TUTORIAL SESSION 2 - 2024
Instruction: Each student represents a problem in tutorial session. Your solution must contain two
main parts: a fundamental principle related to this problem and your solution for the problem.
Section 1: Structure of simple solid
Problem 1:
1.1. Determine the net number of Na+ and Cl- ions in the sodium chloride unit cell.
1.2. Consider the unit cells shown here for the three different structures that are commonly observed
for metallic elements.
a. Which structure(s) correspond to the densest packing of atoms?
b. Which structure(s) corresponds to the least dense packing of atoms?
1.3. Calcium has a cubic closest packed structure as a solid. Assuming that calcium has an atomic
radius of 197 pm, calculate the density of solid calcium.
1.4. Iron has a density of 7.86 g/cm3 and crystallizes in a body centered cubic lattice. Show that only
68% of a body-centered lattice is actually occupied by atoms, and determine the atomic radius of iron.
1.5. The structures of some common crystalline substances are shown below. Show that the net
composition of each unit cell corresponds to the correct formula of each substance.
1.5. The unit cell for nickel arsenide is shown below. What is the formula of this compound?
1.6. Perovskite is a mineral containing calcium, titanium, and oxygen. Two different representations of
the unit cell are shown below. Show that both these representations give the same formula and the
same number of oxygen atoms around each titanium atom.
1.7. Rhenium oxide crystallizes with a structure that has a primitive cubic lattice, as shown here. In
the image on the left, the sizes of the ions have been reduced to show the entire unit cell.
(a) How many atoms of each type are there per unit cell?
(b) Use the ionic radii of rhenium (0.70 Å) and oxygen (1.26 Å) to estimate the length of the edge of
the unit cell.
(c) Use your answers to parts (a) and (b) to estimate the density of this compound
1.8. Two patterns of packing different types of spheres are shown here. For each structure
(a) Draw the two-dimensional unit cell
(b) Determine the angle between the lattice vectors, g, and whether the lattice vectors are the
same length or of different lengths
(c) Determine the type of two-dimensional lattice
Problem 2:
2.1. Selenium is a semiconductor used in photocopying machines. What type of semiconductor would
be formed if a small amount of indium impurity is added to pure Selenium?
2.2. The band gap in aluminum phosphide (AlP) is 2.5 electron-volts (1 eV = 1.6 x 10-19 J). What
wavelength of light is emitted by an AlP diode?
2.3. The electronic structure of a doped semiconductor is shown here.
(a) Which band, A or B, is the valence band?
(b) Which band is the conduction band?
(c) Which band consists of bonding molecular orbitals?
(d) Is this an example of an n-type or p-type doped semiconductor?
(e) If the semiconductor is germanium, which of the following elements could be the dopant: Ga, Si, or
P?
2.4. Classify the following as n- or p- doped semiconductors:
(a) Ga doped Ge
(b) As doped Si
(c) In0.49As0.51
2.5. GaAs and GaP (Eg = 2.26 eV) make solid solutions that have the same crystal structure as the
parent materials, with As and P randomly distributed throughout the crystal. GaP xAs1-x exists for any
value of x. If we assume that the band gap varies linearly with composition between x = 0 and x = 1,
estimate the band gap for GaP0.5As0.5. What wavelength of light does this correspond to?
2.6. The valence band of a semiconductor is made up of bonding molecular orbitals and the conduction
band of antibonding molecular orbitals.
(a) Given this fact would you expect n-type doping to strengthen or weaken the bonds in a
semiconductor?
(b) Would you expect p-type doping to strengthen or weaken the bonds in a semiconductor?
Problem 3:
The diagram shows the unit cell of calcium carbide. Calcium is positioned at the corners and centre of
the unit cell. Some of the atoms are completely contained within the boundaries of a single unit cell.
Only a fraction of atoms centred on corners, edges, or faces are contained within a single unit cell. The
density of calcium carbide is 2.20 g cm−3 and the values of x and y are both 3.88 Å. Calculate the value
of z.
Problem 4:
Catalysts are substances that accelerate the rate of reactions by allowing them to proceed in a lower
energy pathway. The catalytic activity of the catalysts is generally determined by the turnover frequency
(TOF), which is calculated by dividing the molar amount of the product to the mole of active catalyst
and the time (TOF = mole product/(mole catalyst x time)). A typical hydrolysis of BNH6 was carried out
in 10.0 mL of water by using 100.0 mM BNH6 and 5.0 mg of CuPt/C catalyst (CuPt alloy nanoparticles
supported on carbon black containing 8.2 wt% Pt atom). 67.25 mL of hydrogen gas was generated in
5 minutes.
a. Assuming the catalytic reaction is performed under standard conditions (1 atm and 273.15 K),
calculate the TOF (𝑚𝑖𝑛−1) of the CuPt/C catalyst in terms of only Pt atoms in the hydrolysis of BNH6
by considering the volume of the hydrogen gas generated.
As a result of detailed crystal analysis of a synthesized Cux Pt y alloy nanoparticles (the subscripts
indicate molar percentages of the atoms in the alloy structure), it was determined that the face centered
cubic (fcc) unit cell was formed by Pt atoms and the Pt atoms on the face of the fcc unit cell are
supposed to be replaced with Cu atoms to form Cux Pt y displacement alloy nanoparticles. According to
this information, answer the following questions.
b. Determine the composition of the alloy nanoparticles by finding x and y in the Cux Pt y .
c. Sketch the shape of the described crystal unit cell of Cux Pt y alloy nanoparticles by showing the
position of all atoms on the unit cell.
Problem 5:
Correct any inaccuracies in the following descriptions of Group 14 chemistry:
(a) None of the elements in this group is a metal.
(b) At very high pressures, diamond is a thermodynamically stable phase of carbon.
(c) Both CO2 and CS2 are weak Lewis acids and the hardness increases from CO2 to CS2.
(d) Zeolites are layered materials exclusively composed of aluminosilicates.
(e) The reaction of calcium carbide with water yields ethylene and this product reflects the presence of
a highly basic C2 2- ion in calcium carbide.
