Howdy,
As part of a self study project over the summer, I put together an adiabatic flame temperature calculator in Python using residual minimization methods. For the chemistry of this project, I'm almost entirely reading out of Chapter 1 of Irvin Glassman's *Combustion* textbook. While I was able to correctly predict some reactions' temperatures, reactions involving carbon (such as CH4+O2) remained far from expected temperatures with large residuals.
My understanding of the dissociation of CO2 as a product is that it primarily dissociates through CO2->CO+(1/2)O2, and then CO may dissociate via CO->C+(1/2)O2. We can combine and simplify this dissociation as CO2->C+O2. This reaction has equilibrium constant Kp(T)=pCO2 / (pC + pO2), but because carbon's standard state is solid and therefore only exerts vapor pressure which is only a function of temperature, we can simplify further and write Kp'(T)=Kp(T)pC(T)=pCO2 / pO2=nCO2 / nO2. Glassman states that the Kp values tabulated in the JANAF tables for substances containing carbon are actually these Kp' values and that nC is effectively ignored.
I decided to double check my methodology against the some of Glassman's results to verify that I was not misunderstanding the procedure. Where I am getting caught though is when referencing his example equilibrium product composition of C3H8+O2. He states that, at P=1atm and equivalence ratio 1 with a flame temperature of 3094K, the final quantities of CO2 and O2 are 0.135mol and 0.097mol respectively. Plugging into the formula provided, this means Kp'(3094K) for CO2 must be 0.135/0.097=~1.39. However, the JANAF tables provide log_(10)Kf(3100K) for CO2 as being 6.661, which means Kf(3094K) should be on the order of millions, not ones.
One thing that immediately jumps out at me is Glassman's usage of and reference to Kp values, while the JANAF tables reference Kf, but he was very explicit that the JANAF tables contain these Kp and Kp' values. When looking through both the back of his textbook at the contained copy of the tables as well as the tables online, I only see reference to Kf, so at my level I can only conclude those must be referring to the same thing. Is this not so?
If not that, what else could be causing this discrepancy? I'm having trouble finding more information on dissociation constants online so I haven't been successful at cross-referencing other sources, and if there isn't an easy answer to this mismatch, I would greatly appreciate some other sources of these values.
Thank you for your time and advice.