CHE 323 SOLVED PROBLEM SET

CHAPTER 3
SOLID STATE CHEMISTRY

Group Member Contribution Member's Signature

Conceptual: 3, 6, 7, 13, 17
Aliban, Mikaelah C. Numerical: 3, 6, 7, 13

Conceptual: 1, 9, 10, 11, 20

Aana, Morgan Numerical: 1, 9, 10, 11

Conceptual: 4, 5, 14, 16, 19

Olegario, Kevin A. Numerical: 4, 5, 14, 16

Conceptual: 2, 8, 12, 15, 18

Variacion, Manuel A. Numerical: 2, 8, 12, 15

Total No. Conceptual Questions Answered: 20

Total No. of Numerical Problems Answered: 16

Date & Time Submitted:

Date & Time Received:

Teacher's Signature:
1. A unit cell of an ionic crystal is the same as the formula unit.

An ionic crystal, their unit cells do not share ions with other unit cells near it but can form bonds
with it to form a larger object. They have at least two atoms in their base which are ionized.
Charge neutrality demands that the total charge in the base must be zero; so we always need
ions with opposing charge. Ionic crystals are not necessarily cubic; perovskite is essentially a
cubic primitive, but may be distorted and turn orthorhombic. The number of cations and anions
do not need to be equal, but they need to reflect the stoichiometry of a compound. An example
would be magnesium chloride, magnesium is a cation with 2+ and chloride is an anion with -1.
By stoichiometry, you will need two chloride ions for each magnesium ion.For MgCl 2 the lattice
must be an array of chloride anions with only half that number of magnesium ion. The ionic
crystal actually may contain more than one formula unit. Using Na Cl crystal for example.

N a4 C l 4 , but each Na
NaCl contains 4 Na ions and 4 Cl ions. This might seem to be then a
ion only takes of share of its chloride ion neighbors. Therefore, the simplest way of writing it
then would be NaCl.

2. Which of the following is incorrect?

(a) Molecular solids have high melting points

(b) The binding forces in a molecular solid include London dispersion forces

(c) Ionic solids have high melting points

(d) Ionic solids are insulators

The binding forces in a molecular solid are the London dispersion forces only (van der Waals
forces); these forces are weak, resulting in pairwise interatomic binding energies on the order of
1/100 those of covalent, ionic, and metallic bonds. Binding energies tend to increase with
increasing molecular size and polarity. Ionic solids are held by electrostatic forces (ionic
bonding). Electrostatic forces are very strong when the charges are high, the distance between
the nuclei of the atoms is also small. The amount of energy required to break this electrostatic
force is quite high making the melting point of ionic solids relatively high. Ionic solids are
insulators because of the absence of free ions, they only become conductive when dissolved in
a polar solvent. This makes the ions become free and can start conduction.

The incorrect statement is (a) because London dispersion forces present in molecular solids are
weaker than ionic or covalent bonds, molecular solids have relatively low melting point.
3. The sphere packing giving rise to a hexagonal structure is:

Letter A, ...ABABAB... since this alternating sequence between A

and B suggests that the layers are arranged alternately, and evey
other layer is the same. This is the characteristic of a hexagonal
structure.

4. Doping Se with As would produce a p-type semiconductor with increased conductivity

compared with pure Se.

As has one less valence electron than Se so the resulting semiconductor would be a p-type.
This would increase the conductivity due to holes that the electrons can jump into.

5. Only the primitive lattice has no extinctions or systematic absences.

It is indicated in the extinction rule that for a primitive lattice: no extinctions. If you describe the
same structure using a primitive lattice you will not find additional or absent reflections. Only the
indexing of the calculated reflections will be changed. However, translation parts of symmetry
elements always create systematic extinctions.

6. A certain metal fluoride crystallizes in such a way that the fluoride ions occupy simple
cubic lattices, while the metal ions occupy body centers of half the cubes. What is the
formula of the metal fluoride?

Flouride ions

Metal ion

The 4 corners each contribute 1/8 of the number of

fluoride ions while the 4 middle points contribute
1/4. (4 x 1/8) + (4 x 1/4) = 2 fluoride ions.

Therefore, for every 2 fluoride ions, there is one metal ion. The formula of the metal fluoride is
MF2.

7. The following information one needs to know about in order for a solid to be well
characterized except

A, the type of analytical method used is not an important information for a solid to be
well characterized because whatever the analytical method is used, the goal of any method is
the same: to identify and quantify the characteristics of a solid so that it can be characterized
well. All the other choices are important in characterizing the solid.

8. the following are variables that govern the X-ray diffraction technique except

(a) The type of radiation

(b) The sample

 (c) The detector

(d) The size of equipment

X-ray diffraction tells us the structure of the atomic and molecular structure of a crystal.

The type of
radiation
is a variable because the
diffraction of light greatly depends on the wavelength of the light.
In

phase

constructive

interference occurs when the radiation of light is directly flashed down on the slit of the
equipment. The sample is the one responsible for giving of the different types of radiation, on
where it is strongest and where it is weakest. The detector can also make variables to the data
on x-ray diffraction. Using a scintillation detector, it utilizes x-ray photons colliding on a
scintillator which produces blue visible light. It has high quantum efficiency and very low dead
time thus making it an ideal detector for point intensity measurements. Another detector is a
gas-filled detector. It utilizes x-ray photons to ionize inert gases such as argon and xenon. Gas
filled detectors are able to detect data at a whole range of scattering angles. Each equipment
has its specific use and is used for different purposes. The size of the equipment will not matter
to x-ray diffraction because the even if the size of the equipment increases, the ones used for
detecting the diffracted light must stay the same since it needs to detect these rays at certain
dimensions

9. Metals > Ceramics > Polymers

Crystallinity refers to the degree of structural order of a solid. The solids crystallinity is measured
by how its arranged; the more arranged and orderly it is (repeating patterns) the more crystalline
it is. From the three materials (Polymers, Metals and Ceramics), the least crystalline of the
bunch are polymers. The catch is polymers can actually be crystalline, but these types of
polymers are not favored at all because they are too brittle for utility. Crystalline polymers are
brittle as mentioned above, amorphous polymers are highly favored because it is elastic,
bendable and tough. An example would be our high dependence on plastic, it fits the three
criteria said above. Polymers is the least crystalline of the three, so the most crystalline of them
would either be metal or ceramic. Metal is the most crystalline because of the nature of its
bonding. It is more orderly because the identity of the molecules in metals is that they are all the
same, every single one of them is the same metal. If you compare them with ceramics or
polymers, these contain different atoms.
An example of a metal is iron if zoomed with a lens that can see atoms you can see that they
are all iron atoms bonded to each other. Now let us compare it with a polymer such as
polystyrene, a synthetic aromatic polymer made up of carbon and hydrogen atoms. These
atoms are also bonded differently from each other. Polystyrene can also have different
arrangement with its molecules and one polystyrene molecule is relatively longer than one
molecule of iron, thus iron is more capable of being more arranged than polystyrene. Ceramics
are more crystalline than polymers because ceramics contain tiny crystalline regions within a
non-crystalline matrix. This makes the ceramic hard.

10. Diffraction occurs when the dimensions of the diffracting object are much larger than
the wavelength of radiation because it occurs when the dimensions of the diffracting
object are comparable to the wavelength of radiation.

When the slit of the diffracting object is comparable to the wavelength of the radiation, you can
think of a light source firing directly down the slit (the blue lines). the point sources are then in
phase if the wavelength is comparable to the dimension of the diffracting object, meaning there
is no delay of all the point sources. Now if you change the wavelength to that is not comparable
to the dimension of the diffracting object, it would be like the red lines in the picture above. Now
in this case it will not be in phase because unlike the blue lines, the point sources will be
delayed by a different amount. Diffraction actually still occurs in this case but it is generally most
pronounced when the dimensions of the diffracting object is comparable to the wavelength of
radiation.
11. How does a lattice differ from a structure? Describe the procedure for identifying the
type and size of a cubic unit cell

Molecular Structure

-Is made up by chemically bonding two or more atoms of the same element or different
elements.

-Do not have charge

-Can be very large such as hemoglobin or very small such as hydrogen gas

-molecules do not have a three-dimensional structure

-It can be a solid, liquid or gas

Lattice

-Is a mathematical phenomenon

-has a three- dimensional ordered arrangement of basic units (these basic units can be a
molecule, an atom or an ion)

-these are crystalline structures because it features repeating units

-they have higher molecular weights than molecules

-It is a solid

Determining the type of cubic unit cell

The cubic unit cell is simple cubic if each unit cell contains 1 atom

There are eight corners in the cubic unit cell which has an atom at each corner. These atoms
are shared by its neighbor unit cells, thus only 1/8 of an atom is present in each corner of a
simple cubic unit cell.

8 corners ( 18 corner
atom
)=1 atom
The cubic unit cell is body-centered cubic if each unit cell contains 2 atoms

It has a similar structure to that of a simple cubic but with the addition of an atom in the center
of a unit cell. Thus it is
 8 corners ( 18 corner
atom
)+1 atomincenter=2 atoms
The cubic unit cell is face-centered cubic if each unit cell contains 4 atoms

It has a similar structure to that of a simple cubic but with the addition of four atoms at the
faces of the cubic unit cell. Just like the corner atoms, these face atoms are also shared with its
unit cell neighbors, thus only of an atom is present in each face of a face-centered cubic unit
cell

8 corners ( 18 corner
atom
)+6 fac es( 12 atom
face )
=4 atoms

Measuring distance between particles

Measuring the distance between particles is possible by using the Bragg Equation. It allows us
to calculate the distance between planes of atoms in a crystal from the pattern of diffraction of x-
rays of known wavelength.

n = 2d sin T

n=order of reflection

d=ionic radius

T=glancing angle

=wavelength
12. What is a unit Cell?

A unit cell is the most basic and least volume consuming repeating structure of any solid. It is
used to visually simplify the crystalline patterns solids arrange themselves in. When the unit cell
repeats itself, the network is called a lattice.

13. Describe the difference between space lattice and unit cell.

A space lattice is an array of points showing how particles (atoms, ions or molecules) are
arranged at different sites in three dimensional spaces, while the unit cell is defined as the
smallest repeating unit in space lattice which, when repeated over again, results in a crystal of
the given substance. Therefore, the space lattice consists a number of unit cells and the unit cell
represents the basic pattern repeated alll throughout the lattice.

14. What is meant by a (100) plane?

The orientation of a crystal plane may be defined by considering how the plane intersects the
main crystallographic axes of the solid. The first number indicates that an atom intersects the
plane once every unit cell while the last two digits indicated that the other two planes are
intersected infinitely.

15. What is meant by systematic absence? How do they rise?

In crystallography, symmetry is used to characterize crystals, identify repeating parts of

molecules, and simplify both data collection and nearly all calculations. Also, the symmetry of
physical properties of a crystal such as thermal conductivity and optical activity must include the
symmetry of the crystal.Systematic absences or extinctions occur when the structure factor is
zero, due either to the centering of the lattice or to the presence of glide or screw symmetry
elements. Conversely, the conditions for a reflection to exist and not to be systematically absent,
are called reflection conditions. They rise by means of micro-translation. In particular cell
centering, screw axes, and glide plane operations can be identified by the fact that they cause
certain groups of diffraction points to be systematically absent.

16. Explain how metallic conductors and semiconductors are identified and explain their
electrical and optical properties in terms of band theory.

A useful way to visualize the difference between conductors, insulators and semiconductors is
to plot the available energies for electrons in the materials. Instead of having discrete energies
as in the case of free atoms, the available energy states form bands. Crucial to the conduction
process is whether or not there are electrons in the conduction band. In insulators the electrons
in the valence band are separated by a large gap from the conduction band, in conductors like
metals the valence band overlaps the conduction band, and in semiconductors there is a small
enough gap between the valence and conduction bands that thermal or other excitations can
bridge the gap. With such a small gap, the presence of a small percentage of a doping material
can increase conductivity dramatically.

The interband optical absorption or emission of a quantum well will be caused by transitions
between hole and electron subbands. The selection rules are determined by the overlap
between the electron and hole wavefunctions. Wavefunctions of the same quantum number (or
quantum numbers differing by two) will have similar (spatial) shapes and the transition will be
strong; wavefunctions whose quantum numbers differ by one will be of opposite symmetry, and
so transitions between them will be weak.

17. How many lattice points are there in a unit cell of:

a. a face-centered lattice

There are 4 lattice points in an FCC unit cell. Each of the lattice
points on the faces give 1/2 and the corners 1/8 contribution to
the total lattice points. ( 18 8 from the corners plus 12 6 from
the faces = 4 lattice points).
b. a body-centered lattice

There are 2 lattice points in a BCC unit cell. Each of the lattice
point on the body center give 1 and the corners 1/8 contribution
to the total lattice points. ( 18 8 from the corners plus 1 1 from
the body center = 2 lattice points).

18. Argon, copper, sodium chloride and carbon dioxide all crystallize in the FCC
structure. How can this be when their physical properties are so different?

Face-centered cubic (FCC) refers to a crystal structure consisting of an atom at each cube
corner and an atom in the center of each cube face. It is a close-packed plane in which on each
face of the cube atoms are assumed to touch along face diagonals. The crystal structure is not
the only factor that affects the physical property of a compound, it is important to note that
different elements have different values in lattice parameter, atomic radius, atomic mass and
density. Also the type of bonding matters. Sodium chloride is taken as a typical ionic
compound.Ionic substances form giant ionic lattices containing oppositely charged ions. They
have high melting and boiling points, and conduct electricity when melted or dissolved in water.
Carbon dioxide on the other hand, has a covalent bond. The molecules are held together by
weak forces so these substances have low melting and boiling points. They do not conduct
electricity. Copper has a metallic type of bonding. Metallic bonds are mediated by strong
attractive forces. This property contributes to the low volatility, high melting and boiling points,
and high density of most metals.

19.Describe the caesium-chloride and rock-salt structures in terms of the occupation of

hole in expanded close-packed lattices.

The CsCl Structure.

One of the simplest structural types for 1:1 salts, which is observed when the cation and the
anion are close to the same size, is the cesium chloride structure. Cesium chloride crystallizes
in a simple cubic unit cell with one cesiuim ion and one chloride ion, per lattice point. Since
there is 1 lattice point per unit cell, there is one CsCl formula unit per unit cell. The cesium
chloride unit cell is shown schematically in the following figure:
At first glance the cell looks bodycentered, but it is not because the sphere at the center is not
the same as the ones at the corners. The 8 red spheres at the corners each belong to 8 unit
cells and therefore contribute only one red sphere to the unit cell (1/8 x 8 = 1). The cell also
contains a whole purple sphere in its interior, so there is one red sphere and one purple sphere
per unit cell. This gives a 1 to 1 ratio of red to purple, which is the correct ratio for CsCl. So
which is the cesium ion and which is the chloride ion? The answer is it doesnt matter. You can
view the lattice as a simple cubic array of chloride ions with a cesium ion in the center of each
unit cell, or as a simple cubic array of cesium ions with a chloride ion in the center of each unit
cell. Alternatively, the structure has been described as interlocking simple cubic lattices of
anions and cations. When an ion lies in the center of a cube in which the counter ions occupy
the corners, the ion in the center is said to be in a cubic hole. In the cesium chloride structure,
both the cesium ion and the chloride ion have coordination numbers of 8. Some other
compounds that adopt the cesium chloride structure are cesium bromide and thallium chloride.

The NaCl Structure.

The sodium chloride structure is another cubic structure commonly adopted by 1 to 1 salts. A
model of the sodium chloride unit cell is shown to the left below, where the sodium ions are
represented by white spheres and the chloride ions by gold spheres. The structure is face
centered cubic, with one sodium ion and one chloride ion per lattice point. Since there are 4
lattice points per unit cell this gives a total of 4 NaCl moieties per unit cell. You can come to the
same conclusion by counting spheres in the unit cell. Notice that the goldcolored chloride ions
have the same arrangement as in a facecentered metal with a cubic closepacked structure.
Therefore there are a total of 4 chloride ions per cell (1 from the 8 corners plus 3 from the 6
faces). The sodium ions (white spheres) occupy the octahedral holes created by the chloride
ions. This alone tells you there are 4 per cell. Or you can count: there is a sodium ion on each of
the cell edges and one in the center of the cell, for a total of 4 sodium ions per unit cell. Notice
that the ratio of Na+ to Cl is 4:4 or 1:1.

If the positions of the sodium ions and the chloride ions were interchanged, the same extended
structure would result, and the sodium chloride structure is sometimes described as two
interpenetrating facecentered cubic lattices. This can be seen by inspecting the extended
structure to the right of the unit cell. Finally, both the cation and the anion have a coordination
number of 6, as each is surrounded by an octahedron of counterions.

20. Explain why there are two arrangements for the closet packing of spheres rather than
a single one

The figure above shows tightly packed atoms, each available space being labeled A,B and C.

If you add the B molecules, there is no longer space for C molecules to occupy. The first layer
areA molecules, the second layer B molecules. The third layer then may be placed on the
hollows left by C, In such an arrangement the first and the third layers are exactly identical. This
arrangement of close packing of spheres is referred to as ABA arrangement of packing of
spheres. Alternatively, the third layers may be placed on the second set of hollows which were
marked C in the first layer. These hollows were left uncovered while arranging the second layer
of spheres. This arrangement of packing is denoted as ABC type of packing. ABA, because of is
hexagonal symmetry is also known as hexagonal close packing of spheres (hcp). When ABC
arrangement is continued, the system then has a cubic symmetry, this is also known as cubic
close packing of spheres (ccp).