12.5 On the basis of ionic charge and ionic radii given in Table 12.

3, predict crystal structures for the following materials: (a) CsI, (b) NiO, (c) KI, and (d) NiS. Justify your selections.

Solution This problem calls for us to predict crystal structures for several ceramic materials on the basis of ionic charge and ionic radii. (a) For CsI, using data from Table 12.3
rCs + rI 0.170 nm = 0.773 0.220 nm

Now, from Table 12.2, the coordination number for each cation (Cs+) is eight, and, using Table 12.4, the predicted crystal structure is cesium chloride. (b) For NiO, using data from Table 12.3
rNi2 + rO 2 0.069 nm = 0.493 0.140 nm

The coordination number is six (Table 12.2), and the predicted crystal structure is sodium chloride (Table 12.4). (c) For KI, using data from Table 12.3
rK + rI 0.138 nm = 0.627 0.220 nm

The coordination number is six (Table 12.2), and the predicted crystal structure is sodium chloride (Table 12.4). (d) For NiS, using data from Table 12.3
rNi2 + rS 2 0.069 nm = 0.375 0.184 nm

The coordination number is four (Table 12.2), and the predicted crystal structure is zinc blende (Table 12.4).

12.7 Compute the atomic packing factor for the rock salt crystal structure in which rC/rA = 0.414.

Solution This problem asks that we compute the atomic packing factor for the rock salt crystal structure when rC/rA = 0.414. From Equation 3.2
VS VC

APF =

With regard to the sphere volume, VS, there are four cation and four anion spheres per unit cell.
4 3 + (4) 4 r 3 VS = (4) rA 3 3 C

Thus,

But, since rC/rA = 0.414

16 3 3 r 1 + (0.414 ) 3 = (17.94) rA 3 A

VS =

Now, for rC/rA = 0.414 the corner anions in Table 12.2 just touch one another along the cubic unit cell edges such that
2 (rA + rC )] VC = a 3 = [

3 =[ 2 (rA + 0.414 rA )] = (22.62) rA 3

Thus

APF =

VS VC

3 (17.94) rA 3 (22.62) rA

= 0.79

12.14 Magnesium oxide has the rock salt crystal structure and a density of 3.58 g/cm3. (a) Determine the unit cell edge length. (b) How does this result compare with the edge length as determined from the radii in Table 12.3, assuming that the Mg2+ and O2- ions just touch each other along the edges?

Solution (a) This part of the problem calls for us to determine the unit cell edge length for MgO. The density of MgO is 3.58 g/cm3 and the crystal structure is rock salt. From Equation 12.1
n( AMg + AO ) n( AMg + AO ) = VC N A a3 N A

Or, solving for a

n( AMg + AO ) 1/ 3 a = NA

Inasmuch as there are 4 formula units per unit cell for the rock salt crystal structure, and the atomic weights of magnesium and oxygen are 24.31 and 16.00 g/mol, respectively, when we solve for a from the above equation

(4 formula units/unit cell)(24.31 g/mol + 16.00 g/mol) 1/ 3 a= (3.58 g/cm 3)(6.022 10 23 formula units/mol)

= 4.21 10 -8 cm = 0.421 nm

(b) The edge length is determined from the Mg2+ and O2- radii for this portion of the problem. Now for the rock salt crystal structure

a = 2 rMg 2+ + 2 rO 2-

From Table 12.3

a = 2(0.072 nm) + 2(0.140 nm) = 0.424 nm

4 (1) (2) (3) (4)

Check CsCl. 1 Cs 1 Cl 0 In one unit cell, there are one Cs and one Cl atoms. Assume the volume of the unit cell is V, we have:

V = mCs + mCl , V = a 3
in which is the density and m cs , mCl denote the mass of Cs and Cl atoms.

a = 3.96

13.13 The viscosity of a glass varies with temperature according to the relationship
Q = A exp vis RT

where Qvis is the energy of activation for viscous flow, A is a temperature-independent constant, and R and T are, respectively, the gas constant and the absolute temperature. A plot of ln versus l/T should be nearly linear, and with a slope of Qvis/R. Using the data in Figure 13.7, (a) make such a plot for the borosilicate glass, and (b) determine the activation energy between temperatures of 500 and 900C.

Solution (a) Below is shown the logarithm viscosity versus reciprocal of temperature plot for the

borosilicate glass, using the data in Figure 13.7. The dashed line has been drawn through the data points corresponding to temperatures between 500 and 900C (as stipulated in the problem statement).

(b) The activation energy, Qvis, may be computed according to

ln 1 ln 2 ln =R = R 1 1 1 T1 T2 T

Qvis

where R is the gas constant, and

ln is the slope of the dashed line that has been constructed. 1 T

Taking 1/T1 and 1/T2 as 0.8 10-3 and 1.3 10-3 K-1, respectively, then the corresponding values of
T T

ln 1 and ln 2 are 10.59 and 32.50. Therefore,

Qvis

10.59 32.50 ln 1 ln 2 = (8.31 J/mol K) =R 3 1 3 1 1 1 0.8 10 K 1.3 10 K T1 T2

= 364,000 J/mol

13.10 What is the distinction between glass transition temperature and melting temperature?

Solution The glass transition temperature is, for a noncrystalline ceramic, that temperature at which there is a change of slope for the specific volume versus temperature curve (Figure 13.6). The melting temperature is, for a crystalline material and upon cooling, that temperature at which there is a sudden and discontinuous decrease in the specific-volume-versus-temperature curve.

9. A 10. E