Lattice energies, alkali halides

LATTICE ENERGY ALKALI HALIDES IN KCAL/MOLE ... 

Lattice energies, alkali metal salt values, amides and, 196 azides and, 198-199 bifluorides and, 199 borofluorides and, 203 borohydrides and, 197 chalcogenides and, 192,193 cyanates and, 199-200 cyanides and, 196-197 halides and, 189, 190 hydrides and, 189, 191, 192 hydrosulfides and, 195-196 hydroxides and, 192,194, 195 nitrates and, 201 superoxides and, 197-198 thiocyanates and, 200 alkaline earth salt values, acetylides and, 198 carbonates and, 202-203 chalcogenides and, 192, 193 imides and, 196 peroxides and, 198 calculation uses, absolute enthalpies and, 206 electron affinity determination and, 203-204... 

Figure 4,4 Standard enthalpies of formation (A// and lattice energies (plotted as —t/O for alkali metal halides and hydrides.

These trends are apparent In the values of lattice energy that appear in Table Notice, for example, that the lattice energies of the alkali metal chlorides decrease as the size of the cation increases, and the lattice energies of the sodium halides decrease as the size of the anion increases. Notice also that the lattice energy of MgO is almost four times the lattice energy of LiF. Finally, notice that the lattice energy of Fc2 O3, which contains five ions in its chemical formula, is four times as large as that of FeO, which contains only two ions in its chemical formula. 

The alkali halides cire noted for their propensity to form color-centers. It has been found that the peak of the band changes as the size of the cation in the alkali halides increases. There appears to be an inverse relation between the size of the cation (actually, the polarizability of the cation) and the peak energy of the absorption band. These are the two types of electronic defects that are found in ciystcds, namely positive "holes" and negative "electrons", and their presence in the structure is related to the fact that the lattice tends to become charge-compensated, depending upon the type of defect present. 

A more direct link with molecular volumes holds for alkali halides, because the lattice energy (IT) is inversely proportional to interatomic distance or the cube root of molecular volume (MV). The latter has been approximated by a logarithmic function which gives a superior data fit. Plots of AH against log(MV) are linear for alkali halides 37a). Presumably, U and AH can be equated because AH M, ) is a constant in a series, and AH (halide )) is approximately constant when the anion is referred to the dihalogen as the standard state. 

As was indicated in Sec. 1.2, the conclusion that the deformation phenomena play the smallest role in NaF was based first on the statement that its heat of sublimation (S) constitutes among the alkali halides the largest fraction of the lattice energy (17). The corresponding data in Table 5 show that the gradation of this fraction, SjU, is in fact closely parallel to that of the degree of polarity p both properties show a... 

TABLE 1.16 Lattice energies of some alkali and alkaline earth metal halides at 0 K... 

It is not yet possible to measure lattice energy directly, which is why the best experimental values for the alkali halides, as listed in Table 1.16, are derived from a thermochemical cycle. This in itself is not always easy for compounds other than the alkali halides because, as we noted before, not all of the data is necessarily available. Electron affinity values are known from experimental measurements for... 

Br- (g). The electron affinity of Br (g) is calculable by the method of lattice energies. Selecting the crystal RbBr, because Rb+ and Br have exactly the same nuclear structure, and taking the exponent of the repulsive term to be 10, we have computed, for the reaction, RbBr (c) = Rb+ (g)+Br g), Dz= —151.2 whence the electron affinity of Br (g) becomes 87.9. Using the lattice energies of the alkali bromides as calculated by Sherman,1 we have computed the values 89.6, 85.6, 84.6, 83.6, and 89.6, respectively. Butkow,1 from the spectra of gaseous TIBr, deduced the value 86.5. From data on the absorption spectra of the alkali halides, Lederle1 obtained the value 82. See also Lennard-Jones.2... 

Experimental and calculated lattice energies ( —U ) of alkali halides (kJ mal )... 

However, in the last two decades it has been shown experimentally [1,7, 8,12-14] and theoretically [15-18] that in many wide-gap insulators including alkali halides the primary mechanism of the Frenkel defect formation is subthreshold, i.e., lattice defects arise from the non-radiative decay of excitons whose formation energy is less than the forbidden gap of solids, typically 10 eV. These excitons are created easily by X-rays and UV light. Under ionic or electron beam irradiations the main portion of the incident particle... 

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