Enthalpies of formation and bond dissociation energies of lower alkyl hydroperoxides and related hydroperoxy and alkoxy radicals

John M. Simmie; Gráinne Black; Henry J. Curran; John P. Hinde

doi:10.1021/jp711360z

Enthalpies of formation and bond dissociation energies of lower alkyl hydroperoxides and related hydroperoxy and alkoxy radicals

John M. Simmie
, Gráinne Black
, Henry J. Curran
, John P. Hinde

Research output: Contribution to a Journal (Peer & Non Peer) › Article › peer-review

102 Citations (Scopus)

Abstract

The enthalpies of formation and bond dissociation energies, D(ROO - H), D(RO - OH), D(RO - O), D(R - O₂) and D(R - OOH) of alkyl hydroperoxides, ROOH, alkyl peroxy, RO, and alkoxide radicals, RO, have been computed at CBS-QB3 and APNO levels of theory via isodesmic and atomization procedures for R = methyl, ethyl, n-propyl and isopropyl and n-butyl, ferf-butyl, isobutyl and sec-butyl. We show that D(ROO - H) ≈ 357, D(RO-OH) ≈ 190 and D(RO - O) ≈ 263 kJ mol^-1 for all R, whereas both D(R - OO) and D(R - OOH) strengthen with increasing methyl substitution at the α-carbon but remain constant with increasing carbon chain length. We recommend a new set of group additivity contributions for the estimation of enthalpies of formation and bond energies.

Original language	English
Pages (from-to)	5010-5016
Number of pages	7
Journal	Journal of Physical Chemistry A
Volume	112
Issue number	22
DOIs	https://doi.org/10.1021/jp711360z
Publication status	Published - 5 Jun 2008

Authors (Note for portal: view the doc link for the full list of authors)

Authors
Simmie, JM,Black, G,Curran, HJ,Hinde, JP
Simmie, JM;Black, G;Curran, HJ;Hinde, JP

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10.1021/jp711360z

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title = "Enthalpies of formation and bond dissociation energies of lower alkyl hydroperoxides and related hydroperoxy and alkoxy radicals",

abstract = "The enthalpies of formation and bond dissociation energies, D(ROO - H), D(RO - OH), D(RO - O), D(R - O2) and D(R - OOH) of alkyl hydroperoxides, ROOH, alkyl peroxy, RO, and alkoxide radicals, RO, have been computed at CBS-QB3 and APNO levels of theory via isodesmic and atomization procedures for R = methyl, ethyl, n-propyl and isopropyl and n-butyl, ferf-butyl, isobutyl and sec-butyl. We show that D(ROO - H) ≈ 357, D(RO-OH) ≈ 190 and D(RO - O) ≈ 263 kJ mol-1 for all R, whereas both D(R - OO) and D(R - OOH) strengthen with increasing methyl substitution at the α-carbon but remain constant with increasing carbon chain length. We recommend a new set of group additivity contributions for the estimation of enthalpies of formation and bond energies.",

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year = "2008",

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doi = "10.1021/jp711360z",

language = "English",

volume = "112",

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journal = "Journal of Physical Chemistry A",

issn = "1089-5639",

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T1 - Enthalpies of formation and bond dissociation energies of lower alkyl hydroperoxides and related hydroperoxy and alkoxy radicals

AU - Simmie, John M.

AU - Black, Gráinne

AU - Curran, Henry J.

AU - Hinde, John P.

PY - 2008/6/5

Y1 - 2008/6/5

N2 - The enthalpies of formation and bond dissociation energies, D(ROO - H), D(RO - OH), D(RO - O), D(R - O2) and D(R - OOH) of alkyl hydroperoxides, ROOH, alkyl peroxy, RO, and alkoxide radicals, RO, have been computed at CBS-QB3 and APNO levels of theory via isodesmic and atomization procedures for R = methyl, ethyl, n-propyl and isopropyl and n-butyl, ferf-butyl, isobutyl and sec-butyl. We show that D(ROO - H) ≈ 357, D(RO-OH) ≈ 190 and D(RO - O) ≈ 263 kJ mol-1 for all R, whereas both D(R - OO) and D(R - OOH) strengthen with increasing methyl substitution at the α-carbon but remain constant with increasing carbon chain length. We recommend a new set of group additivity contributions for the estimation of enthalpies of formation and bond energies.

AB - The enthalpies of formation and bond dissociation energies, D(ROO - H), D(RO - OH), D(RO - O), D(R - O2) and D(R - OOH) of alkyl hydroperoxides, ROOH, alkyl peroxy, RO, and alkoxide radicals, RO, have been computed at CBS-QB3 and APNO levels of theory via isodesmic and atomization procedures for R = methyl, ethyl, n-propyl and isopropyl and n-butyl, ferf-butyl, isobutyl and sec-butyl. We show that D(ROO - H) ≈ 357, D(RO-OH) ≈ 190 and D(RO - O) ≈ 263 kJ mol-1 for all R, whereas both D(R - OO) and D(R - OOH) strengthen with increasing methyl substitution at the α-carbon but remain constant with increasing carbon chain length. We recommend a new set of group additivity contributions for the estimation of enthalpies of formation and bond energies.

UR - https://www.scopus.com/pages/publications/46049098434

U2 - 10.1021/jp711360z

DO - 10.1021/jp711360z

M3 - Article

SN - 1089-5639

VL - 112

SP - 5010

EP - 5016

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 22

ER -

Enthalpies of formation and bond dissociation energies of lower alkyl hydroperoxides and related hydroperoxy and alkoxy radicals

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