Metals standard electrode potentials

It is noteworthy that solubility of the formed metal alkoxide is in many cases even more important for the reaction than the values of the metal standard electrode potentials or the mobility of protons of the alcohol. The following examples illustrate this statement. Despite higher acidity of MeOH in comparison with EtOH(pK= 15.5 and 16, respectively), the insoluble Ca(OMe)2 is formed very slowly in comparison with the soluble derivatives Ca(OEt)2 or Mg(OMe)2 (both latter compounds crystallize from solutions as solvates) [1646]. Aluminum readily reacts with PrOH with the formation of the highly soluble Al(OPrf)3 even in the absence of the catalyst (pK ROH = 18, E°AP7Al,ld = -1.66 V). On the other hand, polymeric Al(OMe)3 and Al(OEt)3 are formed only on prolonged refluxing of the metal with alcohols in xylene (140°C) in the presence of HgCl2 and I2 [1301]. 

Table 5.12 Electrochemical series of metals (standard electrode potential in V).

Ionization energies are fairly constant across the first transition series. Values of the first ionization energies are about the same as for the group 2 metals. Standard electrode potentials gradually increase in value across the series. With the exception of the oxidation of Cu to Cu, however, all these elements are more readily oxidized than hydrogen. This means these metals reduce H (aq) to H2(g). Additional comments on electrode potentials, some supported by electrode potential diagrams, are found throughout the chapter. 

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. 

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) ... 

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 ... 

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)... 

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. ... 

When metals are arranged in the order of their standard electrode potentials, the so-called electrochemical series of the metals is obtained. The greater the negative value of the potential, the greater is the tendency of the metal to pass into the ionic state. A metal will normally displace any other metal below it in the series from solutions of its salts. Thus magnesium, aluminium, zinc, or iron will displace copper from solutions of its salts lead will displace copper, mercury, or silver copper will displace silver. 

It must be emphasised that standard electrode potential values relate to an equilibrium condition between the metal electrode and the solution. Potentials determined under, or calculated for, such conditions are often referred to as reversible electrode potentials , and it must be remembered that the Nernst equation is only strictly applicable under such conditions. 

The potentials of the metals in their 1 mol U salt solution are all related to the standard or normal hydrogen electrode (NHE). For the measurement, the hydrogen half-cell is combined with another half-cell to form a galvanic cell. The measured voltage is called the normal potential or standard electrode potential, E° of the metal. If the metals are ranked according to their normal potentials, the resulting order is called the electrochemi-... 

In the introductory chapter we stated that the formation of chemical compounds with the metal ion in a variety of formal oxidation states is a characteristic of transition metals. We also saw in Chapter 8 how we may quantify the thermodynamic stability of a coordination compound in terms of the stability constant K. It is convenient to be able to assess the relative ease by which a metal is transformed from one oxidation state to another, and you will recall that the standard electrode potential, E , is a convenient measure of this. Remember that the standard free energy change for a reaction, AG , is related both to the equilibrium constant (Eq. 9.1)... 

Nowadays, tables of standard electrode potentials are used instead of the electromotive series. They include electrode reactions not only of metals but also of other substances [Table 3.1 for detailed tables, see the books of Lewis and Rendall (1923) and Bard et al. (1985)]. 

The standard electrode potential [1] of an electrochemical reaction is commonly measured with respect to the standard hydrogen electrode (SHE) [2], and the corresponding values have been compiled in tables. The choice of this reference is completely arbitrary, and it is natural to look for an absolute standard such as the vacuum level, which is commonly used in other branches of physics and chemistry. To see how this can be done, let us first consider two metals, I and II, of different chemical composition and different work functions 4>i and 4>ii-When the two metals are brought into contact, their Fermi levels must become equal. Hence electrons flow from the metal with the lower work function to that with the higher one, so that a small dipole layer is established at the contact, which gives rise to a difference in the outer potentials of the two phases (see Fig. 2.2). No work is required to transfer an electron from metal I to metal II, since the two systems are in equilibrium. This enables us calculate the outer potential difference between the two metals in the following way. We first take an electron from the Fermi level Ep of metal I to a point in the vacuum just outside metal I. The work required for this is the work function i of metal I. 

Worked Example 7.19 We immerse a piece of silver metal into a solution of silver ions at unit activity and at s.t.p. The potential across the cell is 0.799 V when the SHE is the negative pole. What is the standard electrode potential E of the Ag+, Ag couple ... 

The review of Martynova (18) covers solubilities of a variety of salts and oxides up to 10 kbar and 700 C and also available steam-water distribution coefficients. That of Lietzke (19) reviews measurements of standard electrode potentials and ionic activity coefficients using Harned cells up to 175-200 C. The review of Mesmer, Sweeton, Hitch and Baes (20) covers a range of protolytic dissociation reactions up to 300°C at SVP. Apart from the work on Fe304 solubility by Sweeton and Baes (23), the only references to hydrolysis and complexing reactions by transition metals above 100 C were to aluminium hydrolysis (20) and nickel hydrolysis (24) both to 150 C. Nikolaeva (24) was one of several at the conference who discussed the problems arising when hydrolysis and complexing occur simultaneously. There appear to be no experimental studies of solution phase redox equilibria above 100°C. 

In order to estimate the standard electrode potential of a metal ion a Born-Haber cycle consisting of the following three steps may be considered, 19> 12°1 (Fig. 21) ... 

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... 

Thus, the overall reaction [Eq. (8.2)] is the outcome of the combination of two different partial reactions, Eqs. (8.4) and (8.5). As mentioned above, these two partial reactions, however, occur at one electrode, the same metal-solution interphase. The equilibrium (rest) potential of the reducing agent, E eq,Red [Eq. (8.5)] must be more negative than that of the metal electrode, E eq,M [Eq. (8.4)], so that the reducing agent Red can function as an electron donor and as an electron acceptor. This is in accord with the discussion in Section 5.7 on standard electrode potentials. 

We now return to the case of codeposition of metals whose standard electrode potentials are wide apart. As stated, the deposition potentials [Eq. (11.2)] are brought together by complexing the more noble metal ions, as illustrated below for the case of the codeposition of copper and zinc as brass. 

Americium and californium have been prepared by the reduction, using noble metals and hydrogen at temperatures greater than 1110 °C, of the oxides MOj 5. A new determination has been made of the heat of dissolution of Am in aqueous HCl, and the standard enthalpies of a series of Am compounds and ions have been reported (Table 1). The standard electrode potential of the Am -Am" couple was +2.06 + 0.01 V, making the metal only slightly more electropositive than Pu. 

Symbol Cd atomic number 48 atomic weight 112.41 a Group IIB (Group 12) metallic element ionization potential 8.994eV electron configuration [Kr]4di°5s2 valence state +2 standard electrode potential, E° -0.40V. The isotopes and their natural relative abundance are ... 

Hard blue-white metal body-centered cubic crystal density 7.19 g/cm melts at 1,875°C vaporizes at 2,199°C electrical resistivity at 20°C, 12.9 microhm-cm magnetic susceptibility at 20°C, 3.6x10 emu standard electrode potential 0.71 V (oxidation state 0 to -i-3). 

The most common oxidation states of iron are +2 (ferrous) and -i-3 (ferric). The standard electrode potential for Fe —> Fe2+ + 2e- is -0.440 volts. Thus, the metal can replace hydrogen from water at ordinary temperatures ... 

Symbol Nd atomic number 60 atomic weight 144.24 a rare earth lanthanide element a hght rare earth metal of cerium group an inner transition metal characterized by partially filled 4/ subshell electron configuration [Xe]4/35di6s2 most common valence state -i-3 other oxidation state +2 standard electrode potential, Nd + -i- 3e -2.323 V atomic radius 1.821 A (for CN 12) ionic radius, Nd + 0.995A atomic volume 20.60 cc/mol ionization potential 6.31 eV seven stable isotopes Nd-142 (27.13%), Nd-143 (12.20%), Nd-144 (23.87%), Nd-145 (8.29%), Nd-146 (17.18%), Nd-148 (5.72%), Nd-150 (5.60%) twenty-three radioisotopes are known in the mass range 127-141, 147, 149, 151-156. 

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