The Adsorption of Aromatic Hydrocarbons at the Gold Electrolyte Interface

Dahms, Harald; Green, Mino

doi:10.1149/1.2425587

Cited by 73 publications

(26 citation statements)

References 4 publications

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“…It is immediately obvious that the free energy of adsorption of monocarboxylic acids on a copper cathode is markedly dependent on the coverage, becoming increasingly negative with increasing 0. This coverage dependence, which is much the same as that observed by Bockris and Swinkels (7) for the adsorption of n-decylamine on copper, can presumably be attributed to spontaneous lateral interaction in the adsorbed phase (7,9).…”

Section: Discussionsupporting

confidence: 85%

Cathode Overpotential and Electrosorption Effects of Normal Monocarboxylic Acids during Electrodeposition of Copper

Loutfy

Sukava

1971

J. Electrochem. Soc.

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The cathode overpotential and electrosorption effects of some normal monocarboxylic acids during electrodeposition of copper were studied galvanostatically at current densities up to 20 mA-cm -2. Equations were derived by means of which overpotential increments caused by the blocking action of adsorbed additive can be used to calculate the separate adsorption free-energy contributions of the carboxyl and methylene groups in the additive molecule, and also a coverage-dependent lateral interaction free energy arising primarily from dipole-dipole interaction between adjacent carboxyl groups in the adsorbed phase. The carboxyl group contribution was found to be --1570 cal mole -1 at zero coverage, while the methylene group contribution was --704 cal mole-' and independent of coverage.

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Section: Discussionsupporting

confidence: 85%

Cathode Overpotential and Electrosorption Effects of Normal Monocarboxylic Acids during Electrodeposition of Copper

Loutfy

Sukava

1971

J. Electrochem. Soc.

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“…The C 2 values obtained for the two peaks fittings are one order of magnitude lower than those of C 1 in agreement with capacitance values obtained for thicker gold oxide layers [18]. The adsorption of aromatic molecules on free gold/ vacuum surface is generally higher than that of aliphatic molecules because of the role played by the interaction of porbitals with metal orbitals, in agreement with the acid-base theory of surfaces (Goodvan Oss) [23]. Therefore, we can assume that the aromatic adsorption in our case is stronger than that with aliphatic compounds.…”

Section: Contact Angle Measurementssupporting

confidence: 87%

Gold oxide films grown in the confined aqueous layer between gold and organic solvents

Gassa

Zerbino

Meyra

et al. 2014

Journal of Electroanalytical Chemistry

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The properties of anodic passive films potentiostatically formed on polycrystalline gold in aqueous phosphate solutions were studied using voltammetry, electrochemical impedance spectroscopy, and contact angle measurements. The nature of the gold oxide layer was analyzed as a function of a potential holding in the aqueous double layer charge region at the interface between gold and the aqueous layer confined by insoluble organic solvents (hexane, chloroform, anisole, butyl acetate, xylene, and isopropyl ether). Different growth conditions change the homogeneity of the oxide layer leading to different passive properties. A synergetic effect on the gold oxidation of hydrogen dissolved in both the bulk metal and the confined aqueous layer is discussed.

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“…Under ideal conditions, the electrochemical potential of the adsorbed organic entity in Eq. [2] may be written ~org, ads --~'%rg, ads "~ RT In e [3] and the electrochemical potential of the adsorbed water is given by ~w, ads =V~ ads Jr-RT In (1 --e) [4] The electrochemical potentials of the adsorbate in aqueous solution are written by ~org, sol = ]~~ sol 2r RT In Xorg" sol [5] /~w, sol : ~~ sol -t-RT In Xw, sol [6] where Xor~, sol and Xw. ~ol are the tool fractions of organic and water, respectively.…”

Section: Resultsmentioning

confidence: 99%

Adsorption of 3‐phenyl‐1‐propanol on Gold Electrode from Perchloric Acid Solutions

Katoh

Koseki

1984

J. Electrochem. Soc.

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Adsorption parameters of 3-phenyl-l-propanol and some other co-phenyl alkanols were calculated after the isotherm of 0/(1 -O)" = Kad~' Xorg. The adsorption peaks appeared at 0.70 and 0.35V (vs. SCE) for the adsorbate. The peak near 0.70V seems to be due to ~r-electron interaction of the benzene ring and another peak at 0.35V to the alcohol group as side chain. The peak height of coverage-potential curve at 0.35V became larger depending upon the number of carbon atoms in the aliphatic alcohol group on the benzene ring. The differential capacity was measured by a rapid rectangular single-pulse technique, and the voltage-time curve was memorized electrically set by a "Wave Memory." Then, the reproducibility of the_capacity measurement became approximately within -+6%. The values of n and the standard free energy of adsorption (AG ~ of the adsorbate at 0.70V were calculated as 2.8 and -7.4 kcal/mol, respectively.In the adsorption of benzene compounds on electrode surface, the ~-electron interaction between the adsorbed molecule and the electrode surface plays a dominant role (1). As reported in a previous paper (2), the adsorption peak of benzoic acid appears at 0.60V (vs. SCE), and the peak seems to be due to adsorption of benzene ring by its ;~-electron interaction on the gold electrode. In this report, adsorption of 3-phenyl-l-propanol (PPA) on gold electrode was studied. The adsorption peak was found at 0.70V. However, we found out that the new peak appeared at 0.35V. Peak height of the coverage-potential curve became larger depending upon the number of carbon atoms in the aliphatic alcohol group on the benzene ring from the coverage data of benzyl alcohol, 2-phenyl ethanol, and 3-phenyl-l-propanol. Kinetic parameters were calculated after the concept of competitive adsorption by Bockris and Swinkels (3, 4), Dahms and Green (5), and Conway and Dhar (6). They assumed that one molecule of an organic substance took the place of n molecules of water on the electrode surface. Lawrence and Parsons (7) calculated the n value from the geometrical ratio of the area occupied by the organic molecule to the one by water molecule. Dahms and Green (5) calculated the value for adsorption of aromatic hydrocarbons on gold electrode with radiotracer technique. ExperimentalGold electrode.--The gold electrode which was used as the working electrode which was made from polycrystalline pure gold (99.99%, Tokuriki Manufacturing Company Limited) and was sheathed in a Teflon rod (2). The electrode surface was polished before each series of electrochemical works with very fine emery papers and then polished with dilute suspension of 600 mesh dichromium trioxide polishing powder. The electrode surface was reduced by setting the potential near --0.20V for 20 min or more. The surface condition of the reducing process was observed by drawing a cyclic voltammetric curve of the gold electrode. The apparent surface area of the electrode was 0.049 cm 2, and the roughness factor as calculated with the method of Brummer and Makrides (8) wa...

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The Adsorption of Aromatic Hydrocarbons at the Gold Electrolyte Interface

Cited by 73 publications

References 4 publications

Cathode Overpotential and Electrosorption Effects of Normal Monocarboxylic Acids during Electrodeposition of Copper

Cathode Overpotential and Electrosorption Effects of Normal Monocarboxylic Acids during Electrodeposition of Copper

Gold oxide films grown in the confined aqueous layer between gold and organic solvents

Adsorption of 3‐phenyl‐1‐propanol on Gold Electrode from Perchloric Acid Solutions

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