Thermodynamic parameters and group additivity ring corrections for three- to six-membered oxygen heterocyclic hydrocarbons

Document Type

Article

Publication Date

3-27-1997

Abstract

Ideal gas thermodynamic properties (ΔHf°298, S°298, and Cp(T), 300 ≤ T/K ≤ 1500) for 34 cyclic oxygenated hydrocarbons are calculated using the PM3 method, including 12 species on which data are not previously reported. Enthalpies of formation obtained using PM3 are further corrected by -1.642 + 0.882ΔHf°298,PM3, which is obtained by comparison to experimentally-determined ΔHf°298 of 10 cyclic oxygenated hydrocarbon molecules. Enthalpies of formation (ΔHf°298, in kcal mol-1) and entropy (S°298, in cal mol-1 K-1) for 12 species are calculated as follows: -57.24 and 64.10 for 1,3-dioxetane, 25.08 and 61.36 for dioxirene, -4.62 and 68.16 for 1,2-dioxolene, -49.03 and 66.11 for 1,3-dioxolene, 16.72 and 68.21 for 1,2,3-trioxolene, -32.96 and 73.79 for 1,2-dioxane, -11.45 and 75.07 for 3,4-dihydro-1,2-dioxin, -57.44 and 72.62 for 2,4-dihydro-1,3-dioxin, -59.82 and 73.30 for 1,2,4-trioxane, -13.05 and 74.80 for 1,2,3-trioxane, -38.08 and 74.68 for 1,2,4-trioxene, and 9.14 and 74.68 for 1,2,3-trioxane, respectively. ΔH°298 of seven molecules is different from previously estimated values by more than 4 kcal mol-1. Our recommended ΔHf°298 values (in kcal mol-1) are: dioxirane (-2.47), 1,2-dioxetane (-6.38), 2,3-dihydrofuran (-23.52), 2,5-dihydrofuran (-20.90), 1,2-dioxolane (-27.42), 1,2,4-trioxolane (-59.12), and 3,6-dihydro-1,2-dioxin (-9.80). The standard deviations of ΔHf°298 and S°298 values determined in the present study are evaluated as 2.89 kcal/mol and 1.15 cal mol-1 K-1. Group Additivity ring corrections for corresponding heterocyclics are derived.

Identifier

0031101934 (Scopus)

Publication Title

Journal of Physical Chemistry A

External Full Text Location

https://doi.org/10.1021/jp9629497

ISSN

10895639

First Page

2471

Last Page

2477

Issue

13

Volume

101

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