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Pre-Particle Chemistry in Soot Formation

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Particulate Carbon

Abstract

Species and reactions involved in the early stages of soot formation prior to the formation of particles have been studied in flat low pressure flames of benzene using a molecular beam mass spectrometer system. In a near-sooting (equivalence ratio φ = 1.8) benzene-oxygen-argon flame, the profiles of molar flux versus distance from the burner for several reactant, intermediate, and product species were calculated from the mole fraction profiles. The flux profiles indicate that CO, C6H6O and C5H6 are early intermediates in the ring destruction process but that C2H2 is not. The flux profiles of C6H6 and C2H2 are consistent with benzene consumption by OH addition and the OH + C6H6 reaction having a much larger rate coefficient than OH + C2H2. A mechanism is outlined for production of C1, C2, C3, C4 and C5 species from benzene that is consistent with the flux profiles of intermediate species. The production of more hydrogenated species from those of low H/C ratio as they diffuse toward the burner surface is discussed.

Relative measurements of high molecular weight material (> 200 amu) as the fuel equivalence ratio is increased past the sooting limit (φ = 1.9) in benzene flames suggest a sequential growth process from polycyclic aromatic hydrocarbons (PAH) in the mass range 120–210 amu to higher molecular weight hydrocarbons and then to soot. A preliminary analysis of reaction mechanisms suggests that the role of the aromatic hydrocarbon is to provide a structure capable of stabilizing by internal aromatic substitution reactions radicals formed from addition of non-aromatic species. The presence of PAH in the oxidation zone of sooting C2H2 flames was also observed and suggests that aromatics may play a similar role in flames of non-aromatic fuels.

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References

  1. J.D. Bittner, and J. B. Howard, Alternative Hydrocarbon Fuels: Combustion and Chemical Kinetics, (C. T. Bowman and J. Birkeland, ed.) Prog. in Astro. and Aero., Vol. 62 (1978), p. 335, AIAA.

    Google Scholar 

  2. H.F. Butze, and R. C. Ehlers, “Effect of Fuel Properties on Performance of a Single Aircraft Turbojet Combustor”, NASA TM-71789, (1975).

    Google Scholar 

  3. W. S. Blazowski, Sixteenth Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, Pa. (1977), p. 1631.

    Google Scholar 

  4. N. J. Friswell, Comb. Sci. and Tech., Vol. 19 (1979), p. 119.

    Article  CAS  Google Scholar 

  5. S. T. Minchin, J. oflnst. Petrol. Tech., Vol. 17 (1931), p. 102.

    CAS  Google Scholar 

  6. A. E. Clarke, T. G. Hunter, and F. H. Garner, J. of Petrol. Tech., Vol. 32 (1946), p. 627.

    CAS  Google Scholar 

  7. R. A Hunt, Jr., Ind. and Eng. Chem., Vol. 45 (1953), p. 602.

    Article  CAS  Google Scholar 

  8. R. L. Schalla, and G. E. McDonald, Ind. and Eng. Chem., Vol. 45 (1953), p. 1497.

    Article  CAS  Google Scholar 

  9. K. P. Schug, Y. Manheimer-Timnat, P. Yoccarino, and I. Glassman, Comb. Sci. and Tech., Vol. 22 (1980), p. 235.

    Article  CAS  Google Scholar 

  10. J. C. Street, and A. Thomas, Fuel, Vol. 34 (1955), p. 4.

    CAS  Google Scholar 

  11. J. J. Macfarlane, F. H. Holderness, and F. S. E. Witcher, Comb. and Flame, Vol. 8 (1964), p. 215.

    Article  Google Scholar 

  12. F. J. Wright, Twelfth Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, PA., (1969), p. 867.

    Google Scholar 

  13. W. S. Blazowski, R. B. Edelman, and P. T. Harsha, “Fundamental Characterization of Alternate Fuel Effects in Continuous Combustion Systems,” Technical Progress Report prepared for DOE Contract EC-77-C-03–1543, (1978).

    Google Scholar 

  14. B. S. Haynes, H. Jander, and H. Gg. Wagner, Ber. Bunsenges. Phys. Chem., Vol. 84 (1980), p. 585.

    Article  CAS  Google Scholar 

  15. G. Prado, J. Jagoda, K. Neoh, and J. Lahaye, Eighteenth Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, PA, (1981), to be published.

    Google Scholar 

  16. S. C. Graham, J. B. Homer, and J. L. J. Rosenfeld, Proc. Roy. Soc. Loud., Vol. 344 (1975), p. 259.

    Article  CAS  Google Scholar 

  17. D. B. Scully, and R. A. Davies, Comb. and Flame, Vol. 9 (1965), p. 185.

    Article  CAS  Google Scholar 

  18. R. A. Davies, D. B. Scully, Comb. and Flame, Vol. 10 (1966), p. 165.

    Article  CAS  Google Scholar 

  19. C. P. Fenimore, G. W. Jones, and G. E. Moore, Sixth Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, PA, (1957), p. 242.

    Google Scholar 

  20. J. D. Bittner, Ph.D thesis, Department of Chemical Engineering, M.I.T., (1980).

    Google Scholar 

  21. J. D. Bittner, and J. B. Howard, Eighteenth Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, PA, (1981), to be published.

    Google Scholar 

  22. R. M. Fristrom, and A. A. Westenberg, “Flame Structure”, McGraw-Hill, N.Y. (1965), pp. 74–80.

    Google Scholar 

  23. D. F. Fairbanks and C. R. Wilke, Ind. and Eng. Chem., Vol. 42, (1950), p. 471.

    Article  CAS  Google Scholar 

  24. R. M. Fristrom, and A. A. Westenberg, op. cit., p. 276.

    Google Scholar 

  25. R. A. Svehla, “Estimated Viscosities and Thermal Conductivities of Gases at High Temperatures,” NASA Technical Report R-132 (1962).

    Google Scholar 

  26. J. O. Hirschfelder, C. F. Curtiss, and R. B. Bird, “Molecular Theory of Gases and Liquids”, J. Wiley and Sons, N.Y., (1964), p. 1112.

    Google Scholar 

  27. L. S. Tee, S. Gotoh, and W. E. Stewart, Ind. and Eng. Chem. Fundam., Vol. 5 (1966), p. 356.

    Article  Google Scholar 

  28. R. C. Reid, J. M. Prausnitz, and T. K. Sherwood, The Properties of Gases and Liquids“, 3rd ed., McGraw-Hill, N.Y., (1977), pp. 24 and 551.

    Google Scholar 

  29. R. S. Brokaw, Ind. Eng. Chem. Process Des. Dev., Vol. 8 (1969), p. 240.

    Article  CAS  Google Scholar 

  30. A. Savitsky and M. J. E. Golay, Anal. Chem., Vol 36 (1964), p. 1627.

    Article  Google Scholar 

  31. J. Steinier, and Y. Termonia, J. Deltour, Anal. Chem., Vol. 44 (1972), p. 1906.

    Article  CAS  Google Scholar 

  32. R. A. Bonanno, P. Kim, J. H. Lee, and R. B. Timmons, J. Chem. Phys., Vol. 57 (1972), p. 1377.

    Article  Google Scholar 

  33. T. M. Sloane, J. Chem. Phys., Vol. 67 (1977), p. 2267.

    Article  CAS  Google Scholar 

  34. G. Boocock, and R. J. Cvetanovic, Can. J. Chem., Vol. 39 (1961), p. 2436.

    Article  CAS  Google Scholar 

  35. P. Kim, J. H. Lee, R.J. Bonanno, and R. B. Timmons, J. Chem. Phys., Vol. 59 (1973), p. 4593.

    Article  CAS  Google Scholar 

  36. M. C. Sauer, Jr., and B. Ward, J. Phys. Chem., Vol. 71 (1967), p. 3971.

    Article  CAS  Google Scholar 

  37. R. A. Perry, R. Atkinson, and J. N. Pitts, Jr., J. Phys. Chem., Vol. 81 (1977), p. 296.

    Article  CAS  Google Scholar 

  38. I. Mani, M. C. Sauer, Jr., Adv. Chem. Ser., Vol. 82 (1968), p. 142.

    Article  Google Scholar 

  39. S. J. Sibener, R. J. Buss, P. Casavecchia, T. Hirooka, and Y. T. Lee, J. Chem. Phys., Vol. 72 (1980), p. 4341.

    Article  CAS  Google Scholar 

  40. R. Cypres, and B. Bettens, Tetrahedron, Vol. 30 (1974), p. 1253.

    Article  CAS  Google Scholar 

  41. F. Slemr, and P. Warneck, Ber. Bunsenge. Phys. Chem., Vol. 79 (1975), p. 152.

    Article  CAS  Google Scholar 

  42. J. R. Kanofsky, D. Lucas, F. Pruss, and D. Gutman, J. Phys. Chem., Vol. 78 (1974), p. 311.

    Article  CAS  Google Scholar 

  43. H. Gg. Wagner, and R. Zellner, Ber. Bunsenges. Phys. Chem., Vol. 76 (1972), p. 518.

    CAS  Google Scholar 

  44. K. H. Homann, W. Schwanebeck, and J. Warnatz, Ber. Bunsenges. Phys. Chem., Vol. 79 (1975), p. 536.

    Article  CAS  Google Scholar 

  45. H. Niki, and B. Weinstock, J. Chem. Phys., Vol. 45 (1966), p. 3468.

    Article  CAS  Google Scholar 

  46. K. H. Homann, J. Warnatz, and C. Wellman, Sixteenth Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, PA, (1977), p. 853.

    Google Scholar 

  47. J. Peeters and G. Mahnen, “Combustion Institute European Symposium”, Academic Press, N.Y., (1973), p. 53.

    Google Scholar 

  48. R. Atkinson and J. N. Pitts, Jr., J. Phys. Chem., Vol. 79 (1975), p. 295.

    Article  CAS  Google Scholar 

  49. A. J. Colussi, J. L. Singleton, R. S. Irwin, and R. J. Cvetanovic, J. Phys. Chem., Vol. 79 (1975), p. 1900.

    Article  CAS  Google Scholar 

  50. D. A. Hansen, R. Atkinson, and J. N. Pitts, Jr., J. Phys. Chem., Vol. 79 (1975), p. 1763.

    Article  CAS  Google Scholar 

  51. F. H. Field, and J. L. Franklin, “Electron Impact Phenomena and the Properties of Gaseous Ions”, Academic Press, N.Y., (1970), pp. 239–522.

    Google Scholar 

  52. S. M. Faist, “Analysis of Stable Species in a Benzene-Oxygen-Argon Laminar Premixed Flame by Chemical and Spectroscopic Techniques: Applications to Soot Formation and Combustion Chamber Deposits”, M.S. thesis, Department of Chemical Engineering, M.I.T., (1979).

    Google Scholar 

  53. D. B. Olson, H. F. Calcote, Eighteenth Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, PA, (1981), to be published.

    Google Scholar 

  54. J. D. Bittner, Comment following paper by P. Michaud, J. L. Delfau, and A. Barassin, Eighteenth Symposium (International) on Combustion, The Combustion Institute, Pits-burgh, PA, (1981), to be published.

    Google Scholar 

  55. P. Michaud, J. L. Delfau, A. Barassin, Eighteenth Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, PA, (1981), to be published.

    Google Scholar 

  56. R. D. Smith, Comb. and Flame, Vol. 35 (1979), p. 179.

    Article  CAS  Google Scholar 

  57. R. D. Smith, J. Phys. Chem., Vol. 83 (1979), p. 1553.

    Article  CAS  Google Scholar 

  58. J. H. Kent, H. Jander, and H. Gg. Wagner, Eighteenth Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, PA, (1981), to be published.

    Google Scholar 

  59. S. W. Benson, “Thermochemical Kinetics”, J. Wiley and Sons, N.Y. (1976).

    Google Scholar 

  60. S. E. Stein, D. M. Golden, and S. W. Benson, J. Phys. Chem. Vol. 81 (1977), p. 314.

    Article  CAS  Google Scholar 

  61. Handbook of Chemistry of Physics“, 60th ed., (R. C. Weast, ed.). CRC Press, Boca Raton, FL, (1979), p. F-231.

    Google Scholar 

  62. M. Cowperthwaite, and S. H. Bauer, J. Chem. Phys., Vol. 36 (1962), p. 1743.

    Article  CAS  Google Scholar 

  63. T. Flitcroft, H. A. Skiner, M. C. Whiting, Trans. Faraday Soc., Vol. 53 (1957), p. 784.

    Article  CAS  Google Scholar 

  64. T. L. Flitcroft, and H. A. Skinner, Trans. Faraday Soc., Vol. 54 (1958), p. 47.

    Article  CAS  Google Scholar 

  65. H.A. Skinner, and A. Snelson, Trans. Faraday Soc., Vol. 55 (1959), p. 404.

    Article  CAS  Google Scholar 

  66. S. E. Stein, and D. M. Golden, J. Org. Chem., Vol. 42 (1977), p. 839.

    Article  CAS  Google Scholar 

  67. M. J. Perkins, in “Free Radicals”, (J. Kochi, ed.), J. Wiley and Sons, N.Y., (1973), p. 231.

    Google Scholar 

  68. J. D. Bittner, J. A. Cole, J. P. Longwell, and J. B. Howard, manuscript in preparation.

    Google Scholar 

  69. B. D. Crittendon, and R. Long, Comb. and Flame, Vol. 20 (1973), p. 359.

    Article  Google Scholar 

  70. K. H. Homann, and H. Gg. Wagner, Eleventh Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, PA, (1967), p. 371.

    Google Scholar 

  71. A. Di Lorenzo, A. D’Alessio, V. Cincotti, S. Masi, P. Menna, and C. Venitozzi, Eighteenth Symposium (International) on Combustion, The Combustion Institute, Pittsburgh, PA, (1981), to be published.

    Google Scholar 

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Authors and Affiliations

  1. Massachusetts Institute of Technology, Cambridge, Massachusetts, USA

    J. D. Bittner & J. B. Howard

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  1. J. D. Bittner
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Editors and Affiliations

  1. Engine Research Department, General Motors Research Laboratories, Warren, Michigan, USA

    Donald C. Siegla (Symposium Cochairman) (Symposium Cochairman)

  2. Physics Department, General Motors Research Laboratories, Warren, Michigan, USA

    George W. Smith (Symposium Cochairman) (Symposium Cochairman)

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Bittner, J.D., Howard, J.B. (1981). Pre-Particle Chemistry in Soot Formation. In: Siegla, D.C., Smith, G.W. (eds) Particulate Carbon. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-6137-5_5

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  • DOI: https://doi.org/10.1007/978-1-4757-6137-5_5

  • Publisher Name: Springer, Boston, MA

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