Electron photoemission as a new method for studying the electric double layer structure and the kinetics of electrochemical reactions

Rotenberg, Z. A.; Lakomov, V.I.; Pleskov, Yu. V.

doi:10.1016/s0022-0728(70)80236-4

Cited by 34 publications

(16 citation statements)

References 11 publications

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“…The recently developed mercury-coated nickel minigrid electrode (11) was used in a thin layer configuration during cyclic voltammetric experiments and as a thin layer electrolysis cell for spectroelectrochemical studies (2,3,13). The OTTLE which served as the working electrode was constructed according to established procedures (2,11).…”

Section: Methodsmentioning

confidence: 99%

“…The OTTLE which served as the working electrode was constructed according to established procedures (2,11). There was some concern that diffusion of unreacted material from the reservoir cup and the edges of the OTTLE cell could affect the mechanism and kinetics of the reoxidation.…”

Section: Methodsmentioning

confidence: 99%

“…We can describe the energetics of these equilibria in terms of the total surface free energy for the idealized model system G = (70 --n)A [11] where 7o ----the interracial free energy of the hydrophobic phase/water interface, ~ ----the surface pressure of the hydrophilic film, and A ~ the total area. For example, with Eq.…”

Section: Subunit Dissociation Reactions As Colloidal Phenomenamentioning

confidence: 99%

“…The resultant spectropotentiostatic studies (2, 3) of cobalamins have revealed a previously unobserved sequence of intermediates and steps are involved in the reoxidation mechanism of the cob (I)alamins in this biologically significant reaction (4-10). Optically transparent thin layer electrode (OTTLE) cells (11,12) have been used in conjunction with a Harrick rapid scanning spectrophotometer to study the reoxidation mechanism of cob (I)alamins (2). The reoxidation sequence of cob (I)alamins investigated by spectropotentiostatic and autooxidation techniques has yielded consistent results.…”

Section: A Thin Layer Spectroelectrochemical Study Of Cob(i)alamin Tomentioning

confidence: 99%

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Hemoglobin Reactions as Interfacial Phenomena

Blank

1976

J. Electrochem. Soc.

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ConclusionsThrough the use of flash irradiation and high speed potentiostatic monitoring, currents clearly related to electron photoemission have been observed. Although the expected dependences on electrode potential and scavenger presence were obtained, the time dependence of the observed flash photocurrents was found to be governed primarily by the prevailing electrochemical cell time-constant to such a large degree that they can only be explained as capacitive charging currents in response to a virtually instantaneous flash-induced electron injection into the double layer.The charging current model for the photoemissioninitiated currents, and the experimental results on which it is based, are consistent with the known chemical and physical processes that actually occur for a wide range of scavenging situations. Furthermore, for certain specialized cases (e.g., NO~-) in which the secondary scavenging reactions proceed sufficiently slowly, the time dependence of flash photocurrents can be related directly to the reaction rates of scavenging intermediates. In these cases, useful chemical information concerning eaq-chemistry and scavenging reactions can be obtained. ABSTRACTThe reactions of hemoglobin with various ligands lead to conformational changes in the macromolecule.The free energy of these changes can be eestimated in terms of the surface free energy of a miereemulsion droplet of the same size and surface charge as the hemoglobin molecule. Calculations on the basis of this model yield an equilibrium constant that varies with pH, as in the acid and alkaline Bohr effects, and with the ionic strength. The model also provides a physical meaning for the empirical constant in the oxygen binding equation, as well as some insight into the dissociation equilibrium of the hemoglobin tetramers. This approach to equilibria involving globular proteins should be useful for estimating the effects of conformational changes and subunit interactions in other systems.The study of macromolecules as interracial systems, i.e., the chemistry of hydrophilic colloids, was the first * Electrochemical Society Active Member.) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 130.15.241.167 Downloaded on 2015-03-10 to IP

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Subunit Dissociation Reactions As Colloidal Phenomenamentioning

confidence: 99%

Section: A Thin Layer Spectroelectrochemical Study Of Cob(i)alamin Tomentioning

confidence: 99%

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Hemoglobin Reactions as Interfacial Phenomena

Blank

1976

J. Electrochem. Soc.

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“…: This effect has been included in a "modified 5/2 Law" threshold theory for IPE (21,22) which has been experimentally verified on Hg and Pb electrodes (23). Deviations from this "modified 5/2 Law" due to the presence of charged adsorbates have also been observed (13,24). These deviations have been attributed to modifica tions in the interfacial barrier in the dilute portion of the double layer due to changes in the effective charge on the electrode surface arising from the adsorbate ions.…”

Section: B Historical Survey Of In Situ Photoemissionmentioning

confidence: 94%

Study of the metal-electrolyte interface by in situ photoemission

Grider

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Electrochemical Effects Produced by Light‐induced Electron Emission

Barker

1971

Ber Bunsenges Phys Chem

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Direct evidence for light‐induced deposition of electrons in the solution near a mercury cathode is obtained by studying the coulostatic photopotential produced by a short duration light pulse. Similar studies permit the evaluation of rate constants for electron scavenging and the diffusion coefficient of the OH radical. The mechanisms of the photo‐currents produced by NO−3, NO−2 and H3O+ are discussed.

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Electron photoemission as a new method for studying the electric double layer structure and the kinetics of electrochemical reactions

Cited by 34 publications

References 11 publications

Hemoglobin Reactions as Interfacial Phenomena

Hemoglobin Reactions as Interfacial Phenomena

Study of the metal-electrolyte interface by in situ photoemission

Electrochemical Effects Produced by Light‐induced Electron Emission

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