High-temperature pyrolysis of isoprenoid hydrocarbon p-menthane using ReaxFF molecular dynamics simulation

The pyrolysis chemistry of p-menthane, a promising ?drop-in? fuel of bio-derived isoprenoid hydrocarbon, has not been well understood especially under high temperatures. In this work, the pyrolysis of p-menthane is further investigated using molecular dynamics simulations with the reactive force-field interatomic potential (ReaxFF) under 2600 K. It is found that the scission of isopropyl and the ring-open reaction in the site adjacent to the isopropyl are two predominant initiations of p-menthane decomposition in our simulations. The main generation and consumption channels of important products, such as methane and ethylene, are also tracked by the straightforward scrutinize on simulation trajectories. In addition, a detailed reaction scheme of the hightemperature pyrolysis is proposed. The apparent activation energy calculated from our reactive molecular dynamics simulations in the temperature range from 2200 K to 3000 K is 232 kJ mol- 1, which is reasonably consistent with our experimental result of 225 ? 5 kJ mol- 1. In summary, the simulation results provided by ReaxFF are helpful to explain pyrolysis processes readily, which is the effective verification and extension of previous experimental studies.

Automated summary

The pyrolysis chemistry of p-menthane was investigated using ReaxFF molecular dynamics simulations, revealing that the scission of isopropyl and the ring-open reaction adjacent to isopropyl are key steps in p-menthane decomposition. Important product generation and consumption pathways were tracked, and a detailed reaction scheme was proposed. The apparent activation energy calculated from simulations matched experimental results, demonstrating the effectiveness of using ReaxFF simulations to explain and extend previous experimental studies.