Double Layer Investigation

In connection with the foregoing, double layers of course also play an important role in electroanalysis. Transfer of. say, electroactive ions through the polarized mercury-solution interface is preceded by passage through the double layer. Therefore current-potential plots depend in principle on double layer properties. Historically, it was his interest In charge-transfer and corrosion problems that induced Grahame to start his seminal double layer Investigations. 

Reported studies deal with measurements of the electrode potential of zero charge Epzc [698, 699], double layer investigations [700-702] and studies of electrode reaction mechanisms [703, 704] for an overview, see also [693, 697], Numerous studies (beyond many conducted ex situ) deal with intrinsically conducting polymers, particularly photogenerated mobile charge carriers [705-707]. 

As a furtlier example for tire meaning of ex situ investigations of emersed electrodes witli surface analytical teclmiques, results obtained for tire double layer on poly crystalline silver in alkaline solutions are presented in figure C2.10.3. This system is of scientific interest, since tliin silver oxide overlayers (tliickness up to about 5 nm) are fonned for sufficiently anodic potentials, which implies tliat tire adsorjDtion of anions, cations and water can be studied on tire clean metal as well as on an oxide covered surface [55, 56]. For tire latter situation, a changed... 

Figure C2.10.3. Ex situ investigation of the electrochemical double layer on Ag after hydrophobic emersion from 1 M NaClO + 0.1 M NaOH. (a) Peak deconvolution of the XPS 01s signals after emersion at +0.2 V A surface...

Flecht D and Strehblow FI-FI 1997 XPS investigations of the electrochemical double layer on silver in alkaline chloride solutions J. Electroanal. Chem. 440 211-17... 

Further investigations were carried out at lipid double layers and at phospholipids of membranes. Lipid-lipid and lipid-protein interactions were recognized by diazirine labeling (79PNA2595). 

We ean use H to investigate both the bulk and surfaee properties of ionie systems. Although this paper is essentially devoted to the double layer, in the next seetion we summarize some results obtained for bulk phases. On this example we ean eheek the construetion of the Hamiltonian and illustrate how this approaeh works. In addition, in the simplest ease we ean go beyond the MFA and do an exaet ealeu-lation. 

The capacitance. The electrical double layer may be regarded as a resistance and capacitance in parallel see Section 20.1), and measurements of the electrical impedance by the imposition of an alternating potential of known frequency can provide information on the nature of a surface. Electrochemical impedance spectroscopy is now well established as a powerful technique for investigating electrochemical and corrosion systems. 

A Fig. 4 a —g. Some interface analysis techniques applied to polymers. Mostly the interface of a double layer system of polymer A/polymer B on a substrate (silicon wafer (Si) or glass) is investigated. In some cases deuterated (D) versus protonated (H) polymer films are used. Techniques and abbreviations are explained in the text and in Table 2... 

The electrical double-layer structure at Ga/DMF, In(Ga)/DMF, and Tl(Ga)/DMF interfaces upon the addition of various amounts of NaC104 as a surface-inactive electrolyte has been investigated by differential capacitance, as well as by the streaming electrode method.358 The capacitance of all the systems was found to be independent of the ac frequency, v. The potential of the diffuse layer minimum was independent of... 

The pc-Bi/aqueous solution interface has been studied mainly by Palm et a/.666-669 Ea= and other fundamental characteristics were obtained. The electrical double-layer structure at a bismuth solid drop electrode with remelted surface (BiDER/H20) was investigated by Salve... 

First attempts to study the electrical double layer at A1 electrodes in aqueous and nonaqueous solutions were made in 1962-1965,182,747,748 but the results were not successful.190 The electrical double-layer structure at a renewed Al/nonaqueous solution of surface-inactive electrolytes such as (CH3)4NBF4) (CH3)4NC104, (CH3>4NPF6, and (C4H9)4NBF4, has been investigated by impedance.749-751 y-butyrolactone (y-BL), DMSO, and DMF have been used as solvents. In a wide region of E [-2.5 [Pg.128]

The electrical double-layer structure of a Pt/DMSO interface has been investigated using the potentiostatic pulse method.805 The value of C at E = const, as well as the potential of the diffuse layer minimum, have been found to depend on time, and this has been explained by the chemisorption of DMSO dipoles on the Pt surface, whose strength depends on time. Eg=Q has been found11 at E = -0.64 V (SCE in H2O). 

The first studies of the electrical double-layer structure at Sn + Pb and Sn + Cd solid drop electrodes in aqueous surface-inactive electrolyte solutions were carried out by Kukk and Piittsepp.808 Alloys with various contents of Pb (from 0.2 to 98%) were investigated by impedance.615,643,667,816 Small amounts of Pb caused dramatic shifts of toward more negative values. For alloys with Pb bulk content 0.2%, was the same as for pc-Pb. The was independent of Crf and frequency. C xt Cjl plots were linear, with/pz very close to unity. Thus the surface of Sn + Pb alloys behaves as if it were geometrically smooth, and Pb appears to be the surface-active component. 

Figure 8.13. (a) Cyclic voltammetric investigation of the Ir02/YSZ interface (inset shows the circuit used to model the data)19 and (b) Effect of catalyst-electrode mass on the polarization resistance Rp and the double layer capacitance Cd.19 Scan rate 20 mV/s, T=380°C, pO2=20 kPa. 

An increase in pressure will also affect the rate of the diffusion of molecules to and from the electrode surface it will cause an increase in the viscosity of the medium and hence a decrease in diffusion controlled currents. The consequences of increased pressure on the electrode double layer and for the adsorption of molecules at the electrode surface are unclear and must await investigation. 

Various methods have been employed for the determination of E of liquid and solid metals. Besides purely electrochemical ones (e.g. measurement of the differential double layer capacity (see also chapter 4.2)) further techniques have been used for the investigation of the surface tension at the solid/electrolyte solution phase boundary. The employed methods can be grouped into several families based on the meas-... 

The mechanical friction between the electrode surfaee under investigation and a suitable probe depends on the electrode potential showing a maximum at Ep-. Of various experimental setups reviewed previously [69Boc2] the most recent one is used to measure the frietion between a test eleetrode in wire shape and a cylindrical slider sitting on the wire [69Boel]. Results are interpreted in terms of the repulsion of double layers being present on the wire and the slider [69Boe2]. (Data obtained with this method are labelled F). 

The results shown above build on a thorough investigation of water interaction and effects related to the electrical field in the double layer near the surface. While these details are important when doing the simulations, they are less important for the understanding of the results presented above. We have therefore chosen to present them here at the end of the section. 

Clearly, then, the chemical and physical properties of liquid interfaces represent a significant interdisciplinary research area for a broad range of investigators, such as those who have contributed to this book. The chapters are organized into three parts. The first deals with the chemical and physical structure of oil-water interfaces and membrane surfaces. Eighteen chapters present discussion of interfacial potentials, ion solvation, electrostatic instabilities in double layers, theory of adsorption, nonlinear optics, interfacial kinetics, microstructure effects, ultramicroelectrode techniques, catalysis, and extraction. 

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