Enthalpies of formation and group additivity of alkyl peroxides and trioxides

Document Type

Article

Publication Date

12-4-1997

Abstract

Alkyl peroxides, trioxides, and the corresponding radicals are important in atmospheric chemistry, photochemical smog formation, and combustion processes, but accurate and widely accepted enthalpy data for these species are not available. In this work we verify enthalpy data for several compounds and derive the corresponding group values for use in the group additivity method. Isodesmic reactions and ab initio calculations (MP4SDTQ/6-31G*//MP2/6-31G* and G2) are used to determine enthalpies of formation for the following compounds (in kcal mol-1): CH3OOH (-31.8), C2H5OOH (-39.9), iPrOOH (iPr = (CH3)2-CH-, -49.0), (CH3)3COOH (tBu = (CH3)3C-, -58.4), (PrOO· (-15.1), tBuCOO· (-25.2), CH3OOCH3 (-31.0), C2H5OOC2H5 (-47.2), iPrOOiPr, (-65.4), tBuOOtBu (-84.2), HOOOH (-23.0), CH3OOOH (-22.2), CH3OOOCH3 (-21.4). Our results on isodesmic reactions indicate that group additivity is an accurate method to estimate enthalpies (ΔHf°298) of alkyl peroxides and trioxides. Bond enthalpies are determined as follows: HOOO-H (82.6), CH3O2-H (86.6), C2H5O2-H (86.1), iPrO2-H (86.0), tBuO2-H (85.3), HOOOH (35.8), CH3O-OCH3 (38.8), CH3OO-OH (34.2), CH3O-OOH (29.6), CH3O-OOCH3 (28.0), iPr-OO (36.6), tBu-OO (37.5). The recommended enthalpy group values of (O/C/O) and (O/O2) are -5.5 and 9.6 kcal mol-1, respectively.

Identifier

0031553236 (Scopus)

Publication Title

Journal of Physical Chemistry A

External Full Text Location

https://doi.org/10.1021/jp972103i

ISSN

10895639

First Page

9505

Last Page

9510

Issue

49

Volume

101

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