1999
DOI: 10.1021/ja991350s
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The Ionization Energy of CF3:  When Does Entropy Matter in Gas-Phase Reactions?

Abstract: A minor controversy has emerged recently over the value of the ionization energy of the trifluoromethyl radical, CF3. Solid evidence appears to support both high values, IEa ≈ 9.05 eV, and low values, IEa ≈ 8.65 eV. Examining the assumptions made in the analysis of the various experimental results shows that the root of the discrepancy is the role of entropy in low-pressure, gas-phase ion chemistry. The proper treatment of entropy has, itself, been a more fundamental controversy for a long time. In the zero-pr… Show more

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Cited by 29 publications
(41 citation statements)
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References 51 publications
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“…In addition, Irikura 13 has suggested that some of the low values of the AIE (<8.6 eV) from ion-molecule chemical reactions may be in doubt, because entropy effects have been ignored in determining whether such reactions may proceed at a reasonable rate. Our result does not add significantly to this controversy.…”
Section: Discussionmentioning
confidence: 99%
See 1 more Smart Citation
“…In addition, Irikura 13 has suggested that some of the low values of the AIE (<8.6 eV) from ion-molecule chemical reactions may be in doubt, because entropy effects have been ignored in determining whether such reactions may proceed at a reasonable rate. Our result does not add significantly to this controversy.…”
Section: Discussionmentioning
confidence: 99%
“…12,13 It seems unlikely that this method will ever be able to give an accuracy in the DIE better than ca. ± 0.1 eV, when an extrapolation of over 1 eV, as here, is involved.…”
Section: Discussionmentioning
confidence: 99%
“…The experimental results for the first four hydrates have been primarily evaluated in the context of the computed energies (enthalpies) of hydration; for these hydrates, the computed DG 298 values are less favorable due to the entropy of association, but predict the observed hydration. A key issue is whether the exothermicity, DH 298 , or the exoergicity, DG 298 , should be considered in the evaluation of gas-phase reactions [51]. At very low pressures (e.g., \10…”
Section: Absence Of Pentahydratesmentioning
confidence: 99%
“…This analysis is restricted to considerations of enthalpy, and we have ignored possible entropic effects. 15 Entropic factors will oppose the endothermicity for reactions in which there is an increase in the number of species between reactants and products, and we note that for most of the reactions in this study there is either no change or an increase of one or two. However, entropy effects are only likely to be significant if the enthalpy change of a reaction is close to zero.…”
Section: Resultsmentioning
confidence: 60%