Chapter 16 HW
Chapter 16 HW
Chapter 16
Liquid and Solids
7. Vapor Pressure: The pressure exerted by the vapor of a liquid when the vapor and the
liquid are in dynamic equilibrium. The vapor pressure reflects the fact that within a
system there is a distribution of energies that molecules can have, therefore, some
molecules will have enough energy to overcome the intermolecular forces and enter
into the gas phase. All liquids have some vapor pressure. The stronger the
intermolecular forces the smaller the vapor pressure. All solids also have a vapor
pressure. This is why if you leave ice in the freezer for a long time it “disappears.” The
vapor pressure of solids is less than the vapor pressure of liquids. As the temperature
increases the molecules have more energy, therefore, more molecules can escape into
the gas phase (vapor pressure increases). When the vapor pressure is equal to the
atmospheric pressure the solution boils.
9. a) Surface Tension
As the intermolecular forces increase (↑), surface tension increases (↑).
b) Viscosity
As the intermolecular forces increase (↑), the viscosity increases (↑).
c) Melting Point
As the intermolecular forces increase (↑), the melting point increases (↑).
d) Boiling Point
As the intermolecular forces increase (↑), the boiling point increases (↑).
e) Vapor Pressure
As the intermolecular forces increase (↑), the vapor pressure decreases (↓).
In order for Hydrogen bonding to occur there must be a hydrogen atom that is bonded
to an O, N, or F atom. Since O, N, and F are extremely electronegative they cause the
electron on hydrogen to spend most of the time around the O, N, or F. This generates a
partial positive charge on the hydrogen atom and a partial negative charge on the O, N,
or F atom. The partial positive charge on the H atom is attracted to a partial negative
charge on the O, N, or F atom in an adjacent molecule.
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In order for dipole-dipole forces to be present, a molecule must be polar. The partial
positive end of one molecule is attracted to the partial negative end of another
molecule. Hydrogen Bonding is just an extreme case of dipole-dipole forces. In both
cases a dipole must be present. The magnitude of the dipole is usually larger for
hydrogen bonding than pure dipole-dipole forces.
There is overlap between the strengths. Look at the table in problem 20 – benzene
(which only has London dispersion forces) has a higher boiling point than acetone
(which has dipole-dipole and London dispersion forces). Therefore, the London
dispersion forces must be greater than the dipole-dipole forces in this case.
13. ΔHfus is the energy needed for water to go from a solid to a liquid and ΔHvap is the energy
needed for water to go from a liquid to a gas. When water goes from a solid to a liquid
the molecules are still very close to each other, therefore, very few of the hydrogen
bonding forces will have to be overcome. When water goes from a liquid to a gas, the
molecules must spread out; therefore, most of the hydrogen bonding forces will have to
be overcome. This results in ΔHvap being larger than ΔHfus.
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16. a) OCS will have stronger intermolecular forces because it is a polar molecule
therefore, it will have dipole-dipole forces between molecule. While CO2 is a
nonpolar molecule therefore, there are only London dispersion forces between
molecules.
b) Both SeO2 and SiO2 are bent molecules making both of them polar which results
in them having the following intermolecular forces: dipole-dipole forces and
London forces. SeO2 will have stronger intermolecular forces because it is a
larger molecule than SO2 and the larger the molecule the less energy it takes to
generate instantaneous dipole moments.
c) H2NCH2CH2NH2 will have stronger intermolecular forces than CH3CH2CH2NH2
because H2NCH2CH2NH2 has the ability to form double the hydrogen bond with
neighboring molecules than CH3CH2CH2NH2.
d) H2CO will have stronger intermolecular forces than CH3CH3.
H2CO is a polar molecule and will have both dipole-dipole forces and London
dispersion forces while CH3CH3 is a non-polar molecule and will only have
London dispersions forces.
e) CH3OH will have stronger intermolecular forces than H2CO
Hydrogen-bonding can occur between neighboring molecules in CH3OH, where
as the strongest intermolecular force in H2CO is dipole-dipole forces.
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f) Highest boiling point, largest intermolecular forces
HF H-bonging, dipole-dipole, and London dispersion (highest boiling
point)
HCl dipole-dipole, and London dispersion
HBr dipole-dipole, and London dispersion
g) Lowest vapor pressure, largest intermolecular forces
CH3CH2CH3 London dispersion
CH3OCH3 dipole-dipole, and London dispersion
CH3CH2 CH2OH H-bonding, dipole-dipole, and London dispersion
(lowest vapor pressure)
19. a) The more spread out the molecule is the easier it is to align instantaneous dipole
moments. Therefore n-pentane (larger intermolecular forces) has a higher
boiling point than neopentane.
b) HF is capable of H-bonding while HCl is not, therefore, HF has a higher boiling
point than HCl.
c) LiCl is an ionic compound, which is ionic bonds which are stronger than any type
of intermolecular forces. Therefore, LiCl has a higher boiling point than HCl.
d) The larger the molecule the larger the London forces, therefore, n-hexane has a
larger boiling point than n-pentane.
All of the molecule are nonpolar therefore, the only intermolecular force that they have
is London dispersion forces. The larger the molecule the larger the London dispersion
forces. In addition, benzene/naphthalene are flat molecules make them able to get
closer to other benzene/naphthalene molecules which increases the strength of the
London dispersion forces.
Therefore in order of decreasing intermolecular forces
Naphthalene > benzene > carbon tetrachloride
Naphthalene would be expected to have the greatest boiling point, melting point, and
ΔHvap and carbon tetrachloride would be expected to have the smallest boiling point,
melting point, and ΔHvap
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Acetone Acetic acid Benzoic acid
If we look at all six molecules we might guess that the order of decreasing
intermolecular forces is:
benzoic acid>acetic acid>acetone>naphthalene>benzene>carbon tetrachloride
However, the data shows the acetone and naphthalene are out of place from what we
might expect. This is a result of two factors. Acetone is a small molecule, therefore,
although it does have dipole-dipole forces and London dispersion forces the London
dispersion forces are small due to the size making it seem out of order. Naphthalene
only has London dispersion forces but since it is a large flat molecule; the London
dispersion forces are large making it have a higher boiling point than acetic acid (which
is small) even though acetic acid is able to H-bond.
21. The only intermolecular forces that Ar has are London dispersion forces. Argon is a
small atom, therefore, the atom/molecule that has the boiling point closest to argon
must be small and only have London dispersion forces.
Cl2 London dispersion
HCl dipole-dipole, and London dispersion
F2 London dispersion
NaF Ionic
HF H-bonding, dipole-dipole, and London dispersion
F2 is smaller than Cl2, therefore, it is closer in size to argon causing F2 to have the closest
boiling point to argon.
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23. CH3CH2OH H-bonding, dipole-dipole, and London dispersion
CH3CH2CH3 London dispersion
CH3COCH3 dipole-dipole, and London dispersion
In order of increasing intermolecular forces:
CH3CH2CH3 < CH3COCH3 < CH3CH2OH
The greater the intermolecular forces the higher the boiling point.
As the intermolecular forces increase the boiling point increases.
In order of increasing boiling point:
CH3CH2CH3 < CH3OCH3 < CH3CH2OH
29. Water is a polar molecule and wax is a nonpolar molecule. The water molecules have
the lowest energy when surrounded by other polar molecules. If the water beads, then
more water molecules can be surround by the polar water molecules instead of by the
nonpolar wax molecules. Therefore, the overall energy for water to bead is less than if
the water lied flat on the wax surface. In addition, because water can H-bond it results
in additional stability for water molecules to be surrounded by other water molecules.
33. a) Crystalline solids form ordered arrays and amorphous solids do not.
b) Ionic solids are formed from a metal and a nonmetal held together by ionic
bonds (a positive ion attracted to a negative ion) and molecular solids are
formed from two nonmetals covalently bonded to form molecules. Molecules
held together by forces: intermolecular hydrogen-bonding, dipole-dipole, and/or
London forces.
c) In covalent network solids, the atoms form a covalent network through the
entire system (one large molecule all held together by sharing electrons) and in
molecular solids the molecules are discrete and held together by intermolecular
forces.
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d) In covalent network solids, the electrons are localized (insulators and
semiconductors) and in metallic solids, the electrons are delocalized (metals).
40. Molecular Solids: Are formed from covalent molecules that have relatively weak forces
between the molecules.
Covalent Networks: Are commonly formed by boron, carbon, and silicon atoms and
molecules. Instead of forming individual molecules, covalent networks have covalent
bonds through the extent of the solid.
Atomic Solids: Solid formed by only 1 type of atom. Note: If the elements form a
diatomic molecule, an atomic solid will not be formed and instead a molecular solid will
form.
Ionic Solids: Needs both a metal and a nonmetal to form.
Metallic Solids: Contain only metal elements.
a) Molecular b) Covalent network c) Atomic/Covalent network
d) Molecular e) Atomic/metallic f) Molecular
g) Ionic h) Molecular i) Ionic
j) Atomic/Metallic k) Ionic l) Molecular
m) Covalent network n) Ionic o) Molecular
p) Ionic
43. nλ=2dsinθ
(1)(1.54 Ȧ)=2dsin(14.22°)
d=3.13 Ȧ
45. Cubic closed pack systems (face centered cubic) - Fig 16.15 - have 4 atoms per unit cell
Calculate the mass of the Ca atoms
1 𝑚𝑜𝑙 𝐶𝑎 40.08 𝑔 𝐶𝑎 −22
4 𝐶𝑎 𝑎𝑡𝑜𝑚𝑠(6.022×10 23 𝐶𝑎 𝑎𝑡𝑜𝑚𝑠)( 1 𝑚𝑜𝑙 𝐶𝑎 ) = 2.66 × 10 𝑔
Calculate the volume of the unit cell
The atoms in the face of the unit cell touch. Therefore, the length of one of the sides of
the unit cell can be calculated using the Pythagorean Theorem.
ℎ2 = 𝑠12 + 𝑠22
(4𝑟)2 = 2𝑙 2
2
(4(197 × 10−10 𝑐𝑚)) = 2𝑙 2
𝑙 = 5.57 × 10−8 𝑐𝑚
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𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 = (5.57 × 10−8 𝑐𝑚)3 = 1.73 × 10−22 𝑐𝑚3
𝑚 2.66 × 10−22 𝑔 𝑔
𝑑= = = 1.54 𝑐𝑚3
𝑉 1.73 × 10−22 𝑐𝑚3
48. Faced centered cubic crystals have 4 atoms per unit cell.
𝑚
𝑑=
𝑉
If we calculate the volume of the unit cell we will be able to calculate the mass of the 4
atoms.
Calculate the volume of the unit cell
𝑚
𝑑=
𝑉
𝑔 𝑚
10.5 𝑐𝑚3 =
(4.09 × 10−8 𝑐𝑚)3
𝑚 = 7.18 × 10−22 𝑔
Calculate the mass of 1 atom
𝑚 7.18 × 10−22 𝑔
= = 1.80 × 10−22 𝑔
4 4
Calculate molar mass
1 𝑔
𝑚𝑁𝑎 = (1.80 × 10−22 𝑔) (6.022 × 1023 𝑚𝑜𝑙
) = 108 𝑚𝑜𝑙
Therefore, X is silver
81. A volatile liquid vaporizes easily. Volatile liquids have large vapor pressures. The
intermolecular forces are small in volatile liquids.
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86. The question wants us to find the boiling point, which is the temperature when the
vapor pressure equals the external pressure.
𝑃𝑣𝑎𝑝1 ∆𝐻𝑣𝑎𝑝 1 1
𝑙𝑛 ( )= ( − )
𝑃𝑣𝑎𝑝2 𝑅 𝑇2 𝑇1
At sea leave water boils at 100.°C. Therefore, at 100.°C the vapor pressure is 760. Torr.
𝐽
760. 𝑡𝑜𝑟𝑟 40,700 𝑚𝑜𝑙 1 1
𝑙𝑛 ( )= 𝐽 ( − )
520. 𝑡𝑜𝑟𝑟 8.3145 𝑚𝑜𝑙∙𝐾 𝑇2 373𝐾
𝑇2 = 363𝐾 = 90. ℃
The highest temperature that liquid water can be at is the boiling temperature.
Therefore, the question is asking what the pressure would have to be to raise the boiling
temperature of water to 350.°C.
𝐽
760. 𝑡𝑜𝑟𝑟 40,700 𝑚𝑜𝑙 1 1
𝑙𝑛 ( )= 𝐽 ( − )
𝑃𝑣𝑎𝑝2 8.3145 𝑚𝑜𝑙∙𝐾 623𝐾 373𝐾
𝑃𝑣𝑎𝑝2 = 147,000 𝑡𝑜𝑟𝑟
87. The question wants you to find the normal boiling point (which is the boiling point at 1
atm). At the boiling point the vapor pressure equals the external pressure. Before you
can calculate the normal boiling point you must determine ΔHvap.
𝑃𝑣𝑎𝑝1 ∆𝐻𝑣𝑎𝑝 1 1
𝑙𝑛 ( )= ( − )
𝑃𝑣𝑎𝑝2 𝑅 𝑇2 𝑇1
213 𝑡𝑜𝑟𝑟 ∆𝐻𝑣𝑎𝑝 1 1
𝑙𝑛 ( )= 𝐽 ( − )
836 𝑡𝑜𝑟𝑟 8.3145 𝑚𝑜𝑙∙𝐾 353𝐾 313𝐾
𝐽
∆𝐻𝑣𝑎𝑝 = 31,400 𝑚𝑜𝑙
Find the normal boiling point
𝐽
213 𝑡𝑜𝑟𝑟 31,400 𝑚𝑜𝑙 1 1
𝑙𝑛 ( )= 𝐽 ( − )
760. 𝑡𝑜𝑟𝑟 8.3145 𝑚𝑜𝑙∙𝐾 𝑇2 313𝐾
𝑇2 = 350. 𝐾 = 77℃
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∆𝐻𝑣𝑎𝑝 1
89. 𝑙𝑛(𝑃𝑣𝑎𝑝 ) = − (𝑇 ) + 𝐶
𝑅
8 y = -16695x + 18.744
7
6
5
ln(Pvap)
4
y = -19043x + 18.64 Li
3
2 Mg
1
0
0 0.0005 0.001 0.0015
T-1 (K-1)
You can plug in the pressure in any units that you want but the temperature must be in
Kelvin.
∆𝐻𝑣𝑎𝑝
− = −𝑠𝑙𝑜𝑝𝑒
𝑅
Li
∆𝐻𝑣𝑎𝑝
− 𝐽 = −19,043𝐾
8.3145 𝑚𝑜𝑙∙𝐾
𝑘𝐽
∆𝐻𝑣𝑎𝑝 = 158,000 𝑚𝑜𝑙
Mg
∆𝐻𝑣𝑎𝑝
− 𝐽 = −16,695𝐾
8.3145 𝑚𝑜𝑙∙𝐾
𝑘𝐽
∆𝐻𝑣𝑎𝑝 = 139,000 𝑚𝑜𝑙
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Mg
∆𝐻𝑣𝑎𝑝 𝑟𝑖𝑠𝑒
𝑠𝑙𝑜𝑝𝑒 = − =
𝑅 𝑟𝑢𝑛
∆𝐻𝑣𝑎𝑝 𝑙𝑛(760. 𝑚𝑚𝐻𝑔) − 𝑙𝑛(1 𝑚𝑚𝐻𝑔)
− 𝐽 = = −16,718𝐾
8.3145 𝑚𝑜𝑙∙𝐾 1 1
−
1383𝐾 893𝐾
𝐽 𝑘𝐽
∆𝐻𝑣𝑎𝑝 = 139,000 𝑚𝑜𝑙 = 139 𝑚𝑜𝑙
The bonding is stronger in Li than in Mg because you have to raise the temperature of
the Li higher than that of Mg to get to the same vapor pressure.
91.
Heat
Since ΔHvap is 4 times larger than ΔHfus line 4 should be 4 times longer than line 2.
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𝑞 = 𝑛𝐶∆𝑇 therefore, ∆𝑇 = 𝑛𝐶 𝑞 making the slope of the line inversely
proportional to the heat capacity. Since the solid had the largest heat capacity it
should have the smallest (least steep slope). The gas has the smallest heat
capacity, therefore, it should have the largest (most steep slope).
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103. A = Solid B = Liquid C = Gas
D = Solid and gas E = Solid, liquid, and gas F = Liquid and gas
G = Liquid and gas H = Gas
The triple point is E
The normal boiling point is where the dotted line (showing 1 atm) meets the liquid/gas
solid line between regions B and C. To get the temperature for the normal boiling point
read the temperature off the x axis.
The normal freezing point is where the dotted line (showing 1 atm) meets the
solid/liquid solid line between regions A and B. To get the temperature for the normal
freezing point read the temperature off the x axis.
The critical point is G
The solid is denser than the liquid. This can be determined by looking at the slope of the
line between the solid and the liquid. If you increase the pressure, at a constant
temperature, the slope of the line will result in more of the denser substance forming.
In this case more solid forms, therefore, the solid is denser than the liquid.
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