11 Liquids, Solids, and

Intermolecular
Forces
Problems by Topic
Intermolecular Forces
11.47 (a) dispersion forces
(b) dispersion forces, dipole–dipole forces, and hydrogen bonding
(c) dispersion forces and dipole–dipole forces
(d) dispersion forces

11.49 (a) dispersion forces and dipole–dipole forces

(b) dispersion forces, dipole–dipole forces, and hydrogen bonding
(c) dispersion forces
(d) dispersion forces

11.51 (a) CH4 < (b) CH3CH3 < (c) CH3CH2Cl < (d) CH3CH2OH. The first two molecules only exhibit dispersion
forces, so the boiling point increases with increasing number of electrons. The third molecule also exhibits
dipole–dipole forces, which are stronger than dispersion forces. The last molecule exhibits hydrogen
bonding. Since these are by far the strongest intermolecular forces in this group, the last molecule has the
highest boiling point.

11.53 (a) CH3OH has the higher boiling point since it exhibits hydrogen bonding.
(b) CH3CH2OH has the higher boiling point since it exhibits hydrogen bonding.
(c) CH3CH3 has the higher boiling point since it has the larger number of electrons.

11.55 (a) Br2 has the higher vapour pressure since it has the smaller number of electrons.
(b) H2S has the higher vapour pressure since it does not exhibit hydrogen bonding.
(c) PH3 has the higher vapour pressure since it does not exhibit hydrogen bonding.

11.57 (a) cis‐1,2‐difluoroethene would have the higher enthalpy of vaporization because it is polar and, thus,
has dipole–dipole interactions. This occurs because the fluorine atoms are on one side of the
molecule, whereas trans‐1,2‐difluoroethene has the fluorine atoms on opposite sides and is thus
nonpolar.
(b) 1,1,1,2,2,2‐hexachloroethane has many more valence electrons than ethane and is therefore more
polarizable and has stronger dispersion forces; this gives a larger enthalpy of vaporization.

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Chapter 11 Liquids, Solids, and Intermolecular Forces 231

(c) 2‐ethanol displays strong hydrogen bonding interactions between molecules, whereas propane
does not; it has weaker dispersion forces only. Therefore, ethanol has a higher enthalpy of
vaporization.

Surface Tension, Viscosity, and Capillary Action

11.59 Water will have the higher surface tension since it exhibits hydrogen bonding, a strong intermolecular
force. Acetone cannot form hydrogen bonds.

11.61 Compound A will have the higher viscosity since it can interact with other molecules along the entire
molecule. The more branched isomer has a smaller surface area allowing for fewer interactions. Also the
molecule is very flexible and the molecules can get tangled with each other.

11.63 In a clean glass tube the water can generate strong adhesive interactions with the glass (due to the dipoles
at the surface of the glass). Water experiences adhesive forces with glass that are stronger than its cohesive
forces, causing it to climb the surface of a glass tube. When grease or oil coats the glass this interferes with
the formation of these adhesive interactions with the glass, since oils are nonpolar and cannot interact
strongly with the dipoles in the water. Without experiencing these strong intermolecular forces with oil,
the water’s cohesive forces will be greater and it will be drawn away from the surface of the tube.

Vaporization and Vapour Pressure

11.65 The water in the 12 cm diameter beaker will evaporate more quickly because there is more surface area
for the molecules to evaporate from. The vapour pressure will be the same in the two containers because
the vapour pressure is the pressure of the gas when it is in dynamic equilibrium with the liquid
(evaporation rate = condensation rate). The vapour pressure is dependent only on the substance and the
temperature. The 12 cm diameter container will reach this dynamic equilibrium faster.

11.67 The boiling point and higher heat of vaporization of oil are much higher than that of water, so it will not
vaporize as quickly as the water. The evaporation of water cools your skin because evaporation is an
endothermic process.

11.69 Given: 915 kJ from candy bar, water d = 1.00 g mL–1 Find: L(H2O) vaporized at 100.0 °C
Other:  vap H o  40.7 kJ mol 1
Conceptual Plan: q  mol H2O  g H2O  mL H2O  L H2O
1 mol 18.01 g 1.00 mL 1L
40.7 kJ 1 mol 1.00 g 1000 mL

1 mol 18.02 g 1.00 mL 1L

Solution: 915 kJ      0.405 L H 2 O
40.7 kJ 1 mol 1g 1000 mL
Check: The units (L) are correct. The magnitude of the answer (< 1 L) makes physical sense because we
are vaporizing about 22 moles of water.

11.71 Given: 0.95 g water condenses on iron block 75.0 g at Ti = 22 °C Find: Tf (iron block)
Other:  vap H o  44.0 kJ mol 1 ; CFe = 0.449 J g–1 °C–1 from text
Conceptual Plan: g H2O  mol H2O  qH2 O (kJ)  qH2 O (J)  qFe then qFe, mFe, Ti  Tf
1 mol 44.0 kJ 1000 J
qH2O  qFe q  mC s (Tf  Ti )
18.01 g 1 mol 1 kJ

1 mol 44.0 kJ 1000 J

Solution: 0.95 g     2319.64 J then qH2 O  qFe  2319.64 J then
18.02 g 1 mol 1 kJ
q  m Cs (Tf  Ti ). Rearrange to solve for Tf.

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232 Chapter 11 Liquids, Solids, and Intermolecular Forces

 J 
 75.0 g  0.449  22 C   2319.64 J
m CsTi  q  g  C 

Tf    91C.
m Cs J
75.0 g  0.449
g  C
Check: The units (°C) are correct. The temperature rose, which is consistent with heat being added to the
block. The magnitude of the answer (91 °C) makes physical sense because even though we have ~ 201 of a
mole, the energy involved in condensation is very large.

11.73 Given: Temperature (K) Pressure (mbar) Find:  vap H (NH 3 ) and normal boiling point
200 87.1
210 179.1
220 340.9
230 608.0
235 795.9
Conceptual Plan: To find the heat of vaporization, use Excel or similar software to make a plot of the
natural log of vapour pressure (ln P) as a function of the inverse of the temperature in K (1/T). Then fit
the points to a line and determine the slope of the line. Since the slope =  vap H /R , we find the heat
of vaporization as follows:
slope   vap H /R   vap H = slope  R then J  kJ.
1 kJ
1000 J

For the normal boiling point, use the equation of the best fit line, substitute 1013.25 mbar for the
pressure and calculate the temperature.
Solution: Data was plotted in Excel.
The slope of the best fitting line is 2969.3 K, the ln  is 19.321.
 8.314 J  2.46868  10 4 J 1 kJ
 vap H  slope  R  ( 2969.3 K)      24.7 kJ mol 1
 K mol  mol 1000 J
To find the temperature:
1
ln P  2969.3 K    19.321 
T 
1
ln1013.25  2969.3 K    19.321 
T 
1
2969.3 K    19.321  6.92092 
T 
2969.3 K
T  239 K
12.40008
Check: The units (kJ mol–1 and K) are correct. The magnitudes of the answers (25 kJ mol–1 and 239 K) are
consistent with other values in the text.

11.75 Given: ethanol,  vap H   38.56 kJ mol 1 ; normal boiling point = 78.4 °C Find: PEthanol at 15 °C
Conceptual Plan: °C  K and kJ  J then  vap H  , T1, P1, T2  P2
1000 J P2  vap H  1 1
K = °C + 273.15 ln    
1 kJ P1 R  T2 T1 

Solution: T1 = 78.4 °C + 273.15 = 351.6 K; T2 = 15 °C + 273.15 = 288 K;

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Chapter 11 Liquids, Solids, and Intermolecular Forces 233

38.56 kJ 1000 J J P2  vap H  1 1 

  3.856  10 4 P  1.01 bar ln     . Substitute values in equation.
mol 1 kJ mol 1 P1 R  T2 T1 
J
3.856  10 4
P2 mol  1 1 
ln      2.91302 
1.01 bar J  288 K 351.6 K 
8.314
K  mol
P2
 e 2.91302  0.054311  P2  0.054311  1.01 bar  0.0548 bar = 55 mbar
1.01 bar
Check: The units (bar) are correct. Since 15 °C is significantly below the boiling point, we expect the
answer to be much less than 1.01 bar.

Sublimation and Fusion

11.77 Given: P1 ice = 1.949 Torr at T1 = –10.0 °C; P2 ice = 0.774 Torr at T2 = –20.0 °C
Find: enthalpy of vaporization of ice and Pvap at –30.0 °C
Conceptual Plan: use the Clausius–Clapeyron equation to determine the enthalpy of vaporization of
ice and then use the equation again to determine Pvap at –30.0 °C.
0.001333 bar
Solution: P1  1.949 Torr   2.598  10 3 bar and
1 Torr
0.001333 bar
P2  0.774 Torr   1.032  10 3 bar. Also T1 = –10.0 °C + 273.15 = 263.15 K and
1 Torr
T2 = –20.0 °C + 273.15 = 253.15 K. Putting this together in the Clausius–Clapeyron equation gives:
1.032  10 3 bar  vap H   1 1 
ln     . Rearrange to solve for  vap H .
2.598  10 bar 8.314 J K 1 mol 1  253.15 K 263.15 K 
3

1.032  10 3 bar 8.314 J K 1mol 1

 vap H   ln   51,176 J mol 1 . Converted to kJ mol–1 this is an
2.598  10 3 bar  1 1 
 253.15 K  263.15 K 
 
enthalpy of vaporization of 51.2 kJ mol–1.
To obtain the vapour pressure at –30.0 °C, first convert T3 = –30.0 + 273.15 = 243.15 K and plug it all back
into the Clausius–Clapeyron equation as follows:
P3 51,200 J mol 1  1 1  P3
ln  1 
  , which gives ln  1.92.
3 1
2.598  10 bar 8.314 J K mol  243.15 K 263.15 K  2.598  10 3 bar
P3
Solving for P3 we obtain  e 1.92 thus, 0.147(2.598  10–3 bar)(1 Torr/1.333  10–3 bar)
2.598  10 3 bar
= 0.286 Torr

11.79 Given: 65.8 g water freezes Find: energy released Other:  fus H   6.02 kJ mol 1 from text
Conceptual Plan: g H2O  mol H2O  qH2 O (kJ)  qH2 O (J)
1 mol 6.02 kJ 1000 J
18.01 g 1 mol 1 kJ

1 mol 6.02 kJ 1000 J

Solution: 65.8 g     21982 J  2.20  10 4 J released or 22.0 kJ released
18.02 g 1 mol 1 kJ
Check: The units (J) are correct. The magnitude (22000 J) makes sense since we are freezing about
3 moles of water. Freezing is exothermic, so heat is released.

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234 Chapter 11 Liquids, Solids, and Intermolecular Forces

11.81 Given: 8.5 g ice; 255 g water Find: T of water

Other:  fus H   6.0 kJ mol 1 ; CH2 O  4.18 J g 1 C1 from text
Conceptual Plan: The first step is to calculate how much heat is removed from the water to melt the ice.
qice = –qwater so g (ice)  mol (ice)  qfus (kJ)  qfus (J)  qwater (J) then q, m, Cs  T1
1 mol 6.0 kJ 1000 J
qwater  qice q  mCS T1
18.01 g 1 mol 1 kJ

Now we have slightly cooled water (at a temperature of T1) in contact with 0.0 °C water, and we can
calculate a second temperature drop of the water due to mixing of the water that was ice,
so qice   qwater with m, Cs  T2 with T1  T2   TTotal .
q  mCS T2 then set qice = –qwater TTotal  T1  T2

1 mol 6.0 kJ 1000 J

Solution: 8.5 g     2.83176  10 3 J, q water  qice  2.83176  10 3 J
18.01 g 1 mol 1 kJ
q 2.83176  10 3 J
q  mCS T . Rearrange to solve for T . T1    2.6567 C.
mCS J
255 g  4.18
g  C
q  mCS T substitute in values and set qice  qH2 O .
J
qice  miceCice (Tf  Ticei )  8.5 g  4.18  (Tf  0.0 C) 
g  C
J
qwater  mwaterC water Twater2  255 g  4.18  Twater2 
g  C
8.5 Tf  255Twater2  255(Tf  Tf1 ). Rearrange to solve for Tf. 8.5 Tf + 255 Tf = 255 Tf1 
263.5 Tf = 255 Tf1  Tf = 0.96774 Tf1 but ΔT1 = (Tf1 – Ti1) = –2.6567 °C which says that
Tf1 = Ti1 – 2.6567 °C and ΔTTotal = (Tf – Ti1) so
ΔTTotal = 0.96774 Tf1 – Ti1 = 0.96774(Ti1 – 2.6567 °C) – Ti1 = –2.6567 °C – 0.03226 Ti1.
This implies that the larger the initial temperature of the water, the larger the temperature drop. If the initial
temperature was 90 °C, the temperature drop would be 5.6 °C. If the initial temperature was 25 °C,
the temperature drop would be 3.5 °C. If the initial temperature was 5 °C, the temperature drop would be
2.8 °C. This makes physical sense because the lower the initial temperature of the water, the less kinetic energy
it initially has and the smaller the heat transfer from the water to the melted ice will be.
Check: The units (°C) are correct. The temperature drop from the melting of the ice is only 2.7 °C because
the mass of the water is so much larger than the ice.

11.83 Given: 10.0 g ice Ti = –10.0 °C to steam at Tf = 110.0 °C Find: heat required (kJ)
Other:  fus H   6.02 kJ mol 1 ;  vap H   40.7 kJ mol 1 ; Cice = 2.09 J g–1 °C–1; Cwater = 4.18 J g–1 °C–1;
Csteam = 2.01 J g–1 °C–1
Conceptual Plan: Follow the heating curve in Figure 11.39. qTotal = q1 + q2 + q3 + q4 + q5 where q1, q3, and
q5 are heating of a single phase then J  kJ and q2 and q4 are phase transitions.
1 kJ 1 mol H
q  mC S (Tf  Ti ) qm 
1000 J 18.01 g 1 mol

Solution:
J 1 kJ
q1  miceC ice (Ticef  Ticei )  10.0 g  2.09  (0.0 C  ( 10.0 C ))  209 J   0.209 kJ,
g  C 1000 J

1 mol  fus H 1 mol 6.02 kJ

q2  m    10.0 g    3.343 kJ,
18.01 g 1 mol 18.01 g 1 mol
J 1 kJ
q3  mwaterC water (Twaterf  Twateri )  10.0 g  4.18  (100.0 C  0.0 C )  4180 J   4.18 kJ,
g  C 1000 J

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Chapter 11 Liquids, Solids, and Intermolecular Forces 235

1 mol  vap H 1 mol 40.7 kJ

q4  m    10.0 g    22.599 kJ,
18.01 g 1 mol 18.01 g 1 mol
J
q5  msteamCsteam (Tsteamf  Tsteami )  10.0 g  2.01  (110.0 C  110.0 C )
g  C
1 kJ
 201 J   0.201 kJ.
1000 J
qTotal  q1  q2  q3  q4  q5  0.209 kJ  3.343 kJ  4.18 kJ  22.599 kJ  0.201 kJ  30.5 kJ
Check: The units (kJ) are correct. The total amount of heat is dominated by the vaporization step. Since
we have less than 1 mole we expect less than 41 kJ.

Phase Diagrams
11.85 (a) solid
(b) liquid
(c) gas
(d) supercritical fluid
(e) solid/liquid equilibrium
(f) liquid/gas equilibrium
(g) solid/liquid/gas equilibrium

11.87 Given: nitrogen, normal boiling point = 77.3 K, normal melting point = 63.1 K, critical temperature = 126.2
K, critical pressure = 2.55  104 Torr, triple point at 63.1 K and 94.0 Torr
Find: sketch phase diagram. Does nitrogen have a stable liquid phase at 1 atm?

Nitrogen has a stable liquid phase at 1 atm.

Note that the axes are not to scale.

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236 Chapter 11 Liquids, Solids, and Intermolecular Forces

11.89 (a) 0.036 mbar, the higher of the two triple points
(b) The rhombic phase is more dense because if we start in the monoclinic phase at 100 °C and increase
the pressure, we will cross into the rhombic phase.

The Uniqueness of Water

11.91 Water has a low molar mass (18.01 g mol–1), yet it is a liquid at room temperature. Water’s high boiling
point for its molar mass can be understood by examining the structure of the water molecule. The bent
geometry of the water molecule and the highly polar nature of the O–H bonds result in a molecule with
a significant dipole moment. Water’s two O–H bonds (hydrogen directly bonded to oxygen) allow a water
molecule to form very strong hydrogen bonds with four other water molecules, resulting in a relatively
high boiling point.

11.93 Water has an exceptionally high specific heat capacity, which has a moderating effect on the climate of
coastal cities. Also, its high ∆vapH causes water evaporation and condensation to have a strong effect on
temperature. A tremendous amount of heat can be stored in large bodies of water. Heat will be absorbed
or released from large bodies of water preferentially over land around it. In some cities, such as
Vancouver, for example, the daily fluctuation in temperature can be less than 10 °C. This same moderating
effect occurs over the entire planet, two‐thirds of which is covered by water. In other words, without
water, the daily temperature fluctuations on our planet might be more like those on Mars, where
temperature fluctuations of 63 °C have been measured between early morning and midday.

Types of Solids and Their Structures

11.95 Given: X‐ray with λ  154 pm, maximum reflection angle of   28.3; assume n = 1
Find: distance between layers
Conceptual Plan: λ ,  , n  d
nλ  2d sin 

nλ 1  154 pm
Solution: nλ  2 d sin  . Rearrange to solve for d. d    162 pm.
2 sin  2 sin 28.3
Check: The units (pm) are correct. The magnitude (164 pm) makes sense since n = 1 and the sin is always
<1. The number is consistent with interatomic distances.

11.97 (a) 8 corner atoms  (1/8 atom / unit cell) = 1 atom / unit cell
(b) 8 corner atoms  (1/8 atom / unit cell) + 1 atom in centre = (1 + 1) atoms / unit cell = 2 atoms / unit cell
(c) 8 corner atoms  (1/8 atom / unit cell) + 6 face‐centred atoms  (1/2 atom / unit cell) = (1 + 3)
atoms/unit cell = 4 atoms / unit cell

11.99 Given: platinum, face‐centred cubic structure, r = 139 pm Find: edge length of unit cell and density (g cm–3)
Conceptual Plan: r  l and l  V (pm3)  V (cm3) and M, FCC structure  m then m, V  d
(1 cm)3 4 atoms M
l2 2 r V  l3 m  d  m /V
(1010 pm)3 unit cell N A

Solution: l  2 2r  2 2  139 pm  393.151 pm  393 pm and

(1 cm)3
V  l 3  (393.151 pm )3   6.07682  10 23 cm 3 and
(1010 pm )3
4 atoms M 4 atoms 195.09 g 1 mol g
m      1.295848  10 21 then
unit cell N A unit cell 1 mol 6.022  10 23 atoms unit cell

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Chapter 11 Liquids, Solids, and Intermolecular Forces 237

g
1.295848  10 21
m unit cell
d   21.3 cm 3
V cm 3
6.07682  10 23
unit cell
Check: The units (pm and g cm–3) are correct. The magnitude (393 pm) makes sense because it must be
larger than the radius of an atom. The magnitude (21 g cm–3) is consistent for Pt from Chapter 1.

11.101 Given: rhodium, face‐centred cubic structure, d = 12.41 g cm–3 Find: r (Rh)
Conceptual Plan: M, FCC structure  m then m, V  d then V (cm3)  l (cm)  l (pm) then l  r
4 atoms M 1010 pm
m  d = m/V V  l3 l2 2 r
unit cell N A 1 cm

4 atoms M 4 atoms 102.905 g 1 mol g

Solution: m       6.835271  10 22
unit cell N A unit cell 1 mol 6.022  10 23 atoms unit cell
g
6.835271  10 22 3
m m unit cell  5.507873  10 23 cm
then d  . Rearrange to solve for V. V  
V d 12.41 g cm 3 unit cell
then V  l 3 . Rearrange to solve for l.
1010 pm
l  3 V  3 5.507873  1023 cm 3  3.804831  108 cm   380.4831 pm then l  2 2r.
1 cm
l 380.4831 pm
Rearrange to solve for r. r  
 134.5 pm.
2 2 2 2
Check: The units (pm) are correct. The magnitude (135 pm) is consistent with an atomic diameter.

11.103 Given: polonium, simple cubic structure, d = 9.3 g cm–3; r = 167 pm; M = 209 g mol–1 Find: estimate NA
Conceptual Plan: r  l and l  V (pm3)  V (cm3) then d, V  m then M, SC structure  m
(1 cm)3 1 atom M
m 
3
l = 2r V  l d = m/V
(1010 pm)3 unit cell N A

(1 cm)3
Solution: l  2r  2  167 pm  334 pm and V  l 3  (334 pm )3   3.72597  10 23 cm 3 then
(1010 pm )3

m g 3.72597  10 23 cm 3 g
d . Rearrange to solve for m. m  d V  9.3   3.46515  10 22
V cm 3 unit cell unit cell
1 atom M
then m   . Rearrange to solve for NA.
unit cell N A
1 atom M 1 atom 209 g 1 unit cell
NA       6.0  10 23 atoms mol–1.
unit cell m unit cell 1 mol 3.46515  10 22 g
Check: The units (atoms mol–1) are correct. The magnitude (6  1023) is consistent with Avogadro’s number.

11.105 (a) atomic, since Ar is an atom

(b) molecular, since water is a molecule
(c) ionic, since K2O is an ionic solid
(d) atomic, since iron is a metal

11.107 LiCl has the highest melting point since it is the only ionic solid in the group. The other three solids are
held together by intermolecular forces, while LiCl is held together by stronger coulombic interactions
between the cations and anions of the crystal lattice.

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238 Chapter 11 Liquids, Solids, and Intermolecular Forces

11.109 (a) HOOH, there are more ways to make hydrogen bonds in HOOH than in CH3OH.
(b) SiCl4 because it has a higher molar mass and therefore has stronger dispersion forces
(c) Xe because it has a higher molar mass and therefore has stronger dispersion forces
(d) CaO because the ions have greater charge and therefore stronger coulombic interactions

11.111 The Ti atoms occupy the corner positions and the centre of the unit cell: 8 corner atoms  (1/8 atom / unit
cell) + 1 atom in centre = (1 + 1) Ti atoms / unit cell = 2 Ti atoms / unit cell. The O atoms occupy four
positions on the top and bottom faces and two positions inside the unit cell: 4 face‐centred atoms 
(1/2 atom / unit cell) + 2 atoms in the interior = (2 + 2) O atoms / unit cell = 4 O atoms / unit cell. Therefore,
there are 2 Ti atoms / unit cell and 4 O atoms / unit cell, so the ratio Ti:O is 2:4 or 1:2. The formula for the
compound is TiO2.

11.113 In CsCl: The Cs atoms occupy the centre of the unit cell: 1 atom in centre = 1 Cs atom / unit cell. The Cl
atoms occupy corner positions of the unit cell: 8 corner atoms  (1/8 atom / unit cell) = 1 Cl atom / unit cell.
Therefore, there is 1 Cl atom / unit cell and 1 Cl atom / unit cell, so the ratio Cs:Cl is 1:1. The formula for
the compound is CsCl, as expected.

In BaCl2: The Ba atoms occupy the corner positions and the face‐centred positions of the unit cell: 8 corner
atoms  (1/8 atom / unit cell) + 6 face‐centred atoms  (1/2 atom / unit cell) = (1 + 3) Ba atoms / unit cell =
4 Ba atoms / unit cell. The Cl atoms occupy eight positions inside the unit cell: 8 Cl atoms / unit cell.
Therefore, there are 4 Ba atoms / unit cell and 8 Cl atoms / unit cell, so the ratio Ba:Cl is 4:8 or 1:2. The
formula for the compound is BaCl2, as expected.

Cumulative Problems
11.115 The general trend is that melting point increases with increasing number of electrons. This is due to the
fact that the electrons of the larger molecules are held more loosely and a stronger dipole moment can be
induced more easily. HF is the exception to the rule. It has a relatively high melting point due to strong
intermolecular forces due to hydrogen bonding.

11.117 (a) i < iii < ii

The general trend is that boiling point increases with increasing number of electrons. This is due to the
fact that the electrons of the larger molecules are held more loosely and a stronger dipole moment can be
induced more easily. Since chlorine is a third period element this is even more the case than for
oxygen and nitrogen which are second period elements.

(b) iv < i < iii < ii

Compounds iv and i have only dispersion forces; therefore, the molecule with the larger number of
electrons has the higher boiling point. Compound iii has dipole–dipole interactions in addition to
dispersion forces, which increased the boiling point and Compound ii has H‐bonding, dipole–dipole
interactions, and dispersion forces and thus has the highest boiling point of the four compounds.
11.119 (a) All molecules shown in the plot partake in hydrogen bonding, but water is able to form a
network of hydrogen bonds. The boiling point for water, therefore, does not follow an “expected”
trend based on the figure.
(b) The boiling points of the alcohols increase as the alkyl chain gets larger because they have more
electrons and are more polarizable. The dispersion forces are thus increased.

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Chapter 11 Liquids, Solids, and Intermolecular Forces 239

11.121 Given: PH2 O  23.76 Torr at 25 °C; 1.25 g water in 1.5 L container Find: m (H2O) as liquid
Conceptual Plan: °C  K and Torr  atm then P, V, T  mol(g)  g(g) then g(g), g(l)i  g(l)f
1 atm 18.01 g
K = °C + 273.15 PV  nRT g(l)f  g( l)i  g( g )
760 Torr 1 mol
1 atm
Solution: T = 25 °C + 273.15 = 298 K, 23.76 Torr   0.0312632 atm then PV  nRT .
760 Torr
PV 0.0312632 atm  1.5 L
Rearrange to solve for n. n    0.00191768 mol in the gas phase then
RT L  atm
0.08206  298 K
K  mol
18.01 g
0.00191768 mol   0.0345375 g in gas phase then
1 mol
g(l)f  g(l)i  g(g)  1.25 g  0.0345375 g  1.22 g remaining as liquid. Yes, there is 1.22 g of liquid.
Check: The units (g) are correct. The magnitude (1.2 g) is expected since very little material is expected to
be in the gas phase.

11.123 Since we are starting at a temperature that is higher and a

pressure that is lower than the triple point, the phase tran‐
sitions will be gas  liquid  solid, or condensation fol‐
lowed by freezing.

11.125 The ideal gas law assumes that there are no forces between the molecules. At these high pressures,
ammonia molecules are closer to one another, so the hydrogen bonds between ammonia molecules are
able to take effect and will pull on one another strongly, decreasing the volume. This is different than for
something like argon, where even at these high pressures, the weak dispersion forces have little
effect on the volume. Argon will better obey the ideal gas law, even at these pressures.

11.127 Given: Ice: T1 = 0 °C exactly, m = 53.5 g; Water: T1 = 75 °C, m = 115 g Find: Tf

Other:  fus H   6.0 kJ mol 1 ; Cwater = 4.18 J g–1 °C–1
Conceptual Plan: qice = –qwater so g (ice)  mol (ice)  qfus (kJ)  qfus (J)  qwater (J) then
1 mol 6.02 kJ 1000 J
qwater  qice
18.01 g 1 mol 1 kJ

q, m, Cs  ΔT then Ti, T  T2 now we have slightly cooled water in contact with 0.0 °C water
q  mC S T T  T2  Ti

so qice = –qwater with m, Cs, Ti  Tf

q  mC S (Tf  Ti ) then set qice = –qwater
1 mol 6.02 kJ 1000 J
Solution: 53.5 g     1.78828  10 4 J, q water  qice  1.78828  10 4 J
18.01 g 1 mol 1 kJ
q 1.78828  10 4 J
q  mCs T . Rearrange to solve for ΔT. T    37.2017 C then
mCs J
155 g  4.18
g  C
T  T2  Ti . Rearrange to solve for T2. T2  T  Ti  37.2017 C  75 C  37.798 C
q  mCs (Tf  Ti ) substitute in values and set qice = –qwater.

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240 Chapter 11 Liquids, Solids, and Intermolecular Forces

J
qice  miceC ice (Tf  Ticei )  53.5 g  4.18  (Tf  0.0 C) 
g  C
J
q water   mwaterC water (Tf  Twater2 )  155 g  4.18  (Tf  37.798 C).
g  C
Rearrange to solve for Tf.
53.5 Tf  115(Tf  37.798 C)  53.5 Tf  115 Tf  4346.8 C  4346.8 C  168.5 Tf
4346.8 C
 Tf   25.8 C  26 C.
168.5
Check: The units (°C) are correct. The temperature is between the two initial temperatures. Since the ice
mass is about half the water mass, we are not surprised that the temperature is closer to the original ice
temperature.

11.129 Given: Home: 6.0 m  10.0 m  2.2 m; T = 30 °C, PH2 O  85% of PH 2 O Find: m (H2O) removed
Other: PH 2 O  31.8 Torr from text
Conceptual Plan: l, w, h  V (m3)  V (cm3)  V (L) and PH 2 O  PH2 O (Torr)  PH2O (atm) and
(100 cm)3 1L 1 atm
V  lwh PH2O  0.85 PH 2O
(1 m)3 1000 cm 3 760 Torr

°C  K then P, V, T  mol (H2O)  g (H2O)

18.01 g
K = °C + 273.15 PV  nRT
1 mol

(100 cm )3 1L
Solution: V  l w h  6.0 m  10.0 m  2.2 m  132 m 3    1.32  10 5 L,
(1 m)3 1000 cm 3

1 atm
PH2 O  0.85 PH 2 O  0.85  31.8 Torr   0.035566 atm, T  30 C  273.15  303 K,
760 Torr
then PV  nRT . Rearrange to solve for n.
PV 0.035566 atm  1.32  10 5 L 18.01 g
n   188.81 mol then 188.81 mol   3.4  10 3 g to remove.
RT L  atm 1 mol
0.08206  303 K
K  mol
Check: The units (g) are correct. The magnitude of the answer (ca. 3400 g) makes sense since the volume
of the house is so large. We are removing almost 200 moles of water.

11.131 CsCl has a higher melting point than AgI because of its higher coordination number. In CsCl, one anion
bonds to eight cations (and vice versa), while in AgI, one anion bonds only to four cations.

11.133 (a) Atoms are connected across the face diagonal (c), so c = 4r.
(b) From the Pythagorean Theorem c2 = a2 + b2, from part (a) c = 4r, and for a cubic structure a = l, b = l
so (4r )2  l 2  l 2  16r 2  2l 2  8r 2  l 2  l  8r 2  l  2 2r.

11.135 Given: diamond, V (unit cell) = 0.0454 nm3; d = 3.52 g cm–3 Find: number of carbon atoms in a unit cell
Conceptual Plan: V (nm3)  V (cm3) then d, V  m  mol  atoms
(1 cm)3 1 mol 6.022  10 23 atoms
d = m/V
(107 nm)3 12.01 g 1 mol

(1 cm)3 m
Solution: 0.0454 nm 3   4.54  10 23 cm 3 then d  . Rearrange to solve for m.
7
(10 nm) 3 V

g
m  dV  3.52  4.54  10 23 cm 3  1.59808  10 22 g then
cm 3

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Chapter 11 Liquids, Solids, and Intermolecular Forces 241

1.59808  10 22 g 1 mol 6.022  10 23 atoms C atoms C atoms

    8.01 8
unit cell 12.01 g 1 mol unit cell unit cell
Check: The units (atoms) are correct. The magnitude (8) makes sense because it is a fairly small number
and our answer is within calculation error of an integer.

11.137 (a) CO2(s)  CO2(g) at 194.7 K

(b) CO2(s)  triple point at 216.5 K  CO2(g) just above 216.5 K
(c) CO2(s)  CO2(l) at somewhat above 216 K  CO2(g) at around 250 K
(d) CO2(s)  CO2 above the critical point where there is no distinction between liquid and gas. This
change occurs at about 300 K.

11.139 Given: metal, d = 7.8748 g cm–3; l = 0.28664 nm, body‐centred cubic lattice Find: M
Conceptual Plan: l  V (nm3)  V (cm3) then d, V  m then m, FCC structure  M
(1 cm)3 2 atoms M
V  l3 d = m/V m 
(107 nm)3 unit cell N A

(1 cm)3 m
Solution: V  l 3  (0.28664 nm)3  0.02355105602 nm 3   2.355105602  10 23 cm 3 then d  .
(107 nm )3 V
g
Rearrange to solve for m. m  dV  7.8748  2.355105602  10 23 cm 3  1.854598559  10 22 g then
cm 3
2 atoms M
m  . Rearrange to solve for M.
unit cell N A
unit cell unit cell 6.022  10 23 atoms 1.854598559  10 22 g
M  NA  m     55.842 g mol 1
2 atoms 2 atoms 1 mol unit cell
 55.84 g mol 1 iron.
Check: The units (g mol–1) are correct. The magnitude (55.8) makes sense because it is a reasonable atomic
mass for a metal and it is close to that for iron.

Challenge Problems
11.141 Given: KCl, rock salt structure Find: density (g cm–3) Other: r (K+) = 133 pm; r (Cl–) = 181 pm from Chapter 8
Conceptual Plan: Rock salt structure is a face‐centred cubic structure with anions at the lattice points
and cations in the holes between lattice sites  assume r = r(Cl–), but M = M(KCl)
r(K+), r(Cl–)  l and l  V (pm3)  V (cm3) and, FCC structure  m then m, V  d.
(1 cm)3 4 formula units M
from Figure 11.55 l = 2r(Cl–) + 2r(K+) V  l3 m  d = m/V
(1010 pm)3 unit cell NA

Solution: l = 2r(Cl–) + 2r(K+) = 2(181 pm) + 2(133 pm) = 628 pm and

(1 cm)3
V  l 3  (628 pm )3   2.47673  10 22 cm 3 and
(1010 pm )3
4 formula units M 4 formula units 74.55 g 1 mol
m    
unit cell NA unit cell 1 mol 6.022  1023 formula units
g
 4.951976  10 22
unit cell
g
4.951976  10 22
m unit cell
then d    1.99940g cm 3  2.00 g cm 3
V cm 3
2.47673  10 22
unit cell

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242 Chapter 11 Liquids, Solids, and Intermolecular Forces

Check: The units (g cm–3) are correct. The magnitude (2 g cm–3) is reasonable for a salt density. The
published value is 1.98 g cm–3. This method of estimating the density gives a value that is close to the
experimentally measured density.

11.143 Decreasing the pressure will decrease the temperature of liquid nitrogen. Because the nitrogen is
boiling, its temperature must be constant at a given pressure. As the pressure decreases, the boiling point
decreases, and therefore so does the temperature. Remember that vaporization is an endothermic process,
so as the nitrogen vaporizes it will remove heat from the liquid, dropping its temperature. If the pressure
drops below the pressure of the triple point, the phase change will shift from vaporization to sublimation
and the liquid nitrogen will become solid.

11.145 Given: cubic closest‐packing structure = cube with touching spheres of radius = r on alternating corners
of a cube Find: body diagonal of cube and radius of tetrahedral hole
Solution: The cell edge length = l and l 2  l 2  (2r )2  2l 2  4r 2  l 2  2r 2 . Since body diagonal = BD is the
hypotenuse of the right triangle formed by the face diagonal and the cell edge we have
( BD)2  l 2  (2r )2  2r 2  4r 2  6r 2  BD  6r. The radius of the tetrahedral hole = rT is half the body
diagonal minus the radius of the sphere or
BD 6r  6   6 2  3 2  2 2   3  2 
rT  r  r   1 r   r   r    r  0.22474r.
2 2  2   2     2 
     2 2  

11.147 Given: 1.00 L water, Ti = 298 K, Tf = 373 K vapour; PCH4  1.00 atm Find: V (CH4)
Other:  comb H  (CH 4 )  890.4 kJ mol 1 ; Cwater = 75.2 J mol–1 K–1;  vap H  (H 2O)  40.7 kJ mol 1 , d = 1.00 g mL–1
Conceptual Plan: L  mL  g  mol then heat liquid water: n, Cs, Ti, Tf  q1water (J)
1000 mL 1.00 g 1 mol
1L 1.00 mL 18.01 g q  mC S (Tf  Ti )

vaporize water: nwater,  vap H   q2water ( J) then calculate total heat q1water, q2water  qwater (J) then
q  nH q1water  q2water  q water

qwater (J)   qCH4comb (J)  nCH4 finally nCH4 , P, T  V

qwater =  qCH4 comb q  nH PV  nRT

1000 mL 1.00 g 1 mol

Solution: 1.00 L     55.5247 mol H 2 O
1L 1.00 mL 18.01 g
J
q1water = nwater Cwater (Tf – Ti) = 55.5247 mol  75.2  (373 K  298 K)  3.1315936  10 5 J
mol  K
 313.15936 kJ,
kJ
q2water  n vap H  55.5247 mol  40.7  2.259855  10 3 kJ
mol
q1water + q2water = qwater  313.15936 kJ  2.259855  10 3 kJ  2.57301465  10 3 kJ
qwater  qCH4 comb  2.57301465  10 3 kJ then qCH4 comb  nCH4 comb H. Rearrange to solve for n.
qCH4 2.57301465  10 3 kJ
nCH 4    2.8897289 mol then PV = nRT.
 CH4 comb H kJ
890.4
mol
L  atm
2.8897289 mol  0.08206  298 K
nRT mol  K
Rearrange to solve for V. V    70.665085 L  70.7 L.
P 1.00 atm
Check: The units (L) are correct. The volume (71 L) is reasonable since we are using about 3 moles of
methane.

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Chapter 11 Liquids, Solids, and Intermolecular Forces 243

11.149 PTotal  PN2  PH2 O  Pethanol

PN2 : Use Boyle’s law to calculate P1V1  P2 V2 . Rearrange to solve for P2.
V1 1.0L
P2  P1  1.01 bar   0.3367 bar
V2 3.0L
For water and ethanol, we need to calculate the pressure if all of the liquid were to vaporize in the 3.0 L
apparatus. PV = nRT. Rearrange to solve for P.
nRT 1 mol L  bar 1
Pwater   2.0 g   8.314462  10 2  308 K   0.9479 bar H2O
V 18.01 g K  mol 3.00 L
Since this pressure is greater than the vapour pressure of water at this temperature (0.05576 bar), then
PH2 O = 0.05576 bar.
nRT 1 mol L  bar 1
Pethanol   0.50 g   8.314462  10 2  308 K   0.09264 bar ethanol
V 46.07 g K  mol 3.00 L
Since this pressure is less than the vapour pressure of ethanol at this temperature (0.1356 bar), all of the
liquid will vaporize and Pethanol  0.09264 bar.
Finally, the total pressure is
PTotal = PN2 + Pwater + Pethanol = 0.3367 bar + 0.05576 bar + 0.09264 bar
= 0.4851 bar = 0.46 bar or 0.48 atm (Remember 1 atm = 1.01 bar)

Conceptual Problems
11.151 A container with a larger surface area will evaporate more quickly because there is more surface area for
the molecules to evaporate from. Vapour pressure is the pressure of the gas when it is in dynamic equi‐
librium with the liquid (evaporation rate = condensation rate). The vapour pressure is dependent only on
the substance and the temperature. The larger the surface area, the more quickly it will reach this equilib‐
rium state.

11.153 The triple point will be at a lower temperature since the fusion equilibrium line has a positive slope. This
means that we will be increasing both temperature and pressure as we travel from the triple point to the
normal melting point.

11.155 The liquid segment will have the least steep slope because it takes the most kJ mol–1 to raise the
temperature of the phase.

11.157 The heat of fusion of a substance is always smaller than the heat of vaporization because the number
of interactions between particles that are broken is less in fusion than in vaporization. When we melt a
solid, the particles have increased mobility, but are still strongly interacting with other liquid particles.
In vaporization, all of the interactions between particles must be broken (gas particles have essentially no
intermolecular interactions) and the particles must absorb enough energy to move much more rapidly.

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