CHAPTER 10

LIQUIDS AND SOLIDS

Questions
12.

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 CC and CH
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.

13.

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 OH covalent bonds.

14.

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
NH, OH, and FH 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.

15.

Atoms have an approximately spherical shape (on average). It is impossible to pack spheres
together without some empty space among the spheres.

16.

Critical temperature: The temperature above which a liquid cannot exist; i.e., the gas cannot
be liquified by increased pressure.
Critical pressure: The pressure that must be applied to a substance at its critical temperature
to produce a liquid.

341

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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).
17.

Evaporation takes place when some molecules at the surface of a liquid have enough energy
to break the intermolecular forces holding them in the liquid phase. When a liquid
evaporates, the molecules that escape have high kinetic energies. The average kinetic energy
of the remaining molecules is lower; thus the temperature of the liquid is lower.

18.

A crystalline solid will have the simpler diffraction pattern because a regular, repeating
arrangement is necessary to produce planes of atoms that will diffract the X rays in regular
patterns. An amorphous solid does not have a regular repeating arrangement and will
produce a complicated diffraction pattern.

19.

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, plumbers 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.

20.

Equilibrium: There is no change in composition; the vapor pressure is constant.

Dynamic: Two processes, vapor liquid and liquid vapor, are both occurring but with
equal rates, so the composition of the vapor is constant.

21.

a. As the strength of the intermolecular forces increase, the rate of evaporation decreases.
b. As temperature increases, the rate of evaporation increases.
c. As surface area increases, the rate of evaporation increases.

22.

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 Chteliers 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.

23.

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.

24.

The phase change H2O(g) H2O(l) releases heat that can cause additional damage. Also,
steam can be at a temperature greater than 100C.

25.

Sublimation will occur, allowing water to escape as H2O(g).

CHAPTER 10

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343

26.

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.

27.

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.

28.

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 sixmembered rings. Each carbon atom in a particular layer of graphite is surrounded by
three other carbons in a trigonal planar arrangement. This requires sp 2 hybridization.
Each carbon has an unhybridized p atomic orbital; all of these p orbitals in each sixmembered ring overlap with each other to form a delocalized 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 Na 2CO3, B2O3, and
K2O, with each compound serving a specific purpose relating to the properties of glass.

29.

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
London dispersion forces. H2O exhibits the relatively strong hydrogen-bonding
interactions. The differences in strength is evidenced by the solid-phase changes that

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occur at 1 atm. CO2(s) sublimes at a relatively low temperature of 78C. In sublimation,

all of the intermolecular forces are broken. However, H2O(s) doesnt have a phase change
until 0C, and in this phase change from ice to water, only a fraction of the intermolecular
forces are broken. The higher temperature and the fact that only a portion of the
intermolecular forces are broken are attributed to the strength of the intermolecular forces
in H2O(s) as compared to CO2(s).
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 OH 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.
30.

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.

31.

If TiO2 conducts electricity as a liquid, then it is an ionic solid; if not, then TiO2 is a network
solid.

32.

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).

33.

The mathematical equation that relates the vapor pressure of a substance to temperature is:
ln Pvap =
y

H vap 1
+C
R T
m
x +b

CHAPTER 10

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345

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.
34.

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
Intermolecular Forces and Physical Properties
35.

36.

Ionic compounds have ionic forces. Covalent compounds all have London dispersion (LD)
forces, whereas polar covalent compounds have dipole forces and/or hydrogen bonding
forces. For hydrogen-bonding (H-bonding) forces, the covalent compound must have either a
NH, OH, or FH bond in the molecule.
a. LD only

b. dipole, LD

d. ionic

e. LD only (CH4 is a nonpolar covalent compound.)

f.

g. ionic

dipole, LD

a. ionic

c. H-bonding, LD

b. dipole, LD (LD = London dispersion)

c. LD only

d. LD only (For all practical purposes, a C H bond can be considered as a nonpolar

bond.)
e. ionic

f.

LD only

g. H-bonding, LD

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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.
c. H2NCH2CH2NH2; more extensive hydrogen bonding (H-bonding) is possible because
two NH2 groups are present.
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.

38.

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.

39.

a. Neopentane is more compact than n-pentane. There is less surface-area contact among
neopentane molecules. This leads to weaker London dispersion (LD) forces and a lower
boiling point.
b. HF is capable of H-bonding; HCl is not.
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.
d. n-Hexane is a larger molecule, so it has stronger LD forces.

40.

The electrostatic potential diagrams indicate that ethanol and acetone are polar substances,
and that propane is a nonpolar substance. Ethanol, with the OH 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 forces. Because all three
compounds have about the same molar mass, the relative strengths of the London dispersion
forces should be about the same. 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.

41.

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.

CHAPTER 10

LIQUIDS AND SOLIDS

347

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.

42.

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 F 2 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 HOOH 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 Hfusion.

Properties of Liquids
43.

The attraction of H2O for glass is stronger than the H2OH2O attraction. The miniscus is
concave to increase the area of contact between glass and H2O. The HgHg attraction is
greater than the Hgglass attraction. The miniscus is convex to minimize the Hgglass
contact.

44.

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.

45.

The structure of H2O2 is HOOH, 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.

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46.

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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.

Structures and Properties of Solids

n
1 154 pm
=
= 313 pm = 3.13 10 10 m
2 sin
2 sin 14.22

47.

n = 2d sin , d =

48.

d=

n
2 154 pm
=
= 408 pm = 4.08 10 10 m
2 sin
2 sin 22.20

49.

2 d sin
2 1.36 10 10 m sin 15.0o
=
= 7.04 10 11 m = 0.704 = 70.4 pm
n
1

50.

n
1 2.63 A
n = 2d sin , d =
= 4.91 = 4.91 1010 m = 491 pm

o
2 sin
2 sin 15.55

n
2 2.63 A
sin =
= 0.536, = 32.4

o
2d
2 4.91 A
51.

A cubic closest packed structure has a face-centered cubic unit cell. In a face-centered cubic
unit, there are:
8 corners

1 / 8 atom
1 / 2 atom
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

2l2 = 16r2
l=r 8

l = r 8 = 197 10 12 m

8 = 5.57 10 10 m = 5.57 10 8 cm

Volume of a unit cell = l3 = (5.57 10 8 cm)3 = 1.73 10 22 cm3

CHAPTER 10

LIQUIDS AND SOLIDS

Mass of a unit cell = 4 Ca atoms

Density =

52.

349
1 mol Ca

6.022 10

23

atoms

40.08 g Ca
= 2.662 10 22 g Ca
mol Ca

mass
2.662 10 22 g

= 1.54 g/cm3
volume
1.73 10 22 cm 3

There are four Ni atoms in each unit cell. For a unit cell:

density =

mass
= 6.84 g/cm3 =
volume

4 Ni atoms

1 mol Ni
58.69 g Ni

23
mol Ni
6.022 10 atoms
l3

Solving: l = 3.85 10 8 cm = cube edge length

For a face-centered cube:

(4r)2 = l 2 + l 2 = 2l 2
l

4r

r 8 = l, r = l / 8
r = 3.85 10 8 cm / 8
r = 1.36 10 8 cm = 136 pm

53.

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.
The mass of atoms in a unit cell is:
mass = 4 Pb atoms

Density =

1 mol Pb
6.022 10

23

atoms

207.2 g Pb
= 1.38 10 21 g
mol Pb

mass
1.38 10 21 g

= 11.6 g/cm3
volume
1.19 10 22 cm 3

From Exercise 51, 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 .
r=

l
8

492 pm
8

= 174 pm = 1.74 10 10 m

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54.

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LIQUIDS AND SOLIDS

The volume of a unit cell is:

V = l3 = (383.3 1010 cm)3 = 5.631 1023 cm3
There are four Ir atoms in the unit cell, as is the case for all face-centered cubic unit cells.
The mass of atoms in a unit cell is:
mass = 4 Ir atoms

Density =

55.

1 mol Ir
6.022 10

23

atoms

192 .2 g Ir
= 1.277 1021 g
mol Ir

mass
1.277 10 21 g

= 22.68 g/cm3

23
3
volume
5.631 10
cm

A face-centered cubic unit cell contains four atoms. For a unit cell:
mass of X = volume density = (4.09 10 8 cm)3 10.5 g/cm3 = 7.18 10 22 g
mol X = 4 atoms X

Molar mass =

56.

1 mol X
6.022 10

7.18 10 22 g X
6.642 10 24 mol X

23

atoms

= 6.642 10 24 mol X

= 108 g/mol; the metal is silver (Ag).

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 51).
Radius = r = l / 8 = 392 1012 m / 8 = 1.39 1010 m = 1.39 108 cm
The volume of a unit cell is l3, so the mass of the unknown metal (X) in a unit cell is:
volume density = (3.92 108 cm)3

21.45 g X
cm

= 1.29 1021 g X

Because each face-centered unit cell contains four atoms of X:

mol X in unit cell = 4 atoms X

1 mol X
6.022 10 23 atoms X

= 6.642 1024 mol X

Therefore, each unit cell contains 1.29 1021 g X, which is equal to 6.642 1024 mol X.
The molar mass of X is:
1.29 10 21 g X
6.642 10 24 mol X

= 194 g/mol

The atomic mass would be 194 u. From the periodic table, the best choice for the metal is
platinum.

CHAPTER 10
57.

LIQUIDS AND SOLIDS

351

For a body-centered unit cell, 8 corners

1 / 8 Ti
+ 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

23
mol Ti
6.022 10 atoms
density = 4.50 g/cm3 =
3
l
Solving: l = edge length of unit cell = 3.28 10 8 cm = 328 pm
Assume Ti atoms just touch along the body diagonal of the cube, so body diagonal =
4 radius of atoms = 4r.
The triangle we need to solve is:

4r

l 2

3.28 x 10 -8 cm

(3.28 x 10 -8cm) 2

(4r)2 = (3.28 10 8 cm)2 + [(3.28 10 8 cm) 2 ]2, r = 1.42 10 8 cm = 142 pm

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 .
58.

From Exercise 57:

16r2 = l 2 + 2l 2
4r

l = 4r/ 3 = (2.309)r
l = 2.309(222 pm) = 513 pm = 5.13 10 8 cm

l 2

In a body-centered cubit unit cell, there are two atoms per unit cell. For a unit cell:

density =

mass

volume

2 atoms Ba

1 mol Ba
137.3 g Ba

23
mol Ba
6.022 10 atoms
(5.13 10

cm )

3.38 g
cm 3

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59.

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LIQUIDS AND SOLIDS

If gold has a face-centered cubic structure, then there are four atoms per unit cell, and from
Exercise 51:
2l2 = 16r2
4r

l = r 8 = (144 pm) 8 = 407 pm

l = 407 1012 m = 4.07 108 cm

l

4 atoms Au

Density =

1 mol Au
197.0 g Au

mol Au
6.022 10 23 atoms
= 19.4 g/cm3
8
3
(4.07 10 cm )

If gold has a body-centered cubic structure, then there are two atoms per unit cell, and from
Exercise 57:
16r2 = l2 + 2l2
4r

l = 4r/ 3 = 333 pm = 333 1012 m

l = 333 1010 cm = 3.33 108 cm

l 2

2 atoms Au
Density =

1 mol Au
197.0 g Au

23
mol Au
6.022 10 atoms
= 17.7 g/cm3
8
3
(3.33 10 cm )

The measured density of gold is consistent with a face-centered cubic unit cell.
60.

If face-centered cubic:
l = r 8 = (137 pm) 8 = 387 pm = 3.87 10 8 cm
4 atoms W

density =

1 mol
183 .9 g W

23
mol
6.022 10 atoms
(3.87 10

cm )

If body-centered cubic:
l =

4r
3

4 137 pm
3

= 316 pm = 3.16 10 8 cm

= 21.1 g/cm3

CHAPTER 10

LIQUIDS AND SOLIDS

2 atoms W

density =

353

1 mol
183 .9 g W

23
mol
6.022 10 atoms
(3.16 10

cm )

= 19.4 g/cm3

The measured density of tungsten is consistent with a body-centered unit cell.

61.

In a face-centered unit cell (a cubic closest packed structure), the atoms touch along the face
diagonal:

(4r)2 = l2 + l2

4r

l=r 8
Vcube = l 3 = (r 8 )3 = (22.63)r3

There are four atoms in a face-centered cubic cell (see Exercise 51). Each atom has a volume
of (4/3)r3 = volume of a sphere.
Vatoms = 4

4
3

r3 = (16.76)r3

Vatoms
(16.76) r 3

= 0.7406, or 74.06% of the volume of each unit cell is occupied by

Vcube
( 22.63) r 3
atoms.

So

In a simple cubic unit cell, the atoms touch along the cube edge l:

2(radius) = 2r = l

2r

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)r3 = volume of a sphere.
Vatom =

4
3

r3 = (4.189)r3

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Vatom
(4.189)r 3
= 0.5236, or 52.36% of the volume of each unit cell is occupied by

Vcube
8r 3
atoms.
So

A cubic closest packed structure (face-centered cubic unit cell) packs the atoms much more
efficiently than a simple cubic structure.
62.

From Exercise 57, 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 .
Volume of unit cell = l3 = (4r/ 3 )3 = (12.32)r3
Volume of atoms in unit cell = 2

So

4
3

r3 = (8.378)r3

Vatoms (8.378)r 3

= 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 cm3
Volume of unit cell = 2 Fe atoms

mol Fe 7.86 g
6.022 10 23 atoms

= 2.36 10 23 cm3

Volume = l3 = 2.36 10 23 cm3, l = 2.87 10 8 cm

l = 4r/ 3 , r = l 3 / 4 = 2.87 10 8 cm

3 / 4 = 1.24 10 8 cm = 124 pm

63.

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).

64.

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.

65.

In has fewer valence electrons than Se. Thus Se doped with In would be a p-type
semiconductor.

CHAPTER 10

LIQUIDS AND SOLIDS

355

66.

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.

67.

Egap = 2.5 eV 1.6 10 19 J/eV = 4.0 10 19 J; we want Egap = Elight = hc/, so:

34
8
hc (6.63 10 J s) (3.00 10 m/s)
=
= 5.0 10 7 m = 5.0 102 nm
E
4.0 10 19 J

68.

(6.626 10 34 J s) (2.998 10 8 m/s)

hc

E=
= 2.72 10 19 J = energy of band gap
9

730. 10 m

69.

Sodium chloride structure: 8 corners

12 edges

1 / 8 Cl
1 / 2 Cl
+ 6 faces
= 4 Cl ions
corner
face

1 / 4 Na
+ 1 Na+ at body center = 4 Na+ ions; NaCl is the formula.
edge

Cesium chloride structure: 1 Cs+ ion at body center; 8 corners

1 / 8 Cl

= 1 Cl ion
corner

CsCl is the formula.

Zinc sulfide structure: There are four Zn2+ ions inside the cube.
8 corners

1 / 8 S2
1 / 2 S2
+ 6 faces
= 4 S2 ions; ZnS is the formula.
corner
face

Titanium oxide structure:

4 faces

70.

8 corners

1 / 8 Ti 4
+ 1 Ti4+ at body center = 2 Ti4+ ions
corner

1 / 2 O 2

+ 2 O2 inside cube = 4 O2 ions; TiO2 is the formula.

face

Both As ions are inside the unit cell. 8 corners

1 / 4 Ni
1/ 8 Ni
+ 4 edges
= 2 Ni ions
edge
corner

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.
71.

There is one octahedral hole per closest packed anion in a closest packed structure. If onehalf 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.

356
72.

CHAPTER 10

LIQUIDS AND SOLIDS

There are two tetrahedral holes per closest packed anion. Let f = fraction of tetrahedral holes
filled by the cations.
Na2O: Cation-to-anion ratio =

2
2f
, f = 1; all the tetrahedral holes are filled by Na+

1
1
cations.

CdS: Cation-to-anion ratio =

1 2f
1
, f ; one-half the tetrahedral holes are filled by
1
1
2 Cd2+ cations.

ZrI4: Cation-to-anion ratio =

1
2f
1
, f ; one-eighth the tetrahedral holes are filled
4
1
8
by Zr4+ cations.

73.

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.

74.

A repeating pattern in the two-dimensional structure is:

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.
75.

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.

76.

Mn ions at 8 corners: 8(1/8) = 1 Mn ion; F ions at 12 edges: 12(1/4) = 3 F ions; the formula
is MnF3. Assuming fluoride is 1 charged, then the charge on Mn is +3.

77.

From Figure 10.35, MgO has the NaCl structure containing 4 Mg2+ ions and 4 O2 ions per
face-centered unit cell.
4 MgO formula units

1 mol MgO
6.022 10

23

atoms

40.31 g MgO
= 2.678 10 22 g MgO
1 mol MgO

CHAPTER 10

LIQUIDS AND SOLIDS

357

Volume of unit cell = 2.678 10 22 g MgO

1 cm 3
= 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 l 4 rO2 , rO2

2 4.21 10 8 cm
= 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:
l = 2 rO 2 2 rMg 2 , 4.21 10 8 cm = 2(1.49 10 8 cm) + 2 rMg 2 , rMg 2 = 6.15 10 9 cm
78.
Assuming K+ and Cl just touch along the cube edge l:
l = 2(314 pm) = 628 pm = 6.28 108 cm
Volume of unit cell = l3 = (6.28 108 cm)3

The unit cell contains four K+ and four Cl ions. For a unit cell:
4 KCl formula units

density =

1 mol KCl
74.55 g KCl

23
mol KCl
6.022 10 formula units
(6.28 10 8 cm )3

= 2.00 g/cm3
79.

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.
Body diagonal = 2 rCs 2 rCl 3 l , l = length of cube edge
In each unit cell:
mass = 1 CsCl formula unit

1 mol CsCl
6.022 10

23

formula units

168.4 g CsCl
mol CsCl

= 2.796 10 22 g
volume = l 3 = 2.796 10 22 g CsCl

1 cm 3
= 7.04 10 23 cm3
3.97 g CsCl

l 3 = 7.04 10 23 cm3, l = 4.13 10 8 cm = 413 pm = length of cube edge

358

CHAPTER 10

LIQUIDS AND SOLIDS

2 rCs 2 rCl 3 l 3(413 pm) = 715 pm

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.
80.

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
70.94 g MnO
cm

6.022 10 23 formula units MnO

= 4.00 formula units MnO
mol MnO4

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 .
l = 4.47 108 cm = 2rMn 2 + 2(1.40 108 cm), rMn 2 = 8.35 108 cm = 84 pm
81.

82.

83.

a. CO2: molecular

b. SiO2: network

c. Si: atomic, network

d. CH4: molecular

e. Ru: atomic, metallic

f.

I2: molecular

g. KBr: ionic

h. H2O: molecular

i.

NaOH: ionic

j.

k. CaCO3: ionic

l.

PH3: molecular

U: atomic, metallic

a. diamond: atomic, network

b. PH3: molecular

c. H2: molecular

d. Mg: atomic, metallic

e. KCl: ionic

f.

quartz: network

g. NH4NO3: ionic

h. SF2: molecular

i.

Ar: atomic, group 8A

j.

k. C6H12O6: molecular

Cu: atomic, metallic

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.

CHAPTER 10

LIQUIDS AND SOLIDS

359

b. 8 1/8 = 1 atom from corners + 1 atom at body center; empirical formula = NiTi
c. Both have a coordination number of 8 (both are surrounded by 8 atoms).
84.

Al: 8 corners

1/8 Al
1/2 Ni
= 1 Al; Ni: 6 face centers
= 3 Ni
corner
face center

The composition of the specific phase of the superalloy is AlNi3.

85.

Structure 1 (on left)

8 corners

6 faces

1/ 8 Ca
= 1 Ca atom
corner

1/ 2 O
= 3 O atoms
face

1 Ti at body center. Formula = CaTiO3

Structure 2 (on right)

8 corners

1/ 8 Ti
= 1 Ti atom
corner

12 edges

1/ 4 O
= 3 O atoms
corner

1 Ca at body center. Formula = CaTiO3

In the extended lattice of both structures, each Ti atom is surrounded by six O atoms.
86.

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.

87.

a. Y: 1 Y in center; Ba: 2 Ba in center

Cu: 8 corners

O: 20 edges

1 / 4 Cu
1 / 8 Cu
= 1 Cu, 8 edges
= 2 Cu, total = 3 Cu atoms
edge
corner

1/ 4 O
1/ 2 O
= 5 oxygen, 8 faces
= 4 oxygen, total = 9 O atoms
edge
face

Formula: YBa2Cu3O9
b. The structure of this superconductor material follows the second perovskite structure
described in Exercise 85. 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.

360

CHAPTER 10

LIQUIDS AND SOLIDS

c. Y, Ba, and Cu are the same. Some oxygen atoms are missing.
12 edges

1/ 4 O
1/ 2 O
= 3 O, 8 faces
= 4 O, total = 7 O atoms
edge
face

Superconductor formula is YBa2Cu3O7.

88.

a. Structure (a):

1/ 8 Tl
= 1 Tl
corner

Ba: 2 Ba inside unit cell; Tl: 8 corners

Cu: 4 edges

O: 6 faces

1 / 4 Cu
= 1 Cu
edge

1/ 4 O
1/ 2 O
+ 8 edges
= 5 O; Formula = TlBa2CuO5.
edge
face

Structure (b):
Tl and Ba are the same as in structure (a).
Ca: 1 Ca inside unit cell; Cu: 8 edges

O: 10 faces

1 / 4 Cu
= 2 Cu
edge

1/ 4 O
1/ 2 O
+ 8 edges
= 7 O; Formula = TlBa2CaCu2O7.
edge
face

Structure (c):
Tl and Ba are the same, and two Ca are located inside the unit cell.
Cu: 12 edges

1 / 4 Cu
1/ 4 O
1/ 2 O
= 3 Cu; O: 14 faces
+ 8 edges
=9O
edge
edge
face

Formula = TlBa2Ca2Cu3O9.
Structure (d):

Following similar calculations, formula = TlBa2Ca3Cu4O11.

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).
c. TlBa2CuO5: 3 + 2(2) + x + 5(2) = 0, x = +3
Only Cu3+ is present in each formula unit.
TlBa2CaCu2O7: 3 + 2(2) + 2 + 2(x) + 7(2) = 0, x = +5/2
Each formula unit contains 1 Cu2+ and 1 Cu3+.

CHAPTER 10

LIQUIDS AND SOLIDS

361

TlBa2Ca2Cu3O9: 3 + 2(2) + 2(2) + 3(x) + 9(2) = 0, x = +7/3

Each formula unit contains 2 Cu2+ and 1 Cu3+.
TlBa2Ca3Cu4O11: 3 + 2(2) + 3(2) + 4(x) + 11(2) = 0, x = +9/4
Each formula unit contains 3 Cu2+ and 1 Cu3+.
d. This superconductor material achieves variable copper oxidation states by varying the
numbers of Ca, Cu, and O in each unit cell. The mixtures of copper oxidation states are
discussed in part c. The superconductor material in Exercise 87 achieves variable copper
oxidation states by omitting oxygen at various sites in the lattice.

Phase Changes and Phase Diagrams

89.

If we graph ln Pvap versus 1/T with temperature in Kelvin, the slope of the resulting straight
line will be Hvap/R.
Pvap
1 torr
10.
100.
400.
760.

ln Pvap
0
2.3
4.61
5.99
6.63

T (Li)
1023 K
1163
1353
1513
1583

1/T

T (Mg)
4

9.775 10 K
8.598 104
7.391 104
6.609 104
6.317 104

893 K
1013
1173
1313
1383

1/T
11.2 104 K1
9.872 104
8.525 104
7.616 104
7.231 104

For Li:
We get the slope by taking two points (x, y) that are on the line we draw. For a line,
slope = y/x, or we can determine the straight-line equation using a calculator. The
general straight-line equation is y = mx + b, where m = slope and b = y intercept.
The equation of the Li line is: ln Pvap = 1.90 104(1/T) + 18.6, slope = 1.90 104 K

362

CHAPTER 10

LIQUIDS AND SOLIDS

Slope = Hvap/R, Hvap = slope R = 1.90 104 K 8.3145 J/Kmol

Hvap = 1.58 105 J/mol = 158 kJ/mol
For Mg:
The equation of the line is: ln Pvap = 1.67 104(1/T) + 18.7, slope = 1.67 104 K
Hvap = slope R = 1.67 104 K 8.3145 J/Kmol
Hvap = 1.39 105 J/mol = 139 kJ/mol
The bonding is stronger in Li because Hvap is larger for Li.
90.

We graph ln Pvap vs 1/T. The slope of the line equals Hvap/R.

T(K)

103/T (K1) Pvap (torr)

273
283
293
303
313
323
353

Slope =

3.66
3.53
3.41
3.30
3.19
3.10
2.83

14.4
26.6
47.9
81.3
133
208
670.

ln Pvap
2.67
3.28
3.87
4.40
4.89
5.34
6.51

6.6 2.5
(2.80 10

4600 K =

H vap
R

3.70 10 3 ) K 1

H vap
8.3145 J/K mol

= 4600 K

, Hvap = 38,000 J/mol = 38 kJ/mol

To determine the normal boiling point, we can use the following formula:
H vap
P
ln 1 =
R
P2

1
1

T1
T2

At the normal boiling point, the vapor pressure equals 1.00 atm or 760. torr. At 273 K, the
vapor pressure is 14.4. torr (from data in the problem).
38,000 J/mol 1
1
14.4

, 3.97 = 4.6 103(1/T2 3.66 103)

ln
=
273 K
760 . 8.3145 J/K mol T2

8.6 104 + 3.66 103 = 1/T2 = 2.80 103, T2 = 357 K = normal boiling point

CHAPTER 10
91.

LIQUIDS AND SOLIDS

363

At 100.C (373 K), the vapor pressure of H2O is 1.00 atm = 760. torr. For water, Hvap =
40.7 kJ/mol.
P
ln 1
P
2

H vap 1
P H vap 1
1
1

or ln 2

P
R T2
R T1
T1
T2

520 . torr 40.7 10 3 J/mol 1

1

, 7.75 105 =
=
ln

760
.
torr
8.3145
J/K

mol
373
K
T

7.75 105 = 2.68 103

1
T2

92.

1
T2

= 2.76 103, T2 =

1
1

T2
373 K

1
2.76 10 3

= 362 K or 89C

At 100.C (373 K), the vapor pressure of H2O is 1.00 atm. For water, Hvap = 40.7 kJ/mol.
P H vap 1
P H vap 1
1
1

or ln 2

ln 1

P
R
T
T
P
R
T
T
2
2
1
1
1
2

P2
40.7 10 3 J/mol 1
1

, ln P2 = 0.51, P2 = e0.51 = 1.7 atm

ln

8.3145 J/K mol 373 K

388 K
1.00 atm
40.7 10 3 J/mol 1
1
3.50

ln

8.3145 J/K mol 373 K
T2
1.00

2.56 104 = 2.68 103

93.

P
ln 1
P
2

1
1
, 2.56 10 4

T2

373 K

1
1
1
,
= 2.42 103, T2 =
= 413 K or 140.C
T2 T2
2.42 10 3

H vap 1
H vap

836 torr
1
1
1

, ln

R T2
353 K
T1
213 torr 8.3145 J/K mol 313 K

Solving: Hvap = 3.1 104 J/mol; for the normal boiling point, P = 1.00 atm = 760. torr.
760 . torr
3.1 10 4 J/mol 1
1
1
1

,
=
ln

= 3.4 10 4
213
torr
8.3145
J/K

mol
313
K
T
313
T

1
1

T1 = 350. K = 77C; the normal boiling point of CCl4 is 77C.

94.

P
ln 1
P
2

H vap
H vap 1

1 760 torr
1
1

, ln

R
400.
torr
8.3145
J/K
mol 291.1 K
307.8
K
T

2
1

Solving: Hvap = 2.83 104 J/mol = 28.3 kJ/mol

364

CHAPTER 10

LIQUIDS AND SOLIDS

95.

96.

a. The plateau at the lowest temperature signifies the melting/freezing of the substance.
Hence the freezing point is 20C.
b. The higher temperature plateau signifies the boiling/condensation of the substance. The
temperature of this plateau is 120C.
c. X(s) X(l) H = Hfusion; X(l) X(g) H = Hvaporization
The heat of fusion and the heat of vaporization terms refer to enthalpy changes for the
specific phase changes illustrated in the equations above. In a heating curve, energy is
applied at a steady rate. So the longer, higher temperature plateau has a larger enthalpy
change associated with it as compared to the shorter plateau. The higher temperature
plateau occurs when a liquid is converting to a gas, so the heat of vaporization is greater
than the heat of fusion. This is always the case because significantly more intermolecular
forces are broken when a substance boils than when a substance melts.

97.

a. Many more intermolecular forces must be broken to convert a liquid to a gas as compared
with converting a solid to a liquid. Because more intermolecular forces must be broken,
much more energy is required to vaporize a liquid than is required to melt a solid.
Therefore, Hvap is much larger than Hfus.
b. 1.00 g Na

1 mol Na
2.60 kJ

= 0.113 kJ = 113 J to melt 1.00 g Na

22.99 g
mol Na

c. 1.00 g Na

1 mol Na 97.0 kJ

= 4.22 kJ = 4220 J to vaporize 1.00 g Na

22.99 g
mol Na

d. This is the reverse process of that described in part c, so the energy change is the same
quantity but opposite in sign. Therefore, q = 4220 J; i.e., 4220 of heat will be released.

CHAPTER 10
98.

LIQUIDS AND SOLIDS

Melt: 8.25 g C6H6

365

1 mol C6 H 6
9.92 kJ

= 1.05 kJ
78.11 g
mol C6 H 6

Vaporize: 8.25 g C6H6

1 mol C6 H 6
30.7 kJ

= 3.24 kJ
78.11 g
mol C6 H 6

As is typical, the energy required to vaporize a certain quantity of substance is much larger
than the energy required to melt the same quantity of substance. A lot more intermolecular
forces must be broken to vaporize a substance as compared to melting a substance.
99.

To calculate qtotal, break up the heating process into five steps.

H2O(s, 20.C) H2O(s, 0C), T = 20.C; let sice = specific heat capacity of ice:
q1 = sice m T =

2.03 J
o

g C

5.00 102 g 20.C = 2.0 104 J = 20. kJ

H2O(s, 0C) H2O(l, 0C), q2 = 5.00 102 g H2O

H2O(l, 0C) H2O(l, 100.C), q3 =

1 mol
6.02 kJ

= 167 kJ
18.02 g
mol

4.2 J
5.00 102 g 100.C = 2.1 105J = 210 kJ
o
g C

H2O(l, 100.C) H2O(g, 100.C), q4 = 5.00 102 g

H2O(g, 100.C) H2O(g, 250.C), q5 =

1 mol
40.7 kJ

= 1130 kJ
18.02 g
mol

2.0 J
5.00 102 g 150.C = 1.5 105 J
g oC
= 150 kJ

qtotal = q1 + q2 + q3 + q4 + q5 = 20. + 167 + 210 + 1130 + 150 = 1680 kJ

100.

H2O(g, 125C) H2O(g, 100.C), q1 = 2.0 J/gC 75.0 g (25C) = 3800 J = 3.8 kJ
H2O(g, 100.C) H2O(l, 100.C), q2 = 75.0 g

1 mol
40.7 kJ

= 169 kJ
18.02 g
mol

H2O(l, 100.C) H2O(l, 0C), q3 = 4.2 J/gC 75.0 g (100.C) = 32,000 J = 32 kJ

To convert H2O(g) at 125C to H2O(l) at 0C requires (3.8 kJ 169 kJ 32 kJ =) 205 kJ
of heat removed. To convert from H2O(l) at 0C to H2O(s) at 0C requires:
q4 = 75.0 g

1 mol
6.02 kJ

= 25.1 kJ
18.02 g
mol

This amount of energy puts us over the 215 kJ limit (205 kJ 25.1 kJ = 230. kJ). Therefore, a mixture of H2O(s) and H2O(l) will be present at 0C when 215 kJ of heat is removed
from the gas sample.

366
101.

CHAPTER 10
Total mass H2O = 18 cubes

LIQUIDS AND SOLIDS

30.0 g
1 mol H 2 O
= 540. g; 540. g H2O
= 30.0 mol H2O
18.02 g
cube

Heat removed to produce ice at 5.0C:

2.03 J
4.18 J
6.02 103 J

540 . g 22.0 o C +
540 . g 5.0 o C
30.0 mol +

mol
gC

gC

= 4.97 104 J + 1.81 105 J + 5.5 103 J = 2.36 105 J

2.36 105 J

102.

1 g CF2 Cl 2
= 1.49 103 g CF2Cl2 must be vaporized.
158 J

Heat released = 0.250 g Na

1 mol
368 kJ

= 2.00 kJ
22.99 g
2 mol

To melt 50.0 g of ice requires: 50.0 g ice

1 mol H 2 O 6.02 kJ

= 16.7 kJ
18.02 g
mol

The reaction doesn't release enough heat to melt all of the ice. The temperature will remain at
0C.
103.

A: solid

B: liquid

D: solid + vapor

E: solid + liquid + vapor

F: liquid + vapor

G: liquid + vapor

triple point: E

C: vapor

H: vapor

critical point: G

Normal freezing point: Temperature at which solid-liquid line is at 1.0 atm (see following
plot).
Normal boiling point: Temperature at which liquid-vapor line is at 1.0 atm (see following
plot ).

1.0
atm

nfp

nbp

Because the solid-liquid line equilibrium has a positive slope, the solid phase is denser than
the liquid phase.
104.

a. 3

CHAPTER 10

LIQUIDS AND SOLIDS

367

b. Triple point at 95.31C: rhombic, monoclinic, gas

Triple point at 115.18C: monoclinic, liquid, gas
Triple point at 153C: rhombic, monoclinic, liquid
c. From the phase diagram, the monoclinic solid phase is stable at T = 100.C and P = 1
atm.
d. Normal melting point = 115.21C; normal boiling point = 444.6C; the normal melting
and boiling points occur at P = 1.0 atm.
e. Rhombic is the densest phase because the rhombic-monoclinic equilibrium line has a
positive slope, and because the solid-liquid equilibrium lines also have positive slopes.
f.

No; P = 1.0 10 5 atm is at a pressure somewhere between the 95.31 and 115.18C triple
points. At this pressure, the rhombic and gas phases are never in equilibrium with each
other, so rhombic sulfur cannot sublime at P = 1.0 10 5 atm. However, monoclinic
sulfur can sublime at this pressure.

g. From the phase diagram, we would start off with gaseous sulfur. At 100.C and ~1 105
atm, S(g) would convert to the solid monoclinic form of sulfur. Finally at 100.C and
some large pressure less than 1420 atm, S(s, monoclinic) would convert to the solid
rhombic form of sulfur. Summarizing, the phase changes are S(g) S(monoclinic)
S(rhombic).
105.

a. two
b. Higher-pressure triple point: graphite, diamond and liquid; lower-pressure triple point at
107 Pa: graphite, liquid and vapor
c. It is converted to diamond (the more dense solid form).
d. Diamond is more dense, which is why graphite can be converted to diamond by applying
pressure.

106.

The following sketch of the Br2 phase diagram is not to scale. Because the triple point of Br2
is at a temperature below the freezing point of Br2, the slope of the solid-liquid line is
positive.

100
Solid
Pressure (atm)

Liquid

1
0.05

Gas
-7.3 -7.2

59

Temperature ( oC)

320

368

CHAPTER 10

LIQUIDS AND SOLIDS

The positive slopes of all the lines indicate that Br2(s) is more dense than Br2(l), which is
more dense than Br2(g). At room temperature (~22C) and 1 atm, Br2(l) is the stable phase.
Br2(l) cannot exist at a temperature below the triple-point temperature of 7.3C or at a
temperature above the critical-point temperature of 320C. The phase changes that occur as
temperature is increased at 0.10 atm are solid liquid gas.
107.

Because the density of the liquid phase is greater than the density of the solid phase, the slope
of the solid-liquid boundary line is negative (as in H2O). With a negative slope, the melting
points increase with a decrease in pressure, so the normal melting point of X should be
greater than 225C.

108.

760

P
(torr)

g
280

-121

-112

-107

T(C)

From the three points given, the slope of the solid-liquid boundary line is positive, so Xe(s) is
more dense than Xe(l). Also, the positive slope of this line tells us that the melting point of
Xe increases as pressure increases. The same direct relationship exists for the boiling point of
Xe because the liquid-gas boundary line also has a positive slope.

Additional Exercises
109.

As the physical properties indicate, the intermolecular forces are slightly stronger in D2O than
in H2O.

110.

CH3CO2H:

H-bonding + dipole forces + London dispersion (LD) forces

CH2ClCO2H:

H-bonding + larger electronegative atom replacing H (greater dipole) + LD

forces

CH3CO2CH3:

Dipole forces (no H-bonding) + LD forces

From the intermolecular forces listed above, we predict CH3CO2CH3 to have the weakest
intermolecular forces and CH2ClCO2H to have the strongest. The boiling points are
consistent with this view.

CHAPTER 10
111.

LIQUIDS AND SOLIDS

369

At any temperature, the plot tells us that substance A has a higher vapor pressure than substance B, with substance C having the lowest vapor pressure. Therefore, the substance with
the weakest intermolecular forces is A, and the substance with the strongest intermolecular
forces is C.
NH3 can form hydrogen-bonding interactions, whereas the others cannot. Substance C is
NH3. The other two are nonpolar compounds with only London dispersion forces. Because
CH4 is smaller than SiH4, CH4 will have weaker LD forces and is substance A. Therefore,
substance B is SiH4.

112.

As the electronegativity of the atoms covalently bonded to H increases, the strength of the
hydrogen-bonding interaction increases.
N HN < N H O < O HO < O HF < F HF
weakest
strongest

113.

8 corners

1/ 4 F
1/ 8 Xe
+ 1 Xe inside cell = 2 Xe; 8 edges
+ 2 F inside cell = 4 F
edge
corner

The empirical formula is XeF2.

114.

One B atom and one N atom together have the same number of electrons as two C atoms. The
description of physical properties sounds a lot like the properties of graphite and diamond, the
two solid forms of carbon. The two forms of BN have structures similar to graphite and
diamond.

115.

B2H6: This compound contains only nonmetals, so it is probably a molecular solid with
covalent bonding. The low boiling point confirms this.
SiO2: This is the empirical formula for quartz, which is a network solid.
CsI: This is a metal bonded to a nonmetal, which generally form ionic solids. The
electrical conductivity in aqueous solution confirms this.
W: Tungsten is a metallic solid as the conductivity data confirm.

116.

Ar is cubic closest packed. There are four Ar atoms per unit cell, and with a face-centered
unit cell, the atoms touch along the face diagonal. Let l = length of cube edge.
Face diagonal = 4r = l 2 , l = 4(190. pm)/ 2 = 537 pm = 5.37 108 cm

Density

117.

mass

volume

24.7 g C6H6

4 atoms

1 mol
39.95 g

23
mol
6.022 10 atoms
= 1.71 g/cm3
8
3
(5.37 10 cm )

1 mol
= 0.316 mol C6H6
78.11 g

370

CHAPTER 10

PC6H 6
118.

nRT

0.316 mol

LIQUIDS AND SOLIDS

0.08206 L atm
293 .2 K
K mol
= 0.0760 atm, or 57.8 torr
100 .0 L

In order to set up an equation, we need to know what phase exists at the final temperature. To
heat 20.0 g of ice from 10.0 to 0.0C requires:
q=

2.03 J
20.0 g 10.0C = 406 J
g C

To convert ice to water at 0.0C requires:

q = 20.0 g

1 mol
6.02 kJ
= 6.68 kJ = 6680 J

18.02
mol

To chill 100.0 g of water from 80.0 to 0.0C requires:

q=

4.18 J
100.0 g 80.0C = 33,400 J of heat removed
g C

From the heat values above, the liquid phase exists once the final temperature is reached (a
lot more heat is lost when the 100.0 g of water is cooled to 0.0C than the heat required to
convert the ice into water). To calculate the final temperature, we will equate the heat gain by
the ice to the heat loss by the water. We will keep all quantities positive in order to avoid sign
errors. The heat gain by the ice will be the 406 J required to convert the ice to 0.0C plus the
6680 J required to convert the ice at 0.0C into water at 0.0C plus the heat required to raise
the temperature from 0.0C to the final temperature.
Heat gain by ice = 406 J + 6680 J +
Heat loss by water =

4.18 J
20.0 g (Tf 0.0C) = 7.09 103 + (83.6)Tf
g C

4.18 J
100.0 g (80.0C Tf) = 3.34 104 418Tf
g C

Solving for the final temperature:

7.09 103 + (83.6)Tf = 3.34 104 418Tf, 502Tf = 2.63 104, Tf = 52.4C
119.

1.00 lb

454 g
= 454 g H2O; a change of 1.00F is equal to a change of 5/9C.
lb

The amount of heat in J in 1 Btu is

4.18 J
5
454 g C = 1.05 103 J = 1.05 kJ.
gC
9

It takes 40.7 kJ to vaporize 1 mol H2O (Hvap). Combining these:

1.00 10 4 Bu 1.05 kJ 1 mol H 2 O

= 258 mol/h; or:

h
Btu
40.7 kJ

258 mol 18.02 g H 2O

= 4650 g/h = 4.65 kg/h

h
mol

CHAPTER 10
120.

LIQUIDS AND SOLIDS

371

The critical temperature is the temperature above which the vapor cannot be liquefied no
matter what pressure is applied. Since N2 has a critical temperature below room temperature
(~22C), it cannot be liquefied at room temperature. NH3, with a critical temperature above
room temperature, can be liquefied at room temperature.

ChemWork Problems
The answers to the problems 121-130 (or a variation to these problem) are found in OWL.
These problems are also assignable in OWL.

Challenge Problems
131.

H = qp = 30.79 kJ; E = qp + w, w = PV
w = PV = 1.00 atm(28.90 L) = 28.9 L atm

101 .3 J
= 2930 J
L atm

E = 30.79 kJ + (2.93 kJ) = 27.86 kJ

132.

XeCl2F2, 8 + 2(7) + 2(7) = 36 e

polar (Bond dipoles do

not cancel each other.)

nonpolar (Bond dipoles

cancel each other.)

These are two possible square planar molecular structures for XeCl2F2. One structure has the
Cl atoms 90 apart; the other has the Cl atoms 180 apart. The structure with the Cl atoms 90
apart is polar; the other structure is nonpolar. The polar structure will have additional dipole
forces, so it has the stronger intermolecular forces and is the liquid. The gas form of XeCl 2F2
is the nonpolar form having the Cl atoms 180 apart.
133.

A single hydrogen bond in H2O has a strength of 21 kJ/mol. Each H2O molecule forms two
H bonds. Thus it should take 42 kJ/mol of energy to break all of the H bonds in water.
Consider the phase transitions:

Hsub = 6.0 kJ/mol + 40.7 kJ/mol = 46.7 kJ/mol; it takes a total of 46.7 kJ/mol to convert
solid H2O to vapor. This would be the amount of energy necessary to disrupt all of the
intermolecular forces in ice. Thus (42 46.7) 100 = 90.% of the attraction in ice can be
attributed to H bonding.

372
134.

CHAPTER 10
1 gal

LIQUIDS AND SOLIDS

3785 mL 0.998 g 1 mol H 2 O

210. mol H2O

gal
mL
18.02 g

From Table 10.8, the vapor pressure of H2O at 25C is 23.756 torr. The water will evaporate
until this partial pressure is reached.

nRT
V=
=
P

0.08206 L atm
298 K
K mol
= 1.64 105 L
1 atm
23.756 torr
760 torr

210 . mol

Dimension of cube = (1.64 105 L 1 dm3/L)1/3 = 54.7 dm

54.7 dm

1m
1.094 yards
3 ft

18.0 ft
10 dm
m
yard

The cube has dimensions of 18.0 ft 18.0 ft 18.0 ft.

135.

The structures of the two C2H6O compounds (20 valence e) are:

exhibits relatively strong hydrogen bonding

does not exhibit hydrogen bonding

The liquid will have the stronger intermolecular forces. Therefore, the first compound
(ethanol) with hydrogen bonding is the liquid and the second compound (dimethyl ether) with
the weaker intermolecular forces is the gas.
136.

Benzene

Naphthalene
H

H
H

LD forces only

H
H

LD forces only

CHAPTER 10

LIQUIDS AND SOLIDS

373

Note: London dispersion (LD) forces in molecules such as benzene and naphthalene are
fairly large. The molecules are flat, and there is efficient surface-area contact between
molecules. Large surface-area contact leads to stronger London dispersion forces.
Cl

Carbon tetrachloride (CCl4) has polar bonds but is a nonpolar

molecule. CCl4 only has LD forces.

C
Cl

Cl
Cl

In terms of size and shape, the order of the strength of LD forces is: CCl4 < C6H6 < C10H8
The strengths of the LD forces are proportional to size and are related to shape. Although the
size of CCl4 is fairly large, the overall spherical shape gives rise to relatively weak LD forces
as compared to flat molecules such as benzene and naphthalene. The physical properties
given in the problem are consistent with the order listed above. Each of the physical
properties will increase with an increase in intermolecular forces.
Acetone

Acetic acid
O

O
H 3C

H 3C

CH 3

LD, dipole

LD, dipole, H-bonding

Benzoic acid
O
C

LD, dipole, H-bonding

We would predict the strength of interparticle forces of the last three molecules to be:
acetone < acetic acid < benzoic acid
polar

H-bonding

H-bonding, but large LD forces because of greater size

and shape

This ordering is consistent with the values given for boiling point, melting point, and Hvap.
The overall order of the strengths of intermolecular forces based on physical properties are:
acetone < CCl4 < C6H6 < acetic acid < naphthalene < benzoic acid
The order seems reasonable except for acetone and naphthalene. Because acetone is polar,
we would not expect it to boil at the lowest temperature. However, in terms of size and
shape, acetone is the smallest molecule, and the LD forces in acetone must be very small
compared to the other molecules. Naphthalene must have very strong LD forces because of
its size and flat shape.

374

CHAPTER 10

LIQUIDS AND SOLIDS

137.

NaCl, MgCl2, NaF, MgF2, and AlF3 all have very high melting points indicative of strong
intermolecular forces. They are all ionic solids. SiCl4, SiF4, F2, Cl2, PF5, and SF6 are nonpolar
covalent molecules. Only London dispersion (LD) forces are present. PCl3 and SCl2 are polar
molecules. LD forces and dipole forces are present. In these eight molecular substances, the
intermolecular forces are weak and the melting points low. AlCl3 doesn't seem to fit in as
well. From the melting point, there are much stronger forces present than in the nonmetal
halides, but they aren't as strong as we would expect for an ionic solid. AlCl3 illustrates a
gradual transition from ionic to covalent bonding, from an ionic solid to discrete molecules.

138.

Total charge of all iron ions present in a formula unit is +2 to balance the 2 charge from the
one O atom. The sum of iron ions in a formula unit is 0.950. Let x = fraction Fe2+ ions in a
formula unit and y = fraction of Fe3+ ions present in a formula unit.
Setting up two equations: x + y = 0.950 and 2x + 3y = 2.000
Solving: 2x + 3(0.950 x) = 2.000, x = 0.85 and y = 0.10

0.10
= 0.11 = fraction of iron as Fe3+ ions
0.95
If all Fe2+, then 1.000 Fe2+ ion/O2 ion; 1.000 0.950 = 0.050 = vacant sites. 5.0% of the
Fe2+ sites are vacant.
139.

Assuming 100.00 g:
1 mol
1 mol
28.31 g O
= 1.769 mol O; 71.69 g Ti
= 1.497 mol Ti
16.00 g
47.88 g

1.769
1.497
= 1.182;
= 0.8462; the formula is TiO1.182 or Ti0.8462O.
1.497
1.769
For Ti0.8462O, let x = Ti2+ per mol O2 and y = Ti3+ per mol O2. Setting up two equations and
solving:
x + y = 0.8462 (mass balance) and 2x + 3y = 2 (charge balance)
2x + 3(0.8462 x) = 2, x = 0.539 mol Ti2+/mol O2- and y = 0.307 mol Ti3+/mol O2

0.539
100 = 63.7% of the titanium ions are Ti2+ and 36.3% are Ti3+ (a 1.75 : 1 ion ratio).
0.8462
140.

First, we need to get the empirical formula of spinel. Assume 100.0 g of spinel:

1 mol Al
= 1.40 mol Al
26.98 g Al

37.9 g Al

17.1 g Mg

45.0 g O

1 mol Mg
= 0.703 mol Mg
24.31 g Mg

1 mol O
= 2.81 mol O
16.00 g O

The mole ratios are 2 : 1 : 4.

Empirical formula = Al2MgO4

CHAPTER 10

LIQUIDS AND SOLIDS

375

Assume each unit cell contains an integral value (x) of Al2MgO4 formula units. Each
Al2MgO4 formula unit has a mass of 24.31 + 2(26.98) + 4(16.00) = 142.27 g/mol.
x formula units

Density =

1 mol
142.27 g

23
mol
3.57 g
6.022 10 formula units

8
3
(8.09 10 cm )
cm 3

Solving: x = 8.00
Each unit cell has 8 formula units of Al2MgO4 or 16 Al, 8 Mg, and 32 O ions.
141.

mass Mn volume Cu
volume Cu
Density Mn
mass Mn

Density Cu
volume Mn mass Cu
mass Cu
volume Mn
The type of cubic cell formed is not important; only that Cu and Mn crystallize in the same
type of cubic unit cell is important. Each cubic unit cell has a specific relationship between
the cube edge length l and the radius r. In all cases l r. Therefore, V l3 r3. For the
mass ratio, we can use the molar masses of Mn and Cu since each unit cell must contain the
same number of Mn and Cu atoms. Solving:

volumeCu
(rCu )3
densityMn
massMn
54.94 g/mol

densityCu
massCu
volumeMn
63.55 g/mol (1.056 rCu )3
3

density Mn
1
= 0.8645
= 0.7341
density Cu
1.056
densityMn = 0.7341 densityCu = 0.7341 8.96 g/cm3 = 6.58 g/cm3
142.

a. The arrangement of the layers is:

Layer 1

Layer 2

Layer 3

A total of 20 cannon balls will be needed.

b. The layering alternates abcabc, which is cubic closest packing.
c. tetrahedron

Layer 4

376

CHAPTER 10

143.

As P is lowered, we go from a to b on the phase

diagram. The water boils. The boiling of water is
endothermic, and the water is cooled (b c),
forming some ice. If the pump is left on, the ice
will sublime until none is left. This is the basis of
freeze drying.

P
c

LIQUIDS AND SOLIDS

b
T

144.

w = PV; assume a constant P of 1.00 atm.

V373 =

nRT
=
P

1.00 mol

0.08206 L atm
373 K
K mol
= 30.6 L for 1 mol of water vapor
1.00 atm

Because the density of H2O(l) is 1.00 g/cm3, 1.00 mol of H2O(l) occupies 18.0 cm3 or
0.0180 L.
w = 1.00 atm(30.6 L 0.0180 L) = 30.6 L atm
w = 30.6 L atm

101.3 J
= 3.10 103 J = 3.10 kJ
L atm

E = q + w = 40.7 kJ 3.10 kJ = 37.6 kJ

37.6
100 = 92.4% of the energy goes to increase the internal energy of the water.
40.7
The remainder of the energy (7.6%) goes to do work against the atmosphere.
145.

For a cube: (body diagonal)2 = (face diagonal)2 + (cube edge length)2

In a simple cubic structure, the atoms touch on cube edge, so the cube edge = 2r, where r
= radius of sphere.

2r

2r
Face diagonal =

(2r) 2 (2r) 2 =

4r 2 4r 2 = r 8 = 2 2 r

Body diagonal =

(2 2 r) 2 (2r) 2 = 12 r 2 = 2 3 r

The diameter of the hole = body diagonal 2(radius of atoms at corners).

CHAPTER 10

LIQUIDS AND SOLIDS

377

Diameter = 2 3 r 2r; thus the radius of the hole is:

The volume of the hole is
146.

2 3 r 2r
( 3 1)r
2

3 1r .
3

Using the ionic radii values given in the question, lets calculate the density of the two
structures.
Normal pressure: Rb+ and Cl touch along cube edge (form NaCl structure).
Cube edge = l = 2(148 + 181) = 658 pm = 6.58 108 cm; there are four RbCl units per unit
cell.
4(85.47) 4(35.45)
Density = d =
= 2.82 g/cm3
6.022 10 23 (6.58 10 8 ) 3
High pressure: Rb+ and Cl touch along body diagonal (form CsCl structure).
2r- + 2r+ = 658 pm = body diagonal = l 3 , l = 658 pm/ 3 = 380. pm
Each unit cell contains 1 RbCl unit: d =

85.47 35.45
= 3.66 g/cm3
6.022 10 23 (3.80 10 8 ) 3

The high-pressure form has the higher density. The density ratio is 3.66/2.82 = 1.30. We
would expect this because the effect of pressure is to push things closer together and thus
increase density.

Integrative Problems
147.

Molar mass of XY =

19.0 g
= 144 g/mol
0.132 mol

X: [Kr] 5s24d10; this is cadmium, Cd.

Molar mass Y = 144 112.4 = 32 g/mol; Y is sulfur, S.
The semiconductor is CdS. The dopant has the electron configuration of bromine, Br.
Because Br has one more valence electron than S, doping with Br will produce an n-type
semiconductor.
148.

Assuming 100.00 g of MO2:

23.72 g O

1 mol O
= 1.483 mol O
16.00 g O

1.483 mol O

1 mol M
= 0.7415 mol M
2 mol O

378

CHAPTER 10
100.00 g 23.72 g = 76.28 g M; molar mass M =

LIQUIDS AND SOLIDS

76.28 g
= 102.9 g/mol
0.7415 mol

From the periodic table, element M is rhodium (Rh).

The unit cell for cubic closest packing is face-centered cubic (4 atoms/unit cell). The atoms
for a face-centered cubic unit cell are assumed to touch along the face diagonal of the cube,
so the face diagonal = 4r. The distance between the centers of touching Rh atoms will be the
distance of 2r, where r = radius of Rh atom.
Face diagonal =

2 l, where l = cube edge.

Face diagonal = 4r = 2 269.0 10 12 m = 5.380 10 10 m

2 l = 4r = 5.38 10 10 m, l =

4 atoms Rh

Density =

149.

P
ln 1
P
2

5.38 10 10 m
2

= 3.804 10 10 m = 3.804 10 8 cm

1 mol Rh
102.9 g Rh

23
mol Rh
6.0221 10 atoms
= 12.42 g/cm3
8
3
(3.804 10 cm )

H vap 1
1
296 J 200.6 g

= 5.94 104 J/mol Hg

; H vap

R T2
g
mol
T1

2.56 10 3 torr 5.94 10 4 J/mol 1

ln

P2
8.3145 J/K mol 573 K
298.2 K

2.56 10 3 torr
= 11.5, P2 = 2.56 10 3 torr/e 11.5 = 253 torr
ln

P
2

1 atm
253 torr
15.0 L
760 torr
PV

n=
= 0.106 mol Hg
0.08206 L atm
RT
573 K
K mol

0.106 mol Hg

6.022 10 23 atoms Hg
= 6.38 1022 atoms Hg
mol Hg

Marathon Problem
150.

q = s m T; heat loss by metal = heat gain by calorimeter. The change in temperature for
the calorimeter is T = 25.2C 0.2C 25.0C 0.2C. Including the error limits, T can
range from 0.0 to 0.4C. Because the temperature change can be 0.0C, there is no way that
the calculated heat capacity has any meaning.

CHAPTER 10

LIQUIDS AND SOLIDS

379

The density experiment is also not conclusive.

d=

4g
= 10 g/cm3 (1 significant figure)
0.42 cm 3

dhigh =

5g
= 12.5 g/cm3 = 10 g/cm3 to 1 sig fig
0.40 cm 3

dlow =

3g
= 7 g/cm3
3
0.44 cm

From Table 1.5, the density of copper is 8.96 g/cm3. The results from this experiment cannot
be used to distinguish between a density of 8.96 g/cm3 and 9.2 g/cm3.
The crystal structure determination is more conclusive. Assuming the metal is copper:
3

1 10 10 cm
2.16 10 22 cm 3
volume of unit cell = (600. pm)

1
pm

Cu mass in unit cell = 4 atoms

d=

1 mol Cu
6.022 10

23

atoms

63.55 g Cu
= 4.221 10 22 g Cu
mol Cu

mass
4.221 10 22 g

= 1.95 g/cm3
22
3
volume
2.16 10
cm

Because the density of Cu is 8.96 g/cm3, then one can assume this metal is not copper. If the
metal is not Cu, then it must be kryptonite (as the question reads). Because we dont know the
molar mass of kryptonite, we cannot confirm that the calculated density would be close to 9.2
g/cm3.
To improve the heat capacity experiment, a more precise balance is a must and a more precise
temperature reading is needed. Also, a larger piece of the metal should be used so that T of
the calorimeter has more significant figures. For the density experiment, we would need a
more precise balance and a more precise way to determine the volume. Again, a larger piece
of metal would help in order to ensure more significant figures in the volume.