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CHAPTER 10
Questions
14. Since the boiling point of water is less than the boiling point of C25H52, the nonpolar
hydrocarbon has the stronger intermolecular forces. Because C25H52 is a nonpolar compound,
it only exhibits London dispersion forces. We generally consider these forces to be weak.
However, with compounds that have large molar masses such as C25H52, these London
dispersion forces add up significantly and can overtake the relatively strong hydrogen-
bonding interactions in water. This is the case here.
15. Answer a is correct. Intermolecular forces are the forces between molecules that hold the
substances together in the solid and liquid phases. Hydrogen bonding is a specific type of
intermolecular forces. In this figure, the dotted lines represent the hydrogen bonding
interactions that hold individual H2O molecules together in the solid and liquid phases. The
solid lines represent the O−H covalent bonds.
16. Hydrogen bonding occurs when hydrogen atoms are covalently bonded to highly
electronegative atoms such as oxygen, nitrogen, or fluorine. Because the electronegativity
difference between hydrogen and these highly electronegative atoms is relatively large, the
N−H, O−H, and F−H bonds are very polar covalent bonds. This leads to strong dipole forces.
Also, the small size of the hydrogen atom allows the dipoles to approach each other more
closely than can occur between most polar molecules. Both of these factors make hydrogen
bonding a special type of dipole interaction.
17. Ideal gas molecules are assumed to exhibit no intermolecular forces and are assumed to be
volumeless. Real gases deviate from ideal gas behavior because real gases do exhibit
intermolecular forces and real gas molecules do have a volume. Between two gases, the gas
with the weaker intermolecular forces and the smaller size should behave more ideally at
some conditions. Both N2 and CO have similar size (molar mass), but the nonpolar N2
molecules only exhibit London dispersion forces while the polar CO molecules exhibit
additional dipole force. N2 will have the weaker intermolecular forces and should behave
more ideally than CO.
18. Doping silicon involves the replacing of a small fraction of the silicon atoms with other
atoms. These other atoms (dopants) either add electrons at an energy near that of the
conduction band in silicon (n-type) or creates holes (unfilled energy levels) at energies in the
previously filled molecular orbitals in silicon (p-type). Both n-type and p-type
semiconductors increase conductivity by creating an easier path for electrons to jump from
filled to unfilled energy levels.
19. Atoms have an approximately spherical shape (on average). It is impossible to pack spheres
together without some empty space among the spheres.
365
366 CHAPTER 10 LIQUIDS AND SOLIDS
20. Critical temperature: The temperature above which a liquid cannot exist; i.e., the gas cannot
be liquefied by increased pressure.
Critical pressure: The pressure that must be applied to a substance at its critical temperature
to produce a liquid.
The kinetic energy distribution changes as one raises the temperature (T4 > Tc > T3 > T2 >
T1). At the critical temperature Tc, all molecules have kinetic energies greater than the
intermolecular forces F, and a liquid can't form. Note: The various temperature distributions
shown in the plot are not to scale. The area under each temperature distribution should be
equal to each other (area = total number of molecules).
21. An alloy is a substance that contains a mixture of elements and has metallic properties. In a
substitutional alloy, some of the host metal atoms are replaced by other metal atoms of
similar size, e.g., brass, pewter, plumber’s solder. An interstitial alloy is formed when some
of the interstices (holes) in the closest packed metal structure are occupied by smaller atoms,
e.g., carbon steels.
Dynamic: Two processes, vapor → liquid and liquid → vapor, are both occurring but with
equal rates, so the composition of the vapor is constant.
23. a. As the strength of the intermolecular forces increase, the rate of evaporation decreases.
24. H2O(l) → H2O(g) ∆H° = 44 kJ/mol; the vaporization of water is an endothermic process.
In order to evaporate, water must absorb heat from the surroundings. In this case, part of the
surroundings is our body. So, as water evaporates, our body supplies heat, and as a result,
our body temperature can cool down. From Le Châtelier’s principle, the less water vapor in
the air, the more favorable the evaporation process. Thus the less humid the surroundings,
the more favorably water converts into vapor, and the more heat that is lost by our bodies.
25. C2H5OH(l) → C2H5OH(g) is an endothermic process. Heat is absorbed when liquid ethanol
vaporizes; the internal heat from the body provides this heat, which results in the cooling of
the body.
26. The phase change H2O(g) → H2O(l) releases heat that can cause additional damage. Also,
steam can be at a temperature greater than 100°C.
CHAPTER 10 LIQUIDS AND SOLIDS 367
28. Water boils when the vapor pressure equals the external pressure. Because the external
pressure is significantly lower at high altitudes, a lower temperature is required to equalize
the vapor pressure of water to the external pressure. Thus food cooked in boiling water at
high elevations cooks at a lower temperature, so it takes longer.
29. The strength of intermolecular forces determines relative boiling points. The types of
intermolecular forces for covalent compounds are London dispersion forces, dipole forces,
and hydrogen bonding. Because the three compounds are assumed to have similar molar mass
and shape, the strength of the London dispersion forces will be about equal among the three
compounds. One of the compounds will be nonpolar, so it only has London dispersion forces.
The other two compounds will be polar, so they have additional dipole forces and will boil at
a higher temperature than the nonpolar compound. One of the polar compounds will have an
H covalently bonded to either N, O, or F. This gives rise to the strongest type of covalent
intermolecular forces, hydrogen bonding. The compound that hydrogen bonds will have the
highest boiling point, whereas the polar compound with no hydrogen bonding will boil at a
temperature in the middle of the other compounds.
30. a. Both forms of carbon are network solids. In diamond, each carbon atom is surrounded by
a tetrahedral arrangement of other carbon atoms to form a huge molecule. Each carbon
atom is covalently bonded to four other carbon atoms.
The structure of graphite is based on layers of carbon atoms arranged in fused six-
membered rings. Each carbon atom in a particular layer of graphite is surrounded by
three other carbons in a trigonal planar arrangement. This requires sp2 hybridization.
Each carbon has an unhybridized p atomic orbital; all of these p orbitals in each six-
membered ring overlap with each other to form a delocalized π electron system.
b. Silica is a network solid having an empirical formula of SiO2. The silicon atoms are
singly bonded to four oxygens. Each silicon atom is at the center of a tetrahedral
arrangement of oxygen atoms that are shared with other silicon atoms. The structure of
silica is based on a network of SiO4 tetrahedra with shared oxygen atoms rather than
discrete SiO2 molecules.
Silicates closely resemble silica. The structure is based on interconnected SiO4 tetrahedra.
However, in contrast to silica, where the O/Si ratio is 2 : 1, silicates have O/Si ratios
greater than 2 : 1 and contain silicon-oxygen anions. To form a neutral solid silicate,
metal cations are needed to balance the charge. In other words, silicates are salts
containing metal cations and polyatomic silicon-oxygen anions.
When silica is heated above its melting point and cooled rapidly, an amorphous
(disordered) solid called glass results. Glass more closely resembles a very viscous
solution than it does a crystalline solid. To affect the properties of glass, several different
additives are thrown into the mixture. Some of these additives are Na2CO3, B2O3, and
K2O, with each compound serving a specific purpose relating to the properties of glass.
31. a. Both CO2 and H2O are molecular solids. Both have an ordered array of the individual
molecules, with the molecular units occupying the lattice points. A difference within each
solid lattice is the strength of the intermolecular forces. CO2 is nonpolar and only exhibits
368 CHAPTER 10 LIQUIDS AND SOLIDS
Related to the intermolecular forces are the relative densities of the solid and liquid
phases for these two compounds. CO2(s) is denser than CO2(l), whereas H2O(s) is less
dense than H2O(l). For CO2(s) and for most solids, the molecules pack together as close
as possible; hence solids are usually more dense than the liquid phase. H2O is an
exception to this. Water molecules are particularly well suited for hydrogen bonding
interaction with each other because each molecule has two polar O−H bonds and two
lone pairs on the oxygen. This can lead to the association of four hydrogen atoms with
each oxygen atom: two by covalent bonds and two by dipoles. To keep this arrangement
(which maximizes the hydrogen-bonding interactions), the H2O(s) molecules occupy
positions that create empty space in the lattice. This translates into a smaller density for
H2O(s) as compared to H2O(l).
b. Both NaCl and CsCl are ionic compounds with the anions at the lattice points of the unit
cells and the cations occupying the empty spaces created by anions (called holes). In
NaCl, the Cl− anions occupy the lattice points of a face-centered unit cell, with the Na+
cations occupying the octahedral holes. Octahedral holes are the empty spaces created by
six Cl− ions. CsCl has the Cl− ions at the lattice points of a simple cubic unit cell, with the
Cs+ cations occupying the middle of the cube.
32. Because silicon carbide is made from Group 4A elements, and because it is extremely hard,
one would expect SiC to form a covalent network structure similar to diamond.
33. Chalk is composed of the ionic compound calcium carbonate (CaCO3). The electrostatic
forces in ionic compounds are much stronger than the intermolecular forces in covalent
compounds. Therefore, CaCO3 should have a much higher boiling point than the covalent
compounds found in motor oil and in H2O. Motor oil is composed of nonpolar C−C and C−H
bonds. The intermolecular forces in motor oil are therefore London dispersion forces. We
generally consider these forces to be weak. However, with compounds that have large molar
masses, these London dispersion forces add up significantly and can overtake the relatively
strong hydrogen-bonding interactions in water.
34. The interparticle forces in ionic solids (the ionic bonds) are much stronger than the
interparticle forces in molecular solids (dipole forces, London forces, etc.). The difference in
intermolecular forces is most clearly shown in the huge difference in melting points between
ionic and molecular solids. Table salt and ordinary sugar are both crystalline solids at room
temperature that look very similar to each other. However, sugar can be melted easily in a
saucepan during the making of candy, whereas the full heat of a stove will not melt salt.
When a substance melts, some interparticle forces must be broken. Ionic solids (salt) require
a much larger amount of energy to break the interparticle forces as compared to the relatively
weak forces in molecular solids (sugar).
CHAPTER 10 LIQUIDS AND SOLIDS 369
35. The mathematical equation that relates the vapor pressure of a substance to temperature is:
ΔH vap 1
ln Pvap = − +C
R T
y m x +b
This equation is in the form of the straight-line equation (y = mx + b) If one plots ln Pvap
versus 1/T with temperature in Kelvin, the slope (m) of the straight line is −∆Hvap/R. Because
∆Hvap is always positive, the slope of the straight line will be negative.
36. The typical phase diagram for a substance shows three phases and has a positive-sloping
solid-liquid equilibrium line (water is atypical). A sketch of the phase diagram for I2 would
look like this:
s
l
g
P 90
torr
115o C
T
Statements a and e are true. For statement a, the liquid phase is always more dense than the
gaseous phase (gases are mostly empty space). For statement e, because the triple point is at
90 torr, the liquid phase cannot exist at any pressure less than 90 torr, no matter what the
temperature. For statements b, c, and d, examine the phase diagram to prove to yourself that
they are false.
Exercises
f. dipole, LD g. ionic
39. a. OCS; OCS is polar and has dipole-dipole forces in addition to London dispersion (LD)
forces. All polar molecules have dipole forces. CO2 is nonpolar and only has LD forces.
To predict polarity, draw the Lewis structure and deduce whether the individual bond
dipoles cancel.
b. SeO2; both SeO2 and SO2 are polar compounds, so they both have dipole forces as well
as LD forces. However, SeO2 is a larger molecule, so it would have stronger LD forces.
d. H2CO; H2CO is polar, whereas CH3CH3 is nonpolar. H2CO has dipole forces in addition
to LD forces. CH3CH3 only has LD forces.
e. CH3OH; CH3OH can form relatively strong H-bonding interactions, unlike H2CO.
40. Ar exists as individual atoms that are held together in the condensed phases by London
dispersion forces. The molecule that will have a boiling point closest to Ar will be a nonpolar
substance with about the same molar mass as Ar (39.95 g/mol); this same size nonpolar
substance will have about equivalent strength of London dispersion forces. Of the choices,
only Cl2 (70.90 g/mol) and F2 (38.00 g/mol) are nonpolar. Because F2 has a molar mass
closest to that of Ar, one would expect the boiling point of F2 to be close to that of Ar.
41. a. Ar and HCl have similar molar masses, so the London dispersion forces in each
substance should be about the same. However, HCl is a polar compound while Ar is
nonpolar. HCl has additional dipole forces so it boils at a higher temperature.
c. LiCl is ionic, and HCl is a molecular solid with only dipole forces and LD forces. Ionic
forces are much stronger than the forces for molecular solids.
42. The electrostatic potential diagrams indicate that ethanol and acetone are polar substances,
and that propane is a nonpolar substance. Ethanol, with the O−H covalent bond, will exhibit
relatively strong hydrogen bonding intermolecular forces in addition to London dispersion
forces. The polar acetone will exhibit dipole forces in addition to London dispersion forces,
and the nonpolar propane will only exhibit London dispersion (LD) forces. Therefore,
ethanol (with the H-bonding capacity) should have the highest boiling point, with polar
acetone having the next highest boiling point, and the nonpolar propane, with the weakest
intermolecular forces, will have the lowest boiling point.
CHAPTER 10 LIQUIDS AND SOLIDS 371
43. Boiling points and freezing points are assumed directly related to the strength of the
intermolecular forces, whereas vapor pressure is inversely related to the strength of the
intermolecular forces.
a. HBr; HBr is polar, whereas Kr and Cl2 are nonpolar. HBr has dipole forces unlike Kr and
Cl2. So HBr has the stronger intermolecular forces and the highest boiling point.
b. NaCl; the ionic forces in NaCl are much stronger than the intermolecular forces for
molecular substances, so NaCl has the highest melting point.
c. I2; all are nonpolar, so the largest molecule (I2) will have the strongest LD (London
Dispersion) forces and the lowest vapor pressure.
d. N2; nonpolar and smallest, so it has the weakest intermolecular forces.
e. CH4; smallest, nonpolar molecule, so it has the weakest LD forces.
f. HF; HF can form relatively strong H-bonding interactions, unlike the others.
g. CH3CH2CH2OH; H-bonding, unlike the others, so it has strongest intermolecular forces.
44. a. CBr4; largest of these nonpolar molecules, so it has the strongest LD (London
Dispersion) forces.
b. F2; ionic forces in LiF are much stronger than the molecular forces in F2 and HCl. HCl
has dipole forces, whereas the nonpolar F2 does not exhibit these. So F2 has the weakest
intermolecular forces and the lowest freezing point.
c. CH3CH2OH; can form H-bonding interactions, unlike the other covalent compounds.
d. H2O2; the H−O−O−H structure has twice the number of H-bonding sites as compared to
HF, so H2O2 has the stronger H-bonding interactions and the greatest viscosity.
e. H2CO; H2CO is polar, so it has dipole forces, unlike the other nonpolar covalent
compounds, so H2CO will have the highest enthalpy of vaporization.
f. I2; I2 has only LD forces, whereas CsBr and CaO have much stronger ionic forces. I2 has
the weakest intermolecular forces, so it has smallest ΔHfusion.
Properties of Liquids
45. The attraction of H2O for glass is stronger than the H2O‒H2O attraction. The meniscus is
concave to increase the area of contact between glass and H2O. The Hg‒Hg attraction is
greater than the Hg‒glass attraction. The meniscus is convex to minimize the Hg‒glass
contact.
46. Water is a polar substance, and wax is a nonpolar substance; they are not attracted to each
other. A molecule at the surface of a drop of water is subject to attractions only by water
molecules below it and to each side. The effect of this uneven pull on the surface water
molecules tends to draw them into the body of the water and causes the droplet to assume the
shape that has the minimum surface area, a sphere.
372 CHAPTER 10 LIQUIDS AND SOLIDS
47. The structure of H2O2 is H‒O‒O‒H, which produces greater hydrogen bonding than in water.
Thus the intermolecular forces are stronger in H2O2 than in H2O, resulting in a higher normal
boiling point for H2O2 and a lower vapor pressure.
48. CO2 is a gas at room temperature. As melting point and boiling point increase, the strength of
the intermolecular forces also increases. Therefore, the strength of forces is CO2 < CS2 <
CSe2. From a structural standpoint, this is expected. All three are linear, nonpolar molecules.
Thus only London dispersion forces are present. Because the molecules increase in size from
CO2 < CS2 < CSe2, the strength of the intermolecular forces will increase in the same order.
nλ 1 × 154 pm
49. nλ = 2d sin θ, d = = = 313 pm = 3.13 × 10 −10 m
2 sin θ 2 × sin 14.22°
nλ 2 × 154 pm
50. d= = = 408 pm = 4.08 × 10 −10 m
2 sin θ 2 × sin 22.20°
53. A cubic closest packed structure has a face-centered cubic unit cell. In a face-centered cubic
unit, there are:
1 / 8 atom 1 / 2 atom
8 corners × + 6 faces × = 4 atoms
corner face
The atoms in a face-centered cubic unit cell touch along the face diagonal of the cubic unit
cell. Using the Pythagorean formula, where l = length of the face diagonal and r = radius of
the atom:
l2 + l2 = (4r)2
4r
l 2l2 = 16r2
l=r 8
l
CHAPTER 10 LIQUIDS AND SOLIDS 373
54. There are four Ni atoms in each unit cell. For a unit cell:
1 mol Ni 58.69 g Ni
4 Ni atoms × ×
mass 6.022 × 10 atoms
23 mol Ni
density = = 6.84 g/cm3 =
volume l3
Solving: l = 3.85 × 10 −8 cm = cube edge length
4r (4r)2 = l 2 + l 2 = 2l 2
l
r 8 = l, r = l / 8
r = 3.85 × 10 −8 cm / 8
r = 1.36 × 10 −8 cm = 136 pm
l
55. The unit cell for cubic closest packing is the face-centered unit cell. The volume of a unit cell
is:
V = l 3 = (492 × 10 −10 cm)3 = 1.19 × 10 −22 cm3
There are four Pb atoms in the unit cell, as is the case for all face-centered cubic unit cells.
From Exercise 53, the relationship between the cube edge length l and the radius r of an atom
in a face-centered unit cell is l = r 8 .
l 492 pm
r= = = 174 pm = 1.74 × 10 −10 m
8 8
374 CHAPTER 10 LIQUIDS AND SOLIDS
The volume of the unit cell is l3 where l = cube edge length. For a unit cell of polonium:
1 mol Po 209 g Po
1 Po atom × ×
mass 6.022 × 10 23 atoms mol Po
density = = 9.2 g/cm3 = 3
volume l
In a simple cubic unit cell, the atoms touch along the cube edge l:
2(radius) = 2r = l
2r l 2r = 3.35 × 10 −8 cm
r = 1.7 × 10 −8 cm
57. A face-centered cubic unit cell contains four atoms. For a unit cell:
7.18 × 10 −22 g X
Molar mass = = 108 g/mol; the metal is silver (Ag).
6.642 × 10 − 24 mol X
58. For a face-centered unit cell, the radius r of an atom is related to the length of a cube edge l
by the equation l = r 8 (see Exercise 53).
The volume of a unit cell is l3, so the mass of the unknown metal (X) in a unit cell is:
21.45 g X
volume × density = (3.92 × 10−8 cm)3 × = 1.29 × 10−21 g X
cm 3
Because each face-centered unit cell contains four atoms of X:
1 mol X
mol X in unit cell = 4 atoms X × = 6.642 × 10−24 mol X
6.022 × 10 23 atoms X
Therefore, each unit cell contains 1.29 × 10−21 g X, which is equal to 6.642 × 10−24 mol X.
CHAPTER 10 LIQUIDS AND SOLIDS 375
1 / 8 Ti
59. For a body-centered unit cell, 8 corners × + Ti at body center = 2 Ti atoms.
corner
All body-centered unit cells have two atoms per unit cell. For a unit cell where l = cube edge
length:
1 mol Ti 47.88 g Ti
2 atoms Ti × ×
6.022 × 10 atoms
23 mol Ti
density = 4.50 g/cm3 = 3
l
Assume Ti atoms just touch along the body diagonal of the cube, so body diagonal =
4 × radius of atoms = 4r.
4r
l 3.28 x 10 -8 cm
l √2
(3.28 x 10 -8cm) √ 2
For a body-centered unit cell (bcc), the radius of the atom is related to the cube edge length
by: 4r = l 3 or l = 4r/ 3 .
16r2 = l2 + 2l2
4r l = 4r/ 3 = 2.309 r
l
In a body-centered cubic unit cell, there are two atoms per unit cell. For a unit cell:
1 mol Ba 137.3 g Ba
2 atoms Ba × ×
mass 6.022 × 10 atoms
23
mol Ba 3.38 g
density = = −8
=
volume (5.13 × 10 cm) 3
cm 3
61. If gold has a face-centered cubic structure, then there are four atoms per unit cell, and from
Exercise 53:
2l2 = 16r2
4r
l l = r 8 = (144 pm) 8 = 407 pm
1 mol Au 197.0 g Au
4 atoms Au × ×
6.022 × 10 atoms
23
mol Au
Density = −8
= 19.4 g/cm3
(4.07 × 10 cm) 3
If gold has a body-centered cubic structure, then there are two atoms per unit cell, and from
Exercise 59:
16r2 = l2 + 2l2
4r
l l = 4r/ 3 = 333 pm = 333 × 10−12 m
The measured density of gold is consistent with a face-centered cubic unit cell.
If body-centered cubic:
4r 4 × 137 pm
l= = = 316 pm = 3.16 × 10 −8 cm
3 3
1 mol 183.9 g W
2 atoms W × ×
6.022 × 10 atoms
23 mol
density = −8
= 19.4 g/cm3
(3.16 × 10 cm) 3
63. In a face-centered unit cell (a cubic closest packed structure), the atoms touch along the face
diagonal:
(4r)2 = l2 + l2
4r
l l=r 8
Vcube = l 3 = (r 8 )3 = (22.63)r3
There are four atoms in a face-centered cubic cell (see Exercise 53). Each atom has a volume
of (4/3)πr3 = volume of a sphere.
4
Vatoms = 4 × πr3 = (16.76)r3
3
Vatoms (16.76)r 3
So = = 0.7406, or 74.06% of the volume of each unit cell is occupied by
Vcube (22.63)r 3
atoms.
In a simple cubic unit cell, the atoms touch along the cube edge l:
2(radius) = 2r = l
2r l
Vcube = l3 = (2r)3 = 8r3
There is one atom per simple cubic cell (8 corner atoms × 1/8 atom per corner = 1 atom/unit
cell). Each atom has an assumed volume of (4/3)πr3 = volume of a sphere.
378 CHAPTER 10 LIQUIDS AND SOLIDS
4
Vatom = πr3 = (4.189)r3
3
Vatom (4.189)r 3
So = = 0.5236, or 52.36% of the volume of each unit cell is occupied by
Vcube 8r 3
atoms.
A cubic closest packed structure (face-centered cubic unit cell) packs the atoms much more
efficiently than a simple cubic structure.
64. From Exercise 59, a body-centered unit cell contains two net atoms, and the length of a cube
edge l is related to the radius of the atom r by the equation l = 4r/ 3 .
Vatoms (8.378)r 3
So = = 0.6800 = 68.00% occupied
Vcube (12.32)r 3
To determine the radius of the Fe atoms, we need to determine the cube edge length l.
1 mol Fe 55.85 g Fe 1 cm 3
Volume of unit cell = 2 Fe atoms × ×
× 23 mol Fe × 7.86 g
6.022 10 atoms
= 2.36 × 10 −23 cm3
65. Doping silicon with phosphorus produces an n-type semiconductor. The phosphorus adds
electrons at energies near the conduction band of silicon. Electrons do not need as much
energy to move from filled to unfilled energy levels, so conduction increases. Doping silicon
with gallium produces a p-type semiconductor. Because gallium has fewer valence electrons
than silicon, holes (unfilled energy levels) at energies in the previously filled molecular
orbitals are created, which induces greater electron movement (greater conductivity).
66. A rectifier is a device that produces a current that flows in one direction from an alternating
current that flows in both directions. In a p-n junction, a p-type and an n-type semiconductor
are connected. The natural flow of electrons in a p-n junction is for the excess electrons in the
n-type semiconductor to move to the empty energy levels (holes) of the p-type
semiconductor. Only when an external electric potential is connected so that electrons flow in
this natural direction will the current flow easily (forward bias). If the external electric
potential is connected in reverse of the natural flow of electrons, no current flows through the
system (reverse bias). A p-n junction only transmits a current under forward bias, thus
converting the alternating current to direct current.
CHAPTER 10 LIQUIDS AND SOLIDS 379
67. In has fewer valence electrons than Se. Thus Se doped with In would be a p-type
semiconductor.
68. To make a p-type semiconductor, we need to dope the material with atoms that have fewer
valence electrons. The average number of valence electrons is four when 50-50 mixtures of
Group 3A and Group 5A elements are considered. We could dope with more of the Group 3A
element or with atoms of Zn or Cd. Cadmium is the most common impurity used to produce
p-type GaAs semiconductors. To make an n-type GaAs semiconductor, dope with an excess
Group 5A element or dope with a Group 6A element such as sulfur.
69. Egap = 2.5 eV × 1.6 × 10 −19 J/eV = 4.0 × 10 −19 J; we want Egap = Elight = hc/λ, so:
1 / 8 Cl − 1 / 2 Cl −
71. Sodium chloride structure: 8 corners × + 6 faces × = 4 Cl− ions
corner face
1 / 4 Na +
12 edges × + 1 Na+ at body center = 4 Na+ ions; NaCl is the formula.
edge
1 / 8 Cl −
Cesium chloride structure: 1 Cs+ ion at body center; 8 corners × = 1 Cl− ion
corner
CsCl is the formula.
Zinc sulfide structure: There are four Zn2+ ions inside the cube.
1 / 8 S2− 1 / 2 S2−
8 corners × + 6 faces × = 4 S2− ions; ZnS is the formula.
corner face
1 / 8 Ti 4+
Titanium oxide structure: 8 corners × + 1 Ti4+ at body center = 2 Ti4+ ions
corner
1/2 O 2−
4 faces × + 2 O2− inside cube = 4 O2− ions; TiO2 is the formula.
face
1 / 8 Ni 1 / 4 Ni
72. Both As ions are inside the unit cell. 8 corners × + 4 edges × = 2 Ni ions
corner edge
The unit cell contains 2 ions of Ni and 2 ions of As, which gives a formula of NiAs. We
would expect As to form 3− charged ions when in ionic compounds, so Ni exists as 3+
charged ions in this compound.
380 CHAPTER 10 LIQUIDS AND SOLIDS
73. There is one octahedral hole per closest packed anion in a closest packed structure. If one-
half of the octahedral holes are filled, then there is a 2 : 1 ratio of fluoride ions to cobalt ions
in the crystal. The formula is CoF2, which is composed of Co2+ and F− ions.
74. There are two tetrahedral holes per closest packed anion. Let f = fraction of tetrahedral holes
filled by the cations.
2 2f
Na2O: Cation-to-anion ratio = = , f = 1; all the tetrahedral holes are filled by Na+
1 1
cations.
1 2f 1
CdS: Cation-to-anion ratio = = , f = ; one-half the tetrahedral holes are filled by
1 1 2
Cd2+ cations.
1 2f 1
ZrI4: Cation-to-anion ratio = = , f = ; one-eighth the tetrahedral holes are filled
4 1 8
by Zr4+ cations.
75. In a cubic closest packed array of anions, there are twice the number of tetrahedral holes as
anions present, and an equal number of octahedral holes as anions present. A cubic closest
packed array of sulfide ions will have four S2− ions, eight tetrahedral holes, and four
octahedral holes. In this structure we have 1/8(8) = 1 Zn2+ ion and 1/2(4) = 2 Al3+ ions
present, along with the 4 S2− ions. The formula is ZnAl2S4.
Assuming the anions A are the larger circles, there are four anions completely in this
repeating square. The corner cations (smaller circles) are shared by four different repeating
squares. Therefore, there is one cation in the middle of the square plus 1/4 (4) = 1 net cation
from the corners. Each repeating square has two cations and four anions. The empirical
formula is MA2.
77. 8 F− ions at corners × 1/8 F−/corner = 1 F− ion per unit cell; Because there is one cubic hole
per cubic unit cell, there is a 2 : 1 ratio of F− ions to metal ions in the crystal if only half of
the body centers are filled with the metal ions. The formula is MF2, where M2+ is the metal
ion.
78. Corners are shared by 8 cubic unit cells and edges are shared by 4 unit cells. Re ions at 8
corners: 8(1/8) = 1 Re ion; O ions at 12 edges: 12(1/4) = 3 O ions; the formula is ReO3.
Assuming the oxygen ion is a −2 charge, then the charge on Re is +3.
CHAPTER 10 LIQUIDS AND SOLIDS 381
79. From Figure 10.36, MgO has the NaCl structure containing 4 Mg2+ ions and 4 O2− ions per
face-centered unit cell.
1 mol MgO 40.31 g MgO
4 MgO formula units × × = 2.678 × 10 −22 g MgO
6.022 × 10 23
atoms 1 mol MgO
1 cm 3
Volume of unit cell = 2.678 × 10 −22 g MgO × = 7.48 × 10 −23 cm3
3.58 g
Volume of unit cell = l3, l = cube edge length; l = (7.48 × 10 −23 cm3)1/3 = 4.21 × 10 −8 cm
For a face-centered unit cell, the O2− ions touch along the face diagonal:
2 × 4.21 × 10 −8 cm
2 l = 4 rO 2− , rO 2− = = 1.49 × 10 −8 cm
4
The cube edge length goes through two radii of the O2− anions and the diameter of the Mg2+
cation, so:
80.
The unit cell contains four K+ and four Cl− ions. For a unit cell:
1 mol KCl 74.55 g KCl
4 KCl formula units × ×
6.022 × 10 formula units
23 mol KCl
density =
(6.28 × 10 −8 cm) 3
= 2.00 g/cm3
81. CsCl is a simple cubic array of Cl− ions with Cs+ in the middle of each unit cell. There is one
Cs+ and one Cl− ion in each unit cell. Cs+ and Cl− ions touch along the body diagonal.
1 cm 3
volume = l 3 = 2.796 × 10 −22 g CsCl × = 7.04 × 10 −23 cm3
3.97 g CsCl
The distance between ion centers = rCs + + rCl − = 715 pm/2 = 358 pm
From ionic radius: rCs + = 169 pm and rCl − = 181 pm; rCs + + rCl − = 169 + 181 = 350. pm
The distance calculated from the density is 8 pm (2.3%) greater than that calculated from
tables of ionic radii.
82. a. The NaCl unit cell has a face-centered cubic arrangement of the anions with cations in
the octahedral holes. There are four NaCl formula units per unit cell, and since there is a
1 : 1 ratio of cations to anions in MnO, then there would be four MnO formula units per
unit cell, assuming an NaCl-type structure. The CsCl unit cell has a simple cubic
structure of anions with the cations in the cubic holes. There is one CsCl formula unit per
unit cell, so there would be one MnO formula unit per unit cell if a CsCl structure is
observed.
Formula units of MnO 5.28 g MnO 1 mol MnO
= (4.47 × 10 −8 cm) 3 × 3
×
Unit cell cm 70.94 g MnO
6.022 × 10 23 formula units MnO
× = 4.00 formula units MnO
mol MnO 4
From the calculation, MnO crystallizes in the NaCl type structure.
b. From the NaCl structure and assuming the ions touch each other, then l = cube edge
length = 2rMn 2+ + 2rO 2− .
85. a. The unit cell consists of Ni at the cube corners and Ti at the body center or Ti at the cube
corners and Ni at the body center.
b. 8 × 1/8 = 1 atom from corners + 1 atom at body center; empirical formula = NiTi
1/8 Al 1/2 Ni
86. Al: 8 corners × = 1 Al; Ni: 6 face centers × = 3 Ni
corner face center
The composition of the specific phase of the superalloy is AlNi3.
In the extended lattice of both structures, each Ti atom is surrounded by six O atoms.
88. With a cubic closest packed array of oxygen ions, we have 4 O2− ions per unit cell. We need
to balance the total −8 charge of the anions with a +8 charge from the Al3+ and Mg2+ cations.
The only combination of ions that gives a +8 charge is 2 Al3+ ions and 1 Mg2+ ion. The
formula is Al2MgO4.
There are an equal number of octahedral holes as anions (4) in a cubic closest packed array
and twice the number of tetrahedral holes as anions in a cubic closest packed array. For the
stoichiometry to work out, we need 2 Al3+ and 1 Mg2+ per unit cell. Hence one-half of the
octahedral holes are filled with Al3+ ions, and one-eighth of the tetrahedral holes are filled
with Mg2+ ions.
b. The structure of this superconductor material follows the second perovskite structure
described in Exercise 87. The YBa2Cu3O9 structure is three of these cubic perovskite unit
cells stacked on top of each other. The oxygen atoms are in the same places, Cu takes the
place of Ti, two of the calcium atoms are replaced by two barium atoms, and one Ca is
replaced by Y.
384 CHAPTER 10 LIQUIDS AND SOLIDS
c. Y, Ba, and Cu are the same. Some oxygen atoms are missing.
1/ 4 O 1/ 2 O
12 edges × = 3 O, 8 faces × = 4 O, total = 7 O atoms
edge face
Superconductor formula is YBa2Cu3O7.
1/ 2 O 1/ 4 O
O: 6 faces × + 8 edges × = 5 O; Formula = TlBa2CuO5.
face edge
Structure (b):
1/ 2 O 1/ 4 O
O: 10 faces × + 8 edges × = 7 O; Formula = TlBa2CaCu2O7.
face edge
Structure (c):
Tl and Ba are the same, and two Ca are located inside the unit cell.
1 / 4 Cu 1/ 2 O 1/ 4 O
Cu: 12 edges × = 3 Cu; O: 14 faces × + 8 edges × =9O
edge face edge
Formula = TlBa2Ca2Cu3O9.
b. Structure (a) has one planar sheet of Cu and O atoms, and the number increases by one
for each of the remaining structures. The order of superconductivity temperature from
lowest to highest temperature is (a) < (b) < (c) < (d).
Jos minäkin saan jotain sanoa, lausui nyt Ryppylän isäntä, joka
tähän saakka oli ääneti kuunnellut toisten keskustelua, niin minä
pelkään, että Hietamäen haltia on ollut vääränä hirtenä ja
pahentanut meidän asiamme.
Sitä ei voi kieltää, vaikka meillä oli hyvät kortit, olemme pelin
menettäneet. Ja sentähden on meillä tässä tuumimista, jos
tappiotamme vielä voidaan auttaa.
Juur nin, me ottamm’ yks pien’ maksu iskultakin, kun nimens tai
buumerkin kirjoitta, selitti lähemmin Järvelän herra.
*****
Kyllä mar se niin onkin, kuin matami sanoo, tuumasi siihen rouva.
Mutta eikös tuolla Hietamäen isännällä sitten ole mitään syytä siihen,
niinkuin valttari kuului sanovan?
Niin minäkin sen uskon, myönsi rouva. Nuo miehet luulevat kaikki
asiat tietävänsä, mutta meidän huomaavaisuuttamme he sentään
saavat kiittää, että asiat tulevat selville.
Mikä heidän toimensa oli, sen sai kuulla eräältä sellaiselta kulkija-
ritarilta, hänen lauluissaan: »Minä olen huutavan ääni korvessa, joka
valmistan herralleni tietä, kokoon nimiä ja puumerkkiä».