Electrodes, oxidation-reduction standard

Determination of Standard Oxidation-Reduction Potentials.—In principle, the determination of the standard potential of an oxidation-reduction system involves setting up electrodes containing the oxidized and reduced states at known activities and measuring the potential B by combination with a suitable reference electrode insertion of the value of B in the appropriate form of equation (3) then permits B to be calculated. The inert metal employed in the oxidation-reduction electrode is frequently of smooth platinum, clthough platinized platinum, mercury and particularly gold are often used. 

The Standard Potential of the Mercurous-Mercuric Electrode. A method for obtaining standard potentials of oxidation-reduction electrodes which utilizes the best procedure so far developed in this field is the one that was used by Fopoff and associates. The method may be illustrated by the determination of the standard potential of the mercurous-mercuric electrode. The type of cell used by Popoff, Riddick, Worth and Ough1 was... 

Some standard oxidation/reduction electrode potentials of fundamental technetium... 

Two methods are used to measure pH electrometric and chemical indicator (1 7). The most common is electrometric and uses the commercial pH meter with a glass electrode. This procedure is based on the measurement of the difference between the pH of an unknown or test solution and that of a standard solution. The instmment measures the emf developed between the glass electrode and a reference electrode of constant potential. The difference in emf when the electrodes are removed from the standard solution and placed in the test solution is converted to a difference in pH. Electrodes based on metal—metal oxides, eg, antimony—antimony oxide (see Antimony AND ANTIMONY ALLOYS Antimony COMPOUNDS), have also found use as pH sensors (8), especially for industrial appHcations where superior mechanical stabiUty is needed (see Sensors). However, because of the presence of the metallic element, these electrodes suffer from interferences by oxidation—reduction systems in the test solution. 

In addition to simple dissolution, ionic dissociation and solvolysis, two further classes of reaction are of pre-eminent importance in aqueous solution chemistry, namely acid-base reactions (p. 48) and oxidation-reduction reactions. In water, the oxygen atom is in its lowest oxidation state (—2). Standard reduction potentials (p. 435) of oxygen in acid and alkaline solution are listed in Table 14.10- and shown diagramatically in the scheme opposite. It is important to remember that if or OH appear in the electrode half-reaction, then the electrode potential will change markedly with the pH. Thus for the first reaction in Table 14.10 O2 -I-4H+ -I- 4e 2H2O, although E° = 1.229 V,... 

The oxidation-reduction potential or redox potential ( h) is a measure of the tendency of a solution to be oxidizing or reducing. Oxidation and reduction are basically electrical processes that are readily measiued by an electrode potential. All measurements are referred to die standard hydrogen electrode, the potential of which is taken as 0.00 V at 298 K, the H2 pressure as 101325 N/m (1 atm) and activities of H2 and as unity. When the half-cell reaction is written as an oxidation reaction ... 

The reduction-oxidation potential (typically expressed in volts) of a compound or molecular entity measured with an inert metallic electrode under standard conditions against a standard reference half-cell. Any oxidation-reduction reaction, or redox reaction, can be divided into two half-reactions, one in which a chemical species undergoes oxidation and one in which another chemical species undergoes reduction. In biological systems the standard redox potential is defined at pH 7.0 versus the hydrogen electrode and partial pressure of dihydrogen of 1 bar. 

Chlorine reactions may be classified broadly under two types (i) oxidation-reduction and (ii) substitution reactions. The standard electrode potential for Cr — V2CI2 + e in aqueous solution is -1.36 V. Some examples of both types are highlighted briefly below ... 

Many half-reactions of interest to biochemists involve protons. As in the definition of AG °, biochemists define the standard state for oxidation-reduction reactions as pH 7 and express reduction potential as E °, the standard reduction potential at pH 7. The standard reduction potentials given in Table 13-7 and used throughout this book are values for E ° and are therefore valid only for systems at neutral pH Each value represents the potential difference when the conjugate redox pair, at 1 m concentrations and pH 7, is connected with the standard (pH 0) hydrogen electrode. Notice in Table 13-7 that when the conjugate pair 2ET/H2 at pH 7 is connected with the standard hydrogen electrode (pH 0), electrons tend to flow from the pH 7 cell to the standard (pH 0) cell the measured E ° for the 2ET/H2 pair is -0.414 V... 

Both the ions of Ag+ and Cif are easily complexed by ammonia (amine) and the corresponding complexes are very stable [204]. In the system of silver-ammonia complex ions the oxidation-reduction standard electrode potential of silver is expressed by... 

When a biochemical half-reaction involves the production or consumption of hydrogen ions, the electrode potential depends on the pH. When reactants are weak acids or bases, the pH dependence may be complicated, but this dependence can be calculated if the pKs of both the oxidized and reduced reactants are known. Standard apparent reduction potentials E ° have been determined for a number of oxidation-reduction reactions of biochemical interest at various pH values, but the E ° values for many more biochemical reactions can be calculated from ArG ° values of reactants from the measured apparent equilibrium constants K. Some biochemical redox reactions can be studied potentiometrically, but often reversibility cannot be obtained. Therefore a great deal of the information on reduction potentials in this chapter has come from measurements of apparent equilibrium constants. 

Because any two oxidation-reduction reactions can be combined to make a cell, the tabulation of standard electrode potentials becomes a very efficient way of calculating cell potentials under standard conditions. As indicated by Eq. (54), if the electrode reactions involve the metals of the cell terminals, the metal-metal potential due to the cell terminals is automatically included in the result. A short table of standard electrode potentials is given in Table 2. 

While the redox titration method is potentiometric, the spectroelectrochemistry method is potentiostatic [99]. In this method, the protein solution is introduced into an optically transparent thin layer electrochemical cell. The potential of the transparent electrode is held constant until the ratio of the oxidized to reduced forms of the protein attains equilibrium, according to the Nemst equation. The oxidation-reduction state of the protein is determined by directly measuring the spectra through the tranparent electrode. In this method, as in the redox titration method, the spectral characterization of redox species is required. A series of potentials are sequentially potentiostated so that different oxidized/reduced ratios are obtained. The data is then adjusted to the Nemst equation in order to calculate the standard redox potential of the proteic species. Errors in redox potentials estimated with this method may be in the order of 3 mV. 

TABLE 16.3 Selected Standard Electrode Potentials for Oxidation-Reduction Half Reactions... 

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. 

Approximate Determination of Standard Potentials.—Many studies have been made of oxidation-reduction systems with which, for one reason or another, it is not possible to obtain accurate results this may be due to the difficulty of applying activity corrections, uncertainty as to the exact concentrations of the substances involved, or to the slowness of the establishment of equilibrium with the inert metal of the electrode. It is probable that whenever the difference in the number of electrons between the oxidized and reduced states, i.e., the value of n for the oxidation-reduction system, is relatively large the processes of oxidation and reduction occur in stages, one or more of which may be slow. In that event equilibrium between the system in the solution and the electrode will be established slowly, and the measured potential may be in error. To expedite the attainment of the equilibrium a potential mediator may be emploj cd this is a substance that undergoes reversible oxidation-reduction and rapidly reaches equilibrium with the electrode. 

Ionization in Stages.—When a metal yields two positive ions, and M +, there are three standard potentials of the system these are the potentials of the electrodes M, and M, in addition to the oxidation-reduction potential If the values of these standard... 

The Co(bipy)3+ ion is a useful catalyst for a number of borohydride reductions, e.g., organic nitro compounds are reduced smoothly to amines at pH 6.5-7 the true reducing agent is Co(bipy)3+. The oxidation-reduction potential for Co(I)/Co(II) is 0.91 volt (vs. standard calomel electrode in 50% aqueous ethanol) and this should fall between the potentials of the other reactants (709). Catalytic reductions of organic halogen compounds may be achieved (436), and the system is reactive to small molecules such as NgO (38). 

Ferroin With the introduction of Ce(IV) as an oxidant and the evaluation of the formal potential of the Ce(rV)-Ce(III) couple, the need for indicators with higher electrode potentials became evident. The indicator ferroin, tris(l,10-phenanthroline)-iron(II), was discovered by Walden, Hammett, and Chapman, and its standard potential was evaluated at 1.14 V. Hume and KolthofiF found that the formal potential was 1.06 V in 1 M hydrochloric or sulfuric acid. The color change, however, occurs at about 1.12 V, because the color of the reduced form (orange-red) is so much more intense than that of the oxidized form (pale blue). From Figure 15-1 it can be seen that ferroin should be ideally suited to titrations of Fe(II) and other reductants with Ce(lV), particularly when sulfuric acid is the titration medium. It has the further advantages of undergoing a reversible oxidation-reduction reaction and of being relatively stable even in the presence of oxidant. 

Table 2 Standard oxidation-reduction potentials 25° C, volts Di. hydrogen electrode...

The standard electrode potential for an oxidation-reduction process is often called the standard redox potential of the pair of ions involved. A table of redox potentials finds immediate application in inorganic chemistry. 

Standard electrode potential data are available for an enormous number of halfreactions. Many have been determined directly from electrochemical measurements. Others have been computed from equilibrium studies of oxidation/reduction systems and from thermochemical data associated with such reactions. Table 18-1 contains standard electrode potential data for several half-reactions that we will be considering in the pages that follow. A more extensive listing is found in Appendix 5. ... 

How is an oxidation/reduction titration curve generated through the use of standard electrode potentials for the analyte species and the volumetric titrant ... 

Chapter 18 Introduction to Electrochemistry 490 Chapter 19 Applications of Standard Electrode Potentials 523 Chapter 20 Applications of Oxidation/Reduction Titrations 560 Chapter 21 Potentiometry 588... 

---