Reactions rotating disc

The rotating-disc is also well suited to tlie study of coupled chemical reactions [2, 4]. 

Zembura has made specific use of the rotating disc for investigation of the effect of flow on corrosion reactions. This work has shown that it is possible to determine the type of control (activation or concentration polarisation) of zinc dissolving in 0.1 N Na2S04 (de-aerated), which followed closely the predicted increase in hydrogen ion reduction as the flow rate increased, and proved that in this example... 

Platinum has also had its share of attention in recent years. The effect of phosphoric acid concentration on the oxygen evolution reaction kinetics at a platinum electrode using 0-7 m-17-5 m phosphoric acid at 25°C has been studied with a rotating disc electrode . The characteristics of the ORR are very dependent on phosphoric acid concentration and H2O2 is formed as an intermediate reaction. Also, platinum dissolution in concentrated phosphoric acid at 176 and 196°C at potentials up to 0-9 (SHE) has been reported . 

Kassner used a rotating disc, for which the hydrodynamic conditions are well defined, to study the dissolution kinetics of Type 304 stainless steel in liquid Bi-Sn eutectic. He established a temperature and velocity dependence of the dissolution rate that was consistent with liquid diffusion control with a transition to reaction control at 860 C when the speed of the disc was increased. The rotating disc technique has also been used to investigate the corrosion stability of both alloy and stainless steels in molten iron sulphide and a copper/65% calcium melt at 1220 C . The dissolution rate of the steels tested was two orders of magnitude higher in the molten sulphide than in the metal melt. 

The viscosity (dynamic, 17, or kinematic, v) and density, p (Eq. 47), influence the dissolution rate if the dissolution is transport-controlled, but not if the dissolution is reaction-controlled. In transport-controlled dissolution, increasing 17 or v will decrease D (Eq. 53), will increase h (Eqs. 46 and 49) and will reduce J (Eqs. 51 and 52). These effects are complex. For example, if an additional solute (such as a macromolecule) is added to the dissolution medium to increase 17, it may also change p and D. The ratio of 17/p = v (Eq. 47) and D directly influence h and J in the rotating disc technique, while v directly influences the Reynolds number (and hence J) for transport-controlled dissolution in general [104]. 

In contrast to the rotating disc electrode, mass transport to the ring is nonuniform. Nevertheless, the thickness of the diffusion layer Spj, which depends on the coordinate x in the direction of flow, and the rate of mass transport can be calculated. We consider a simple redox reaction, and rewrite Eq. (14.5) in the form ... 

None of the set-ups discussed so far provides stirring of the electrolyte for bubble removal or for enhancement of the reaction rates. A standard set-up developed to study kinetic electrode processes is the rotating disc electrode [11]. The electrode is a small flat disc set in a vertical axle. The hydrodynamic flow pattern at the disc depends on rotation speed and can be calculated. An additional ring electrode set at a different potential provides information about reaction products such as, for example, hydrogen. However, because this set-up is designed to study kinetic processes and is usually equipped with a platinum disc, it becomes inconvenient if silicon samples of different geometries have to be mounted. 

Benzoquinones are conveniently prepared in solution by the anodic oxidation of catechols. 1,2-Quinones are unstable in solution but they have a sufficient lifetime for the redox process to be reversible at a rotating disc electrode. Reaction involves two electrons and two protons and the half-wave potential varies with pH at 25 °C according to Equation 6.1. Some redox potentials for catechols and hy-droquinones are given m Table 6.6. 

Oxidation of ketone phenylhydrazones generates a radical-cation centre on the nitrogen atom adjacent to the benzene ring. The radical-cation is delocalised by both the hydrazone group and the phenyl ring. Reactions of 1,3,5-triphenyl-A -pyazolines illustrate the properties of these radical-cations. Two one-electron waves are seen at a rotating disc electrode in acetonitrile and for 1,3.5-triphenyl-pyrazoline, Ey. = 0.82 and 1.68 V vs. see [33]. The delocalised radical-cation is... 

Fig. 11. Electrode kinetics at the rotating disc electrode [eqn. (122)]. (a) Curve A, iL vs. co1/2 curve B, i vs. CO1/2 at a lower overpotential showing the effect of electrode kinetics where curve B is the line obtained if the reaction were reversible, (b) Analysis of curve B in (a) by plotting T1 vs. G0-1/2. k[ is obtained from the intercept and D from the slope.

Modification of the convective-diffusion equation involves addition of terms to take account of the preceding reaction. Thus, for the rotating disc electrode, we obtain... 

Recently, a numerical solution has been obtained for the LSV response to a homogeneous catalytic reaction at an electroactive-monolayer-film-covered rotating disc electrode [279]. 

Fig. 5.18 Concentration profile for dissolution and first-order reaction for a dissolving solid on a rotated disc.

The rale of collection of Brownian particles under the influence of interaction forces between the collector surface and the particles is calculated by (a) incorporating the interaction forces in the rate constant of a virtual, first order, chemical reaction taking place on the surface of the collector, and by (b) solving the convective diffusion equation subject to that chemical reaction as a boundary condition. Several geometries (sphere, cylinder, rotating disc) are considered for the collector. 

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