Thermal ignition revisited with two-dimensional molecular dynamics: role of fluctuations in activated collisions

TL;DR

This study uses two-dimensional molecular dynamics simulations to explore how fluctuations influence thermal ignition in gases, revealing two distinct non-equilibrium regimes with different ignition behaviors and times.

Contribution

It provides new insights into the role of molecular fluctuations in thermal ignition, especially in non-equilibrium conditions, through detailed 2D molecular dynamics modeling.

Findings

Ignition delay is longer than continuum predictions at low activation energies.

Larger domains exhibit shorter ignition delays at high activation energies.

Results align with experimental observations of low-temperature auto-ignition phenomena.

Abstract

The problem of thermal ignition in a homogeneous gas is revisited from a molecular dynamics perspective. A two-dimensional model is adopted, which assumes reactive disks of type A and B in a fixed area that react to form type C products if an activation threshold for impact is surpassed. Such a reaction liberates kinetic energy to the product particles, representative of the heat release. The results for the ignition delay are compared with those obtained from the continuum description assuming local thermodynamic equilibrium, in order to assess the role played by molecular fluctuations. Results show two regimes of non-equilibrium ignition whereby ignition occurs at different times as compared to that from the continuum description. The first regime is at low activation energies, where the ignition time is found to be higher than that expected from theory for all values of heat release, in agreement with predictions from Prigogine and Xhrouet who attribute this departure to non-equilibrium effects. Results suggest the ignition is spatially homogeneous in this regime. The second regime occurs at high activation energies and sufficiently large heat release values. In this regime, ignition times are found to be dependent on domain size, with larger domains yielding shorter ignition delays than expected. Results for larger systems agree with the expectations by Prigogine and Mahieu, who predict a non-equilibrium reaction rate larger than expected for a homogeneous system in equilibrium. Results yield a large variance for ignition times under these conditions, suggesting a departure from homogeneous combustion. The results obtained are in qualitative agreement with experimental observations of auto-ignition at relatively low temperatures, where hot-spot ignition and associated ignition delays lower than predicted are generally observed.