Introductory Chemistry Atoms First 5th

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Chapter

7
Intermolecular Forces
and the phases of Matter

7.1 See solution in textbook.

7.2 HF. Because F is more electronegative than Br, the dipole moment of the H–F bond is greater than
the dipole moment of the H–Br bond. Consequently, the partial charges in HF are greater than those
in HBr, resulting in a stronger attraction between HF molecules than between HBr molecules and a
higher boiling point for HF.
7.3

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7.4 H2O. Because O is more electronegative than S, the dipole moment of the O–H bonds is greater than
the dipole moment of the S–H bonds. Consequently, the partial charges in H2O are greater than those
in H2S, resulting in a stronger attraction between H2O molecules than between H2S molecules and a
higher boiling point for H2O.
7.5 See solution in textbook.
7.6 Both ethylene and polyethylene are nonpolar molecules. Therefore, the only intermolecular forces
involved are London forces. Polyethylene is a very large molecule containing many electrons, which
means many London forces between molecules and consequently a high melting point, making this
substance a solid at room temperature. The much smaller ethylene molecule contains a relatively
small number of electrons. This means relatively few London forces between molecules and low
melting and boiling points, making this substance a gas at room temperature.

7.7 (a) One electron from each H, five from N:

One electron from each H, five from P:

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 (b) NH3 is polar because the H–N electronegativity difference causes the bonding electrons to be
closer to the N. PH3 is nonpolar because there is no H–P electronegativity difference.
(c) In PH3, because this molecule has more electrons (18) than NH3 (10 electrons).
(d) PH3 because of stronger London forces. This is in fact not the case, however. See Practice
Problem 7.8 for additional information.
7.8 See solution in textbook.

7.9
7.10 (a) Because HF is the only one of the four compounds where the molecules can hydrogen bond.
(Hydrogen bonds are possible only with H–N, H–O, or H–F bonds.)
(b) Because HI has more electrons than HBr or HCl and therefore stronger intermolecular London
forces and a higher boiling point.
7.11 See solution in textbook.
7.12 Both iron and sodium chloride are nonmolecular solids. The forces holding iron and sodium chloride
together are true bonds—metallic bonds in iron and ionic bonds in NaCl. Because both bonds are
very strong, high temperatures are required to break them in order to melt either solid.
7.13 The intermolecular London forces holding the lattice together.
7.14 Ionic, network, and metallic solids have high melting points because true chemical bonds must be
broken in order to melt these substances. Molecular solids have low melting points because here
melting involves breaking only intermolecular attractive forces, which are weaker than true bonds.
(a) Metallic; the element Zr is classified as a metal.
(b) Metallic; the element Pb is classified as a metal.
(c) Ionic; Ca is a group 2 element that ionizes to Ca2+ , and it is combined with the nonmetal N in the
form of N 3- ions.
(d) Network; the very high sublimation point tells you this is a nonmolecular solid. The absence of
ions tells you it is not an ionic nonmolecular solid. That C is classified as a nonmetal tells you
graphite is not a metallic nonmolecular solid. Therefore it must be a network nonmolecular solid.
(e) Molecular; indicated by the low melting point.
7.15 They move constantly in straight-line paths at very high speeds, changing direction only when they
collide with one another or with the walls of their container.
7.16 (a) Cooling a gas slows the molecules down to a speed at which they are not moving fast enough to
overcome the attractive forces that cause them to condense to the liquid phase.
(b) The substance would remain gaseous as there would be no attractive forces causing gas parti-
cles to aggregate and form a more condensed phase. This is almost the case for helium, which

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 is made of very small He atoms. Helium remains gaseous at very low temperatures, all the way
down to 4 K! It then finally liquefies.
7.17 When heat is added to a substance, the average kinetic energy of particles increases, and so does
the speed with which they are moving. When enough heat is added, particles have too much kinetic
energy to maintain significant intermolecular attractions with one another. That’s when solids—in
which particles are relatively still—melt, and liquids—in which particles are moving in a more or less
“organized” fashion—boil. With an increase in the kinetic energy of particles, there is a progressive
weakening of intermolecular attractive forces, which ultimately get completely broken, resulting in the
formation of the least “organized” phase, namely, gas.
7.18 Yes. Molecules in the liquid phase are still very much in motion. They are jostling past one another
constantly but remain in close proximity to one another.
7.19 Heating causes the molecules of the liquid to move faster and faster until they have enough energy to
overcome the attractive forces holding them in the liquid phase. When they overcome the attractive
forces, they escape into the gas phase.
7.20 That the temperature at which H2O1g2 becomes H2O1l2 is much higher than the temperature at
which N21g2 becomes N21l2 tells you that water has the stronger intermolecular attractive forces.
The stronger these attractive forces, the higher the temperature at which the gas condenses.
7.21 Because in both solids and liquids the molecules are very close to one another. They are condensed
into a volume much smaller than what the gas phase occupies.
7.22 Because gas molecules are not bound to one another the way molecules in solids and liquids are. Gas
molecules are essentially independent of one another and can travel around in the entire volume of
their container.
7.23 Gases have the least order, with the molecules moving everywhere in the volume of the container.
Solids have the most order, with the molecules essentially fixed in position and unable to migrate.
The order in liquids is between that in solids and that in gases; the molecules are confined to the
liquid but free to migrate throughout the liquid.
7.24 (a) C–D. The greater dipole moment of C–D means stronger intermolecular attractive forces, which
means less energy needs to be removed from the liquid in order to form a solid. Therefore C–D
freezes at a higher temperature than the less polar A–B.
(b) C–D. The stronger intermolecular attractive forces mean more energy must be added to the liquid
in order for the molecules to overcome the attractive forces and escape into the gas phase.
7.25 The intermolecular forces holding the molecules together are dipole–dipole interactions.
δ +H Br δ−
δ+ δ− δ+ δ−
H Br H
•• •
Br
7.26 London forces are the result of the partial charge separation that develops and disappears
instantaneously. The charge separation is due to momentary electron imbalances and occurs
constantly in all molecules, both polar and nonpolar.
7.27 CBr4. Both molecules are nonpolar and therefore their liquid phase involves only London forces.
Because CBr4 is the larger molecule, it has more electrons and therefore stronger London forces.
The stronger the London forces, the higher the boiling point.
7.28 (1) Chloromethane is a polar molecule, and therefore the molecules in the liquid are subject to
dipole–dipole interactions, which are absent in the nonpolar CH4. (2) Chloromethane is the larger
molecule and therefore the molecules in the liquid experience stronger London forces.

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7.29 Because propane molecules are much smaller than octane molecules, there are weaker London forces
between propane molecules. Weaker London forces to overcome allow the propane molecules to
separate more easily and enter the gas phase.
7.30 The strength of London forces depends on the size of the molecules involved. For this reason, the
sum of the London forces holding a group of large molecules together can be greater than the
dipole–dipole forces holding a group of small molecules together.
7.31 (a) HF is more polar because the H–F electronegativity difference is greater than the H–Cl
electronegativity difference.
(b) For HF, because the partial charges in the HF molecules are greater than those in the HCl mol-
ecules, leading to a larger dipole moment in HF.
(c) HF. Because they have the larger dipole moment, HF molecules experience stronger intermolecu-
lar forces, and stronger intermolecular forces mean less energy needs to be removed to change
HF(g) to HF(l). That HF liquifies first is another way of saying HF has the higher condensation
temperature. Because condensation temperature (gas S liquid) and boiling temperature
(liquid S gas) are numerically equal, HF also has the higher boiling point.
(d) Yes; HCl experiences greater London forces because it is the larger molecule and so contains
more electrons.
7.32 Because the hydrogen bonds formed by the –OH groups are much stronger than the London forces
between molecules.
7.33 (a) CCl4; both molecules are nonpolar, so the only intermolecular attractive forces at work here
are the London forces, which correlate with the total number of electrons. CCl4 has more
electrons (74) than CS2 (38).
(b) Cl2; both molecules are nonpolar, so the only intermolecular attractive forces at work here are the
London forces, which correlate with the total number of electrons. Cl2 has more electrons (34)
than F2 (18).
(c) NH3; both molecules have a total of 10 electrons, so the London forces will not be a differentiat-
ing factor. Dipole–dipole intermolecular attractions as well as hydrogen-bonding are both
possible for the polar NH3 but are absent for the nonpolar CH4.
(d) CI4; while CI4 is nonpolar and can interact via London forces only, it has a much larger number
of electrons (218) than the polar CH3Cl (26). This example shows that, for large molecules, such
as CI4, London forces can provide stronger attractions than dipole–dipole interactions present
between some polar molecules.
7.34 Because waxes are very large molecules, they contain many electrons, and therefore the London forc-
es between wax molecules are quite strong, strong enough to make waxes solid at room temperature.
7.35 (b) will not form hydrogen bonds. Hydrogen bonds cannot form without the molecules containing
O–H, N–H, and/or F–H bonds. In a molecule of CH3OCH3 (dimethyl ether), there is no hydrogen
atom attached to the oxygen atom, as the Lewis dot diagram below shows:
H H
H C O C H
H H
7.36 The hydrogen atom has only one electron. For this reason, the atom resembles a naked proton when
bonded to a very electronegative atom, and its partial positive charge is very high because a proton

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 carries a full positive charge. The interaction between the highly d + H on one molecule and the
highly d - atom on another molecule is very strong.
7.37 The compound with the higher boiling point must have hydrogen-bonding.
7.38 (a) Because molecular size increases as you go from H2S to H2Se to H2Te. Larger molecules mean
more electrons, and therefore the intermolecular London forces to be overcome are greatest in
H2Te, giving this compound the highest boiling point.
(b) H2O is the only compound of the four in which hydrogen-bonding is possible.
7.39 We mean the momentary dipole caused (induced) in one molecule by instantaneous electron
imbalance in a neighboring molecule.
7.40 Because hydrogen bonds are not covalent bonds within a molecule (which we represent by solid
lines).
7.41 Because there are numerous N–H groups in the molecule. The H atom in an N–H can hydrogen bond
either to some other N in the molecule or to an O.
7.42 DNA molecules must be very stable but still able to break into two strands when involved in protein
building. Covalent bonds would be too strong to allow the strands to break apart, and London forces
would be too weak to provide the connection needed between the two strands.
7.43 If the nonpolar molecules are much larger than the polar molecules, the London forces in the nonpo-
lar liquid will be quite substantial and can be stronger than the dipole–dipole interactions in the polar
liquid. The greater London forces make the boiling point of the nonpolar liquid higher than that of
the polar liquid.
7.44 A molecular substance is made up of individual molecules. The substance is held together by inter-
molecular attractive forces between the molecules. A nonmolecular substance is an array of ions or
atoms bonded together by covalent, ionic, or metallic bonds. There are no discrete molecules in a
nonmolecular substance.
7.45 Sometimes. Compounds containing a group IA (1) or IIA (2) metal plus a nonmetal are usually ionic
and therefore nonmolecular. Metals are nonmolecular compounds. It is generally not possible, how-
ever, to look at the formula of a covalent compound and tell whether its solid phase is molecular or
nonmolecular.
7.46 A repeating pattern of positive and negative ions held together by ionic bonds.
7.47 Because nonmolecular solids are held together by much stronger forces—namely, covalent, ionic, or
metallic bonds. Molecular solids are held together only by the much weaker intermolecular attractive
forces—London forces, dipole–dipole interactions, and hydrogen bonding.
7.48 A network covalent substance is a nonmolecular solid that consists of a large network of atoms held
together by covalent bonds. Examples include diamond and quartz.
7.49 The high melting points of some metals, such as gold and iron, are evidence that metallic bonds can
be as strong as ionic or covalent bonds.
7.50 (a) KI; ionic bonds between K+ and I - ions are stronger than intermolecular forces (mostly hydrogen
bonds and dipole–dipole interactions) between molecules of HI.
(b) Na 2O; ionic bonds between Na+ and O2- ions are stronger than intermolecular forces (mostly
hydrogen bonds and dipole–dipole interactions) between molecules of H2O.
(c) CaF2; ionic bonds between Ca2+ and F - ions are stronger than intermolecular forces (mostly
hydrogen bonds and dipole–dipole interactions) between molecules of HF.

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 (d) SiO2; covalent bonds between Si and O atoms in the network solid of SiO2 are stronger than
intermolecular interactions between molecules of CO2.
7.51 (a) Metallic; potassium is classified as a metal.
(b) Ionic; made of K+ and Cl - ions.
(c) Network; the high melting point tells you this is a nonmolecular solid. The absence of ions tells
you it is not ionic, that P is a nonmetal tells you it is not metallic, and so it must be a network
nonmolecular solid.
(d) Molecular solid, indicated by the relatively low melting point.
7.52 The smaller the distance between two molecules, the greater the attraction between them.
7.53 Because the attraction is the result of opposite partial charges attracting each other to form a hydro-
gen bond. If the molecules are oriented d + to d + or d - to d - , there can be no hydrogen bond formed:

7.54 The molecules move faster and faster because the added heat energy increases their kinetic energy
(energy of motion).
7.55 Because density defines the number of molecules per unit volume, there must be more water
molecules per unit volume in the (denser) liquid phases than in the solid phase. (The molecules are
packed more tightly in the liquid phase.)
7.56 (d); (a) and (b) describe the solid phase; (c) describes the gas phase.
7.57 The intermolecular forces between Br2 molecules are greater than those between F2 molecules or
Cl2 molecules.
7.58 (a) and (b) because they are nonpolar molecules. The As–H bond is considered nonpolar because
the electronegativity difference for these two atoms is so slight 12.1 - 2.02; the molecular dipole
moment is therefore zero in AsH3, making the molecule nonpolar. CO2 is a linear molecule because
there are two bonding groups and no lone pairs around C, causing the two opposed C–O dipole
moments to cancel and make the molecule nonpolar:

H2O and SeCl2 are bent molecules because in each case there are two bonding groups and two lone
pairs around the central atom. Because of this nonlinear shape, the two bond dipole moments in each
molecule do not cancel. The molecular dipole moment is therefore nonzero, leading to dipole–dipole
intermolecular forces:

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7.59 CH4 because it is both smaller and nonpolar. That CH4 contains fewer electrons than CH2Cl2 means
weaker London forces in CH4 than in CH2Cl2; weaker London forces to overcome allows CH4 to
enter the gas phase at a lower temperature. That CH4 is nonpolar means there are no intermolecular
dipole–dipole attractions to be overcome. Because CH2Cl2 is slightly polar, there is also the possi-
bility of intermolecular dipole–dipole attractions, which require more heat energy to overcome and
therefore give CH2Cl2 a higher boiling point, making it more likely than CH4 to be liquid at room
temperature.
7.60 (d), because an H–N bond, H–O bond, or H–F bond must be present in order for hydrogen bonds to
form.
7.61 To determine relative boiling points, you must first determine the types of intermolecular forces in
each substance. The weaker these forces, the easier it is to separate the molecules and consequently
the lower the boiling point. (a) and (b) are nonpolar molecules, meaning only London forces. (c) has
an –OH group, which means hydrogen bonds. (d) is polar, which means dipole–dipole attractions.
Because hydrogen bonds are the strongest of the three, (c) should have the highest boiling point.
7.62 (b), because C2H2 is small and nonpolar, the only intermolecular forces are London forces. Weak
intermolecular forces mean it takes very little heat energy to get C2H2 molecules moving fast enough
to overcome the London forces and enter the gas phase. Both (a), an ionic compound, and (c), a
metal, typically have very high melting and boiling points. (d) is polar, and therefore the dipole–
dipole intermolecular forces are stronger than the London forces of (b).
7.63 (a) CH3OH hydrogen bonding; CH3Cl dipole–dipole forces; CH3CH3 London forces; CH3CH2CH3
London forces.
(b) CH3CH3 6 CH3CH2CH3 6 CH3Cl 6 CH3OH. The reason nonpolar CH3CH3 has a lower
boiling point than nonpolar CH3CH2CH3 is that CH3CH3 is smaller and therefore fewer London
forces are at work in a sample of CH3CH3.
7.64

7.65 In CH2Cl2, the d + portion of one molecule attracts the d - portion of another:

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7.66 (a) CH4 6 Cl2 6 Br2 6 CBr4
(b) All four molecules are nonpolar, meaning that in each liquid the only intermolecular forces
are London forces, which increase as the molecules become larger and therefore contain more
electrons. CH4 is the smallest of the four, with 10 electrons, followed by Cl2 (34 electrons),
Br2 (70 electrons), and CBr4 (146 electrons).
7.67 (a) H2 6 CH4 6 HCl 6 CH3OH
(b) H2 and CH4 are both nonpolar, meaning only the weakest intermolecular forces—London
forces—are operating. Because H2 has fewer electrons than CH4, H2 has weaker London forces
and therefore the lower boiling point. In polar HCl, dipole–dipole attractions are present, and
in polar CH3OH, the –OH means hydrogen-bonding is present. Because hydrogen bonds are
stronger than dipole–dipole interactions, HCl has a lower boiling point than CH3OH.
7.68 (a) and (d) because they are nonpolar. The two polar compounds, (b) and (c), experience dipole–
dipole intermolecular forces in addition to London forces. CBr4 is tetrahedral (four bonding groups,
no lone pairs around C), with the four Br arranged so that the individual bond dipole moments
cancel; the molecular dipole moment is therefore zero, and the molecule is nonpolar:

CH3Br is also a tetrahedron (four bonding groups, no lone pairs around C), but now there is only one
bond dipole moment because the three C–H bonds are considered nonpolar. The molecular dipole
moment is therefore nonzero, and the molecule is polar:

PBr3 is pyramidal (three bonding groups, one lone pair around P) and has a nonzero molecular dipole
moment, making it a polar molecule:

BBr3 has a trigonal planar shape (three bonding groups, no lone pairs around B). The three B–Br
dipole moments, because they are all in the same plane, cancel to give a zero molecular dipole
moment and a nonpolar molecule:

7.69 (a) London forces. Each B–F bond is polar, but the symmetry of the trigonal planar molecule causes
the three B–F dipole moments to cancel one another. The molecule is therefore nonpolar, and so
only London forces are possible.
(b) Hydrogen-bonding, because of the –OH group.

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 (c) London forces. That Xe is a noble gas tells you there are no ionic or covalent bonds. It’s not a
molecule and therefore you can rule out dipole–dipole interactions. Hydrogen-bonding is
impossible because there are no –OH, –NH, or –FH groups.
(d) Hydrogen-bonding, because of the HF “groups.”
(e) Both dipole–dipole and London forces present; dipole–dipole is the stronger force.
7.70 (a) because it is an ionic compound and (c) because it is a metal.
7.71 SiO2 is a network solid held together by covalent bonds. At room temperature, the atoms do not have
anywhere near the energy required to break these bonds, which means the substance is a solid.
In a sample of CO2, only London forces act between molecules. These forces are so weak that even
at room temperature the CO2 molecules have enough energy to overcome them, making CO2 a gas at
room temperature.
7.72 C2H6 6 CH3OH 6 NaCl 6 SiO2. Molecular substances generally have lower melting points than
nonmolecular substances, and the molecular substance with the weakest intermolecular forces is the
one with the lowest melting point. Because C2H6 is a molecular substance and has only nonpolar
C–H and C–C bonds, only London forces, the weakest intermolecular forces, are present. In CH3OH,
there is hydrogen-bonding because of the –OH group, and therefore this molecular substance has a
melting point higher than that of C2H6. NaCl is an ionic nonmolecular solid, and, as noted in the text-
book, SiO2 is a network nonmolecular solid. Thus you expect these two substances to have melting
points much higher than those of C2H6 and CH3OH. To get the proper ranking NaCl 6 SiO2, recall
that the textbook mentions the melting point of NaCl as being 800 °C and that of SiO2 as being above
1700 °C.
7.73 The substance having the stronger intermolecular forces has the higher boiling point, and hydrogen
bonds are stronger than London forces. Thus ethylene glycol boils at the higher temperature because
of the two –OH groups and the hydrogen-bonding they make possible. Pentane is essentially nonpo-
lar because it contains only nonpolar C–C and C–H bonds. For this reason, the only intermolecular
forces in pentane are London forces.
7.74

7.75 (a) Because C–C bonds are nonpolar, each graphite sheet must be nonpolar. This means the only at-
tractive forces between sheets are London forces.
(b) Because the London forces between sheets in graphite are relatively weak, the sheets can slip
past one another, making graphite slippery. The carbon atoms in diamond are all locked in
position by extremely strong covalent bonds, preventing the atoms from moving and making
diamond a very hard substance.

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7.76 Because in diamond and NaCl, melting involves breaking covalent and ionic bonds, respectively.
Melting ice, a molecular solid, requires breaking only hydrogen bonds. Because no covalent bonds
are broken when ice melts, this substance cannot be used for a covalent/ionic comparison.
7.77 The valence electrons in a piece of metal are free to move about the entire lattice of metal atoms.
7.78 Boiling point increases because the strength of the London forces between atoms increases down the
group as the number of electrons per atom increases.
7.79 Because eicosane is so large—a string of 20 carbon atoms bonded to 42 hydrogen atoms—it
contains a large number of electrons. The resulting London forces between molecules combine to
produce an overall intermolecular attraction that is stronger than the hydrogen-bonding between
water molecules. The substance with the greater intermolecular attraction has the higher melting and
boiling points.
7.80 Absolutely nothing because melting involves breaking bonds between molecules (intermolecular
bonds); it does not involve any covalent bonds inside the molecules (intramolecular bonds).
7.81 CO2 6 SO2 6 CH3CH2OH 6 Al. CO2 is nonpolar (linear shape), meaning only London forces are
possible. SO2 is polar (bent shape) and experiences stronger dipolar attractive forces between mol-
ecules, giving it a higher boiling point than CO2. Hydrogen-bonding is the strongest intermolecular
force in CH3CH2OH, giving this substance a higher boiling point than either CO2 or SO2. Al is a
metal, and the metallic bond is stronger than either London forces or hydrogen bonds, giving this
substance the highest boiling point of the four.
7.82 (a) goes with TiCl4 and (b) goes with ZrCl4 (even though each Zr is bound to six Cl atoms, the
bridging ones are only 1> 2 owned by each Zr atom). This makes TiCl4 a molecular compound, with
only weak London forces between the nonpolar molecules, giving rise to a low melting point. ZrCl4,
on the other hand, is nonmolecular (it is network covalent). To melt it requires breaking Zr–Cl polar
covalent bonds, which is quite difficult. Thus it has a very high melting point.
7.83 NH3 would appear to have too high a boiling point (it should be lower than NF3, not higher). The
reason it is higher is it can hydrogen bond. The hydrogen bonds between NH3 molecules make it
harder to boil.
7.84 The molecules are aligned such that the d - side of one is close to the d - side of another, and the
d + side of one is close to the d + side of another. Both are repulsive situations.
7.85 (b) would have the higher boiling point because it is polar and has both London forces and dipolar
forces of attraction between molecules. (a) is nonpolar and has just London forces of attraction
between molecules.
7.86 Going from a linear to a bent geometry would convert CO2 from nonpolar to polar, giving it another
(dipolar) intermolecular attractive force. This would increase its melting point.
7.87 Answers may vary. Examples are shown below.
(a) An ion–dipole interaction

(b) A dipole-induced dipole interaction

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 (c) A dipole–dipole interaction

(d) London forces

(e) Hydrogen-bonding
NA

7.88 (a) NA (b) NA (c)

7.89
In compound A the O and H form an intramolecular hydrogen bond, as shown above. Therefore
there is less intermolecular hydrogen-bonding than in compound B, where the hydrogen-bonding is
holding the molecules more tightly to each other.
7.90 4 6 2 6 3 6 1 6 5
The boiling points generally increase with an increase in molar mass. However, the compound
involving hydrogen-bonding (#3) has a much higher boiling point (b.p.) than would be expected
based on molar mass. Note also that the compound involving only London forces (#5) has the highest
b.p. because of its large molar mass.

Answers to Concept Questions:

1. (c), 2. (a), 3. (b), 4. (d), 5. (d), 6. (c), 7. (c), 8. (b), 9. (b), 10. (d)

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