Reduction reaction electrolytic

For example, for iron in aqueous electrolytes, tlie tliennodynamic warning of tlie likelihood of corrosion is given by comparing tlie standard electrode potential of tlie metal oxidation, witli tlie potential of possible reduction reactions. 

Electroless Electrolytic Plating. In electroless or autocatalytic plating, no external voltage/current source is required (21). The voltage/current is suppHed by the chemical reduction of an agent at the deposit surface. The reduction reaction must be catalyzed, and often boron or phosphoms is used as the catalyst. Materials that are commonly deposited by electroless plating (qv) are Ni, Cu, Au, Pd, Pt, Ag, Co, and Ni—Fe (permalloy). In order to initiate the electroless deposition process, a catalyst must be present on the surface. A common catalyst for electroless nickel is tin. Often an accelerator is needed to remove the protective coat on the catalysis and start the reaction. 

The term electrochromism was apparently coined to describe absorption line shifts induced in dyes by strong electric fields (1). This definition of electrocbromism does not, however, fit within the modem sense of the word. Electrochromism is a reversible and visible change in transmittance and/or reflectance that is associated with an electrochemicaHy induced oxidation—reduction reaction. This optical change is effected by a small electric current at low d-c potential. The potential is usually on the order of 1 V, and the electrochromic material sometimes exhibits good open-circuit memory. Unlike the well-known electrolytic coloration in alkaU haUde crystals, the electrochromic optical density change is often appreciable at ordinary temperatures. 

Coulometry measures the amount of cunent flowing dirough a solution in an electrochemical oxidation or reduction reaction and is capable of measuring at ppm or even ppb levels of reactive gases. Thus a sample of ambient air is drawn through an electrolyte in a cell and the required amount of reactant is generated at the electrode. This technique tends to be non-specific, but selectivity can be enhanced by adjustment of pH and electrolyte composition, and by incorporation of filters to remove interfering species. 

The battery acts as an electron pump, pushing electrons into the cathode, C, and removing diem from the anode, A. To maintain electrical neutrality, some process within the cell must consume electrons at C and liberate them at A. This process is an oxidation-reduction reaction when carried out in an electrolytic cell, it is called electrolysis. At the cathode, an ion or molecule undergoes reduction by accepting electrons. At the anode, electrons are produced by the oxidation of an ion or molecule. 

The design of a AA-size alkaline manganese dioxide cell is shown in Fig. 1 (Sec. 3.1). Primary and secondary alkaline batteries are constructed in the same way and can be manufactured on essentially the same machinery. The separator material, electrode formulation, and the Mn02 Zn balance are different. Rechargeable cells are zinc-limited to prevent a discharge beyond the first electron-equivalent of the MnOz reduction. The electrolyte is 7-9 mol L KOH. The electrode reactions are ... 

Several significant electrode potentials of interest in aqueous batteries are listed in Table 2 these include the oxidation of carbon, and oxygen evolution/reduction reactions in acid and alkaline electrolytes. For example, for the oxidation of carbon in alkaline electrolyte, E° at 25 °C is -0.780 V vs. SHE or -0.682 V (vs. Hg/HgO reference electrode) in 0.1 molL IC0 2 at pH [14]. Based on the standard potentials for carbon in aqueous electrolytes, it is thermodynamically stable in water and other aqueous solutions at a pH less than about 13, provided no oxidizing agents are present. 

An electrolytic method for removing CaO from CaCl2 was suggested by Barletta, et.al.17 The salt is electrolyzed in a cell with a graphite consumable anode. Oxygen is removed at the anode where it reacts with carbon to form CO and C02. Calcium ions are reduced to metal at the cathode. Thus, the electrolytic reduction reaction should be... 

A fuel cell consists of an ion-conducting membrane (electrolyte) and two porous catalyst layers (electrodes) in contact with the membrane on either side. The hydrogen oxidation reaction at the anode of the fuel cell yields electrons, which are transported through an external circuit to reach the cathode. At the cathode, electrons are consumed in the oxygen reduction reaction. The circuit is completed by permeation of ions through the membrane. 

Analytical methods based upon oxidation/reduction reactions include oxidation/reduction titrimetry, potentiometry, coulometry, electrogravimetry and voltammetry. Faradaic oxidation/reduction equilibria are conveniently studied by measuring the potentials of electrochemical cells in which the two half-reactions making up the equilibrium are participants. Electrochemical cells, which are galvanic or electrolytic, reversible or irreversible, consist of two conductors called electrodes, each of which is immersed in an electrolyte solution. In most of the cells, the two electrodes are different and must be separated (by a salt bridge) to avoid direct reaction between the reactants. 

The electrochemical reduction reactions of the central metallotetraphenylporphyrin moieties are, fortunately, much more straightforwardly analyzed (1,2). With few exceptions, when transferred to a fresh supporting electrolyte solution, films formed from ECP reactions like Fig. 2A exhibit electrochemical reduction waves at or very near the potentials observed for reductions of the corresponding monomers dissolved in solutions. For example, a film formed oxidatively as in Fig. 2A gives in fresh electrolyte the reductive gyclic voltammogram of Fig. 2B. 

Kashiwazaki67 has fabricated a complementary ECD using plasma-polymerized ytterbium bis(phthalocyanine) (pp—Yb(Pc)2) and PB films on ITO with an aqueous solution of 4M KC1 as electrolyte. Blue-to-green electrochromicity was achieved in a two-electrode cell by complementing the green-to-blue color transition (on reduction) of the pp—Yb(Pc)2 film with the blue (PB)-to-colorless (PW) transition (oxidation) of the PB. A three-color display (blue, green, and red) was fabricated in a three-electrode cell in which a third electrode (ITO) was electrically connected to the PB electrode. A reduction reaction at the third electrode, as an additional counter electrode, provides adequate oxidation of the pp Yb(Pc)2 electrode, resulting in the red coloration of the pp—Yb(Pc)2 film. 

Polyaniline (PANI) was investigated as electrocatalyst for the oxygen reduction reaction in the acidic and neutral solutions. Galvanostatic discharge tests and cyclic voltammetry of catalytic electrodes based on polyaniline in oxygen-saturated electrolytes indicate that polyaniline catalyzes two-electron reduction of molecular oxygen to H2O2 and HO2". 

It should be noted here, that not only the (chemical and morphological) composition of the protective layers at the basal plane surfaces and prismatic surfaces is different, but that these layers also have completely different functions. At the prismatic surfaces, lithium ion transport into/ffom the graphite structure takes place by intercalation/de-intercalation. Here the formed protective layers of electrolyte decomposition products have to act as SEI, i.e., as transport medium for lithium cations. Those protective layers, which have been formed on/at the basal plane surfaces, where no lithium ion transport into/from the graphite structure takes place, have no SEI function. However, these non-SEI layers still protect these anode sites from further reduction reactions with the electrolyte. 

In order to study the identity and nature of the intermediate, Aylmer-K.elly et al. (1973) employed modulated specular reflectance spectroscopy. They studied the reduction reaction at a lead cathode in both aqueous and non-aqueous electrolytes. A phase-sensitive detection system was employed by the authors, locked-in to the frequency of the potential modulation. The potential was modulated at 30 Hz between the reference potential of — 1.0 V vs. Ag/AgCl and a more cathodic limit. 

Bao 5Sr0 5Co08Fe0 2O3 (BSCF) shows extremely high electrochemical activity for the 02 reduction reaction at intermediate temperatures. Shao and Flaile [105] applied BSCF as cathode to a doped ceria electrolyte cell and achieved the power densities of... 

The consequences of the electrochemical reduction of high valence chromium species would be the precipitation of Cr203 solid phase at the cathode-electrolyte interface boundary. These led to the hypothesis that the degradation mechanism of LSM cathode is dominated by an electrochemical reduction of high valence vapor species of chromium (Cr03 and C OH O to solid phase Cr203 in competition with the 02 reduction reaction, followed by the chemical reaction with LSM to form (Cr,Mn)304 phases at the TPB, blocking the active sites [174-180], The process is written as follows [174] ... 

A battery is an electrochemical cell, and is defined as a device comprising two or more redox couples (where each couple comprises two redox states of the same material). An oxidation reaction occurs at the negative pole of the battery in tandem with a reduction reaction at the positive pole. Both reactions proceed with the passage of current. The two redox couples are separated physically by an electrolyte. 

Electroanalytical techniques are an extension of classical oxidation-reduction chemistry, and indeed oxidation and reduction processes occur at the surface of or within the two electrodes, oxidation at one and reduction at the other. Electrons are consumed by the reduction process at one electrode and generated by the oxidation process at the other. The electrode at which oxidation occurs is termed the anode. The electrode at which reduction occurs is termed the cathode. The complete system, with the anode connected to the cathode via an external conductor, is often called a cell. The individual oxidation and reduction reactions are called half-reactions. The individual electrodes with their half-reactions are called half-cells. As we shall see in this chapter, the half-cells are often in separate containers (mostly to prevent contamination) and are themselves often referred to as electrodes because they are housed in portable glass or plastic tubes. In any case, there must be contact between the half-cells to facilitate ionic diffusion. This contact is called the salt bridge and may take the form of an inverted U-shaped tube filled with an electrolyte solution, as shown in Figure 14.2, or, in most cases, a small fibrous plug at the tip of the portable unit, as we will see later in this chapter. 

Carbon is unique among chemical elements since it exists in different forms and microtextures transforming it into a very attractive material that is widely used in a broad range of electrochemical applications. Carbon exists in various allotropic forms due to its valency, with the most well-known being carbon black, diamond, fullerenes, graphene and carbon nanotubes. This review is divided into four sections. In the first two sections the structure, electronic and electrochemical properties of carbon are presented along with their applications. The last two sections deal with the use of carbon in polymer electrolyte fuel cells (PEFCs) as catalyst support and oxygen reduction reaction (ORR) electrocatalyst. 

Figure 6.12 Linear-sweep voltammogram for the reduction reaction, O - - ne" —> R, at a solid electrode, shown as a function of the scan rate u. The solution was under diffusion control, which was achieved by adding inert electrolyte and maintaining a still solution during potential ramping. Note that the x-axis has been normalized to , that is, thex-axis represents an overpotential. Reproduced from Greef, R., Peat, R., Peter, L.M., Pletcher, D. and Robinson, J., Instrumental Methods in Electrochemistry, Ellis Horwood, Chichester, 1990, with permission of Profes.sor D. Pletcher, Department of Chemistry, University of Southampton, Southampton, UK.

Figure 9. Schematic porous electrode structure (A) Electrons from the external circuit flow in the current collector which has contact to the conductive matrix in the electrode structure. The redox reaction at the electrode produces electrons that enter the external circuit and flow through the load to the cathode, where the reduction reaction at the cathode accepts the electron from the external circuit and the reduction reaction. The ions in the electrolyte carry the current through the device. (B) The reaction distribution in the porous electrode is shown for the case where the conductivity of the electrode matrix is higher than the conductivity of the electrolyte.

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