Diffusion-limited current

Diffusion at Microelectrodes The total diffusion-limited current is composed of the planar flux and radial flux diffusion components ... 

Often, we need only a qualitative estimate that is, we want to know whether the limiting current is raised or lowered by migration relative to the purely diffusion-limited current, or whether a, is larger or smaller than unity. It is evident that a, will be larger than unity when migration and diffusion are in the same direction. This is found in four cases for cations that are reactants in a cathodic reaction (as in the example above) or products in an anodic reaction, and for anions that are reactants in an anodic reaction or products in a cathodic reaction. In the other four cases (for cations that are reactants in an anodic or products in a cathodic reaction, and for anions that are reactants in a cathodic or products in an anodic reaction), we have a, < 1, a typical example being the cathodic deposition of metals from complex anions. 

FIG. 24 Steady-state diffusion-limited current for the reduction of oxygen in water at an UME approaching a water-DCE (O) and a water-NB (A) interface. The solid lines are the characteristics predicted theoretically for no interfacial kinetic barrier to transfer and for y = 1.2, Aj = 5.5 (top solid curve) or y = 0.58, = 3.8 (bottom solid curve). The lower and upper dashed lines denote the... 

The driving force for the transfer process was the enhanced solubility of Br2 in DCE, ca 40 times greater than that in aqueous solution. To probe the transfer processes, Br2 was recollected in the reverse step at the tip UME, by diffusion-limited reduction to Br . The transfer process was found to be controlled exclusively by diffusion in the aqueous phase, but by employing short switching times, tswitch down to 10 ms, it was possible to put a lower limit on the effective interfacial transfer rate constant of 0.5 cm s . Figure 25 shows typical forward and reverse transients from this set of experiments, presented as current (normalized with respect to the steady-state diffusion-limited current, i(oo), for the oxidation of Br ) versus the inverse square-root of time. 

FIG. 28 Normalized steady-state diffusion-limited current vs. UME-interface separation for the reduction of oxygen at an UME approaching an air-water interface with 1-octadecanol monolayer coverage (O)- From top to bottom, the curves correspond to an uncompressed monolayer and surface pressures of 5, 10, 20, 30, 40, and 50 mN m . The solid lines represent the theoretical behavior for reversible transfer in an aerated atmosphere, with zero-order rate constants for oxygen transfer from air to water, h / Q mol cm s of 6.7, 3.7, 3.3, 2.5, 1.8, 1.7, and 1.3. (Reprinted from Ref. 19. Copyright 1998 American Chemical Society.)... 

In a typical voltammetric experiment, a constant voltage or a slow potential sweep is applied across the ITIES formed in a micrometer-size orifice. If this voltage is sufficiently large to drive some IT (or ET) reaction, a steady-state current response can be observed (Fig. 1) [12]. The diffusion-limited current to a micro-ITIES surrounded by a thick insulating sheath is equivalent to that at an inlaid microdisk electrode, i.e.,... 

Assuming that the orifice is disk-shaped, one can calculate the steady-state diffusion-limiting current to a pipette from Eq. (1). However, current values about three times higher than expected from Eq. (1) were measured for interfacial IT [18] and ET [5]. The following empirical equation for the limiting current at a pipette electrode was proposed [18bj ... 

Unlike solid electrodes, the shape of the ITIES can be varied by application of an external pressure to the pipette. The shape of the meniscus formed at the pipette tip was studied in situ by video microscopy under controlled pressure [19]. When a negative pressure was applied, the ITIES shape was concave. As expected from the theory [25a], the diffusion current to a recessed ITIES was lower than in absence of negative external pressure. When a positive pressure was applied to the pipette, the solution meniscus became convex, and the diffusion current increased. The diffusion-limiting current increased with increasing height of the spherical segment (up to the complete sphere), as the theory predicts [25b]. Importantly, with no external pressure applied to the pipette, the micro-ITIES was found to be essentially flat. This observation was corroborated by numerous experiments performed with different concentrations of dissolved species and different pipette radii [19]. The measured diffusion current to such an interface agrees quantitatively with Eq. (6) if the outer pipette wall is silanized (see next section). The effective radius of a pipette can be calculated from Eq. (6) and compared to the value found microscopically [19]. 

The silanization of the surface of a glass pipette may be necessary for different reasons [19]. If the pipette is to be filled with an aqueous solution, its outer wall should be made hydrophobic to prevent the formation of a thin aqueous film that may cause large deviations of the experimental diffusion-limiting current from the theory (see Section II.B). Experimental voltammograms were found to quantitatively agree with the theory after the aqueous layer was eliminated by silanizing the outer pipette wall. 

The radii of both orifices can be either on a micrometer or a submicrometer scale. If the device is micrometer-sized, it can be characterized by optical microscopy. The purposes of electrochemical characterization of a dual pipette are to determine the effective radii and to check that each of two barrels can be independently polarized. The radius of each orifice can be evaluated from an IT voltammogram obtained at one pipette while the second one is disconnected. After the outer surface of glass is silanized, the diffusion-limiting current to each water-filled barrel follows Eq. (1). The effective radius values calculated from that equation for both halves of the d-pipette must be close to the values found from optical microscopy. 

If we consider the limiting current ( ,) to be confined to a merely diffusion-limited current (id), we can consider its value as follows. As an example we take the cathodic reduction of a Zn2+ solution with a considerable amount of KC1. We chose an Eapp value greater than Eiecomp of Zn2+ and less than decomp of K +, so that only Zn2+ is reduced. The transport of electricity is completely provided for by the excess of K+ and Cl ions and hence Zn2+ ions can reach the cathode only by diffusion. Suppose [Zn2+ ] in the bulk of the solution is equal to C and at the cathode surface is equal to c the latter therefore determines the electrode potential. For diffusion perpendicular to the electrode surface we have Fick s first law ... 

These results are plausible since according to Sand a two-fold concentration of a component yields a four-fold transition time. Now, these features show, in contrast to the net separation and pure additivity of polarographic waves and their diffusion-limited currents as concentration functions, that in chrono-potentiometry the transition times of components in mixtures are considerably increased by the preceding transition times of any other more reactive component, which complicates considerably the concentration evaluation of chronopotentiograms. 

There are, however, obvious limitations. It is not possible to make a very small spherical electrode, because the leads that connect it to the circuit must be even much smaller lest they disturb the spherical geometry. Small disc or ring electrodes are more practicable, and have similar properties, but the mathematics becomes involved. Still, numerical and approximate explicit solutions for the current due to an electrochemical reaction at such electrodes have been obtained, and can be used for the evaluation of experimental data. In practice, ring electrodes with a radius of the order of 1 fxm can be fabricated, and rate constants of the order of a few cm s 1 be measured by recording currents in the steady state. The rate constants are obtained numerically by comparing the actual current with the diffusion-limited current. 

H. -C. Shin et al., A study on the simulated diffusion-limited current transient of a self-affine fractal electrode based upon the scaling property, J. Electroanal. Chem., 531 p. 101, Copyright 2002, with permission from Elsevier Science. 

Figure 8. Simulated current transients obtained from the self-affine fractal profiles h(x) of various morphological amplitudes rj of (a) 0.1, 0.3, and 0.5 (b) 1.0, 2.0, and 4.0 in h(x) = 7]fws(x). Reprinted from H.-C. Shin et al., A study on the simulated diffusion-limited current transient of a self-affine fractal electrode based upon the scaling property, J. Electroanal. Chem., 531, p. 101, Copyright 2002, with permission from Elsevier Science.

Channel techniques employ rectangular ducts through which the electrolyte flows. The electrode is embedded into the wall [33]. Under suitable geometrical conditions [2] a parabolic velocity profile develops. Potential-controlled steady state (diffusion limiting conditions) and transient experiments are possible [34]. Similar to the Levich equation at the RDE, the diffusion limiting current is... 

Example 6.2. Calculate the diffusion limiting current density for the deposition of a metal ion at a cathode in a quiescent (unstirred) solution assuming a diffusion layer thickness 8 of 0.05 cm. The concentration of ions in the bulk (cj,) is 10 moEL (10 moEcm ), the same as in Example 6.1. The diffusion coefficient D of in the unstirred solution is 2 X lO cm /s. Using Eq. (6.83), we calculate that the limiting diffusion current density for this case is... 

A limiting current insensitive to changes in electrode potential and below the convective-diffusion limiting current indicates that a chemical step is rate-determining and precedes the charge transfer step in the overall electrode reaction (CE mechanism). 

Diffusion-limited currents at hydrodynamic electrodes under laminar flow conditions3... 

M represents the diffusion-limited current of X that would be observed if it were electroactive. Thus, the ring current begins to increase from zero... 

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