Platinum electrodes potential range

At a platinum electrode, potentials of about 3 V (versus Ag/AgCl) can be reached, and the limiting reaction is the discharge of the supporting electrolyte. The useful range in cathodic direction is very dependent on the water content. 

The use of an infrared microscope enables the investigation of the surface of rather small electrodes. The resulting miniaturization of the necessary electrochemical cell allows its operation as a fiow cell in thin layer arrangement [242]. Combined with a rapid-scan FTIR spectrometer, acquisition of infrared spectra during electrode potential scans at a rate of d /dr = 200 mV-s are possible. The time resolution is equivalent to one complete spectrum recorded every 2.6 mV. The formation of various reaction intermediates of methanol oxidation in alkaline solution at a platinum electrode could be assigned to specific electrode potential ranges. 

The limited anodic potential range of mercury electrodes has precluded their utility for monitoring oxidizable compounds. Accordingly, solid electrodes with extended anodic potential windows have attracted considerable analytical interest. Of the many different solid materials that can be used as working electrodes, the most often used are carbon, platinum, and gold. Silver, nickel, and copper can also be used for specific applications. A monograph by Adams (17) is highly recommended for a detailed description of solid-electrode electrochemistry. 

Finally, the electrode potential may affect the overall process by determining the state of oxidation of the electrode surface. It is well known that m aqueous solution a platinum electrode has a bare surface only over the narrow potential range from approximately -t-0-4 V to -tO-8 V versus N.H.E. at more cathodic potentials it is covered by adsorbed hydrogen atoms while at more anodic potentials it is covered by... 

The surface of the platinum electrode can be studied conveniently in the potential range between 0 and 1.7 V (RHE), where in inert solutions (not containing substances able to be oxidized or reduced), the surface is ideally polarizable. At a more negative potential, cathodic hydrogen evolution starts, whereas at more positive potentials, oxygen is evolved anodicaUy. 

The galvanostatic and potentiodynamic charging curves of platinum electrodes shift approximately 60 mV in the negative direction when the solution pH is raised by 1 unit. This implies that when potentials which refer to the equilibrium potential of a hydrogen electrode in the same solution (RHE) are used, these curves remain practically at the same place within a wide range of solution pH. Hence, we shall use this scale while analyzing these curves. 

Solid metal electrodes are usually polished mechanically and are sometimes etched with nitric acid or aqua regia. Purification of platinum group metal electrodes is effectively achieved also by means of high-frequency plasma treatment. However, electrochemical preparation of the electrode immediately prior to the measurement is generally most effective. The simplest procedure is to polarize the electrode with a series of cyclic voltammetric pulses in the potential range from the formation of the oxide layer (or from the evolution of molecular oxygen) to the potential of hydrogen evolution (Fig. 5.18F). 

The anodic evolution of oxygen takes place at platinum and other noble metal electrodes at high overpotentials. The polarization curve obeys the Tafel equation in the potential range from 1.2 to 2.0 V with a b value between 0.10 and 0.13. Under these conditions, the rate-controlling process is probably the oxidation of hydroxide ions or water molecules on the surface of the electrode covered with surface oxide ... 

Our investigations showed that in mixed melts of eutectic composition carbamide-NH4(K)Cl, the oxidation and reduction of melt constituents take place mainly independently of each other. The anodic process at platinum electrodes in the range of potentials below 0.9V is associated with the direct oxidation of carbamide to secondary and tertiary amide compounds, accumulation of ammonium ions in the melt, and evolution of the same gaseous products as in carbamide electrolysis [8], The cathodic process is accompanied by the formation of ammonia, CO, and C02, i.e. of the same products as in pure- carbamide electrolysis. In contrast to carbamide melt, a large amount of hydrogen appears in the cathode gases of the mixed melt, and in the anode gases of the carbamide-KCl melt, the presence of chlorine has been established at potentials above 0.9V. In the... 

In situ FTIR spectra of a platinum electrode immersed in 0,1 M NaH2POA/NaOH pH 4.4 electrolyte contair ollected every 100mV after the reference spectrum taken at -0.5 V vs. SCE. (a) The 0=0, region for the potential r C02 region, showing spectra collected over the full spectral range. From P.A. Christensen and A, Hamnett, unpu... 

The accessible potential ranges for platinum and mercury electrodes, in the commonest organic solvents are reported in Table 1. It is noted that gold exhibits characteristics very similar to platinum. 

An important parameter for electrochemical solutions is the range of the electrical potential within which they are electroinactive. In other words, the anodic or cathodic windows they have available in which investigations on the redox properties of various compounds can be performed. We have already reported in Table 1 Figure 9 shows graphically the potential ranges of the most common solutions at a platinum electrode. 

ControUed-potential oxidations of a number of primary, secondary, and tertiary alkyl bromides at platinum electrodes in acetonitrile have been investigated [10]. For compounds such as 2-bromopropane, 2-bromobutane, tert-butyl bromide, and neopentyl bromide, a single Ai-alkylacetamide is produced. On the other hand, for 1-bromobutane, 1-bromopentane, 1-bromohexane, 1-bromo-3-methylbutane, and 3-bromohexane, a mixture of amides arises. It was proposed that one electron is removed from each molecule of starting material and that the resulting cation radical (RBr+ ) decomposes to yield a carbocation (R" "). Once formed, the carbocation can react (either directly or after rearrangement) with acetonitrile eventually to form an Al-alkylacetamide, as described above for alkyl iodides. In later work, Becker [11] studied the oxidation of 1-bromoalkanes ranging from methyl to heptyl bromide. He observed that, as the carbon-chain length is increased, the coulombic yield of amides decreases as the number of different amides increases. 

---