Oscillations of the EQCM frequency response in the course of open-circuit copper dissolution in aqueous solutions of H2SO4 and CuSO4

Inzelt, György

doi:10.1016/0022-0728(93)80153-9

Cited by 19 publications

(5 citation statements)

References 14 publications

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“…Thus, by integrating the voltammetric current, voltmassograms may be obtained. Their comparison with the mass changes measured directly with the EQCM 6,7,[21][22][23][24][25][26] can yield valuable information on the electrochemical processes. Alternatively, if Faraday's law is applicable, the mass change determined with the EQCM corresponds to a current flow I EQCM…”

mentioning

confidence: 99%

“…Thus, by integrating the voltammetric current, voltmassograms may be obtained. Their comparison with the mass changes measured directly with the EQCM 6,7,[21][22][23][24][25][26] . [28][29][30][31][32][33] While this might lead to remarkable reaction dynamics, 34,35 it is highly undesirable in the present experiments because it would diminish the value of the EQCM results on CuCl.…”

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confidence: 99%

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An EQCM Study of the Electrochemical Copper(II)/Copper(I)/Copper System in the Presence of PEG and Chloride Ions

Doblhofer

Wasle

Soares

et al. 2003

J. Electrochem. Soc.

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The charge-transfer reaction between copper͑II͒ and copper electrodes is studied in electrolytes that are similar to galvanic copper baths, 2.2 M H 2 SO 4 ϩ 0.3 M CuSO 4 ϩ chloride ions (c Cl р 1 ϫ 10 Ϫ2 M͒, and polyethyleneglycol 1500 ͑PEG, c PEG р 4 ϫ 10 Ϫ3 M͒. Electrochemical quartz crystal microbalance ͑EQCM͒ measurements are conducted, mainly under conditions of cyclic voltammetry. The formation and dissolution of CuCl on the electrode surface at c Cl у 2 mM is demonstrated, a notable shift of the pseudo-equilibrium potential associated with CuCl deposition is analyzed, and the inhibition of the charge-transfer reaction by the PEG/Cl Ϫ surface layer is characterized. It is shown that the inhibiting layer forms by reaction between the adsorbate-covered copper electrode and PEG, i.e., neither Cu ϩ nor Cu ϩϩ from the electrolyte are required. Numerical simulations of the processes as well as parallel experiments conducted with electrolytes not containing Cu͑II͒ support the proposed mechanisms, in particular the role of the intermediate Cu ϩ .

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confidence: 99%

“…Thus, by integrating the voltammetric current, voltmassograms may be obtained. Their comparison with the mass changes measured directly with the EQCM 6,7,[21][22][23][24][25][26] . [28][29][30][31][32][33] While this might lead to remarkable reaction dynamics, 34,35 it is highly undesirable in the present experiments because it would diminish the value of the EQCM results on CuCl.…”

mentioning

confidence: 99%

An EQCM Study of the Electrochemical Copper(II)/Copper(I)/Copper System in the Presence of PEG and Chloride Ions

Doblhofer

Wasle

Soares

et al. 2003

J. Electrochem. Soc.

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“…Instead, the complex character of nucleation phenomena in the passive (salt layer) film formation/dissolution is presumably responsible for the chaos observed. The formation of such passive layers was later confirmed by Inzelt [49] who has reported the oscillatory mass changes during the Cu dissolution in H 2 SO 4 þ CuSO 4 medium, manifesting itself by oscillating electrochemical quartz crystal microbalance response. The chaotic courses were analyzed in terms of one-dimensional Poincaré maps (Fig.…”

Section: The Oscillatory Electrodissolution Of Coppermentioning

confidence: 77%

Temporal Instabilities in Corrosion Processes

Orlik

2012

Monographs in Electrochemistry

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“…The electrochemical quartz crystal microbalance (EQCM) is sensitive enough to measure electrode mass changes at monolayer level or less. [26][27][28] During electrochemical oxidation of small organic molecules, 29,30 dissolution of copper 31 and deposition of Cu/Cu 2 O layers 32,33 periodic oscillations in electrode potential and mass have been studied using the EQCM. In the only reported EQCM study of BZ systems, 34 the frequency response was interpreted solely in terms of macroscopic solution properties (viscosity and density).…”

Section: Introductionmentioning

confidence: 99%

New insights into the Belousov-Zhabotinskii reaction derived from EQCM measurements at a gold electrode

Jusys

Bruckenstein

Hillman

2011

Phys. Chem. Chem. Phys.

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Electrochemical quartz crystal microbalance experiments were used to study the classical Belousov-Zhabotinskii (BZ) homogeneous oscillating system. This system involves 2 × 10(-3) M Ce(III), 0.28 M malonic acid and 0.063 M bromate as the main initial components in 1 M sulfuric acid solution. The gold-evaporated electrodes on a 10 MHz AT-cut quartz crystal were used for potentiometric and amperometric studies while the changes in crystal frequency provided mass data. Under open-circuit conditions, during the BZ reaction, oscillations of the gold electrode potential in the range ca. 0.8 to 1.07 V (SCE) with a period about 80 s occurred. They were accompanied by periodic 10-15 ng [i.e. ca. 45-70 ng cm(-2)] changes in the electrode mass. At more positive potentials a decrease in electrode mass occurred, while the mass increased at more negative potentials. At a constant applied electrode potential, corresponding to either the upper or the lower potential limit attained under open-circuit conditions, periodic pulses of cathodic current occurred and were accompanied by mass changes. A continuous decrease in the electrode mass occurred at 1.06 V. A detailed examination of the gold electrode behavior in the solutions containing individual components of the system using cyclic voltammetry and quartz crystal microgravimetry provided the information needed to interpret the mass changes that occur in the complete system. No significant changes in the electrode mass occurred in sulfuric acid solution in the potential range where current and mass oscillations take place in the full BZ reaction solution. The same result was found in sulfuric acid solutions containing either Ce(III) or malonic acid. Dissolution of gold occurred in a sulfuric acid solution containing bromate or bromide ions. Adsorption of bromide ions on gold electrode occurred in Br(-)-containing sulfuric acid solution at more negative potentials. In the BZ system, dissolution of gold in the presence of oxidizing (bromate) and complexing (bromide) species causes the decrease in the electrode mass that accompanies the positive potential jump under open-circuit conditions, or the current pulse that occurs at more negative applied constant potentials. Cathodic current pulses occurring at a constant electrode potential (either 0.8 or 1.06 V) are associated with the reduction of Ce(IV) formed as a result of periodic homogeneous oxidation of Ce(III) by bromate. Bromide ions formed in the course of the BZ reaction appear to play a significant role in electrode mass changes, causing a mass decrease at more positive potentials due to dissolution of gold, and a subsequent mass increase at more negative potentials due to adsorption processes.

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Oscillations of the EQCM frequency response in the course of open-circuit copper dissolution in aqueous solutions of H2SO4 and CuSO4

Cited by 19 publications

References 14 publications

An EQCM Study of the Electrochemical Copper(II)/Copper(I)/Copper System in the Presence of PEG and Chloride Ions

An EQCM Study of the Electrochemical Copper(II)/Copper(I)/Copper System in the Presence of PEG and Chloride Ions

Temporal Instabilities in Corrosion Processes

New insights into the Belousov-Zhabotinskii reaction derived from EQCM measurements at a gold electrode

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