Are any reactions fast enough for soot formation?

tl;dr In order to stop soot pollution, we need to know what reactions cause soot to form. We used the computer to work out how fast a variety of different reactions between soot molecules to see what reactions could be forming soot. Most of the reactions are too slow and suggest larger molecules are required. 

Soot continues to be a problem for our climate by warming the atmosphere and melting ice. It also damages our bodies and causes significant health impacts. Some recent studies are coming out showing a strong relationship between polluted areas and places where the COVID-19 virus has taken many lives. For example in 66 administrative regions in Italy, Spain, France and Germany, 78% of COVID-19 deaths occurred in the five most polluted regions. (Ogen 2020). With a recent study based in the USA finding that for every 1 microgram per cubic metre of PM2.5 soot pollution is associated with an 11% increase in COVID-19 death rate? (Wu et al. Sci. Adv. 2020). Frustratingly we are still unable to describe how soot forms at the molecular scale and this is inhibiting our ability to reduce the emission of these toxic pollutants.

In this paper, my coworkers and I were able to run a series of calculations on the computer to systematically compare the speed of many reactions thought to happen in the flame. We refined a table of bond energies that we proposed in a previous paper (see this blog post) and by reordering the grid we found that we could categorise reactions into four main classes depending on the type of reactive site involved. 

Next we computed the reaction rate between each of these bonds using transition state theory. This involved computationally stretching the bonds until they were about to break and then determining the likelihood of a collision between these molecules leading to that transition state and ultimately the product with the bond formed. This allowed for a map of reaction rates versus temperature to be plotted and for the various reactions to be compared. 

Surprisingly we found that for all of the reactions between these small aromatics the reaction rates are too low to explain soot formation. This includes all of the mechanisms proposed to date involving small aromatic molecules found in flames. 

So we looked for various effects that could stabilise and enhance the reactions as the molecules enlarge. We found that for the localised pi-radicals the dispersion forces could enhance the equilibrium constant for dimerisation. It is unknown how this effect will impact the forward and backward rate constants but it is suggestive of an enhancement to the forward rate. 

There is more work to be done to work out whether this stabilisation of the larger localised pi-radical dimers will speed up the reactions to explain soot formation and whether they are in high enough concentration. However, we think the main contribution of this paper is being able to rule out a large number of possible reactions that have previously been proposed for soot formation. This is discussed in more detail in the review article that is currently online as a preprint.