Kinetics of ionic conductance. Part 1.—Energies of activation and the constant volume principle

Brummer, S. B.; Hills, G. J.

doi:10.1039/tf9615701816

Cited by 96 publications

(33 citation statements)

References 1 publication

(3 reference statements)

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“…The dielectric constants for EtBr and EtC1 are nearly the same, but p(EtBr) > p(EtC1), which shows more directly the importance of viscosity since n(EtBr) > ~(EtC1). Other publications have also stressed the role of viscosity in low-temperature solution resistance (1,42).…”

Section: Resultsmentioning

confidence: 99%

Liquid Phase Electrochemistry at Ultralow Temperatures

Ching

McDevitt

Peck

et al. 1991

J. Electrochem. Soc.

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Fluid electrolyte solutions based on mixtures of butyronitrile (PrCN) and ethyl chloride (EtCl) with Bu4NPF6 or Bu4NClO4 as electrolyte freeze below −180°C and provide excellent media for cryogenic electrochemical experiments. A 1:2 mixture of PrCN and EtCl exhibits the best combination of freezing point and ionic conductivity for ultralow temperature electrochemistry. Diffusion coefficients for bis(pentamethylcyclopentadienyl) iron false(Cp2*normalFefalse) are measurable by potential step chronoamperometry down to −160°C using a conventionally sized electrode, but the resistivity of the solvent mixture is such that potential sweep voltammetry benefits from the use of microdisk (10 and 25 μm diam Pt) or microband (0.2 μm wide Au) electrodes. Voltammetry at a chemically modified electrode down to −170°C is presented for the case of thin films of normalpoly‐false[normalOsfalse(normalbpy)2false(normalvpy)2false]false[PF6]2 .

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Section: Resultsmentioning

confidence: 99%

Liquid Phase Electrochemistry at Ultralow Temperatures

Ching

McDevitt

Peck

et al. 1991

J. Electrochem. Soc.

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“…Charge transport in electrolyte solutions can be viewed as a succession of random jumps of the ions, limited by an average activation barrier. 65 The associated Eyring activation enthalpy for charge transport, DH z , which is the transference-number weighted average of the corresponding DH z values of the constituent ions, can be determined, 65,66 as the slope of a plot of the temperature dependence of…”

Section: Ion Transportmentioning

confidence: 99%

“…65 The associated Eyring activation enthalpy for charge transport, DH z , which is the transference-number weighted average of the corresponding DH z values of the constituent ions, can be determined, 65,66 as the slope of a plot of the temperature dependence of L N since…”

Section: Ion Transportmentioning

confidence: 99%

Association of ionic liquids in solution: a combined dielectric and conductivity study of [bmim][Cl] in water and in acetonitrile

Bešter‐Rogač

Stoppa

Hunger

et al. 2011

Phys. Chem. Chem. Phys.

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Ion association of the ionic liquid [bmim][Cl] in acetonitrile and in water was studied by dielectric spectroscopy for salt concentrations c r 1. Only contact ion pairs were detected in both solvents. Standard-state enthalpy, entropy and heat capacity changes of ion association were derived, as well as the activation enthalpy of charge transport and the limiting conductivity of the cation, l). These data, in conjunction with effective solvation numbers obtained from the dielectric spectra, suggest that the solvation of [bmim] + is much weaker in water than in acetonitrile.

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“…Before the details of the approximations are called into question, it may be noted that the observed value is unremarkably high, ~22 kcal mole -1 (9). It involves intra-as well as intermolecular transformations, it is always a complex quantity and it is seldom a discriminating factor (10). It involves intra-as well as intermolecular transformations, it is always a complex quantity and it is seldom a discriminating factor (10).…”

Section: [ O Ln (I/t) ]mentioning

confidence: 99%

The Pressure Coefficient of the Hydrogen Electrode Reaction

Hills¹,

Kinnibrugh²

1966

J. Electrochem. Soc.

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on active platinum electrodes is controlled by diffusion of molecular hydrogen. Results I obtained about 13 years ago ~A showed that the rate of the over-all reaction was unusually reproducible over a period of up to 16 days while the a-c impedance changed rather rapidly with time. Hence, it is probable that the over-all process does not depend on anything happening at the electrode surface. Similarly, the activation energy for the over-all process was about 5 kcal which is the order expected for a diffusion process. These results were interpreted somewhat differently in the paper cited. The more recent work by Frumkin's co-workers also supports the diffusion mechanism.G. C. Barker (communicated): From discussion remarks there now seems to be recognition of the fact that the polarization observed with clean smooth platinum and with some other metals is largely concentration polarization resulting from nucleation difficulties in the formation of gaseous hydrogen. I wish merely to point out that bubble formation at a clean surface free from re-entrant cavities is made difficult by the fact that the metal surface is wetted by the solution. 25 With a more hydrophobic platinum surface produced by deposition of one or more monolayers of stearic acid, bubble formation occurs much more readily and, despite the contamination of the surface the overpotential during hydrogen deposition in unstirred solution, is often smaller than for a completely clean surface. Ready formation of bubbles during gas deposition at electrodes is often indicative of surface contamination. ABSTRACTThe various criteria for the mechanism of the hydrogen electrode reaction are considered with particular reference to the pressure coefficient of the reaction rate. The techniques of studying electrode processes at pressures up to 1500 atm are described, and the volume of activation derived for the hydrogen evolution reaction has been found to be--3.4 ml mole -1. This negative value is not in accord with either of the two mechanisms usually proposed for this reaction. It suggests that the rate-determining step is the stage e (metal) --> e (aq)) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 138.251.14.35 Downloaded on 2015-03-08 to IP

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Kinetics of ionic conductance. Part 1.—Energies of activation and the constant volume principle

Cited by 96 publications

References 1 publication

Liquid Phase Electrochemistry at Ultralow Temperatures

Liquid Phase Electrochemistry at Ultralow Temperatures

Association of ionic liquids in solution: a combined dielectric and conductivity study of [bmim][Cl] in water and in acetonitrile

The Pressure Coefficient of the Hydrogen Electrode Reaction

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