Half-wave potential polarographic determination

For an irreversible reduction the half-wave potential is determined not only by the standard electrode potential but also by the polarographic overvoltage. For a simple electrode process the metal ion-solvent interaction is mainly responsible for the polarographic overvoltage and hence E[ j of such irreversible reductions may also be considered as a function of the solvation 119f... 

Like benzenoid hydrocarbons, pyridine-like heterocycles give well-developed two-electron waves on reduction at the dropping mercury electrode. The latter are polarographically much more reducible than the former. This can be explained easily in terms of the HMO theory It is assumed (cf. ref. 3) that the value of the half-wave potential is determined essentially by the energy of the lowest free 7r-molecular orbital (LFMO) of the compound to be reduced, and for models of hetero analogues this quantity is always lower than that for the parent hydrocarbons. Introduction of an additional heteroatom into the molecule leads to a further enhancement of the ease of polarographic reducibility.95 On the other hand, anodic oxidation of the heterocyclic compounds is so much more difficult in comparison with benzenoid hydrocarbons that they are not oxidizable under the usual polarographic conditions. An explanation in terms of the HMO theory is obvious. 

Partition coefficients in the octanol-pH 7.4-phosphate-buffer system. c Nitrothiazole oxidation-reduction potentials (volts) as calculated from their half-wave potentials, as determined using a Polarecord E 261 polarograph (Metrohm AG, Herisau, Switzerland) and a saturated Ag/AgCl reference electrode. Measurements were performed at 20°C and a drop time of 1 drop/2.8 sec. The compounds were dissolved in 1 ml dimethyl formamide and added to 24 ml of a borax-potassium biphosphate buffer of pH 7.3 [prepared according to J. M. Kolthoff, J. Biol. Chem. (1925) 68, 135]. A pH of 7.4 resulted. Standard error of determination 3 mv. 

A polarographic study has been made on a variety of monocyclic thiophene 1,1-dioxides, benzo[b] thiophene 1,1-dioxides, and dibenzothiophene 5,5-dioxides and their related compounds, and half-wave potentials were determined [267-271]. The examples given in Fig. 4 are representative [271]. 

Using these assumptions and conventions, Imoto and co-workers have correlated a number of series of reactions of thiophenes and furans. The reactions studied are the acid-base equilibria pK values) and the acid catalyzed methylations (thiophenes only) of thiophene-and furan-carboxylic acids and the alkaline hydrolyses of their ethyl esters the side-chain bromination of the a-acetylthiophenes, and the a-mercuration of thiophenes and the polarographic half-wave potentials of the methyl esters of thiophene- and furan-carboxylic acids and of nitrothiophenes. The pK values were determined and the ester hydrolyses studied for all three substitution orientations in the thiophene series. For the 4-R-2-Y and 5-R-2-Y series, the p-values do not appear significantly different and the data could probably be combined into a single series unfortunately, however, no limits of accuracy are reported for the p-values, and some of the raw data are not readily available so recalculation is not easily possible. For the 5-R-3-Y series the p-values deviate considerably from the other values however, whereas they are higher for the pK values, they are lower for the ester hydrolyses, and it is possible that the differences are neither systematic nor significant. 

The shift of the half-wave potentials of metal ions by complexation is of value in polarographic analysis to eliminate the interfering effect of one metal upon another, and to promote sufficient separation of the waves of metals in mixtures to make possible their simultaneous determination. Thus, in the analysis of copper-base alloys for nickel, lead, etc., the reduction wave of copper(II) ions in most supporting electrolytes precedes that of the other metals and swamps those of the other metals present by using a cyanide supporting electrolyte, the copper is converted into the difficultly reducible cyanocuprate(I) ion and, in such a medium, nickel, lead, etc., can be determined. 

Thus, the peak separation can be used to determine the number of electrons transferred, and as a criterion for a Nemstian behavior. Accordingly, a fast one-electron process exhibits a AEp of about 59 mV Both the cathodic and anodic peak potentials are independent of die scan rate. It is possible to relate the half-peak potential (Ep/2. where the current is half of the peak current) to the polarographic half-wave potential, El/2 ... 

In the course of our polarographic studies on organic cations we determined the half-wave potentials, 1/2, for various arylmethylium ions [1-11]. The aim of the present work is to extract from these values some new information concerning the relative magnitude of their solvation enthalpies in three very different solvents. A comparison of our results [obtained in methanesulphonic acid (MSA) and dichloromethane (DCM)] with those of Volz and Lotsch [12] [obtained in cyanomethane (CM) solutions] yields some useful conclusions. 

Neutral (1 M LiCl) and alkaline (1 M NaOH) solutions of TcO in the concentration range of 10 to 10 M have been investigated polarographically with direct and alternating current . Four irreversible waves are observed (Fig. 12). The first two waves with the half-wave potentials of —0.85 V and —1.15 V vs. SCE are clearly recognizable in alkaline solution. They correspond to the electron transition n = 2 and n = 3 and can be used for the analytical determination of technetium. The third and fourth wave are not diffusion controlled and influenced... 

Suitable conditions for the quantitative polarographic determination of technetium as pertechnetate are given by Miller et al. who propose a 0.1 M KCl solution of pH 10 or a phosphate buffer solution of pH 7. Since in pH 7 buffer the current is directly proportional to the concentration of technetium over the range of 0.1 to 1.1 ppm, this medium has been used for the determination of low concentrations of technetium in solutions of fission products by the standard addition technique. The half-wave potential of the used wave is —0.68 V vs. SCE. The reaction appears to be irreversible (Fig. 13). It has been found that neither rhenium, ruthenium nor other fission products interfere. However, tetraphenyl-arsonium chloride is reduced at a more positive potential than is pertechnetate therefore, (QH5) AsCl, if present, must be separated. 

Tlte reduction potential for an alkyl or benzyl radical, relative to that of the carbon-halogen bond from which it is derived, is important in determining the isolated products. Products are derived either by radical or by carbanion chemistry. The half-wave potential for the second polarographic wave of alkyl halides is connected with reduction of the radical. Sophisticated methods have been devised for deducing radical reduction potentials in cases where (his second wave is not seen. Values are collected in Table 4.4. 

Polarographic reductions have been studied for many kinds of metal ions and in a variety of lion-aqueous solvents. Large amounts of data on half-wave potentials are available and have been compiled in some books and reviews [18]. However, many of the old data were obtained using different reference electrodes or aqueous SCE, for which the problem of the liquid junction potential exists (Section 6.1.2). Gritzner [19] compiled half-wave potentials for metal ions as values referred to the BCr+/BCr system, which was recommended by IUPAC. Some of these are listed in Table 8.2. The potential of the BCr+/BCr system is not seriously affected either by the presence of water and other impurities or by differences in experimental conditions. Thus, although the determination of the half-wave poten-... 

In a systematic polarographic investigation180 the half-wave potentials of a number of 1,2,4-thiadiazoles were determined and the results correlated with their structures. Measurements were made in neutral buffered solutions, the salt concentration being kept constant by the addition of lithium chloride. 

That is, hox(AtXH)= - / (ArX ). For this type of reaction, E (ArX ) is positive. Hence, the more positive this value, the more difficult it is to oxidize the compound. For many phenols and anilines, polarographic half-wave potentials, Zs1/2(ArX"), determined at pH values where the compound is present in its neutral form, are available. These values should reasonably parallel the oxidation potentials of the compounds, and therefore can also be used to relate oxidation rate constants ... 

When dehydration occurs as a consecutive reaction, its effect on polarographic curves can be observed only, if the electrode process is reversible. In such cases, the consecutive reaction affects neither the wave-height nor the wave-shape, but causes a shift in the half-wave potentials. Such systems, apart from the oxidation of -aminophenol mentioned above, probably play a role in the oxidation of enediols, e.g. of ascorbic acid. It is assumed that the oxidation of ascorbic acid gives in a reversible step an unstable electroactive product, which is then transformed to electroinactive dehydroascorbic acid in a fast chemical reaction. Theoretical treatment predicted a dependence of the half-wave potential on drop-time, and this was confirmed, but the rate constant of the deactivation reaction cannot be determined from the shift of the half-wave potential, because the value of the true standard potential (at t — 0) is not accessible to measurement. 

The measurement of polarographic half-wave potentials is usually a simple, fast procedure, often considerably faster and less tedious than determination of rate or equilibrium constants. Elucidation of the mechanism of an electrode process (or better that part of it which must be understood for quantitative treatment of the potentials) and the choice of the most suitable conditions for measurement of comparable values of half-wave potentials is usually simpler and less time-consuming than the elucidation of the mechanism of a chemical reaction. This is largely due to the fact that in electrode processes the reactant (electron or electrode) is always the same. 

Methyl-5-mercapto-l,2,3,4-tetrazole (see Section 4.1) is a possible impurity and degradation product of moxalactam which can be determined by polarographic techniques (67). It is oxidized at a dropping mercury electrode in a pH 5.8 buffer. The concentration of the impurity tetrazole is proportional to the sum of the currents for the adsorption prewave and the main wave (half-wave potentials of about -0.20 V and -0.05 V vs SCE, respectively). 

The following table lists the polarographic half-wave potentials (E1/2, in volts, vs. SCE, the standard calomel electrode) of inorganic cations and the supporting electrolyte used during the determination.1 5 All supporting electrolyte solutions are aqueous unless noted. See page 629 for a description of the concentration nomenclature. 

The importance of solvent effects can be extracted from correlations of half-wave potentials determined by CV or polarographic methods with other measures of oxidizability, especially gas-phase free energies of ionization and ionization potentials. Within a series of unsubstituted metallocenes that differ only by the metal, the oxidation potentials of the compounds in solution and their gas-phase free energies of ionization vary directly (Fig. 17),154, 60 indicating that the effect of solvent is consistent from one metallocene to another. 

---