2017-2018

4TCH403

Inorganic Chemistry

Exercise Booklet

Corresponding author : Graziella GOGLIO

graziella.goglio@u-bordeaux.fr
Exercise 1: The different families of materials

After describing the following materials in terms of composition, specify whether they are a
ceramic, metal or metal alloy, a polymer or a composite. Name an application for each of these
materials.

Alumina, Polyvinyl chloride, Teflon, Bronze, Steel, Talcum, Titanium Oxide, Quartz,
Magnetite, Cermet, Nitinol, Barium titanate, Polyethylene, SiC/SiC, Polyethylene
terephthalate.

Exercise 2: Point defects in a copper crystal network

The main point defects in the crystallographic network of a pure metal such as copper are
vacancies and self-interstitials.
1- Describe what is the nature of the disorder introduced into a crystal respectively by a
vacancy and a self-interstitial,
2- At any temperature T (K), a given number of vacancies or self interstitial point defects
may exist in equilibrium within the crystal.
2.1- Given that the enthalpy of formation of a vacancy in the copper crystal is 1 eV,
calculate the concentration of vacancies in a copper crystal at a temperature of 25, 250, 500,
750 1080 and 1100 ° C (Tt of Cu = 1083 ° C)
2.2- Respond to the same question for the relative number of self-interstitials knowing
that for this type of defects, Hf = 4 eV.

Exercise 3: Energy of vacancies formation in a metal

Calculate the energy required to form a mole of vacancies in a metal. The concentration in
vacancies was measured experimentally as a function of temperature:

Temperature 300 600 800 1000 1200 1300 1350

(K)
nt/N 2.62 10-15 5.18 10-8 3.4 10-6 4.22 10-5 2.3 10-4 4.3 10-4 5.8 10-4

Calculate the enthalpy of formation of one mole of vacancies. Deduce the enthalpy of formation
of 1 vacancy.

Exercise 4: Determination of the nature of defects in a material

To metals A and B, with molar masses MA and MB, where MA < MB, form a single phase AmBn = γ
over a composition domain limited by the molar fractions
XB min=X1=0.5 and XB max=X2=0.8.
Density measurements p of various composites show that the density of γ decreases as XB
increases.
1- Determine the range of chemical composition for this solid solution γ.
2- Within this solid solution, the continuous transition from x1 to x2 results in the presence
of a single type of defect.
2.1- Determine the three possible types of defects.
2.2- Establish using the composition corresponding to x 1 the expression that gives the
chemical formula for each case for each pattern. Specify for each the range for the
quantities of defects.
3- Express, assuming a constant lattice volume, the density of each of the three solid solutions
as a function of p(x1).
4- Deduce the real nature of the defect in γ.
Exercise 5: Substitutions in covalent materials

Given:
Element Molar mass Electronegativity Covalent radius
(g mol-1) (Pauling scale) (pm)
Carbon 12.011 2.5 -
Silicon 28.086 1.8 118
Germanium 72.59 1.8 122

1- What is the common feature between C, Si and Ge?

2- Silicon and germanium both crystallize as carbon does, in the diamond structure.
2.1- Project the diamond structure in the plane (xOy) and label the z coordinate
2.2- Indicate the number of nearest neighbors and determine the shortest atom-atom
distance as a function of the lattice parameter a.
2.3- Knowing that silicon density is 2.3 g cm-3, deduce the lattice parameter of silicon and the
shortest Si-Si distance. Compare this result with the radius of covalently bound silicon.
3- Ge and Si are totally miscible in the solid state.
3.1- Give the reasons allowing this total miscibility
3.2- A 27.9 wt% mixture of silicon in germanium yields a substitutional solid solution with a
lattice parameter of 5.54 Å. Calculate the lattice parameter of germanium.

Exercise 6: Substitutions in metallic materials

Calculate the lattice parameter of a substitutional solid solution containing 72 wt% iron and 28
wt% chromium.

Given:
M(Fe) = 55.847 g mol-1 M(Cr) = 51.996 g mol-1
R(Fe) = 1.24 Å R(Cr) = 1.29 Å
Fe and Cr structure : body-centered

Exercise 7: Point defects in ionic crystals

The ionic crystal of NaCl crystallizes in a face-centered cubic unit cell.

1- The lattice parameter of NaCl is a=0.552 nm. The ionic radii are respectively 96 pm for
the cation and 180 pm for the anion. Show and justify the relationship between the lattice
parameter and the ionic radii.
2- Calculate the density of NaCl considering the following data:
M(Na)=22.99 g mol-1 and M(Cl)=35.5 g mol-1
3- In these crystals, some Schottky defects can form. Give the definition of a Schottky defect
in an ionic crystal.
4- In real NaCl crystals we determine there exist 5% Schottky defects and in another 5%
Frenkel defects. Calculate the solid density for both cases.
5- Justify the following data considering the nature of the chemical bond in the materials
listed in the table below:

Material Young’s Melting point

modulus (GPa) (K)
Sodium 5 370
Sodium chloride 37 1073
Exercise 8: A lacunar oxide

As many transition oxides, niobium oxide Nb2O5 can form a nonstoichimetric compound at high
temperature, resulting in the formation of doubly ionized oxygen vacancies at high temperature.

1- Write the equation describing the equilibrium between this oxide and dioxygen.
2- The electronic charges liberated during this reaction induce valency defects which interact
with cations in normal positions in the crystalline network.
2.1- What is the nature of these valency defects?
2.2- Write the charge transfer mechanism responsible for electronic conduction.
3- Demonstrate that during the conditions defined above, the concentration of ionized O2-
vacancies scales with the partial oxygen pressure, PO2.
4- The difference in stoichiometry of the Nb2O5-x oxide, always proportional to the vacancy
concentration x, also varies with temperature. One measures, under PO2= 10-13 bar:

T(°C) 927 977 1027 1077 1127 1177 1227

- ln X 2.54 2.30 2.05 1.82 1.59 1.41 1.21
Determine the standard enthalpy of formation of the vacancies, ΔfH°.

Exercise 9: Nonstoichiometry in NiO

Let’s consider NiO: Structure type NaCI

a=4.159 Å
M(Ni)= 58.7 g mol-1 M(O)=16 g mol-1

1- Calculate the density, ρ0, of the stoichiometric material.

2- Chemical analyses reveal a non-stoichiometry in NiO. The material can be described by the
formula NiOx with x having an interval of [1.0; 1.1].
2.1- What are the three possible types of defects? For each defect type, write the
chemical formula of the material, introducing a variable (such as l, s or i) that describes
the defect formation appearing in the ideal, stoichiometric compound.
2.2- Establish the expression of x as a function of l, s and i. Determine the minimum and
maximum values of x forming the limits for l, s and i.
2.3- For each type of defect, establish an expression for the density ρ as a function of ρ0
for l, s and i. Calculate the density of the NiOx material assuming the largest
nonstoichiometry (x=1.1).
2.4- The density of the Ni01.1 material is characterized by pycnometry, and determined to
be 6.41 g cm-3. What is the nature of the defect?
2.5- Considering the nature of the defect identified in the previous question, determine the
kind of conduction expected for NiOx.
2.5.1- Explain the formation of this defect, and specifically indicate whether it is
favoured by large or small oxygen partial pressures (a text is expected rather
than an equation).
2.5.2- Establish the equation of the defect formation in the Kröger Vink notation.
2.5.3- Does this defect induce a change to the cation valency? Justify your
answer.
2.5.4- Deduce from the nature of the charge carriers the kind of conduction, then
the relationship between the charge carrier concentration and the oxygen partial
pressure.
2.5.5- Conclude with by expressing the conductivity as a function of the oxygen
partial pressure.
Exercise 10: Non-stoichiometry of the pyrrhotites

Pyrrhotite, FeS, is a covalent compound that crystallizes in a hexagonal structure, in which

the iron atoms occupy the octahedral sites of a compact network of sulfur atoms. Its cell
parameters are: a=3.45 Å and c=5.70 Å.

Pyrrhotite is actually nonstoichiometric, with a formula Fe uS, where u belongings between

the [0.875; 1.0] interval. The variation of cell parameters within the solid solution should be
considered to be negligible.
Given: M(Fe)=55.87 g mol-1 and M(S)=32.06 g mol-1
1- Calculate the density of the stoichiometric FeS crystal.
2- Establish as a function of u the expression of the density of FeuS pyrrhotites when:
a) It is an interstitial solid solution
b) It is a lacunar solid solution
3- The density of Fe0,875S is about 4.5 g.cm-3. Deduce the nature of the
nonstoichiometry in pyrrhotites.
Clarify the chemical composition of Fe0,875S by taking into account electron transfers.

Exercise 11: Linear defects

Characterize the defect below from the layout of the Burgers ‘s circuit:

0000000
000
 Exercise 12 : Dislocation motion

1- A linear defect moves when a sufficient level of shear stress  is applied to it. Is the stress
required for the dislocation motion higher in Si or Fe? Suppose the same dislocation in Si
crystal and Fe crystal. Please, justify your answer.
2- Show that the figure below displays two dislocations of opposite sign. Represent the final shape
of the crystal when a stress field  is applied. The two possible orientations for will be
considered.

Exercise 13 : Microstructure of pure zirconium

Describe this image. What are the defects highlighted? What is the mean size of grains?
Exercise 14 : Austenite microstructure

The microstructure below corresponds to austenite, a solid solution of face-centered cubic crystal
structure.

(magnification : X 325)

1- Identify the defects in the austenite in this micrograph.

2- Determine approximately the mean size (in µm ) of the austenite grains.
3- How are the 2D defects highlighted?
4- What are the other possible defects in austenite?

Exercise 15 : 3D defects

Copper (FCC) has a radius of 0.128 nm. The incorporation of tin of radius 0.151 nm gives
bronze having 3 at% tin and 97 at% copper.

1- Bronze retains the fcc structure to form a solid solution. Its lattice parameter increases, its
value at 3 at% tin is 0.364 nm. Justify the tin substitution and calculate the density of this bronze.

2- In realty, tin-saturated copper leads to Cu3Sn precipitation in the copper matrix. This
compound has an orthorhombic structure with lattice parameters:
a=0,434 nm, b=0,556 nm and c=3,81 nm
Calculate the number of tin and copper atoms in a cell knowing that the density of this compound
is 8.94 g/cm3
3- Assuming that precipitates are distributed in the matrix in the cell shape defined above, their
26 3
volume density would be 10 /m . In fact, they are parallelepiped needles such as a'= 100a,
19 3
b'=100b, c'= 1000c and their volume density then becomes 10 /m . Show that the growth of
precipitates leads to a decrease of internal energy. The copper matrix/Cu3Sn interface energy is
0,8J/m2.

MCu=63,55 g mol-1, MSn=118,69 g mol-1

Exercise 16: Properties and microstructure of a copper-aluminium system

Let us consider the copper-aluminium system

Given: R(Al)=1.431 Å M(Al)=26.981 g mol-1 FCC structure

R(Cu)=1.278 Å M(Cu)=63.546 g mol-1 FCC structure

The experimental lattice parameters for both copper and aluminium were determined using X-ray
diffraction. The following values were obtained:

aexp(Al)=4.04901 Å

aexp(Cu)=3.61503 Å

1. Are these lattice parameter values in accordance with theory? Explain your response.
2. Solid solution
a) Explain why Cu and Al cannot form a total solid solution via substitution.
b) The phase SSmax is the maximum solubility of copper in aluminium, having a lattice
parameter of 4.04864 Å. Calculate the molar fractions of copper and aluminium in SSmax.
Hint: conserve 5 digits after the decimal point in your calculations.
3. Precipitation within the Cu matrix. If the quantity of introduced copper is greater than that
defined in the previous question, the obtained material contains AlyCuz precipitates dispersed in
the SSmax matrix. A elemental chemical analysis shows that AlyCuz contains 54.08% copper, by
mass.
a) Determine the composition of AlyCuz.
b) Explain the impact of the AlyCuz precipitates on the mechanical properties of the SSmax
matrix in comparison to the properties of pure Al and AlyCuz-SSmax. Hint: First compare Al
and SSmax.

Exercise 17: Thermal and crystallographic analysis of coral

Coral is a natural ceramic mainly composed of calcium carbonate (CaCO3) (M = 100.08

g/mol). During the stage of biomineralization, it crystallizes as aragonite. This ceramic also
possesses another crystalline variety, which is calcite (See the table below).

Aragonite Calcite
Crystal System Orthorhombic Hexagonal
Lattice parameters (Å) a=4.9623 a=4.990
b=7.968
c=5.7439 c=17.002
Density 2.93 2.72
ρ (g/cm3)

1- Calculate the number of patterns in each lattice.

2- During heat treatment, aragonite is transformed into calcite. Calculate the volume variation
(ΔV/V) associated with this transformation.
3- Explain the transformations that occur during heating and cooling from the dilatometric
analysis. Comment on the stability of both aragonite and calcite.
4- Calculate the thermal coefficient of expansion of calcium carbonate.
5- Assuming that the properties of coral are isotropic, show that the dilatometry curve is
coherent with the calculation made in question 2.
6- Coral is used medically as a bone substitute. Before its implantation, coral must be heat-
treated at 500 °C to remove the organic compounds. Determine the volume of coral to use so
that the implant will accommodate a cubic cavity of 1 cm3.

heating

cooling

Temperature (°C)

Exercise 18: Problem of thin layer deposition

A technician meets the following problem: he or she tries to deposit a layer of diamond by
PVD (Physical Vapor Deposition) on a copper substrate. For this, the substrate must be
treated at high temperature. Under the deposition conditions, we observe a diamond layer on
Cu (see Figure a) below). This layer contains no defect and adheres to the substrate.
However, after cooling the material to ambient temperature, the technician observes that the
layer cracks and then bursts (see Figure b below).

Diamond layer diamond

Copper substrate copper

a) Formation of the diamond layer on b) The diamond layer on the Cu substrate

Cu substrate during deposition after the deposition and cooling to
(T > Tambient) ambient conditions (T = Tambient)

Explain why the layer cracks and then bursts.

Exercise 19: Intrinsic properties

1- We give the following values of Young’s modulus E:

1) 0.7 GPa 2) 40 GPa 3) 250 GPa 4) 400 GPa 5) 450 GPa 6) 1000 GPa
Attribute to each of the following materials the corresponding E value:
a) Silicon carbide b) Magnesia (MgO)
c) Alumina d) Magnesium
e) Polyethylene f) Diamond

2- We give the following values of melting point Tm:

1) 113.7 °C 2) 660 °C 3) 800.7 °C 4) 2053 °C
Attribute to each of the following materials the corresponding Tm value:
a) Aluminium b) Diiodide (I2)
c) Alumina d) Sodium chloride