48 Introduction to Materials: Chemical Bonding 2-5 2-5

Interatomic Distances 49

2-5 INTERATOMIC DISTANCES

Coulombic forces. The ionic bond will be used to illustrate the balance between
Although in the case of diatomic molecules there is bonding and coordination of only attractive and repulsive forces in materials. The force Fe developed between two
two atoms, most materials involve a coordination of many atoms into an integrated point charges is related to the quantity of the two charges Z 1 q and Z 2 q, and their
structure. Two main factors, interatomic distances and spatial arrangements, are of separation distance a 1 _1 as follows:
importance. Let us therefore consider them in some detail.
The forces of attraction between atoms, which we considered in the preceding Fe= -ko(Z1q)(Z2q)fai-2· (2-5.1)
sections, pull the atoms together; but what keeps the atoms from being drawn still For ions, Z is the valence ( + or -)and q is 0.16 x 10- 18 coulomb. The propor-
closer together? It should be apparent from the preceding figures and the discussion tionality constant k 0 depends on the units used.*
that there is much vacant "space" in the volume surrounding the nucleus of an atom.
The existence of this space is evidenced by the fact that neutrons can move through
Electronic repulsive forces. The repelling force FR between the electronic fields of two
the fuel and the other materials of a nuclear reactor, traveling among many atoms
atoms or ions is also an inverse function with distance, but to a higher power:
before they are finally stopped (see Fig. 6--10.1).
FR = -bnf«;.:.l. •(2-5.2)
Both b and n are empirical constants, with n equal to approximately 9 in ionic solids.
2
Comparing, Fe oc a- , and FR oc a- 10 . Thus, the attractive forces predominate at
greater distances of atomic separation, and the repulsive forces predominate at closer
interatomic spacings (Fig. 2-5.2(a)). The equilibrium spacing, o-a', is a natur~l result
when
Fig. 2-5.1. Balance of forces (ceramic ring
magnets). Downward force on upper ring is Fe+ FR = 0. (2-5.3).
caused by gravity. Upward force is caused by
A tension force is required to overcome the predominant forces of attraction if the
magnetic repulsion . Space remains between the
two magnets at the equilibrium position. spacing is to be increased. Conversely, a compressive force has to be applied to push
(Of course the forces in this analogy are not the atoms closer together against the rapidly increasing electronic repulsion.
identical to those between atoms; however, the The equilibrium spacing is a very precise distance for a given pair of atoms, or
principle is comparable.) Courtesy North American ions. It ~n be measured to five significant figures by x-ray diffraction (Chapter 3),
Phillips Co.
if temperature and other factors are controlled. It takes a large force/area to stretch
or compress thot distance as much as one percent. (Based on Young's modulus, this
is a stress of 300,000 p~i (2000 M Pa) for steel.) It is for this reason that the hard ball
The space between atoms is caused by interatomic repulsive forces, which exist
provides a usable model for atoms for many purposes where strength or atom arrange-
in addition to the interatomic attractive forces described above. Primarily because ments are considered. t
the close proximity of two atoms places too many electrons into interacting locations,
mutual repulsion results. The equilibrium distance is that distance at which the
repulsive and the attractive forces are equal. An analogy may be made between the Bonding energy. The sum of the above two forces provides us with a basis for bond-
interatomic distances among atoms and the spacing between the two ring magnets ing energies (Fig. 2-5.2(b)). Since energy is the product of force and distance,
of Fig. 2-5.1. (In this example, the magnets are aligned to give repulsion rather than
attraction.) Of course the forces in this analogy are not identical to those between
atoms; however, the principle is comparable. The top ring magnet is moved by a
E = I (Fe + FR) da. (2-5.4)

force (gravity) toward the lower ring magnet (which in this case is fixed by the con-
"' With SI units, k 0 is 9 x 109 V · m/C; since k 0 = 1/4nE0 •
tainer). Since the force of gravity is essentially constant over the distance considered
here, the top magnet falls to the point where it is repulsed by an equal magnetic t The hard-ball model is not suitable for all explanations of atomic behavior. For example,
n neutr:on (which doesn't have a charge), can travel through the space among the atoms
force, of opposite direction. Because the repulsive force increases as an inverse without being affected by the electronic repulsive forces just described. Likewise, atomic
function of the distance, equilibrium distance is achieved. Note that the magnets nuclei can be vibrated vigorously by increased thermal energy, with only a small expansion
remain separated by space. of the average interatomic spacing. Finally, by a momentary distortion of their electrical
fields, atoms can move past one another in a crowded solid. (See diffusion in Chapter 4.)
 2- 6 Interatomic Distances 61
50 Introduction to Materials: Chemical Bonding

We will use infinite atomic separation as our energy reference, ED="' = 0. As we

bring the atoms together, energy is released in an amount equal to the shaded area 'ji
of Fig. 2-5.2{a). The amount of energy released is shown in Fig. 2-5.2(b). Note,
however, that at o-a', where F = 0 = dE fda, there is a minimum of energy because
I
energy would have to be supplied to force the atoms still closer together. The depth
of this energy well, ED="' - Emin• represents the bonding energy, because that much
I
energy would be released (-) as two atoms are brought together (at 0°K). The data
g ~
of Table 2-3.1 lists such values for covalent bonds.* ""
~ ' '

~f
'"
gj~~S~m-;r-~
~ 0 ,•.. . ....... t. i
~ r;:;::::= a, Interatomic spacing
2R r+R
§
(a) (b)

Fig. 2-5.2. Interatomic distances.

(a) The equilibrium spacing o-a' is
l 0 a' (a)
Fig. 2-5.3. Bond lengths. The distance of minimum energy between two adjacent atoms
Is the bond length. It is equal to the sum of the two radii. (a) In a pure metal, all atoms
have the same radius. (b) In an ionic solid, the radii are different because the two adjacent ions
the distance at which the attractive are never identical.
forces equal the repulsive forces.
(b) The lowest potential energy
occurs when o-a' is the interatomic
distance. Since E = jF da, the Several factors can change this distance. The first is temperature. Any increase
shaded area of (a) equals the depth
of the energy trough in (b). ~ R·-~1 \I _,.---- a, Interatomic spacing
in energy above the minimum point shown in Fig. 2-5.2(b) will increase the mean
distance !>ecause of the asymmetric shape of the energy trough. This increase in the
~ mean spacing between atoms accounts for the thermal expansion of materials.
"" Emin Ionic valence also influences interatomic spacing. The ferrous iron ion (Fe 2 +)
has a radius of0.74 A, which is smaller than that of the metallic iron atom (Appendix
0 a' (b) B). Since the two outer valence electrons have been 1c:moved (Fig. 2-5.4), the remain-
ing 24 electrons are pulled in closer to the nucleus, which still maintains a positive
The schematic representation of Fig. 2-5.2 will be useful to us on various oc- charge of 26. A further reduction in interatomic spacing is observed when another
casions in subsequent sections, when we pay attention to elastic moduli, thermal electron is removed to produce the ferric ion (Fe 3 +). The radius of this ion is 0.64 A,
expansion, theoretical strengths, melting and vaporization temperatures, etc. or only about one-half that of metallic iron.
A negative ion is larger than its corresponding atom. Since there are more
Atomic and ionic radii. The equilibrium distance between the centers of two neighbor- electrons surrounding the nucleus than there are protons in the nucleus, the added
ing atoms may be considered to be the sum of their radii (Fig. 2-5.3). In metallic electrons are not as closely attracted to the nucleus as were the original electrons.
iron, for example, the mean distance between the centers of the atoms is 2.482 A A third factor affecting the size of the atom or ion is the number of adjacent
(angstrom unitst) at room temperature. Since both atoms are the same, the radius Lloms. An iron atom has a radius of 1.241 A when it is in contact with eight adjacent
of the iron atom is 1.241 A. iron atoms, which is the normal arrangement at room temperature. If the atoms are
rearranged to place this one iron atom in contact with twelve other iron atoms, the
* Their attractions are not the same as the coulombic forces which were presented in Eq. radius of each atom is increased slightly, to 1.269 A. With more adjacent atoms, there
(2-5.1). However, an energy well of the same type may be visualized.
is more electronic repulsion from neighboring atoms, and consequently the interatomic
t The metallic radii used in this book are from the ASM Metals Handbook, Vol. I. The
distances are increased.
ionic radii are patterned after Ahrens.
·"-t"