DOCSLIB.ORG

A STUDY of the KINETICS of the CHLORA MINE-AMMONIA and CHLORAMIBE-HYDRAZIME REACTIONS in LIQUID AMMONIA DISSERTATION P R E S

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
A STUDY of the KINETICS of the CHLORA MINE-AMMONIA and CHLORAMIBE-HYDRAZIME REACTIONS in LIQUID AMMONIA DISSERTATION P R E S A STUDY OF THE KINETICS OF THE CHLORA MINE-AMMONIA AND CHLORAMIBE-HYDRAZIME REACTIONS IN LIQUID AMMONIA DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State U n iv ersity By FRANCIS NASH COLLIER, Jr. B .S c ., M.Sc. The Ohio State University 195^ Approved by: A dviser Department of Chemistry ACKNOWLEDGMENTS The candidate is grateful for the sympathy and understanding of Dr. Harry H. Sisler, who was so patient during the prolonged interruptions in the work occas­ ioned by the last illness of the candidate’s mother. Dr. Sisler’s encouragement and enthusiasm served as an ever present stimulant to the endeavor from the first. The candidate wishes to express his appreciation of the help of Dr. Jack G. Calvert, who undertook responsibility for the problem late in its development, and who has been so generous w ith time and e f fo r t in the difficult task of interpreting the data. His suggestions and careful attention to details have been of inestimable value in preparing this manuscript. The candidate wishes to acknowledge the assistance of the Davison Chemical Company, d iv is io n of W. R. Grace and Company, which sponsored the resea rch , and to thank the E. I. du Pont de Nemours and Company, I n c ., which supported the teaching fellowship held by the candidate for the academic year 1955- 56. TABLE OF CONTENTS Page ILTiiOL UOXIGH. 1 Industrial b'ignificance of Hydrazine. 1 History of the naschig Synthesis of H ydrazine ............................................................ 2 Studies of the Oxidation of Hydrazine in Aqueous Solution ................................................. 6 Synthesis of Hydrazine in Liquid Ammonia ................................................................. 8 Proposed Mechanisms for the Formation of Hydrazine ........................................... 9 Proposed Mechanisms for the Oxidation of Hydrazine ....................................................-. 11 Statement of the Problem ................................. 13 Hi L. r JUj j. '»1 X i I Cj. L P j. i*0 0 JZi XJ d i l-l.1i S ............ 1 ( P reparations and P u rific a tio n of reagents ....... 17 Ammonia ................................................................. 17 Ammonium Chloride .......... 17 Chloramine . ............................................ 19 hydrazine. ...................... ..... 27 A p p a r a tu s ...................................................................... 36 Conductivity cell ...................................... 36 C onductivity bridge and a u x ilia ry capacitances ................................ 41 Thermostatic bath...................................... 41 Accessory glassw are................................. 47 i i i TA.BLB OF COPiTDhfS (cont'd) Page Calibration of the Conductivity Cell. 48 lurpose of the calibration. ..... 4-8 Calibration procedure ....................................... 49 Calibration data ............................................... 51 Measurements of reaction r.a t e ......................... 64 ■Separation of the two reactions . 64. lie action mixture composed initially of chioramine in liquid ammonia .................................................................. 73 heaction mixture composed initially of clilore,mine and hydrazine or chloramine, hydrazine, and ammonium chloride in liquid ammonia ......................................................... 84 Determination of the Stoichiometry of the Decomposition Reaction .............................. 8 8 heed for the measurement of the stoichiometry of the decomposi­ tion rea c oi on • . .. 88 oummary of methods for ascertaining the stoichiometry of the decom­ position reaction .............................. 89 Procedure for measuring the stoichio­ metry of the decomposition reaction by the method of gas e v o l u t i o n . .............................................. 91 Procedure for measuring the stoichio­ metry of the decomposition reaction by the use of weighed samples of hydrazine. ...... 95 iv T&BLk OF G0FiInI-iT3 (cont'd) rage Procedure for the measurement of the stoichiometry of the decomposition reaction by comparison of pre- break and post break quantities of ammonium c h lo rid e ..................... 97 DkIs& fiiiD m o u ijlt . 98 reduction of the Calibration Data of the Conduc tivity Cells to an qua tion in Two Param eters ................................................ 98 Methods of Calculating concentration in the reaction m ixture .......................................... 99 results of the Stoichiometry .--.ea sure men t . 108 r e s u lts by the method gas e v o l u t i o n ......................................................109 results by the method of weighed samples of hydra sine ...........................112 he suits by the method of comparison of pre-break and post break quantities of ammonium chloriue . 114 Keaction hate measurement Data ....... 11$ Specific keaction hate Constants for the Formation keaction . 276 D erivation of an expression for the specific reaction rate constant for the formation reaction. 276 The values of the specific reaction rate constants of the formation r e a c tio n ........................................................................2 79 Post break values of the formation reaction rate constants ...................... 288 v TABLE OF COhTERTS (c o n t'd ) Fage Order of the Foramtion Reaction .......................................293 Derivation of the expression used to test the order of the formation r e a c t i o n ..................................................................294 Observed order of the formation r e a c t i o n ..................................................................295 Thermodynamic Constants of the Formation Reaction ................................................. 297 The E ffect of Ammonium Chloride on the Rate of the Formation Reaction .... 303 D ISOUEo IQli . ,........................................................................... 310 Mechanism of the Formation Reaction ................................310 The mechanism of the formation reaction as proposed by Audrieth, Colton, and Jones ......................................................311 The mechanism of the formation reaction as proposed by Bodenstein, Oahn and Powell ........................... ..... 312 The mechanism of the formation reaction as proposed by wiberg and ocnm idt ...........................................................312 Effect of fixed base on the formation r e a c t i o n .....................................................313 Effect of ammonium chloride on the formation reaction . 316 The effect of change of solvent on the rate of the formation reaction . 321 The kinetic salt effect................................323 The order of the formation reaction. 325 vi TABLE OF COHTSiiTS (c o n t'd ) Page Quaternary hydrazinium salts, intermediates of the for­ mation reaction ..................................326 Mechanism of the Decomposition Reaction. 329 Evidence of the isolation of the formation reaction from the decomposition reaction in pre-break regions ............................331 Comparison of the temperature coefficient of the formation and decomposition reactions. 335 The effect of concentrations on y i e l d s ................................................ 336 Factors affecting the length of the induction period of the decomposition reaction .... 338 E valuation of r a t e s .......................................344 SUMMARY...........................................................................................................355 BIBLIOGRAPHY............................................................................................■ 358 AUTOBIOGRAPHY ....................................................................................... 362 v ii LIST OF TABLES Table. P a a a 1. Calibration Data of Capillaries for Use in Flow M e t e r s .. ................. 28 2. Calibration Data for Conductivity Cells.... 52 3. Calculation of Slope and Intercept for Conductivity Cell Calibration Grapfis.. 100 4. Calculation of the Corrected Final Reciprocal Resistance and Equivalent Ammonium Chloride Concentration for the Rate Experiments Rl”^5 through R44.-38 ..................................... 104 5. Calculation of Ratios of Ammonium Chloride to Nitrogen in the Reaction Products of the Decomposition R eaction by the Method of Gas Evolution, ................................................................. I l l 6. Calculation of the Ratios of Ammonium C hloride Formed to Hydrazine Con­ sumed in the Decom position R eaction by the Use of Weighed Samples of H ydrazine ............................................................................... 113 7. Calculation of the Ratios of JSmraonium C hloride Formed to Hydrazine Con­ sumed in the Decomposition Reaction by the Comparision of Pre-Break and Post Break Quantities of Ammonium Chloride ............................................................................ 116 8. Rate Measurement Data of Experiment R l- ? 5............. 119 9. Rate Measurement Data of Experiment R2"? 5.......................................................................................... 122 10. Rate Measurement7 1- Data of ExperimentA 5 ................................ 125 v i i i LIST OF TABLES (co n t!d) ^abl e. jPftga 11. Rate Measurement Data of Experiment R4“7 5.................................................................................... 128 1 2 . Rate Measurement Data of Experiment R5”7 5...................................................................................
Load more

Recommended publications
  • Triazene (H2NNNH) Or Triimide (HNHNNH) Markofçrstel,[A, D] Yetsedaw A
    DOI:10.1002/cphc.201600414 Articles On the Formation of N3H3 Isomers in Irradiated Ammonia Bearing Ices:Triazene (H2NNNH) or Triimide (HNHNNH) MarkoFçrstel,[a, d] Yetsedaw A. Tsegaw,[b] Pavlo Maksyutenko,[a, d] Alexander M. Mebel,[c] Wolfram Sander,[b] and Ralf I. Kaiser*[a, d] The remarkable versatility of triazenesinsynthesis, polymer theoretical studies with our novel detection scheme of photo- chemistry and pharmacology has led to numerousexperimen- ionization-driven reflectron time-of-flight mass spectroscopy tal and theoretical studies.Surprisingly,only very little is we can obtain information on the isomersoftriazene formed known aboutthe most fundamental triazene:the parentmole- in the films. Using isotopically labeled starting material, we can cule with the chemical formula N3H3.Here we observe molecu- additionally gain insightinthe formation pathways of the iso- lar,isolated N3H3 in the gas phase after it sublimes from ener- mers of N3H3 under investigation and identify the isomers getically processed ammonia and nitrogen films. Combining formedastriazene (H2NNNH) andpossibly triimide(HNHNNH). 1. Introduction During the last decades, triazenes—a class of organic mole- life time of at least 1mswas also inferred as an intermediate cules carrying the =N N=N moiety—have received substan- in the radiolysis of an aqueous solution of hydrazine based on À À tial attention both from the theoretical and organic chemistry asingle absorption feature at 230 nm.[6] The cyclic isomer of [1] communities. Derived from cis-and trans-triazene (HN=NNH2 ; triazene, cyclotriazane, was first reported crystallographically in Scheme1), the substituted counterparts have significant appli- zeolite A, where it was stabilized by asilver cation as [1a,c] [1d] + [7] + cations in synthetic chemistry, polymer science, and phar- Ag(N3H3) .
    [Show full text]
  • Durham E-Theses
    Durham E-Theses Halogenated diazines and triazines Wood, D. E. How to cite: Wood, D. E. (1978) Halogenated diazines and triazines, Durham theses, Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/8324/ Use policy The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that: • a full bibliographic reference is made to the original source • a link is made to the metadata record in Durham E-Theses • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders. Please consult the full Durham E-Theses policy for further details. Academic Support Oce, Durham University, University Oce, Old Elvet, Durham DH1 3HP e-mail: [email protected] Tel: +44 0191 334 6107 http://etheses.dur.ac.uk UNIVERSITY OF Du'RKAM A THESIS entitled HALOGENATED DIAZINES AND TRIAZINES Submitted by D E. WOOD (Grey), B Sc (London) The copyright of this thesis rests with the author No quotation from it should be published without his prior written consent and information derived from it should be acknowledged A candidate for the degree of Doctor of Philosophy 19 78 sr i i > j J To my MoLhcr and FaLhcr WLLII Lh.inks for .ill LhaL Lhey have done ACKNOWLEDGEMLNTS I would like LO express my thanks Lo Professor R D Chambers i under whose guidance this research was undertaken, for considerable encouragement, advice and discussion Thanks are due to Dr R S Matthews for his expert advice with n in r.
    [Show full text]
  • Risto Laitinen/August 4, 2016 International Union of Pure and Applied Chemistry Division VIII Chemical Nomenclature and Structur
    Approved Minutes, Busan 2015 Risto Laitinen/August 4, 2016 International Union of Pure and Applied Chemistry Division VIII Chemical Nomenclature and Structure Representation Approved Minutes of Division Committee Meeting in Busan, Korea, 8–9 August, 2015 1. Welcome, introductory remarks and housekeeping announcements Karl-Heinz Hellwich (KHH) welcomed everybody to the meeting, extending a special welcome to those who were attending the Division Committee meeting for the first time. He described house rules and arrangements during the meeting. KHH also regretfully reported that it has come to his attention that since the Bangor meeting in August 2014, Prof. Derek Horton (Member, Division VIII task groups on Carbohydrate and Flavonoids nomenclature; Associate Member, IUBMB-IUPAC Joint Commission on Biochemical Nomenclature) and Dr. Libuse Goebels, Member of the former Commission on Nomenclature of Organic Chemistry) have passed away. The meeting attendees paid a tribute to their memory by a moment of silence. 2. Attendance and apologies Present: Karl-Heinz Hellwich (president, KHH) , Risto Laitinen (acting secretary, RSL), Richard Hartshorn (past-president, RMH), Michael Beckett (MAB), Alan Hutton (ATH), Gerry P. Moss (GPM), Michelle Rogers (MMR), Jiří Vohlídal (JV), Andrey Yerin (AY) Observers: Leah McEwen (part time, chair of proposed project, LME), Elisabeth Mansfield (task group chair, EM), Johan Scheers (young observer, day 1; JS), Prof. Kazuyuki Tatsumi (past- president of the union, part of day 2) Apologies: Ture Damhus (secretary, TD), Vefa Ahsen, Kirill Degtyarenko, Gernot Eller, Mohammed Abul Hashem, Phil Hodge (PH), Todd Lowary, József Nagy, Ebbe Nordlander (EN), Amélia Pilar Rauter (APR), Hinnerk Rey (HR), John Todd, Lidija Varga-Defterdarović.
    [Show full text]
  • Ger'g .Tyson Jr
    July 14, 1964 ' G. N. TYSON, JR 3,140,582 ROCKET PROPULSION METHOD USING BORON AND NITROGEN COMPOUNDS Filed April 14, 1959 Ger'g .Tyson Jr. INVENTOR. I", u .12) ATTORNEYS 3,l4,582 Patented July 14,, 1964 2 The nitrogen containing compound and the boron con 3,140,582 taining compound are reacted in such proportions that all ROCKET PROPULSION METHOD USING BORON of the nitrogen and all of the boron react to produce AND NOGEN COMPOUNDS boron nitride, the carbon is released as elemental carbon George N. Tyson, Jr., Claremont, Calif., assignor to Olin Mathieson Chemical Corporation, a corporation of and large volumes of hydrogen gas are produced. Virginia Nitrogen containing compounds which can be employed Filed Apr. 14, 1959, Ser. No. 806,396 as reactants include the saturated hydronitrogens such 20 Claims. (Cl. 60-354) as ammonia, hydrazine, triazane, tetrazane; the unsaturated hydronitrogens such as diimide, triazene, tetrazene, iso This invention relates to a method for producing large 10 tetrazene, ammonium azide, hydrazine azide, and hydra volumes of hot gases in a short period of time, which zoic acid; alkyl hydrazines such as methyl hydrazine, un large volumes of hot gases are useful for many purposes symmetrical dimethyl hydrazine, ethyl hydrazine, unsym including imparting thrust to jet propelled devices such metrical diethyl hydrazine; alkylamines including mixed al as rockets. kylamines such as methylamine, dimethylamine, trimeth Jet propelled devices are essentially of two types: those 15 ylamine, ethylamine, diethylamine, triethylarnine, methyl which depend upon an external source for a portion of ethyl amine, n-propylamine, isopropylamine, di-n-propyl the propellant, and those in which the propellant is en amine, tri-n-propylamine, methyl propyl amine, ethyl prop tirely contained within the device.
    [Show full text]
  • Large Intermediates in Hydrazine Decomposition: a Theoretical Study of the N₃H₅ and N₄H₆ Potential Energy Surfaces
    Large Intermediates in Hydrazine Decomposition: A Theoretical Study of the N₃H₅ and N₄H₆ Potential Energy Surfaces The MIT Faculty has made this article openly available. Please share how this access benefits you. Your story matters. Citation Grinberg Dana, Alon et al. "Large Intermediates in Hydrazine Decomposition: A Theoretical Study of the N₃H₅ and N₄H₆ Potential Energy Surfaces." Journal of Physical Chemistry A 123, 22 (May 2019): 4679-4692 © 2019 American Chemical Society As Published http://dx.doi.org/10.1021/acs.jpca.9b02217 Publisher American Chemical Society (ACS) Version Author's final manuscript Citable link https://hdl.handle.net/1721.1/124015 Terms of Use Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. The Journal of Physical Chemistry This document is confidential and is proprietary to the American Chemical Society and its authors. Do not copy or disclose without written permission. If you have received this item in error, notify the sender and delete all copies. Large Intermediates in Hydrazine Decomposition: A Theoretical Study of the N3H5 and N4H6 Potential Energy Surfaces Journal: The Journal of Physical Chemistry Manuscript ID jp-2019-02217p.R1 Manuscript Type: Article Date Submitted by the n/a Author: Complete List of Authors: Grinberg Dana, Alon; Massachusetts Institute of Technology, Chemical Engineering Moore, Kevin; Argonne National Laboratory, Gas Phase Chemical Dynamics Jasper, Ahren; Argonne National Laboratory, Gas Phase Chemical Dynamics Green, William; Massachusetts Institute of Technology, Chemical Engineering ACS Paragon Plus Environment Page 1 of 60 The Journal of Physical Chemistry 1 2 3 4 5 Large Intermediates in Hydrazine Decomposition: A Theoretical Study of the 6 7 N3H5 and N4H6 Potential Energy Surfaces 8 9 1 2 2 1 10 Alon Grinberg Dana , Kevin B.
    [Show full text]
  • Detection of the Elusive Triazane Molecule (N3H5) in the Gas Phase
    DOI:10.1002/cphc.201500560 Communications Detection of the Elusive Triazane Molecule (N3H5)inthe Gas Phase MarkoFçrstel,[a] PavloMaksyutenko,[a] BrantM.Jones,[a] Bing-Jian Sun,[b] Shih-Hua Chen,[b] Agnes. H.-H. Chang,*[b] and Ralf I. Kaiser*[a] We report the detection of triazane (N3H5)inthe gas phase. Tri- ful and only potential decompositionproducts of triazane azane is ahigher order nitrogen hydride of ammonia (NH3) (N3H5)—diazane (HNNH) and ammonia (NH3)—could be sam- [1c] [1d] and hydrazine (N2H4)offundamentalimportance for the un- pled. Finally,Fuji et al. made an effort to detect free tria- derstanding of the stability of single-bonded chains of nitro- zane in the microwave discharge of hydrazine, but only the + gen atomsand apotentialkey intermediate in hydrogen–nitro- lithium salt of triazane (LiN3H5 )and the triazane cation + gen chemistry. The experimental resultsalongwith electronic- (N3H5 )could be identified. Therefore, whether free triazane structurecalculations reveal that triazane presentsastable (N3H5)can surviveprompt dissociation in the gas phase has re- molecule with anitrogen–nitrogen bond length that is afew mained an unanswered question. This lack of experimental evi- picometers shorter than that of hydrazineand has alifetime dence on the stability of triazane has triggered substantial exceeding 6 2 msatasublimation temperature of 170 K. Tria- computational efforts.[1a,b] An evaluation of the thermodynamic Æ zane was synthesized throughirradiation of ammonia ice with stability, accounting for hydrogen bonding as well as hyper- energetic electrons and was detected in the gas phase upon conjugation effects, reveals three triazane conformers with C1 sublimation of the ice through soft vacuum ultraviolet (VUV) and Cs symmetries, which range in stability within 24 kJ 1 [1a,b] photoionization coupled with areflectron-time-of-flight mass molÀ .
    [Show full text]
  • Download PDF 1.71 MB
    The Dynamics of Electron-Induced Formation of N-2 and N-3 Species from Condensed Ammonia Jane L. Zhu Advisor: Christopher R. Arumainayagam, Ph.D. Department of Chemistry, Wellesley College Submitted in Partial Fulfillment of the Prerequisites for Honors in Chemistry April 2016 © Jane L. Zhu i Acknowledgements First and foremost, I have nothing but the utmost thanks for my advisor, Chris Arumainayagam. You have taught me so much over the past four years. Thank you for always pushing me to be a better scholar and scientist. More importantly, thank you for believing in me. Thank you to my thesis committee – Professor Mala Radhakrishnan and Professor Carla Verschoor. Your constructive criticisms, advice, and encouragement have been tremendously helpful during this process, especially during some of the more frustrating and stressful times. Thank you also to Professor Ellen Hildreth for graciously agreeing to serve as my honors visitor. Many thanks to the incredible chemistry department and science center staff. Thank you Professor Paul Reisberg for your immense support over the last several years. Special thanks to George Dai, Larry Knowles, and John DeBolt – you all have been so gracious with your time and efforts, especially when problems arose with our ultrahigh vacuum chamber. I would also like to thank my brilliant lab mates. Without you all, this thesis would not have been possible. Thank you all for always being so willing to come into lab bright and early in the morning and staying until midnight to help me with experiments and data analysis. I will miss you all dearly. I also cannot overstate my gratitude for my former lab mates, Katie Shulenberger’14 and Katherine Tran’15, for starting this ammonia project.
    [Show full text]
  • Stereochemistry of Simple Molecules Inside Nanotubes and Fullerenes: Unusual Behavior of Usual Systems
    molecules Review Stereochemistry of Simple Molecules inside Nanotubes and Fullerenes: Unusual Behavior of Usual Systems Valerij Kuznetsov 1,2 1 Ufa State Aviation Technical University, K. Marksa, 12, Ufa 450008, Russia; [email protected] 2 Ufa State Petroleum Technological University, Kosmonavtov, 1, Ufa 450062, Russia Academic Editor: Bagrat Shainyan Received: 7 May 2020; Accepted: 21 May 2020; Published: 23 May 2020 Abstract: Over the past three decades, carbon nanotubes and fullerenes have become remarkable objects for starting the implementation of new models and technologies in different branches of science. To a great extent, this is defined by the unique electronic and spatial properties of nanocavities due to the ramified π-electron systems. This provides an opportunity for the formation of endohedral complexes containing non-covalently bonded atoms or molecules inside fullerenes and nanotubes. The guest species are exposed to the force field of the nanocavity, which can be described as a combination of electronic and steric requirements. Its action significantly changes conformational properties of even relatively simple molecules, including ethane and its analogs, as well as compounds with C–O, C–S, B–B, B–O, B–N, N–N, Al–Al, Si–Si and Ge–Ge bonds. Besides that, the cavity of the host molecule dramatically alters the stereochemical characteristics of cyclic and heterocyclic systems, affects the energy of pyramidal nitrogen inversion in amines, changes the relative stability of cis and trans isomers and, in the case of chiral nanotubes, strongly influences the properties of R- and S-enantiomers. The present review aims at primary compilation of such unusual stereochemical effects and initial evaluation of the nature of the force field inside nanotubes and fullerenes.
    [Show full text]
  • Chemical Resistance Guide
    04/16 CHEMICAL RESISTANCE GUIDE PRIMARY FLUID SYSTEMS INC. 1050 COOKE BLVD., BURLINGTON, ONTARIO L7T 4A8 TEL:(905)333-8743 FAX:(905)333-8746 1-800-776-6580 email: [email protected] www.primaryfluid.com INDEX PAGE Disclaimer .................................................................................................... 3 Material Guide .............................................................................................. 4 Chemical Guide ............................................................................................ 5 – 22 Chemical Formulas ...................................................................................... 23 - 35 2 Primary Fluid Systems Inc CALL TOLL FREE 1-800-776-6580 PRIMARY FLUID SYSTEMS INC. DISCLAIMER Primary Fluid Systems Inc. takes no responsibility for the enclosed information in use with product selection against chemical resistance. The data in the following tables were obtained from numerous sources in the industry, and believed to be reliable but cannot be guaranteed. The information is intended as a general guide for material selection. The end user should be aware of the fact that actual service conditions will affect the chemical resistance. It is recommended that you cross reference this guide with one or two others to insure consistency. All data provided is based on testing at 70ºF [21ºC]. Thermoplastics, Metals and Elastomers have outstanding resistance to a wide range of chemical reagents. Such resistance, however, is a function A* Excellent – No Effect both of
    [Show full text]
  • Pyrolysis of Hydrazine Derivatives and Related Compounds with N-N Single Bonds
    Accepted Manuscript Title: Pyrolysis of hydrazine derivatives and related compounds with N-N single bonds Author: Abd-El Aal M. Gaber Curt Wentrup PII: S0165-2370(17)30020-7 DOI: http://dx.doi.org/doi:10.1016/j.jaap.2017.03.016 Reference: JAAP 4003 To appear in: J. Anal. Appl. Pyrolysis Received date: 7-1-2017 Revised date: 10-3-2017 Accepted date: 15-3-2017 Please cite this article as: A.-E.A.M. Gaber, C. Wentrup, Pyrolysis of hydrazine derivatives and related compounds with N-N single bonds, Journal of Analytical and Applied Pyrolysis (2017), http://dx.doi.org/10.1016/j.jaap.2017.03.016 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. 1 Pyrolysis of hydrazine derivatives and related compounds with N-N single 2 bonds 3 4 Abd-El Aal M. Gabera,* and Curt Wentrupb,* 5 6 a Chemistry Department, Faculty of Science, Assiut University, Assiut 71516, Egypt 7 b School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, 8 Queensland 4072, Australia 9 10 ∗Corresponding authors, E-mail addresses: [email protected] (Gaber), [email protected] (Wentrup). 11 12 Highlights 13 Pyrolysis of all types of hydrazine derivatives are reviewed 14 N-aminoheterocycles, N-aminoisocyanides, and N-aminoisocyanates are included 15 Aminimides, azimines, and tri-, tetra-, penta- and hexazenes are covered 16 Pyrolyses in solution, in the solid state, and under flash vacuum pyrolysis conditions 17 18 ABSTRACT 19 Pyrolysis of hydrazines and their derivatives often results in homolytic cleavage of the N-N 20 bonds, but molecular rearrangements and eliminations are also observed in many cases.
    [Show full text]
  • NBO Applications, 2008
    NBO 2008 (Jan-Dec) - 910 references Compiled by Emily Wixson; Updated by Ariel Neff 4/16/13 Adalsteinsson, H.; Debusschere, B. J.; Long, K. R.; Najm, H. N. Components for atomistic-to-continuum multiscale modeling of flow in micro- and nanofluidic systems Scientific Programming, (16): 297-313 2008. Adcock, W.; Trout, N. A. Diastereofacial selectivity in some 4-substituted (X) 2-adamantyl derivatives: electronic versus steric effects Journal of Physical Organic Chemistry, (21): 68-72 2008. Agapito, F.; Nunes, P. A.; Costa Cabral, B. J.; Borges dos Santos, R. A.; Martinho Simoes, J. A. Energetic differences between the five- and six-membered ring hydrocarbons: Strain energies in the parent and radical molecules Journal of Organic Chemistry, (73): 6213-6223 2008. Aguilar-Castro, L.; Tlahuextl, M.; Mendoza-Huizar, L. H.; Tapia-Benavides, A. R.; Tlahuext, H. Hydrogen bond studies in substituted N-(2-hydroxyphenyl)-2-[(4- methylbenzenesulfonyl)amino]acetamides Arkivoc: 210-226 2008. Alajarin, M.; Cabrera, J.; Pastor, A.; Sanchez-Andrada, P.; Bautista, D. Polar hetero-Diels-alder reactions of 4-alkenylthiazoles with 1,2,4-triazoline-3,5-diones: An experimental and computational study Journal of Organic Chemistry, (73): 963-973 2008. Albertin, G.; Antoniutti, S.; Baldan, D.; Castro, J.; Garcia-Fontan, S. Preparation of benzyl azide complexes of iridium(III) Inorganic Chemistry, (47): 742-748 2008. Alcoba, D. R.; Ona, O. Determination of energies and electronic densities of functional groups according to partitionings in the physical space Journal of Physical Chemistry A, (112): 10023-10028 2008. Alia, J. D.; Vlaisavljevich, B. Prediction of molecular properties including symmetry from quantum-based molecular structural formulas, VIF Journal of Physical Chemistry A, (112): 9784-9795 2008.
    [Show full text]
  • GLOSSARY of CLASS NAMES of ORGANIC COMPOUNDS and REACTIVE INTERMEDIATES BASED on STRUCTURE (IUPAC Recommendations 1995)
    Pure &App/. Chem., Vol. 67, Nos 819, pp. 1307-1375, 1995. Printed in Great Britain. (B 1995 IUPAC INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY ORGANIC CHEMISTRY DMSION COMMISSION ON NOMENCLATURE OF ORGANIC CHEMISTRY (III. 1) COMMISSION ON PHYSICAL ORGANIC CHEMISTRY (III.2) GLOSSARY OF CLASS NAMES OF ORGANIC COMPOUNDS AND REACTIVE INTERMEDIATES BASED ON STRUCTURE (IUPAC Recommendations 1995) Prepared for publication by G.P. MOSS, P.A.S. SMITH and D. TAVERNIER Cornpodtion of the ZZZ.1 & 111.2 Working Party (1980-1994): H.J.T. Bos, A.J. Boulton, E.W. Godly, P. Griinanger, A.D. McNaught, G.P. Moss, R. PanicO, J. Rigaudy, P.A.S. Smith (Conwnorfiom ZZZ, I), J.H. Stocker, D. Tavernier, R.A.Y. Jones, J. March, J.M. McBnde, P. Miiller (Conwnorfim 111.2). Membership of the Commission on Nomenclature of Organic Chemistry during the preparation of this document (1980-1994) was as follows: Titular Members: 0. Achmatowicz (Poland) 1979-1987; H. J. T. Bos (Netherlands) 1987- , Vice-Chairman, 1991- ; J. R. Bull (Republic of South Africa) 1987-1993; H. A. Favre (Canada) 1989- , Chairman, 1991- ; P. M. Giles, Jr. (USA) 1989- ; E. W. Godly (UK) 1987-1993. Secretary, 1989-1993 ; D. Hellwinkel (Federal Republic of Germany) 1979-1987, Vice- Chairman, 1981-1987; B. J. Herold (Portugal) 1994- ; K. Hirayama (Japan) 1975-1983; M. V. KisakUrck (Switizrland) 1994- ; A. D. McNaught (UK) 1979-1987; G. P. Moss (UK) 1977- 1987, Chairinan, 1981- 1987, Vice-Chainnun, 1979-1981; R. Panico (Francc) 1981-1991, Vice- Chairman, 1989-1991; W. H. Powell (USA) Secretary, 1979-1989; J.
    [Show full text]