The detailed chemical structures of low-pressure premixed laminar flames fueled

by three simple unsaturated

C5H8O2 esters, the methyl crotonate (MC), methyl methacrylate (MMA), and ethyl p
ropenoate
(EPE), are investigated using tunable synchrotron vacuum ultraviolet (VUV) photo
ionization mass spectrometry.
Significant differences in the compositions of key reaction intermediates betwee
n these flames
under similar flame conditions are observed. The results enable further refineme
nt and validation of a
detailed chemical kinetic reaction mechanism, which is largely based on a previo
us model for saturated
esters. Detailed kinetic modeling describes how these differences are related to
molecular structures, leading
to unique fuel destruction pathways for each of these isomers. Meanwhile, the ef
fect of carbon carbon double
bonds on the combustion chemistry of small fatty acid esters is addressed.
The photon energies used in the present experiments
and the photoionization cross sections
used to determine the molecule-specific mole fraction
profiles are provided in Table 1. We estimate
an accuracy of 20% for the major species mole
fraction profiles, but for some intermediates, especially
those with unknown photoionization cross
sections, the error can be as large as a factor of
2 or 3. However, relative comparisons between
the mole fractions in the three flames provide significantly
higher accuracy.
Flame temperatures are measured using laserinduced
fluorescence (LIF) from naturally present
OH in the A X (0 0) transition under flame conditions
unperturbed by the sampling cone [29]. The
resulting error in the flame temperature is about
100 K in the post-flame and reaction zones and
may be larger in the preheat zone due to the
relatively lower OH concentration. The effect of
temperature uncertainties on modeling results
has been illustrated in Reference [10] for flames
of methyl formate with similar conditions studied
here. As in our past studies, no adjustments of the
temperature profiles were made. Species profiles
measured using a probe are often found to require
small spatial shifts to account for the influence of
the probe, and in the present work the modeling
results for species mole fractions were shifted 1
2 mm away from the burner to better match the
experimental results.