An Experimental and Theoretical Investigation of 1-Butanol Pyrolysis

Abstract

Bioalcohols are a promising family of biofuels. Among them, 1-butanol has a strong potential as a substitute for petrol. In this manuscript, we report on a theoretical and experimental characterization of 1-butanol thermal decomposition, a very important process in the 1-butanol combustion at high temperatures. Advantage has been taken of a flash pyrolysis experimental set-up with mass spectrometric detection, in which the brief residence time of the pyrolyzing mixture inside a short, resistively heated SiC tube allows the identification of the primary products of the decomposing species, limiting secondary processes. Dedicated electronic structure calculations of the relevant potential energy surface have also been performed and RRKM estimates of the rate coefficients and product branching ratios up to 2,000 K are provided. Both electronic structure and RRKM calculations are in line with previous determinations. According to the present study, the H 2 O elimination channel leading to 1-butene is more important than previously believed. In addition to that, we provide experimental evidence that butanal formation by H 2 elimination is not a primary decomposition route. Finally, we have experimental evidence of a small yield of the CH 3 elimination channel.

Theoretical study on the insertion reaction of CH(X2) into the oh bond in n-C4H9OH

“…Particularly, the calculated C-H bond in the CH radical at the BHandHLYP/6-311++G(3df,2p) level of theory is 1,110 Ǻ agreeing well with the experimental value of 1.120 Ǻ by Huber et al [16]. Similarly, for n-C 4 H 9 OH, our bond lengths, and angles are also in agreement with previous results published by Rosi et al [17] (see Table 1). Thus, the comparisons show that it is appropriate to use the BHandHLYP/6-311++G(3df,2p) method.…”

“…First, the molecular structures of the studied components were optimized by BHandHLYP/6-311++G(3df,2p) method and then compared with experimental or calculated values from the literature [16,17]. The results in Table 1 for the reactants (n-C 4 H 9 OH and CH) show a good agreement with the previously published ones.…”

“…Comparison of geometrical structures of reactants (n-C 4 H 9 OH and CH) calculated with BHandHLYP and the literature[16,17].…”

A Computational Study on the Insertion of N(2D) into a C—H or C—C Bond: The Reactions of N(2D) with Benzene and Toluene and Their Implications on the Chemistry of Titan

“…For all the stationary points, the energy was computed also at the higher level of calculation CCSD(T) [ 36 – 38 ] using the same correlation consistent aug-cc-pVTZ basis set [ 35 ] and the B3LYP/aug-cc-pVTZ optimized geometries, following a well established computational scheme [ 39 – 49 ]. The accuracy of the employed approach, in particular as far as basis set completeness is concerned, has been recently investigated [ 50 ]. Both the B3LYP and the CCSD(T) energies were corrected to 0 K by adding the zero point energy correction computed using the scaled harmonic vibrational frequencies evaluated at B3LYP level.…”