Cyclopentane combustion chemistry. Part I: Mechanism development and computational kinetics

Abstract Cycloalkanes are significant constituents of conventional fossil fuels, in which they are one of the main contributors to soot formation, but also significantly influence the ignition characteristics below ∼900 K. This paper discusses the development of a detailed high- and low-temperature oxidation mechanism for cyclopentane, which is an important archetypical cycloalkane. The differences between cyclic and non-cyclic alkane chemistry, and thus the inapplicability of acyclic alkane analogies, required the detailed theoretical investigation of the kinetics of important cyclopentane oxidation reactions as part of the mechanism development. The cyclopentyl + O 2 reaction was investigated at the UCCSD(T)-F12a/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory in a time-dependent master equation framework. Comparisons with analogous cyclohexane or non-cyclic alkane reactions are presented. Our study suggests that beyond accurate quantum chemistry the inclusion of pressure dependence and especially that of formally direct kinetics is crucial even at pressures relevant for practical application.

[1]  Aamir Farooq,et al.  Cyclopentane combustion. Part II. Ignition delay measurements and mechanism validation , 2017 .

[2]  S. Paulson,et al.  ON THE UNCERTAINTIES IN THE RATE COEFFICIENTS FOR OH REACTIONS WITH HYDROCARBONS, AND THE RATE COEFFICIENTS OF THE 1,3,5-TRIMETHYLBENZENE AND M-XYLENE REACTIONS WITH OH RADICALS IN THE GAS PHASE , 1998 .

[3]  Hans-Heinrich Carstensen,et al.  High-pressure rate rules for alkyl + O2 reactions. 1. The dissociation, concerted elimination, and isomerization channels of the alkyl peroxy radical. , 2011, The journal of physical chemistry. A.

[4]  Wing Tsang,et al.  Thermal decomposition of cyclopentane and related compounds , 1978 .

[5]  Kuiwen Zhang,et al.  An experimental and kinetic modeling study of n-hexane oxidation , 2015 .

[6]  John M. Simmie,et al.  Effects of molecular structure on oxidation reactivity of cyclic hydrocarbons: Experimental observations and conformational analysis , 2010 .

[7]  W. Green,et al.  Role of O2 + QOOH in low-temperature ignition of propane. 1. Temperature and pressure dependent rate coefficients. , 2012, The journal of physical chemistry. A.

[8]  B. L. Kalra,et al.  Rates of reactions of cyclopropane, cyclobutane, cyclopentene,and cyclohexene in the presence of boron trichloride , 1984 .

[9]  John M. Simmie,et al.  Uniqueness in the low temperature oxidation of cycloalkanes , 2010 .

[10]  William L. Roberts,et al.  Compositional effects on the ignition of FACE gasolines , 2016 .

[11]  M. P. Burke,et al.  Reformulation and solution of the master equation for multiple-well chemical reactions. , 2013, The journal of physical chemistry. A.

[12]  J. Bozzelli,et al.  Thermochemical properties and bond dissociation energies of C3-C5 cycloalkyl hydroperoxides and peroxy radicals: cycloalkyl radical + (3)O2 reaction thermochemistry. , 2012, The journal of physical chemistry. A.

[13]  Thomas J. Bruno,et al.  Methodology for Formulating Diesel Surrogate Fuels with Accurate Compositional, Ignition-Quality, and Volatility Characteristics , 2012 .

[14]  Joe V. Michael,et al.  Shock tube measurements of high temperature rate constants for OH with cycloalkanes and methylcycloalkanes , 2009 .

[15]  James A. Miller,et al.  From the Multiple-Well Master Equation to Phenomenological Rate Coefficients: Reactions on a C3H4 Potential Energy Surface , 2003 .

[16]  James A. Miller,et al.  Formally direct pathways and low-temperature chain branching in hydrocarbon autoignition: the cyclohexyl + O2 reaction at high pressure. , 2008, Physical chemistry chemical physics : PCCP.

[17]  James A. Miller,et al.  Master equation methods in gas phase chemical kinetics. , 2006, The journal of physical chemistry. A.

[18]  André L. Boehman,et al.  Experimental study of cyclohexane and methylcyclohexane oxidation at low to intermediate temperature in a motored engine , 2009 .

[19]  M. P. Burke,et al.  Comment on "When Rate Constants Are Not Enough". , 2016, The journal of physical chemistry. A.

[20]  B Sirjean,et al.  Detailed kinetic study of the ring opening of cycloalkanes by CBS-QB3 calculations. , 2006, The journal of physical chemistry. A.

[21]  S. M. Sarathy,et al.  Modeling Ignition of a Heptane Isomer: Improved Thermodynamics, Reaction Pathways, Kinetics, and Rate Rule Optimizations for 2-Methylhexane. , 2016, The journal of physical chemistry. A.

[22]  André L. Boehman,et al.  Oxidation chemistry of cyclic hydrocarbons in a motored engine: Methylcyclopentane, tetralin, and decalin , 2010 .

[23]  Ravi X. Fernandes,et al.  A rapid compression machine study of the low temperature combustion of cyclohexane at elevated pressures , 2013 .

[24]  C. Westbrook,et al.  Detailed chemical kinetic modeling of cyclohexane oxidation. , 2006, The journal of physical chemistry. A.

[25]  Jeffrey Santner,et al.  An experimental and modeling study of propene oxidation. Part 1: Speciation measurements in jet-stirred and flow reactors , 2014 .

[26]  S. M. Sarathy,et al.  Comprehensive chemical kinetic modeling of the oxidation of 2-methylalkanes from C7 to C20 , 2011 .

[27]  Edward R. Ritter,et al.  THERM: THERMODYNAMIC PROPERTY ESTIMATION FOR GAS PHASE RADICALS and MOLECULES , 1991, Proceeding of Data For Discovery.

[28]  Majed A. Alrefae,et al.  An experimental and modeling study of propene oxidation. Part 2: Ignition delay time and flame speed measurements , 2015 .

[29]  P. Glaude,et al.  Theoretical kinetic study of the reactions of cycloalkylperoxy radicals. , 2009, Journal of Physical Chemistry A.

[30]  Warren E. Stewart,et al.  Molecular Parameters for Normal Fluids. Lennard-Jones 12-6 Potential , 1966 .

[31]  Thomas A. Litzinger,et al.  A jet fuel surrogate formulated by real fuel properties , 2010 .

[32]  Frédérique Battin-Leclerc,et al.  An experimental and modeling study of the low- and high-temperature oxidation of cyclohexane. , 2013, Combustion and flame.

[33]  V. S. Jorish,et al.  Thermodynamic properties of twenty-one monocyclic hydrocarbons , 1986 .

[34]  William H Green,et al.  Intramolecular hydrogen migration in alkylperoxy and hydroperoxyalkylperoxy radicals: accurate treatment of hindered rotors. , 2010, The journal of physical chemistry. A.

[35]  S. Klippenstein,et al.  Theory, measurements, and modeling of OH and HO2 formation in the reaction of cyclohexyl radicals with O2. , 2007, Physical chemistry chemical physics : PCCP.

[36]  Stephen J. Klippenstein,et al.  Uncertainty propagation in the derivation of phenomenological rate coefficients from theory: A case study of n-propyl radical oxidation , 2013 .

[37]  H. Curran,et al.  Revisiting the Kinetics and Thermodynamics of the Low-Temperature Oxidation Pathways of Alkanes: A Case Study of the Three Pentane Isomers. , 2015, The journal of physical chemistry. A.

[38]  William H. Green,et al.  Capturing pressure‐dependence in automated mechanism generation: Reactions through cycloalkyl intermediates , 2003 .

[39]  R. Walker,et al.  Addition of cyclopentane to slowly reacting mixtures of H2+ O2 between 673 and 783 K: reactions of H and OH with cyclopentane and of cyclopentyl radicals , 1995 .

[40]  W. Demore,et al.  Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether , 1999 .

[41]  W. Demore,et al.  Measurement and estimation of rate constants for the reactions of hydroxyl radical with several alkanes and cycloalkanes. , 2006, The journal of physical chemistry. A.

[42]  Stephen J. Klippenstein,et al.  Transition State Theory for Multichannel Addition Reactions: Multifaceted Dividing Surfaces , 2003 .

[43]  Thomas A. Litzinger,et al.  The experimental evaluation of a methodology for surrogate fuel formulation to emulate gas phase combustion kinetic phenomena , 2012 .

[44]  Bryan W. Weber,et al.  Experiments and modeling of the autoignition of methylcyclohexane at high pressure , 2014, 1706.02996.

[45]  Pierre-Alexandre Glaude,et al.  The autoignition of cyclopentane and cyclohexane in a shock tube , 2007 .

[46]  W. Green,et al.  New pathways for formation of acids and carbonyl products in low-temperature oxidation: the Korcek decomposition of γ-ketohydroperoxides. , 2013, Journal of the American Chemical Society.

[47]  W. Tsang.  Mechanism and rate constants for the decomposition of 1-pentenyl radicals. , 2006, The journal of physical chemistry. A.

[48]  C. McEnally,et al.  Experimental study of fuel decomposition and hydrocarbon growth processes for cyclohexane and related compounds in nonpremixed flames , 2004 .

[49]  Yingjia Zhang,et al.  Shock Tube and Kinetic Modeling Study of Cyclopentane and Methylcyclopentane , 2015 .

[50]  William J. Pitz,et al.  Oxidation and combustion of the n-hexene isomers: A wide range kinetic modeling study , 2008 .

[51]  Henry J. Curran,et al.  Rate constant estimation for C1 to C4 alkyl and alkoxyl radical decomposition , 2006 .

[52]  Paulo M. Nunes,et al.  Energetic differences between the five- and six-membered ring hydrocarbons: strain energies in the parent and radical molecules. , 2008, The Journal of organic chemistry.

[53]  Donald R Burgess,et al.  Shock tube study of the decomposition of cyclopentyl radicals , 2011 .

[54]  J. Bott,et al.  A shock tube study of the reaction of the hydroxyl radical with H2, CH4, C-C5H10, and i-C4H10 , 1989 .

[55]  F. P. Tully,et al.  Hydrogen-atom abstraction from alkanes by hydroxyl radical. 6. Cyclopentane and cyclohexane , 1987 .

[56]  Robert Shaw,et al.  A compilation of kinetic parameters for the thermal degradation of n‐alkane molecules , 1980 .

[57]  C. Taatjes,et al.  Infrared Frequency-Modulation Probing of Product Formation in Alkyl + O2 Reactions: III. The Reaction of Cyclopentyl Radical (c-C5H9) with O2 between 296 and 723 K , 2001 .

[58]  R. Atkinson.  Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes , 2003 .

[59]  Charles J. Mueller,et al.  Recent progress in the development of diesel surrogate fuels , 2009 .

[60]  S. Mani Sarathy,et al.  Elucidating reactivity regimes in cyclopentane oxidation: Jet stirred reactor experiments, computational chemistry, and kinetic modeling , 2017 .

[61]  John M. Simmie,et al.  Modeling and Experimental Investigation of Methylcyclohexane Ignition in a Rapid Compression Machine , 2005 .

[62]  A. Miyoshi,et al.  Systematic computational study on the unimolecular reactions of alkylperoxy (RO2), hydroperoxyalkyl (QOOH), and hydroperoxyalkylperoxy (O2QOOH) radicals. , 2011, The journal of physical chemistry. A.

[63]  Hans-Heinrich Carstensen,et al.  High-pressure rate rules for alkyl + O2 reactions. 2. The isomerization, cyclic ether formation, and β-scission reactions of hydroperoxy alkyl radicals. , 2012, The journal of physical chemistry. A.

[64]  T. Dransfield,et al.  Absolute rate constants for the reaction of OH with cyclopentane and cycloheptane from 233 to 351 K. , 2012, The journal of physical chemistry. A.

[65]  A. Dean,et al.  Reactions of allylic radicals that impact molecular weight growth kinetics. , 2015, Physical chemistry chemical physics : PCCP.

[66]  Zhuangjie Li,et al.  Kinetics study of the reaction of OH radicals with C5-C8 cycloalkanes at 240-340 K using the relative rate/discharge flow/mass spectrometry technique. , 2013, The journal of physical chemistry. A.