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Decomposition Studies of Isopropanol in a Variable Pressure Flow Reactor
Ist Teil von
Zeitschrift für physikalische Chemie (Neue Folge), 2015-06, Vol.229 (6), p.881-907
Ort / Verlag
Munich: De Gruyter Oldenbourg
Erscheinungsjahr
2015
Link zum Volltext
Quelle
De Gruyter journals
Beschreibungen/Notizen
Alternatives to traditional petroleum derived transportation fuels,
particularly alcohols, have been investigated increasingly over the
last 5 years. Isopropanol has received little attention
despite bridging the gap between smaller alcohols (methanol and
ethanol) and the next generation alcohols (butyl alcohols) to be used
in transportation fuels. Previous studies have shown that
decomposition reactions that dehydrate are important in the
high-temperature oxidation of alcohols. Here we report new data on the
dehydration reaction for isopropanol
(
OH → C
+ H
O)
in a Variable Pressure Flow Reactor at 12.5 atm pressure
and temperatures from 976–1000 K. Pyrolysis experiments
are performed in the presence of a radical trapper (1,3,5
trimethyl benzene or toluene) to inhibit secondary reactions of
radicals with the fuel and product species. The recommended rate
constant for the dehydration reaction is determined using an indirect
method along with Latin Hypercube sampling to estimate uncertainties.
Comparison of the rate constant data to previous works show that the
reaction is considerably more rapid than the high level theoretical
predictions of Bui et al. (Bui et al., J. Chem. Phys., 2002). The
dehydration reaction rate for isopropanol is well described by
= 8.52 × 10
exp (− 30, 667/
) with an estimated
uncertainty of
= 0.0195.
The C–C bond fission reaction is also investigated, but
the insensitivity of the decomposition data to this reaction results
in an uncertainty in the determined rate constants to approximately
2 orders of magnitude. Theoretical estimates lie within these
experimental uncertainties.