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Solutions Manual to accompany Introduction to Chemical Principles 11th 0321814630 / 97803218

CHAPTER 6
LIQUIDS AND SOLIDS

6.2 (a) London forces, dipole-dipole; (b) London forces, dipole-dipole;

(c) London forces, dipole-dipole; (d) London forces, dipole- dipole,
hydrogen bonding.

6.4 (b) and (d), O 2 and CO 2 do not have dipole moments.

6.6 (a) H 2Se (-42C vs. 61C) because H2Se has higher molar mass than H2S

and both molecules do not form hydrogen bonding; (b) NaCl (1413 oC vs.
23.8 oC) because it is an ionic compound as opposed to a molecular
compound; (c) NH3 (33 oC vs. 88 oC) because hydrogen bonding is
important in ammonia but not phosphine; (d) SiF4 (95.2 oC vs. 112 oC)
because it has more electrons with which to form stronger London forces.

6.8 (a) BF3 is a trigonal planar molecule whereas ClF3 is T-shaped. The

latter will be polar and should have the higher boiling point. BF3 boils at

99.9C; ClF3 boils at 11.3C. (b) SF4 is seesaw shaped whereas CF4 is

tetrahedral. The former should be polar and have the higher boiling point.
The greater number of electrons of SF4 also contribute to the higher

boiling point. SF4 boils at 40C; CF4 boils at 129C. (c) Both
molecules are planar but the cis form will have a dipole moment and the
trans form will not. This will give the cis form dipole-dipole interactions
not present in the other molecule, giving it the higher boiling point. The
cis compound boils at 60.3C whereas the trans compound boils at
47.5C.

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162 Chapter 6 Liquids and Solids

6.10 (a) Xe, the only intermolecular force between noble gases is London force,
and Xe has larger atomic size and stronger London force; (b) SF4,
because SF4 has dipole-dipole interaction that SF6 does not have. (c)
NH3, because NH3 has hydrogen bonding but not PH3(phosphine); (d)
K2S, because K2S has ion-ion interactions between ions, which is much
stronger than dipole-dipole interaction (and London (dispersion) forces) in
H2S.

6.12 Only molecules with H attached to the electronegative atoms N, O, and F

can hydrogen bond. Of the molecules given, only (b) CH 3 COOH and

(c) CH 3 CH 2 OH have hydrogen attached to oxygen, so these are the only

ones that can undergo hydrogen bonding.

6.14 Arrangement III should possess the strongest intermolecular attractions

because the molecules are oriented with hydrogen atoms directed toward
the lone pairs on nitrogen atoms of neighboring molecules. This geometry
allows hydrogen bonding to occur more readily than in arrangement I or
II.

6.16 Based on the Lewis structure of NO2 (bent) and N2O (linear) as shown
below, NO2 has dipole-dipole interaction intermolecular forces that N2O
does not have.

6.18 The ionic radius of Li+ is 76 pm and that of K+ is 138 pm. The ratio of
energies will be given by
 Chapter 6 Liquids and Solids 163

 Z 
Ep   

 d
2

 Z   1  
EpLi+   =  2 
d 
 (76  100) 
2
 
 Z    1  
EpK+   =  2 
d 
  (138  100) 
2


The electric dipole moment of the water molecule () will cancel:

E     1  / (76  100) 2    1 (238) 2 

Ratio  pLi =  =
2    = 1.83
2 
E     1  / (138  100)    1 (176) 
 pK 
The attraction of the Li+ ion will be stronger than that of the K+ ion
because it has smaller radius while the charge is the same as that of K+.

6.20 (a) Could be either true or false; (b) is in error; (c) justified by data; (d)
justified by data.

6.22 Yes, we would expect the energy of interaction between two rotating
molecules to be temperature dependent. As the temperature is raised, the
volume will increase, the molecules will be farther apart, r in the
denominator of Eq. 4 will increase, and the potential energy of interaction
will be reduced in magnitude. In addition, the rate of rotation will
increase with the temperature so the time when the dipoles are aligned
favorably is likely to be reduced.

6.24 (a) As temperature increases, boiling point will not change but it will
reach its boiling point sooner because increase of temperature will weaken
the intermolecular forces; (b) viscosity will decrease with the increase of
temperature because molecules move past one another easier at higher
temperature; (c) surface tension also decrease as the increase of
temperature because molecules are easier to be separated from each other
164 Chapter 6 Liquids and Solids

due to the input of thermal energy (harder to pull molecules together).

6.26 (a) Ethanol should have a greater viscosity than dimethyl ether because
ethanol can hydrogen bond while dimethyl ether cannot. (b) Propanone
(a.k.a. acetone) should be more viscous than butane because it is more
polar than butane.

6.28 C6H6 < H2O < CH3CH2OH < CH2OHCH2OH < CH2OHCHOHCH2OH
In order to predict relative viscosities we need to consider both the
strength of intermolecular forces and the tendency of the molecules to get
tangled like spaghetti (see Figure 5.13). Since glycerol,
CH2OHCHOHCH2OH, can form several hydrogen bonds per molecule
and it has a long chain structure, it has both strong intermolecular forces
and the tendency to get tangled. Ethylene glycol, CH2OHCH2OH, is just
one –CH-OH- unit smaller than glycerol, so we would expect it to be less
viscous than glycerol but more viscous than ethanol, CH3CH2OH. The
relative viscosities of ethanol, water, and benzene are given in Figure 5.12.

6.30 Molecules with stronger intermolecular forces tend to have higher surface
tension. Using this principle along with the data given in Table 5.3 we can
match the values with the substances as follows: H2O 72.75,
CH3(CH2)4CH3 18.43, C6H6 28.85, CH3CH2OH 22.75, CH3COOH 27.80.
Note that units for surface tension are mN/m.

6.32 Hydrogen ions can “migrate” through a solution much faster than other
ions because they essentially do not really have to move at all. The
hydrogen bonding network readily allows the shifting of hydrogen bonds,
so that a proton can become available in solution almost instantaneously
anywhere without any specific individual proton actually having to move
any great distance. It amounts to the migration of a unit of positive charge
through the network of hydrogen-bonded water molecules. Any other
 Chapter 6 Liquids and Solids 165

molecule or ion would have to migrate through the solution normally, as

an intact unit.

6.34 Assuming that we can ignore any elliptical deformation of the cross-
sectional area occupied by the liquid in the tube as it is tilted, and that the
surface tension is a constant, all of the factors in the expression seem to be
independent of the tip angle,   However, we should note that when the
tube is verticle, i.e.,  = 0°,
2
h  l cos 
gdr

where l is the length of the tube occupied by liquid and cos  0   1 . As

 gets larger, cos  gets smaller. Since all of the factors on the right-
hand side of the equation are constant, it appears that we can expect the
height of the meniscus above the zero level, h , to remain the same while
the length of the liquid in the tube, l , grows in counterbalance to the
decrease in cos  .
[Note that some physics textbooks represent the height to which a liquid
will rise in a capillary tube in terms of a contact angle,  , between the
liquid and the side of the tube. This angle reflects the difference between
liquid-solid and liquid-vapor surface tensions. It is not the same as the tip
angle called  in this problem.]

6.36 (a) Solid methane is held together only by London forces, whereas
chloromethane is held in solid form by both London forces and dipole-
dipole forces. Acetic acid will exhibit London forces, dipole-dipole
interactions, and hydrogen bonding. (b) The melting points should
increase in the order:
CH 4 (183C)  CH 3 Cl (  97C)  CH 3 COOH (16C) .

6.38 (a) ionic; (b) molecular; (c) network; (d) ionic; (e) metallic
166 Chapter 6 Liquids and Solids

6.40 Substance X: molecular solid; substance Y: network; substance Z: ionic

6.42 For a picture of the simple, a.k.a. primitive, cubic unit cell, see Figures
5.28 and 5.33a. (a) There are eight atoms at the eight corners of the unit
cell. One-eighth of each of these atoms will lie in the unit cell for a total of
one atom per unit cell. (b) Each atom will be bonded to six atoms that
form an octahedron. (c) The edge length of the unit cell for a primitive
cubic cell will be twice the atomic radius of the atom or 334 pm in this
case.

6.44 (a) In a fcc structure, there are 4 atoms in each unit cell, a = length of
side for a unit cell = 81/2r, The atomic mass (M) of strontium is 87.62
g·mol-1
4M / N A 4M
d= =
(8 r )
1/ 2 3
N A (81 / 2 r )3

4 atoms  (87.62 g  mol 1 )

= 1 8
= 2.59 g·cm-3
(6.022  10 atom  mol )  (8  2.15  10 cm)
23 1/ 2 3

(b) In a bcc structure, there are 2 atoms in each unit cell, and a = the
length of the side of a bcc unit cell = 4r/31/2. The atomic mass (M) of
europium is 151.97 g·mol-1. The density of europium is:
2M / N A 2M
d= =
( 4r / 3 )
1/ 2 3
N A (4r / 31 / 2 )3

2 atoms  (151.97 g  mol 1 )

= 1 8
= 4.83 g·cm-3
(6.022  10 atom  mol )  (4  2.04  10 cm / 3 )
23 1/ 2 3

6.46 a  length of unit cell edge

mass of unit cell
V 
d
 Chapter 6 Liquids and Solids 167

 107.87 g Ag 
(1 unit cell)  
(a) V  a 3   mol Ag  
10.5 00 g  cm3
 1 mol Ag   4 atoms 
  
 6.02 21 10 atoms Ag   1 unit cell 
23

a  4.08 64  108 cm

2a 2 (4.08 64  108 cm)

For an fcc cell, a  8 r,  r 
4 4
8
 1.44 48  10 cm or 144.48 pm

 52.0 0 g Cr 
(1 unit cell)  
(b) V  a 3   1 mol Cr  
7.19 0 g  cm3
 1 mol Cr   2 atoms 
  
 6.02 2  10 atoms Cr   1 unit cell 
23

a  2.88 5  108 cm
3a 3 (2.88 5  108 cm)
r   1.24 9  108 cm  124.9 pm
4 4

6.48 Let’s assume that vanadium metal structure is ccp (fcc). In ccp structure,
there are 4 rhodium atoms in each unit cell. The atomic mass (M) of
vanadium is 50.942 g·mol-1. Therefore, the density of vanadium is:
d = m/a3, m = mass of one unit cell = 4M/NA, a = the length of the side of
a fcc unit cell = 81/2r
4M / N A 4M
d= =
(8 r )
1/ 2 3
N A (81 / 2 r )3

4 atoms  (50.942 g  mol 1 )

= = 6.50 g·cm-3
(6.022  10 23 atom  mol 1 )  (81 / 2  1.32  10 8 cm) 3
Then we assume the vanadium metal structure is bcc. In bcc structure,
there are 2 vanadium atoms in each unit cell, and a = the length of the side
of a bcc unit cell = 4r/31/2. The density of vanadium is:
168 Chapter 6 Liquids and Solids

2M / N A 2M
d= =
( 4r / 3 )
1/ 2 3
N A (4r / 31 / 2 )3

2 atoms  (50.942 g  mol 1 )

= = 5.97 g·cm-3
(6.022  10 23 atom  mol 1 )  (4  1.32  10 8 cm / 31/ 2 ) 3
The density value for the bcc structure is closer to 6.11 g·cm-3. Therefore,
vanadium metal is body-centered cubic structure.

6.50 (a) In the fcc geometry, the unit cell will contain four atoms of Kr. The
density will be given by
4 atoms 83.80 g Kr 1 mol Kr
mass in unit cell   
unit cell mol Kr 6.022  1023 atoms
 5.566  1022 g  unit cell1
3
 1012 m 100 cm 
volume of unit cell   559 pm   
 pm m 
 1.75  1022 cm3  unit cell1

mass in unit cell 5.566  1022 g  unit cell1

density   22 1
 3.18 g  cm3
volume of unit cell 1.75  10 cm  unit cell
3

(b) The face diagonal of the unit cell will equal four times the radius of
the Kr atom:
2a4r
2a 2 (559 pm)
r   198 pm
4 4
4 4
(c) V   r 3   (198 pm)3  3.25  107 pm3
3 3
(d) Volume occupied by the four Kr atoms in one unit cell
 4(3.25  107 pm3 )  1.30  108 pm3 . The volume of the unit will be

(559 pm)3  1.75  108 pm3 . The percent of occupied space will be given
by
1.30  108 pm3
 100  74.3% . The percent of empty space is 25.7%.
1.75  108 pm3
 Chapter 6 Liquids and Solids 169

6.52 Recall from plane geometry that in an equilateral triangle, the altitudes,
perpendicular bisectors of the sides, and angle bisectors coincide and
divide each other in the ratio 2:1.

Since the vertical line in the sketch above is the altitude, a , of the
equilateral triangle that connects the centers of the large circles, we can set
a  3 x . Then two-thirds of its length is below the center of the small
circle. From the sketch, we can see that 2 x  rlarge  rsmall .

We can use the Pythagorean Theorem to get x in terms of rlarge .

(2rlarge ) 2  rlarge
2
 a2
a 2  3rlarge
2

a  3rlarge  3 x
rlarge
x
3
Recall 2 x  rlarge  rsmall , so

 rlarge 
2   rlarge  rsmall
 3 
rsmall  1.1547 rlarge  rlarge  0.1547 rlarge

In other words, the radius of the cavity is 15.5% as large as the radius of
the large disks. A CD has a radius of 61 +/−1 mm with a measured cavity
170 Chapter 6 Liquids and Solids

radius between three close-packed disks of 9 +/−1 mm. This experimental

result is in good agreement with our geometrical treatment since
0.155  61  9.5 .

6.54 (a) Each unit cell of Uranium carbide has 4 uranium and 4 carbon.
Uranium carbide has a (6,6)-coordination. (b) The formula of
uranium carbide is UC.

6.56 (a) anions: 8 corners  18 atom  corner 1  6 faces  12 atom  face 1  4

atoms; cations: 12 edges  14 atom  edge 1  1 atom in center  4 atoms;

the cation to anion ratio is thus 4 : 4 or 1 : 1.
(b) calcium ions at corners of cell and at face centers:
8 corners  18 atom  corner 1  6 faces  12 atom  face 1  4 atoms; fluoride
ions:
8 atoms in tetrahedral sites within the face-centered cubic lattice of Ca2+
ions; these atoms lie completely within the unit cell.
Ratio of Ca : F = 4 : 8 or 1 : 2, giving an empirical formula of CaF2
(c) CaF2 has (8,4)-coordination

6.58 (a) Uranium oxide has (8,4)-coordination (each uranium has 8 oxide ions
and each oxide ion has 4 uranium ion); (b) 8 atoms in tetrahedral sites
within the face-centered cubic lattice of uranium ions; these atoms lie
completely within the unit cell. Ratio of U : O = 4 : 8 or 1 : 2, giving an
empirical formula of UO2

133 pm
6.60 (a) ratio   0.796, predict cesium-chloride structure with (8,8)
167 pm
coordination;
 Chapter 6 Liquids and Solids 171

102 pm
(b) ratio   0.464, predict rock-salt structure with (6,6)
220 pm
coordination;
100 pm
(c) ratio   0.543, predict rock-salt structure with (6,6)
184 pm
coordination;

6.62 (a) In the rock-salt structure, the unit cell edge length is equal to two
times the distance between centers of the oppositely charged ions. Thus
for MgO, a = 2 × 212 pm = 424 pm. The volume of the unit cell will be
given by converting to cm3:
3
 1010 cm  -23 3
V =  424 pm   = 7.62  10 cm
 1 pm 
There are four formula units in the unit cell so the mass in the unit cell will
be given by
40.31 g MgO
4 MgO molecules 
1 mol MgO
mass in unit cell = = 2.68  10-22 g
6.022  10 molecules  mol 1
23

The density will be given by the mass in the unit cell divided by the
volume of the unit cell:
2.68 1022 g
d= 23
= 3.52 g·cm-3
7.62 10 cm 3

(b) For the cesium-chloride structure, it is the body diagonal that

represents two times the distance between the cation and anion centers.
Thus the body diagonal is equal to 568 pm.
For a cubic cell, the body diagonal = 3 a = 568 pm; a = 328 pm
3
3  1010 cm 
V = a =  328 pm   = 3.53  10-23 cm-3
 1 pm 

There is one formula unit of CaS in the unit cell, so the mass in the unit
cell will be given by
172 Chapter 6 Liquids and Solids

72.144 g CaS
1 CaS molecules 
1 mol CaS
mass in unit cell = 1
= 1.20  10-22 g
6.022  10 molecules  mol
23

1.20  1022 g
d=  23
= 3.40 g·cm-3
3.53  10 cm 3

 133 pm 
6.64 (a) ratio =   = 0.88, predict cesium-chloride structure.
 151 pm 

 151 pm 
(b) ratio =   = 0.69, predict rock-salt (NaCl) structure.
 220 pm 

6.66 (a) The volume of each unit cell is (562.8 pm)3. The volume of the whole
single crystal of NaCl is (1.00 mm)3 or (1.00 x 109 pm)3. The number of
 (1.00  109 pm)3  18
unit cells is:   = 5.61 x 10 unit cells
 (562.8 pm) 
3

(b) Each NaCl unit cell contains 4 NaCl. The moles of NaCl present in
 4 NaCl molecules 
the crystal: 5.61 x 1018 unit cells x  x
 1unit cell 

 1mole NaCl  -5
  = 3.73 × 10 mole NaCl
 6.022  10 NaCl molecule 
23

6.68 (a) The N atoms fit the pattern for a trigonal planar arrangement of three
objects—two bonds and one lone pair for one nitrogen atom, and three
bonds for the other. This corresponds to sp2 hybridization. The bond
angles are all close to 120 .

O
H3C

N N
O
CH3
O
 Chapter 6 Liquids and Solids 173

(b) The multiple bond structure of this molecule gives rise to the rigid
rod-like nature of the molecule. The alternating double bonds that allow
electrons to be delocalized extend from one ring across the bridging N
atoms to the other ring. To maintain the delocalization, the phenyl rings do
not rotate about the O—N axis. Thus, the entire molecule is like a stiff,
flat rod. Only the CH3 groups rotate. Another feature that enhances the
tendency to form liquid crystalline materials is the inclusion of the
aromatic rings. The  -bonds in aromatic rings show a strong tendency to
stack one upon another; this helps orient the molecules in the liquid
crystalline array. (c) There is an infinite number of answers here.
Basically, any molecule that has a fairly rigid backbone structure without
too many dangling appendages to interfere with the packing will be a
possible liquid crystalline material.

6.70 The strategy employed here is simply to modify the attached groups with a
view toward disrupting some of the London interactions that the molecule
will have with its neighbors, thus allowing the molecules more freedom to
move with respect to each other—if the intermolecular forces are too
strong, the material will be held in the solid state longer. One must be
careful, because too much disruption of these forces will also destroy the
liquid crystal order as well. This is still a matter of trial and error in many
cases. For example, the molecule

O
H3C

C N
H
CH3
C
CH3
CH3
174 Chapter 6 Liquids and Solids

is very similar to p-azoxyanisole but has a liquid crystal range of 21C–

47C. It would be expected that the bulky t-butyl group (C(CH 3 )3 )

would help to disrupt the orderly packing of the molecule.

6.72 The rodlike shape enable the molecules to stack together like dry,
uncooked spaghetti: they lie parallel to one another but free to slide past
one another along their long axes. The polar groups will line the molecules
up like soldiers on parade (aligned in rows) and form double layers, with
their polar heads facing outward on each side of the sheet (when they are in
contact with polar solvent such as water).

6.74 Substance (b), C11H14N+Br-, would be a better choice as an ionic liquid

solvent. The reason is that it has a relative larger organic cation, which has
a large nonpolar region to dissolve nonpolar organic compounds.
Substance (a) is not an ionic liquid.

6.76 (a) The PF3 Lewis structure is:

, the molecular shape is trigonal pyramidal and it is a polar

molecule. It can participate dipole-dipole interactions.
(b) The PF5 Lewis structure is:

, the molecular shape is trigonal bipyramidal and it is a

nonpolar molecule. It cannot participate dipole-dipole interactions.
 Chapter 6 Liquids and Solids 175

6.78 (a) The ion-ion potential energy ratio will be given by

z1 z2
V
d
zz
VLiCl  1 2
d Li-Cl
z1 z2
VKCl 
d K-Cl
z1 z2 1
V   d Li-Cl d d
ratio  Li
V     Li-Cl  K-Cl
z1 z2 1 d Li-Cl
 K 
d K-Cl d K-Cl
From the ionic radii in Figure 1.48 we can calculate the LiCl and KCl
distances to be
d Li-Cl  76 pm  181 pm  257 pm
d K-Cl  138 pm  181 pm  319 pm
319 pm
ratio   1.24
257 pm
(b) The ratio for the ion-dipole interaction is derived as follows:
 z 
V
d2
 z  1 
VLi  
d2 (76) 2
 z  1 
VK   
d2 (138) 2
The electric dipole moment of the water molecule () will cancel:

V    1  /(76) 2 (138) 2
ratio  Li
V      3.30
  1  /(138)
2
 K (76) 2

(c) Because the ion-dipole interactions are proportional to d 2 and the ion-
ion interactions directly proportional to d, the relative importance of
hydration will be much larger for the smaller lithium ion.

6.80 (a) A body-centered cubic lattice has two atoms per unit cell. For this cell,
the relation between the radius of the atom r and the unit cell edge length
176 Chapter 6 Liquids and Solids

a is derived from the body diagonal of the cell, which is equal to four
times the radius of the atom. The body diagonal is found from the
Pythagorean theorem to be equal to
3 a.
4r 3a
4r
a
3
The volume of the unit cell is given by
3
4r
V a  
3

 3
If r is given in pm, then a conversion factor to cm is required:
3
 4 r 1012 m 10 cm 
V a  3
  
 3 pm m 

Because there are two atoms per bcc unit cell, the mass in the unit cell will
be given by
 2 atoms   M 
mass    1 
 unit cell   6.022 10 atoms  mol 
23

The density will be given by

 2 atoms   M 
  1 
mass of unit cell unit cell   6.022  10 atoms  mol 
23

d  3
volume of unit cell  4 r 1012 m 100 cm 
   
 3 pm m 
 2 atoms   M 
  1 
unit cell   6.022  10 atoms  mol 
23


 2.309  1010 r 
3


 2.698  10  M
5

r3
or

r 3
 2.698  10  M
5

density
 Chapter 6 Liquids and Solids 177

where M is the molar mass in g  mol1 and r is the radius in pm.

For the fcc unit cell, the relation between the radius of the atom r and the
unit cell edge length a is
4r 2 a
4r
a
2
The volume of the unit cell is given by
3
4r
V a  
3

 2
If r is given in pm, then a conversion factor to cm is required:
3
 4 r 1012 m 100 cm 
V a   3
 
 2 pm m 

Because there are four atoms per fcc unit cell, the mass in the unit cell will
be given by

 4 atoms   M 
mass    1 
 unit cell   6.022  10 atoms  mol 
23

The density will be given by

 4 atoms   M 
  1 
mass of unit cell unit cell   6.022  10 atoms  mol 
23

d  3
volume of unit cell  4 r 1012 m 100 cm 
   
 2 pm m 
(2.936  105 ) M

r3
or

(2.936  105 ) M
r 3
d
where M is the molar mass in g  mol1 and r is the radius in pm.
Setting these bcc and fcc equations equal to each other (because both are
equal to r) and cubing both sides, we obtain
178 Chapter 6 Liquids and Solids

(2.936  105 ) M (2.698  105 ) M


d fcc d bcc
The molar mass M is the same and will cancel from the equation.
(2.936  105 ) (2.698  105 )

d fcc d bcc
Rearranging, we get
(2.936  105 )
d fcc  d bcc
(2.698  105 )
 1.088 d bcc
(c) For the different alkali metals, we calculate the results given in the
following table:

Gas Density bcc Density fcc Molar mass Radius (pm)

3 3 1
(g cm ) (g cm ) (g  mol )
Li 0.53 0.58 6.94 152
Na 0.97 1.0 22.99 186
K 0.86 0.94 39.10 231
Rb 1.53 1.66 85.47 247
Cs 1.87 2.03 132.91 268

(d) Li, Na, and K all have densities less than that of water and should
float, but not for long, as they all react violently with water to form
MOH(aq) and H 2 (g) .

6.82 The number of oxide ions is equal to 12 edges  1

4 oxide ion in the unit
cell per edge, for a total of three. For the niobium atoms, there will be six
faces with 1
2 of the niobium atom per face inside the cell, also for a total
of three. The empirical formula will be NbO, with three formula units in
the unit cell.
 Chapter 6 Liquids and Solids 179

6.84 (a) The oxidation state on uranium must balance the charge due to the
oxide ions. If 2.17 oxide ions are present with a charge of 2 per oxide
ion, then the uranium must have an average oxidation state of +4.34.
(b) This is most easily solved by setting up two equations in two
unknowns. We know that the total charge on the uranium atoms present
must equal +4.34, so if we multiply the charge on each type of uranium by
the fraction of uranium present in that oxidation state and sum the values,
we should get 4.34.
Let x = fraction of U 4 , y = fraction of U5 , then
4x + 5y = 4.34
Also, because we are assuming that all the uranium is either +4 or +5, the
fractions of each present must add up to 1:
x+y=1
Solving these two equations simultaneously, we obtain y = 0.34, x = 0.66.

6.86 (a) False. In order for the unit cell to be considered body centered, the
atom at the center must be identical to the atoms at the corners of the unit
cell. (b) True. The properties of the unit cell in general must match the
properties of the bulk material. (c) True. This is the basis for Bragg's
law. (d) False. The angles that define the values of the unit cell can have
any value, the only restriction being that opposing faces of the unit cell
must be parallel.

6.88 There are several ways to draw unit cells that will repeat to generate the
entire lattice. Two examples are shown below. The choice of unit cell is
determined by conventions that are beyond the scope of this text (the
smallest unit cell that indicates all of the symmetry present in the lattice is
typically the one of choice).
180 Chapter 6 Liquids and Solids

(a)

(b)

6.90 (a) The gases with the larger van der Waals’ a parameter are: (i) Ne;
(ii) O2; (iii) CO2; (iv) H2CO; (v) CH3(CH2)10CH3. (b) The gases with the
larger van der Waals’ b parameter are: (i) Br2; (ii) F2; (iii) CH3CH2CH3;
(iv) Kr; (v) SO2.

6.92 (a) The octahedral hole is considerably bigger than the tetrahedral hole
and can accommodate an ion with a radius about 3.7 times that of the
tetrahedral hole.
(b) If the anions are close packed in a cubic close-packed array, the unit
cell will be a fcc unit cell. The octahedral sites will lie at the body center
 Chapter 6 Liquids and Solids 181

of the cell and at the center of each edge. If the unit cell is divided into
octants, then there will be a tetrahedral site at the center of each octant. In
the cubic close-packed geometry, the face diagonal of the unit cell will
represent four times the radius of the anion:
4 rAnion  a 2

If a cation occupies the octahedral site along the unit cell edge (a cation at
the very center of the cell will be identical), then the maximum size it can
have if the anions are close-packed will be when 2 rAnion  2 rCation  a .
Combining these two relationships, we see that the radius of the cation
will be
a 2 a 2 2 2
2 rCation, octahedral  a  2 rAnion  a  2    a   a  
 4  2  2 
The distance between the cation and the anion in a tetrahedral site will be
given by 1
4 the body diagonal of the cell, which will correspond to

rCation, tetrahedral  rAnion .

a 3
rCation, tetrahedral  rAnion 
4
a 3 a 3 a 2 a ( 3  2)
rCation, tetrahedral   rAnion   
4 4 4 4
The ratio of rCation, octahedral to rCation, tetrahedral will thus be given by

2 2 2 2
a    
 2   2 
ratio    3.7
a ( 3  2)/4 ( 3  2)/4
Notice that the value of a will cancel in the calculation, so that the ratio is
independent of the actual edge length.
(c) If half the tetrahedral holes are filled, there will be four cations in the
unit cell. The fcc cell will have a total of four anions from contributions of
atoms at the corners and face centers, so the empirical formula will be
MA.
182 Chapter 6 Liquids and Solids

6.94 The calcium fluoride lattice is based upon a face-centered cubic unit cell
with the Ca 2 ions occupying the corners and face centers. The F ions
are located in the centers of the eight tetrahedral cavities found within the
face-centered cell. In the unit cell there are four formula units of CaF2.
Using this information and the density, we can calculate the volume of the
unit cell.
 78.08 g  mol1 
 1 
(4 formula units  unit cell 1 )
6.022  10 formula units  mol 
23

V 
3.180 g  cm 3
V  1.631  1022 cm3  1.631  108 pm3
The occupied volume is calculated from the size of the ions using their
ionic radii [r (Ca 2 )  100 pm; r (F )  133 pm].
4 4
VCa 2    r 3   (100 pm)3  4.19  106 pm3
3 3
4 4
VF   r 3   (133 pm)3  9.85  106 pm3
3 3
The total volume occupied is
4(4.19  106 pm3 )  8(9.85  106 pm3 )  9.56  107 pm3 . The percent of
empty space will be given by
(1.631  108 pm3  9.56  107 pm3 )
 100  41.4%
1.631  108 pm3
41.4% of the space is empty.

6.96 (a) The molar heat capacities for graphite, diamond, and SiO2 are:

C(graphite) C(diamond) SiO2

Molar heat capacity
8.53 6.11 44.43
(Jmol-1·K-1)

From this data, it is clear that the Dulong-Petit Law does not apply well to
 Chapter 6 Liquids and Solids 183

network solid because the heat capacity per atom is very different for
these network substances.
(b) The molar heat capacities of benzoic acid, urea, and glycine are:
benzoic acid urea glycine
Molar heat capacity
146.8 93.14 99.2
(Jmol-1·K-1)
Heat capacity per
mole of atoms 9.787 11.64 9.92
(JK-1mole of atom-1)
From this data, it is clear that the Dulong-Petit Law does not apply well to
Molecular compounds because the heat capacities per mole of atoms are
different for these molecular substances. Actually, Dulong and Petit’s law
only fits elements that have simple crystal structures, with low vibrational
frequencies. The molecular compounds are not crystalline materials.

6.98 In face-centered cube (rock-salt structure), there is one cation between two
anions on the edge. The available space distance between two F- ions is:
edge distance – (2 × 133). Based on the following data:
LiF NaF KF RbF CsF
Space distance between
302 386 488 530 584
two F- on the edge (pm)
The diameter of the
152 204 276 304 334
cation (pm)
none of these are “close-packed” because the available space between two
F- ions is much larger than the diameters of cations for all of the molecules.

6.100 The Coulomb potential energy of interaction for the point charge with the
dipole can be represented by the sum of the repulsive and attractive terms
q1 q2
as given by equation 1, Ep  . To avoid confusion, we will call the
4  r
184 Chapter 6 Liquids and Solids

point charge z since each end of the dipole is q or  q . The distance to

l
one end of the dipole is r  and the distance to the oppositely
2
l
charged end is r  . So the potential energy at the point charge is
2
   
 kq kq  kq  1 1 
Ep  z    z   
 r  l r  l  r 
1
l
1 
l 
 2 2  2r 2r 
1
where k  and z is the magnitude of the point charge.
4 
l
Since l  r , it is also true that  1 . Using the expansion given in
2r
1 l
the problem,  1  x  ..., with x = , gives
(1  x) 2r

1 l 1 l
 1 and  1 .
l 2r l 2r
1 1
2r 2r
Then the expression for the potential energy becomes
kq  l l  kq  2l   kql
Ep  z 1  1  = z    z 2
r  2r 2r  r  2r  r
1
Substituting k  and  = ql
4 
z
Ep  
4  r 2
Note that this expression agrees with equation 2.

6.102 Just as molecules have polarity, surfaces of solids have polarity. By

carrying out the silylation reaction, the surface of the glass will become
less polar because the Si(CH 3 )3 groups are nonpolar. Therefore, polar
liquids will not adhere to the surface quite so readily. This will also
eliminate the hydrogen bonds that form between liquids such as water, and
 Chapter 6 Liquids and Solids 185

other molecules that can participate in hydrogen bonding, and the surface
of glass.

6.104 (a) The Lewis structures of ethylammonium nitrate (EAN) and the formal
charge of each atom are showing as follows:

00 0
+ -1
H H H -
O
0 0
00 +1
H C C sp3 N H -1 N +1
sp3 sp3 0
O 2 O
sp
H H H
00 0

(b) The hybridization schemes of C and N atoms are assigned in the

Lewis structure of (a).
(c) The anion (NO3-). N5+ can be reduced to a lower oxidation state by
a reducing agent.
(d) CH3CH2NH2 + HNO3  CH3CH2NH3+ NO3- (acid-base)

 PV   (0.960 atm)(2.00 L) 
(e) nethylamine =   =  1 1
 =
 RT   (0.08206 L  amt  K  mol )(296.2 K ) 
0.0790 mole
nnitric acid = (0.250 L)(0.240M) = 0.0600 mole (limiting reagent)
Theoretical yield = 0.0600 mol HNO3
 (1 mole EAN )   108.104 gEAN 
x     = 6.49 g EAN
 1 mole HNO3   1 mole EAN 
 4.10 
Percentage yield =   x 100% = 63.2%
 6.49 
(f) The forces hold EAN together in the solid contain ion-ion,
hydrogen bonding, and London forces. NaCl and NaBr only have
ion-ion and London forces to hold them together (No H-bonding
involved). However, the ion-ion forces in NaCl and NaBr are much
Solutions Manual to accompany Introduction to Chemical Principles 11th 0321814630 / 97803218

186 Chapter 6 Liquids and Solids

stronger than that those of EAN because of the smaller ion sizes of
NaCl and NaBr.
(g) As the ion size increases, the distance between ions will increase
and the ion-ion forces will decrease, and the melting point will
decrease.

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