CRYSTAL DEFECTS

RESPONSE PROBLEMS

1. Calculate the vacancy fraction in copper (Cu) at (a) 20 C and (b) the melting point, 1085 C. Measurements have
determined the values of the enthalpy of vacancy formation, Hv , to be 1.03 eV and the entropic prefactor, A, to be 1.1.

2. In iridium (Ir), the vacancy fraction, nv/N, is 3.091  105 at 1234 C and 5.26  103 at the melting point. Calculate the
enthalpy of vacancy formation, Hv.

3. A formation energy of 2.0 eV is required to create a vacancy in a particular metal. At 800 C there is one vacancy for
every 10,000 atoms.
(a) At what temperature will there be one vacancy for every 1,000 atoms?
(b) Repeat the calculation, but this time with an activation energy of 1.0 eV. Note the big change in the temperature
interval necessary to obtain the same change in vacancy concentration as was the case with an activation energy of
2.0 eV.

4. In iron (Fe) the energy associated with the generation of a vacancy is 1.05 eV. At what temperature (T) in °C will one out
of 105 lattice sites be vacant?

5. On appropriate schematic drawings show the generation and characteristics of Schottky defects in (a) a closed-packed
metal, (b) an ionic crystal and (c) a semiconductor.

6. In NaCl, the cations are more mobile than the anions. What effect, if any, do you expect small amounts of the following
impurities to have on the conductivity of NaCl crystals: (a) AgCl, (b) MgCl2, (c) NaBr, (d) Na2O?

7. Confirm the presence of iron vacancies for a sample of wustite which has a unit cell dimension of 428.2 pm, an Fe:O ratio
of 0.910 and an experimental density of 5.613 × 103 kg m−3.

8. How would you expect charge neutrality to be maintained in TiO1.25?

9. An ionic crystal of the MX2 type forms Schottky defects, for which the energy of formation is 200 kJ/mole. By how much
should the temperature be reduced from 2000 K in order to reduce the concentration of anion vacancies by a factor of
10?

10. How would you expect the formation of colour centres to affect the density of the crystal?

11. Stoichiometric titanium (II) oxide and magnesium oxides have densities of 4.93 and 3.58 g cm 3 respectively. X-ray
diffraction studies have shown that both have the NaCl structure, with unit cell edges of 416.2 and 421.2 pm respectively.
Assume that the presence of vacancies does not affect the cell edge lengths. Estimate the percentage of vacancies in
these solids.

12. From theoretical considerations it is concluded that the (activation) energy required to form an interstitial atom in copper
(Cu) is about 4 eV. Assuming this value to be correct, determine the equilibrium concentration of these defects
(defects/cm3) at 1350 K.

13. Undoped β-alumina demonstrates a maximum conductivity and minimum activation energy when the sodium excess is
around 20 to 30 mole%. Thereafter, further increase in the sodium content causes the conductivity to decrease. By
contrast, β-alumina crystals doped with Mg2+ have a much higher conductivity than do undoped crystals. Explain these
observations.