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# MSE3094 (Staley) HW#2 Solutions

1/28/11

1) Covalently bonded materials are less dense than metallic or ionically bonded ones because covalent bonds are directional in nature whereas metallic and ionic are not; when bonds are directional, the atoms cannot pack together in as dense a manner, yielding a lower mass density. In other words, limitations on the coordination number in covalently bonded materials make them tend to have lower densities at a given atomic mass. For example, note the densities of the following materials: Ti (metal): Zn (metal): ZrO2 (ionic oxide): AgF (ionic salt): Si (covalent semiconductor): Ge (covalent semiconductor): =4.5 g/cc (atomic weight of 48) =7.1 g/cc (atomic weight of 65) =6.0 g/cc (average atomic weight of 41) =5.9 g/cc (average atomic weight of 63) =2.3 g/cc (atomic weight of 28) =5.3 g/cc (atomic weight of 73)

2) The percent ionic character is a function of the electron negativities of the ions XA and XB according to Equation (2.10). The electronegativities of the elements are found in Figure 2.7. a) For MgS, XMg = 1.2 and XS = 2.5, and therefore, %ionicity = (1 - exp[-(2.5-1.2)2 / 4]) x100% = 34.5% [mostly covalent or mixed] b) For GaAs, XGa = 1.6 and XAs = 2.0, and therefore, %ionicity = (1 - exp[-(2.0-1.6)2 / 4]) x100% = 3.9%[almost entirely covalent] c) For CsF, XCs = 0.7 and XF = 4.0, and therefore, %ionicity = (1 - exp[-(4.0-0.7)2 / 4]) x100% = 93.4% [almost entirely ionic] d) For FeO, XFe = 1.8 and XO = 3.5, and therefore, %ionicity = (1 - exp[-(3.5-1.8)2 / 4]) x100% = 51.4% [mixed covalent/ionic]

3) We are asked to show that the atomic packing factor for BCC is 0.68. The atomic packing factor is defined as the ratio of sphere volume to the total unit cell volume, or
APF = VS VC

Since there are two spheres associated with each unit cell for BCC
" 4!R 3 % 8!R3 VS = 2(sphere volume) = 2 \$ '= \$ 3 ' 3 # &

Also, the unit cell has cubic symmetry, that is VC = a3. But a depends on R according to Equation (3.3), and
! 4R \$ 3 64R 3 VC = # & = " 3% 3 3

Thus, APF =

8!R / 3 64R 3 / 3 3

= 0.68

4) This problem asks that we calculate the theoretical densities of Al and Mg. a) Since Al has an FCC crystal structure, n = 4, and VC = ( 2 R 2 ) . Also, R = 0.143 nm (1.43 x 10-8 cm) and AAl = 26.98 g/mol. Employment of Equation (3.5) yields
! = (4 atoms/unit cell)(26.98 g/mol) 3 " % -8 23 atoms/mol # (2)(1.43 x 10 cm) 2 /(unit cell) & 6.023 x 10 \$ '
3

( )]

= 2.71 g/cm3 The value given in the table inside the front cover is 2.71 g/cm3. b) Magnesium has an HCP crystal structure, and from Problem 3.7,
VC = 3 3 a 2c 2

## and, since c = 1.624a and a = 2R = 2(1.60 x 10-8 cm) = 3.20 x 10-8 cm

3 3 3 (1.624) 3.20 x 10-8 cm

VC =

## = 1.38 x 10!22 cm3 /unit cell

Also, there are 6 atoms/unit cell for HCP. Therefore the theoretical density is
! = nAMg VC NA

(6 atoms/unit cell)(24.31 g/mol) = 1.75 g/cm3 -22 cm3 /unit cell 6.023 x 1023 atoms/mol 1.38 x 10

)(

## The value given in the table is 1.74 g/cm3.

5) A material in which atomic bonding is predominantly ionic in nature is less likely to form a noncrystalline solid upon solidification than a covalent material because covalent bonds are directional whereas ionic bonds are non-directional; it is more difficult for the atoms in a covalent material to assume positions giving rise to an ordered structure. 6) a) For NiS, from Table 12.3:
r
Ni 2+ S
2!

## 0.069 nm = 0.375 0.184 nm

The coordination number is four (Table 12.2), & the predicted structure is zinc blende (Table 12.4). b) For CsI from Table 12.3:
rCs + rI ! = 0.170nm = .772727 0.220nm

The coordination number is eight (Table 12.2), and the predicted crystal structure is cesium chloride.
rK + = 0.138nm = 0.985714 0.140nm

## c) For K2O from Table 12.3: rO 2 !

The coordination number is eight (Table 12.2). The formula unit here is A2X and the predicted crystal structure is anti-fluorite (like the fluorite structure in Table 12.4, but with twice as many cations as anions). d) For CuBr from Table 12.3:
rCu + rBr ! = 0.096nm = 0.489796 0.196nm

The coordination number is 6 (Table 12.2), & the predicted structure is rock salt.

A NOTE ABOUT WHAT HAPPENS IF CATIONS ARE LARGER THAN ANIONS: For BaF2 from Table 12.3, by our normal method we would find that:

## rBa 0.136nm = = 1.0226 rF 0.133nm

2+ "

However, in cases where the ratio of cation to anion exceeds 1.00 (i.e., when the anion is smaller), we must flip the ratio over and when we do this we get a corrected value of ! 0.133/0.136=0.978. Thus, the coordination number is eight, and given that the formula unit here is AX2, the predicted crystal structure is fluorite.

7) The basic unit common to all silicate ceramics is the silica tetrahedron which is composed of a single silicon atom surrounded by four equidistant oxygen atoms. The silicon atoms occupy the openings (interstitials) between the oxygen atoms and share four valence electrons with the oxygen atoms through covalent bonding. Silicate ceramics can be composed of tetrahedrons that share three corner atoms creating layered silicates (clay, talc, mica) or four corner atoms creating framework silicates (quartz, tridymite). Because of covalent bonding, silica can also form into glassy structures with no longrange repeat unit. Images of many long-range silicate structures are given in Ch.3. 8) Some properties you might cite that vary between diamond and graphite are:

Diamond is the hardest substance known. Graphite is soft & slippery to touch. Diamond is a transparent substance whereas graphite is black and opaque. Diamond is a poor conductor of electricity, but is a good conductor of heat. Graphite on the other hand is a good conductor of heat and electricity.

Diamond has Carbon atoms covalently bonded to 4 other Carbon atoms and sigma bonds that strongly overlap creating the hard rigid structure. Graphite has covalent bonding between Carbons in the same layer but these covalent bonds do not tie the entire crystal structure together. Secondary bonds are responsible for holding the layers together. Views of these, slightly different from those in the text, are shown below.

Structure of Diamond

Structure of Graphite