Electron transport in mixtures of liquid methane and ethane

Bakale, G.; Tauchert, Wolfgang; Schmidt, Werner F.

doi:10.1063/1.431168

Cited by 30 publications

(8 citation statements)

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“…Electron mobilities had been measured previously for this system (27). It was not possible, however, to obtain agreement between experimental results and theory with any set of physically realistic parameters.…”

Section: Resultsmentioning

confidence: 92%

Photoelectric determination of V₀ values and electron ranges in some cryogenic liquids

Tauchert¹,

Jungblut²,

Schmidt³

1977

Can. J. Chem.

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Section: Resultsmentioning

confidence: 92%

Photoelectric determination of V₀ values and electron ranges in some cryogenic liquids

Tauchert¹,

Jungblut²,

Schmidt³

1977

Can. J. Chem.

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“…From the slopes of the lines in Figure 6 the volume change of reaction 1 under various conditions can be calculated from AVT = dAGJdP = -RT d In K/dP (7) The volume changes (see Table III) are in the range -80 to -100 cm3/mol. If we assume no change in size of the toluene molecule when it becomes an anion, there are two possible sources of this volume change: a positive volume of the electron in n-hexane and electrostriction of the solvent by the toluene anion.…”

Section: Discussionmentioning

confidence: 99%

Electron attachment to toluene in n-hexane and 2,2-dimethylbutane at high pressure

Itoh¹,

Nishikawa²,

Holroyd³

1993

J. Phys. Chem.

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The effect of dilute concentrations of toluene on the electron mobility in two isomeric hexanes was studied as a function of pressure from 1 bar to 3 kbar and at selected temperatures between 9 and 60 O C . The effect of toluene on the mobility is small at 1 bar but quite large at the higher pressures. The results are interpreted in terms of reversible electron attachment to a toluene species which is the monomer in n-hexane. For this reaction AHr is -1 2.0 kcal/mol in n-hexane at 2.5 kbar. In 2,Zdimethylbutane attachment to a dimeric species is indicated. The volume changes for these attachment reactions are large, between -80 and -100 cm3/mol. In hexane the volume changes are attributed in part to the electrostriction of the solvent by the toluene anion and in part to a positive molar volume of the electron. IntrodllctionElectron attachment to molecules with large negative electron affinity like toluene occurs reversibly in n-pentane as solvent at high pressure.' e-+ toluene * tolueneAlthough not observed in dilute solution at 1 bar, such reactions are favored at high pressure by two energetic factors: namely (i) the enhanced stabilization of the product ion and (ii) the destabilization of the electron in the solvent at high pressure.* These equilibria shift rapidly with pressure because of the very large negative volume changes of reaction (approximately -100 cm3/mol). The polarization energy of the product anion can be estimated from the Born equation and dielectric constant of the solvent. The energy level of the electron in each solvent is not as well-known especially at high pressure. Some guidance is available, however, from recent photoelectric measurements of VO, the quasi-free state energy of the electron, which show that thequasi-free state energy of the electron increases with press~re.~ The present study was done to elucidate the effect of solvent on reaction 1, to investigate the role of the electron energy level, and to learn more about the volume changes in such reactions.In n-hexane the energy level of the electron is expected to be comparable to that in n-pentane and therefore reaction 1 should occur at high pressure. Attachment to toluene, however, was not anticipated to be very important in 2,2-dimethylbutane (DMB) at high pressure based on the following reasoning. The polarization energy of the T anion in DMB is comparable to that in n-pentane. Thus the energetics depend on the ground-state energy of the electron in DMB. The latter energy is reported to be -0.42 eV at 1 bar.2 The ground state in n-hexane is at -0.33 eV at 1 bar? These energies will be higher at high pressure, but if the differenceisatleastasgreat at highpressure, then theequilibrium constant, Kl, should be SO times smaller in DMB than in n-hexane.We havemeasured themobilityoftheelectron indilutesolutions of toluene in n-hexane and 2,2-dimethylbutane at various temperatures as a function of pressure to 3 kbar. The results are very different for these two isomeric hexanes and suggest that at high pressure electrons attach reve...

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“…(16), the electron decay in reaction 2 and regeneration in [4] are the only reactions involving a inonitorable species; consequently, having no mass analysis capability precludes our detailing the intermediates and products specified in [2]- [7]. Therefore, we are limited to a mechanism which involves only electrons: viz.…”

Section: Resultsmentioning

confidence: 99%

“…Within this field of electrons in liquids, techniques have developed from simply measuring the mobilities of electrons (2)(3)(4) to measuring field effects on the electron drift velocity (5)(6)(7), electron recombination and attachment rates (8)(9)(10)(11)(12)(13), and the energy dependence of electron attachment processes (1,14). In this paper we adc!…”

Section: Introductionmentioning

confidence: 99%

Negative ion–molecule reactions in liquid argon following electron capture by N₂O

Bakale¹,

Sowada²,

Schmidt³

1977

Can. J. Chem.

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Electrons produced in liquid argon by a short burst of X rays react readily with dissolved N2O with a bimolecular rate constant of 5.8 × 10−10 cm3/s or 3.5 × 1011 M−1 s−1. The addition of H2 or CO to the Ar/N2O solution results in a fast and slower component in the decay of the electron current. We assume that O− ions are formed in the reaction of electrons with N2O and then react with H2 to give[Formula: see text]or with CO to give[Formula: see text]The addition of CH4 does not regenerate electrons since the reaction[Formula: see text]is thought to occur. Reaction 12 is in agreement with the fact that CO2 does not react with electrons in liquid argon.

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Electron transport in mixtures of liquid methane and ethane

Abstract: The mobility of excess electrons in liquid mixtures of methane and ethane was measured over the entire range of composition at T=111 °K. Field dependent mobilities were observed at higher field strengths. The data are discussed on the basis of the quasifree and localized electron models.

Cited by 30 publications

References 13 publications

Photoelectric determination of V₀ values and electron ranges in some cryogenic liquids

Photoelectric determination of V₀ values and electron ranges in some cryogenic liquids

Electron attachment to toluene in n-hexane and 2,2-dimethylbutane at high pressure

Negative ion–molecule reactions in liquid argon following electron capture by N₂O

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Electron transport in mixtures of liquid methane and ethane

Abstract: The mobility of excess electrons in liquid mixtures of methane and ethane was measured over the entire range of composition at T=111 °K. Field dependent mobilities were observed at higher field strengths. The data are discussed on the basis of the quasifree and localized electron models.

Cited by 30 publications

References 13 publications

Photoelectric determination of V0 values and electron ranges in some cryogenic liquids

Photoelectric determination of V0 values and electron ranges in some cryogenic liquids

Electron attachment to toluene in n-hexane and 2,2-dimethylbutane at high pressure

Negative ion–molecule reactions in liquid argon following electron capture by N2O

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Photoelectric determination of V₀ values and electron ranges in some cryogenic liquids

Photoelectric determination of V₀ values and electron ranges in some cryogenic liquids

Negative ion–molecule reactions in liquid argon following electron capture by N₂O