CHEM1902/4 2014-N-2 November 2014

Marks
• The cubic form of boron nitride (borazon) is the second-hardest material after 5
diamond and it crystallizes with the structure shown below. The large spheres
represent the nitrogen atoms and the smaller spheres represent boron atoms.

From the unit-cell shown above, determine the empirical formula of boron nitride.

There are N atoms on the corners and on the faces of the unit cell:

• There are 8 N atoms on the corners. These contribute 1/8 to the unit cell
giving a total of 8 × 1/8 = 1 N atom.
• There are 6 N atoms on the faces. These contribute 1/2 to the unit cell
giving a total of 6 × 1/2 = 3 N atoms.
• There are a total of 1 + 3 = 4 N atoms in the unit cell.

There are B atoms inside the unit cell:

• There are 4 B atoms completely inside the cell. These contribute only to
this unit cell giving a total of 4 × 1 = 4 B atoms.

The formula is therefore B4N4 which simplifies to BN.

Answer: BN

Determine the oxidation state of the boron atoms.

Nitrogen has an oxidation number of –III (or -3) to complete its octet. To ensure
neutrality, boron must be +III (or +3).

Answer: +III (or +3)

ANSWER CONTINUES ON THE NEXT PAGE
CHEM1902/4 2014-N-2 November 2014

The cubic form of boron nitride is more thermally stable in air than diamond. Provide
a reasonable explanation for this observation.

Boron and nitrogen have different electronegativities, with N more

electronegative than B. This leads to partial δ+ and δ- charges on B and N
respectively. These charges give the bonds partial ionic character and this acts to
increase the strength of the bonds.

A protective layer of B2O3 forms on the surface of BN in the presence of air. For
diamond, gaseous CO2 forms at high temperatures which leads to thermal
degradation rather than protection.
CHEM1102 2014-N-3 November 2014
Marks
• A simplified phase diagram for iron is shown below, with the solid part divided into 5
the body-centred cubic (BCC) and face-centred cubic (FCC) phases.

fast slow

Which form of iron is stable at room temperature and pressure?

BCC form

If molten iron is cooled slowly to around 1200 °C and then cooled rapidly to room
temperature, the FCC form is obtained. Draw arrows on the phase diagram to
indicate this process and explain why it leads to the FCC form as a metastable phase.

The slow cooling leads to the most stable form at 1200 oC – the FCC form. Fast
cooling to room temperature does not allow the atoms to re-arrange; they are
stuck in the FCC form as considerable re-arrangement is needed to turn this in
the BCC form.

The structure is stuck in the FCC arrangement even though BCC is more stable.

The line dividing the BCC and FCC forms is almost, but not quite vertical. Predict
which way this line slopes and explain your answer.

BCC is less dense than FCC – the latter is a close packed structure so has the
maximum possible density whereas the former is not closed packed.

Applying pressure will favour the more dense structure as it takes up less space.
Increasing pressure therefore favours the FCC structure. The line between BCC
and FCC has a negative slope (\). If the system is on the line and the pressure is
increased, the system moves into the FCC region.
CHEM1902/4 2012-N-2 November 2012
Marks
• PdO is used as a hydrogenation catalyst and it crystallizes with the tetragonal 8
structure shown below. NiO has a variety of uses and crystallizes with the rocksalt
structure. The large spheres represent the oxygen atoms and the smaller spheres
represent palladium or nickel atoms.

palladium(II) oxide, PdO nickel(II) oxide, NiO

Show the structure on the left is consistent with the formula PdO.

In the unit cell there are:

4 Pd atoms
1 O atom in the centre
2 × ½ = 1 O atom at the top and bottom faces
4 × ¼ = 1 O atom at the equatorial edges
8 × ⅛ = 1 O atom at the corners

This gives unit cell formula of Pd4O4 and thus empirical formula of PdO.

What is the coordination number about each metal atom?

Pd: 4 Ni: 6

The radius of the Pd2+ ion is 86 pm, that of the Ni2+ ion is 69 pm. Give a reason why
the larger ion has a smaller coordination number.

Pd2+ (d8) prefers square planar coordination and thus has a lower coordination
number than Ni2+. The ionic model would predict that the larger Pd2+ ion would
have a higher coordination than Ni2+. The preference of Pd2+ for square planar
coordination overrides this.

Does either structure contain a close-packed arrangement of O2– ions?

PdO: YES / NO NiO: YES / NO

If YES, indicate the layers on the unit cell(s) above. See coloured layers above
CHEM1902/4 2010-N-2 November 2010
Marks
• SrFeO3 crystallises with the perovskite structure, shown below. The structure is cubic 9
with iron atoms on each corner, oxygen atoms at the centre of each face and
a strontium atom at the centre of the cube. Mixed metal oxides such as this are of
current research interest because of their magnetic and possible superconducting
properties.

Show the structure is consistent with the formula SrFeO3 and give the coordination
numbers of the Sr, Fe and O atoms.

There is a Fe atom on each of the 8 corners, each of which is shared between 8

cells so contribute 1/8 to each: number of Fe atoms = 8 × 1/8 = 1.

There is a O atom on each of the 6 faces, each of which is shared between 2 cells
so contribute 1/2 to each: number of O atoms = 6 × 1/2 = 3.

There is a single Sr atom which is at the centre and is unshared: number of Sr

atoms = 1.

The formula is thus FeSrO3.

Each Fe atom is surrounded by 12 O atoms: it has a coordination number of 12.

Each Sr atom is surrounded by 6 O atoms: it has a coordination number of 6.

Each O atom is surrounded by 2 Sr atoms, at a distance of 0.5a, and 4 Fe atoms,

at a distance of 0.707a. As coordination number is defined as the number of
nearest neighbours, it is 2.

Using the box notation to represent atomic orbitals, work out how many unpaired
electrons are present on the iron cation in this compound.

As Sr2+ and 3O2- are present, iron must have an oxidation number of +4. As iron
has 8 valence electrons, Fe4+ has (8 – 4) = 4 valence electrons and a d4
configuration. These are arranged in the five d orbitals to minimise repulsion by
maximising the number of unpaired spins:

↑ ↑ ↑ ↑
There are 4 unpaired electrons

ANSWER CONTINUES ON THE NEXT PAGE

CHEM1902/4 2010-N-2 November 2010

It is possible to substitute the Sr2+ ions at the centre of the unit cell by La3+ ions to
make a series of compounds with the formula La1-xSrxFeO3 with 0 ≤ x ≤ 1. Suggest
why this substitution is achieved without significant change to the unit cell
dimensions and describe how charge balance is achieved in these compounds.

La3+ has a similar size to Sr2+ as they are diagonally related on the Periodic
Table. La3+ has an extra shell but has a higher charge. As a result, La3+ is able to
occupy the same position in the unit cell as Sr2+ without the unit cell being
strained.

Each time a La3+ replaces a Sr2+, a Fe4+ is reduced to Fe3+ to ensure charge
balance is maintained.
CHEM1902/1904 2009-N-3 November 2009
Marks
• Shown below is the energy profile for the separation of Na+ from H2O. Draw energy 6
profiles for the separation of Mg2+ from Cl– and for the breaking of the C–C bond in
ethane to the same scales (approximately).

Mg2+ Cl–

C C
Energy

Na+ OH2
Na+⋅⋅⋅⋅⋅OH2

C–C

Mg2+⋅⋅⋅⋅⋅Cl–
Separation

There is an activation energy (barrier) for the breaking of a covalent bond. For
an ionic bond and an ion-dipole interaction, the energy just increases with
separation. Due to the charges, the ion-ion interaction is harder to break than
the ion-dipole interaction.

Name the inter- or intra-molecular forces involved in each of these three interactions.

Na+ OH2 ion - dipole

Mg2+ Cl– ion – ion (ionic bond)

C C covalent bond

Explain why bonds such as C–C are generally considered to be stronger than
interactions such as that between Mg2+ and Cl–.

The covalent bond has a large energy barrier (activation energy) that must be
overcome to break the bond. Ionic bonds do not have this barrier, but have a
larger overall ∆H.
CHEM1902/1904 2009-N-6 November 2009
Marks
• The diagram below shows the structure of an alloy of copper and gold with a 5
gold atom at each of the corners and a copper atom in the centre of each of the faces.
The unit cell dimension (edge length, a) for this alloy is 0.36 nm.

= Au = Cu
What is the chemical formula of the alloy?

There are 8 Au atoms on the corners. Each of these contribute 1/8 to the unit cell:
number of Au atoms = 8 × 1/8 = 1
There are 6 Cu atoms on the face. Each of these contribute 1/2 to the unit cell:
number of Cu atoms = 6 × 1/2 = 3
The ratio of Cu to Au atoms is therefore 3 : 1 and the formula is Cu3Au.

Answer: Cu3Au

Given that pure gold is 24 carat and gold alloyed with 25% by weight of another
metal is termed 18 carat gold, what carat gold is this alloy?

The molar mass of Cu3Au is:

molar mass = (3 × 63.55 (Cu) + 1 × 196.97 (Au)) g mol-1 = 387.62 g mol-1.

As 1 mol of Cu3Au contains 1 mol of Au, the percentage by weight of gold in Cu3Au
is:

.
percentage by weight = × 100 % = 50 %
.
As a 100 % alloy is 24 carat and a 75% alloy is 18 carat, a 50 % alloy is 12 carat.

Answer: 12 carat

What is the volume of the unit cell?

As the unit cell is cubic:

volume = (side length)3 = a3 = (0.36 × 10-9 m)3 = 4.7 × 10–29 m3

Answer: 4.7 × 10–29 m3

ANSWER CONTINUES ON THE NEXT PAGE
CHEM1902/1904 2009-N-6 November 2009

What is the density of the alloy?

From above, the unit cell contains 1 Au atom and 3 Cu atoms:

mass of gold = 196.97 g mol-1 / 6.022 × 1023 mol–1 = 3.271 × 10-22 g
mass of copper = 3 × 63.55 g mol-1 / 6.022 × 1023 mol–1 = 3.166 × 10-22 g
mass of unit cell = (3.271 × 10-22 + 3.166 × 10-22) g = 6.437 × 10-22 g
The density is therefore:
density = mass / volume
= 6.437 × 10-22 g / 4.7 × 10–29 m3 = 1.4 × 107 g m-3
As 1 m = 100 cm, 1 m3 = (100)3 cm3 = 105 cm3:
density = 14 g cm-3

Answer: 14 g cm-3
CHEM1902/1904 2009-N-7 November 2009
Marks
Shown below is the phase diagram for the Cu/Au system. Describe what would be
3
seen as a sample of the alloy is heated from 900 to 1100 oC.

liquid

solid

The solid would warm to 950 °C where melting would begin.

From 950 - 960 °C, the solid and liquid phases would co-exist. This should be
compared to the behaviour of a pure substance where there is no increase in
temperature whilst the solid melts.
Above 960 °C, only liquid is present.
CHEM1902/1904 2008-N-8 November 2008
Marks
• The diagram below shows the structure of an oxide of rhenium. The unit cell is cubic 5
with rhenium at each of the corners and oxygen in the centre of each of the edges.

= Re =O
What is the chemical formula of this oxide?

There are 8 Re atoms on the corners, each contributing 1/8 to the unit cell: total
number of Re atoms = 8 × 1/8 = 1.

There are 12 O atoms on the edges, each contributing 1/4 to the unit cell: total
number of O atoms = 12 × 1/4 = 3.

The formula is thus ReO3.

Answer: ReO3

What are the coordination numbers of rhenium and oxygen in this compound?

Re: 6 (octahedral) O: 2 (linear)

There is a large hole at the centre of the cell that in some compounds is occupied by a
cation. What is the coordination number of a cation occupying this site?

12 coordinate.

Given that the density of this oxide is 7.1 g cm–3, calculate the length of the cell edge.
(The structure is cubic.)

The unit cell contains one formula unit of ReO3.

The formula mass of ReO3 is (186.2 (Re) + 3 × 16.00 (O)) = 234.2 g mol-1.

This is the mass of 1 mol. The mass of 1 formula unit is therefore:

mass = = 234.2 g mol-1 / 6.022 × 1023 mol–1 = 3.889 × 10-22 g

ANSWER CONTINUES ON THE NEXT PAGE

CHEM1902/1904 2008-N-8 November 2008

As density = mass / volume,

volume = mass / density = (3.889 × 10-32 g) / (7.1 g cm-3) = 5.48 × 10-23 cm3

As the cell is cubic, if the side length is a, the volume is a3 and,

a = (5.48 × 10-23 cm3)1/3 = 3.8 × 10-8 cm = 3.8 × 10-10 m or 380 pm.

Answer: 380 pm
CHEM1902/1904 2007-N-6 November 2007
Marks
• The diagram below shows the structure of perovskite, a mineral made up of calcium 5
(at each of the corners), oxygen (in the centre of each of the faces), and titanium
(at the centre of the cube). The unit cell dimension (edge length, a) for perovskite
is 0.38 nm.
a
a
calcium

oxygen

a
titanium

What is the chemical formula of perovskite?

There are eight Ca2+ ions on the corners of the cube. These are each shared
between eight unit cells: number of Ca2+ ions = 8 × 1 8 = 1.

There is a single, unshared Ti4+ ion at the cube centre.

There are six O2- ions at the centres of the faces of the cube. These are each shared
between two cubes: number of O2- ions = 6 × 1 2 =3.

Overall, Ca2+ : Ti4+ : O2- = 1 : 1 : 3. The formula is CaTiO3.

Answer: CaTiO3

What is the volume of the unit cell?

The length of the side of the cube = a = 0.38 nm. As V = a3,

V = (0.38 × 10-9 m)3 = 5.5 × 10-29 m3

Answer: 5.5 × 10-29 m3

What is the density of perovskite? Give your answer in g cm–3.

CHEM1902/1904 2007-N-6 November 2007

M
As the atomic mass is the mass of a mole, the mass of one atom is . From
Na
above, each unit cell contains 1 Ca2+, 1 Ti4+ and 3 O2-. The mass of one cell is
therefore:

M Ca M M 1
mass of cell = + Ti +3 O = (40.08 + 47.88 + 16.00) g
Na Na Na Na
1
= × 135.96 g = 2.258 × 10-22 g
Na

As 1 cm = 0.01 m, 1 cm3 = (0.01)3 m3 = 1 × 10-6 m3. From above, V = 5.5×10-29 m3

so,

volume = 5.5 × 10-29 / 1 × 10-6 cm3 = 5.5 × 10-23 cm3.

Hence,

mass (g) 2.258 × 10−22 g

density = = = 4.1 g cm-3
3 −23
volume (cm ) 5.5 × 10 cm 3

Answer: 4.1 g cm-3

ANSWER CONTINUES ON THE NEXT PAGE
CHEM1902/1904 2007-N-6 November 2007

What is the density of perovskite? Give your answer in g cm–3.

M
As the atomic mass is the mass of a mole, the mass of one atom is . From
Na
above, each unit cell contains 1 Ca2+, 1 Ti4+ and 3 O2-. The mass of one cell is
therefore:

M Ca M M 1
mass of cell = + Ti +3 O = (40.08 + 47.88 + 16.00) g
Na Na Na Na
1
= × 135.96 g = 2.258 × 10-22 g
Na

As 1 cm = 0.01 m, 1 cm3 = (0.01)3 m3 = 1 × 10-6 m3. From above, V = 5.5×10-29 m3

so,

volume = 5.5 × 10-29 / 1 × 10-6 cm3 = 5.5 × 10-23 cm3.

Hence,

mass (g) 2.258 × 10−22 g

density = = = 4.1 g cm-3
3 −23
volume (cm ) 5.5 × 10 cm 3

Answer: 4.1 g cm-3

CHEM1102 2005-J-2 June 2005
Marks
• Many elemental metals crystallise in one of three cubic forms, either with a face- 3
centred cubic, a body-centred cubic or a simple cubic unit cell. Explain the main
differences and similarities between these different crystalline forms.

All three are based on a cubic unit cell:

• The simple cubic form has atoms on each corner so that the atoms are
stacked directly one on top of the other. As the 8 atoms are shared with eight
other cubes, each contributes 1/8 to the cell so that the cell contains 8 × 1/8 =
1 atom. The atoms touch along the edges of the cube.
• The body centred cubic form has at an additional atom in the cube centre,
giving a total of 2 atoms in the cell. The atoms touch along the cube
diagonal.
• The face centred cubic form has atoms on each corner and atoms at the
centre of each face (with no atom at the centre of the cube). The atoms on
the face centres are shared with two other cubes and so contribute 1/2 to the
cell. The cell contains 8 × 1/8 (corner) + 6 × 1/2 (face) = 4. The atoms touch
along the face diagonals.
• The face centred cubic form is the only close packed structure and is the
most dense.
• In a face centred cubic structure, 74% of the space is occupied. In a body
centred cubic, 68% is occupied. In a simple cubic structure, 52% is
occupied.