Nondissociative Electron Attachment to Aromatic Hydrocarbons

Christophorou, L. G.; Blaunstein, R.P.

doi:10.2307/3572726

Cited by 32 publications

(7 citation statements)

References 14 publications

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“…generally speaking, a fast reaction in these liquids. This contrasts with a slow rate reported for the gas phase [22]. In n-hexane at 298 K the rate constants for attachment to styrene and xmethylstyrene are 7.7.…”

Section: Electron Attachmentcontrasting

confidence: 59%

Equilibrium Reactions of Excess Electrons with Aromatics in Non‐polar Solvents

Holroyd¹

1977

Ber Bunsenges Phys Chem

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The excess electron in non‐polar solvents is shown to undergo the reversible reaction: e− + A ⇄ A−, with the solutes (A): triphenylene, phenanthrene, naphthalene, styrene and α‐methylstyrene. This was demonstrated by a pulse conductivity method which permitted measurement of both the attachment and detachment rates. The attachment rate constants are very large, near 1013 mol−1 · l · s−1 in (CH3)4Si and 2,2,4‐trimethylpentane solvents and a little less than 1012 mol−1 · l · s−1 in n‐hexane. The detachment rates are very solvent and temperature dependent, characterized by large pre‐exponential factors (1018 ‐ 1023 s−1) which facilitate the very endothermic detachment reactions. The equilibrium data show that these reactions occur with large decreases in enthalpy (‐67 to −109 kJ/mol) and large decreases in entropy (‐84 to −204 J mol K). The equilibrium constants at 298° increase with electron affinity of the solute and also change with solvent. The results show that the ground state energy of the electron changes from liquid to liquid: for tetramethylsilane ΔHsoln) (e−) = −0.64 eV, for 2,2,4‐trimethylpentane ΔHsoln(e−) = −0.40 eV and for n‐hexane ΔHsoln(e−) = −0.18 eV.

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Section: Electron Attachmentcontrasting

confidence: 59%

Equilibrium Reactions of Excess Electrons with Aromatics in Non‐polar Solvents

Holroyd¹

1977

Ber Bunsenges Phys Chem

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“…N,N-dimethylaniline is more easily ionizable, I 1g = 7.12 eV [33], and perfluoro-n-hexane and 1,4-benzoquinone attaches electrons [34,35]. Both properties are considered for 1-methylnaphthalene, commonly found in naphthenic oils, I 1g = 7.97 eV [33,36,37]. In order to investigate the effect of a dipole moment and the degree of fluorination for an electron-attaching molecule [38], the additive 1,1-difluorocyclopentane was included, which, in contrast to perfluoro-n-hexane, has a non-zero dipole moment in its equilibrium geometry.…”

Section: Liquidsmentioning

confidence: 99%

Effects of additives on prebreakdown phenomena in liquid cyclohexane: I. Streamer initiation

Ingebrigtsen¹,

Lundgaard²,

Åstrand³

2007

J. Phys. D: Appl. Phys.

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Conduction currents and streamer initiation in cyclohexane with various additives have been investigated with fast impulses applied to a point-to-plane gap. The studied additives are perfluoro-n-hexane, N,N-dimethylaniline, 1-methylnaphthalene, di-n-propylether, 1,1-difluorocyclopentane and 1,4-benzoquinone, representing molecules with different electrochemical properties. We have used shadowgraphic imaging and a differential charge-measurement technique with a sensitivity of 0.1 pC to integrate currents induced to the point electrode, below and in the same voltage range where streamers first appeared. Effects on streamer initiation are found only for point anode streamers with the additive 1-methylnaphthalene, requiring higher voltages for initiation. We have observed transient conduction currents of measurable magnitudes in the nano to microampere range for voltages around initiation in all samples with a point anode and in 10 out of 21 samples with a point cathode. For a point anode, the more easily ionizable additives N,N-dimethylaniline and 1-methylnaphthalene induced somewhat larger currents. The results may be considered to support a hypothesis of electron avalanche induced streamer initiation, in that transient currents are induced by the ions left behind by the avalanches that are not sufficiently developed to initiate streamers.

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“…Negative ion reactions are assumed to be negligible, for the formation of anion fragments from 100-eV electron impact has been reported to be several orders of magnitude less likely than positive ion formation.6•15 Although negative molecular ion formation, path iv of reaction 1, has been cited in electrical discharge induced rearrangements of aromatic hydrocarbons at 1 atm pressure,5 the necessity for third body collisional stabilization of such species renders their intermediacy at pressures below 10-3 Torr exceedingly improbable. 28 Cation intermediates are the source of the 2-butenes. Two routes are possible for production of C4H8 from these ions: rearrangement via expulsion of a neutral fragment or neutralization.…”

Section: Discussionmentioning

confidence: 99%