Kinetic Model Completeness
Kinetic Model Completeness
Kinetic Model Completeness
Note that this definition of complete does NOT assume that the rate constants or any
other parameters in the model are correct, just that the reactions excluded from the model
are indeed negligible.
If you believe you can list all possible reactions of the species in the model, a necessary
condition for a model to be complete is that the rates of these reactions to form species
not included in the model must be smaller than some error tolerance; this approach was
introduced by R.G. Susnow et al. (1997). However, this condition is not sufficient: e.g.
one of the minor neglected species could be a catalyst or catalyst poison with a very big
influence on the kinetics at very low concentrations. If the kinetics are strictly linear you
can show that this necessary condition is sufficient (Matheu et al. 2002, 2003); an
important example of strictly linear kinetics are the ordinary master equations used to
compute pressure-dependent reaction rates.
Of course, you usually do not know all the possible reactions. But for purposes of kinetic
model reduction one usually assumes that the initial “full” model is complete; you are
satisfied if the reduced model reproduces the full model to within some error tolerances
under some reaction conditions.
Sensitivity Analyses
A. Definitions of Sensitivities
Suppose you have a model you think is complete at some reaction condition, and you
have some estimates for k and Yo so you can numerically solve
The derivatives in this expansion are sometimes called the sensitivities, though – watch
out! - in practice what are usually reported are the corresponding unitless normalized
sensitivities:
One would often like to know the “Green’s function sensitivity” ∂yi(t)/∂ym(t’) i.e. how
much species i at time t would have changed if a little bit of species m was added at time
t’. This can be computed as an ‘initial concentration sensitivity’ by setting to=t’ and
Yo=Y(t’). However, it is usually impractical to do this for many values of t’.
The instantaneous sensitivities do not depend on the history of the system, they will be
the same numbers regardless of how the system got to its present state Y.
Finally, sensitivities are partial derivatives, so it is important to know what other
variables are being held constant – you can get very different numerical values depending
on what you hold constant. In particular, it is important to know whether the
thermochemistry is being held constant, or whether all the forward and reverse rates are
individually being held constant. The former is generally preferred since you are usually
more confident in the thermochemical parameter values than the kinetic parameters, and
also there are usually fewer thermochemical parameters than reverse rate constants.
(Though if you are highly uncertain about the thermochemistry of some of your species,
you will also be interested in the sensitivity to those thermochemical parameters!). If the
forward and reverse rates are treated separately, it is very important to look at
sensitivities with respect to both the forward and the corresponding reverse rate
simultaneously: if they are opposite in sign and nearly equal in magnitude, it means you
are really sensitive to the thermochemistry, not the kinetics. (This usually happens when
that reaction is fast and nearly equilibrated.)
B. Computing Sensitivities
The other sensitivities are pretty hard to compute, they all require solving rather large
systems of differential equations. For example:
defining Sin(t) = dyi(t)/dDn evaluated on the reference trajectory Y(t) we can rewrite this:
Flux Analyses
It is often very helpful to examine the rates at which each of the reactions in the system
are proceeding. In particular, you will want to know which reactions have high net rates.
By considering the forward and reverse rates separately, you can also identify the
reactions which are in quasi-equilibrium. Often only the reactions which have high net
rates, high sensitivities, or which are quasi-equilibrated really matter for the kinetics.
Almost certainly you cannot model the system correctly if you leave out a reaction with a
high net rate or a high sensitivity.
Very often it is interesting to know which reactions contribute the most to the
instantaneous formation or destruction of a key species. Often a species will be involved
in dozens of reactions, but only three or four have significant net rates. CHEMKIN will
make these net rate plots for you.
A problem with net rates is that all the species in quasi-steady-state, and all the fast
reactions which are nearly equilibrated, will have net rates near zero. It is therefore often
interesting to look at the formation and destruction rates or the forward and reverse rates
separately.