Electrode potential, standard

The standard electrode potential is a characteristic of bulk metal reflecting the capacity of a metal to generate positive ions in aqueous solution. Eight studies used standard electrode potential (E°) to predict cation toxicity (Table 5.5). All these studies were 

Chemical Abstract Service Registry Numbers Ions That Appeared in Table 3 of Walker et al 

Ion CASRNs for Metals That Appeared More Than 10 Times in Table 3 of Walker et al. (2003) 22541-90-8 22537-50-4 

Source Appeared in J.D. Walker, M. Enache, and J.C. Dearden. Quantitative Cationic Activity Relationships for Predicting Toxicity of Metals. Environ. Toxicol. Chem. 22 (2003) 1916-1935, T-3. 

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For example, for iron in aqueous electrolytes, tlie tliennodynamic warning of tlie likelihood of corrosion is given by comparing tlie standard electrode potential of tlie metal oxidation, witli tlie potential of possible reduction reactions. 

For many purposes the hydrogen electrode is not convenient and it can be replaced by another cell of known standard electrode potential. A well-known example is the calomel cell shown in Figure 4.5. 

Iodine has the lowest standard electrode potential of any of the common halogens (E = +0.54 V) and is consequently the least powerful oxidising agent. Indeed, the iodide ion can be oxidised to iodine by many reagents including air which will oxidise an acidified solution of iodide ions. However, iodine will oxidise arsenate(lll) to arsenate(V) in alkaline solution (the presence of sodium carbonate makes the solution sufficiently alkaline) but the reaction is reversible, for example by removal of iodine. 

Generally the solubility of a given metal halate decreases from chlorate(V) to iodatef and many heavy metal iodates(V) are quantitatively insoluble. Like their parent acids, the halates(V) are strong oxidising agents, especially in acid solution their standard electrode potentials are given below (in volts) ... 

Source Values are compiled from the following sources Bard, A. J. Parsons, R. Jordon, J., eds. Standard Potentials in Aqueous Solutions. Dekker New York, 1985 Milazzo, G. Carol , S. Sharma, V. K. Tables of Standard Electrode Potentials. Wiley London, 1978 Swift, E. H. Butler, E. A. Quantitative Measurements and Chemical Equilibria. Freeman New York, 1972. 

Reductions. Hydrazine is a very strong reducing agent. In the presence of oxygen and peroxides, it yields primarily nitrogen and water with more or less ammonia and hydrazoic acid [7782-79-8]. Based on standard electrode potentials, hydrazine in alkaline solution is a stronger reductant than sulfite but weaker than hypophosphite in acid solution, it falls between and Ti ( 7). 

Thermodynamic data (4) for selected manganese compounds is given ia Table 3 standard electrode potentials are given ia Table 4. A pH—potential diagram for aqueous manganese compounds at 25°C is shown ia Figure 1 (9). 

Oxidation Reactions. Potassium permanganate is a versatile oxidizing agent characterized by a high standard electrode potential that can be used under a wide range of reaction conditions (100,133—141). The permanganate ion can participate in a reaction in any of three distinct redox couples. 

The standard electrode potential for zinc reduction (—0.763 V) is much more cathodic than the potential for hydrogen evolution, and the two reactions proceed simultaneously, thereby reducing the electrochemical yield of zinc. Current efficiencies slightly above 90% are achieved in modem plants by careful purification of the electrolyte to bring the concentration of the most harmful impurities, eg, germanium, arsenic, and antimony, down to ca 0.01 mg/L. Addition of organic surfactants (qv) like glue, improves the quaUty of the deposit and the current efficiency. 

Solution Potential. The standard electrode potential of aluminum (A1 + 3e) is —1.66 V on the standard hydrogen scale and —1.99 V... 

To calculate the open circuit voltage of the lead—acid battery, an accurate value for the standard cell potential, which is consistent with the activity coefficients of sulfuric acid, must also be known. The standard cell potential for the double sulfate reaction is 2.048 V at 25 °C. This value is calculated from the standard electrode potentials for the (Pt)H2 H2S04(yw) PbS04 Pb02(Pt) electrode 1.690 V (14), for the Pb(Hg) PbS04 H2S04(yw) H2(Pt) electrode 0.3526 V (19), and for the Pb Pb2+ Pb(Hg) 0.0057 V (21). 

The standard electrode potentials for the reduction of HOCl in acid solution are given below (87). 

The thermodynamics of electrochemical reactions can be understood by considering the standard electrode potential, the potential of a reaction under standard conditions of temperature and pressure where all reactants and products are at unit activity. Table 1 Hsts a variety of standard electrode potentials. The standard potential is expressed relative to the standard hydrogen reference electrode potential in units of volts. A given reaction tends to proceed in the anodic direction, ie, toward the oxidation reaction, if the potential of the reaction is positive with respect to the standard potential. Conversely, a movement of the potential in the negative direction away from the standard potential encourages a cathodic or reduction reaction. 

See p. 435 for discussion of standard electrode potentials and their use. It is convenliona] to write the halfreactions as (oxidized form) = (reduced form). Since... 

A. J. Bard, R. Parsons and J. Jordan Standard Potentials in Aqueous Solution, Marcel Dekker, New York, 1985, 834 pp. G. Milazzo and S. CarOli, Tables of Standard Electrode Potentials, Wiley, New York, 1978, 421 pp. 

Milazzo and S. Caroli, Tables of Standard Electrode Potentials, p. 229, Wiley-Interseienee, New York, 1978. 

The standard electrode potentials , or the standard chemical potentials /X , may be used to calculate the free energy decrease —AG and the equilibrium constant /T of a corrosion reaction (see Appendix 20.2). Any corrosion reaction in aqueous solution must involve oxidation of the metal and reduction of a species in solution (an electron acceptor) with consequent electron transfer between the two reactants. Thus the corrosion of zinc ( In +zzn = —0-76 V) in a reducing acid of pH = 4 (a = 10 ) may be represented by the reaction ... 

Direct subtraction of the standard electrode potential would have given the incorrect value u2+/cu = 0-346 - 0-522 = -0- 176 V.)... 

The equilibrium potentials and E, can be calculated from the standard electrode potentials of the H /Hj and M/M " " equilibria taking into account the pH and although the pH may be determined an arbitrary value must be used for the activity of metal ions, and 0 1 = 1 is not unreasonable when the metal is corroding actively, since it is the activity in the diffusion layer rather than that in the bulk solution that is significant. From these data it is possible to construct an Evans diagram for the corrosion of a single metal in an acid solution, and a similar approach may be adopted when dissolved O2 or another oxidant is the cathode reactant. 

The metal with the more negative corrosion potential in the environmental conditions prevailing (note that the standard electrode potentials are seldom applicable and the galvanic series can be misleading)... 

M Weight loss of iron (mg) Weight loss of M (mg) Difference in standard electrode potentials vt... 

It should be noted that the simple Nernst equation cannot be used since the standard electrode potential is markedly temperature dependent. By means of irreversible thermodynamics equations have been computed to calculate these potentials and are in good agreement with experimentally determined results. 

The values in Table 2.16 show how the potentials obtained under service conditions differ from the standard electrode potentials which are frequently calculated from thermodynamic data. Thus aluminium, which is normally coated with an oxide film, has a more noble value than the equilibrium potential 3 + / = — 1-66V vs. S.H.E. and similar considerations apply to passive stainless steel (see Chapter 21). 

The standard electrode potential of magnesium is given, along with the potentials of other metals, in Table 4.17 and the steady-state potentials of magnesium in various solutions are listed in Table 4.18. ... 

Atomic number Atomic weight Crystal structure Melting Density Thermal Electrical resistivity (at 20°C) Temperature coefficient of resistivity Specific Thermal Standard electrode potential Thermal neutron absorption cross-section. 

As may be seen from the diagram, silver in highly alkaline solution corrodes only within a narrow region of potential, provided complexants are absent. It is widely employed to handle aqueous solutions of sodium or potassium hydroxides at all concentrations it is also unaffected by fused alkalis, but is rapidly attacked by fused peroxides, which are powerful oxidising agents and result in the formation of the AgO ion Table 6.6 gives the standard electrode potentials of silver systems. 

Table 6.6 Standard electrode potentials of some silver systems ...

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