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Measuring and Predicting Sooting Tendencies of Oxygenates, Alkanes, Alkenes, Cycloalkanes, and Aromatics on a Unified Scale
Measuring and Predicting Sooting Tendencies of Oxygenates, Alkanes, Alkenes, Cycloalkanes, and Aromatics on a Unified Scale Dhrubajyoti D. Dasa,1, Peter St. Johnb,1, Charles S. McEnallya,∗, Seonah Kimb, Lisa D. Pfefferlea aYale University, Department of Chemical and Environmental Engineering, New Haven CT 06520 bNational Renewable Energy Laboratory, Golden CO 80401 Abstract Soot from internal combustion engines negatively affects health and climate. Soot emissions might be reduced through the expanded usage of appropriate biomass-derived fuels. Databases of sooting indices, based on measuring some aspect of sooting behavior in a standardized combustion environment, are useful in providing information on the comparative sooting tendencies of different fuels or pure compounds. However, newer biofuels have varied chemical structures including both aromatic and oxygenated functional groups, making an accurate measurement or prediction of their sooting tendency difficult. In this work, we propose a unified sooting tendency database for pure compounds, including both regular and oxygenated hydrocarbons, which is based on combining two disparate databases of yield-based sooting tendency measurements in the literature. Unification of the different databases was made possible by leveraging the greater dynamic range of the color ratio pyrometry soot diagnostic. This unified database contains a substantial number of pure compounds (≥ 400 total) from multiple categories of hydrocarbons important in modern fuels and establishes the sooting tendencies of aromatic and oxygenated hydrocarbons on the same numeric scale for the first time. Using this unified sooting tendency database, we have developed a predictive model for sooting behavior applicable to a broad range of hydrocarbons and oxygenated hydrocarbons. The model decomposes each compound into single-carbon fragments and assigns a sooting tendency contribution to each fragment based on regression against the unified database. -
Transport of Dangerous Goods
ST/SG/AC.10/1/Rev.16 (Vol.I) Recommendations on the TRANSPORT OF DANGEROUS GOODS Model Regulations Volume I Sixteenth revised edition UNITED NATIONS New York and Geneva, 2009 NOTE The designations employed and the presentation of the material in this publication do not imply the expression of any opinion whatsoever on the part of the Secretariat of the United Nations concerning the legal status of any country, territory, city or area, or of its authorities, or concerning the delimitation of its frontiers or boundaries. ST/SG/AC.10/1/Rev.16 (Vol.I) Copyright © United Nations, 2009 All rights reserved. No part of this publication may, for sales purposes, be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, electrostatic, magnetic tape, mechanical, photocopying or otherwise, without prior permission in writing from the United Nations. UNITED NATIONS Sales No. E.09.VIII.2 ISBN 978-92-1-139136-7 (complete set of two volumes) ISSN 1014-5753 Volumes I and II not to be sold separately FOREWORD The Recommendations on the Transport of Dangerous Goods are addressed to governments and to the international organizations concerned with safety in the transport of dangerous goods. The first version, prepared by the United Nations Economic and Social Council's Committee of Experts on the Transport of Dangerous Goods, was published in 1956 (ST/ECA/43-E/CN.2/170). In response to developments in technology and the changing needs of users, they have been regularly amended and updated at succeeding sessions of the Committee of Experts pursuant to Resolution 645 G (XXIII) of 26 April 1957 of the Economic and Social Council and subsequent resolutions. -
Edinburgh Research Explorer
View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Edinburgh Research Explorer Edinburgh Research Explorer Organometallic Neptunium Chemistry Citation for published version: Arnold, P, Dutkiewicz, MS & Walter, O 2017, 'Organometallic Neptunium Chemistry', Chemical Reviews. https://doi.org/10.1021/acs.chemrev.7b00192 Digital Object Identifier (DOI): 10.1021/acs.chemrev.7b00192 Link: Link to publication record in Edinburgh Research Explorer Document Version: Peer reviewed version Published In: Chemical Reviews General rights Copyright for the publications made accessible via the Edinburgh Research Explorer is retained by the author(s) and / or other copyright owners and it is a condition of accessing these publications that users recognise and abide by the legal requirements associated with these rights. Take down policy The University of Edinburgh has made every reasonable effort to ensure that Edinburgh Research Explorer content complies with UK legislation. If you believe that the public display of this file breaches copyright please contact [email protected] providing details, and we will remove access to the work immediately and investigate your claim. Download date: 11. May. 2020 Organometallic Neptunium Chemistry Polly L. Arnold,*a Michał S. Dutkiewicz,a,b Olaf Walter,b [a] EaStCHEM School of Chemistry, University of Edinburgh, The King’s Buildings, Edinburgh, EH9 3FJ, UK. E-mail: [email protected]. [b] European Commission, DG Joint Research Centre, Directorate G - Nuclear Safety and Security, Advanced Nuclear Knowledge – G.I.5, Postfach 2340, D-76125, Karlsruhe, Germany. ABSTRACT Fifty years have passed since the foundation of organometallic neptunium chemistry, and yet only a handful of complexes have been reported, and even fewer fully characterised. -
Secondary Organic Aerosol Formation from the Ozonolysis of Cycloalkenes and Related Compounds*
252 Chapter 7 Secondary Organic Aerosol Formation from the Ozonolysis of Cycloalkenes and Related Compounds* * This chapter is reproduced by permission from “Secondary organic aerosol formation from ozonolysis of cycloalkenes and related compounds” by M.D. Keywood, V. Varutbangkul, R. Bahreini, R.C. Flagan, J.H. Seinfeld, Environmental Science and Technology, 38 (15): 4157-4164, 2004. Copyright 2004, American Chemical Society. 253 7.1. Abstract The secondary organic aerosol (SOA) yields from the laboratory chamber ozonolysis of a series of cycloalkenes and related compounds are reported. The aim of this work is to investigate the effect of the structure of the hydrocarbon parent molecule on SOA formation for a homologous set of compounds. Aspects of the compound structures that are varied include the number of carbon atoms present in the cycloalkene ring (C5 to C8), the presence and location of methyl groups, and the presence of an exocyclic or endocyclic double bond. The specific compounds considered here are cyclopentene, cyclohexene, cycloheptene, cyclooctene, 1-methyl-1-cyclopentene, 1-methyl-1- cyclohexene, 1-methyl-1-cycloheptene, 3-methyl-1-cyclohexene, and methylene cyclohexane. SOA yield is found to be a function of the number of carbons present in the cycloalkene ring, with increasing number resulting in increased yield. Yield is enhanced by the presence of a methyl group located at a double-bonded site but reduced by the presence of a methyl group at a non-double bonded site. The presence of an exocyclic double bond also leads to a reduced yield relative to the equivalent methylated cycloalkene. On the basis of these observations, the SOA yield for terpinolene relative to the other cyclic alkenes is qualitatively predicted, and this prediction compares well to measurements of SOA yield from the ozonolysis of terpinolene. -
Epoxidation of Cyclopentene, Cyclohexene and Cycloheptene by Acetylperoxyl Radicals
Epoxidation of Cyclopentene, Cyclohexene and Cycloheptene by Acetylperoxyl Radicals J. R. Lindsay Smith, D. M. S. Smith, M. S. Stark* and D. J. Waddington Department of Chemistry, University of York, York, YO10 5DD, United Kingdom To further the current understanding of how peroxyl radicals add to C=C double bonds,eg. 1-3 a series of cyclic alkenes (cyclopentene, cyclohexene and cycloheptene) were reacted with acetylperoxyl radicals over the temperature range 373 - 433 K, via the co- oxidation of acetaldehyde, the cyclic alkene and a reference alkene. The resulting epoxides were monitored by GC-FID, allowing the determination of the Arrhenius parameters given in Table 1 for these addition reactions. 3 -1 -1 -1 Alkene log10(A / dm mol s ) Eact / kJ mol cyclopentene 9.7±0.6 31.2±5.0 cyclohexene 7.7±0.7 17.4±5.3 cycloheptene 8.8±0.8 25.5±6.5 cis-2-butene4 8.1±0.5 22.9±3.8 Table 1: Arrhenius parameters for the addition of acetylperoxyl radicals to cyclic alkenes and cis-2-butene. Parameters for cis-2-butene are also given for comparison,4 as it would be expected that a relatively unstrained cycloalkene would behave in a similar manner to this non-cyclic alkene; this is indeed found to be so, with no statistically significant difference between cyclohexene and cis-2-butene. Indeed the measured activation energy for cyclohexene fits in well with correlation between charge transfer ( Ec) and activation energy that is known to exist for the addition of acetylperoxyl to acyclic mono-alkenes.1 Cyclopentene however does have a significantly larger pre-exponential factor and activation energy than either cyclohexene or cis-2-butene. -
Cycloalkanes, Cycloalkenes, and Cycloalkynes
CYCLOALKANES, CYCLOALKENES, AND CYCLOALKYNES any important hydrocarbons, known as cycloalkanes, contain rings of carbon atoms linked together by single bonds. The simple cycloalkanes of formula (CH,), make up a particularly important homologous series in which the chemical properties change in a much more dramatic way with increasing n than do those of the acyclic hydrocarbons CH,(CH,),,-,H. The cyclo- alkanes with small rings (n = 3-6) are of special interest in exhibiting chemical properties intermediate between those of alkanes and alkenes. In this chapter we will show how this behavior can be explained in terms of angle strain and steric hindrance, concepts that have been introduced previously and will be used with increasing frequency as we proceed further. We also discuss the conformations of cycloalkanes, especially cyclo- hexane, in detail because of their importance to the chemistry of many kinds of naturally occurring organic compounds. Some attention also will be paid to polycyclic compounds, substances with more than one ring, and to cyclo- alkenes and cycloalkynes. 12-1 NOMENCLATURE AND PHYSICAL PROPERTIES OF CYCLOALKANES The IUPAC system for naming cycloalkanes and cycloalkenes was presented in some detail in Sections 3-2 and 3-3, and you may wish to review that ma- terial before proceeding further. Additional procedures are required for naming 446 12 Cycloalkanes, Cycloalkenes, and Cycloalkynes Table 12-1 Physical Properties of Alkanes and Cycloalkanes Density, Compounds Bp, "C Mp, "C diO,g ml-' propane cyclopropane butane cyclobutane pentane cyclopentane hexane cyclohexane heptane cycloheptane octane cyclooctane nonane cyclononane "At -40". bUnder pressure. polycyclic compounds, which have rings with common carbons, and these will be discussed later in this chapter. -
Alkenes and Alkynes
02/21/2019 CHAPTER FOUR Alkenes and Alkynes H N O I Cl C O C O Cl F3C C Cl C Cl Efavirenz Haloprogin (antiviral, AIDS therapeutic) (antifungal, antiseptic) Chapter 4 Table of Content * Unsaturated Hydrocarbons * Introduction and hybridization * Alkenes and Alkynes * Benzene and Phenyl groups * Structure of Alkenes, cis‐trans Isomerism * Nomenclature of Alkenes and Alkynes * Configuration cis/trans, and cis/trans Isomerism * Configuration E/Z * Physical Properties of Hydrocarbons * Acid‐Base Reactions of Hydrocarbons * pka and Hybridizations 1 02/21/2019 Unsaturated Hydrocarbons • Unsaturated Hydrocarbon: A hydrocarbon that contains one or more carbon‐carbon double or triple bonds or benzene‐like rings. – Alkene: contains a carbon‐carbon double bond and has the general formula CnH2n. – Alkyne: contains a carbon‐carbon triple bond and has the general formula CnH2n‐2. Introduction Alkenes ● Hydrocarbons containing C=C ● Old name: olefins • Steroids • Hormones • Biochemical regulators 2 02/21/2019 • Alkynes – Hydrocarbons containing C≡C – Common name: acetylenes Unsaturated Hydrocarbons • Arene: benzene and its derivatives (Ch 9) 3 02/21/2019 Benzene and Phenyl Groups • We do not study benzene and its derivatives until Chapter 9. – However, we show structural formulas of compounds containing a phenyl group before that time. – The phenyl group is not reactive under any of the conditions we describe in chapters 5‐8. Structure of Alkenes • The two carbon atoms of a double bond and the four atoms bonded to them lie in a plane, with bond angles of approximately 120°. 4 02/21/2019 Structure of Alkenes • Figure 4.1 According to the orbital overlap model, a double bond consists of one bond formed by overlap of sp2 hybrid orbitals and one bond formed by overlap of parallel 2p orbitals. -
Spatial Variability of Air Pollutants in a Megacity Characterized by Mobile Measurements: Chemical Homogeneity Under Haze Conditions
Supplementary Material for Spatial variability of air pollutants in a megacity characterized by mobile measurements: Chemical homogeneity under haze conditions Reza Bashiri Khuzestani1,a,★, Keren Liao1,★, Qi Chen1,*, Ying Liu1, Yan Zheng1, Xi Cheng1, Tianjiao Jia1, Xin Li1, Shiyi Chen1, Guancong Huang1 1State Key Joint Laboratory of Environmental Simulation and Pollution Control, BIC-ESAT and IJRC, College of Environmental Sciences and Engineering, Peking University, Beijing, 100871, China aNow at: Faculty of Civil, Water and Environmental Engineering, School of Engineering, Shahid Beheshti University, Tehran, Iran. ★These authors contributed equally to this work. *Correspondence to: Qi Chen ([email protected]) Table S1. The average concentrations of the 52 VOC species measured in this study compared with literature. These species are tentatively categorized into three groups including hydrocarbons (Group 1), aldehydes and ketones (Group 2), and acids and anhydrides (Group 3). Category Mean ± sd Mean ± sd * * Formula Assigned Name m/z KPTR Urban Suburb /Group (non-haze) (haze) + (CH3OH)H Methanol 33.033 2.22 n/a 16.82±14.81 44.69±15.96 11.77-51.76 3.4-5.6 + (C2H2O)H Ketenes 43.018 2.21 2 2.12±1.84 5.42±1.42 + (C2H4O)H Acetaldehyde 45.033 3.36 2 2.72±2.00 6.07±1.63 1.88-15.81 0.83-1.23 + (C2H6O)H Ethanol 47.049 2.18 n/a 25.35±32.19 98.28±32.17 + (C3H4O)H Acrolein; MTBE 57.033 3.35 2 0.30±0.27 0.60±0.14 (C H O)H+ Acetone + propanal 59.049 3 2 1.20±1.18 4.67±0.97 2.48-7.92 1.59-3.42 3 6 Isoprene; fragmentation of 2- methyl-3- + (C5H8)H buten-2-ol (MBO); fragmentation of 69.07 1.94 1 0.38±0.35 0.76±0.20 cyclohexanes species Methyl vinyl ketone + methacrolein; ted + (C4H6O)H 71.049 3.83 2 0.16±0.14 0.36±0.09 0.28-0.42 0.13-0.22 crotonaldehyde; ISOPOOH + (C4H8O)H Methyl ethyl ketone + butanals 73.065 3.48 2 1.56±2.45 1.51±0.44 0.86-2.53 0.38-0.81 Calibra + (C6H6)H Benzene 79.054 1.97 1 0. -
Edinburgh Research Explorer
Edinburgh Research Explorer Organometallic Neptunium Chemistry Citation for published version: Arnold, P, Dutkiewicz, MS & Walter, O 2017, 'Organometallic Neptunium Chemistry', Chemical Reviews. https://doi.org/10.1021/acs.chemrev.7b00192 Digital Object Identifier (DOI): 10.1021/acs.chemrev.7b00192 Link: Link to publication record in Edinburgh Research Explorer Document Version: Peer reviewed version Published In: Chemical Reviews General rights Copyright for the publications made accessible via the Edinburgh Research Explorer is retained by the author(s) and / or other copyright owners and it is a condition of accessing these publications that users recognise and abide by the legal requirements associated with these rights. Take down policy The University of Edinburgh has made every reasonable effort to ensure that Edinburgh Research Explorer content complies with UK legislation. If you believe that the public display of this file breaches copyright please contact [email protected] providing details, and we will remove access to the work immediately and investigate your claim. Download date: 29. Sep. 2021 Organometallic Neptunium Chemistry Polly L. Arnold,*a Michał S. Dutkiewicz,a,b Olaf Walter,b [a] EaStCHEM School of Chemistry, University of Edinburgh, The King’s Buildings, Edinburgh, EH9 3FJ, UK. E-mail: [email protected]. [b] European Commission, DG Joint Research Centre, Directorate G - Nuclear Safety and Security, Advanced Nuclear Knowledge – G.I.5, Postfach 2340, D-76125, Karlsruhe, Germany. ABSTRACT Fifty years have passed since the foundation of organometallic neptunium chemistry, and yet only a handful of complexes have been reported, and even fewer fully characterised. Yet increasingly, combined synthetic/spectroscopic/computational studies are demonstrating how covalently binding, soft, carbocyclic organometallic ligands provide an excellent platform for advancing the fundamental understanding of the differences in orbital contributions and covalency in f-block metal – ligand bonding. -
Research Quarterly
RESEARCH 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr QUARTERFirst QuarterL 2015Y Actinide Research Quarterly About the cover ARCH RESE Y The crystalline structure of plutonium in its elemental form, and in molecules and First Quarter 2015 103 102 101 QUARTERL 100 Lr compounds with other elements, is the basis for understanding the intriguing 99 No 98 Md 97 Fm 96 Es 95 Cf 94 Bk 93 Cm 92 Am 91 Pu 90 U Np 89 Th Pa chemistry, physics, and engineering of plutonium molecules and compounds. Ac Colored balls stacked according to the given crystalline symmetry of the five solid allotropes of plutonium are shown, left to right: α (monoclinic), β (body- centered monoclinic), γ (face-centered orthorhombic), δ (face-centered cubic), and ε (body-centered cubic). The graph is the original diffraction pattern for elemental plutonium. The background image is a PuCoGa5 single crystal with an underlying tetragonal symmetry that exhibits the unique electronic property of superconductivity associated with this symmetry. Glenn T. Seaborg Institute for Transactinium Science/Los Alamos National Laboratory The Seaborg Institute welcomes Brian L. Scott as guest editor for this special Actinide Research Quarterly issue showcasing the rich science and history of the crystallography of actinides. A staff scientist at Los Alamos National Laboratory, Brian has extensive experience in structure determination using single-crystal and powder x-ray diffraction techniques. He has explored molecular and solid-state structures in a variety of materials ranging from bioinorganic molecules to plutonium-based superconductors. -
Studies on Photochemical Reactions of Simple Alkenes
Title STUDIES ON PHOTOCHEMICAL REACTIONS OF SIMPLE ALKENES Author(s) 井上, 佳久 Citation Issue Date Text Version ETD URL http://hdl.handle.net/11094/1547 DOI rights Note Osaka University Knowledge Archive : OUKA https://ir.library.osaka-u.ac.jp/ Osaka University STUDIESON PHOTOCHEMICAL REACTIONS CF SIMPLE ALKENES YOSHIHISA INOUE OSAKA UNIVERSITY OSAKA, JAPAN JANUARY, 1977 ii Preface The work of thi's•theSis 'was performed under the guiqance of Professor Hiroshi Sakurai at the ZnstituteofScientific and lndustrial Research, Osaka University. I arn deeply grateÅíul to Professor Hiroshi Sakurai for his appro- priate guidance and continuOus encouragernent throughout this work since 1972. : am aiso grateful to Professor Yoshinobu Odaira-who initiated me into the organic photochemistry in 1971-1972. : arn indebted to Assistant Professor Setsuo Takamuku for his invaluable discussions throughout the work. Many thanks are given to Drs. Yoshiki Okarrtoto, Chyongjin Pac, Susumu Toki, and Yasuo Shige- mitsu for their helpful suggestions through the stimulating discussions with me. T would like to express my gratitude to Mr. Kazuyoshi Mori- tsugut Mr. Masahiro Kadohira, and Ms. Yoko Kunitomi for their collabo- rations in the course of experiment. Finally I wish to thank all the members of Sakurai Laboratory for their warm friendship. t- ..<2IZI Yoshihisa Inoue Suita, Osaka January, Z977 iii List of Papers The contents of this thesis are composed of the following papers. 1) Mercury Photosensitized Rbaction of Cycloheptene. Mechanism of Norcarane Formation Y. Tnoue, M. Kadohira, S. Takasnuku, and H. Sakurait Tetrahedron Lett., 459(1974). 2) Vapor-phase Photolysis of cis-- and trans-4i5-Diraethylcyclohexenes Y. rnoue, S. -
United States Patent Office
3,258,488 United States Patent Office Patented June 28, 1966 2 ether, xylene, toluene, tetralin, cumene and tetrahydro 3,258,488 DIBENZOADCYCLOHEPTENEDERIVATIVES furan, and compatible mixtures of such solvents. The Claude I. Judd, Mequon, and Alexander E. Drukker and reaction can be effected at room temperature or elevated John H. Biel, Milwaukee, Wis., assignors to Colgate temperatures, depending on the reactivity of the alkali Palmolive Company, a corporation of Delaware metal compound used in the process. The reaction is No Drawing. Filed Aug. 12, 1963, Ser. No. 301,658 substantially complete in 1 to 4 hours. Following ter 3 Claims. (C. 260-570.8) mination of the reaction the product can be isolated, if desired, but this is ordinarily not done since it can be This is a continuation-in-part of abandoned application used as present in the reaction mixture in the next step. Serial No. 21,610 filed April 12, 1960. 10 Reaction between the alkali metal salt of 5H-dibenzo This invention relates to novel chemical compounds ad-cycloheptene and the disubstituted aminoalkyl ha and processes of preparing the same. More particularly, lide can be effected by bringing the reactants together in a this invention is concerned with novel basic dibenZSu suitable inert high boiling liquid reaction medium such berene derivatives and processes of producing such com as dioxane, toluene, Xylene, ethyl ether, tetralin, cumene pounds. and tetrahydrofuran. The reaction mixture from the According to the present invention there are provided formation of the alkali metal 5H-dibenzo(a,d)-cyclo novel basic 5H-dibenzoad-cycloheptene derivatives of heptene can be used as the reactant and solvent source the formula to which the appropriate aminoalkyl halide reactant can be added.