Chem 213 Winter 2004

Solutions to Problem Set 2

(Please let me know of any typographical or logical errors)

1) (i) Draw a plan diagram for the sodium oxide Na2O structure, indicating clearly the positions
(along z) of the various ions. 1/2 0, 1

Na2O = antifluorite, close packed y Na = 1/4, 3/4

0, 1
O2! anions with Na+ cations
filling all the Td holes, i.e.,

x
(ii) Sketch the appearance of the [1,1,0] plane in sodium oxide, and calculate the surface density of
(a) cations and (b) anions in the [1,1,0] plane. Assume the unit cell edge length = r.

Area of box = %2r × r = %2r2.

Cation density = 4/%2r2 = 2%2/r2.
Anion density = 2/%2r2 = %2/r2.

3) (i) Rhenium trioxide ReO3 and calcium titanate CaTiO3 have related structures. Draw plan diagrams
of each, indicating clearly the positions (along z) of the various ions, and illustrating the difference
between the two structures.
0, 1 0, 1
0, 1 0, 1
1/2
1/2
y y Ca2+
1/2
Re2+
Ti2+

02- 02-
x x
(ii) What is the nearest neighbour coordination number of Re/Ti in these two structures?

Coordination number of Re and Ti = 6.

(iii) What is nearest neighbour coordination number of Ca inCaTiO3?

Coordination number of Ca = 12.

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3) A simple sketch of the unit cell for perovskite is shown at the right.

(i) How many Ca atoms are there per unit cell? Ti4+
(ii) How many Ti atoms are there per unit cell?
(iii)How many oxygens atoms are there per unit cell?
O2-
(iv) What is the chemical formula?
(v) Into how many parts (zones) does a set of 222 planes Ca2+
divide the unit cell?
(vi) Sketch a set of 222 planes.

(i) One interior Ca atom/cell º 1 Ca/cell.

(ii) 8 corner Ti’s (at 1/8) º 1 Ti/cell.

(iii) 12 edge oxygens (at 1/4) º 3 O/cell.

(iv) Perovskite is CaTiO3.

(v) A set of hkl planes divides a cell into h + h + l zones Ti O Ti

between the planes, dividing the a (x direction) edge O O
into h equal parts, the b (y direction) edge into k equal Ti Ti
O O
parts, and the c (z direction) edge into l equal parts. O
Ca
O
(vi) The 222 planes thus intersect the unit cell at 0.5 a, 0.5 O Ti O Ti
b and 0.5 c, with parallel planes at 0 and 1 on each O O
axis. Since every lattice point is identical, each
Ti O Ti
corner may be considered to be an origin (0,0,0).

4) Calculate the d-spacings for the following crystal planes in an orthorhombic unit cell with a = 3.0 D,
b = 4.0 D, c = 5.0 D.

h, k, l = 0, 0, 1; 0, 1, 0; 0, 1, 1; 1 0 0;
1, 0, 1; 1, 1, 0; 1, 1, 1

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Here is a spreadsheet, prepared using the standard expression for any orthorhombic cell:

h k l 1/d 2
d, in D 1 h2 k 2 l 2
2 = 2 + 2 +
0 0 1 0.040 5.000 d a b c2
0 1 0 0.063 4.000
0 1 1 0.103 3.123
1 0 0 0.111 3.000
1 0 1 0.151 2.572
1 1 0 0.174 2.400
1 1 1 0.214 2.164

Which of the above reflections will be observed if the cell is (a) I-centered, (b) C-centered?

Here are the rules for systematic absences:

Lattice Type Condition for reflection to be observed

Primitive, P None
Body centred, I h + k + l = 2n
Face centred, F h, k, l either all odd or all even
Side centred, C h + k = 2n
Rhombohedral, R -h + k + l = 3n

Accordingly, the following systematic absences will occur for the above:

if the cell is I-centred, (0, 0, 1), (0, 1, 0), (1, 0, 0) and (1, 1, 1) (absent)
if the cell is C-centred, (0, 1, 0), (0, 1, 1), (1, 0, 0), (1, 0, 1) (absent)

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5) A cubic alkali metal halide salt has its first six lines with d-spacing 4.08, 3.53, 2.50, 2.13, 2.04 and
1.77 D. Assign Miller indices to the lines and calculate the value of the unit cell dimension. The salt
has a density of 3.126 D. What is the alkali halide?

d hkl allowed a hkl allowed a

Ang fcc D Primitive D
h, k, l even or odd no absences

4.08 111 7.07 100 4.08

3.53 200 7.06 110 4.99
2.5 220 7.07 111 4.33
2.13 311 7.06 200 4.26
2.04 222 7.07 210 4.56
1.77 400 7.08 211 4.34

This is another spreadsheet exercise. Alkali metals halides are mainly fcc structures, save
for those that have the CsCl (primitive) lattices. If you work backwards from d to the a value
(remember a = b = c), bear in mind the systematic absences for the different lattices, you will
get consistency for the right solution - and inconsistency for the wrong solution. As the table
above illustrates, it is clearly a fcc arrangement, with a cell repeat of 7.06D. In the fcc cell
for MX, the edge distance is 2r+ + 2rG . If you look up ionic radii, you see that 2r+ + 2rG for
KI is 6.88D. If we assume this guess (i.e., KI) is correct, we can then calculate the density,
using the formula in class notes, or working from first principles:

There are, in total, 4 K’s and 4 I’s per cell. Thus, the density D = 4 (KI)’s /(7.06)3 D3,

= 0.0114 KI’s D-3

= 0.0114 KI’s D-3 ×[1/(6.02 × 1023 KI’s mol-1) × 166.0 g mol-1 ×1024 D3 cm-3
= 3.14 g cm-3

This calculated value matches the experimental value well, so our guess was right. (OK,
so I knew the answer ahead of time, but it looks good!)

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6) Sodium oxide Na2O adopts the anti-fluorite structure.

((i) What is the coordination number of (a) the cations 4 (b) the anions 8

(ii) Sketch the {1,0,0} and {1,1,0} planes, indicating clearly the position and identity of the ions.

1/4, 3/4 3/4, 3/4

1/2, 1/2
= Na+

= O2-

1/4, 1/4 3/4, 1/4

7) Shown below is the X-ray powder pattern for silver metal, measured with Mo X-rays (8 = 1.5478
D). Silver possesses a cubic cell.

A
Line 22 (deg)

A 38.18
B B 44.37
C 64.56
C D D 77.54
E 81.69
F 98.09
0 10 20 30 40 50 60 70 80 90 100

(i) Name and sketch the possible Bravais lattices for a cubic system?

Primitive P Body-centered I Face centered F

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 (ii) Given your response to part (i), index (with h, k, l values) the first six lines (A - F) for the
different possible cells.

Using the rules provided in class:

Line A B C D E F

P (h,k,l) 100 110 111 200 210 211

I (h,k,l) 110 200 211 220 310 222

F (h,k,l) 111 200 220 311 222 400

(iii) Use the theta values provided to determine which is the correct lattice type. (Hint: do not
perform any more calculations than are necessary to pinpoint the correct lattice.)

From Bragg’s law, the following d-spacings can be calculated. (Only the first three
lines are necessary to identify the cell.)

Line A B C D E F
2 (deg) 19.59 22.18 32.28 38.77 40.85 49.05
d (D) 2.357 2.042 1.444 1.231 1.179 1.021

Calculation of a (= b = c) using d-spacing formula:

P 2.357 2.888 (no consistency)

I 3.333 4.084 (no consistency)
F 4.082 4.084 (consistency)

Conclusion: The cell is face centered, with a = 4.08 D

(iv) Determine the nearest neighbour Ag-Ag distance.

In a face centred cell, the nearest neighbour Ag-Ag distance will be ½ of the face diagonal, or (%2/2) a =
2.88 D.

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8) (i) Shown below are two different views of representative monoclinic and triclinic cells. Define
the values of these unit cell parameters a, b and c, and the angles ", $ and (.

Monoclinic: a … b … c, and the angles " = ( = 90°, $ … 90°.

Triclinic: a … b … c, and the angles " … ( … $ … 90°.

Monoclinic Triclinic

c c
b b
a a
(ii) Use these diagrams to prove whether it is possible to have an I-centered monoclinic or triclinic
lattice, i.e., does such an arrangement constitute a unique Bravais lattice, or can it be represented in
terms of a simpler arrangement (another Bravais lattice).

I-centered monoclinic simplifies I-centered triclinic simplifies

to C-centered cell to a primitive cell

U5+

Na+

Scheme A Scheme B Scheme C

9) Compare the point groups of the following three molecules in the Schoenflies and Hermann Mauguin
schemes: (i) Ni(CN)42- (square planar), (ii) benzene, (iii) PtCl62-.

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(i) Ni(CN)42- contains a 4-fold axis, a z C2 axis and a horizontal mirror plane. In
Schoenflies notation it is D4h. In “H-M” terminology we assign the four-fold axis as z. Is
there a mirror plane z to this? Yes, so we have 4/m as our first term. In the other two
directions there are also mirror planes, so we denote both of these as m also. Our H-M
notation is therefore 4/mmm, although 4/mm would suffice. In fact, a longer notation, where
we would specify the 2-fold axes and their perpendicular mirrors would be 4/m2/m/2/m. So
depending on how picky we are, we can get different answers!

(ii) Benzene is planar and has a 6-fold axis, a z C2 axis and a horizontal mirror plane. By
Schoenflies this would be D6h. Using the same logic (?) as above, our H-M group would be
denoted as 6/m2/m2/m, 6/mmm or 6/mm depending how specific we wish to be.

(iii) PtCl62- is an octahedral anion. In Schoenflies notation this would simply be Oh. In H-
M we first realize this is a cubic group. For these we list in the conventional H-M order z,
x+y+z, x+y. We set the highest order axis (4-fold) to z. There is a z mirror so the first term
is 4/m. The second term in a cubic group is always a & 3 or 3 (notation varies). That’s
because if we go in the x+y+z direction, that’s down the 3-fold axis. Finally, in the x+y
direction there are 2-fold axes and z mirrors (sticking out of each edge of the octahedron)
so our last term is 2/m. Our symbol should therefore be 4/m&
m&
3 2/m, but usually we see this as
3 m or m3m in short notation.

If you have the uneasy feeling that there is more convention than logic to the H-M “system”
then join the party.

11) What point groups result from the combination of two intersecting mirror planes at (a) 90° to each
other, (b) 60°, (c) 45°?

Here again, just think in Schoenflies notation, and then transcribe. Thus (a) is C2v, or mm2,
(b) is C6v, or 6mm, and (c) is C4v, or 4mm.

12) Na3UF8 is described as being based on a fluorite structure but “owing to the arrangement of the cations
the unit cell is doubled in one direction and is a bc tetragonal cell”. Draw the unit cell of Na3UF8,
showing only the cation positions. State any assumptions you make about how the cations should be
arranged.

We can start with a unit cell and double it in one direction, a, as shown in Scheme A. We
then have to decide where to put the cations. Recall that in the fluorite structure we have an

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fcc array of cations. So our first guess for generic cation positions is that shown in Scheme
B.

Next we double check that we have the correct number of cations in the cell. If we add these
up we come up with 8(1/8) + 4(1/4) + 10(1/2) + 1 = 8. We have four cations total, so this
indicates no cation vacancies and two formula units per cell (Z = 2).

Now we have to order the cations, keeping those with the greatest charge furthest apart. The
charges are Na+ and U5+. There are several permutations possible, but we must remember
to work within the constraints of tetragonal symmetry. This means, for example, that we
cannot put two U and two Na in the bottom of the cell. We are left with only a few
possibilities, one of which places U in all the corner and edge sites. But the arrangement
that keeps the U5+ as far apart as possible is that show in Scheme C. Notice how we have
minimized repulsion and kept our stoichiometry correct.

r 13) TiO has the sodium chloride structure, and the shortest Ti-O contact is
2.09 D. Calculate the density of TiO in g cm-3 . Compare your predicted
value with the experimental value of 4.92 g cm-3 , and account for any
differences between the two numbers.

Here is a fcc unit cell. In the unit cell both the Ti and O atoms are
fcc (interpenetrating arrays). There are a total of four Ti’s and four
O’s in the cell, and r = 4.18 D. Hence:

mass of one cell = (4 molecules) × 1/[6.02 × 1023 molecules/mol]

× [47.9 + 16.0] g/mol
= 4.24 × 10-22 g

The density, mass/volume = (4.24 × 10-22 g )/ (4.18 × 10-8 cm) 3 = 5.81 g cm-1 . This value
is a lot larger than that observed experimentally. The difference arises from the presence of
Schottky defects - missing ions - in the lattice.

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14) Shown below are packing diagrams for C6H2N2S4, monoclinic space group P21/c, a = 3.9033(8), b
= 14.8231(18), c = 14.0680(20) D, " = 90.0, $ = 95.835(14), ( = 90.0°. Identify the unit cell vectors
and all the symmetry operations (any rotation and/or screw axes, mirror glide planes, inversion
centres). Also indicate the value of Z, the number of molecules in the unit cell.

N N

S S
S S

It takes a while to sort out directions, but it is easy once you recognize that the angle between
a and c is 90°, as is that between b and c. Given that a is much shorter than b or c, the above
labelling scheme emerges. There are then two glide planes perpendicular to c, and two
screw axes, at (at x = ½ and y =1/4 and 3/4) in the c direction (perpendicular to the glides),
that can then be dropped in. The inversion centre is simple. Note that, in the absence of
information on a, b and c, you could distinguish the screw axes from the glide planes by
noting the positions of the hydrogens. The glide planes keep the H’s up (or down), while the
screws will turn them over. The number of molecules in the unit cell is straightforward, Z
=4.

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