Initiation reactions in the high temperature decomposition of styrene

The thermal decomposition of styrene was investigated in a combined experimental, theory and modeling study with particular emphasis placed on the initial dissociation reactions. Two sets of shock tube/time-of-flight mass spectrometry (TOF-MS) experiments were performed to identify reaction products and their order of appearance. One set of experiments was conducted with a miniature high repetition rate shock tube at the Advanced Light Source at Lawrence Berkeley National Laboratory using synchrotron vacuum ultraviolet photoionization. The other set of experiments was performed in a diaphragmless shock tube (DFST) using electron impact ionization. The datasets span 1660-2260 K and 0.5-12 atm. The results show a marked transition from aromatic products at low temperatures to polyacetylenes, up to C₈H₂, at high temperatures. The TOF-MS experiments were complemented by DFST/LS (laser schlieren densitometry) experiments covering 1800-2250 K and 60-240 Torr. These were particularly sensitive to the initial dissociation reactions. These reactions were investigated theoretically and revealed the dissociation of styrene to be a complex multichannel process with strong pressure and temperature dependencies that were evaluated with multi-well master equation simulations. Simulations of the LS data with a mechanism developed in this work are in excellent agreement with the experimental data. From these simulations, rate coefficients for the dissociation of styrene were obtained that are in good agreement with the theoretical predictions. The simulation results also provide fair predictions of the temperature and pressure dependencies of the products observed in the TOF-MS studies. Prior experimental studies of styrene pyrolysis concluded that the main products were benzene and acetylene. In contrast, this study finds that the majority of styrene dissociates to create five styryl radical isomers. Of these, α-styryl accounts for about 50% with the other isomers consuming approximately 20%. It was also found that C-C bond scission to phenyl and vinyl radicals consumes up to 25% of styrene. Finally the dissociation of styrene to benzene and vinylidene accounts for roughly 5% of styrene consumption. Comments are made on the apparent differences between the results of this work and prior literature.