Previously, I applied the calorimetric method using an exact model, i.e. the "competitive" adsorption model shown by Lylykangas (2004). He also fit his data to a "non-competitive" model shown below, but the parameters for that model were not reported in the dissertation.
The hydrogen adsorption term is insignificant so the above model reduces to the following:
Comparing to the competitive adsorption model, the only difference is the power of the bracketed term in the denominator. In the competitive model used to generate the data for my simulation of the analytical procedure, the power was 2.
Using the inexact non-competitive model, the best fit of the hydrogen flow data is shown in the figure below.
The plot above is the only means the researcher has to evaluate the model unless a sample is taken. However, for this simulation study, we can compare the concentrations from the data with the model.
Conclusion: The method worked very well using an alternative, inexact Langmuir-Hinshelwood model. The results also indicate that some lack-of-fit to the hydrogen flow curve does not necessarily mean that the model obtained cannot be used for design.
Lylykangas (2004) ISBN 951-22-6912-0 (print), 951-22-6913-9 (pdf, available at http://lib.hut.fi/Diss/)