Platinum as electrode

A cell constructed with magnesium and platinum as electrodes, and a dry ethereal solution of ethyl bromide containing a small amount of previously prepared Grignard reagent as solution, gave electromotive forces of from 0.5 to 1.5 volts. 

For the HOR, exhibiting an exchange current density in the range of io = 10 A/cm with platinum as electrode material [9], only a small overvoltage arises even by drawing a current density of technical interest, e.g., 1 A/cm, due to the fact that the H2 molecule is easily split into two adsorbed H atoms (Tafel reaction), followed by the transfer of one electron per H atom (Volmer reaction) to the electrode generating two hydrated H". Alternatively, one electron is transferred to an adsorbed H2 molecule, followed by a split into a hydrated and an adsorbed H atom. In a consecutive step, the second H atom is oxidized (Heyrovsky reaction). 

What one can consider as the first electrochemical sensor, i.e., a modified electrode surface dedicated to a specific target analyte, was a platinum electrode, covered by a protective membrane, the Clark electrode, for the determination of O2 in blood.The first biosensor was based on the determination with such Clark electrode of O2 depletion induced by glucose oxidase activity in the presence of glucose.These two examples show the importance of platinum as electrode material. It will be seen below that gold was also widely used for the development of chemically modified electrodes, especially due to the strong interaction with thiol-functionalized organic molecules allowing the formation of self-assembled monolayers (SAM). ... 

Experimentally, the aqueous iron(II) is titrated with cerium(IV) in aqueous solution in a burette. The arrangement is shown in Figure 4.6, the platinum indicator electrode changes its potential (with reference to a calomel half-cell as standard) as the solution is titrated. Figure 4.7 shows the graph of the cell e.m.f. against added cerium(IV). At the equivalence point the amount of the added Ce (aq) is equal to the original amount of Fe (aq) hence the amounts of Ce (aq) and Fe (aq) are also equal. Under these conditions the potential of the electrode in the mixture is ( - - f)/2 this, the equivalence point, occurs at the point indicated. 

Does the platinum working electrode serve as the cathode or the anode in this analysis ... 

This method involves very simple and inexpensive equipment that could be set up m any laboratory [9, 10] The equipment consists of a 250-mL beaker (used as an external half-cell), two platinum foil electrodes, a glass tube with asbestos fiber sealed m the bottom (used as an internal half-cell), a microburet, a stirrer, and a portable potentiometer The asbestos fiber may be substituted with a membrane This method has been used to determine the fluoride ion concentration in many binary and complex fluondes and has been applied to unbuffered solutions from Willard-Winter distillation, to lon-exchange eluant, and to pyrohydrolysis distil lates obtained from oxygen-flask or tube combustions The solution concentrations range from 0 1 to 5 X 10 M This method is based on complexing by fluonde ions of one of the oxidation states of the redox couple, and the potential difference measured is that between the two half-cells Initially, each cell contains the same ratio of cerium(IV) and cerium(tll) ions... 

The properties of platinum as an inert electrode in a variety of electrolytic processes are well known, and in cathodic protection it is utilised as a thin coating on a suitable substrate. In this way a small mass of Pt can provide a very large surface area and thus anodes of this type can be operated at high current densities in certain electrolyte solutions, such as seawater, and can be economical to use. 

The action of platinum microelectrodes has been extensively studied Trials carried out by Peplow have shown that lead/ platinum bi-electrodes can be used in high velocity seawater at current densities up to 2 000 Am and that blister formation with corrosion under the blisters is decreased by the presence of platinum microelectrodes. The current density range in which the anode is normally operated is 200-750 Am with the maximum working current density quoted as 1 000 Am The consumption rate of theje anodes ranged from 0-0014 kg A y at 500Am , but increased to 0-003 kg... 

Place the prepared copper acetate solution in the beaker and add 10 mL of 20 per cent potassium iodide solution. Set the stirrer in motion and add distilled water, if necessary, until the platinum plate electrode is fully immersed. Use a saturated calomel reference electrode, and carry out the normal potentiometric titration procedure using a standard sodium thiosulphate solution as titrant. 

The polarographic determination of metal ions such as Al3 + which are readily hydrolysed can present problems in aqueous solution, but these can often be overcome by the use of non-aqueous solvents. Typical non-aqueous solvents, with appropriate supporting electrolytes shown in parentheses, include acetic acid (CH3C02Na), acetonitrile (LiC104), dimethylformamide (tetrabutyl-ammonium perchlorate), methanol (KCN or KOH), and pyridine (tetraethyl-ammonium perchlorate), In these media a platinum micro-electrode is employed in place of the dropping mercury electrode. 

When the electrode is placed in an aqueous solution of glucose which has been suitably diluted with a phosphate buffer solution (pH 7.3), solution passes through the outer membrane into the enzyme where hydroxen peroxide is produced. Hydrogen peroxide can diffuse through the inner membrane which, however, is impermeable to other components of the solution. The electrode vessel contains phosphate buffer, a platinum wire and a silver wire which act as electrodes. A potential of 0.7 volts is applied to the electrodes (the apparatus shown in Fig. 16.17 is suitable) with the platinum wire as anode. At this electrode the reaction H202->02 + 2H+ +2e takes place, and the oxygen produced is reduced at the silver cathode ... 

No experiments appear to have been made with such cells, although the equation has been verified with oxygen at different partial pressures in admixture with nitrogen, with platinum electrodes and hot solid glass as electrolyte (Haber and Moser). A similar case is that of two amalgams of a metal, of different concentrations, as electrodes, and a solution of a salt of the metal as electrolyte (G. Meyer, 1891). Here we must take the osmotic pressures of the metals in the amalgams, Pi, P2, and, for an 7i-valent metal ... 

FIG. 26 Cyclic voltammograms of 40 monolayers of Langmuir-Schaefer films of cytochrome P450SCC on indium-tin oxide glass plate (ITO) in 10 mM phosphate buffer at a scan rate of 20 mV/s between 0.4 and —0.4 V vs. Ag/AgCl. LS films on ITO worked as the working electrode, platinum as the counter, and Ag/AgCl as the reference electrode. Cholesterol dissolved in X-triton 100 was added 50 p.1 at a time (1) with cholesterol, (2) 50 p.1 of cholesterol, (3) 100 p.1 cholesterol, and (4) 150 p.1 of cholesterol. 

The only species which need be present in the cell initially are the reactants, zinc atoms, and Cu2+ ions. In other words, the anode of the cell must be made of zinc and the solution surrounding the cathode must contain Cu2+ ions. On the other hand, the products of the reaction, copper atoms and Zn2+ ions, need not be present when the cell is set up. A platinum wire can be substituted for the copper rod copper ions plate out as readily on platinum as on copper. Any positive ion which does not react with zinc can replace the Zn2+ ions surrounding the zinc electrode. A solution of Na2S04 or KN03 works as well as a solution of ZnS04. 

We and others have been involved in the study of such systems including Cu/Au(lll),85 86 Ag/Au(lll),87 Pb/Ag(lll),88 and Cu/Pt(lll).89 The first three systems involved the use of epitaxially deposited metal films on mica as electrodes.90 92 Such deposition gives rise to electrodes with well-defined single-crystalline structures. In the last case a bulk platinum single crystal was employed. Because of the single-crystalline nature of the electrodes, polarization dependence studies could be used to ascertain surface structure. 

This system was subsequently investigated by Christensen et at. (1990) also using in situ FTIR, who observed identical product features (see Figure 3.48). In order first to compare directly the IR spectrum of oxalate generated in situ, the authors took advantage of the surface reactivity of Pt and the poor diffusion of species to and from the thin layer. Thus, a solution of oxalic acid in the electrolyte was placed in the spectroelectrochemical cell, the potential of the platinum working electrode stepped to successively lower values and spectra taken at each step. The spectra were all normalised to the reference spectrum collected at the base potential of 0 V vs. SCE. As a result of the deprotonation of adventitious water ... 

Application of transition metal hexacyanoferrates for development of biosensors was first announced by our group in 1994 [118]. The goal was to substitute platinum as the most commonly used hydrogen peroxide transducer for Prussian blue-modified electrode. The enzyme glucose oxidase was immobilized on the top of the transducer in the polymer (Nation) membrane. The resulting biosensor showed advantageous characteristics of both sensitivity and selectivity in the presence of commonly tested reductants, such as ascorbate and paracetamol. 

This method in some ways resembles the technique for ASV [321,322]. The analytical device is based on a three-electrode system (1) a glassy carbon electrode, which serves as a cathode (2) a saturated calomel electrode (SCE), which is the reference electrode and (3) a platinum counter-electrode during electrolysis. 

On the other hand, the only component present in the electrolysis cell that can be reduced is water, no matter what metal the electrode material is made from. So the formation of H2 gas by the reduction of water is unaffected when platinum, Cu or most other common metals are used as electrodes. 

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