The Problem of the Single Ion Activity

Bates, Roger G.

doi:10.5796/kogyobutsurikagaku.46.480

Cited by 8 publications

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“…The values of the single-ion activities of H + and Cl – , once thought to be elusive and the subject of disputes to date, − can be estimated to the extent of the accuracy of the liquid junction potential, as Frank pointed out and Bates remarked in relation to the determination of pH. Filling a new liquid in a glass tube in the old-fashioned cell enables us to estimate those values much more reliably and readily than relying on a KCl-type salt bridge or an elaborate calculation of the liquid junction potential.…”

Section: Discussionmentioning

confidence: 99%

Determination of Single-Ion Activities of H⁺ and Cl^– in Aqueous Hydrochloric Acid Solutions by Use of an Ionic Liquid Salt Bridge

Sakaida

Kakiuchi

2011

J. Phys. Chem. B

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Single-ion activities of H(+) and Cl(-) in aqueous hydrochloric acid solutions up to 500 mmol·dm(-3) HCl have been determined, independently of each other, with reasonable accuracy, 95% confidence interval of log(10)γ being ±0.012 at 25 °C, by use of an ionic liquid salt bridge inserted in a Harned cell. The geometric averages of those activities agree well with the literature values of the mean ionic activity of HCl determined with a Harned cell up to an ionic strength of 500 mmol·dm(-3). The agreement supports the assumption used in estimating the single-ion activities, that is, the liquid junction potentials on both sides of the ionic liquid salt bridge stay constant, within the confidence interval of the cell voltage, ± 1 mV, over the concentration range of HCl between 10 and 500 mmol·dm(-3). The single-ion activity coefficient values of H(+) and Cl(-) over the concentration range studied show fairly good agreement with the recent theoretical predictions by the "smaller-ion-shell" model proposed by Fraenkel (Mol. Phys. 2010, 108, 1435; J. Phys. Chem. B 2011, 115, 557), which fact is significant and implicative in physical and analytical chemistry of electrolyte solutions.

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Section: Discussionmentioning

confidence: 99%

Determination of Single-Ion Activities of H⁺ and Cl^– in Aqueous Hydrochloric Acid Solutions by Use of an Ionic Liquid Salt Bridge

Sakaida

Kakiuchi

2011

J. Phys. Chem. B

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“…Polymer electrolyte fuel cells ͑PEFCs͒ have attracted great interest for their applications to vehicles and residential co-generation systems, [1][2][3][4] because of their high power density and low operation temperature. Although the power density has attained the target, the efficiency of the fuel system should be improved further for real commercialization.…”

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confidence: 99%

Analysis of Oxygen Reduction on Pt Microelectrode with Polymer Electrolytes of Various Exchange Capacities

Mitsushima

Araki

Kamiya

et al. 2002

J. Electrochem. Soc.

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In order to obtain an improved design of a polymer electrolyte fuel cell cathode, the oxygen reduction reaction on a Pt microelectrode with proton exchange membranes of various exchange capacities has been investigated. The measurements were performed by chronoamperometry for determination of the diffusion coefficient and oxygen solubility, and by slow scan voltammetry for reaction kinetics with the microelectrode in the temperature range 20 to 70°C. The results of chronoamperometry and slow scan voltammetry were analyzed by the fitting of analytic equations and digital simulation. The diffusion coefficients increased with temperature and exchange capacity. On the other hand, the solubilities increased with a decrease in temperature and exchange capacity. The dependences of the diffusion coefficient on temperature and exchange capacity were larger than those of the solubility. Accordingly, the permeabilities, which are the product of the diffusion coefficient and the solubility, increased with temperature and exchange capacity. Although the dependence of the exchange current densities on the exchange capacity was not clear, the exchange current densities were 10−9 to 10−8Acm−2 in the high potential region and about 10−6Acm−2 in the low potential region. © 2002 The Electrochemical Society. All rights reserved.

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Classified Bibliography of Electroanalytical Applications

Venkatesan

1984

Comprehensive Treatise of Electrochemistry

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The Problem of the Single Ion Activity

Cited by 8 publications

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Determination of Single-Ion Activities of H⁺ and Cl^– in Aqueous Hydrochloric Acid Solutions by Use of an Ionic Liquid Salt Bridge

Determination of Single-Ion Activities of H⁺ and Cl^– in Aqueous Hydrochloric Acid Solutions by Use of an Ionic Liquid Salt Bridge

Analysis of Oxygen Reduction on Pt Microelectrode with Polymer Electrolytes of Various Exchange Capacities

Classified Bibliography of Electroanalytical Applications

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The Problem of the Single Ion Activity

Cited by 8 publications

References 0 publications

Determination of Single-Ion Activities of H+ and Cl– in Aqueous Hydrochloric Acid Solutions by Use of an Ionic Liquid Salt Bridge

Determination of Single-Ion Activities of H+ and Cl– in Aqueous Hydrochloric Acid Solutions by Use of an Ionic Liquid Salt Bridge

Analysis of Oxygen Reduction on Pt Microelectrode with Polymer Electrolytes of Various Exchange Capacities

Classified Bibliography of Electroanalytical Applications

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Product

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Determination of Single-Ion Activities of H⁺ and Cl^– in Aqueous Hydrochloric Acid Solutions by Use of an Ionic Liquid Salt Bridge

Determination of Single-Ion Activities of H⁺ and Cl^– in Aqueous Hydrochloric Acid Solutions by Use of an Ionic Liquid Salt Bridge