C3S5) …...………….…….……………..... 84 3.4.1 Structure Determination of [Ca(H2O)7](C6S10)…………..………………… 84 3.4.2 Discussion the structure of [Ca(H2O)7](C6S10)...………………………....… 90 III 3.4.3 Structure Determination of [Sr(H2O)9](C6S10)…..……….……………....… 93 3.4.4 Discussion of the structure of [Sr(H2O)9](C6S10) ………….………………. 100 2- 3.4.5 Discussion and Comparison of (C6S10) Anions………………………...…. 102 2- 3.5 Tetraphenylarsonium Salts of β-(C3S5) …………...……..…………………...... 105 3.5.1 Tetraphenylarsonium Salts Prepared in Air……...………..........................… 105 3.5.1.1 Structure Determination of [AsPh4]2(C3S5) ·2H2O…....………………….. 105 3.5.1.2 Discussion the Structure of [AsPh4]2(C3S5) ·2H2O……………………..… 111 3.5.1.3 Structure Determination of [AsPh4](HC3S5)…………………………..…. 114 3.5.1.4 Discussion the Structure of [AsPh4](HC3S5)……………........................... 119 3.5.1.5 Structure Determination of [AsPh4]2(C3S6O3) ·3H2O.................................. 122 3.5.1.6 Discussion the Structure of [AsPh4]2(C3S6O3) ·3H2O……………………. 129 3.5.2 Tetraphenylarsonium Salts Prepared under Exclusion of Air………………. 131 3.5.2.1 Structure Determination of [AsPh4](C3S4H)……………........................... 131 3.5.2.2 Discussion the Structure of [AsPh4](C3S4H).………………………..…… 136 3.6 Conclusion………………………………………………………………………… 139 3.7 References…………………………………………………………………...……. 142 IV Tables Page Table 1 Crystallographic data and details of the structure determination of [Mg(H2O)6](C4S4)………………...……………….……………….……… 21 2 Table 2 Positional parameters, equivalent isotropic parameters Ueq /Å for the non-H atoms and displacement isotropic parameters for H atoms in the structure of [Mg(H2O)6](C4S4)…..…………...........................................................…. 22 2 Table 3 Anisotropic displacement parameters Uij [Å ] for the non-H atoms in the structure of [Mg(H2O)6](C4S4)………………………………………....…... 22 Table 4 Selected bond lengths Å and angles /° for [Mg(H2O)6](C4S4)……………...... 23 Table 5 Crystallographic data and details of the structure determination of [Ca(H2O)4](C4S4)………………....……………..……………………..…… 29 2 Table 6 Positional parameters, equivalent isotropic parameters Ueq- / Å for the non- H atoms and displacement isotropic parameters for H atoms in the structure of [Ca(H2O)4](C4S4)……………………………………….……... 30 2 Table 7 Anisotropic displacement parameters Uij [Å ] for the non-H atoms in the structure of [Ca(H2O)4](C4S4).……….………………………………..….... 31 Table 8 Selected bond lengths / Å and angles ° for [Ca(H2O)4](C4S4)……………..... 32 Table 9 Crystallographic data and details of the structure determination of [Sr(H2O)4](C4S4)………………...……………………………...……….… 36 2 Table 10 Positional parameters, equivalent isotropic parameters Ueq / Å for the non-H atoms and displacement isotropic parameters for H atoms in the structure of [Sr(H2O)4](C4S4)……..........………………………………....... 37 2 Table 11 Anisotropic displacement parameters Uij / [Å ] for the non-H atoms in the structure of [Sr(H2O)4](C4S4)……………….………………………………….…..…. 37 Table 12 Selected bond lengths Å and angles ° for [Sr(H2O)4](C4S4)…………...….... 38 Table 13 Comparison of the positions for [Sr(H2O)4](C4S4) and [Ca(H2O)4](C4S4)... 43 Table 14 Crystallographic data and details of the structure determination of [Ba4K2(H2O)16](C4S4)5………….................................................................... 46 V 2 Table 15 Positional parameters, equivalent isotropic parameters Ueq Å for the non-H atoms and displacement isotropic parameters for H atoms in the structure of [Ba4K2(H2O)16](C4S4)5………………………………………..…………. 47 2 Table 16 Anisotropic displacement parameters Uij / [Å ] for the non-H atoms in the structure of [Mg(H2O)6](C4S4)…………..…….………………………….... 49 Table 17 Selected bond lengths Å and angles / ° for [Ba4K2(H2O)16](C4S4)5………… 50 -1 Table 18 Infrared and Raman data (cm ) for the tetrathiosquarate and its complexes.. 57 Table 19 Crystallographic data and details of the structure determination of [Fe(H2O)2](C4S4)·4H2O…………………………………………………….. 62 2 Table 20 Positional parameters,
Load more

Recommended publications
  • (12) Patent Application Publication (10) Pub. No.: US 2015/0000118A1 ZHAO Et Al
    US 2015 0000118A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2015/0000118A1 ZHAO et al. (43) Pub. Date: Jan. 1, 2015 (54) METHOD FOR MANUFACTURING (52) U.S. Cl. GRAPHENE-INCORPORATED CPC ..................................... H0IM 10/04 (2013.01) RECHARGEABLE L-ION BATTERY USPC ......................... 29/623.3; 29/623.1; 29/623.5 (71) Applicants:XIN ZHAO, New York, NY (US); (57) ABSTRACT Minjie Li, New York, NY (US) A method for manufacturing a graphene-incorporated rechargeable Li-ion battery discloses a graphene-incorpo (72) Inventors: XIN ZHAO, New York, NY (US); rated rechargeable Li-ion battery with enhanced energy and Minjie Li, New York, NY (US) power delivery abilities. The method comprises the steps (a) fabricating a high-performance anode film based on graphene or graphene hybrid; (b) introducing a desired amount of (21) Appl. No.: 13/927,125 lithium into the anode material to produce a prelithiated graphene-based anode; (c) constructing a full cell utilizing a (22) Filed: Jun. 26, 2013 cathode film and the prelithiated anode film. The graphene based anodes incorporating exfoliated graphene layers over Publication Classification come the large irreversible capacity and initial lithium ion consumption upon pre-lithiation, and demonstrate remark (51) Int. Cl. ably enhanced specific capacity and rate capability over con HIM I/04 (2006.01) ventional anodes. Patent Application Publication Jan. 1, 2015 Sheet 1 of 4 US 2015/0000118A1 Figure 1A Figure 1B 20 Figure 2. Patent Application Publication Jan. 1, 2015 Sheet 2 of 4 US 2015/0000118A1 Graphene nanoplatelet Partially oxidized GP Molecule intercalation Further exfoliation Xaaaaad Wash and dry Partially oxidized few-layer Gnp Mixing with conductive additive and binder Formulated Gnp anode Lithiation Prelithiated Gnp anode Figure 3.
    [Show full text]
  • United States Patent (19) (11) Patent Number: 4,859,572 Farid Et Al
    United States Patent (19) (11) Patent Number: 4,859,572 Farid et al. (45) Date of Patent: Aug. 22, 1989 54 DYE SENSTIZED PHOTOGRAPHIC IMAGING SYSTEM FOREIGN PATENT DOCUMENTS 0223587A 5/1987 European Pat. Off, . (75) Inventors: Samir Y. Farid; Roger E. Moody, 2083832A 3/1982 United Kingdom . both of Rochester, N.Y. OTHER PUBLICATIONS (73) Assignee: Eastman Kodak Company, Volman et al., Advances in Photochemistry, vol. 13, in the Rochester, N.Y. chapter titled "Dye Sensitized Photopolymerization' 21 Appl. No.: 189,002 by D. F. Eaton, pp. 427 to 488, John Wiley & Sons (1986). 22) Filed: May 2, 1988 Farid et al., U.S. Ser. Nos. 933,712, 933,658,933,660, 51 Int. Cl." ................................................ G03C 1/68 and 933,657, all filed Nov. 21, 1986, and commonly (52) U.S. Cl. ..... ... 430/281; 430/914; assigned (Now issued as Farid et al U.S. Pat. Nos. 430/915; 430/916; 522/25; 522/26; 522/27; 4,743,528; 4,743,529; 4,743,530; and 4,743,531). 522/28; 522/31 Primary Examiner-Paul R. Michl (58) Field of Search ............... 430/915, 281, 916,914; Assistant Examiner-C. D. R. Dee 522/25, 28, 63, 27, 26, 31 Attorney, Agent, or Firm-Carl O. Thomas 56) References Cited (57) ABSTRACT U.S. PATENT DOCUMENTS A photographic imaging system is disclosed comprised 4,050,934 9/1977 Turner .................................. 96/1 R of a hardenable organic component containing ethyl 4,289,842 9/1981 Tan et al. ... ... 430/270 enic unsaturation sites and an initiator system for ethyl 4,307,182 12/1981 Dalzell et al.
    [Show full text]
  • Landolt-Börnstein Indexes of Organic Compounds Subvolumes A-I by V
    Landolt-Börnstein Indexes of Organic Compounds Subvolumes A-I By V. Vill, C. Bauhofer, G. Peters, H. Sajus, P. Weigner, LCI-Publisher and Chemistry Department of the University of Hamburg All printed index material has been used to build up the comprehensive Scidex database index developed by LCI Publisher GmbH, Hamburg For further information please visit www.lci-publisher.com From this database a CD-ROM and two online versions were derived. The first is attached to each of the printed subvolumes and the latter are offered for free use at the following addresses: Scidex Database online with graphical structure search on http://lb.chemie.uni-hamburg.de/ Or the easy to use html version on http://lb.chemie.uni-hamburg.de/static/ Landolt-Börnstein Numerical Data and Functional Relationships in Science and Technology New Series / Editor in Chief: W. Martienssen Index of Organic Compounds Subvolume A Compounds with 1 to 7 Carbon Atoms Editor: V. Vill Authors: V. Vill, G. Peters, H. Sajus 1 3 ISBN 3-540-66203-0 Springer-Verlag Berlin Heidelberg New York Library of Congress Cataloging in Publication Data Zahlenwerte und Funktionen aus Naturwissenschaften und Technik, Neue Serie Editor in Chief: W. Martienssen Index of Organic Compounds A: Editor: V. Vill At head of title: Landolt-Börnstein. Added t.p.: Numerical data and functional relationships in science and technology. Tables chiefly in English. Intended to supersede the Physikalisch-chemische Tabellen by H. Landolt and R. Börnstein of which the 6th ed. began publication in 1950 under title: Zahlenwerte und Funktionen aus Physik, Chemie, Astronomie, Geophysik und Technik.
    [Show full text]
  • Emission Load of Car Service Interiors
    Vol. 62, 2016 (3): 122–128 Res. Agr. Eng. doi: 10.17221/5/2015-RAE Emission load of car service interiors I. Vitázek1, D. Michalíková1, B. Vitázková2, J. Klúčik1 1Department of Transport and Handling, Faculty of Engineering, Slovak University of Agriculture in Nitra, Nitra, Slovak Republic 2Department of Machines and Production Systems, Faculty of Engineering, Slovak University of Agriculture in Nitra, Nitra, Slovak Republic Abstract Vitázek I., Michalíková D., Vitázková B., Klúčik J. (2016): Emission load of car service interiors. Res. Agr. Eng., 62: 122–128. Car service centres are specific in terms of production of pollutants. The aim of the paper is to assess the quality of indoor environment of car service interiors with respect to the safe range of oxocarbon emission limits, concentration of gaseous and solid aerosols of selected chemical pollutants and occupational noise exposure. Measurements of concen- tration and exposure time indicated that the permitted limits were kept. CO concentration reached values in the range from 0 to 10 ppm, CO2 concentration was observed in the range from 493 to 967 ppm. Concentration of solid aerosol of polyester bitumen reached the maximum value of 0.37 mg/m3, while for gaseous aerosol (e.g. toluene) it equalled 8.114 mg/m3. Measurements of chemical factors were carried out and evaluated by companies with appropriate accredi- tation. Occupational Exposure Limits (OELs) were higher in case of all selected substances. OEL was not demonstrably exceeded at any chemical factor. Noise emissions approached the limit values; therefore, hearing protection is required. Keywords: indoor environment; gaseous emissions; chemical factor; emission limits; noise When undertaking the occupation, time spent in climate of workplaces, residential premises and the workplace may add up to more than a half of the other spaces.
    [Show full text]
  • Some Unusual, Astronomically Significant Organic Molecules
    'lL-o Thesis titled: Some Unusual, Astronomically Significant Organic Molecules submitted for the Degree of Doctor of Philosophy (Ph,D.) by Salvatore Peppe B.Sc. (Hons.) of the Department of Ghemistty THE UNIVERSITY OF ADELAIDE AUSTRALIA CRUC E June2002 Preface Gontents Contents Abstract IV Statement of Originality V Acknowledgments vi List of Figures..... ix 1 I. Introduction 1 A. Space: An Imperfect Vacuum 1 B. Stellff Evolution, Mass Outflow and Synthesis of Molecules 5 C. Astronomical Detection of Molecules......... l D. Gas Phase Chemistry.. 9 E. Generation and Detection of Heterocumulenes in the Laboratory 13 L.2 Gas Phase Generation and Characterisation of Ions.....................................16 I. Gas Phase Generation of Ions. I6 A. Positive Ions .. I6 B. Even Electron Negative Ions 17 C. Radical Anions 2t tr. Mass Spectrometry 24 A. The VG ZAB 2}lF Mass Spectrometer 24 B. Mass-Analysed Ion Kinetic Energy Spectrometry......... 25 III. Characterisation of Ions.......... 26 A. CollisionalActivation 26 B. Charge Reversal.... 28 C. Neutralisation - Reionisation . 29 D. Neutral Reactivity. JJ rv. Fragmentation Behaviour ....... 35 A. NegativeIons.......... 35 Preface il B. Charge Inverted Ions 3l 1.3 Theoretical Methods for the Determination of Molecular Geometries and Energetics..... ....o........................................ .....39 L Molecular Orbital Theory........ 39 A. The Schrödinger Equation.... 39 B. Hartree-Fock Theory ..44 C. Electron Correlation ..46 D. Basis sets............ .51 IL Transition State Theory of Unimolecular Reactions ......... ................... 54 2. Covalently Bound Complexes of CO and COz ....... .........................58 L Introduction 58 tr. Results and Discussion........... 59 Part A: Covalently bound COz dimers (OzC-COr)? ............ 59 A. Generation of CzO¿ Anions 6I B. NeutralCzO+........
    [Show full text]
  • Assessment of Carbon Monoxide (Co) Level in Enugu Metropolis Monitoring Industrial and Residential Area
    ASSESSMENT OF CARBON MONOXIDE (CO) LEVEL IN ENUGU METROPOLIS MONITORING INDUSTRIAL AND RESIDENTIAL AREA BY ADIKE JOSEPH .N. CHE/2007/123 PROJECT REPORT SUBMITTED TO THE DEPARTMENT OF CHEMICAL ENGINEERING FACULTY OF ENGINEERING CARITAS UNIVERSITY, AMORJI-NIKE ENUGU STATE AUGUST, 2012 TITLE PAGE ASSESSMENT OF CARBON MONOXIDE (CO) LEVEL IN ENUGU METROPOLIS MONITORING INDUSTRIAL AND RESIDENTIAL AREA BY ADIKE JOSEPH .N. CHE/2007/123 PROJECT REPORT SUBMITTED TO THE DEPARTMENT OF CHEMICAL ENGINEERING, FACULTY OF ENGINEERING IN PARTIAL FULFILLMENT OF THE REQUIREMENT FOR THE AWARD OF BACHELOR OF ENGINEERING, DEGREE IN CHEMICAL CARITAS UNIVERSITY AMORJI-NIKE ENUGU STATE AUGUST, 2012 CERTIFICATION This is to certify that this work was down under the supervision of Supervisor‟s name Engr Ken Ezeh Signature------------------ ------------------------------ date ------------------------------ Head of Department ------------------------------------------------------------------------ Signature ------------------------------------------------ Date ------------------------------ External supervisor ------------------------------------------------------------------------- Signature ------------------------------------------------- Date ------------------------------ Department of Chemical Engineering Caritas University Amorji-Nike Enugu DEDICATION This project was dedicated to Jesus the Saviour for all his marvelous deeds in my life, more especially for seeing me through all my university years and to my dearly parents Mr. and Mrs. Adike, N. Joseph, for all their contributions, encouragement, love, understanding and care for me and the family. ACKNOWLEDGEMENT To Jesus the Saviour be the glory to whom I depend on I wish to thank the Almighty God for giving me the opportunity, knowledge and wisdom to under take my university task successfully. My profound gratitude goes to my supervisor, Engr. (Mr.) Ken Ezeh for is invaluable supervision and unremitting attention. I wish also to acknowledge my lecturers in the person of Engr. Prof. J.I.
    [Show full text]
  • Supporting Information © Wiley-VCH 2006 69451 Weinheim, Germany
    Supporting Information © Wiley-VCH 2006 69451 Weinheim, Germany “Sulflower”: a new form of carbon sulfide Konstantin Yu. Chernichenko, Viktor V. Sumerin, Roman V. Shpanchenko, Elizabeth S. Balenkova, Valentine G. Nenajdenko* Carbon sulfide forms. Stable at usual conditions: [1] [2] [3] [4] 2. C3S8 C4S6 C4S6 C4S6 S S S S S S S S S S S S S S S S S S S S S S S S S S [5] [6] [5] [7] C5S7 C6S8 C6S8 C6S8 C6S10 S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S [1] [8] [9, 10] C6S12 C8S8 C9S9 S S S S S S S S S S S S S S S S S S S S S S S S S S S S S Polymeric forms: [11] [12] [13] [5] [6] 1. Black CS2 (CS)n (C3S2)n (C3S5)n C8S8 S S S S S S S S S S n S S S n Quantum chemical calculations: Density-functional calculations were performed within Perdew–Burke–Ernzerhof generalized gradient approximation[14] using scalar-relativistic[15] one-electron Hamiltonian and extended basis sets of Gaussian functions as implemented in a recent version of the original computer code.[16] We have used a preliminary version of scalar-relativistic basis sets of TZ2p, finite nucleus model was used. Fast riMP2 method[17] was used with cc-pVDZm basis set. We have calculated energy of unstrained C2S fragment from linear dependence of full energies of 2,3-b- annulated oligothiophenes C2+2nSnH4 (n=1…5) – starting from thiophene to helical pentathiophene: S S S S S S S S S S S S S S S n Full energies, Hartree PBE riMP2 1 -553.91315 -552.03413 2 -1029.26725 -1025.7063 3 -1504.62259 -1499.38155 4 -1979.97749 -1973.05662 5 -2455.33167 -2446.73137 PBE riMP2 -500 -1000 -1500 -2000 Full energy, Hartree -2500 1 2 3 4 5 n Graph linearizations give the energy of unstrained C2S unit in 2,3-b annulated oligothiophenes: E= -78.55825 - 475.35473·n (SD=3.72905E-4), PBE E= -78.35856 – 473.67448·n (SD=1.01E-3), riMP2 A good correlation between two methods has been achieved.
    [Show full text]
  • Croconate Salts. New Bond-Delocalized Dianions, &Q
    JOURNAL OF RESEARCH of the National Bureau of Standards Volume 85, No.2, March·April1980 Pseudo-Oxocarbons. Synthesis of 2, 1,3-Bis-, and 1, 2, 3-Tris (Dicyanomethylene) Croconate Salts. New Bond-Delocalized Dianions, "Croconate Violet" and "Croconate Blue"* Alexander J. Fatiadit National Bureau of Standards, Washington, D.C. 20234 October 24,1979 Synthesis and characteri zation of new bond·delocalized dianions, e.g., 2, 1,3·bis·, 1,2, 3·tris (di cyanomethyl. ene) croconate salts have been described. The dianions re ported represent a new class of aromati c, nonbenze· noid co mpounds, named pseudo·oxocarbons. A study of their physical, analytical and chemical properties offer a new direction in the chemistry of oxocarbons. Key words: Acid; aromatic; bond·delocalized; croco nic; diani on; malononitrile; nonbenzenoid; oxocarbon; salt; synthesis 1. Introduction molecular properties of the croconic salts (e.g. 2 , dipotas­ sium salt) were first seriously investigated when a symmetri­ The bright ye ll ow dipotassium croconate 1 and croconic cal, delocalized structure fo r the dianion 2 was proposed by acid (1 , K = H, 4,5-dihydroxy-4--cyclopentene-l,2,3-trione) Yamada et aJ. [3] in 1958. A few years later [4], the d i anion 2 were first isolated by Gmelin [1]' in 1825, from the black, ex· and the related deltate [5], squarate, rhodizonate, and plosive, side-reaction product (e.g. K6 C6 0 6 + KOC=COK), tetrahydroxyquinone anions were recognized by West et aJ. by the reaction of carbon with potassium hydroxide, in a [2,4] as members of a new class of aromatic oxocarbons pioneer, industrial attempt to manufacture potassium.
    [Show full text]
  • Graphether：A Two-Dimensional Oxocarbon As a Direct Wide-Gap Semiconductor with High Mechanical and Electrical Performances
    Graphether：A Two-Dimensional Oxocarbon as a Direct Wide-Gap Semiconductor with High Mechanical and Electrical Performances Gui-Lin Zhu1‖, Xiao-Juan Ye1,2‖, and Chun-Sheng Liu1,2* 1Key Laboratory of Radio Frequency and Micro-Nano Electronics of Jiangsu Province, College of Electronic and Optical Engineering, Nanjing University of Posts and Telecommunications, Nanjing 210023, China 2School of Engineering, University of British Columbia, Kelowna, BC V1V 1V7, Canada ‖The first two authors contributed equally to this work. *E-mail: [email protected] Abstract: Although many graphene derivatives have sizable band gaps, their electrical or mechanical properties are significantly degraded due to the low degree of π-conjugation. Besides the π-π conjugation, there exists hyperconjugation interactions arising from the delocalization of σ electrons. Inspired by the structural characteristics of a hyperconjugated molecule, dimethyl ether, we design a two-dimensional oxocarbon (named graphether) by the assembly of dimethyl ether molecules. Our first-principle calculations reveal the following findings: (1) Monolayer graphether possesses excellent dynamical and thermal stabilities as demonstrated by its favourable cohesive energy, absence of the soft phonon modes, and high melting point. (2) It has a direct wide-band-gap of 2.39 eV, indicating its potential applications in ultraviolet optoelectronic devices. Interestingly, the direct band gap feature is rather robust against the external strains (-10% to 10%) and stacking configurations. (3) Due to the hyperconjugative effect, graphether has the high intrinsic electron mobility. More importantly, its in-plane stiffness (459.8 N m-1) is even larger than that of 1 graphene. (4) The Pt(100) surface exhibits high catalytic activity for the dehydrogenation of dimethyl ether.
    [Show full text]
  • Generation and Characterization of Hardwood Smoke Inhalation Exposure Atmospheres
    Aerosol Science and Technology ISSN: 0278-6826 (Print) 1521-7388 (Online) Journal homepage: https://www.tandfonline.com/loi/uast20 Generation and Characterization of Hardwood Smoke Inhalation Exposure Atmospheres Jacob D. McDonald , Richard K. White , Edward B. Barr , Barbara Zielinska , Judith C. Chow & Eric Grosjean To cite this article: Jacob D. McDonald , Richard K. White , Edward B. Barr , Barbara Zielinska , Judith C. Chow & Eric Grosjean (2006) Generation and Characterization of Hardwood Smoke Inhalation Exposure Atmospheres, Aerosol Science and Technology, 40:8, 573-584, DOI: 10.1080/02786820600724378 To link to this article: https://doi.org/10.1080/02786820600724378 Published online: 01 Feb 2007. Submit your article to this journal Article views: 355 Citing articles: 17 View citing articles Full Terms & Conditions of access and use can be found at https://www.tandfonline.com/action/journalInformation?journalCode=uast20 Aerosol Science and Technology, 40:573–584, 2006 Copyright c American Association for Aerosol Research ISSN: 0278-6826 print / 1521-7388 online DOI: 10.1080/02786820600724378 Generation and Characterization of Hardwood Smoke Inhalation Exposure Atmospheres Jacob D. McDonald,1 Richard K. White,1 Edward B. Barr,1 Barbara Zielinska,2 Judith C. Chow,2 and Eric Grosjean3 1Lovelace Respiratory Research Institute, Albuquerque, New Mexico, USA 2Desert Research Institute, Reno, Nevada, USA 3Daniel Grosjean and Associates, Inc., Ventura, California, USA INTRODUCTION An inhalation exposure system and operating protocol were de- The National Environmental Respiratory Center (NERC) was veloped that resulted in consistent achievement of targeted expo- established to conduct laboratory research that improves our un- sure concentrations of hardwood smoke without compromising the derstanding of the contributions of individual air contaminants desire to include multiple phases of a burn cycle.
    [Show full text]
  • Conceptual Progress for Explaining and Predicting Self-Organization on Anodized Aluminum Surfaces
    nanomaterials Review Conceptual Progress for Explaining and Predicting Self-Organization on Anodized Aluminum Surfaces Mikhail Pashchanka Department of Chemistry, Eduard-Zintl-Institute, Technical University of Darmstadt, Alarich-Weiss-Straße 12, 64287 Darmstadt, Germany; [email protected] Abstract: Over the past few years, researchers have made numerous breakthroughs in the field of aluminum anodizing and faced the problem of the lack of adequate theoretical models for the interpretation of some new experimental findings. For instance, spontaneously formed anodic alumina nanofibers and petal-like patterns, flower-like structures observed under AC anodizing conditions, and hierarchical pores whose diameters range from several nanometers to sub-millimeters could be explained neither by the classical field-assisted dissolution theory nor by the plastic flow model. In addition, difficulties arose in explaining the basic indicators of porous film growth, such as the nonlinear current–voltage characteristics of electrochemical cells or the evolution of hexagonal pore patterns at the early stages of anodizing experiments. Such a conceptual crisis resulted in new multidisciplinary investigations and the development of novel theoretical models, whose evolution is discussed at length in this review work. The particular focus of this paper is on the recently developed electroconvection-based theories that allowed making truly remarkable advances in understanding the porous anodic alumina formation process in the last 15 years. Some explanation of the synergy between electrode reactions and transport processes leading to self-organization is provided. Finally, future prospects for the synthesis of novel anodic architectures are discussed. Citation: Pashchanka, M. Conceptual Progress for Explaining Keywords: porous anodic alumina (PAA); chaos and self-organization theory; electroconvection; and Predicting Self-Organization on colloidal gel model; anion exchange; DLVO theory; fluid mechanics; surface chemistry; surface Anodized Aluminum Surfaces.
    [Show full text]
  • Carbon Monoxide Poisoning
    CONTINUING MEDICAL EDUCATION: SITARAM SHRESTHA – CARBON MONOXIDE POISONING Carbon monoxide poisoning Sitaram Shrestha Professor, Department of General Practice and Emergency Medicine, Patan Academy of Health Sciences, Lalitpur, Nepal ABSTRACT Carbon monoxide (CO) poisoning may be suicidal, homicidal and in many cases it is accidental. Poisoning is due to formation of carboxyhaemoglobin, which interferes transfers of oxygen and leads to appearance of symptoms.1 Which are not specific and may similar to COVID19. Symptoms depends upon concentration of CO in surroundings. Antidote of CO is oxygen. Keywords: carbon monoxide, poisoning, toxicity CORRESPONDENCE Dr. Sitaram Shrestha Department of General Practice and Emergency Medicine, Patan Academy of Health Sciences, Lalitpur, Nepal Email: [email protected] Journal of General Practice and Emergency Medicine of Nepal. Issue 10: 2021. Available at: www.jgpeman.com, eISSN: 2363-1168 55 CONTINUING MEDICAL EDUCATION: SITARAM SHRESTHA – CARBON MONOXIDE POISONING INTRODUCTION • Low blood pressure Carbon monoxide (CO) Is known since ancient time • Muscle weakness which is tasteless, colour less, odour less and • Rapid or abnormal heartbeat non-irritating gas. It is sometimes termed a silent • Shock killer. As the specific gravity of CO is 0.97, it is • Nausea and vomiting slightly lighter than air. This gas is mainly produced • Unconsciousness by incomplete combustion of organic compounds.2 • Delayed poisoning Carbon monoxide consists of one carbon atom and one oxygen atom, connected by a triple
    [Show full text]