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Chapter 13
The Chemistry of Solids
INSTRUCTORS NOTES
New to the 7th edition was a chapter devoted to the chemistry of solids. The chapter combined content previously
found in a chapter on liquids and solids with the content on bonding in ionic solids. The number of homework
problems with this chapter has been significantly increased in the 8th edition.
We emphasize with our students that although many substances are solids, there are many different ways in which
the atoms and or ions can be arranged (Table 13.1). The steps involved in calculating atom radius or density of a
solid from crystal structure data can be confusing to students. It is helpful to work many examples in lecture.
The ionic and molecular solids pictured in this chapter can be found on the ChemistryNow website in the Molecular
Modeling Database. The ionic solids pictured have been manipulated (by changing the ionic radii) in order to make
the ions appear with the correct radius.
When possible, bring models of ionic solids and/or cubic unit cells to class (available from Klinger Educational
Products, http://www.klingereducational.com) or use the Solid State Model Kit available from the Institute for
Chemical Education (http://ice.chem.wisc.edu) to build smaller models of crystalline solids.
SUGGESTED DEMONSTRATIONS
1.
Solids
Herman, Z.S. Ionic Crystals: A Simple and Safe Lecture Demonstration of the Preparation of NaI
from Its Elements, Journal of Chemical Education 2000, 77, 619.
Cady, S. G. Use of Pom Pons to Illustrate Cubic Crystal Structures, Journal of Chemical Education
1997, 74, 794.
The close packing of spheres (such as the photos on page 595) is easy to do on an overhead projector.
We have also used oranges and grapefruits, as well as Styrofoam balls.
247
Chapter 13
13.2
The area inside the box is a unit cell. Each unit cell contains 2 A squares and 2 B squares,
so the simplest formula is AB.
13.3
8 corner Ca 1/8 = 1 Ca
6 edge O 1/2 = 3 O
1 internal Ti = 1 Ti
8 corner Ti 1/8
= 1 Ti
4 face O 1/2
=2O
1 internal Ti
= 1 Ti
2 internal O
=2O
= 2 Ti total
= 4 O total
=1O
4 internal Cu
= 2 O total
= 4 Cu
= 4 Cu total
There is a ratio of two copper ions to one oxide ion for a formula of Cu2O.
(b) The oxidation number of copper is +1.
13.6
8 internal F = 8 F
248
Chapter 13
13.8
Assume that platinum has a face-centered cubic unit cell. Calculate the density of the unit cell based on
this assumption and compare it with the actual density of platinum:
195.084 g
1 mol Pt
4 atom radius
edge length =
4 139 pm
2
unit cell volume = (edge length) = (3.93 108 cm)3 = 6.07 1023 cm3
1.29578 1021 g
= 21.35 g/cm3
23
3
6.07 10 cm
The calculated density closely matches the actual density (21.45 g/cm3) so the platinum unit cell is most
likely face-centered cubic.
13.9
Use the cell density or the ion radii to calculate the edge length.
Using cell density,
edge length =
4 KI
1 mol KI
166.00 g
1 cm3
Using ionic radii, edge length = 2(K+ radius) + 2(I radius) = 2(133 pm) + 2(220 pm) = 706 pm
Note that one cannot in this problem assume the I- touch along the cell diagonal and use I- radius to find the
edge length. Edge length = 4(I- radius) = 4(220 pm)/21/2 = 622 pm. The size of the ions are such that the Iions cannot touch along the diagonal.
13.10
(8 corner Cl 1/8) = 1 Cl
23
edge length
3
cm = (edge length)
face diagonal
2 edge length
2
3 (edge length)
cube diagonal =
3 412 pm
edge length
face diagonal
cube diagonal
249
Chapter 13
The 1000 2s orbitals will combine to form 1000 molecular orbitals. In the lowest energy state, 500 of these
will be populated by pairs of electrons, and 500 will be empty.
13.12
4 orbitals/Mg atom 6.022 x 1023 Mg atoms/mol = 24.09 x 1023 orbitals/mol = 2.409 x 1024 orbitals/mol.
Each Mg atom has a total of two electrons occupying its four valence orbitals. The molecular orbitals will
consequently similarly be full.
13.13
In metals, thermal energy causes some electrons to occupy higher energy orbitals in the band of molecular
orbitals. For each electron promoted, two singly occupied levels result: a negative electron above the
Fermi level and a positive hole below the Fermi level. Electrical conductivity results because in the
presence of an electric field, these negative electrons will move toward the positive side of the field, and
the positive holes will move toward the negative side.
13.14
A metal can absorb energy of nearly any wavelength, causing an electron to move to a higher energy state.
The now-excited system can immediately emit a photon of the same energy as the electron returns to the
original energy level. This rapid and efficient absorption and reemission of light makes metals appear
shiny.
13.15
In carbon, the band gap is too large for electrons to up in energy from the valence band to the conductance
band, whereas in silicon the band gap is small enough to permit this.
13.16
C > Si > Ge > Sn. The band gap gets smaller with increased metallic character.
13.17
An intrinsic semiconductor is one that naturally can have electrons move across the band gap, whereas an
extrinsic semiconductor requires the addition of dopants in order for it to conduct.
13.18
The aluminum has one less valence electron than the silicon. The Si-Al bonds form a discrete but empty
energy band at a level higher in energy than the valence band but lower than the conduction band. The gap
between the valence and acceptor bands is same, so electrons can be promoted with concurrent generation
of positive holes in the valence band. This is a p-type semiconductor.
13.19
13.20
Lattice energy depends directly on ion charges and inversely on the distance between ions. The sizes of the
Cl, Br, and I ions fall in a relatively narrow range (181, 196, and 220 pm, respectively), and the ion sizes
change by only 1524 pm from one ion to the next. Therefore, their lattice energies are expected to
decrease in a narrow range. The F ion (133 pm), however, is only 74% as large as the Cl ion, so the
lattice energy of NaF is much more negative.
13.21
As the ion-ion distance decreases, the force of attraction between the ions increases. This should make the
lattice more stable, and more energy should be required to melt the compound.
250
Chapter 13
13.22
(a) NaCl
(b) MgO
13.23
Li(s) Li(g)
(c) MgS
fH = +159.37 kJ/mol
Li(g) Li (g) + e
/2 F2(g) F(g)
F(g) + e F (g)
+
IE = +520. kJ/mol
fH = +78.99 kJ/mol
EA = 328.0 kJ/mol
latticeU = 1037 kJ/mol
fH = 607 kJ/mol
13.24
latticeU = 435.4 kJ/mol 80.9 kJ/mol 403 kJ/mol 131.3 kJ/mol (349.0 kJ/mol) = 701.6 kJ/mol
13.25
13.26
13.27
13.28
Ionic: hard, brittle, high melting point, poor electric conductivity as solid while good as liquid, often water
soluble
Metallic: malleable, ductile, good electric conductivity in solid and liquid, good heat conductivity, wide
range of hardness and melting points
Molecular: low to moderate melting points and boiling points, soft, poor electric conductivity in solid and
liquid
Network: wide range of hardness and melting points, poor electric conductivity (with some exceptions)
Amorphous: noncrystalline, wide temperature range for melting, poor electric conductivity (with some
exceptions)
251
Chapter 13
13.29
13.30
13.31
15.5 g
1 mol C6 H6 9.95 kJ
= 1.97 kJ heat evolved (1.97 kJ)
78.11 g
1 mol
The total heat required is the sum of the heat required to (1) heat the solid from 38 C to its melting point
and (2) liquefy the solid at its melting point.
qsolid = (85.21 g Ag)(0.235 J/gK)(1235 K 311 K) = 1.85 104 J
qmelting = (85.21 g Ag)(1 mol Ag/107.9 g)(11.3 kJ/mol)(103 J/kJ) = 8.92 103 J
(a) The positive slope of the solid/liquid equilibrium line indicates that liquid CO2 is less dense than
solid CO2.
(b) gas phase
(c) no
13.34
252
Chapter 13
13.35
The total heat required is the sum of the heat required to (1) heat the liquid from 41.0 C to its boiling
point, (2) vaporize the gas, and (3) heat the vapor to 0.0 C.
qliquid = (10 kg)(103 g/kg)(4.7 J/g.K)(239.9 K 232 K)(1 kJ/103 J) = 4 x 102 kJ
qevaporation = (10 kg)(103 g/kg)(1 mol NH3/17.0 g)(23.33 kJ/mol) = 1.4 x 104 kJ
qgas = (10 kg)(103 g/kg)(2.2 J/g.K)(273.2 K 239.9 K)(1 kJ/103 J) = 7.3 x 102 kJ
qtotal = 4 x 102 kJ + 1.4 x 104 kJ + 7.3 x 102 kJ = 1.5 x 104 kJ
13.36
800
normal
melting
point
700
13.37
600
normal
boiling
point
500
400
300
triple point
200
100
0
50
60
70
80
90
100
Temperature (K)
The estimated vapor pressure at 77 K is approximately 200 mmHg. The solid-liquid equilibrium line has a
positive slope, so the density of liquid O2 is less than that of solid O2.
13.38
3 (edge length)
cube diagonal =
3 316.5 pm
edge length
face diagonal
cube diagonal
548 pm
= 137 pm
4
253
Chapter 13
13.39
2 edge length
face diagonal =
2 409 pm
edge length
face diagonal
578 pm
= 145 pm
4
8 corner Ca /8
= 1 Ca
8 edge C 1/4
=2C
1 internal Ca
= 1 Ca
2 internal C
=2C
= 2 Ca total
= 4 C total
There is a ratio of two calcium ions to four carbon ions for a formula of CaC2.
13.41
23
3
4 Ir atoms 192.22 g 1 cm
1 mol Ir
= 5.659 10 cm
unit cell 1 mol Ir 22.56 g 6.0221 1023 atoms
V = 5.659 10
cm = (edge length)
23
cm = 3.839 10 cm
Assume that vanadium metal has a facecentered cubic unit cell. Calculate the density of the unit cell
based on this assumption and compare it with the actual density of vanadium:
50.94 g
1 mol V
23
= 8.459 10 g
1 mol V 6.022 1023 atoms
23
8.459 10 g 4 V atoms
22
= 3.384 10 g/unit c
mass of unit cell =
1 unit cell
1 V atom
face diagonal = 4 atom radius = 2 edge length
4 atom radius 4 132 pm
=
= 373 pm = 3.73 108 cm
edge length =
2
2
unit cell volume = (edge length)3 = (3.73 108 cm)3 = 5.19 1023 cm3
3.384 1022 g
unit cell density =
= 6.52 g/cm3
5.19 1023 cm3
mass of one V atom =
The calculated density does not agree with the actual density (6.11 g/cm3). If the unit cell is assumed to be
bodycentered cubic, the calculated density is 5.97 g/cm3; simple cubic results in a calculated density of
4.60 g/cm3. The vanadium unit cell is most likely bodycentered cubic.
254
Chapter 13
13.43
Calculate the mass of one CaF2 ion pair and compare this to the mass of one mole of CaF2:
8
(5.46295 10 cm)
22
3.1805 g 1 unit cell
= 1.2963 10 g/CaF2
3
4 CaF2
1 cm
23
78.077 g/1 mol CaF2
= 6.0230 10 CaF2 /mol
22
1.2963 10 g/CaF2
13.44
Calculate the mass of one iron atom and compare this to the mass of one mole of iron.
3
1m
102 cm
23
3
V = 286.65 pm 12
= 2.3554 10 cm
10 pm 1 m
Diagram A:
area of one circle
area covered by circles
r2
=
=
= 0.785 = 78.5%
2
total area
(2 rcircle )
4 r2
Diagram B:
1
1
base height = (2 r)( 3 r)
2
2
1
1
area of circle = r 2
area covered by circles =
2
2
1
2
r
area covered
2
=
= 0.907 = 90.7%
1
area of triangle
(2 r)( 3 r)
2
area of triangle =
13.46
4 3
1 sphere r
volume occupied by spheres
3
100% =
100% = 52%
3
to
ta
l
v
o
lu
me
of
unit
cell
(2
r)
% occupied space =
% empty space = 100 % occupied space = 48%
13.47
8 Si atoms 28.086 g
1 mol Ir
3.731 1022 g
= 2.329 g/cm3
1.602 1022 cm3
Use geometric relationship between Si at cell corner, Si in tetrahedral hole, and Si in center of cell face
along with the cell face diagonal to calculate Si radius.
face diagonal =
2 edge length =
2 543.1 pm = 768.1 pm
255
Chapter 13
sin(109.5/2) =
/ 2 (384.1 pm)
Si-Si distance
109.5/2
Siin center
of cell face Si
Si in
tetrahedral hole
Si
Si
1
/2 face diagonal
Si at cell
corner
Use geometric relationship between C atoms at cell corners and in center of cell faces and Si atoms in
tetrahedral holes along with the SiC distance to calculate face diagonal.
1
sin(109.5/2) =
1
/ 4 (face diagonal)
/ 4 (face diagonal)
=
Si-C distance
188.8 pm
face diagonal
2
8
616.7 pm
= 436.1 pm
23
cm
109.5/2
Cin center
of cell face
Si
Si in
tetrahedral hole
C
C
1
/2 face diagonal
C at cell
corner
4 SiC
40.096 g
1 mol
= 2.663 1022 g
unit cell 1 mol SiC 6.0221 1023 atoms
density =
13.49
2.663 1022 g
= 3.211 g/cm3
8.293 1023 cm3
(a) Mg2+ occupies 1/8 of 8 possible tetrahedral holes and Al3+ occupies 1/2 of 4 available octahedral holes.
(b) Fe2+ occupies 1/8 of 8 possible tetrahedral holes and Cr3+ occupies 1/2 of 4 available octahedral holes.
13.50
EA(2) = 418.0 kJ/mol 2(107.3 kJ/mol) 2(495.9 kJ/mol) 249.1 kJ/mol (141.0 kJ/mol) + 2481 kJ/mol
EA(2) = 748.5 kJ/mol
13.51
140 x 103 J/mol 1 mol/6.022 x 1023 photons 1/6.6260693 x 10-34 J s = 3.5 x 1014 s-1
= c
13.52
Increasing T increases energy available for electrons to jump the band gap.
13.53
Germanium has more metallic character and, thus, a smaller band gap and higher conductivity.
13.54
(a) n-type
(b) n-type
(c) p-type
(d) n-type
13.55
13.56
Molecular solids are made of molecules held together by intermolecular forces. Networks are made of
atoms held together by covalent bonds. Amorphous solids are networks of atoms held together by covalent
bonds but lacking long range order.
256
Chapter 13
13.57
Lead sulfide has the same structure as sodium chloride, not the same structure as ZnS. There are 4 Pb2+
ions and 4 S2 ions per unit cell, a 1:1 ratio that matches the compound formula. Both the unit cell and the
crystals have a cubic shape.
13.58
(a) Volume =
1 CaTiO3
135.9 g
1 mol
1 cm3
edge length =
(b) Assume that the O2 and Ti4+ ions touch along center of cell.
edge length = 2(O2 radius) + 2(Ti4+ radius)
380. pm = 2(140 pm) + 2(Ti4+ radius)
Ti4+ radius = 50. pm
The calculated radius is smaller than the literature value.
13.59
= 2.775 1022 g
unit cell 1 mol BP 6.0221 1023
density =
2.775 1022 g
= 2.55 g/cm3
1.09 1022 cm3
(d) Use geometric relationship shown in 13.35 and 13.36 to calculate BP distance.
109.5/2
B in center
of cell face
P in
tetrahedral hole
B
1
/2 face diagonal
face diagonal =
B at cell
corner
2 edge length =
2 478 pm = 676 pm
sin(109.5/2) =
/ 2 (338 pm)
BP distance
BP distance = 207 pm
13.60
In a face-centered cubic lattice of anions (X) there are a total of four anions per unit cell.
Type of holes occupied by cation (M)
Formula of salt
M2X
MX
MX
257
Chapter 13
13.61
Assuming the spheres are packed in an identical way, the water levels will be identical. A facecentered
cubic lattice, for example, uses 74% of the available volume, regardless of sphere size.
13.62
CoAl2O4:
Co2+:
[Ar]
3d
Al3+:
[He]
2p
[Kr]
4d
5s
Co3+:
diamagnetic
SnCo2O4:
Sn2+:
4s
2s
[Ar]
diamagnetic
5p
3d
1.
-tin has four atoms in the unit cell. -tin has eight atoms in the unit cell.
2.
3.
8 stoms Sn(1 mol/6.022 x 1023 atoms)(118.7 g/ 1 mol) (1 cm3/5.769 g) (1 x 1010 pm/1 cm)3 = 2.734 x 108 pm3
Length = (2.734 x 108 pm3)1/3 = 649.0 pm
4.
The unit cell of -tin (tetragonal lattice) contains 4 atoms. The volume of space occupied by the atom is:
VSn atoms =
4 3
r 4 = 4.70 x 107 pm3
3
4 3
r 8 = 9.39 x 107 pm3
3
258