Electroactive species

SECM Scanning electrochemical microscopy [40] An STM serves as microelectrode to reduce electroactive species Electrochemical reactions on surfaces... 

Electrode processes are a class of heterogeneous chemical reaction that involves the transfer of charge across the interface between a solid and an adjacent solution phase, either in equilibrium or under partial or total kinetic control. A simple type of electrode reaction involves electron transfer between an inert metal electrode and an ion or molecule in solution. Oxidation of an electroactive species corresponds to the transfer of electrons from the solution phase to the electrode (anodic), whereas electron transfer in the opposite direction results in the reduction of the species (cathodic). Electron transfer is only possible when the electroactive material is within molecular distances of the electrode surface thus for a simple electrode reaction involving solution species of the fonn... 

Figure Bl.28.3. Concentration profiles of an electroactive species with distance from the electrode surface during a linear sweep voltaimnogram.

If adsorbed electroactive species are present on the electrode surface, the shape of the cyclic voltaimnogram changes, since the species do not need to difflise to the electrode surface. In this case the peaks are syimnetrical with coincident peak potentials provided the kinetics are fast. 

O, a large current is detected, which decays steadily with time. The change in potential from will initiate the very rapid reduction of all the oxidized species at the electrode surface and consequently of all the electroactive species diffrising to the surface. It is effectively an instruction to the electrode to instantaneously change the concentration of O at its surface from the bulk value to zero. The chemical change will lead to concentration gradients, which will decrease with time, ultimately to zero, as the diffrision-layer thickness increases. At time t = 0, on the other hand, dc-Jdx) r. will tend to infinity. The linearity of a plot of i versus r... 

In potentiometry the potential of an electrochemical cell is measured under static conditions. Because no current, or only a negligible current, flows while measuring a solution s potential, its composition remains unchanged. For this reason, potentiometry is a useful quantitative method. The first quantitative potentiometric applications appeared soon after the formulation, in 1889, of the Nernst equation relating an electrochemical cell s potential to the concentration of electroactive species in the cell. ... 

The size-exclusion and ion-exchange properties of zeoHtes have been exploited to cause electroactive species to align at a zeoHte—water interface (233—235). The zeoHte thus acts as a template for the self-organization of electron transfer (ET) chains that may find function as biomimetic photosynthetic systems, current rectifiers, and photodiodes. An example is the three subunit ET chain comprising Fe(CN)g anion (which is charge-excluded from the anionic zeoHte pore stmcture), Os(bipyridine)3 (which is an interfacial cation due to size exclusion of the bipyridine ligand), and an intrazeoHte cation (trimethylamino)methylferrocene (F J ). A cationic polymer bound to the (CN) anion holds the self-assembled stmcture at an... 

Cha.rging Current. In most cases, appHcation of a voltage to an electrode is iatended to produce an analytically useful current that depends solely on the concentration of the analyte. Unfortunately, current flows even ia the complete absence of the analyte. Thus, the current may have nothing to do with the electroactive species ia the sample. This charging current must be circumvented or otherwise compensated. 

Smaller values of necessitate the appHcation of voltages greater than those calculated from the Nemst equation to obtain a corresponding set of surface concentrations of electroactive species. These voltages are called overpotentials and iadicate chemically related difficulties with the electrolysis. In other words, electron exchange between the electrode and the electroactive species is impeded by the chemistry of the process itself. 

Design possibilities for electrolytic cells are numerous, and the design chosen for a particular electrochemical process depends on factors such as the need to separate anode and cathode reactants or products, the concentrations of feedstocks, desired subsequent chemical reactions of electrolysis products, transport of electroactive species to electrode surfaces, and electrode materials and shapes. Cells may be arranged in series and/or parallel circuits. Some cell design possibiUties for electrolytic cells are... 

In order to achieve good rechargeability, one has to maintain a consistent geometry on both the macro and micro scales, and to avoid electrical disconnection of the electroactive species. 

The general thermodynamic treatment of binary systems which involve the incorporation of an electroactive species into a solid alloy electrode under the assumption of complete equilibrium was presented by Weppner and Huggins [19-21], Under these conditions the Gibbs Phase Rule specifies that the electrochemical potential varies with composition in the single-phase regions of a binary phase diagram, and is composition-independent in two-phase regions if the temperature and total pressure are kept constant. 

If we look at the mechanistic and crystallographic aspects of the operation of polycomponent electrodes, we see that the incorporation of electroactive species such as lithium into a crystalline electrode can occur in two basic ways. In the examples discussed above, and in which complete equilibrium is assumed, the introduction of the guest species can either involve a simple change in the composition of an existing phase by solid solution, or it can result in the formation of new phases with different crystal structures from that of the initial host material. When the identity and/or amounts of phases present in the electrode change, the process is described as a reconstitution reaction. That is, the microstructure is reconstituted. 

The second way in which an electroactive species such as lithium can be incorporated into the structure of an electrode is by a topotactic insertion reaction. In this case the guest species is relatively mobile and enters the crystal structure of the host phase so that no significant change in the structural configuration of the host lattice occurs. 

A quite different approach was introduced in the early 1980s [44-46], in which a dense solid electrode is fabricated which has a composite microstructure in which particles of the reactant phase are finely dispersed within a solid, electronically conducting matrix in which the electroactive species is also mobile. There is thus a large internal reactant/mixed-conductor matrix interfacial area. The electroactive species is transported through the solid matrix to this interfacial region, where it undergoes the chemical part of the electrode reaction. Since the matrix material is also an electronic conductor, it can also act as the electrode s current collector. The electrochemical part of the reaction takes place on the outer surface of the composite electrode. 

When such an electrode is discharged by removal of the electroactive species, the residual particles of the reactant phase remain as relics in the microstructure. This provides fixed permanent locations for the reaction to take place during following cycles, when the electroactive species again enters the structure. Thus this type of con-... 

The kinetic requirements for a successful application of this concept are readily understandable. The primary issue is the rate at which the electroactive species can reach the matrix/reactant interfaces. The critical parameter is the chemical diffusion coefficient of the electroactive species in the matrix phase. This can be determined by various techniques, as discussed above. 

The electrolyte is sandwiched between two electrodes which have different but precisely known chemical potentials for the electroactive species. Since no overall current is allowed to pass the external electric circuit (i.e., =0), integration of Eq. 

The advantages of controlled-potential techniques include high sensitivity, selectivity towards electroactive species, a wide linear range, portable and low-cost instrumentation, speciation capability, and a wide range of electrodes that allow assays of unusual environments. Several properties of these techniques are summarized in Table 1-1. Extremely low (nanomolar) detection limits can be achieved with very small sample volumes (5-20 pi), thus allowing the determination of analyte amounts of 10 13 to 10 15 mol on a routine basis. Improved selectivity may be achieved via the coupling of controlled-potential schemes with chromatographic or optical procedures. 

Hence, the current (at any time) is proportional to the concentration gradient of the electroactive species. As indicated by the above equations, the dififusional flux is time dependent. Such dependence is described by Fick s second law (for linear diffusion) ... 

Which experimental conditions assure that the movement of the electroactive species is limited by diffusion How do these conditions suppress the migration and convection effects ... 

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