DOCSLIB.ORG

Chemical Kinetics of Organophosphorus Fire Suppressants

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Chemical Kinetics of Organophosphorus Fire Suppressants CHEMICAL KINETICS OF ORGANOPHOSPHORUS FIRE SUPPRESSANTS A Dissertation by TRAVIS GLENN SIKES III Submitted to the Office of Graduate and Professional Studies of Texas A&M University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Chair of Committee, Eric L. Petersen Co-Chair of Committee, M. Sam Mannan Committee Members, Timothy Jacobs Waruna Kulatilaka Head of Department, Andreas A. Polycarpou August 2018 Major Subject: Mechanical Engineering Copyright 2018 Travis Sikes ABSTRACT Organophosphorus compounds (OPCs) have significant fire suppression capabilities but are not well understood. Chemical kinetics mechanisms can provide invaluable information about how OPCs suppress flames; however, the currently available OPC mechanisms are deficient and could use further refinement. In this dissertation, two types of experimental data were taken which can be used as benchmarks to improve mechanisms: laminar flame speeds and ignition delay times. In the laminar flame speed experiments, dimethyl methylphosphonate (DMMP), diethyl methylphosphonate (DEMP) diisopropyl methylphosphonate (DIMP), and trimethyl phosphate (TEP) were added to hydrogen/air and methane/air mixtures to assess their suppression capabilities at 0.1% and 0.3% (DMMP only) of the total mixture volume. The experiments were performed in an optically tracked, spherically expanding flame setup at 1 atm and 120 °C. Results show a 30% decrease in laminar flame speed for all OPCs at 0.1% on the methane/air parent mixture. For the hydrogen/air mixtures, the OPCs differentiate themselves by having an increasing suppression effect corresponding with higher carbon moiety, i.e., DIMP (20% overall reduction), > TEP (15%) > DEMP (13%) > DMMP (9%). The OPCs also have an increasing effect with increasing equivalence ratio on hydrogen/air. Ignition delay time experiments were performed in a glass shock tube at ICARE – CNRS. The simple OPCs studied were dimethyl phosphite (DMP), trimethyl phosphate (TMP), and diethyl phosphite (DEP). The OPCs were added as 10% of the fuel in hydrogen/ethylene mixtures diluted with 98% argon. The results show that the three OPCs behave similarly in both ii hydrogen and ethylene mixtures by decreasing the ignition delay time ~30% at high temperatures and then decreasing in effect until the neat and OPC data are indistinguishable. Additionally, quantum chemistry calculations were performed to improve an existing OPC submechanism using ROCBS-QB3 level of theory for thermochemistry and G3X-K for the transition state calculations. The thermochemistry data are an improvement on previous OPC mechanisms, but overall the model does not predict the ignition delay times. Further OPC submechanism improvement is needed to resolve simple OPC reactions so that larger OPC submechanisms will be able to properly predict OPC behavior in applications such as fire suppression. iii ACKNOWLEDGMENTS I would like to thank my advisor, Dr. Eric Petersen. It has been a long journey that began in spring 2011’s undergraduate fluid mechanics class and has led me here. I cannot imagine a better advisor and he is one of the biggest reasons why I’ve come as far as I have. He has taught me persistence in the face of adversity, to always carefully consider all possibilities for anything from an experimental error to developing a new program, and most importantly, through his own example, how to accomplish great things with a strong work ethic. Dr. Petersen is who I imagine as the ideal advisor, teacher, academic, and supervisor. Thank you for taking a chance on me and giving me your support. It has meant more than you may ever know. I would like to thank my committee co-chair, Dr. Sam Mannan, and my committee members, Dr. Jacobs, and Dr. Kulatilaka for their guidance and support throughout the course of this research. I am extremely grateful to Dr. Laurent Catoire for hosting me at ENSTA ParisTech. Through this experience I learned about French culture and was able to live the French life for 6 months. My trip was life changing and I will never forget it. I also thank Dr. Pascal Diévart for his time and patience. He taught me everything I know about quantum chemical modeling, and he has also helped me in performing the transition state theory calculations while I was busy with thermochemistry. A thank you must go to Dr. Nabiha Chaumeix and Dr. Andrea Comandini for their help both professional and personal during my time at CNRS-Orléans. I was only able to iv accomplish the quantity and quality of ignition delay experiments with their experience and expertise. Working with both of them was truly a pleasure. Thanks to my friends and colleagues within the Petersen Research Group. Being able to always have someone that I can bounce ideas off of, get help with a problem, or even just joke around with has made my graduate experience an absolute joy. I only hope that I can one day find another group of coworkers as great as the one I’m leaving, past and present. Finally, a special thanks to my family for their never-ending encouragement and to my wife for her patience during my entire graduate career and her unshakable love. v CONTRIBUTORS AND FUNDING SOURCES This work was supported by a dissertation committee consisting of my committee co-chairs Dr. Eric L. Petersen, Nelson-Jackson professor of the Department of Mechanical Engineering, and Dr. M. Sam Mannan, regents professor of the Department of Chemical Engineering and director of Mary Kay O’Connor Process Safety Center; as well as, my committee members Dr. Timothy Jacobs and Dr. Waruna Kulatilaka, professor and associate professor in the Department of Mechanical Engineering, respectively. During the oral defense Dr. Chad Mashuga, assistant professor in the Department of Chemical Engineering, stood in for Dr. M. Sam Mannan. Flame speed modeling and ignition delay time measurements in Chapter III and Chapter IV were performed with assistance from Dr. Nabiha Chaumeix, Research Director of ICARE-CNRS (Orléans, France), and Dr. Andrea Comandini of ICARE-CNRS. Quantum chemistry modeling efforts in Chapter V were performed in part with Dr. Laurent Catoire, Director of the UCP in ENSTA ParisTech, and Dr. Pascal Diévart, professor at ENSTA Paristech. Dr. Pascal Diévart has performed the Arrhenius parameter calculations for the updated reactions. All other work conducted for the dissertation was completed by the student independently. This research was supported by the Mary Kay O’Connor Process Safety Center, a STEM fellowship from the Chateaubriand Fellowship Program, .and the Defense Threat Reduction Agency (DTRA) under grant number HDTRA1-16-1-0031. vi TABLE OF CONTENTS Page ABSTRACT .......................................................................................................................ii ACKNOWLEDGMENTS ................................................................................................. iv CONTRIBUTORS AND FUNDING SOURCES ............................................................. vi TABLE OF CONTENTS .................................................................................................vii LIST OF FIGURES ........................................................................................................... ix LIST OF TABLES ...........................................................................................................xii CHAPTER I INTRODUCTION AND LITERATURE REVIEW .................................... 1 I.1 References ...................................................................................................... 8 CHAPTER II LAMINAR FLAME SPEED METHODOLOGY .................................... 11 II.1 TAMU Spherically Expanding Flame Facility ............................................ 11 II.2 Experimental Analysis ................................................................................. 16 II.3 References .................................................................................................... 23 CHAPTER III LAMINAR FLAME SPEED MEASUREMENTS.................................. 25 III.1 Methane ........................................................................................................ 28 III.2 Hydrogen ...................................................................................................... 32 III.3 Fire Suppressant Comparison ....................................................................... 36 III.4 Flame Speed Sensitivity Analysis ................................................................ 38 III.5 References .................................................................................................... 41 CHAPTER IV IGNITION DELAY TIME MEASUREMENTS .................................... 44 IV.1 Experimental Facility and Procedure ........................................................... 46 IV.2 Mixtures and Preparation ............................................................................. 53 IV.3 OPC Ignition Delay Times in Hydrogen Mixtures ...................................... 55 IV.4 OPC Ignition Delay Times in Ethylene Mixtures ........................................ 59 IV.5 References .................................................................................................... 63 vii CHAPTER V QUANTUM CHEMISTRY MODELING ................................................ 65 V.1 Heat of Formation ........................................................................................ 65 V.2 Sensible Enthalpy, Specific Heat, and Entropy ...........................................
Load more

Recommended publications
  • A Dicationic Iminophosphane Ying Kai Loh, Chitra Gurnani, Rakesh Ganguly, and Dragoslav Vidović*
    A Dicationic Iminophosphane Ying Kai Loh, Chitra Gurnani, Rakesh Ganguly, and Dragoslav Vidović* Department of Chemistry and Biological Chemistry, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371. Supporting Information Placeholder ABSTRACT: A novel dicationic system containing a PN frag- ment has been synthesized and structurally characterized. Accord- ing to the solid state analysis and theoretical investigation the dica- tionic iminophosphane resonance from is the most appropriate de- scription for the dication. However, the contribution from the phos- phorus mononitride resonance form is not negligible. Neutral two-eletron donor carbenes have proven to be quite versatile ligands for isolation of a wide variety of novel main group 1-4 species. Examples include diatomic allotropes (L-E2-L; L = car- bene, E = B, Si, Ge, P, As, etc)1a of boron, silicon, germanium, phosphorus, arsenic, etc.2-4 Nevertheless, these interesting mole- cules, among numerous other main group species, sparked a debate about the most appropriate way to describe bonding in these com- Figure 1. Recently isolated neutral (A) and radical cationic (B) 5,6 pounds. In particular, the arguments have been focused on phosphorus mononitrides, and general structure for carbones (C). whether the carbene moieties form typical covalent bonds or the Dipp = 2,6-diisopropylphenyl. use of dative bond analogy is also valid. The latest evidence showed that the L-E bonds for L-B2-L are quite strong suggesting a sub- stantial covalent character.6 However, Frenking argued that dative The overall synthesis of the target dication is summarized in bonds could be also very strong by the combination of -donation Scheme 1.
    [Show full text]
  • Copyrighted Material
    PART I METHODS COPYRIGHTED MATERIAL CHAPTER 1 Overview of Thermochemistry and Its Application to Reaction Kinetics ELKE GOOS Institute of Combustion Technology, German Aerospace Center (DLR), Stuttgart, Germany ALEXANDER BURCAT Faculty of Aerospace Engineering, Technion - Israel Institute of Technology, Haifa, Israel 1.1 HISTORY OF THERMOCHEMISTRY Thermochemistry deals with energy and enthalpy changes accompanying chemical reactions and phase transformations and gives a first estimate of whether a given reaction can occur. To our knowledge, the field of thermochemistry started with the experiments done by Malhard and Le Chatelier [1] with gunpowder and explosives. The first of their two papers of 1883 starts with the sentence: “All combustion is accompanied by the release of heat that increases the temperature of the burned bodies.” In 1897, Berthelot [2], who also experimented with explosives, published his two-volume monograph Thermochimie in which he summed up 40 years of calori- metric studies. The first textbook, to our knowledge, that clearly explained the principles of thermochemical properties was authored by Lewis and Randall [3] in 1923. Thermochemical data, actually heats of formation, were gathered, evaluated, and published for the first time in the seven-volume book International Critical Tables of Numerical Data, Physics, Chemistry and Technology [4] during 1926–1930 (and the additional index in 1933). In 1932, the American Chemical Society (ACS) monograph No. 60 The Free Energy of Some Organic Compounds [5] appeared. Rate Constant Calculation for Thermal Reactions: Methods and Applications, Edited by Herbert DaCosta and Maohong Fan. Ó 2012 John Wiley & Sons, Inc. Published 2012 by John Wiley & Sons, Inc. 3 4 OVERVIEW OF THERMOCHEMISTRY AND ITS APPLICATION TO REACTION KINETICS In 1936 was published The Thermochemistry of the Chemical Substances [6] where the authors Bichowsky and Rossini attempted to standardize the available data and published them at a common temperature of 18C (291K) and pressure of 1 atm.
    [Show full text]
  • Injection of Meteoric Phosphorus Into Planetary Atmospheres
    Planetary and Space Science 187 (2020) 104926 Contents lists available at ScienceDirect Planetary and Space Science journal homepage: www.elsevier.com/locate/pss Injection of meteoric phosphorus into planetary atmospheres Juan Diego Carrillo-Sanchez a, David L. Bones a, Kevin M. Douglas a, George J. Flynn b, Sue Wirick c, Bruce Fegley Jr. d, Tohru Araki e, Burkhard Kaulich e, John M.C. Plane a,* a School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, UK b State University of New York at Plattsburgh, Department of Physics, 101 Broad Street, Plattsburg, NY, 12901, USA c Focused Beam Enterprises, Westhampton, NY, 11977, USA d Planetary Chemistry Laboratory, Department of Earth & Planetary Sciences and McDonnell Center for the Space Sciences, Washington University, St Louis, MO, 63130, USA e Diamond Light Source Ltd, Harwell Science & Innovation Campus, Didcot, OX11 0DE, UK ARTICLE INFO ABSTRACT Keywords: This study explores the delivery of phosphorus to the upper atmospheres of Earth, Mars, and Venus via the Cosmic dust ablation of cosmic dust particles. Micron-size meteoritic particles were flash heated to temperatures as high as Planetary atmospheres 2900 K in a Meteor Ablation Simulator (MASI), and the ablation of PO and Ca recorded simultaneously by laser Ablation induced fluorescence. Apatite grains were also ablated as a reference. The speciation of P in anhydrous chondritic Phosphorus thermodynamics porous Interplanetary Dust Particles was made by K-edge X-ray absorption near edge structure (XANES) spec- Zodiacal cloud troscopy, demonstrating that P mainly occurs in phosphate-like domains. A thermodynamic model of P in a sil- icate melt was then developed for inclusion in the Leeds Chemical Ablation Model (CABMOD).
    [Show full text]
  • Review of Chemiluminescence As an Optical Diagnostic Tool for High Pressure Unstable Rockets Tristan Latimer Fuller Purdue University
    Purdue University Purdue e-Pubs Open Access Theses Theses and Dissertations January 2015 Review of Chemiluminescence as an Optical Diagnostic Tool for High Pressure Unstable Rockets Tristan Latimer Fuller Purdue University Follow this and additional works at: https://docs.lib.purdue.edu/open_access_theses Recommended Citation Fuller, Tristan Latimer, "Review of Chemiluminescence as an Optical Diagnostic Tool for High Pressure Unstable Rockets" (2015). Open Access Theses. 1176. https://docs.lib.purdue.edu/open_access_theses/1176 This document has been made available through Purdue e-Pubs, a service of the Purdue University Libraries. Please contact [email protected] for additional information. Graduate School Form 30 Updated 1/15/2015 PURDUE UNIVERSITY GRADUATE SCHOOL Thesis/Dissertation Acceptance This is to certify that the thesis/dissertation prepared By Tristan L. Fuller Entitled REVIEW OF CHEMILUMINESCENCE AS AN OPTICAL DIAGNOSTIC TOOL FOR HIGH PRESSURE UNSTABLE ROCKETS For the degree of Master of Science in Chemical Engineering Is approved by the final examining committee: William E. Anderson Chair Robert P. Lucht Stephen D. Heister Carson D. Slabaugh To the best of my knowledge and as understood by the student in the Thesis/Dissertation Agreement, Publication Delay, and Certification Disclaimer (Graduate School Form 32), this thesis/dissertation adheres to the provisions of Purdue University’s “Policy of Integrity in Research” and the use of copyright material. Approved by Major Professor(s): William E. Anderson Approved by: Weinong W. Chen 7/24/2015 Head of the Departmental Graduate Program Date REVIEW OF CHEMILUMINESCENCE AS AN OPTICAL DIAGNOSTIC TOOL IN HIGH PRESSURE UNSTABLE COMBUSTORS A Thesis Submitted to the Faculty of Purdue University by Tristan L.
    [Show full text]
  • {Download PDF}
    NO! PDF, EPUB, EBOOK Marta Altes | 32 pages | 15 May 2012 | Child's Play International Ltd | 9781846434174 | English | Swindon, United Kingdom trình giả lập trên PC và Mac miễn phí – Tải NoxPlayer Don't have an account? Sign up here. Already have an account? Log in here. By creating an account, you agree to the Privacy Policy and the Terms and Policies , and to receive email from Rotten Tomatoes and Fandango. Please enter your email address and we will email you a new password. We want to hear what you have to say but need to verify your account. Just leave us a message here and we will work on getting you verified. No uses its history-driven storyline to offer a bit of smart, darkly funny perspective on modern democracy and human nature. Rate this movie. Oof, that was Rotten. Meh, it passed the time. So Fresh: Absolute Must See! You're almost there! Just confirm how you got your ticket. Cinemark Coming Soon. Regal Coming Soon. By opting to have your ticket verified for this movie, you are allowing us to check the email address associated with your Rotten Tomatoes account against an email address associated with a Fandango ticket purchase for the same movie. Geoffrey Macnab. Gripping and suspenseful even though the ending is already known. Rene Rodriguez. The best movie ever made about Chilean plebiscites, No thoroughly deserves its Oscar nomination for Best Foreign Film. Anthony Lane. Soren Andersen. Calvin Wilson. A cunning and richly enjoyable combination of high-stakes drama and media satire from Chilean director Pablo Larrain.
    [Show full text]
  • The Formation of Urea in Space I. Ion-Molecule, Neutral-Neutral, and Radical Gas-Phase Reactions
    Astronomy & Astrophysics manuscript no. man_corr c ESO 2018 October 5, 2018 The formation of urea in space I. Ion-molecule, neutral-neutral, and radical gas-phase reactions Flavio Siro Brigiano1, Yannick Jeanvoine1, Antonio Largo2, and Riccardo Spezia1,? 1 LAMBE, Univ Evry, CNRS, CEA, Université Paris-Saclay, 91025, Evry, France e-mail: [email protected] 2 Computational Chemistry Group, Departamento de Quimica Fisica, Facultad de Ciencias, Universidad de Valladolid, Valladolid, Spain Received XX; accepted YY ABSTRACT Context. Many organic molecules have been observed in the interstellar medium thanks to advances in radioastronomy, and very recently the presence of urea was also suggested. While those molecules were observed, it is not clear what the mechanisms respon- sible to their formation are. In fact, if gas-phase reactions are responsible, they should occur through barrierless mechanisms (or with very low barriers). In the past, mechanisms for the formation of different organic molecules were studied, providing only in a few cases energetic conditions favorable to a synthesis at very low temperature. A particularly intriguing class of such molecules are those containing one N–C–O peptide bond, which could be a building block for the formation of biological molecules. Urea is a particular case because two nitrogen atoms are linked to the C–O moiety. Thus, motivated also by the recent tentative observation of urea, we have considered the synthetic pathways responsible to its formation. Aims. We have studied the possibility of forming urea in the gas phase via different kinds of bi-molecular reactions: ion-molecule, neutral, and radical. In particular we have focused on the activation energy of these reactions in order to find possible reactants that could be responsible for to barrierless (or very low energy) pathways.
    [Show full text]
  • WHAT INFLUENCE WOULD a CLOUD BASED SEMANTIC LABORATORY NOTEBOOK HAVE on the DIGITISATION and MANAGEMENT of SCIENTIFIC RESEARCH? by Samantha Kanza
    UNIVERSITY OF SOUTHAMPTON Faculty of Physical Sciences and Engineering School of Electronics and Computer Science What Influence would a Cloud Based Semantic Laboratory Notebook have on the Digitisation and Management of Scientific Research? by Samantha Kanza Thesis for the degree of Doctor of Philosophy 25th April 2018 UNIVERSITY OF SOUTHAMPTON ABSTRACT FACULTY OF PHYSICAL SCIENCES AND ENGINEERING SCHOOL OF ELECTRONICS AND COMPUTER SCIENCE Doctor of Philosophy WHAT INFLUENCE WOULD A CLOUD BASED SEMANTIC LABORATORY NOTEBOOK HAVE ON THE DIGITISATION AND MANAGEMENT OF SCIENTIFIC RESEARCH? by Samantha Kanza Electronic laboratory notebooks (ELNs) have been studied by the chemistry research community over the last two decades as a step towards a paper-free laboratory; sim- ilar work has also taken place in other laboratory science domains. However, despite the many available ELN platforms, their uptake in both the academic and commercial worlds remains limited. This thesis describes an investigation into the current ELN landscape, and its relationship with the requirements of laboratory scientists. Market and literature research was conducted around available ELN offerings to characterise their commonly incorporated features. Previous studies of laboratory scientists examined note-taking and record-keeping behaviours in laboratory environments; to complement and extend this, a series of user studies were conducted as part of this thesis, drawing upon the techniques of user-centred design, ethnography, and collaboration with domain experts. These user studies, combined with the characterisation of existing ELN features, in- formed the requirements and design of a proposed ELN environment which aims to bridge the gap between scientists' current practice using paper lab notebooks, and the necessity of publishing their results electronically, at any stage of the experiment life cycle.
    [Show full text]
  • Alternative Strategies Toward Sustainable Ammonia Synthesis
    Transactions of Tianjin University (2020) 26:67–91 https://doi.org/10.1007/s12209-020-00243-x REVIEW Alternative Strategies Toward Sustainable Ammonia Synthesis Chengcheng Li1,2,3,4 · Tuo Wang1,2,3 · Jinlong Gong1,2,3 Received: 2 January 2020 / Revised: 16 January 2020 / Accepted: 15 February 2020 / Published online: 13 March 2020 © The Author(s) 2020 Abstract As one of the world’s most produced chemicals, ammonia (NH 3) is synthesized by Haber–Bosch process. This century-old industry nourishes billions of people and promotes social and economic development. In the meantime, 3%–5% of the world’s natural gas and 1%–2% of the world’s energy reserves are consumed, releasing millions of tons of carbon dioxide annually to the atmosphere. The urgency of replacing fossil fuels and mitigating climate change motivates us to progress toward more sustainable methods for N 2 reduction reaction based on clean energy. Herein, we overview the emerging advancement for sustainable N2 fxation under mild conditions, which include electrochemical, photo- , plasma-enabled and homogeneous molecular NH3 productions. We focus on NH3 generation by electrocatalysts and photocatalysts. We clarify the features and progress of each kind of NH3 synthesis process and provide promising strategies to further promote sustainable ammonia production and construct state-of-the-art catalytic systems. Keywords Nitrogen fxation · Sustainable ammonia synthesis · Electrocatalyst · Photocatalyst · Ambient conditions Introduction two-component system, with Fe protein as electron-transfer media and FeMo protein as the N2-binding and reduction site Occupying 78% of the atmosphere on the earth in volume (Fig. 1a) [6, 7].
    [Show full text]
  • Chemistry Reduction for Laminar Oxyfuel Combustion
    Chemistry Reduction for Laminar Oxyfuel Combustion Dissertation zur Erlangung des Grades Doktor{Ingenieur der Fakult¨atf¨urMaschinenbau der Ruhr{Universit¨atBochum von Valentin N04 Bomba aus Yegue-Assi, Kamerun Bochum 2016 Dissertation eingereicht am: 15.12.2016 Tag der mündlichen Prüfung: 01.02.2017 Erstgutachter: Prof. Dr.-Ing. B. Rogg Zweitgutachter: Prof. Dr.-Ing. W. Eifler Contents Abstract iii 1 Introduction 1 1.1 Motivation for and Overview on the Reduction of Chemical Mechanisms 2 1.2 Previous Work . 5 1.2.1 Combustion in O2/CO2 Atmospheres . 5 1.2.2 Combustion in Pure Oxygen . 5 1.3 Outline of the Present Work . 7 2 Combustion Geometry and Governing Equations 8 2.1 Diffusion Flames in CounterFlow . 8 2.2 Higher-Order Effects . 13 3 Thermodynamics and Molecular Transport 15 3.1 Equations of State . 15 3.2 Phenomenological Relationships . 16 3.2.1 Stress Tensor . 16 3.2.2 Heat-Flux Vector . 17 3.2.3 Diffusion Velocities . 17 3.3 Transport Coefficients . 18 3.3.1 Simple Property and Data Models . 18 3.3.2 Detailed Property and Data Models . 19 3.3.2.1 Dynamic Viscosities . 20 3.3.2.2 Thermal Conductivities . 20 3.3.2.3 Ordinary-Diffusion Coefficients . 22 3.3.2.4 Thermal-Diffusion Coefficients . 23 3.4 Heat Capacities, Enthalpies and Entropies . 23 4 Chemistry 25 4.1 Ozone Chemistry as an Introductory Example . 25 i 4.2 Phenomenological Expressions of Chemical Kinetics . 25 4.3 Detailed Mechanisms of Elementary Reactions . 27 4.4 Partial Equilibria . 28 4.5 Steady States Species .
    [Show full text]
  • Chemical Kinetics Modelling of Combustion Processes in SI Engines
    Chemical kinetics modelling of combustion processes in SI engines by Ahmed Faraz Khan B.Sc., M.S. Submitted in accordance with the requirements for the degree of Doctor of Philosophy The University of Leeds School of Mechanical Engineering May 2014 The candidate confirms that the work submitted is his own, except where work which has formed part of jointly authored publications has been included. The contribution of the candidate and the other authors to this work has been ex- plicitly indicated below. The candidate confirms that appropriate credit has been given within the thesis where reference has been made to the work of others. The Figure 2.5 in Chapter 2 has been published in a jointly authored publication: A.F.Khan and A.A.Burluka. An Investigation of Various Chemical Kinetic Models for the Prediction of Autoignition in HCCI Engine. ASME 2012 Internal Combustion Engine Division Fall Technical Conference, Vancouver, BC, Canada, September 23 – 26, 2012. Paper No. ICEF2012-92057, pp. 737-745; doi:10.1115/ICEF2012-92057 The content taken from the above publication for use in this thesis was solely generated by the author. The co-author is credited to technical discussion on the results produced in the publication. This copy has been supplied on the understanding that it is copyright material and that no quotation from the thesis may be published without proper acknowl- edgement. The right of Ahmed Faraz Khan to be identified as Author of this work has been asserted by him in accordance with the Copyright, Designs and Patents Act 1988. c 2014 The University of Leeds and Ahmed Faraz Khan i Acknowledgements The completion of this work owes a lot to the contribution and support of so many people in my professional and personal life.
    [Show full text]
  • Virt&L-Comm.9.2016.4
    VIRT&L-COMM.9.2016.4 UNIVERSITÀ DEGLI STUDI DI PERUGIA (IT) DOTTORATO DI RICERCA IN SCIENZE CHIMICHE XXV CICLO SETTORE SCIENTIFICO DISCIPLINARE CHIM/03 IN COTUTELA CON UNIVERSITÉ PAUL SABATIER,TOULOUSE (FR) Molecular Simulations as test beds for bridging High Throughput and High Performance computing Marco Verdicchio RELATORE ITALIANO:RELATORE FRANCESE: Prof. Antonio Laganà Prof. Stefano Evangelisti Università Université degli Studi di Perugia Paul Sabatier, Toulouse ANNO ACCADEMICO 2011/2012 ISSN: 2279-8773 VIRT&L-COMM.9.2016.4 ISSN: 2279-8773 VIRT&L-COMM.9.2016.4 Contents Introduction 1 1 Molecular Simulators 5 1.1 The general Schrödinger equation . 5 1.2 The electronic structure . 6 1.3 The nuclei dynamics . 10 1.4 The chemical kinetics systems . 12 1.5 GEMS the GRID simulator . 15 1.6 The kinetics version of the workflow . 18 1.7 Bridging HTC to HPC . 19 2 Code interoperability in Quantum chemistry and Dynamics 25 2.1 Data of Ab initio Quantum Chemistry . 26 2.2 Data of Quantum Dynamics . 28 2.3 The data model: Q5cost . 29 2.4 The D5cost data model . 32 2.5 The Library . 32 2.6 Tools and Wrappers . 34 2.7 Performance and benchmarks . 37 3 High level ab initio calculations of small systems 41 3.1 Coupled-Cluster study: the electronic wavefunction of tetra- hedral clusters . 41 3.2 Geometry optimizations of the tetrahedral clusters . 48 3.3 No-pair bonding: Cu4 basis sets and correlated orbitals . 55 iii ISSN: 2279-8773 VIRT&L-COMM.9.2016.4CONTENTS 3.4 The no-pair bond state .
    [Show full text]
  • Master's Thesis
    MASTER'S THESIS Reduced Kinetic Mechanism of Methane Oxidation for Rocket Applications Alan Kong 2015 Master of Science (120 credits) Space Engineering - Space Master Luleå University of Technology Department of Computer Science, Electrical and Space Engineering Reduced Kinetic Mechanism of Methane Oxidation for Rocket Applications Author: External Supervisor: Fa Quan Alan Kong Dr. Victor Zhukov Examiner: Dr. Victoria Barabash A thesis submitted in the partial fulfilment of the requirements for the Joint European Master in Space Science and Technology Lule˚aUniversity of Technology Universit´ePaul Sabatier Toulouse III Department of Computer Science, Facult´edes Sciences et d'Ing´enierie Electrical and Space Engineering D´epartement de Physique Division of Space Technology October 2015 Abstract Methane, which has properties intermediate between hydrogen and kerosene, is a fuel of several developed and designed rocket engines. Detailed kinetic mechanisms of methane oxidation consist of around 200 or more reactions and about 40-50 species. At the current moment CFD simulations with the use of detailed methane mechanisms can be performed only on supercomputers. However, detailed kinetic mechanisms can be reduced, taking the specifics of rocket combustion chambers. The aim of the present project is to develop a reduced kinetic mechanism of methane oxidation suitable for CFD simulations for rocket applications. The main objective of this thesis work will be a skeletal kinetic mechanism of methane oxidation which is optimized for rocket application. A full detailed methane kinetic mechanism was chosen and reduced to form a skeletal mechanism for rocket application. The resultant skeletal mechanism contains 23 species and 49 reactions and were validated with two separate set of experimental data of ignition delay time at pressure of 50 atm.
    [Show full text]