Earth Materials. John O'Brien

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Figure 2.14 A model of metallic bonds with delocalized electrons (dark red) surrounding positive charge centers that consist of tightly held lower energy electrons (light red dots) surrounding individual nuclei (blue).

      Minerals containing metallic bonds are generally characterized by the following features:

      2.3.5 Transitional (hybrid) bonds

Transitional or hybrid bonds display combinations of ionic, covalent and/or metallic bond behavior. Some transitional bonds can be modeled as ionic–covalent transitional, others as ionic–metallic or covalent–metallic transitional. A detailed discussion of all the possibilities is beyond the scope of this book, but because most bonds in Earth materials are transitional, it is a subject worthy of mention. The following discussion also serves to illustrate once again the enigmatic behavior of which electrons are capable.

Earlier in this chapter, we defined electronegativity in relation to the periodic table. Linus Pauling developed the concept of electronegativity (En) to help model transitional ionic–covalent bonds. In models of such bonds, electrons are partially transferred from the more metallic, more electropositive element to the less metallic, more electronegative element to produce a degree of ionization and electrostatic attraction typical of ionic bonding. At the same time, the electrons are partially shared between the two elements to produce a degree of electron sharing associated with covalent bonding. Such bonds are best modeled as hybrids or transitions between ionic and covalent bonds. Materials that possess such bonds commonly display properties that are transitional between those of ionically bonded substances and those of covalently bonded substances. Using the electronegativity difference – the difference between the electronegativities of the two elements sharing the bond – Pauling was able to predict the percentages of covalent and ionic bonding, that is, the percentages of electron sharing and electron transfer that characterize ionic–covalent transitional bonds. Figure 2.15 illustrates the relationship between electronegativity difference and the percentages of ionic and covalent bond character that typify the transitional ionic–covalent bonds.

      Where electronegativity differences in transitional ionic–covalent bonds are smaller than 1.68, the bonds are primarily electron‐sharing covalent bonds. Where electronegativity differences are larger than 1.68, the bonds are primarily electron‐transfer ionic bonds. Calculations of electronegativity and bond type lead to some interesting conclusions. For example, when an oxygen atom with En = 3.44 bonds with another oxygen atom with En = 3.44 to form O₂, the electronegativity difference (3.44 − 3.44 = 0.0) is zero and the resulting bond is 100% covalent. The valence electrons are completely shared by the two oxygen atoms. This will be the case whenever two highly electronegative, nonmetallic atoms of the same element bond together. On the other hand, when highly electronegative, nonmetallic atoms bond with strongly electropositive, metallic elements to form ionically bonded substances, the bond is never purely ionic. There is always at least a small degree of electron sharing and covalent bonding. For example, when sodium (Na) with En = 0.93 bonds with chlorine (Cl) with En = 3.6 to form sodium chloride (NaCl), the electronegativity difference (3.6 − 0.93 = 2.67) is 2.67 and the bond is only 83% ionic and 17% covalent. Although the valence electrons are largely transferred from sodium to chloride and the bond is primarily electrostatic (ionic), a degree of electron sharing (covalent bonding) exists. Even in this paradigm of ionic bonding, electron transfer is incomplete and a degree of electron sharing occurs. The bonding between silicon (Si) and oxygen (O), so important in silicate minerals, is very close to the perfect hybrid since the electronegativity difference is 3.44 − 1.90 = 1.54 and the bond is 45% ionic and 55% covalent.

Figure 2.15 Graph showing the electronegativity difference and bond type in covalent–ionic bonds. Percent covalent bonding is indicated by the black line and percent ionic bonding by the blue line.

This simple picture of transitional ionic–covalent bonding does not hold in bonds that involve transition metals. For example, the mineral galena (PbS) has properties that suggest its bonding is transitional between metallic and ionic. In this case some electrons are partially transferred from lead (Pb) to sulfur (S) in the manner characteristic of ionically bonded substances, but some electrons are weakly held in the manner characteristic of metallic bonds. As a result, galena displays both ionic properties (brittle and somewhat soluble) and metallic properties (soft, opaque and a metallic luster). Figure 2.16 utilizes a triangle, with pure covalent, ionic and metallic bonds at the apices, to depict the pure and transitional bonding characteristic of selected minerals, including those discussed above.

Figure 2.16 Triangular diagram representing the bond types of some common minerals.

      2.3.6 Van der Waals and hydrogen bonds

Because the distributions of electrons in the electron cloud are probabilistic and constantly changing, they may be, at any moment, asymmetrically distributed within the electron cloud. This asymmetry gives rise to weak electric dipoles on the surface of the electron cloud; areas of excess negative charge concentration where the electrons are located and areas of negative charge deficit (momentary positive charge) where they are absent. Areas of momentary positive charge on one atom attract electrons in an adjacent atom, thus inducing a dipole in that atom. The areas of excess negative charge on one atom are attracted to the areas of positive СКАЧАТЬ