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M11 Tro4326 04 SSM C11
M11 Tro4326 04 SSM C11
M11 Tro4326 04 SSM C11
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
11.51 (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.
230
Copyright © 2023 Pearson Canada Inc.
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.
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.
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
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
J
75.0 g 0.449 22 C 2319.64 J
m CsTi q g C
Tf 91C.
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
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
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
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 ) qm
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
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?
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.
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.
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
l2 2 r V l3 m d m /V
(1010 pm)3 unit cell N A
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 l2 2 r
unit cell N A 1 cm
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.
11.107 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.
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.
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.
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.
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.
11.125 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.
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
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
(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
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
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 nH q1water q2water q water
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.