Properties of the Electrical Double Layer at a Mercury Surface. I. Methods of Measurement and Interpretation of Results

Grahame, David C.

doi:10.1021/ja01850a014

Cited by 160 publications

(64 citation statements)

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“…The reversible character of the reduction of tetramethyl ammonium ions is in part indicated by the extremely high pseudocapacity, observed by Grahame [769] in the electroreduction of these ions.…”

Section: Mechanism Of Catalytic Hydrogenmentioning

confidence: 95%

Catalytic and Kinetic Waves in Polarography

Mairanovskii¹

1968

129

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Section: Mechanism Of Catalytic Hydrogenmentioning

confidence: 95%

Catalytic and Kinetic Waves in Polarography

Mairanovskii¹

1968

129

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“…Before the film is formed, the film holder is immersed into the solution for at least 2 h. All measurements were performed at 23 C. All curves are fitted by solving the non-linear Poisson Boltzmann equation for two dissimilarly charged surfaces in electrolyte solutions (supplementary information). [46][47][48][49] The surface charge densities are calculated by the well-known Grahame equation 50 from the potentials and the ionic strength resulting from the simulations.…”

Section: Disjoining Pressure and Film Thicknessmentioning

confidence: 99%

Correlation between specific ion adsorption at the air/water interface and long–range interactions in colloidal systems

Schelero

Klitzing

2011

Soft Matter

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Specific ion effects are of high impact in colloid science and dominate processes in aqueous systems from protein folding or precipitation to ordering of particles or macromolecules in bulk solutions. Due to the large internal interface of colloidal systems especially interfacial ion effects are of importance. This paper presents a new insight into the specific ion effects at the air/water interface of monovalent electrolyte solutions and their consequences for long-range interactions in colloidal systems. Solely, in an asymmetric film (i.e. wetting film) one can determine the sign and precise value of the surface potential of the free air/water surface. It is shown that the all over charges of the interfacial region, which are affected by the type of ion, dominate the interfacial forces even over several tens of nm. This is of interest for tailoring the stability of colloidal systems. It is clearly shown that the air/water interface is negatively charged and that both anions and cations affect the surface potential even at very low electrolyte concentrations (10 À4 M).

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“…Grahame also provides similar data for an additional 9 sodium salts [30,31] at negative values of the double layer potential, where the lines all have the same slope of ~ 17 μFcm −2 . We note in Figure 4 that for strong electrolytes (at 1 M solutions), the plot of charge against the potential relative to that at zero charge are quite linear for especially the negative potential and of the same gradient of ~ 17 μFcm −2 .…”

Section: Applications Of the Above Lemmasmentioning

confidence: 70%

Broad Considerations Concerning Electrochemical Electrodes in Primarily Fluid Environments

Jesudason¹

2009

IJMS

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This review is variously a presentation, reflection, synthesis and report with reference to more recent developments of an article – in a journal which has ceased publication – entitled “Some Electrode Theorems with Experimental Corroboration, Inclusive of the Ag/AgCl System” Internet Journal of Chemistry, (http://www.ijc.com), Special Issues: Vol. 2 Article 24 (1999). The results from new lemmas relating charge densities and capacitance in a metallic electrode in equilibrium with an ionic solution are used to explain the data and observed effects due to Esin, Markov, Grahame, Lang and Kohn. Size effects that vary the measured e.m.f. of electrodes due to changes in the electronic chemical potential are demonstrated in experiment and theory implying the need for standardization of electrodes with respect to geometry and size. The widely used Stern modification of the Gouy-Chapman theory is shown to be mostly inapplicable for many of the problems where it is employed. Practical consequences of the current development include the possibility of determining the elusive single-ion activity coefficients of solution ions directly from the expression given by a simplified capacitance theorem, the potential of zero charge and the determination of single ion concentrations of active species in the electrode reactions from cell e.m.f. measurements.

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Properties of the Electrical Double Layer at a Mercury Surface. I. Methods of Measurement and Interpretation of Results

Cited by 160 publications

References 0 publications

Catalytic and Kinetic Waves in Polarography

Catalytic and Kinetic Waves in Polarography

Correlation between specific ion adsorption at the air/water interface and long–range interactions in colloidal systems

Broad Considerations Concerning Electrochemical Electrodes in Primarily Fluid Environments

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