# Why is carbon monoxide the product in reactions that produce high flame temperatures?

I was looking at substances that produce the highest flame temperatures upon combustion. I note that the equations for combustion are producing carbon monoxide rather than carbon dioxide.

$$\ce{(CN)2 + O2 -> 2CO + N2}$$

Why isn't carbon dioxide produced? Why doesn't the production of carbon dioxide give a hotter flame? It seems that a higher flame temperature would be generated by complete combustion. My thinking is that the heat of formation of carbon dioxide is around −400 kJ/mol while the heat of formation of carbon monoxide is around −100 kJ/mol so the additional heat released by producing carbon dioxide should account for carbon dioxide's greater heat capacity.

This is just a guess... But I wonder if this is due to entropic considerations. In the equation you have written, there are two molecules of gas getting converted to three molecules of gas. $\Delta S$ is positive, so it decreases $\Delta G$ as the reaction temperature increases. However, in the reaction $\ce{(CN)2 + 2 O2 = 2 CO2 + N2}$ you have an equal number of gas molecules, so the entropic component of $\Delta G$ will be small.

I'm not really sure why that would matter. At very high temps, the first reaction will presumably have a very large, negative free energy. Of course, the $\Delta G$ for the $\ce{CO2}$ reaction is most likely negative, so you might have to control the feed stoichiometry carefully to ensure that you are getting only the first reaction.

EDIT:

I got the $\Delta G$ values from the NIST-JANAF website, and it doesn't look like the free energy for these reactions is much different at 4000 K.

$\Delta_f G_{(CN)_2}^{0} = 136.036\ \mathrm{kJ\ mol^{-1}}$

$\Delta_f G_{CO}^{0} = -446.485\ \mathrm{kJ\ mol^{-1}}$

$\Delta_f G_{CO_2}^{0} = -393.183\ \mathrm{kJ\ mol^{-1}}$

$\Delta G_{rxn1}^{0} = -1029.005\ \mathrm{kJ\ mol^{-1}}$

$\Delta G_{rxn2}^{0} = -922.397\ \mathrm{kJ\ mol^{-1}}$

EDIT 2:

So, I just read one of the original papers on this type of flame, and it sounds like the thermal stability of the products is an issue as well. I take it that at these very high temperatures, some of the energy can be transferred to bond-breaking processes, which would lower the total flame temperature. $\ce{CO}$ and $\ce{N2}$ have very strong covalent bonds, so perhaps they do not readily dissociate at these temps.

mainly because in high flame areas, oxygen is used up by the fire more rapidly,thus there is less oxygen available,and thus CO carbon monoxide forms.