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Group additivity values for the heat of formation of C2–C8 alkanes, alkyl hydroperoxides, and their radicals

Journal Article · · Combustion and Flame
 [1];  [2];  [1];  [2];  [1]
  1. University of Galway (Ireland)
  2. Argonne National Laboratory (ANL), Argonne, IL (United States)
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A set of 58 group additivity values (GAV) for the calculation of the heat of formation is derived from an extensive and accurate database of 192 ab initio heats of formation. The ab initio values are from companion calculations at the CCSD(T)–F12/cc-pVTZ-F12//B2PLYPD3/cc-pVTZ level of theory employing second order connectivity based hierarchy reference reactions with ANL energies for the reference species. This database of 192 species consists of alkanes (RH), alkyl radicals ($$\dot{\text {R}}$$), alkyl hydroperoxides (RO2H), alkyl-peroxy (R$$\dot{\text {O}}$$2) radicals, and hydroperoxy-alkyl ($$\dot{\text {Q}}$$OOH) radicals of all of the isomers of C2–C5 alkane fuels and a select set of C6–C8 isomers. The GAV and ab initio based enthalpies for this dataset show excellent agreement, with an estimated 2σ uncertainty of 0.9 kcal mol–1. Among the 58 GAV terms, 40 are refinements of previously reported terms, while 18 are newly developed. These new GAV terms are mainly non-next-nearest neighbor interactions (NNI) and β-corrections. The inclusion of these new groups significantly improves the accuracy of the GAV estimates of the heats of formation. Finally, the updated GAVs can be used with increased confidence to estimate the heats of formation of combustion relevant hydrocarbons and oxygenated hydrocarbons and their corresponding radicals, which are important in predicting low-temperature chemistry and are critical in the development of accurate chemical kinetic models.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); Science Foundation Ireland (SFI)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
2474893
Alternate ID(s):
OSTI ID: 1998980
Journal Information:
Combustion and Flame, Journal Name: Combustion and Flame Journal Issue: Part 1 Vol. 257; ISSN 0010-2180
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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Figures / Tables (26)

Scheme 1(p. 4)figure Scheme 1
Table 1(p. 4)table Table 1
Table 2(p. 5)table Table 2
Table 3(p. 5)table Table 3
Fig. 1(p. 6)figure Fig. 1
Fig. 2(p. 7)figure Fig. 2
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Table 4(p. 10)table Table 4
Table 5(p. 12)table Table 5
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Table 8(p. 14)table Table 8
Fig. 11(p. 15)figure Fig. 11
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Fig. 14(p. 17)figure Fig. 14
Table 9(p. 17)table Table 9
Fig. 15(p. 18)figure Fig. 15
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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Ab initio
group additivity
heat of formation
low-temperature oxidation
non-next-neighbor interactions