Tubular electrode: construction

Tubular electrodes. Blaedel et al.161 were the first to introduce the TBE, a tubular electrode. It was constructed by melting a Pt cylinder in a glass capillary (see Fig. 5.25), the total length of Pt being 25.5 mm and its diameter 0.75 mm. The authors originally used it for an enzymatic determination of glucose by means of differential amperometry based on the following sequential reactions"12 ... 

The construction of tubular electrodes may be divided into two basic types integral and demountable. Channel electrodes are only of the latter type. Final dimensions must satisfy the entry length criterion for Poiseuille flow (pp. 370 and 372). 

Fig. 8. Typical tubular electrode assemblies, (a) Integral construction. A, Generator electrode B, detector electrode C, reference electrode D, counter electrode E, porous frits F, ball and socket joints G, epoxy resin, (b) Demountable type. A, Generator electrode B, counter electrode C, Teflon spacers D, reference electrode E, Teflon cell body F, brass thread. (From ref. 128.)...

The small sealed sintered plate Ni-Cd cylindrical and prismatic cell constructions have the favorable characteristics of the pocket/tubular plate constructions with increased energy density. The electrodes are thin and the cells have low internal resistance with excellent high rate and low temperature performance. The stem is rugged and can withstand physical and electrical abuse. It requires minimal maintenance. 

Pocket Plate Electrode. This is the same type of electrode used in pocket plate nickel-cadmium and nickel-iron batteries. Electrodes are prepared by loading nickel hydroxide hydrate active material and a conductive additive (graphite and/or nickel flake) into tubular flat pockets which are then assembled into electrodes. Little interest currently exists in using this type of electrode in nickel-zinc cells since modern cells attempt to utilize lightweight electrode construction. 

A potentiometric determination of saccharin was proposed by Fatibello-Filho et al. [86]. In this method, saccharin was potentiometrically measured using a silver wire coated with a mercury film as the working electrode. With this, the main difficulty was the presence of a precipitate (mercurous saccharinate) that could adsorb on tube walls and the electrode surface. To avoid these undesirable effects, a relocatable filter unit was placed before the flow-through potentiometric cell and a surfactant was added to the carrier solution (Figure 24.12). The same investigation team reported the construction and analytical evaluation of a tubular ion-selective electrode coated with an ion pair formed between saccharinate anion and toluidine blue O cation incorporated on a poly(vinyl chloride) matrix [87]. This electrode was constructed and adapted in a FIA system. The optimum experimental conditions found were an analytical path of 120 cm, an injection sample volume of 500 pL, a pH of 2.5, a flow rate of 2.3 mL/min, and a tubular electrode length of 2.5 cm. 

Tubular Cells. Although the tubular nickel electrode invented by Edison is ahnost always combined with an iron negatwe electrode, a small quantity of cells is produced in wliich nickel in the tubular fomi is used with a pocket cadniium electrode. Tliis type of cell construction is used for low operating temperature environments, where iron electrodes do not perfomi well or where charging current must be limited. 

The detector cell was a three-electrode system consisting of a flow-through nickel working electrode, a saturated calomel reference electrode (SCE), and a stainless steel outlet tubing counter electrode. The tubular-type electrode cell housing was constructed of molded Teflon, which was machined to provide the channels and to accommodate the fittings. The working electrode area was... 

Iron-nickel oxide cells are always vented. Tubular/pocket plate electrodes are constructed as described above and are generally housed in nickel-plated steel cases. Cells with sintered plate electrodes have smaller inter-electrode spacings. They use synthetic fibre fabrics as separators, and plastic containers. 

Amperometric detectors are easily miniaturized with preservation of performance, since their operation is based on reactions at the electrode surface. Using a single carbon fiber or microelectrode as a working electrode allows detector cells of very small volume and in-column detectors to be constructed for use in open tubular and packed capillary column liquid chromatography [189-192]. These microcolumn separation techniques combined with amperometric detection are exploited for the quantitative analysis of volume-limited samples such as the contents of single cells [193,194]. 

The tubular design is probably the best-known design. It has been developed by Westinghouse (now Siemens Power generation) [8]. The first concept that was pursued by Westinghouse consisted of an air electrode supported fuel cell tube. In earlier days the tubes were made from calcium-stabilized zirconia on which the active cell components were sprayed. Nowadays this porous supported tube (PST) is replaced by a doped lanthanum manganite (LaMn) air electrode tube (AES) that increases the power density by about 35 %. The LaMn tubes are extruded and sintered and serve as the air electrode. The other cell components are deposited on this construction by plasma spraying. 

Different miniaturized flow injection analyzers have been constructed using spectrophotometry as a leading detection technique. Besides, electrochemical techniques such as amperometry and potentiometry with chemically modified solidstate electrodes and tubular membrane-based ISEs, respectively, have been proved to be well adapted to multiparametric measurements of inorganic species present in wastewater, using multiple sensor arrays. 

Commercial glass electrodes, mostly for pH measurements, differ in construction because they have to serve different purposes. The electrode tips may have different shapes, including tubular flow-through electrodes (Figure 3). Special electrodes are used under conditions of high pressures or high temperatures or... 

The negative current collector is a perforated nickel-plated steel pocket plate assembly. The tubes are produced from perforated nickel-plated strips that are wound to produce a tube. The tubular construction has one end crimped and the active material is poured into the open end in layers with nickel flakes. Alternatively, a machine automatically introduces the active material and tamps it into the pockets. After filling, the tubes/pockets are crimped and pressed into openings in the nickel-plated steel electrode frame. A similar process is used for the positive electrode. 

The construction of ISEs used in clinical measurements is of the membrane electrode type, i.e., the ion-sensitive membrane separates the sample from an internal reference electrolyte, which is the site of the internal reference element, usually a silver wire covered by silver chloride. The membrane can be shaped to different forms such as flat, convex, tubular, etc. Sodium sensitive membranes are made from special composition glass, the other ion-sensitive membranes from a polymer matrix such as plasticized polyvinylchloride (PVC) or silicon rubber. The particular selectivity of polymer membranes is first of all due to a small percentage of active material, e.g., valinomycin, dissolved in the polymer. Important secondary effects have been attributed to the type and permittivity of the polymer. The useful lifetime of the sensors also depends on the polymer. The time response [13] may again depend on membrane composition. 

---