Thermochemical properties from G3MP2B3 calculations, Set‐2: Free radicals with special consideration of CH2CHC•CH2, cyclo−•C5H5, •CH2OOH, HO•CO, and HC(O)O•

Janoschek, Rudolf; Rossi, Michel J.

doi:10.1002/kin.20035

Cited by 39 publications

(32 citation statements)

References 72 publications

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“…The activation energy we have estimated by direct kinetic experiments is E 1 ≈ 2.3 kJ mol -1 , which basically confirms the assumption of King et al [5]. Therefore, we have re-evaluated the standard enthalpy of formation of acetonyl by taking the experimental data of these authors and making use of our E 1 and auxiliary thermochemical data from recent sources [10], [24], [25], [26]. The recalculation has returned -23 kJ mol -1 for ∆ f H°2 98 (CH 3 COCH 2 ), that is, the very same value as reported by King et al [5].…”

Section: Thermochemical Implicationssupporting

confidence: 81%

Kinetics and mechanism of the reaction of acetonyl radical, CH3C(O)CH2, with Br2

Zügner

Szabó

et al. 2013

Chemical Physics Letters

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The low pressure fast discharge flow method with laser induced fluorescence detection of CH 3 C(O)CH 2 was employed to study the kinetics of the reaction CH 3 C(O)CH 2 + Br 2 → CH 3 C(O)CH 2 Br + Br (1) at 298, 323 and 365 K. The rate coefficient at room temperature is k 1 = (2.33 ± 0.04 (2σ)) × 10 -12 cm 3 molecule -1 s -1 , which increases slightly with increasing temperature. Quantum chemistry (G2) and theoretical rate theory (conventional TST) computations have supplied results in qualitative agreement with experiment. The relatively slow rate of reaction (1) can be due to the resonance stabilization of the acetonyl radical.

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Section: Thermochemical Implicationssupporting

confidence: 81%

Kinetics and mechanism of the reaction of acetonyl radical, CH3C(O)CH2, with Br2

Zügner

Szabó

et al. 2013

Chemical Physics Letters

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“…a The majority of the enthalpies of formation at 298 K for ion and neutral species are taken from standard sources. [29][30][31] Exceptions are more recent experimental values for CF 3 (À466 kJ mol À1 ) and CF þ 3 (406 kJ mol À1 ), 34 c-C 4 F 7 (À1166 kJ mol À1 ) and c-C 4 F þ 7 (À166 kJ mol À1 ), 40 C 3 F 3 (À134 kJ mol À1 ), 33 O(CHF 2 ) 2 (À858 kJ mol À1 ), 46 CF 3 O (À631 kJ mol À1 ) and CF 3 CO (À609 kJ mol À1 ), 47 and C 2 F 4 O (À1004 kJ mol À1 ). 48 b Recombination energy (RE) of reactant ion.…”

Section: Resultsmentioning

confidence: 99%

Threshold photoelectron photoion coincidence spectroscopy and selected ion flow tube cation-molecule reaction studies of cyclic-C4F8

Parkes

Ali

Tuckett

et al. 2006

Phys. Chem. Chem. Phys.

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Using tunable vacuum-UV radiation from a synchrotron, the threshold photoelectron and threshold photoelectron photoion coincidence (TPEPICO) spectra of cyclic-C4F8 in the range 11-25 eV have been recorded. The parent ion is observed very weakly at threshold, 11.60 eV, and is most likely to have cyclic geometry. Ion yield curves and branching ratios have been determined for five fragments. Above threshold, the first ion observed is C3F5+, at slightly higher energy C2F4+, then successively CF+, CF2+ and CF3+ are formed. The dominant ions are C3F5+ and C2F4+, with the data suggesting the presence of a barrier in the exit channel to production of C3F5+ whilst no barrier to production of C2F4+. In complementary experiments, the product branching ratios and rate coefficients have been measured in a selected ion flow tube (SIFT) at 298 K for the bimolecular reactions of cyclic-C4F8 with a large number of atomic and small molecular cations. Below the energy where charge transfer becomes energetically allowed, only one of the ions, CF2+, reacts. Above this energy, all but one of the remaining ions react. Experimental rate coefficients are consistently greater than the collisional values calculated from modified average dipole orientation theory. The inclusion of an additional ion-quadrupole interaction has allowed better agreement to be achieved. With the exception of N+, a comparison of the fragment ion branching ratios from the TPEPICO and SIFT data suggest that long-range charge transfer is the dominate mechanism for reactions of ions with recombination energy between 12.9 and 15.8 eV. For all other ions, either short-range charge transfer or a chemical reaction, involving cleavage and making of new bond(s), is the dominant mechanism.

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“…32,37 Butyl Hydroperoxides, xBuOOH. As before, consideration of the isogeitonic and essentially thermoneutral reaction: nBuOOH + nProH ) nBuOH + nPrOOH yields -202.4 and -202.7 kJ mol -1 based on a ∆H f (nBuOH) of -274.9 ( 0.6 kJ mol -1 at QB3 and APNO levels, respectively.…”

Section: Alkyl Hydroperoxidesmentioning

confidence: 99%

Enthalpies of Formation and Bond Dissociation Energies of Lower Alkyl Hydroperoxides and Related Hydroperoxy and Alkoxy Radicals

et al. 2008

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The enthalpies of formation and bond dissociation energies, D (ROO-H)and D(R-OOH) of alkyl hydroperoxides, ROOH, alkyl peroxy, RO, and alkoxide radicals, RȮ , 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, tert-butyl, isobutyl and sec-butyl. We show that D(ROO-H) ≈ 357, D(RO-OH) ≈ 190 and D(RO-Ȯ ) ≈ 263 kJ mol -1 for all R, whereas both D(R-Ȯ O) and D(R-OOH)strengthen with increasing methyl substitution at the R-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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Thermochemical properties from G3MP2B3 calculations, Set‐2: Free radicals with special consideration of CH₂CHC^•CH₂, cyclo−^•C₅H₅, ^•CH₂OOH, HO^•CO, and HC(O)O^•

Abstract: After a set of 32 free radicals was presented (Int J Chem Kin 34, 550-560, 2002), an additional 60 free radicals (Set-2) were studied and characterized by energy minimum structures, harmonic vibrational wave numbers ω e , moments of inertia I A , I B , and I C , heat capacities C

Cited by 39 publications

References 72 publications

Kinetics and mechanism of the reaction of acetonyl radical, CH3C(O)CH2, with Br2

Kinetics and mechanism of the reaction of acetonyl radical, CH3C(O)CH2, with Br2

Threshold photoelectron photoion coincidence spectroscopy and selected ion flow tube cation-molecule reaction studies of cyclic-C4F8

Enthalpies of Formation and Bond Dissociation Energies of Lower Alkyl Hydroperoxides and Related Hydroperoxy and Alkoxy Radicals

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