In this study, the thermochemistry of C2-C7 unsaturated hydrocarbons (22 alkene and 6 diene molecules) and 16 allylic and 5 super-allylic radicals is determined using high-accuracy quantum chemistry calculations. In addition, the group additivity values (GAVs) of a total of 19 relevant groups are systematically optimized on the basis of the calculated thermochemistry of species clusters. The M06-2X method using the 6-311++G(d,p) basis set is used for the geometry optimizations, vibrational frequency calculations, and internal rotation scans for lower-frequency modes. The composite compound methods, CBS-APNO, G3, and G4, are utilized to derive the average atomization formation enthalpies. The entropy and temperature-dependent heat capacity values of all species are calculated using statistical thermodynamics in MultiWell. These results are in good agreement with literature data. A GAVs optimization is performed on the basis of a statistical analysis: a Bland-Altman plot, which is employed to visualize the agreement between the results from the quantum chemical calculations and the GA method. It is found that the 298 K entropies of the CD/C2, C/CD2/H2, C/C/CD2/H, and C/CD3/H groups disagree by more than 5 cal K-1 mol-1 compared to existing values, while the values for the ALLYLS and ALLYLT radical groups also differ by ∼2.4 and 4.1 cal K-1 mol-1, respectively. The 298 K formation enthalpies of the C/CD2/H2, C/C/CD2/H, C/CD3/H, and ALLYLT groups are modified by more than 1 kcal mol-1, compared to existing values. The updated GAVs can be used with increased confidence to estimate the thermochemical properties of combustion-relevant unsaturated hydrocarbon molecules and their radicals which are critical for the development of accurate chemical kinetic models describing the pyrolysis and oxidation of hydrocarbon and oxygenated hydrocarbon fuels.
Bibliographical noteGenerated from Scopus record by KAUST IRTS on 2023-10-22
ASJC Scopus subject areas
- Physical and Theoretical Chemistry