TY - JOUR
T1 - A computational study on the kinetics of pyrolysis of isopropyl propionate as a biodiesel model
T2 - DFT and ab initio investigation
AU - Shiroudi, Abolfazl
AU - Hirao, Kimihiko
AU - Yoshizawa, Kazunari
AU - Altarawneh, Mohammednoor
AU - Abdel-Rahman, Mohamed A.
AU - El-Meligy, Asmaa B.
AU - El-Nahas, Ahmed M.
N1 - Publisher Copyright:
© 2020 Elsevier Ltd
PY - 2020/12/1
Y1 - 2020/12/1
N2 - This work reports a computational kinetic study on the pyrolysis of isopropyl propionate (IPP) as a biodiesel model using density functional theory (DFT), namely ωB97XD and M06-2X levels. The obtained data are compared with the benchmark CBS-QB3 results. The calculated energy profiles have been supplemented with calculations of rate coefficients and branching ratios over the temperature range 563–651 K and under atmospheric pressure and in the fall-off regime was determined using transition state theory (TST) and statistical Rice-Ramsperger-Kassel-Marcus (RRKM). The obtained results reveal that the formation of propionic acid and propene is the most predominant path both thermodynamically and kinetically. However, production of other species is unlikely to occur except at elevated temperatures, with the hemolytic bond cleavage reactions aren't competitive under the applied temperature range. Comparison with linear methyl and ethyl esters indicates faster reactions for IPP. A good agreement with the available experimental findings has been found. Consistent with higher barrier heights, pressures P > 10−4 bar are necessary to achieve the high-pressure (HP) limit.
AB - This work reports a computational kinetic study on the pyrolysis of isopropyl propionate (IPP) as a biodiesel model using density functional theory (DFT), namely ωB97XD and M06-2X levels. The obtained data are compared with the benchmark CBS-QB3 results. The calculated energy profiles have been supplemented with calculations of rate coefficients and branching ratios over the temperature range 563–651 K and under atmospheric pressure and in the fall-off regime was determined using transition state theory (TST) and statistical Rice-Ramsperger-Kassel-Marcus (RRKM). The obtained results reveal that the formation of propionic acid and propene is the most predominant path both thermodynamically and kinetically. However, production of other species is unlikely to occur except at elevated temperatures, with the hemolytic bond cleavage reactions aren't competitive under the applied temperature range. Comparison with linear methyl and ethyl esters indicates faster reactions for IPP. A good agreement with the available experimental findings has been found. Consistent with higher barrier heights, pressures P > 10−4 bar are necessary to achieve the high-pressure (HP) limit.
KW - DFT
KW - Isopropyl propionate
KW - Kinetics
KW - Pyrolysis
KW - RRKM
KW - Thermochemistry
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U2 - 10.1016/j.fuel.2020.118798
DO - 10.1016/j.fuel.2020.118798
M3 - Article
AN - SCOPUS:85089001169
SN - 0016-2361
VL - 281
JO - Fuel
JF - Fuel
M1 - 118798
ER -