Get 20M+ Full-Text Papers For Less Than $1.50/day. Start a 14-Day Trial for You or Your Team.

Learn More →

The effect of carbon-chain oxygenation in the carbon-carbon dissociation

The effect of carbon-chain oxygenation in the carbon-carbon dissociation Currently, there is a trend of moving away from the use of fossil fuels to the use of biofuels. This modification changes the molecular structure of gasoline and diesel constituents, which should impact pollutant emissions and engine efficiency. An important property of automotive fuels is the resistance to autoignition. The goal of the present work is to evaluate thermochemical and kinetic parameters that govern the carbon-carbon bond dissociation and relate these parameters, in conjunction with molecular properties, to autoignition resistance. Three model reactions were investigated in the present work: dissociation of ethane, ethanol, and ethanal. All studies were conducted at the multiconfigurational level of theory, and the rate coefficients were evaluated from 300 to 2000 K. The comparison of dissociation energies and Arrhenius expressions indicates that autoignition resistance is related to the kinetic control of dissociation reactions and it is possible to relate the higher octane number of ethanol based fuels to the kinetics parameters of carbon-carbon bond fission. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Journal of Molecular Modeling Springer Journals

The effect of carbon-chain oxygenation in the carbon-carbon dissociation

Download PDF
10 pages

Loading next page...
 
/lp/springer-journals/the-effect-of-carbon-chain-oxygenation-in-the-carbon-carbon-mSoCoJmtkn
Publisher
Springer Journals
Copyright
Copyright © 2018 by Springer-Verlag GmbH Germany, part of Springer Nature
Subject
Chemistry; Computer Applications in Chemistry; Molecular Medicine; Computer Appl. in Life Sciences; Characterization and Evaluation of Materials; Theoretical and Computational Chemistry
ISSN
1610-2940
eISSN
0948-5023
DOI
10.1007/s00894-018-3693-9
pmid
29858662
Publisher site
See Article on Publisher Site

Abstract

Currently, there is a trend of moving away from the use of fossil fuels to the use of biofuels. This modification changes the molecular structure of gasoline and diesel constituents, which should impact pollutant emissions and engine efficiency. An important property of automotive fuels is the resistance to autoignition. The goal of the present work is to evaluate thermochemical and kinetic parameters that govern the carbon-carbon bond dissociation and relate these parameters, in conjunction with molecular properties, to autoignition resistance. Three model reactions were investigated in the present work: dissociation of ethane, ethanol, and ethanal. All studies were conducted at the multiconfigurational level of theory, and the rate coefficients were evaluated from 300 to 2000 K. The comparison of dissociation energies and Arrhenius expressions indicates that autoignition resistance is related to the kinetic control of dissociation reactions and it is possible to relate the higher octane number of ethanol based fuels to the kinetics parameters of carbon-carbon bond fission.

Journal

Journal of Molecular Modeling – Springer Journals

Published: Jun 1, 2018

References

  • A review of emission products from bioethanol and its blends with gasoline. Background for new guidelines for emission control
    Manzetti, S; Andersen, O
  • Comparison of combustion characteristics of n-butanol/ethanol-gasoline blends in a HCCI engine
    He, BQ; Bin, LM; Zhao, H
  • Biofuel combustion chemistry: from ethanol to biodiesel
    Kohse-Höinghaus, K; Oßwald, P; Cool, TA
  • Ignition and combustion characteristics of various biodiesel fuels (BDFs)
    Oo, CW; Shioji, M; Nakao, S
  • Bioethanol and gasoline premixing effect on combustion and emission characteristics in biodiesel dual-fuel combustion engine
    Park, SH; Yoon, SH; Lee, CS
  • Effect of ethanol-gasoline blend on NOx emission in SI engine
    Masum, BM; Masjuki, HH; Kalam, MA
  • The effect of compression ratio on the performance, emissions and combustion of an SI (spark ignition) engine fueled with pure ethanol, methanol and unleaded gasoline
    Balki, MK; Sayin, C
  • The effect of ethanol blending on mixture formation, combustion and soot emission studied in an optical DISI engine
    Storch, M; Hinrichsen, F; Wensing, M
  • Optimization of performance and exhaust emission parameters of a SI (spark ignition) engine with gasoline–ethanol blended fuels using response surface methodology
    Najafi, G; Ghobadian, B; Yusaf, T
  • Ethanol-fueled low temperature combustion: a pathway to clean and efficient diesel engine cycles
    Asad, U; Kumar, R; Zheng, M; Tjong, J
  • Gaseous and particulate matter emissions of biofuel blends in dual-injection compared to direct-injection and port injection
    Daniel, R; Xu, H; Wang, C
  • Reduction of fine particulate matter by blending lignite with semi-char in a down-fired pulverized coal combustor
    Huang, Q; Li, S; Li, G
  • Impact of ethanol containing gasoline blends on emissions from a flex-fuel vehicle tested over the worldwide harmonized light duty test cycle (WLTC)
    Suarez-Bertoa, R; Zardini, AA; Keuken, H; Astorga, C
  • Study of the knocking propensity of 2,5-dimethylfuran-gasoline and ethanol-gasoline blends
    Rothamer, DA; Jennings, JH
  • Experimental and modeling study on ignition delay times of dimethyl ether/ n -butane blends at a pressure of 2.0 MPa
    Jiang, X; Zhang, Y; Man, X
  • Flame front analysis of ethanol, butanol, iso-octane and gasoline in a spark-ignition engine using laser tomography and integral length scale measurements
    Aleiferis, PG; Behringer, MK
  • Size distribution, chemical composition and oxidation reactivity of particulate matter from gasoline direct injection (GDI) engine fueled with ethanol-gasoline fuel
    Luo, Y; Zhu, L; Fang, J
  • Terpineol as a novel octane booster for extending the knock limit of gasoline
    Vallinayagam, R; Vedharaj, S; Naser, N
  • Effects of direct injection timing of ethanol fuel on engine knock and lean burn in a port injection gasoline engine
    Zhuang, Y; Hong, G
  • The engine knock analysis - an overview
    Zhen, X; Wang, Y; Xu, S
  • Chemical kinetics of the high pressure oxidation of n-butane and its relation to engine knock
    Pitz, WJ; Westbrook, CK
  • What do we know about the iconic system CH 3 + CH 3 + M ↔ C 2 H 6 + M?
    Golden, BDM
  • Pipek-Mezey localization of occupied and virtual orbitals
    Høyvik, I-M; Jansik, B; Jørgensen, P
  • A fast intrinsic localization procedure applicable for a b i n i t i o and semiempirical linear combination of atomic orbital wave functions
    Pipek, J; Mezey, PG
  • The ORCA program system
    Neese, F
  • Master equation methods for multiple well systems: application to the 1-,2-pentyl system
    Robertson, SH; Pilling, MJ; Jitariu, LC; Hillier, IH
  • Master equation modeling of the unimolecular decompositions of hydroxymethyl (CH2OH) and methoxy (CH3O) radicals to formaldehyde (CH2O) + H
    Dames, EE; Golden, DM
  • A theoretical study of three gas-phase reactions involving the production or loss of methane cations
    Baptista, L; Silveira, EF
  • Evaluation of data for atmospheric models: master equation/RRKM calculations on the combination reaction, BrO + NO2 → BrONO2, a conundrum
    Walsh, R; Golden, DM
  • Kinetics of the chemically activated HSO5 radical under atmospheric conditions -- a master-equation study
    González-García, N; Olzmann, M
  • Theoretical study of the gas-phase ozonolysis of [small beta]-pinene (C10H16)
    Nguyen, LT; Peeters, J; Vereecken, L
  • Multiple-well, multiple-path unimolecular reaction systems. II. 2-methylhexyl free radicals
    Barker, JR; Ortiz, NF
  • Electronic spectra and electronic structure of polyatomic molecules
    Herzberg, G
  • Solid state and gas infrared spectra and normal coordinate analysis of 5 isotopic species of acetaldehyde
    Hollenstein, H; Günthard, HH
  • Rotational isomerism of ethanol and matrix isolation infrared spectroscopy
    Coussan, S; Bouteiller, Y; Perchard, JP; Zheng, WQ
  • Bioethanol-gasoline fuel blends: exhaust emissions and morphological characterization of particulate from a moped engine
    Seggiani, M; Prati, MV; Costagliola, MA
  • Combustion efficiency and engine out emissions of a S.I. Engine fueled with alcohol/gasoline blends
    Costagliola, MA; Simio, L; Iannaccone, S; Prati, MV
  • Predicting the Cetane number of biodiesel fuels from their fatty acid methyl Ester composition
    Mishra, S; Anand, K; Mehta, PS
  • Combustion of fat and vegetable oil derived fuels in diesel engines
    Graboski, MS; McCormick, RL
  • Determination of cetane number of biodiesel and it’s influence on physical properties
    Sivaramakrishnan, K; Ravikumar, P
  • Bond cleavage during Isobutanol thermal decomposition and the breaking of C–C bonds in alcohols at high temperatures
    Rosado-Reyes, C; Tsang, W
  • CASPT2 investigation of ethane dissociation and methyl recombination using canonical variational transition state theory
    Li, H; Chen, B-Z; Huang, M-B
  • Evaluated kinetic data for combustion modeling. Supplement I
    Baulch, DL; Cobos, CJ; Cox, RA
  • Rate constants for the thermal decomposition of ethanol and its bimolecular reactions with OH and D: reflected shock tube and theoretical studies
    Sivaramakrishnan, R; Su, MC; Michael, JV
  • Evaluation of laboratory kinetics and photochemical data for atmospheric chemistry applications
    RA, C
  • Unimolecular reaction dynamics. Theory and experiments
    Baer, T; Hase, WL
  • A reduced chemical kinetic model for HCCI combustion of primary reference fuels in a rapid compression machine
    Tanaka, S; Ayala, F; Keck, JC
  • Fundamental features of hydrocarbon autoignition in a rapid compression machine
    Griffiths, JF; Halford-Maw, PA; Rose, DJ
  • Pyrolysis of ethanol: a shock-tube/TOF-MS and modeling study
    Kiecherer, J; Bänsch, C; Bentz, T; Olzmann, M
  • Decomposition of acetaldehyde: experiment and detailed theory
    Gupte, KS; Kiefer, JH; Tranter, RS
  • Shock-tube and modeling study of acetaldehyde pyrolysis and oxidation
    Yasunaga, K; Kubo, S; Hoshikawa, H
  • Shock-tube study of the thermal decomposition of CH 3 CHO and CH 3 CHO + H reaction
    Bentz, T; Striebel, F; Olzmann, M
  • The dissociation of diacetyl: a shock tube and theoretical study
    Yang, X; Jasper, AW; Kiefer, JH; Tranter, RS
  • A study of ethane decomposition in a shock tube using laser absorption of CH3
    Davidson, DF; Rosa, MD; Hanson, RK; Bowman, CT
  • Shock tube study on the thermal decomposition of ethanol
    Wu, C-W; Matsui, H; Wang, N-S; Lin, MC
  • Experimental and numerical studies of ethanol decomposition reactions
    Li, J; Kazakov, A; Dryer, FL
  • Effect of compression ratio on the emission, performance and combustion characteristics of a gasoline engine fueled with iso-butanol/gasoline blends
    Sayin, C; Balki, MK