Name:

16:635:527 THERMODYNAMICS OF MATERIAL SYSTEMS

Problem Set 6
Due date (to be graded) Monday December 12th, 2022, start of class
Due date (drop dead) Wednesday December 14th, 2022, 4:45pm my office

Put all your answers on these sheets. Attach separate sheets for each question showing all your
working. These question sheets and your answer sheets should all be single-sided. Securely
staple all sheets together in the correct order; question sheet with answer sheets then next
question sheet with answer sheets…etc.

For grader use:

question # 1 2 3

score

1. Propose some defect reactions by which small Al2O3 additions might incorporate into the
structure of MgO – include reaction schemes in Kröger-Vink notation with your answer.
Discuss with reasoning the likelihood that each reaction occurs. Density measurements are
often used to determine the type of defects created when impurities are dissolved in ionic
crystals. If one assumes that the dissolution of alumina in pure magnesia creates vacancies
on the cation sub-lattice, calculate the fractional change in the density of pure MgO when
one wt% of Al2O3 is added to it. Assume that the crystal structure and the lattice parameter
of MgO do not change with the addition of alumina.
1
Answers: 1)
1
2)
2
which/why?
6
  

page 1 of 3 Problem Set 6 ToM 2022.doc

2. Uranium dioxide, UO2, has the fluorite structure with oxygen in the tetrahedral sites of a
FCC array of uranium ions. The free energies of formation of (i) Frenkel defects on the
oxygen sublattice, (ii) Frenkel defects on the uranium sublattice, and (iii) Schottky defects
are 3.0, 9.5 and 6.4 eV respectively.
a) Write down, using Kröger-Vink notation, defect reactions for formation of each of these
three types of defect.
b) Assuming that the only defects present are Frenkel defects on the oxygen sublattice, write
down the condition for electroneutrality. Hence calculate the concentration of vacancies
and interstitials at 1600C associated with these Frenkel defects.
c) Repeat part (b) for Frenkel defects on the uranium sublattice, assuming these are the only
defects present.
d) Repeat part (b) for Schottky defects, assuming these are the only defects present.
e) Which of the three defect reactions dominates in stoichiometric UO2? Comment on your
answer.
f) UO2 can be made non-stoichiometric at high pressures by reducing to UO2x or oxidizing
to UO2+x by changing the oxygen partial pressure. UO2 becomes an intrinsic
semiconductor when non-stoichiometric. Suggest defect reactions for (i) oxidizing and
(ii) reducing environments that might explain this behavior – your answers should be
consistent with your answers to earlier parts of this question.
g) Is UO2 an n-type (conduction by electrons) or p-type (conduction by holes) when under
oxidizing conditions?
1
Answers: i)
1
ii)
1
iii)
½ 1½
b)
½ 1½
c)
½ 1½
d)
¼
e)
½
f.i)
½
f.ii)
¼
g)

page 2 of 3 Problem Set 6 ToM 2022.doc

3. Element A forms a face-centered cubic (FCC) crystal which has a cubic conventional unit
cell with four atoms and eight tetrahedral interstices per unit cell. Careful dilatometric and
diffraction measurements have been used to measure the lattice parameter, a, and molar
volume, V as a function of temperature:
Temperature (K) a (nm) V (cm3mol1)
1040 0.37021 7.6404
1340 0.37113 7.6992
a) Calculate the atom fraction of vacancies at both temperatures. Use a value for
Avogadro’s number of 6.02214151023.
b) Determine values for the excess enthalpy and entropy for formation of a single vacancy,
HV and SV. Give your answers in eV.
3 3 2
Answers: X1040 X1340 HV
2
SV

page 3 of 3 Problem Set 6 ToM 2022.doc