Sample Exercise 12.

1 Calculating Packing Efficiency

It is not possible to pack spheres together without leaving some void spaces between the spheres. Packing
efficiency is the fraction of space in a crystal that is actually occupied by atoms. Determine the packing efficiency
of a face-centered cubic metal.

Solution
Analyze We must determine the volume taken up by the atoms that reside in the unit cell
and divide this number by the volume of the unit cell.
Plan We can calculate the volume taken up by atoms by multiplying the number of atoms per
unit cell by the volume of a sphere, 4πr3/3. To determine the volume of the unit cell, we must
first identify the direction along which the atoms touch each other. We can then use geometry
to express the length of the cubic unit cell edge, a, in terms of the radius of the atoms. Once
we know the edge length, the cell volume is simply a3.
Solve
As shown in Figure 12.12, a face-centered cubic metal has four atoms per unit cell. Therefore,
the volume occupied by the atoms is

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 Sample Exercise 12.1 Calculating Packing Efficiency
Continued

For a face-centered cubic metal the atoms touch along the diagonal of a face of the unit cell:

Therefore, a diagonal across a face of the unit cell is equal to four times the atomic radius, r. Using simple
trigonometry, and the identity we can show that

Finally, we calculate the packing efficiency by dividing the volume occupied by atoms by the volume of the cubic
unit cell, a3:

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 Sample Exercise 12.1 Calculating Packing Efficiency
Continued

Practice Exercise 1
Consider the two-dimensional square lattice of
Figure 12.4. The “packing efficiency” for a two-
dimensional structure would be the area of the atoms
divided by the area of the unit cell, times 100%.
What is the packing efficiency for a square lattice
for atoms of radius a/2 that are centered at the
lattice points? (a) 3.14% (b) 15.7% (c) 31.8%
(d) 74.0% (e) 78.5%

Practice Exercise 2
Determine the packing efficiency by calculating the fraction of space occupied by atoms in a body-centered cubic
metal.

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 Sample Exercise 12.2 Calculating the Density of an Ionic Solid
Rubidium iodide crystallizes with the same structure as sodium chloride. (a) How many iodide ions are there per
unit cell? (b) How many rubidium ions are there per unit cell? (c) Use the ionic radii and molar masses of Rb+
(1.66 Å , 85.47 g/mol) and I– (2.06 Å, 126.90 g/mol) to estimate the density of rubidium iodide in g/cm 3.

Solution
Analyze and Plan
(a) We need to count the number of anions in the unit cell of the sodium chloride structure, remembering that ions
on the corners, edges, and faces of the unit cell are only partially inside the unit cell.
(b) We can apply the same approach to determine the number of cations in the unit cell. We can double-check our
answer by writing the empirical formula to make sure the charges of the cations and anions are balanced.
(c) Because density is an intensive property, the density of the unit cell is the same as the density of a bulk crystal.
To calculate the density we must divide the mass of the atoms per unit cell by the volume of the unit cell. To
determine the volume of the unit cell we need to estimate the length of the unit cell edge by first identifying the
direction along which the ions touch and then using ionic radii to estimate the length. Once we have the length
of the unit cell edge we can cube it to determine its volume.

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 Sample Exercise 12.2 Calculating the Density of an Ionic Solid
Continued

Solve
(a) The crystal structure of rubidium iodide looks just like NaCl with Rb + ions
replacing Na+ and I– ions replacing Cl–. From the views of the NaCl
structure in Figures 12.25 and 12.26 we see that there is an anion at each
corner of the unit cell and at the center of each face. From Table 12.1
we see that the ions sitting on the corners are equally shared by eight unit
cells (1/8 ion per unit cell), while those ions sitting on the faces are equally
shared by two unit cells (1/2 ion per unit cell). A cube has eight corners
and six faces, so the total number of I– ions is 8 (1/8) + 6 (1/2) =
4 per unit cell.

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 Sample Exercise 12.2 Calculating the Density of an Ionic Solid
Continued

(b) Using the same approach for the rubidium cations we see that there is a rubidium ion on each edge and one at the
center of the unit cell. Using Table 12.1 again we see that the ions sitting on the edges are equally shared by four
unit cells (1/4 ion per unit cell), whereas the cation at the center of the unit cell is not shared. A cube has 12 edges,
so the total number of rubidium ions is 12 (1/4) + 1 = 4. This answer makes sense because the number of Rb + ions
must be the same as the number of I– ions to maintain charge balance.
(c) In ionic compounds cations and anions touch each other. In RbI the cations and anions touch along the edge of the
unit cell as shown in the following figure.

The distance the unit cell edge is equal to r(I–) + 2r(Rb+) + r(I–) = 2r(I–) + 2r(Rb+). Plugging in the ionic radii we get
2(2.06 Å) + 2(1.66 Å) = 7.44 Å. The volume of a cubic unit cell is just the edge length cubed. Converting from Å to
cm and cubing we get
Volume = (7.44 × 10–8 cm)3 = 4.12 × 10–22 cm3.

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 Sample Exercise 12.2 Calculating the Density of an Ionic Solid
Continued

From parts (a) and (b) we know that there are four rubidium and four iodide ions per unit cell. Using this result and
the molar masses we can calculate the mass per unit cell

The density is the mass per unit cell divided by the volume of a unit cell

Check The densities of most solids fall between the density of lithium (0.5 g/cm 3) and that of iridium (22.6 g/cm3),
so this value is reasonable.

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 Sample Exercise 12.2 Calculating the Density of an Ionic Solid
Continued

Practice Exercise 1
Given the ionic radii and molar masses of Sc3+
(0.88 Å, 45.0 g/mol) and F– (1.19 Å, 19.0 g/mol)
what value do you estimate for the density of ScF3,
whose structure is shown in Figure 12.27?
(a) 5.99 g/cm3, (b) 1.44 × 1024 g/mol, (c) 19.1 g/cm3,
(d) 2.39 g/m3, (e) 5.72 g/cm3.

Practice Exercise 2
Estimate the length of the cubic unit cell edge and the density of CsCl (Figure 12.25) from the ionic radii of
cesium, 1.81 Å, and chloride, 1.67 Å. (Hint: Ions in CsCl touch along the body diagonal, a vector running from
one corner of a cube through the body center to the opposite corner. Using trigonometry it can be shown that the
body diagonal of a cube is times longer than the edge.)

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 Sample Exercise 12.3 Qualitative Comparison of Semiconductor
Band Gaps
Will GaP have a larger or smaller band gap than ZnS? Will it have a larger or smaller band gap than GaN?

Solution
Analyze The size of the band gap depends on the vertical and horizontal positions of the elements in the periodic
table. The band gap will increase when either of the following conditions is met: (1) The elements are located
higher up in the periodic table, where enhanced orbital overlap leads to a larger splitting between bonding and
antibonding orbital energies, or (2) the horizontal separation between the elements increases, which leads to an
increase in the electronegativity difference and bond polarity.
Plan We must look at the periodic table and compare the relative positions of the elements in each case.
Solve Gallium is in the fourth period and group 3A. Phosphorus is in the third period and group 5A. Zinc and
sulfur are in the same periods as gallium and phosphorus, respectively. However, zinc, in group 2B, is one
element to the left of gallium; sulfur in group 6A is one element to the right of phosphorus. Thus, we would
expect the electronegativity difference to be larger for ZnS, which should result in ZnS having a larger band gap
than GaP. For both GaP and GaN the more electropositive element is gallium. So we need only compare the
positions of the more electronegative elements, P and N. Nitrogen is located above phosphorus in group 5A.
Therefore, based on increased orbital overlap, we would expect GaN to have a larger band gap than GaP.
Check External references show that the band gap of GaP is 2.26 eV, ZnS is 3.6 eV, and GaN is 3.4 eV.

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 Sample Exercise 12.3 Qualitative Comparison of Semiconductor
Band Gaps
Continued

Practice Exercise 1
Which of these statements is false?
(a) As you go down column 4A in the periodic table, the elemental solids become more electrically conducting. (b) As
you go down column 4A in the periodic table, the band gaps of the elemental solids decrease. (c) The valence electron
count for a compound semiconductor averages out to four per atom. (d) Band gap energies of semiconductors range
from ~0.1 to 3.5 eV. (e) In general, the more polar the bonds are in compound semiconductors, the smaller the band gap.

Practice Exercise 2
Will ZnSe have a larger or smaller band gap than ZnS?

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 Sample Exercise 12.4 Identifying Types of Semiconductors
Which of the following elements, if doped into silicon, would yield an n-type semiconductor: Ga, As, or C?

Solution
Analyze An n-type semiconductor means that the dopant atoms must have more valence electrons than the host
material. Silicon is the host material in this case.
Plan We must look at the periodic table and determine the number of valence electrons associated with Si, Ga, As,
and C. The elements with more valence electrons than silicon are the ones that will produce an n-type material upon
doping.
Solve Si is in column 4A, and so has four valence electrons. Ga is in column 3A, and so has three valence electrons.
As is in column 5A, and so has five valence electrons; C is in column 4A, and so has four valence electrons.
Therefore, As, if doped into silicon, would yield an n-type semiconductor.

Practice Exercise 1
Which of these doped semiconductors would yield a p-type material? (These choices are written as host atom:
dopant atom.)
(a) Ge:P (c) Si:Ge (b) Si:Al (d) Ge:S (e) Si:N

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 Sample Exercise 12.4 Identifying Types of Semiconductors
Continued

Practice Exercise 2
Compound semiconductors can be doped to make n-type and p-type materials, but the scientist has to make sure
that the proper atoms are substituted. For example, if Ge were doped into GaAs, Ge could substitute for Ga, making
an n-type semiconductor; but if Ge substituted for As, the material would be p-type. Suggest a way to dope CdSe to
create a p-type material.

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 Sample Integrative Exercise Putting Concepts Together
Polymers that can conduct electricity are called conducting polymers. Some polymers can be made
semiconducting; others can be nearly metallic. Polyacetylene is an example of a polymer that is a semiconductor.
It can also be doped to increase its conductivity.
Polyacetylene is made from acetylene in a reaction that looks simple but is actually tricky to do:

(a) What is the hybridization of the carbon atoms, and the

geometry around those atoms, in acetylene and in
polyacetylene?
(b) Write a balanced equation to make polyacetylene
from acetylene.
(c) Acetylene is a gas at room temperature and pressure
(298 K, 1.00 atm). How many grams of polyacetylene
can you make from a 5.00-L vessel of acetylene gas at
room temperature and room pressure? Assume acetylene
behaves ideally, and that the polymerization reaction
occurs with 100% yield.
(d) Using the average bond enthalpies in Table 8.4, predict
whether the formation of polyacetylene from acetylene
is endothermic or exothermic.
(e) A sample of polyacetylene absorbs light from 300 nm
down to 650 nm. What is its band gap, in electron volts?

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 Sample Integrative Exercise Putting Concepts Together
Continued

Solution
Analyze For part (a) we need to recall what we have learned about sp, sp2, and sp3 hybridization and geometry.
(Section 9.5) For part (b), we need to write a balanced equation. For part (c), we need to use the ideal-gas
equation. (Sections10.4) For part (d), we need to recall the definitions of endothermic and exothermic and
how bond enthalpies can be used to predict overall reaction enthalpies. (Section 8.8) For part (e), we need
to relate the absorption of light to the differences in energy levels between filled and empty states in a material.
(Section 6.3)
Plan For part (a), we should draw out the chemical structures of the reactant and product. For part (b), we need to
make sure the equation is properly balanced. For part (c), we need to convert from liters of gas to moles of gas,
using the ideal-gas equation (PV = nRT); then we need to convert from moles of acetylene gas to moles of
polyacetylene using the answer from part (b); finally, we can convert to grams of polyacetylene. For part (d), we
need to recall that ∆Hrxn = Σ(bond enthalpies of bonds broken) – Σ(bond enthalpies of bonds formed).
(Section 8.8) For part (e), we need to realize that the lowest energy absorbed by a material will tell us its band gap
Eg (for a semiconductor or insulator) and combine E = hν and c = λν together (E = hc/λ) to solve for Eg.

Solve
(a) Carbon always forms four bonds. Thus, each C atom must have a single bond to H and a triple bond to the other
C atom in acetylene. As a result, each C atom has two electron domains and must be sp hybridized. This sp
hybridization also means that the H—C—C angles in acetylene are 180° and the molecule is linear.

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 Sample Integrative Exercise Putting Concepts Together
Continued

We can write out the partial structure of polyacetylene as follows:

Each carbon is identical but now has three bonding electron domains that surround it. Therefore, the
hybridization of each carbon atom is sp2, and each carbon has local trigonal planar geometry with 120° angles.
(b) We can write:

Note that all atoms originally present in acetylene end up in the polyacetylene product.
(c) We can use the idea-gas equation as follows:
PV = nRT
(1.00 atm)(5.00 L) = n(0.08206 L-atm/K-mol)(298 K)
n = 0.204 mol

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 Sample Integrative Exercise Putting Concepts Together
Continued
Acetylene has a molar mass of 26.0 g/mol; therefore, the mass of 0.204 mol is
(0.204 mol)(26.0 g/mol) = 5.32 g acetylene
Note that from the answer to part (b), all the atoms in acetylene go into polyacetylene. Due to conservation of
mass, then, the mass of polyacetylene produced must also be 5.32 g, if we assume 100% yield.
(d) Let’s consider the case for n = 1. We note that the reactant side of the equation in part (b) has one C‚C triple
bond and two C―H single bonds. The product side of the equation in part (b) has one C ═ C double bond, one
C―C single bond (to link to the adjacent monomer), and two C―H single bonds. Therefore, we are breaking
one C ≡ C triple bond and are forming one C ═ C double bond and one C―C single bond. Accordingly, the
enthalpy change for polyacetylene formation is
∆Hrxn = (C ≡ C triple bond enthalpy) – (C ═ C double bond enthalpy) – (C—C single bond enthalpy)
∆Hrxn = (839 kJ/mol) – (614 kJ/mol) – (348 kJ/mol)
= –123 kJ/mol
Because ∆H is a negative number, the reaction releases heat and is exothermic.
(e) The sample of polyacetylene absorbs many wavelengths of light, but the one we care about is the longest one,
which corresponds to the lowest energy.
E = hc/λ
E = (6.626 × 10–34 J s) (3.00 × 108 m s–1)/(650 × 10–9 m)
E = 3.06 × 10–19 J

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 Sample Integrative Exercise Putting Concepts Together
Continued
We recognize that this energy corresponds to the energy difference between the bottom of the conduction band
and the top of the valence band, and so is equivalent to the band gap Eg. Now we have to convert the number to
electron volts. Since 1.602 × 10–19 J = 1 eV, we find that
Eg = 1.91 eV

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