DETAILED KINETIC MODELING OF SOOT FORMATION DURING SHOCK-TUBE PYROLYSIS OF C6H6: DIRECT COMPARISON WITH THE RESULTS OF TIME-RESOLVED LASER-INDUCED INCANDESCENCE (LII) AND CW-LASER EXTINCTION MEASUREMENTS

Abstract

The results of calculations of the main parameters of the soot formation process (τ, k f, SY, and r m) carried out with the use of the detailed kinetic model of soot formation are compared with the experimental measurements of these parameters by the continuous-wave (CW)-laser extinction technique and by the time-resolved laser-induced incandescence (LII) method during C6H6 pyrolysis behind reflected shock waves. The detailed kinetic model of soot formation that is developed incorporates the gas-phase mechanisms of acetylene pyrolysis and the mechanisms of formation of polyaromatic hydrocarbons, polyyne molecules, and pure carbon clusters. It combines the H abstraction/C2H2 addition and polyyne pathways of the soot formation process. The formation, growth, and coagulation of soot precursors and soot particles are described within the framework of the discrete Galerkin technique based on an error-controlled expansion of the size distribution function of heterogeneous species into the orthogonal polynomials of a discrete variable (in particular, the number of monomers in the heterogeneous particle) that makes it possible to preserve a discrete character of any elementary transformations of heterogeneous particles and to describe them as elementary chemical reactions for the heterogeneous particles of all sizes. The comparison of the calculations with the experimental measurements of the induction time τ, observable rate of soot particle growth, k f, and soot yield SY by the CW-laser extinction method in the pyrolysis of benzene/argon mixtures in shock-tube experiments clearly demonstrates that the coincidence is quantitatively good for all the main parameters of soot formation. A particular difference between the values of the mean soot particle radius r m experimentally measured by the time-resolved LII technique and calculated with the help of the detailed kinetic model is observed at the low and high temperatures. The results presented demonstrate the current level of the predictive capabilities of the detailed kinetic model of soot formation and the reliability of the time-resolved LII technique for the quantitative determination of the soot particle sizes.