Voltammetric sizing

Voltammetric Sizing The average size of inert microparticles deposited on an electrode surface has been determined using cyclic voltammetric measurements [45]. This method was proposed to be used for smaller particles (i.e., if optical microscopy is not possible) as an inexpensive alternative solution to scanning electron microscopy (SEM). 

A typical arrangement for a voltammetric electrochemical cell is shown in Figure 11.28. Besides the working, reference, and auxiliary electrodes, the cell also includes a N2 purge line for removing dissolved O2 and an optional stir bar. Electrochemical cells are available in a variety of sizes, allowing for the analysis of solution volumes ranging from more than 100 mL to as small as 50 )+L. 

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.,... 

The use of micropipette electrodes for quantitative voltammetric measurements of ion transfer (IT) and electron transfer (ET) reactions at the ITIES requires knowledge of geometry of the liquid interface. For the micrometer-sized micropipettes, both the orifice radius and the thickness of the pipette wall can be measured microscopically. A typical error of the microscopic determination of a radius was estimated to be 0.5/am for a micropipette and 1 /am for a microhole [24]. 

From the foregoing treatment of voltammetry it is clear that for its application sophisticated apparatus is required, especially the electronics moreover, the construction of the electrodes and their mutual positions within the measuring vessel, of adapted size and without or with stirring, requires great care and experience. For this reason it is often advisable to purchase commercial apparatus, which has reached a high level of sophistication and reliability. Here the most desirable property is smooth recording of the voltammetric curve, which necessitates the kind of automation inherently required in the voltammetric method this is different from advanced automation, which is treated in Part C. 

In a systematical study, Golovin et al. investigated a series of metallocene derivatives in terms of their redox potentials, mass transport properties, and chemical and electrochemical stabilities in both electrochemical test cells and commercial-size AA rechargeable cells.Figure 43 shows the complete voltammetric scan of the ferrocene-containing elec-... 

The electrochemical properties of the two types of iron-cluster-derivatized AuNPs resemble that of the monomeric tetrairon cluster, except that they additionally show adsorption due to their large size, and evidence that all the Fe4 clusters are active at about the same potential, thereby indicating that they are sufficiently remote from one another to behave independently. The changes in the cyclic voltammetric pattern caused by the addition of H2P04 and ATP2- oxoanions evidence recognition features that are very different from those obtained with dendritic ferrocene exoreceptors. In particular, the results show that with these iron-cluster-derivatized AuNPs... 

The introduction of ultramicroelectrodes in the field of voltammetric analysis offers access to cyclic voltammetry experiments that are impossible with conventionally sized macroelectrodes. In addition to analyses in small volumes or at microscopic locations, microelectrodes allow measurements in resistive media and make it possible to perform high scan rate voltammetry [9,10]. 

The voltammetric behavior of the first-order catalytic process in DDPV for different values of the kinetic parameter Zi(= ( 1 + V) Ti) at spherical and disc electrodes with radius ranging from 1 to 100 pm can be seen in Fig. 4.25. For this mechanism, the criterion for the attainment of a kinetic steady state is %2 > 1-5 (Eq. 4.232) [73-75]. In both transient and stationary cases, the response is peakshaped and increases with j2. h is important to highlight that the DDPV response loses its sensitivity toward the kinetics of the chemical step as the electrode size decreases (compare the curves in Fig. 4.25a, c). For the smallest electrode (rd rs 1 pm, Fig. 4.25c), only small differences in the peak current can be observed in all the range of constants considered. Thus, the rate constants that can... 

A voltammetric experiment in a microelectrode array is highly dependent on the thickness of the individual diffusion layers, <5, compared with the size of the microelectrodes themselves, and with the interelectrode distance and the time experiment or the scan rate. In order to visualize the different behavior of the mass transport to a microelectrode array, simulated concentration profiles to spherical microelectrodes or particles calculated for different values of the parameter = fD Ja/r s can be seen in Fig. 5.17 [57] when the separation between centers of... 

Cyclic Voltammetric Behavior of the PPy-GOD Film. Figure 1 shows the cyclic voltammetric curves of a PPy-GOD film (4000 A) in phosphate buffer solution with pH 7.4 at different scan rates. Both anodic and cathodic peaks should correspond to the redox reactions of PPy chains. The peak potentials, which were recorded at the scan rate of 200 mV/s, were -380 mV and -200 mV for cathodic and anodic peaks, respectively. This is similar to the potential shifts of the PPy film doped with large anions (27) such as poly(p-styrenesulfonate). Enzyme protein molecules are composed of amino acid and have large molecular size, which can not move out freely from the PPy-GOD film by the application of the reduction potential. In order to balance the charge of the Pfy-GOD film, cations must move into the film, and redox potentials move toward a more negative potential. This behavior is different from the one observed for the PPy-GOD film, which was prepared in the solution of GOD... 

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