Electrode rotating hemisphere

Theory and Experimental Aspects of the Rotating Hemispherical Electrode... 

The rotating hemispherical electrode (RHSE) was originally proposed by the author in 1971 as an analytical tool for studying high-rate corrosion and dissolution reactions [13]. Since then, much work has been published in the literature. The RHSE has a uniform primary current distribution, and its surface geometry is not easily deformed by metal deposition and dissolution reactions. These features have made the RHSE a complementary tool to the rotating disk electrode (RDE). 

The above problems may be alleviated by the use of a rotating hemispherical electrode (RHSE). In this geometry, the flat circular disk on the RDE is replaced with a metal hemisphere as shown in Fig. 1(a). The theory, experimental setup and methods of application to electrochemical studies are similar to those of the RDE. The advantages of the RHSE are ... 

This article presents a brief account of theory and practical aspects of rotating hemispherical electrodes. The fluid flow around the RHSE, mass transfer correlations, potential profile, and electrochemical application to the investigations of diffusivity, reaction rate constants, intermediate reaction products, passivity, and AC techniques are reviewed in the following sections. 

Fig. 1. Flow near a rotating hemisphere electrode. (a) Dye movement at Re = 1300. (b, c) Spiral flow patterns etched on a copper hemisphere.

To consider the convective mass transfer problem of a rotating hemisphere electrode, we assume that sufficient inert salts are present in the electrolyte that the migrational... 

Fig. 7. Current distribution on a rotating hemispherical electrode at high rotational speed. From [47].

The experimental setup of a rotating hemispherical electrode (RHSE) is similar to that of a rotating disk electrode [50]. The basic system consists of a removable hemispherical electrode, and a variable speed rotator equipped with a provision, such as the slip-ring contact, to make electric connection to the hemispherical electrode during the experiments. 

Fig. 8(a) shows the design of a rotating hemisphere electrode used in the author s laboratory [14], It is composed of a hemisphere electrode, an arcylic support rod, and a tappered brass holder to be attached to a high speed rotator [Fig. 8(b) ]. The electrode is machined into the form of a metal screw with a hemispherical head, and is threaded into the inert acrylic support rod of a larger radius. The design has the advantages that... 

Fig. 8. Construction of a rotating hemisphere electrode (a) and cell setup (b). From [14].

Fig. 9. Types of rotating spherical electrodes reported in the literature, (a) Rotating micro-sphere electrode, (b, c) rotating hemisphere electodes (d) rotating ring-hemisphere electrodes (e) rotating dropping mercury electrode.

The rotating hemisphere electrode has been used to investigate the effect of AC on the electrodissolution and deposition reactions of zinc in zinc chloride [25] and copper in acid copper sulfate solutions [55], AC was found to increase the rate of nucleation and produce more uniform deposit on the zinc electrode. The corrosion of an iron rotating hemisphere in dilute sulfuric acid was investigated by Haili [31] using the AC impedance measurement. 

With its axisymmetric transport and current distribution, the rotating hemispherical electrode complements the rotating disk as a tool for studying electrode processes. Der-Tau Chin provides a valuable overview and summary of the fundamental theory and applications of this interesting device. 

In this section, we consider mass transport-controlled currents to disc and concentric ring electrodes on a planar spinning disc surface. For other less common rotating electrodes, e.g. rotating hemisphere, see Table 3. 

Besides the RDE and DME, other uniformly accessible electrodes under laminar flow have been described. They include the rotating hemispherical and rotating cone electrodes, which were developed to obviate the problem of trapped gas bubbles at the centre of an RDE their use is not widespread. 

The rotating hemispherical electrode, introduced by Chin, ° has a uniform primary current distribution and would therefore be a suitable configuration for experiments conducted under conditions such that the current distribution is not in-... 

D.T. Chin, Theory and Experimental Aspects of the Rotating Hemispherical Electrode, In H. Gerischer and C.W. Tobias (eds). Advances in Electrochemical Science and Engineering, Vol. 1, VCH Publishers, New York (1990), p. 171. 

In electrochemistry, spherical and hemispherical electrodes have been commonly used in the laboratory investigations. The spherical geometry has the advantage that in the absence of mass transfer effect, its primary and secondary current distributions are uniform. However, the limiting current distribution on a rotating sphere is not uniform. The limiting current density is highest at the pole, and decreases with... 

The electric connection to the electrode is made by connecting a copper wire from the brass holder to the threaded portion of the hemisphere electrode. The brass holder is machined to fit snuggly into the steel shaft of a rotator. The rotation of the electrode is provided by a timing pulley connected to a variable speed DC motor. A graphite slipring contact located on the top of the shaft is used to provided electric contact to the RHSE during the experiments. 

Kim and Jorne [37] have used a rotating zinc hemisphere to study the kinetics of zinc dissolution and deposition reactions in concentrated zinc chloride solutions. The electrodeposition reaction of cadmium on mercury was used by Mortko and Cover [43] in their investigation of a rotating dropping mercury electrode their data behaved according to Eqs. (74)-(76). 

The hemispherical electrode may be coupled with a ring [20] to form a rotating ring-hemisphere electrode (RRHSE) as shown as Fig. 9(d). The ability of this combination to detect intermediate reaction products is demonstrated in Fig. 10, where a series of cathodic sweep curves for the reduction of Cu2 + in acidic cupric chloride solution are... 

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