CHAPTER

16 The Solid State

LAIDLER . MEISER . SANCTUARY

Physical Chemistry
Electronic Edition

Problems and Solutions

Chapter 16: The Solid State Crystal Lattices, Unit Cells, Density

Chapter 16
Crystal Lattices, Unit Cells, Density
16.1. How many basis groups are there in

a. An end-centered lattice;
b. A primitive lattice?

Solution

16.2. How many lattice points are there in a unit cell of

a. A face-centered lattice;
b. A body-centered lattice?

Solution

*16.3. a. Determined the efficiency of area utilization in packing circles onto the lattice points of a square lattice.
b. Compare that value with the efficiency of packing circles onto a triangular lattice.
c. Which packing uses area more efficiently and by how much?

Solution

16.4. a. Calculate the percentage of free space (volume of the cell minus the volume of the atoms in the unit cell) in each of the three
cubic lattices if all atoms in each are of equal size and touch their nearest neighbors.
b. Using the calculated values, determine which of the three structures represents the most efficient packing (least amount of used
space).

Solution

16.5. Derive an equation to relate the density D of a right-angled unit cell to its edge lengths a, b, and c and the number of formula units z
per unit cell.

Solution

16-2
Chapter 16: The Solid State Crystal Lattices, Unit Cells, Density

16.6. Silver crystallizes in a face-centered cubic unit cell with a silver atom on each lattice point.

a. If the edge length of the unit cell is 4.0862 Å, what is the atomic radium of silver?
b. Calculate the density of silver.

Solution

16.7. Barium crystallizes with an edge length of 5.025 Å in a body-centered cubic unit cell.

a. Calculate the atomic radius of barium using this information.

b. Calculate the density of barium.

Solution

16.8. Aluminum crystallizes in a face-centered cubic lattice with an aluminum atom on each lattice point with the edge length of the unit
cell equal to 4.0491 Å.

a. Calculate the atomic radius of aluminum.

b. Determine the density of aluminum.

Solution

16.9. Crystals of p, p’-dibromo-α, α’-difluorostilbene [BrC6H4C(F)=]2 are orthorhombic with edge lengths a = 28.32 Å; b = 7.36 Å; c =
6.08 Å. If there are four molecules in a unit cell, calculate the density of the crystal.

Solution

16.10. How many formula units exist in pure crystalline Si, which occurs in a face-centered cubic lattice, if its density is 2.328 99 g cm-3
and its cell length is a = 50431 066 Å? The atomic mass of Si is 28.085 41 g mol-1.

Solution

16-3
Chapter 16: The Solid State Miller Indices and the Bragg Equation

16.11. Sodium chloride crystallizes in a face-centered cubic lattice with four NaCl units per unit cell. If the edge length of the unit cell is
5.629 Å, what is the density of the crystal? Compare your answer to the value given in the CRC Handbook.

Solution

16.12. LiH crystallizes with a face-centered cubic structure. The edge length of the unit cell of LiH is 4.08 Å. Assume anion-anion contact
to calculate the ionic radius of H-. Compare your answer to the value using the radium of Li+ as 0.68 Å.

Solution

16.13. KCl is tetramolecular and crystallizes in a face-centered cubic lattice. If the edge length is 6.278 Å, what is the density of KCl?
Compare your answer to the value in the CRC Handbook.

Solution

16.14. Calcium Fluoride crystallizes in a face-centered cubic lattice where a = b = c, and it has a density of 3.18 g cm-3. Calculate the unit
cell length for CaF2.

Solution

Miller Indices and the Bragg Equation

1 2
16.15. Calculate the Miller indices of the parallel planes in a cubic lattice that intercepts the unit cell length at x = a, y = a , and z = a .
2 3

Solution

16.16. Determine the distance (i.e. d value) of the closest plane parallel to the 100, 110, and 111 faces of the cubic lattice.

Solution

16-4
Chapter 16: The Solid State Miller Indices and the Bragg Equation

16.17. What are the Miller indices of the plane that cuts through the crystal axes at

a. (2a, b, 3c);
b. (2a, -3b, 2c);
c. (a, b, -c);

Solution

16.18. Determine the value of dhkl in terms of the cell constants and angles for

a. The orthorhombic unit cell,

b. The tetragonal unit cell.

Solution

16.19. Calculate the separation between planes in a cubic lattice with unit cell length of 389 pm when the indices are

a. 100;
b. 111;
c. 12 1

Solution

16.20. Copper sulfate single crystals are orthorhombic with unit cells of dimensions a = 488 pm, b = 666 pm, c = 832 pm. Calculate the
diffraction angle from Cu Kα X rays
(λ = 154.18 pm) for first-order reflections from the (100), (010), and (111) planes.

Solution
16.21. Determine the angle of reflection when copper Kα radiation (0.154 18 nm) is incident on a cubic crystal with a lattice constant dhkl of
0.400 nm.

Solution

16-5
Chapter 16: The Solid State Interpretation of X-Ray Data

16.22. Single crystals of FeSO4 are orthorhombic with unit cell dimensions a = 482 pm, b =684 pm, c = 867 pm. Calculate the diffraction
angle from Te Kα, X rays (λ = 45.5 pm) from the (100), (010), and (111) planes

Solution

16.23. Single crystals of Hg(CN)2 are tetragonal with unit cell dimensions a = 967 pm and
c = 892 pm. Calculate the first-order diffraction angles from the (100) and (111) planes when Cu Kα X rays (λ = 154 pm) are used.

Solution

16.24. A two-dimensional lattice is depicted in Figure 16.1 with planes superimposed on it parallel to the third direction. Determine the
Miller indices for each set of planes representing the external habit of the left-hand crystal.

Solution

16.25. The layers of atoms in a crystal are separated by 325 pm. At what angle in a diffractometer will diffraction occur using

a. molybdenum Kα X rays (λ = 70.8 pm);

b. copper Kα X rays (λ = 154 pm)?

Solution

16.26. Calculate the wavelength of an electron that is accelerated through a potential difference of approximately 40 kV.

Solution

Interpretation of X-Ray Data

16.27. Find the X-ray wavelength that would give a second-order reflection (n = 2) with a θ angle of 10.40° from planes with a spacing of
4.00 Å.

Solution

16-6
Chapter 16: The Solid State Interpretation of X-Ray Data

16.28. A substance forms cubic crystals. A powder pattern shows reflections that have either all even or all odd indices. What type of unit
cell does it have?

Solution
16.29. A powder pattern of a cubic material has lines that index as (110), (200), (220), (310), (222), (400). What is its type of unit cell?

Solution

*16.30. The successive sin2θ values obtained from a powder pattern for α-Fe are 1, 2, 3, 4, 5, 6, 7, 8, 9, etc.

a. If iron is in the cubic system, which type of unit cell is present?

b. If a copper X-ray tube is used (λ = 154.18 pm), calculate the length of the side of the unit cell and the value of θ from (100)
planes. The density of α-Fe is 7.90 g cm-3.
c. What is the radium of the iron atom if the central atom in the cubic cell is assumed to be in contact with the corner atoms?

Solution

16.31. Potassium metal has a density of 0.856 g cm-3 and has a body-centered cubic lattice. Calculate the length of the unit cell a and the
distance between (200), (110), and (222) planes. Potassium has an atomic mass of 39.102 g mol-1.

Solution

16.32. Low-angle lines in the Cu Kα powder pattern of KCl are found to be at θ = 14.18°, 20.25°, and 25.10°. Find the crystal type from
these data. (For Cu Kα λ = 154.18 pm.) What other information is needed for a definitive determination?

Solution

16.33. The smallest observed diffraction angle of silver taken with Cu Kα radiation
(λ = 154.18 pm) is 19.176°. This angle is associated with the (111) plane in the cubic close-packed structure of silver.

a. Determine the value of the unit cell length a.

b. If D(Ag) = 10.500 g cm-3 and M = 107.87 g mol-1, calculate the number of atoms in the unit cell.

Solution

16-7
Chapter 16: The Solid State Bonding in Crystals and Metals

16.34. Sodium fluoride is known to form a cubic closed-packed structure. The smallest angle obtained with Cu Kα radiation (λ = 1.5418 Å)
is 16.72° and is derived from the (111) planes. Find the value of a, the unit cell parameter.

Solution

16.35. The X-ray powder pattern of NaCl is taken with a chromium tube giving Cr Kα = 229.1 pm. The θ values of the lines are: 20°36’,
23°58’, 35°4’, 42°21’, 44°43’, 54°20’, 62°17’, 65°16’. From these data determine the value of each dhkl and index the lines. From
the hkl values, show that this is a face-centered system.

Solution

Bonding in Crystals and Metals

1
16.36. Cadmium sulfide has been used as a yellow pigment by artists. The sulfide crystallizes with cadmium occupying of the tetrahedral
2
holes in a closest-packed array of sulfide ions. What is the formula of cadmium sulfide?

Solution

16.37. Rutile is a mineral that contains titanium and oxygen. The structure of rutile may be described as a closest-packed array of oxygen
atoms with titanium in 1 of the octahedral holes. What is the formula of rutile? What is the oxidation number of titanium?
2

Solution

16.38. A tetrahedral hole is shown in Figure 16.33. Determine the largest sphere of radius r that can fit into a tetrahedral hole when the
surrounding four spherical atoms of the lattice are in contact. Let the lattice atom have radium R.

Solution

16.39. An octahedral hole is surrounded by six spheres of radium R in contact. If one-sixth of each of the six coordinating spheres
contributes to the volume of the octahedron surrounding the hole, calculate the maximum radius of the sphere that can be
accommodated.

Solution

16-8
Chapter 16: The Solid State Supplementary Problems

16.40. Calculate the value of ΔEc of the RbBr from the following information: Δ f H = −414 kJ mol −1 ; I (ionization energy, Rb) = 397 kJ
mol-1; Δ sub H (Rb) =
84 kJ mol −1 ; D0(Br2) = 192 kJ mol-1; A (electron affinity, Br) = 318 kJ mol-1.

Solution

Supplementary Problems
16.41. Some of the d spacings for the mineral canfieldite (Ag8SnS6) are 3.23, 3.09, 3.04, 2.81, and 2.74 Å obtained with Cu Kα X rays (λ =
1.5418 Å).

a. Find the corresponding angles of diffraction.

b. This is a cubic system with a = 21.54 Å; determine the hkl values for the first 3 d spacings.

Solution

16.42. A copper selenide mineral (Cu5Se4) called athabascaite is orthorhombic with a = 8.277,
b =11.982, c = 6.441. Strong intensity lines using Cu Kα X rays (λ = 154.18 pm) are observed at 12.95°, 13.76°, and 14.79°.
Determine the d spacings and assign hkl values to these lines.

Solution

1 1 1
*16.43. Zinc blende is the face-centered cubic form of ZnS with Zn at 0, 0, 0; , , 0; 0, , 0;
2 2 2
1 1 1 1 1 1 3 3 3 1 3 3 3 1
, ,0 and with S at , , ; , , ; , , ; , , .
2 2 4 4 4 4 4 4 4 4 4 4 4 4

a. Determine the structure factor from the (111) planes that gives rise to the lowest angle reflection at θ = 14.30° using Cu Kα (λ =
154.18 pm).
b. Calculate the dimension a of the unit cell.

Solution

16-9
Chapter 16: The Solid State Essay Questions

16.44. Calculate the Debye temperature of tungsten that is isotropic (an assumption of the Debye model). The cutoff frequency is given by
1 −1
9N ⎞ 3 ⎛ 1 2 ⎞ 3
ν D = ⎛⎜ ⎟ ⎜ 3 + 3⎟
⎝ 4πV ⎠ ⎝ cl ct ⎠
where
cl = 5.2496 × 105 cm s −1
and
ct = 2.9092 × 105 cm s −1
are the longitudinal and trasverse elastic wave velocities, respectively, in tungsten.

Solution

Essay Questions
16.45. List the 14 Bravais lattices and group them into P, I, F, C, and R cells.
16.46. Explain why the initial X-ray investigation of the two face-centered cubic structures, NaCl and KCl, showed that NaCl was face
centered whereas KCl was simple cubic.
16.47. If ΔH c were required rather than ΔEc , what modification of the Born-Haber cycle would be needed?
16.48. X-ray diffraction is often used to measure residual stress in metals. Suggest that change in the measured parameters allow this
determination.
16.49. Gold diffuses faster in lead at 300°C than does sodium chloride in water at 15°C. Point defects based on vacancies can account for
such high rates. For an ionic material, suggest ways in which such vacancies can occur without altering the stoichiometry of the
crystal.

16-10
Chapter 16: The Solid State Solutions

Solutions
16.1. How many basis groups are there in

a. An end-centered lattice;
b. A primitive lattice?

Solution:

Given: see above

Required: number of basis groups

a. The end-centered lattice has 1 ( 8 ) × 8 + ( 1 2 ) × 2 = 2 lattice points. Since one basis is a

each lattice point, each unit cell has two basis groups.

b. The primitive lattice has one lattice point and there is therefore only one basis group.

Back to Problem 16.1 Back to Top

16-11
Chapter 16: The Solid State Solutions

16.2. How many lattice points are there in a unit cell of

a. A face-centered lattice;
b. A body-centered lattice?

Solution:

Given: see above

Required: number of lattice points

a. A unit cell has 8 lattice points at the corners of a cube; each corner is shared with seven other unit cells. Therefore, only 1/8 of
the 8 belong to a particular face-centered cubic (fcc) cell. Each face has an additional lattice point shared between two cells;
( )
there are therefore 1 × 6 = 3 lattice points in the faces. For the unit cell: 1 (from corners) + 3 (from faces) = 4 lattice points.
2

( 8 ) × 8 corner points. There are thus 1 + 1

b. A body-centered cubic (bcc) lattice has 1 lattice point belonging to the unit cell plus 1
= 2 lattice points.
Back to Problem 16.2 Back to Top

16-12
Chapter 16: The Solid State Solutions

16.3. a. Determined the efficiency of area utilization in packing circles onto the lattice points of a square lattice.
b. Compare that value with the efficiency of packing circles onto a triangular lattice.
c. Which packing uses area more efficiently and by how much?
Solution:

Given: see above

Required: see above

a. Consider the array of circles:

The area belonging to each circle is shown as a dotted box of area 4R 2 . The area of the circle is π R 2 .
π R2
efficiency of filling space = = 0.785 398 163
4 R2
efficiency of filling space = 0.785 or 78.5%

b. Circles on triangular lattice are shown below:

16-13
Chapter 16: The Solid State Solutions

The hexagonal area belonging to a single circle is shown by the dotted lines. The hexagonal area is made up of 12 right triangles,
each having an area of

⎛ 1 ⎞⎛ 1 ⎞ ⎛ 1 ⎞ 2
⎜ R⎟⎜ R⎟ = ⎜ ⎟R
⎝ 2 ⎠⎝ 3 ⎠ ⎝ 2 3 ⎠

The total area is 12 1 ( 2 )

3 R 2 = 2 3 R 2 , and the efficiency of filling space is given by

π R2 π
= = 0.906 899 682
2 3R 2
2 3
efficiency of filling space = 0.907 or 90.7%

c. The triangular form is more efficient by a factor of

90.689 9682
= 1.154 700 538
78.539 8163
= 1.15

Back to Problem 16.3 Back to Top

16-14
Chapter 16: The Solid State Solutions

16.4. a. Calculate the percentage of free space (volume of the cell minus the volume of the atoms in the unit cell) in each of the three
cubic lattices if all atoms in each are of equal size and touch their nearest neighbors.
b. Using the calculated values, determine which of the three structures represents the most efficient packing (least amount of used
space).
Solution:

Given: see above

Required: see above

a. A simple cubic crystal lattice of side 2r contains one atom of radium r.

Free space = volume of cube − volume of atom
4
Free space = ( 2r ) − πr 3
3

3
Free space = 8r − 4.188 790 205r 3
3

Free space = 3.811 209 795r 3

3.811 209 795r 3
Percent free space = × 100 = 47.640 1224%
8r 3
Percent free space = 47.64%

A body-centered cube contains two atoms of radius r in the unit cell. The length of the edge of the cube is calculated using the
Pythagorean theorem:

16-15
Chapter 16: The Solid State Solutions

The diagonal of the cube is 4r.

( 4r ) = d 2 + e2
2

but
d 2 = e2 + e2
so
( 4r ) = 3e2
2

4r
e= (length of edge)
3
3
⎛ 4r ⎞ ⎛4 3⎞
Free space = ⎜ ⎟ − 2 ⎜ 3 πr ⎟
⎝ 3⎠ ⎝ ⎠

Free space = 12.316 805 74r 3 − 8.377 580 41r 3

Free space = 3.939 225 33r 3
3.939 225 33 r 3
Percent free space = × 100
12.316 805 74 r 3
Percent free space = 31.982 523 83%
Percent free space = 31.98%

16-16
Chapter 16: The Solid State Solutions

A face-centered cube contains four atoms of radius r in the unit cell. The length of the edge of the cube is calculated using the
Pythagorean theorem:

( 4r )
2
= e 2 + e 2 = 2e 2
e = 2r 2

( ⎛4
)
⎞
3
Free space = 2 2r − 4 ⎜ πr 3 ⎟
⎝3 ⎠
Free space = 22.627 417r − 16.755 160 82r 3
3

Free space = 5.872 256 18r 3

5.872 256 18 r 3
Percent free space = × 100 = 25.951 951%
22.627 417 r 3
Percent free space = 25.95%

b. The face-centered cube has the least amount of unused space.

Back to Problem 16.4 Back to Top

16-17
Chapter 16: The Solid State Solutions

16.5. Derive an equation to relate the density D of a right-angled unit cell to its edge lengths a, b, and c and the number of formula units z
per unit cell.

Solution:

Given: see above

Required: derive an equation that relates D to a, b, and c and z

The volume of a unit cell with right angles is the product abc of its edges. Since one mole of the crystal contains z unit cells, the molar
abc
volume is Vm = . The molar mass M divided by the molar volume Vm is the density D:
z
M kg ⎛ m3 ⎞ atom
= ÷⎜ × N av ⎟ , where N av is the Avogadro's number in
Vm mol ⎝ atom ⎠ mol
M kg
= =D
Vm m3
Therefore,
M M
D= =
Vm abcN av
z
Mz
D=
abcN av

Back to Problem 16.5 Back to Top

16-18
Chapter 16: The Solid State Solutions

16.6. Silver crystallizes in a face-centered cubic unit cell with a silver atom on each lattice point.

a. If the edge length of the unit cell is 4.0862 Å, what is the atomic radius of silver?
b. Calculate the density of silver.

Solution:

Given: characteristic of silver atom, edge length

Required: atomic radius and density

a. In a face-centered cube containing identical atoms of radius r, the edge length is 2 r 2 . For silver, the edge length is 4.0862 Å.
Edge length = 4.0862 Å = 2r 2
4.0862
r= Å
2 2
r = 1.444 689 865 Å
r = 1.4447 Å

b. The volume of a unit cell is

3
⎛ 10−8 cm ⎞
V = ⎜ 4.0862 Å × ⎟
⎝ Å ⎠
V = 6.822 740 578 × 10−23 cm3

One unit cell contains four atoms, so 1 mol of Ag contains

6.022 × 1023 atoms 1 unit cell
× = 1.5055 × 1023 unit cells mol −1
mol 4 atoms

16-19
Chapter 16: The Solid State Solutions

The mass of 1 mol of Ag is 107.8682 g mol-1. The density is

M 107.8682 g mol −1
D= =
Vm ( )
1.5055 × 1023 cells mol −1 ( 6.822 740 578 × 10−23 cm 3 )

D = 10.501 559 89 g cm −3
D = 10.512 g cm −3

Back to Problem 16.6 Back to Top

16-20
Chapter 16: The Solid State Solutions

16.7. Barium crystallizes with an edge length of 5.025 Å in a body-centered cubic unit cell.

a. Calculate the atomic radius of barium using this information.

b. Calculate the density of barium.

Solution:

Given: characteristics of barium, edge length

Required: atomic radius, density

a. In a body-centered cubic unit cell, the metal atoms are in contact along the diagonal of the cube. The diagonal of the cube forms
a right triangle with the unit cell edge and the diagonal of a face. Use the Pythagorean theorem to determine the length of the
diagonal, d, on the face of the cube in terms of e.

d 2 = e 2 + e 2 = 2e 2
d = 2e

The diagonal of the cube is the length of four atomic radii and can be calculated by again using the Pythagorean theorem.
( Diagonal ) = ( 4r ) = ( 2e ) + e2
2 2 2

( Diagonal )
2
= 16r 2 = 3e 2
Diagonal = 4r = 3e
3e 3
r=
4
=
4
(5.025 Å ) = 2.175 888 827 Å
r = 2.176 Å

b. Given a body-centered cubic structure, each unit cell contains two atoms. Use the unit cell edge length to calculate the unit cell
volume and the volume occupied by each atom. Multiply to obtain the molar volume and divide the gram atomic weight by this
value to obtain density (e = edge length).

16-21
Chapter 16: The Solid State Solutions

V (cell) = e3 = ( 5.025 × 10−8 cm ) = 1.268 843 906 × 10−22 cm3

3

1.268 843 906 × 10−22 cm3 6.344 219 531 × 10−23 cm3
V (atom) = =
2 atoms atom
⎛ 6.344 219 531 × 10 cm ⎞ ⎛ 6.022 × 1023 atoms ⎞
−23 3
V (mole) = ⎜ ⎟×⎜ mol
⎟
⎝ atom ⎠ ⎝ ⎠
38.204 890 02 cm 3
V (mole) =
mol

⎛ 137.33 g ⎞ ⎛ 38.204 890 02 cm ⎞

3
D (Ba) = ⎜ ⎟÷⎜ ⎟
⎝ mol ⎠ ⎝ mol ⎠
⎛ 137.33 g ⎞ ⎛ mol ⎞
D (Ba) = ⎜ ⎟ ×⎜ 3 ⎟
⎝ mol ⎠ ⎝ 38.204 890 02 cm ⎠
D (Ba) = 3.594 566 034 g cm −3
D (Ba) = 3.595 g cm −3

Back to Problem 16.7 Back to Top

16-22
Chapter 16: The Solid State Solutions

16.8. Aluminum crystallizes in a face-centered cubic lattice with an aluminum atom on each lattice point with the edge length of the unit
cell equal to 4.0491 Å.

a. Calculate the atomic radius of aluminum.

b. Determine the density of aluminum.

Solution:

Given: characteristics of aluminum, edge length

Required: atomic radius, density

a. In a body-centered cubic unit cell, the metal atoms are in contact along the diagonal of the cube. The diagonal of the cube forms a
right triangle with the unit cell edge and the diagonal of a face. Use the Pythagorean theorem to determine the length of the diagonal,
d, on the face of the cube in terms of e.

2 ( 4.0491 Å )
r (Al) = = 1.431 573 034 Å
4
r (Al) = 1.432 Å

b. Follow the same procedure for density as used in Problem 16.7, but noting that a face-centered cubic cell contains four atoms per
cell instead of two.

16-23
Chapter 16: The Solid State Solutions

V (cell) = e3 = ( 4.0491 × 10−8 cm ) = 6.638 584 809 × 10−23 cm3

3

6.638 584 809 × 10−23 cm 3 1 cell 6.022 × 1023 atoms

V (mol) = × ×
cell 4 atoms mol
V (mol) = 9.994 389 43 cm 3 mol −1
26.9815 g 1 mol
D (Al) = × = 2.699 664 666 g cm −3
mol 9.994 389 43 cm3
D (Al) = 2.700 g cm −3

Back to Problem 16.8 Back to Top

16-24
Chapter 16: The Solid State Solutions

16.9. Crystals of p, p’-dibromo-α, α’-difluorostilbene [BrC6H4C(F)=]2 are orthorhombic with edge lengths a = 28.32 Å; b = 7.36 Å; c =
6.08 Å. If there are four molecules in a unit cell, calculate the density of the crystal.

Solution:

Given: see above

Required: density of the crystal

From Problem 16.5:

Mz
D= , where N av is the Avogadro's number and M is the molar mass
abcN av

Molar mass of [BrC6H4C(F)=]2 = 373.94 g mol-1

D=
(
4 373.94 g mol −1 )
( ) × (6.022 × 10 )
3
( 28.32 )( 7.36 )( 6.08) Å 3 × 10−8 cm Å −1 23
mol −1

D = 1.959 9569 g cm −3
D = 1.96 g cm −3

Back to Problem 16.9 Back to Top

16-25
Chapter 16: The Solid State Solutions

16.10. How many formula units exist in pure crystalline Si, which occurs in a face-centered cubic lattice, if its density is 2.328 99 g cm-3
and its cell length is a = 50431 066 Å? The atomic mass of Si is 28.085 41 g mol-1.

Solution:

Given: characteristics of Si, its density, cell length, and atomic mass

Required: number of formula

From Problem 16.5:

Mz
D= , where N av is the Avogadro's number and M is the molar mass
abcN av

For a face-centered cubic lattice, all edge lengths are equal, that is a = b = c.
DabcN av
z=
M

( ) (10 ) (6.022 × 10 )
3 3
2.328 99 g cm −3 5.431 066 Å −8
cm Å −1 23
mol −1
z=
28.085 41 g mol −1
z = 7.999 868 501
z =8

Back to Problem 16.10 Back to Top

16-26
Chapter 16: The Solid State Solutions

16.11. Sodium chloride crystallizes in a face-centered cubic lattice with four NaCl units per unit cell. If the edge length of the unit cell is
5.629 Å, what is the density of the crystal? Compare your answer to the value given in the CRC Handbook.

Solution:

Given: characteristics of sodium chloride, edge length

Required: density

Mz
D= , where N av is the Avogadro's number and M is the molar mass
abcN av

For sodium chloride, z = 4, M = 58.45 . As the crystal is a face-centered cubic lattice,

a = b = c = 5.629 Å
Mz
D=
abcN av

D=
(
4 58.45 g mol −1 )
(5.629 Å ) (10 ) (6.022 × 10 )
3 3
−8
cm Å −1 23
mol −1

D = 2.176 7573 g cm −3
D = 2.176 g cm −3
CRC value = 2.165 g cm −3 at 25oC

The lower density given in the handbook may be due to voids and other imperfections in the crystal.

Back to Problem 16.11 Back to Top

16-27
Chapter 16: The Solid State Solutions

16.12. LiH crystallizes with a face-centered cubic structure. The edge length of the unit cell of LiH is 4.08 Å. Assume anion-anion contact
to calculate the ionic radius of H-. Compare your answer to the value using the radium of Li+ as 0.68 Å.

Solution:

Given: LiH characteristics, edge lenth

Required: ionic radius

The structure is face-centered cubic with the hydride ions in contact along the diagonal of the face as shown in the figure.

From the figure,

( 4d ) = 2 ( 4.08 Å )
2 2
−
H

d H − = 1.442 497 834 Å

d H − = 1.44 Å

Another way to look at this problem is to consider that lithium ions fill the space along the edge, giving an edge length of 2rLi+ + 2rH − . The
radius of the hydride ion is computed from the edge length e and the reported radius of Li+ (0.68 Å).

16-28
Chapter 16: The Solid State Solutions

e = 4.08 Å = 2 rLi+ + 2rH −

e = 2 ( 0.68 Å ) + 2 rH −
e − 2 ( 0.68 Å )
rH − =
2
4.08 Å − 1.36 Å
rH − =
2
rH − = 1.36 Å

A recent edition of the CRC Handbook gives two values for Li+: with coordination number 4, its radius is 0.56 Å; with coordination number
6, its radius is 0.76 Å. The value of 0.68 Å just cited is found in an older edition and represents an average value. Any value of rH − will
depend upon the value of rLi+ used in this method. It is common to consider that the anions are in contact with the cations occupying the
open space. There is no requirement that the anions and the cations contact. Therefore, the first method gives a better estimate of the
maximum size of H-.
Back to Problem 16.12 Back to Top

16-29
Chapter 16: The Solid State Solutions

16.13. KCl is tetramolecular and crystallizes in a face-centered cubic lattice. If the edge length is 6.278 Å, what is the density of KCl?
Compare your answer to the value in the CRC Handbook.

Solution:

Given: characteristics of KCl, edge length

Required: density

The molar mass of KCl is 74.55 g mol −1 .

Mz
D=
abcN av

D=
(
4 74.55 g mol −1 )
(6.278 Å × 10 ) (6.022 × 10 )
3
−8
cm Å −1 23
mol −1

D = 2.001 257 414 g cm −3

D = 2.001 g cm −3
CRC value = 1.984 g cm −3

Back to Problem 16.13 Back to Top

16-30
Chapter 16: The Solid State Solutions

16.14. Calcium Fluoride crystallizes in a face-centered cubic lattice where a = b = c, and it has a density of 3.18 g cm-3. Calculate the unit
cell length for CaF2.

Solution:

Given: characteristics of calcium fluoride, density

Required: unit cell length

The molar mass of calcium fluoride is 78.08 g mol −1

There are four calcium ions per unit cell and eight associated fluoride ions. Consequently, z = 4 and rearrangement of
Mz
D= with a = b = c gives
abcN av

a =
3 Mz
=
(
4 78.08 g mol −1 )
DN av ( )(
3.18 g cm −3 6.022 × 1023 mol −1 )
a 3 = 1.630 917 245 × 10−22 cm 3
a = 5.463 580 021 × 10−8 cm
a = 5.46 × 10−8 cm = 5.46 Å = 546 pm

Back to Problem 16.14 Back to Top

16-31
Chapter 16: The Solid State Solutions

1 2
16.15. Calculate the Miller indices of the parallel planes in a cubic lattice that intercepts the unit cell length at x = a, y = a , and z = a .
2 3

Solution:

1 2
Given: cubic lattice, x = a, y = a , and z = a .
2 3

Required: Miller indices

The intercepts along the axes are spaces at a/h, b/k, c/l. For a cubic system

a a a 2a a 3
1a = , h = 1; = , k = 2; = ,l =
h 2 k 3 l 2

Clearing fraction we have

( hkl ) = ( 243)

Back to Problem 16.15 Back to Top

16-32
Chapter 16: The Solid State Solutions

16.16. Determine the distance (i.e. d value) of the closest plane parallel to the 100, 110, and 111 faces of the cubic lattice.

Solution:

Given: see above

Required: see above

The faces are shown in the figures below:

The spacings are calculated from the formula

a
d hkl =
h + k2 + l2
2

Or from trigonometry as demonstrated from the 110 planes:

16-33
Chapter 16: The Solid State Solutions

2
d110 + d110
2
= a2
2
2d110 = a2
a
d110 =
2

The results are

a a
d110 = a d110 = d111 =
2 3

Back to Problem 16.16 Back to Top

16-34
Chapter 16: The Solid State Solutions

16.17. What are the Miller indices of the plane that cuts through the crystal axes at

a. (2a, b, 3c);
b. (2a, -3b, 2c);
c. (a, b, -c);

Solution:

Given: see above

Required: Miller indices

Originals Reciprocals Miller indices

1 1
,1, (362)
a. (2a, b, 3c) 2 3

1 −1 1
, , (323)
b. (2a, -3b, 2c) 2 3 3

c. (a, b, -c) 1,1, −1 (11 1)

Back to Problem 16.17 Back to Top

16-35
Chapter 16: The Solid State Solutions

16.18. Determine the value of dhkl in terms of the cell constants and angles for

a. The orthorhombic unit cell,

b. The tetragonal unit cell.

Solution:

Given: see above

Required: value of dhkl

a. In the orthorhombic system, all three sides are different and all angles are 90°. Therefore, all sine terms are equal to one and all
cosine terms are equal to zero. From Eq. 16.19,

1
2
d hkl = 2
h k2 l2
+ +
a 2 b2 c 2

or

−1 2
⎛ h2 k 2 l 2 ⎞
d hkl =⎜ 2 + 2 + 2⎟
⎝a b c ⎠

b. For the tetragonal system, a = b = c and all angles are 90°. Therefore, all sine terms are equal to one and all cosine terms are equal to
zero. From Eq. 16.19.

1
2
d hkl = 2
h k2 l2
+ +
a 2 b2 c 2

Then with a = b,

16-36
Chapter 16: The Solid State Solutions

1
2
d hkl =
h + k2 l2
2
+ 2
a2 c

or

−1 2
⎛ h2 + k 2 l 2 ⎞
d hkl =⎜ 2
+ 2⎟
⎝ a c ⎠

Back to Problem 16.18 Back to Top

16-37
Chapter 16: The Solid State Solutions

16.19. Calculate the separation between planes in a cubic lattice with unit cell length of 389 pm when the indices are

a. 100;
b. 111;
c. 12 1

Solution:

Given: see above

Required: separation between planes

a
d hkl =
(h + k2 + l2 )
2 12

389 pm
a. d100 =
1
d100 = 389 pm

389 pm 389 pm
b. d111 = =
(1 2 2 12
+ 12 + 1 ) 3
d111 = 224.589 254 7 pm
d111 = 225 pm

389 pm 389 pm
c. d12 1 = =
2 12
⎡12 + 2 2 + ( −1) ⎤ 6
⎣ ⎦
d12 1 = 158.808 585 pm
d12 1 = 159 pm

Back to Problem 16.19 Back to Top

16-38
Chapter 16: The Solid State Solutions

16.20. Copper sulfate single crystals are orthorhombic with unit cells of dimensions a = 488 pm, b = 666 pm, c = 832 pm. Calculate the
diffraction angle from Cu Kα X rays
(λ = 154.18 pm) for first-order reflections from the (100), (010), and (111) planes.

Solution:

Given: characteristics of copper sulfate, cell dimensions, λ = 154.18 pm, planes indices.

Required: diffraction angle.

λ = 2d hkl sinθ λ=154 pm

From Problem 16.18,

16-39
Chapter 16: The Solid State Solutions

1 h2 k 2 l 2
= + +
d 2 a 2 b2 c 2
1 1
2
= 2 ; d100 = a = 488 pm
d100 a
1 1
2
= 2 ; d 010 = b = 666 pm
d 010 b
1 1 1 1 1 1 1
2
= 2+ 2+ 2 = + +
d111 a b c 488 666 8322
2 2

1
2
= 4.199 140 016 × 10−6 + 2.254 506 759 × 10−6 + 1.144 619 083 × 10−6
d111
1
2
= 7.898 265 858 × 10−6
d111
d111 = 355.823 089 3 pm
λ 154 pm
sinθ = = = 0.157 786 885
(
2d100 2 488 pm )
θ100 = 9.078 462 401°
θ100 = 9.08°
λ 154 pm
sinθ = = = 0.115 615 615
(
2d 010 2 666 pm )
θ010 = 6.639 134 078°
θ 010 = 6.64°
λ 154 pm
sinθ = = = 0.216 292 134
(
2d111 2 356 pm )
θ111 = 12.491 345 05°
θ111 = 12.49°
Back to Problem 16.20 Back to Top

16-40
Chapter 16: The Solid State Solutions

16.21. Determine the angle of reflection when copper Kα radiation (0.154 18 nm) is incident on a cubic crystal with a lattice constant dhkl of
0.400 nm.

Solution:

Given: λ = 0.154 18 nm, dhkl = 0.400 nm

Required: angle of reflection

Assuming a first-order reflection,

λ = 2d sin θ
(
0.154 18 nm = 2 0.400 nm sin θ )
sin θ = 0.192 725
θ = 11.111 854 97°
θ = 11.1°

Back to Problem 16.21 Back to Top

16-41
Chapter 16: The Solid State Solutions

16.22. Single crystals of FeSO4 are orthorhombic with unit cell dimensions a = 482 pm, b =684 pm, c = 867 pm. Calculate the diffraction
angle from Te Kα, X rays (λ = 45.5 pm) from the (100), (010), and (111) planes

Solution:

Given: characteristics of FeSO4 crystal, cell dimensions, λ = 45.5 pm, plane indices

Required: diffraction angle

λ = 2d hkl sinθ λ=45.5 pm

From Eq. 16.19 or Problem 16.18,

16-42
Chapter 16: The Solid State Solutions

1 h2 k 2 l 2
2
= 2+ 2+ 2
d hkl a b c
1 1
2
= 2 ; d100 = a = 482 pm
d100 a
1 1
2
= 2 ; d 010 = b = 684 pm
d 010 b
1 1 1 1 1 1 1
2
= 2+ 2+ 2 = + +
d111 a b c 482 684 8672
2 2

1
2
= 4.304 333 603 × 10−6 + 2.137 409 801 × 10−6 + 1.330 337 413 × 10−6
d111
1
2
= 7.772 080 818 × 10−6
d111
d111 = 358.699 974 7 pm
λ 45.5 pm
sinθ = = = 0.047 199 17
(
2d100 2 482 pm )
θ100 = 2.705 318 347°
θ100 = 2.71°
λ 45.5 pm
sinθ = = = 0.033 260 233
(
2d 010 2 684 pm )
θ010 = 1.906 022 56°
θ 010 = 1.91°
λ 45.5 pm
sinθ = = = 0.063 370 473
(
2d111 2 359 pm )
θ111 = 3.633 295 227°
θ111 = 3.63°
Back to Problem 16.22 Back to Top

16-43
Chapter 16: The Solid State Solutions

16.23. Single crystals of Hg(CN)2 are tetragonal with unit cell dimensions a = 967 pm and
c = 892 pm. Calculate the first-order diffraction angles from the (100) and (111) planes when Cu Kα X rays (λ = 154 pm) are used.

Solution:

Given: characteristics of Hg(CN)2 crystal, cell dimensions, λ = 154 pm, plane indices

Required: first-order diffraction angles

λ = 2d hkl sinθ λ=154 pm

From Eq. 16.19 or Problem 16.18,

16-44
Chapter 16: The Solid State Solutions

1 h2 + k 2 l 2
2
= + 2
d hkl a2 c
1 1
2
= 2 ; d100 = a = 967 pm
d100 a
1 12 + 12 12
2
= +
d111 9672 8922
1
2
= 2.138 833 844 × 10−6 + 1.256 811 921 × 10−6
d111
d111 = 542.673 745 5 pm
λ 154 pm
sinθ = = = 0.079 627 714
(
2d100 2 967 pm )
θ100 = 4.567 167 086°
θ100 = 4.57°
λ 154 pm
sinθ = = = 0.141 804 788
(
2d111 2 543 pm )
θ111 = 8.152 295 044°
θ111 = 8.15°

Back to Problem 16.23 Back to Top

16-45
Chapter 16: The Solid State Solutions

16.24. A two-dimensional lattice is depicted in Figure 16.1 with planes superimposed on it parallel to the third direction. Determine the
Miller indices for each set of planes representing the external habit of the left-hand crystal.

Solution:

Given: figure 16.1

Required: Miller indices

The Miller indices depend upon the way in which we draw the unit cell. Four different ways and their corresponding values are shown.
Notice that the right-hand cell has been used for convenience. The planes in the left-hand cell will have exactly the same indices.

Notice that the angle between dots is not exactly 90°. This does not matter since the a vector that determines the reciprocal lattice will be
perpendicular to the actual planes

The indices are A, (0, 1, 0); B, (-1, 1, 0); C, (2, 1, 0), and D, (1, 1, 0).

Back to Problem 16.24 Back to Top

16-46
Chapter 16: The Solid State Solutions

16.25. The layers of atoms in a crystal are separated by 325 pm. At what angle in a diffractometer will diffraction occur using

a. molybdenum Kα X rays (λ = 70.8 pm);

b. copper Kα X rays (λ = 154 pm)?

Solution:

Given: see above

Required: angle of diffraction

a. Let n = 1 in the Bragg equation nλ = 2d sin θ

⎛ λ ⎞
Then θ = sin −1 ⎜ ⎟
⎝ 2d ⎠
⎛ 70.8 ⎞
θ = sin −1 ⎜ ⎟
⎝ 2 × 325 ⎠
θ = sin −1 ( 0.108 923 076 )
θ = 6.253 239 405°
θ = 6.25°

⎛ λ ⎞
b. θ = sin −1 ⎜ ⎟
⎝ 2d ⎠
⎛ 154 ⎞
θ = sin −1 ⎜ ⎟
⎝ 2 × 325 ⎠
θ = sin −1 ( 0.236 923 076 )
θ = 13.705 008 73°
θ = 13.71°

Notice that the shorter the wavelength, the smaller the diffraction angle.

Back to Problem 16.25 Back to Top

16-47
Chapter 16: The Solid State Solutions

16.26. Calculate the wavelength of an electron that is accelerated through a potential difference of approximately 40 kV.

Solution:

Given: see above

Required: wavelength

1 2
The kinetic energy of the electron is mu and is also VQ; it thus follows that
2
12
⎛ 2VQ ⎞
u=⎜ ⎟
⎝ m ⎠
⎛ 2 ( 40 × 103 V )(1.60 × 10−19 C ) ⎞
12

u=⎜ ⎟
⎜ 9.11 × 10−31 kg ⎟
⎝ ⎠
1 V C =1 J
u = (1.405 049 396 × 1016 J kg −1 )
12

Since J = kg m 2 s −2
u = 1.185347795 × 108 m s −1

Substituting into the de Broglie equation (Eq. 11.56) gives

h
λ=
mu
6.63 × 10−34 J s
λ=
( 9.11 × 10−31 kg )(1.19 × 108 m s−1 )
λ = 6.115 728 399 × 10−12 m
λ = 6.12 pm

Back to Problem 16.26 Back to Top

16-48
Chapter 16: The Solid State Solutions

16.27. Find the X-ray wavelength that would give a second-order reflection (n = 2) with a θ angle of 10.40° from planes with a spacing of
4.00 Å.

Solution:

Given: n = 2, θ = 10.40°, plane spacing = 4.00 Å

Required: X-ray wavelength

nλ = 2d sin θ
2d sin θ
λ=
n
2 ( 4.00 Å ) ⎡⎣sin (10.40° ) ⎤⎦
λ=
2
λ = 0.722 076 581 Å
λ = 0.722 Å

Back to Problem 16.27 Back to Top

16-49
Chapter 16: The Solid State Solutions

16.28. A substance forms cubic crystals. A powder pattern shows reflections that have either all even or all odd indices. What type of unit
cell does it have?

Solution:

Given: see above

Required: type of cell

From Figure 16.28, it is determined that the face-centered cubic (fcc) system is the only one that conforms to the data. Note that the
symmetry of the crystal determines which indices will appear.

[image]

Back to Problem 16.28 Back to Top

16-50
Chapter 16: The Solid State Solutions

16.29. A powder pattern of a cubic material has lines that index as (110), (200), (220), (310), (222), (400). What is its type of unit cell?

Solution:

Given: see above, lines indexes

Required: type of unit cell

From Figure 16.28, it can only be bcc

[image]

Back to Problem 16.29 Back to Top

16-51
Chapter 16: The Solid State Solutions

*16.30. The successive sin2θ values obtained from a powder pattern for α-Fe are 1, 2, 3, 4, 5, 6, 7, 8, 9, etc.

a. If iron is in the cubic system, which type of unit cell is present?

b. If a copper X-ray tube is used (λ = 154.18 pm), calculate the length of the side of the unit cell and the value of θ from (100)
planes. The density of α-Fe is 7.90 g cm-3.
c. What is the radium of the iron atom if the central atom in the cubic cell is assumed to be in contact with the corner atoms?

Solution:

Given: see above

Required: see above

a. From Figure 16.28, it is seen that the ratio 7 is not allowed for cubic systems. The ratio must be 2, 4, 6, and so on. Consequently, the
structure is bcc.

b. For a bcc system, a = b = c, z = 2, and from Problem 16.5, D = zMa 3 L or

a =
3
(
2 55.85 g mol −1 )
( 7.90 )(
g cm −3 6.022 × 1023 mol −1 )
a 3 = 2.347 931 004 × 10−23 cm 3
a = 2.863 486 304 × 10−8 cm
a = 286.348 630 4 pm
a = 286 pm

For 100 type planes, d is a/2 since the planes are actually (200). Therefore, from 2d sin θ = nλ ,

154.18 pm
sin θ = = 0.539 090 909
286 pm
θ = 32.621 774 51°
θ = 32.6°

16-52
Chapter 16: The Solid State Solutions

3a
c. The body diagonal is the smallest interatomic distance and has the value . Therefore, the radius is the distance from the center
2
of one Fe atom to the center of the central atom divided by 2:
3a 3 × 286.348 630 4 pm
rFe = =
2×2 4
rFe = 123.992 594 1 pm
rFe = 124.0 pm

Back to Problem 16.30 Back to Top

16-53
Chapter 16: The Solid State Solutions

16.31. Potassium metal has a density of 0.856 g cm-3 and has a body-centered cubic lattice. Calculate the length of the unit cell a and the
distance between (200), (110), and (222) planes. Potassium has an atomic mass of 39.102 g mol-1.

Solution:

Given: characteristics of potassium metal, density, plane indices, atomic mass

Required: length of the unit cell, distance between the given planes

There are two atoms in a body-centered lattice and we may write:

Density =
( number of atoms/cell )( atomic mass ) , where N is the Avogadro's number
av
N av a 3

−3
2 ( 39.102 g mol −1 )
0.856 g cm =
( 6.022 × 10 23
mol −1 ) a 3

a =
3
(
2 39.102 g mol −1 )
(6.022 × 10 23
mol −1 ) (0.856 g cm ) −3

a = 5.333 408 111 × 10−8 cm

a = 533.340 811 1 pm
a = 533.3 pm

Then from the equation

16-54
Chapter 16: The Solid State Solutions

1 533.340 811 1 pm
d hkl = =
(h )
2 12
(h + k2 + l2 )
12
2
+ k2 + l 2

533.340 811 1 pm
For (200) planes, d 200 = = 266.670 405 6 pm
4
d 200 = 266.7 pm
533.340 811 1 pm
For (110) planes, d110 = = 377.128 904 2 pm
2
d110 = 377.1 pm
533.340 811 1 pm
For (222) planes, d 222 = = 153.962 230 4 pm
12
d 222 = 154.0 pm

Back to Problem 16.31 Back to Top

16-55
Chapter 16: The Solid State Solutions

16.32. Low-angle lines in the Cu Kα powder pattern of KCl are found to be at θ = 14.18°, 20.25°, and 25.10°. Find the crystal type from
these data. (For Cu Kα λ = 154.18 pm.) What other information is needed for a definitive determination?

Solution:

Given: pH 7, ∂E /∂T = 2.18 × 10 –5 V K –1

Required: see above

First, determine the d values for the three lines and take their ratios:

λ λ λ
2 d1 = 2d 2 = 2d 3 =
sin (14.18) sin ( 20.25) sin ( 25.10 )
1 1 1
d1 : d 2 : d 3 = : :
sin (14.18) sin ( 20.25) sin ( 25.10 )
d1 : d 2 : d 3 = 4.082 149 659 : 2.889 195 951 : 2.357 381 803
d1 : d 2 : d 3 = 1 : 0.707 763 358 : 0.577485393

From Problem 16.16, for the cubic lattice,

d100 = a
2a
d110 = = 0.707
2
3a
d111 = = 0.5773
3

The ratios thus correspond to the cubic structure. To confirm the structure, if K+ and Cl- reflect equally d = a/2, the theoretical density could
be compared to the experimental value.

Back to Problem 16.32 Back to Top

16-56
Chapter 16: The Solid State Solutions

16.33. The smallest observed diffraction angle of silver taken with Cu Kα radiation
(λ = 154.18 pm) is 19.176°. This angle is associated with the (111) plane in the cubic close-packed structure of silver.

a. Determine the value of the unit cell length a.

b. If D(Ag) = 10.500 g cm-3 and M = 107.87 g mol-1, calculate the number of atoms in the unit cell.

Solution:

Given: see above

Required: value of the unit cell length, number of atoms in the unit cell

λ 154.18 pm
a. d111 = = = 235.877 596 9 pm
2sin θ 2 sin (19.076 )
a
= 235.877 596 9 pm
( h 2
+ k 2
+ l )
2 12

a
= 235.877 596 9 pm
(12 + 12 + 12 )
12

a = 408.551 982 2 pm
a = 408.6 pm

b. The effective volume of each Ag atom is

M 107.87 g mol −1
VAg = =
DN av ( )(
10.500 g m −3 6.022 × 1023 mol −1 )
VAg = 1.705 967 01 × 10−23 cm3
VAg = 1.705 967 01 × 107 pm3
Vcell = a 3 = ( 408.6 pm ) = 6.821 738 806 × 107 pm3
3

16-57
Chapter 16: The Solid State Solutions

The number of atoms per unit cell is

Vcell 6.821 738 806 × 10 pm

7 3

N= = = 3.998 751 89
VAg 1.705 967 01 × 107 pm 3
N =4 This is an indication that Ag is fcc.

Back to Problem 16.33 Back to Top

16-58
Chapter 16: The Solid State Solutions

16.34. Sodium fluoride is known to form a cubic closed-packed structure. The smallest angle obtained with Cu Kα radiation (λ = 1.5418 Å)
is 16.72° and is derived from the (111) planes. Find the value of a, the unit cell parameter.

Solution:

Given: see above

Required: the unit cell parameter

λ 154.2 pm
d111 = =
2sin θ 2 sin (16.72 )
d111 = 267.992 288 4 pm
a a
d111 = =
(h 2
+k +l
2
)
2 12 3
a
267.992 288 4 pm =
3
a = 464.176 259 6 pm
a = 464.2 pm

Back to Problem 16.34 Back to Top

16-59
Chapter 16: The Solid State Solutions

16.35. The X-ray powder pattern of NaCl is taken with a chromium tube giving Cr Kα = 229.1 pm. The θ values of the lines are: 20°36’,
23°58’, 35°4’, 42°21’, 44°43’, 54°20’, 62°17’, 65°16’. From these data determine the value of each dhkl and index the lines. From
the hkl values, show that this is a face-centered system.

Solution:

Given: above data

Required: see above

λ
First, calculate decimal equivalent of θ values and the sin θ. From each value of θ, calculate the value of d hkl = .
2sin θ

229.1 pm
θ sin θ d hkl = hkl a
2sin θ

20°36 ' 20.600 0.351 841 648 325.572 599 6 111 564.0

23°58' 23.967 0.406 210 411 281.996 711 3 200 564.0

35°4 ' 35.067 0.574 533 936 199.378 997 2 220 564.0

42°21' 42.350 0.673 657 707 170.041 845 9 311 563.8

44°43' 44.717 0.703 605 57 162.804 282 5 222 564.0

54°20' 54.333 0.812 419 487 140.998 587 3 400 564.0

62°17 ' 62.283 0.885 255 665 129.397 647 331 564.0

65°16 ' 65.267 0.908 267 352 126.119 253 420 563.9

Ignore the final two columns for the time being.

Assume that NaCl has a cubic crystal structure.

16-60
Chapter 16: The Solid State Solutions

Then

a = d hkl = h 2 + k 2 + l 2

If we index the first three angles obtained from NaCl according to the (100), (110), (111) planes of the simple cubic lattice, the value of a
should be the same in each case.

a = d hkl 12 + 0 + 0 = 325.572 599 6 pm ( 1) = 325.572 599 6 pm

a = d hkl 1 + 1 + 0 = 281.996 711 3 pm ( 2 ) = 398.803 573 7 pm
2 2

a = d hkl 1 + 1 + 1 = 199.378 997 2 pm ( 3 ) = 345.334 553 1 pm

2 2 2

Since the unit cell dimension a is not the same, this does not allow indexing as a simple cubic system.

An attempt to index the first line with d110 gives

a = 325.572 599 6 pm ( )
12 + 12 + 0 = 460.429 185 9 pm

And the next set of hkl values must give the value

a 460.429 185 9 pm
h2 + k 2 + l 2 = = = 1.632 746 651
d hkl 281.996 711 3 pm

No set of integers will give this value.

If the first line is indexed as 111, we have

a = 325.572 599 6 pm ( )
12 + 12 + 12 = 563.908 284 1 pm

And, as in the last case, the next line must be indexed such that

16-61
Chapter 16: The Solid State Solutions

a 563.908 284 1 pm
h2 + k 2 + l 2 = = = 1.999 698 087 = 2
d hkl 281.996 711 3 pm

This allows h, k, or l = 2 corresponding to planes (200), (020), (002).

The rest of the planes can be indexes as listed in the final columns of the table with the corresponding values of a. These correspond to the
lines expected for an fcc structure as listed in Figure 16.20.

Back to Problem 16.35 Back to Top

16-62
Chapter 16: The Solid State Solutions

1
16.36. Cadmium sulfide has been used as a yellow pigment by artists. The sulfide crystallizes with cadmium occupying of the tetrahedral
2
holes in a closest-packed array of sulfide ions. What is the formula of cadmium sulfide?

Solution:
Given: see above

Required: formula of cadmium sulfide

In a closest-packed array there are two tetrahedral holes for each anion. If only half the tetrahedral holes are occupied, the numbers of
anions and cations are equal. The formula for cadmium sulfide is CdS.

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Chapter 16: The Solid State Solutions

16.37. Rutile is a mineral that contains titanium and oxygen. The structure of rutile may be described as a closest-packed array of oxygen
atoms with titanium in 1 of the octahedral holes. What is the formula of rutile? What is the oxidation number of titanium?
2

Solution:

Given: see above

Required: formula of rutile, the oxidation number of titanium

In a closest-packed array, there is one octahedral hole for each anion. If only half of the octahedral holes are occupied by titanium atoms,
there are twice as many oxygen atoms as titanium ions, and the formula as TiO2. With each oxygen as -2, the titanium must be +4.

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16-64
Chapter 16: The Solid State Solutions

16.38. A tetrahedral hole is shown in Figure 16.33. Determine the largest sphere of radius r that can fit into a tetrahedral hole when the
surrounding four spherical atoms of the lattice are in contact. Let the lattice atom have radium R.

Solution:

Given: Figure 16.33, above information

Required: see above

The contributions of the four atoms in contact forming the tetrahedral void may be represented at the corners A, B, C, and D. A plane
through A and B and bisecting the line CD is represented as follows:

Here the atoms at A and B are shown by arcs. The right triangle AGV is similar to the right triangle ABF. Therefore

AG AB 2
= =
AV AF 3

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Chapter 16: The Solid State Solutions

Then the maximum radius of the circle representing the void can be no more than AV − R , that is,

AG R 2
= =
AV R + r 3
3− 2
r= R = 0.224 744 871R
2
r = 0.225R

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Chapter 16: The Solid State Solutions

16.39. An octahedral hole is surrounded by six spheres of radium R in contact. If one-sixth of each of the six coordinating spheres
contributes to the volume of the octahedron surrounding the hole, calculate the maximum radius of the sphere that can be
accommodated.

Solution:

Given: see above

Required: maximum radius

Take a section through an octahedron with sides of unit length:

The diagonal AC is 2.

From the isosceles right triangle,

AC 2
=
AB 1

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Chapter 16: The Solid State Solutions

If r is the radius of the void, then

2 R + 2r 2
=
2R 1
r = 2 R − R = 0.414 213 562 R
r = 0.414 R

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Chapter 16: The Solid State Solutions

16.40. Calculate the value of ΔEc of the RbBr from the following information: Δ f H = −414 kJ mol −1 ; I (ionization energy, Rb) = 397 kJ
mol-1; Δ sub H (Rb) =
84 kJ mol −1 ; D0(Br2) = 192 kJ mol-1; A (electron affinity, Br) = 318 kJ mol-1.

Solution:

Given: above data

Required: value of ΔEc

From Eq. 16.58,

1
ΔEC = −Δ f H + Δ sub H + D0 + I − A
2
⎡ 1 ⎤
ΔEC = ⎢ 414 + 84 + (192 ) + 397 − 318⎥ kJ mol −1
⎣ 2 ⎦
ΔEC = 673 kJ mol −1

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16-69
Chapter 16: The Solid State Solutions

16.41. Some of the d spacings for the mineral canfieldite (Ag8SnS6) are 3.23, 3.09, 3.04, 2.81, and 2.74 Å obtained with Cu Kα X rays (λ =
1.5418 Å).

a. Find the corresponding angles of diffraction.

b. This is a cubic system with a = 21.54 Å; determine the hkl values for the first 3 d spacings.

Solution:

Given: see above

Required: angles of diffraction, hkl values

a. n λ = 2d sin θ

d/pm 323 309 304 284 274

θ 13.81° 14.45° 14.69° 15.75° 16.33°

1 h2 + k 2 + l 2
b. =
d2 a2

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Chapter 16: The Solid State Solutions

For d = 323 pm:

1 1 h2 + k 2 + l 2
= =
d 2 ( 323 pm ) 2
( )
2
21.54 Å × 102 pm Å −1

h 2 + k 2 + l 2 = 44.471 968 48
62 + 2 2 + 2 2 = 36 + 4 + 4 = 44

For d = 309 pm:

1 1 h2 + k 2 + l 2
= =
d 2 ( 309 pm ) 2
( )
2
21.54 Å × 102 pm Å −1

h 2 + k 2 + l 2 = 48.593 081 35
42 + 42 + 42 = 48

For d = 304 pm
1 1 h2 + k 2 + l 2
= =
d 2 ( 304 pm ) 2
( )
2
21.54 Å × 102 pm Å −1

h 2 + k 2 + l 2 = 50.204 683 17
52 + 42 + 32 = 50

Note that other combinations of hkl values are possible, as well as different orders of the values given. As higher values of hkl are
used, more possibilities exist, making it more difficult to decide on the correct values. Help in this task is provided by knowledge of
the lines that are forbidden for the particular crystal type, and of the extinction caused by absorption by different atoms in the crystal
layers.

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16-71
Chapter 16: The Solid State Solutions

16.42. A copper selenide mineral (Cu5Se4) called athabascaite is orthorhombic with a = 8.277,
b =11.982, c = 6.441 Å. Strong intensity lines using Cu Kα X rays (λ = 154.18 pm) are observed at 12.95°, 13.76°, and 14.79°.
Determine the d spacings and assign hkl values to these lines.

Solution:

Given: see above

Required: d spacings, assign hkl values

nλ = 2d sin θ
d12.95° = 344 pm; d13.76° = 324 pm; d14.79° = 302 pm
1 h2 k 2 l 2
= + +
d 2 a 2 b2 c 2

With the values given,

1 h2 k2 l2
= + +
( d /pm )
2
822.72 1198.22 644.12
1 h2 k2 l2
= + +
d 2 676 835.29 1435 683.24 414 864.81

With d = 344 pm, agreement is obtained with h = 2, k = 0, and l = 1 :

1
LHS = 2
= 8.450 513 791 × 10−6
344
22 02 12
RHS = + +
822.72 1198.22 644.12
RHS = 5.909 857 33 × 10−6 + 0 + 2.410 423 772 × 10−6
RHS = 8.320 281 102 × 10−6

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Chapter 16: The Solid State Solutions

With d = 324 pm, agreement is obtained with h = 0, k = 0, and l = 2 :

1
LHS = = 9.525 986 892 × 10−6
324 2
22
RHS = 0 + 0 +
644.12
RHS = 9.641 695 086 × 10−6

With d = 302 pm, agreement is obtained with h = 0, k = 4, and l = 0 :

1
LHS = 2
= 10.964 431 38 × 10−6
302
42
RHS = 0 + +0
1198.22
RHS = 11.144 519 59 × 10−6

In the latter case, agreement is obtained with h = 1, k = 0, and l = 2 (RHS = 11.0 × 10-6), but in view of the crystal type (040) is more likely.

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Chapter 16: The Solid State Solutions

1 1 1
*16.43. Zinc blende is the face-centered cubic form of ZnS with Zn at 0, 0, 0; , , 0; 0, , 0;
2 2 2
1 1 1 1 1 1 3 3 3 1 3 3 3 1
, ,0 and with S at , , ; , , ; , , ; , , .
2 2 4 4 4 4 4 4 4 4 4 4 4 4

a. Determine the structure factor from the (111) planes that gives rise to the lowest angle reflection at θ = 14.30° using Cu Kα (λ =
154.18 pm).
b. Calculate the dimension a of the unit cell.

Solution:

Given: see above

Required: structure factor, dimension a of the unit cell

a. From Eq. 16.38,

N
F ( hkl ) = ∑ f j exp ⎣⎡ 2πi ( hx j + ky j + lz j ) ⎦⎤
j =1

⎡ ⎛1 1⎞ ⎛1 1⎞ ⎛ 1 1 ⎞⎤
F ( hkl ) = f Zn ⎢ exp 2πi ( 0 ) + exp 2πi ⎜ + ⎟ + exp 2πi ⎜ + ⎟ + exp 2πi ⎜ + ⎟ ⎥
⎣ ⎝2 2⎠ ⎝2 2⎠ ⎝ 2 2 ⎠⎦
⎡ ⎛1 1 1⎞ ⎛1 3 3⎞ ⎛ 3 1 3⎞
+ ⎢ f S exp 2πi ⎜ + + ⎟ + exp 2πi ⎜ + + ⎟ + exp 2πi ⎜ + + ⎟
⎣ ⎝4 4 4⎠ ⎝4 4 4⎠ ⎝4 4 4⎠
⎛ 3 3 1 ⎞⎤
+ exp 2πi ⎜ + + ⎟ ⎥ F ( hkl )
⎝ 4 4 4 ⎠⎦
⎡ ⎛ 3πi ⎞ ⎛ 7πi ⎞ ⎤
F ( hkl ) = f Zn ⎡⎣1 + 3exp ( 2πi ) ⎤⎦ + f S ⎢exp ⎜ ⎟ + 3exp ⎜ ⎟⎥
⎣ ⎝ 2 ⎠ ⎝ 2 ⎠⎦
F ( hkl ) = 4 f Zn − 4 i f S

16-74
Chapter 16: The Solid State Solutions

λ
( h2 + k 2 + l 2 )
12
a=
2sin θ
154.18 pm × 3
b. a = 2 ( 0.247 )
a = 540.582 173 1 pm
a = 540.6 pm

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16-75
Chapter 16: The Solid State Solutions

16.44. Calculate the Debye temperature of tungsten that is isotropic (an assumption of the Debye model). The cutoff frequency is given by
1 −1
9N ⎞ 3 ⎛ 1 2 ⎞ 3
ν D = ⎛⎜ ⎟ ⎜ 3 + 3⎟
⎝ 4πV ⎠ ⎝ cl ct ⎠
where
cl = 5.2496 × 105 cm s −1
and
ct = 2.9092 × 105 cm s −1
are the longitudinal and trasverse elastic wave velocities, respectively, in tungsten.

Solution:

Given: see above

Required: Debye temperature of tungsten

The number of atoms per unit volume must be calculated

N N av D
=
V A

Where A is the atomic mass, D is the density, and Nav is the Avogadro’s number.

13 −1 3
⎛ 9N ⎞ ⎛ 1 2 ⎞
νD = ⎜ ⎟ ⎜ 3 + 3⎟
⎝ 4πV ⎠ ⎝ cl ct ⎠

( )( )
13
⎡ −3
6.022 × 1023 mol −1 ⎤
⎢ 9 19.271 g cm ⎥
νD =
⎢ 4π
⎣ (
183.85 g mol −1 ) ⎥
⎦
−1 3
⎡ ⎤
1 2
×⎢ + ⎥
(
⎢ 5.2496 × 105 cm s −1 ) ( 2.9092 × 10 ) ⎥
3 3
5
cm s −1
⎣ ⎦
ν D = 8.004 707 251 × 1012 s −1

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Chapter 16: The Solid State Solutions

Then ΘD =
hν D
=
( )(
6.6262 × 10−34 J s 8.004 707 251 × 1012 s −1 )
kB ( )
1.3807 × 10−23 J K −1
ΘD = 384.1586962 K
ΘD = 384 K

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16-77