Alkali ionization potentials

Table 16.3. Alkali ionization potentials and Rydberg constant.11...

Threshold energies of both reactions differ by the differences of halogen electron affinities and alkali ionization potentials. In all cases reaction (1.27a) is energetically favoured. However, it involves a transition from the ionic electronic ground state into the covalent excited electronic states which lead to atoms. Under some circumstances reaction (1.27b) may be favoured, since the electronic transition in step (1.27a) is forbidden. 

Different efficiency of alkali metal hydroxides seems to be associated with differing ionization potentials. 

According to the ionization potential and electron-transfer work, alkali metals form the following series Li > Na > K, and their hydroxides are arranged in the sequence KOH > NaOH > LiOH as to their inhibitive efficiency relative to thermal destruction of polyolefins. And the efficiency of alkali metals can be represented by the sequence Na > K > Li. This seems to be due... 

Alkali metals are strongly electropositive elements with low (2-3 eV) work function and low ionization potential. Upon adsorption on other metal surfaces they cause a severe (up to 3 eV) lowering of the metal work function, as already established by Langmuir in the early 1920 s. 

The possibility of a barrier which inhibits a reaction in spite of the attractive ion-dipole potential suggests that one should make even crude attempts to guess the properties of the potential hypersurface for ion reactions. Even a simple model for the long range behavior of the potential between neutrals (the harpoon model ) appears promising as a means to understand alkali beam reactions (11). The possibility of resonance interaction either to aid or hinder reactions of ions with neutrals has been suggested (8). The effect of possible resonance interaction on cross-sections of ion-molecule reactions has been calculated (25). The resonance interaction would be relatively unimportant for Reaction 2 because the ionization potential for O (13.61 e.v.) is so different from that for N2 (15.56 e.v.). A case in which this resonance interaction should be strong and attractive is Reaction 3 ... 

A mixture of water/pyridine appears to be the solvent of choice to aid carbenium ion formation [246]. In the Hofer-Moest reaction the formation of alcohols is optimized by adding alkali bicarbonates, sulfates [39] or perchlorates. In methanol solution the presence of a small amount of sodium perchlorate shifts the decarboxylation totally to the carbenium ion pathway [31]. The structure of the carboxylate can also support non-Kolbe electrolysis. By comparing the products of the electrolysis of different carboxylates with the ionization potentials of the corresponding radicals one can draw the conclusion that alkyl radicals with gas phase ionization potentials smaller than 8 e V should be oxidized to carbenium ions [8 c] in the course of Kolbe electrolysis. This gives some indication in which cases preferential carbenium ion formation or radical dimerization is to be expected. Thus a-alkyl, cycloalkyl [, ... 

The choice of the fill material initiating the discharge is very important. Together with a standard mercury fill it is often desirable to incorporate an additive in the fill material that has a low ionization potential [38, 39]. One category of low-ioniza-tion-potential materials is the group of alkali metals or their halides (Lil, Nal) but some other elements, such as Al, Ga, In, T1 [40, 41], Be, Mg, Ca, Sr, La, Pr, or Nd [23, 37, 42], can be used. 

As we have seen, several atomic properties are important when considering the energies associated with crystal formation. Ionization potentials and heats of sublimation for the metals, electron affinities, and dissociation energies for the nonmetals, and heats of formation of alkali halides are shown in Tables 7.1 and 7.2. 

Table 7.1 Ionization Potentials and Heats of Sublimation of Alkali Metals and the Heats of Formation of Alkali Metal Halides. ...

Background alkali metal chemistry. The alkali metals have the lowest ionization potentials of any group in the periodic table and hence their chemistry is dominated by the M+ oxidation state. However, it has been known for some time that a solution of an alkali metal (except lithium) in an amine or ether forms not only M+ ions and solvated electrons but also alkali anions of type M (Matalon, Golden Ottolenghi, 1969 Lok, Tehan Dye, 1972). That is, although an alkali metal atom very readily loses its single s-shell electron ... 

The fact that evaporated potassium arrives at the surface as a neutral atom, whereas in real life it is applied as KOH, is not a real drawback, because atomically dispersed potassium is almost a K+ ion. The reason is that alkali metals have a low ionization potential (see Table A.3). Consequently, they tend to charge positively on many metal surfaces, as explained in the Appendix. A density-of-state calculation of a potassium atom adsorbed on the model metal jellium (see Appendix) reveals that the 4s orbital of adsorbed K, occupied with one electron in the free atom, falls largely above the Fermi level of the metal, such that it is about 80% empty. Thus adsorbed potassium is present as K, with 8close to one [35]. Calculations with a more realistic substrate such as nickel show a similar result. The K 4s orbital shifts largely above the Fermi level of the substrate and potassium becomes positive [36], Table 9.2 shows the charge of K on several metals. 

In the situation as sketched in Figs. A.9 and A. 10a, level 1 remains occupied and level 2 empty, implying that the adsorbate atom retains the same charge as in the free atom. However, other situations can arise also. Suppose that the atom has a low ionization potential, smaller than the work function of the metal. Then the broadened level 1 falls largely above the Fermi level of the metal, with the result that most of the electron density of level 1 ends up on the metal. Hence, the adatom is positively charged (Fig. A. 10b). This happens with alkali atoms on many metal surfaces see for example the discussion of potassium on rhodium in Chapter 9. 

It is tempting to relate the thermodynamics of electron-transfer between metal atoms or ions and organic substrates directly to the relevant ionization potentials and electron affinities. These quantities certainly play a role in ET-thermo-dynamics but the dominant factor in inner sphere processes in which the product of electron transfer is an ion pair is the electrostatic interaction between the product ions. Model calculations on the reduction of ethylene by alkali metal atoms, for instance [69], showed that the energy difference between the M C2H4 ground state and the electron-transfer state can be... 

A number of useful properties of the Group 1 elements (alkali metals) are given in Table 8. They include ionization potentials and electron affinities Pauling, Allred-Rochow and Allen electronegativities ionic, covalent and van der Waals radii v steric parameters and polarizabilities. It should be noted that the ionic radii, ri, are a linear function of the molar volumes, Vm, and the a values. If they are used as parameters, they cannot distinguish between polarizability and ionic size. 

Symbol Cs atomic number 55 atomic weight 132.905 a Group lA (Group 1) alkali metal element electron configuration [Xe]6si atomic radius 2.65 A ionic radius (Cs ) 1.84 A ionization potential 3.89 eV valence +1 natural isotope Cs-133 37 artificial isotopes ranging in mass numbers from 112 to 148 and half-lives 17 microseconds (Cs-113) to 2.3x10 years (Cs-135). 

Symbol Rb atomic number 37 atomic weight 85.468 a Group I (Group 1) alkali metal element electron configuration [Kr] 5si valence -i-l atomic radius 2.43A ionic radius, Rb+ 1.48A atomic volume 55.9 cc/g-atom at 20°C ionization potential 4.177 V standard electrode potential Rb+ + e Rb, E° = -2.98V two naturally-occurring isotopes, Rb-85 (72.165%) and Rb-87 (27.835%) Rb-87 radioactive, a beta emitter with a half-bfe 4.88xl0i° year twenty-seven artificial radioactive isotopes in the mass range 74—84, 86, 88-102. 

Symbol Na atomic number 11 atomic weight 22.9898 a Group lA (Group 1) alkali metal element electron configuration [NejSs valence +1 atomic radius 1.85A ionic radius, Na" in crystals 1.02A (for a coordination number 6) ionization potential 5.139 eV standard electrode potential, E°(Na+ + e Na) -2.71 V one naturally-occurring stable isotope, Na-23 (100%) sixteen artificial radioactive isotopes in the mass range 19-22, 24—35 longest-lived radioisotope, Na-22, ti/2 2.605 year shortest-lived isotope Na-35, ti/2 1.5 ms. 

AHa for the Adsorption of Alkali Metals. If an alkali metal atom is located at an infinite distance from a metal surface at zero potential, then the heat of adsorption comprises the work done in (1) transferring an electron from the atom to the metal, and (2) bringing the positive ion to its equiUbrium distance from the metal surface (127). In the first step, the energy change is (e0 — el), where is the work function of the metal and I is the ionization potential of the alkali metal atom. In the second, the force of attraction on the positive ion at a distance d from the metal surface, i.e., the electrostatic image force, is e /4d hence, the heat Uberated is e /4do, where do is the equilibrium distance of the adsorbed ion from the metal surface. This distance is often assumed to be equal to the ionic radius, which is 1.83 A. for the Na ion. The initial heat of adsorption, therefore, is... 

The anionic catalysts listed earlier react with lactam monomer to first form the salt, which in turn will dissociate to the active species, namely, the lactam anion. A strongly dissociating catalyst in low concentrations, therefore, is always preferable to weakly dissociating catalysts in higher concentrations. The catalytic activity of the various alkali metal and quaternary salts of a lactam generally follows the extent of their ionic dissociation that is controlled by the cation. Activity of a salt decreases with increasing size of the cation due to restricted mobility and decreased ionization potential. 

Being a valuable isotope analytical technique in routine work for high precision isotope ratio measurements, TIMS is applied in many laboratories worldwide for isotope ratio measurements especially for elements with ionization potentials < 7 eV,7 such as alkali and earth alkali elements, rare earth elements (REE), uranium and plutonium. It is advantageous that the interference problem occurs relatively seldom in TIMS, especially if the negative thermal ionization technique for elements and molecules with electron affinities > 2eV (Ir, W, Os, Re, Pt, Cl and Br) is applied. TIMS with multiple ion collectors achieves a precision of up to 0.001 % thus permitting the study... 

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