Department of Chemistry

Faculty of Science
Universiti Putra Malaysia

Module 1 Title SYMMETRY

COURSE CODE Inorganic Chemistry I
Module Code/No UPM/FS/CHY3302
DURATION 6 hours
Learning Resources 1. D.F. Shriver and P.W.Atkin, Inorganic Chemistry, 3rd
Edition,1999, Oxford University Press.

2. G.L. Miessler and D.A Tarr, Inorganic Chemistry, 3rd Edition,

2004, Pearson Prentice Hall.

3.http://www.jce.divched.org/JCEDLib/QBank/collection/ConcepTe
sts/inorsym.html

4.http://chemistry.rutgers.edu/undergrad/chem207/SymmetryGroupT
heory.html

PRIOR Knowledge The idea of symmetry is now an integral part of the conceptual too-
kit used by modern science where models are constructed to explain
the behavior of materials.

Several generalizations which underlie the concept of symmetry in

our everyday life are :-

- Repetitive elements in architecture

- Decoration on craft objects (pottery)
- Artifacts involving symmetric repetition (plaits, matting
fabric)
- Natural objects (bilateral and radially symmetrical plants and
animals : regular and symmetrical natural crystals).
- Ideas of symmetry also emerge naturally from the study of
geometry, in particular from the construction of regular plane
and solid figures.
Some cultures reinforce the examination of symmetry as part of the
process of adapting natural forms for decorative purposes. Muslim
culture forbade the use of natural objects for decorative purposes,
thus driving artists into a study of purely abstract design. This study
provides the basis for much of our modern understanding of the law
symmetry. The Viking culture used natural forms in their decorative
arts, but in a way that avoided symmetrical arrangements. The most
notable examples are found on the long ships which are themselves
among the most complex symmetrical objects ever built by hand.

Areas of application in modern chemistry

❖ Atomic orbitals higher in energy than the s-orbital have wave

functions symmetrically arranged in space; bonding using
these orbitals is geometrically constrained and so imposes
constraints on the architecture of molecules which in turn may
also exhibit symmetrical features.

❖ The phenomenon of optical activity associated with the

asymmetric carbon atom, dextro- and laevorotatory
compounds, racemic mixtures, etc…

❖ The analysis of the vibrational spectra of molecules, chiefly in

infra-red and Raman spectroscopy

❖ Molecular orbital theories of chemical bonding

❖ The analysis of the electronic spectra of transition metal

compounds.

❖ The phenomena of crystal diffraction, and hence structural

analysis based on the techniques of X-ray, neutron and
electron diffraction.

From the process of analysis which has effectively spanned several

centuries it has become clear that there are only four basic symmetry
operations required to reproduce all known ways of repeating an
object in space in a regular way.

SYMMETRY OPERATION and SYMMETRY

ELEMENTS

Note the distinction is made between symmetry operations and

symmetry elements: SYMMETRY OPERATIONS are the motions
applied to the objects which carry it into equivalent configurations;
SYMMETRY ELEMENTS are the loci in space about which this
operations are performed. Symmetry operations are actions,
symmetry elements are objects; it is possible to have more than one
operation associated with a specified element.

A rotation operation is carried out about a linear locus in space called

rotation axis; a reflection is carried out a reflection plane (sometimes
also called a mirror plane); an inversion is performed through in
inversion point and an improper rotation is performed by rotation of
360o/n followed by reflection through a mirror plane perpendicular to
the axis of rotation (a rotation – reflection operation).

Important symmetry operations and symmetry elements

*This symmetry element can be considered as for the whole

molecule
b
Note the equivalences S1 = δ, S2 = i

Each molecule has a set of symmetry operations that describes the

molecule’s overall symmetry; This set of symmetry operation is
called Point Group.

POINT GROUP

Molecules can be assigned to a point group by the following steps.

1. Determine whether the molecule belongs to one of the special

cases of low and high symmetry

2. Find the rotation axis with the highest order Cn for the
molecule-The Principal Axis

3. Does the molecule have any Cn axes perpendicular to the Cn

axis?

4. Does the molecule have the mirror plane (δh horizontal

plane) perpendicular to the Cn axis?
5. Does the molecule have the mirror planes that contain the Cn
axis (δV axis or δd)?

6. Is there any S2n axis collinear with the Cn axis

 Group of Low symmetry

Group of high symmetry

TERMS TO KNOW Symmetry element, Symmetry operation, point group, Rotation,

Identity, Mirror plane, Center of inversion

Learning Outcomes At the end of this module, students are able to:
1. Define symmetry operations and symmetric elements
2. Identify all the symmetry elements in the molecule
3. Generate all the symmetry operation
4. Classify molecules into symmetry point groups
Course Contents Practical Exercise
AND
LEARNING • Identify and list all the symmetry elements in the molecules in
Activities the table below (Table 1.1)
Make use of a molecule model kit to assist you in the
identification of all symmetry elements.
• Sketch the molecule on graph papers, and label all the
symmetry elements present

Classify all the molecules into symmetry point groups by using

Figure 1.1 (Attachment)

Table 1.1 Summary Table of Symmetry Elements

Summary Understanding the symmetry requires careful practice and

imagination so that one able to excel in this perspective. Such topic
forms the fundamental basis to understand the correlation between
structure, composition and properties of a wide variety of materials.

Assignment Develop the multiplication tables for all possible symmetry

operations allowed bh the geometry of water (C2v) and NHF2
(Cs)molecules.
assessment* Not relevant
Department of Chemistry
Faculty of Science
Universiti Putra Malaysia

Module 2 Title THE STRUCTURE OF SOLIDS

COURSE CODE Inorganic Chemistry I
Module Code/No UPM/FS/CHY3302
DURATION 6 hours
Learning Resources 1. D.F.Shriver and P.W.Atkin, Inorganic Chemistry, 3rd Edition,
1999, Oxford University Press.

2. G.L. Miessler and D.A Tarr, Inorganic Chemistry, 3rd Edition,

2004, Pearson Prentice Hall.

3.http://www.kings.edu/chem.purdue.edu/genchem/topicreview/bp/c
h13/structure.html

PRIOR Knowledge The Packing of Spheres in Crystalline Solids

When crystals form, the particles that form the solid pack as tightly
as possible in order to maximize intermolecular attraction.

This can be illustrated by packing the ping-pong balls in some orderly

way. There are four possibilities in arranging the balls

1. Simple Cubic Packing

One way to arrange the spheres is in orderly rows and stacks, with the
spheres in one layer sitting directly on top of those in the previous
layer, so that all layers are identical. (Fig 2.1a and b)

The result is a regular in which the repeating unit is a cube of eight

spheres. This structure is called simple cubic packing.
Each atom in this arrangement can form bonds to its six nearest
neighbors – four in its own layer, one above and one below. Each
sphere is thus said to a coordination number of 6.

Only 52% of the available space is actually occupied by the spheres,

making inefficient use of space and minimizing attractive farces.

2. Body-centered Cubic Packing

Another approach, slightly separate the sphere to form a square-

packed plane in which they do not quite each other, as shown in
figure 2.2

The spheres in the second plane pack above the holes in the first plane
(as in Figure 2.2 (b)).

The spheres in the third plane pack above holes in the second plane.
Sphere in the fourth plane pack above the third plane, and so on.

This structure of repesting pattern is called body-centered body

packing.

Each sphere in this arrangement has a coordination number of 8.

Four neighbour above four below. The space is used quite efficiently
: 68%

The two remaining packing arrangements of spheres are both said to

be closest-packed, hexagonal closest-packed structure and cubic
closest-packed structure.

3. Hexagonal Closest-packed structure.

The first layer of closest-packed structures consists of spheres in

which each sphere touches six nearest neighbors in the plane (Figure
2.3 (a). A second layer is formed by packing spheres above the
triangular holes in the first plane, as shown in (Figure 2.3 (b).
The sphere of the third plane lie directly above the sphere of the
first. This ABAB… pattern of layers gives a lattice with a hexagonal
unit cell, and hence is said to be hexagonal closest-packed
structure (hcp)

Figure 2.3 (a) (b)

Each sphere touches three spheres in the plane above, three spheres
in theplane below and six spheres in the same plane. Thus teh
coordination number is 12.

74% of the space in hexagonal closest packed structure (hcp) is filled.

This is the most efficient way of packing spheres.

4. Cubic Closest-packed Structure

There is another way of stacking closest-packed planes of sphere. The

sphere of the third layer are placed above the holes in the first layer
that were not used to form the second layer (as in Figure 2.4). The
fourth layer of the spheres packs directly above the first. This result
in an ABCABC…. Pattern, which is called cubic closest-packed
structure (ccp). This result in face-centered cubic (fcc) unit cell

The coordination number is 12

Figure 2.4 : Cubic closest packed structure

Interstitials/Holes in Closest-Packed and simple Cubic

Structures.’

There are two kinds of interstitials/ holes (or unoccupied space) in a

closest-packed structure. See Figure 2.5

Figure 2.5

1. An Octahedral Hole
It lies between two oppositely directed planar triangles of spheres in
adjoining layers. There are N octahedral hole, for the N atoms in the
crystal. The hole has local octahedral symmetry.
2. A tetrahedral Hole
This hole is formed by a planar triangle of touching spheres that is
capble by a single spheres lying in the dip (hole) between them. The
apex of the tetrahedron may be directed up (T) or down (T’) in the
crystal.

There are N tetrahedral holes of each type (2N in all).

They are called tetrahedral holes because ions that pack in these
holes are surrounded by four oppositely charge ions arranged toward
the corners of a tetrahedron.

The Structures of Metals

The structures of pure metals can be thought of as identical perfects

spheres. The same can be said about the structure of teh rare gases at
very low temperatures. These substances crystallize in one of four
basic structures: simple cubic (sc), bcc, hcp, ccp.
 Ionic Solids

Many of the ionic solid structures can be regarded as derived from

arrays in which the anions (or sometimes the cations) are stacked
together in fcc or hcp patterns and the counters ions occupy the
octahedral and tetrahedral holes in the lattice. The closest-packed
layer ussually needs to expand in order to accommodate the counters
ions; but this is often a minor pertubation of the anion arrangement.

TERMS TO KNOW Simple cubic packing, Body-centered packing, cubic-closed

packing, Hexagonal-closed packing, Metals, Ionic solids and
Covalent solids

Learning Outcomes At the end of this module, students are able to:
1. Explore how atoms, ions or molecules are arranged in solids
2. Build crystal structures using ping-pong balls. The atoms are
represented by spheres and the solid is the outcome of stacking the
spheres together densely, close-packed arrangement.

Course Contents Practical Exercise

AND
LEARNING The Packing of Spheres in Crystalline Solids
Activities
By using ping-pong balls given to you, assemble the four basic
structures of packing of sphere as described in the theory, i.e: simple
cubic (sc), body-centered cubic packing (bcc), hexagonal closest-
packed structure (hcp) and cubic closest-packed structure (ccp)

1) Based on the models you made above, draw (in 3-dimension)

all the four types of packing arrangements.

2) Draw a unit cell for each of the packing arrangements.

3) Determine the nearest neighbor of each sphere in sc, bcc,hcp

and ccp structures and thus determine the coordination number.

4) Calculate the maximum radius of sphere that may be

accommodated in an octahedral hole in a closest-packed solid, if the
radius of a sphere is r, and that of the hole is rh.

5) Give examples of some metallic elements that crystallize in

sc, bcc, hcp and ccp structures

Summary It is imperative to understand the structure of various solids as their

physical, chemical as well as electrical properties depend strongly
on how the atoms are arranged. This also allows other modifying
 job, e.g. chemical doping, in order to improve further the properties
so that these materials could meet the demands in specific
applications.

Assignment Ionic Solids

Models of the following compounds are made available to you:

CsCl, CsF, ZnS and CaF2
1) Draw the structures of the ionic given
2) What are the coordination numbers of the anion and cation in
each structure?
3) How many Cs+ and Cl- ions are there in the CsCl unit cell?
4) How many Zn2+ and S2- ions are there in the sphalerite unit
cell?
5) CsF adopts NaCl structure but not CsCl. Why?
6) Distinguish the differences among the structures of CsCl, CsF
and CsF2 ?

Covalent Network Solid – Graphite and Diamond structures

You are given model and graphite structures, representing covalent

network solids.

1. Write a short note on the description of structure, bonding and

geometry of diamond and graphite

2. Can you name other covalent network solids apart from diamond
and graphite?

assessment* Not relevant

Department of Chemistry
Faculty of Science
Universiti Putra Malaysia

Module 3 Title CRYSTAL SYSTEMS AND STRUCTURES

COURSE CODE Inorganic Chemistry I
Module Code/No UPM/FS/CHY3302
DURATION 6 hours
Learning Resources 1. D.F.Shriver and P.W.Atkin, Inorganic Chemistry, 3rd
Edition,1999, Oxford University Press.

2. G.L. Miessler and D.A Tarr, Inorganic Chemistry, 3rd Edition,

2004, Pearson Prentice Hall.

3. http://dave.ucsc.edu/myrtreia/crystal.html

PRIOR Knowledge Introduction

Crystals are built up of regular arrangement of atoms in three

dimensions; these arrangement can be represented by a repeat unit
called the unit cell. The unit cell is define as the smallest repeating
unit which shows the full symmetry of the crystal structure. There
are seven independent unit cell shapes that are possible in three
dimensional crystal structures: the seven crystal systems. These are
cubic, tetragonal, orthorhombic, hexagonal, trigonal, monoclinic
and triclinic. Each crystal system is governed by the presence or
absence of symmetry.

The manner of repetition of atoms, ions or molecules in a crystal

can be represented by an array of points; the array is called a lattice
and the points lattice points. The unit cell can then be constructed
by linking the lattice points. There are different ways of linking
these points resulting in different lattice , namely primitive (P),
body centred (I), face centred (F)and side centred (C, B or A).

The combination of crystal system and lattice types result in the

Bravis lattices. There are fourteen possible Bravis lattices.
 Figure 1 shows the 7 crystal systems, unit cell shape and lattice
types that allowed. The lattice type plus unit cell combination is
absent from the table if (a) symmetry requirements are violated, e.g.
C-centred lattice cannot be cubic because it would not have the
necessary three-fold axes or (b) it may be represented by a smaller,
alternative cell, e.g. face-centred tetragonal cell can be redrawn as
a body-centred tetragonal cell; the symmetry is still tetragonal but
the volume is halved.

Figure 1.

TERMS TO KNOW Crystal systems, Bravais Lattices, Rock-salt, Wurtzite, Perovskite,

Spinel

Learning Outcomes At the end of this module, students are able to:

1. List down the 7 crystal systems

2. Draw the 14 Bravis lattices

3. Understand the identities, similarities and differences of the

common structures of metals and ionic compounds.
Course Contents The students are required to observe the given structural models
AND including 7 crystal systems, different metal models, layered-
LEARNING structure models, perovskite and spinel.
Activities
 Based on the observation, draw and answer the following
questions outlined in assignment section.

Summary Several materials are studied herewith as they possess common

structure in most of the solids including metals, e.g. copper,
magnesium, edible salt, dielectric materials and others. This also
sheds lights on the importance of studying their structures,
discovering their atomic arrangement and extending their range of
applications in various areas.

Assignment 3.1 Bravis Lattices

Study the 14 models of Bravis lattices carefully

(a) What is the essential symmetry for each Bravis lattice?
(b) What are the values of α, β and y for each type of unit cell?
(C) Comment on the variations of a, a, b and c for each type of
unit cell.
(d) What is Z, the number of atoms in each of the 14 Bravis
lattices?

3.2 Crystal structures of metals

Study the models of the crystal structures of Mg and Cu carefully.
(a) What are the lattice types for Mg and Cu?
(b) Comment on the crystal symmetry of Mg and Cu.
(c) What are the coordination numbers of Mg and Cu in their
crystal structures?

3.3 Layered structures

Study the models of CdCi2 and CdI2 carefully.
(a) What are the unit types for these two materials?
(b) What are the coordination numbers and geometries for the
cations and anions in these structures?
(c) What are the differences between these two structures?

3.4 Models of rock salt (NaCl), Perovskite (CaTiO3) and

spinel (MgAl2O4)
(a) What type of unit cell does each these structure possess?
(b) Determine Z
(c) Draw the structures.
(d) List down the similarities and differences among these
structures.

assessment* Not relevant

Department of Chemistry
Faculty of Science
Universiti Putra Malaysia

Module 4 Title Synthesis and characterisation of double salts and complex salts
COURSE CODE Inorganic Chemistry I
Module Code/No UPM/FS/CHY3302
DURATION 3 hours
Learning 1. H.F. Walton, Inorganic Preparations, Prentice – Hall.
Resources 2. D.F.Shriver and P.W.Atkin, Inorganic Chemistry, 3rd
Edition,1999, Oxford University Press.
3. G.L. Miessler and D.A Tarr, Inorganic Chemistry, 3rd Edition,
2004, Pearson Prentice Hall.
PRIOR Knowledge Double salt, CuSO4. (NH4)SO4.6H2O
Double salt are formed when two simple salt crystallize in definite,
sample molecular proportions. They have their own crystal form,
which need not be the same as that of either of their component salts.
This is a phenomenon of the solid state; in a solution they are
decomposed completely, or nearly so, into the ions of their
component salts. In this respect doble salts are distinguished from
complex salt, which give complex ions of their own in solution.
Double salt are extreamely numerous. Two example will be
prepared.

Complex Salt
Tetrammine Cupric Sulfate [Cu(NH3)4SO4.H2O]
When Ammonia is added to a solution of a cupric salt, a light blue
precipitate of Cupric Hydroxide is first formed which dissolves in
excess of Ammonia to form a deep purplish-blue solution. The color
is due to the complex ion Cu(NH3)4++.The Sulfatte of this ion is easily
obtained in solid form as the hydrate Cu(NH3)4SO4.H2O.
TERMS TO KNOW Double salts, Complex salts, crystallization, Precipitation

Learning At the end of this module, students are able to:

Outcomes
1. Synthesize double salt and complex salt using wet chemistry
method
2. Characterize and compare the physical and chemical properties
between the prepared salts.
Course Contents AND Double salt Cu SO4 (NH4)2SO4.5H2O
LEARNING
Activities Dissolve 0.03 mole of copper sulfate pentahydrate and 0.03 mole of
ammonium sulfate in 15 ml hot water. Cool slowly. When the
solution is cold, filter off the crystals on a buchner funnel and dry
them on filter paper in air. Weight and record the yield. Examine
them to see if they are homogeneous. Compare their appearance and
 behaviour in solution with that of the complex salt cupric tetrammine
sulfate, Cu(NH3)4SO4.H2O, which will be prepared later. This salt
will be separated in large well-formed crystals if a cold saturated
solution is left to evaporate slowly in the air. The crystals belong to
a monoclinic system.

Complex Salt, Cu(NH3)4SO4.H2O

Dissolve 6.25 grams (0.025 mole) of powdered copper sulfate
pentahydrate in a mixture of 10 ml of concentrated ammonia and 6
ml of water, and slowly add to the blue solution 10 ml of ethyl
alcohol. Allow it to stand for about an hour, finally cooling
thoroughly, and filter the crystals on a buchner funnel. Wash first
with a mixture of equal volumes of alcohol and concentrated
ammonia, then with alcohol, and finally with ether. Dry in a
dessicator over freshly ignited quicklime. The final product must be
dry and free from alcohol. Weight and record the yield.

Another way to precipitate the complex salt from its aqueous

solution is to pour the alcohol carefully over the top the solution and
set aside for a week. As the alcohol slowly diffuses into the aqueous
solution, long needle-like crystal of the tetrammine cupric sulfate
form at the boundary.

Comparison of Properties
Compare the appearance and properties of the double salt,
CuSO4(N43)2SO4.6H2O with the complex salt, Cu(NH3)4SO4.H2O.

Dissolve a tiny amount of each salt in water and compare the UV-
VIS spectra of the resulting solutions.

Summary As a conclusion, typical examples of double salts and complex salts

should be learned and compared in terms of their synthesis,
properties and their potential applications in industries.

Assignment 1. Name three double salts that are important in industry or in

laboratory practice
2. Name 3 other metallic cations that form complex ions with
ammonia
3. When the complex salt dissolved in water, a slight precipitate will
appear. Identify the precipitate and explain its formation?
4. What is the difference between the consitution of tetrammine
cupric sulfate and cupric ammonia sulfate?
assessment* Not relevant
Department of Chemistry
Faculty of Science
Universiti Putra Malaysia

Module 5 Title Synthesis and characterisation of potasium trioxalatoaluminates

COURSE CODE Inorganic Chemistry I
Module Code/No UPM/FS/CHY3302
DURATION 6 hours
Learning 1. Mounir A. Malati, 1999, Experimental Inorganic/ Physical
Resources Chemistry. An Investigative, Integrated Approach to Practical Project
Work. Horwood Publishing Chichester
2. F. Psss and H. Sutcliffe, 1974, Practical Inorganic Chemistry,
Preparation Reaction & Instrument Methods 2nd Edition, Chapman and
Hall.
3. D.F.Shriver and P.W.Atkin, Inorganic Chemistry, 3rd Edition,1999,
Oxford University Press.
4. G.L. Miessler and D.A Tarr, Inorganic Chemistry, 3rd Edition, 2004,
Pearson Prentice Hall.
PRIOR Al3+ ions, like other ions with noble gas configuration, form
Knowledge preferentially complexes with oxygen-coordinating ligands. Unlike
Boron, which forms tetrahedral complexes, the larger aluminium ion
forms octahedral complexes with the chelating ligands which stabilize
the complexes by the chelate effect. Aluminium oxinate is an example
of an octahedral complex where the O and N of the ligand are
coordinated to the aluminium in a six coordinate netral complex. Even
the aluminate ion is best represented as [Al(H2O)2(OH)4]-.. The major
exception is [AlH4]- ions, which are tetrahedral.
Al3+ readily forms the oxalate complex where the two oxygen atoms
of the lligand are coordinated to the metal, to give the complex anion
(Al(C2O4)3]3-. This complex ion has similar crystallographic properties
to the trisoxalato complex ions of iron(III), cobalt (III), and chromium
(III) and is prepared in a similar manner.
TERMS TO KNOW Complex compounds, Sulfates, Oxalates, Chelates, coordination

Learning At the end of this module, students are able to:

Outcomes
1. Synthesize complex compounds of aluminium derived from sulfates
and oxalates

2. determine the oxalate concentaration and compare the reaction of

aluminate complex with various reagents
Course Contents Dissolve ammonium sulfate (7 g of the hexadecahydrate) in 50 cm3 of
AND water and add to this, with stirring, a solution of sodium hydroxide (2.5
LEARNING g in 10 cm3 of water). Filter the freshly precipitate Aluminium
Activities Hydroxide and wash with water. Prepare a solution containing oxalic
acid (4 g of the dehydrate) and potassium oxalate (6 g of the
monohydrate in 50 cm3 of water). Heat the solution with the
aluminium hydroxide prepared earlier until the volume is reduced by
2/3 (Do not boil vigorously or else the complex may decompose).
Filter off undissolved aluminium hydroxide. Cool the filtrate in ice
bath to allow crystallization of the complex to occur. Filter, dry and
record the yield.
Analysis

Determination of Oxalate
Treat an accuracy weighed sample of the complex (0.2 g) in the 100
ml 1 M Sulphuric Acid and heat to 80°C. Titrate the Oxalate with 0.02
M Potassium Permanganate solution. KMnO4 previously standardized
against 0.05 M Na2C2O4 solution. Repeat and calculate the percentage
purity of your preparation.
IR spectrum of the complex
Run FT-IR spectrum (Used UATR sampling accessory).
Complementary work:
1 Investigate the effect of the following reagents on a
solution of the product:
4M Sodium Hydroxide
Sodium Acetate solution
Sodium Carbonate solution
Sodium Orthophosphate solution

Compare the result with those obtained when a sample Aluminium salt
(eg. Aluminum sulphate) is treated with same reagents.

Summary As a conclusion, the preparation technique used for the complex

compounds derived from oxalates and sulfates should be learned.
Meanwhile, the complementary work used to characterize the prepared
samples are of utmost importance for understanding their properties.

Assignment 1. Assign the band and compare them with the bands of the ligand
(Oxalate).

2. Deduce your explanation for those recorded observation in

complementary work.

assessment* Not relevant

Department of Chemistry
Faculty of Science
Universiti Putra Malaysia

Module 6 Title Synthesis and analysis of calsium peroxide

COURSE CODE Inorganic Chemistry I
Module Code/No UPM/FS/CHY3302
DURATION 6 hours
Learning Resources 1. D.F. Shriver and P.W.Atkin, Inorganic Chemistry, 3rd Edition,
1999, Oxford University Press.
2. G.L. Miessler and D.A Tarr, Inorganic Chemistry, 3rd Edition,
2004, Pearson Prentice Hall.
3. http://www.freepatentsonline.com/4101644.html

PRIOR Knowledge Within the subgroups of alkali metals and alkaline-earth metals there
is a decreasing tendency with increasing cation size for the formation
of M(I)2O or M(II)O oxide by a direct combination of the elements.
The small lithium cation, Li+ will form a more stable crystal lattice
with a small anion than with a larger alkali metal cation. With
increasing size of the cation, a more stable crystal structure is obtained
by expanding the lattice and increasing the separation of the cations.
This may be achieved by replacing the oxide ion O2- by a larger anion
such as peroxide, O22- or superoxide O2- ions. The peroxide ion O22-
is larger than the oxide ion O2-. It should be noted that for lithium the
most stable lattice is achieved with a small ion, as in Li2O. For a larger
cation such as Ba2+ or K+ the most stable lattice is achieved with the
larger anion, O22- as seen in BaO2 or K2O2.

TERMS TO KNOW Oxide, Peroxide, Superoxide, lattice, stability

Learning Outcomes At the end of this module, students are able to:

1. Understand the reaction between carbonates and chlorides in the

preparation of metal peroxides

2. Determine the yield of product and water content in hydrated

metal peroxides

Course Contents Add 10 cm3 of concentrated HCl into 10 cm3 of water in a beaker.
AND Cover the beaker with a watch glass and carefully add 5 g calcium
LEARNING carbonate. Heat the solution to dissolve all the CaCO3 and boil to
Activities expel carbon dioxide. If there is still undissolved CaCO3, filter while
it is hot. Add water so that the volume is 20 cm3 and allow the solution
(CaCl2 solution) to cool in ice.
 Dilute 5 cm3 of concentrated ammonia (in a fume cupboard) with 10
cm3 of water, then add 30 cm3 hydrogen peroxide, H2O2 (20% by
volume) and allow to cool in an ice bath. Into this solution, add CaCl2
solution prepared above dropwise.

Allow to stand in ice bath. Filter the product and wash with previously
cooled water and dry in air. Record the volumes of the calcium
chloride and peroxide solutions used in the reaction.
Weight the product and calculate the percentage yield.

Analysis of CaO2.XH2O

The precentage of peroxide is determined by titration against KmnO4.

Weight accurately 0.10 g of calcium peroxide and then dissolve it in
40 cm3 of diluted sulphuric acid in a conical flask. Immediately titrate
the solution with 0.02M KmnO4. repeat the titration at least once and
calculate the % CaO2.XH2O in your sample and % H2O and thus
determine x.

Percentage of Water and the x value in CaO2.XH2O

Weigh 1 g CaO2.XH2O and heat it to constant weight in a porcelain

crucible.

Calculate the weght loss and determine x. Compare the result with
that obtained from above.

Summary As a conclusion, the technique used for the preparation of calcium

peroxide should be learned. The reaction between carbonates and
chlorides will be an important step involved in the synthesis of metal
peroxides.

Assignment 1. Draw and name the crystal structure of CaO2

2. Explain briefly the preparation of the peroxides of group I and II
elements
3. Explain the solubility of the peroxides of group I and II elements
4. Explain the stability of the peroxides of group I and II elements
5. Suggest a method of preparation for Barium peroxide

assessment* Not relevant

Department of Chemistry
Faculty of Science
Universiti Putra Malaysia

Module 7 Title Synthesis and Characterization of Glasses

COURSE CODE Inorganic Chemistry I
Module Code/No UPM/FS/CHY3302
DURATION 3 hours
Learning Resources 1. http://www.practicalchemistry.org/
2. Shriver, D.F. and Atkins, P.W. 1999. Inorganic Chemistry.
3rd ed. London: Oxford Uni. Press.
3. Cotton F.A., Wilkinson, G., Murillo C.A and Bochman M.
1999. Advanced Inorganic Chemistry. 6th ed. John Wiley.
4. West A.R. 1999. Basic Solid State Chemistry. New York:
John Wiley. 2nd ed.
PRIOR Knowledge In this experiment, one will learn about the techniques to prepare
simple lead based glasses using different transition metals. The
changes in the physical and chemical properties of synthesized
glasses are noticeable if different transition metals are used as
dopants. On the other hand, the fundamental aspects of different
types of glasses and their applications in industry shoud be
discussed.

TERMS TO KNOW Glasses, Dopants, Colour change, Band gap

Learning Outcomes At the end of this module, students are able to:

1. Synthesize lead-based glasses using different transition metals

2. Understand the characteristics and applications of different

glasses

Course Contents Weigh 6.5 g of lead (II) oxide, 3.5 g of boric acid and 0.5 g of zinc
AND oxide into the boiling tube and stopper firmly. This should be
LEARNING handled carefully in order to avoid any spills of these chemicals in
Activities this process. Insert the bung in the tube and shake the mixture until
homogeneous, and then transfer into the crucible. Then, use a
straightened paper clip to stir the mixture.

Place the lid on the crucible, and gradually heat up the mixture using
an electrical heater. Heat carefully at first, and then apply stronger
higher heating until the mixture becomes molten and runny. Remove
the crucible from heater and pour one or two drops of the molten
glass onto the white tile. Continue the heating process with the rest
of glass molten. Allow the glass beads to cool for 5 minutes and
 then examine physical appearance of the product. Use a straightened
paper clip to pick up a tiny speck of one of the metal oxides
provided and stir this into the remaining molten mixture. Avoid
using excessive powder else, you will produce a very dark piece of
glass.

Repeat the steps (f)-(h) with different speck of transition metals.

After the experiment, cool down and clean all the apparatus.

Summary This experiment gives exposure for the synthesis and

characterization of lead-based glasses. The effect of different
dopants on the physical and chemical properties could be observed.

Assignment 1. Propose a stoichiometric formula for the synthesized product if

common metal oxides are used

2. Discuss and explain the structure, physical and chemical

properties of prepared glass.

3. Compare the different types of glasses using suitable examples

and their applications.

4. Explain in detail why the colour of the glass changes if different

transition metals are used.

5. What are the other major factors to be considered in the

preparation of glass particularly in the glass industry. Explain the
effect of dopants in the production of glass

6. State the precaution steps in this glass making experiment.

assessment* Not Relevant

Department of Chemistry
Faculty of Science
Universiti Putra Malaysia

Module 8 Title Synthesis and analysis of complexes from borohydride anions

COURSE Inorganic Chemistry I
CODE
Module UPM/FS/CHY3302
Code/No
DURATION 3 hours
Learning 1. D.F.Shriver and P.W.Atkin, Inorganic Chemistry, 3rd Edition, 1999,
Resources Oxford University Press.
2. G.L. Miessler and D.A Tarr, Inorganic Chemistry, 3rd Edition, 2004,
Pearson Prentice Hall.
3. www.science.marshall.edu/castella/chm448/boranes.pdf

PRIOR The borohydride (or tetrahydroborate) anion, BH4-, is widely used in organic
Knowledge chemistry as a reducing agent. However, it also has many uses in inorganic
chemistry, of which two will be explored in this experiment.

Controlled oxidation of the borohydride anion results in the formation of

borane (BH3). Since borane has an empty p-orbital on the boron atom it
normally exists as a dimer (B2H6) which has bridging hydride ligands
involved in electron deficient three centre, two electron bonds. However,
when BH3 is generated in the presence of electron pair donors, L, it can form
adducts, L BH3. Adducts with thf, SMe2, pyridine and Me3N are widely used
as mild organic oxidants, while BH3 is used as a protecting group for
phosphines.
 The borohydride anion can also form complexes with transition metals,
which may adopt a variety of structural types. It may act as an isolated anion
(I), or bond covalently to a metal through monodentate (II), bidentate (III),
or tridentate (IV) hydride bridges. Furthermore, it can potentially act as a
bridging ligand between two metals (V). These structures may be
distinguished by the characteristic vibrations in their infra-red and Raman
spectra.

TERMS TO Borohydride, triphenylphosphineborane, NMR, Oxidation,

KNOW
Learning At the end of this module, students are able to:
Outcomes
1. Prepare triphenylphosphineborane, Ph3PBH3

2. synthesize a transition metal borohydride complex

3. Interpret multinuclear NMR spectra and use infra-red spectrocopy in

characterization

Course 1. Preparation of triphenylphosphine borane, Ph3PBH3

Contents AND
LEARNING • Prepare a solution of NaBH4 (1.0 g, 26 mmol) and Ph3P (7.6 g, 25
Activities mmol) in approx. 40 cm3 of ethylene glycol dimethyl ether
(Monoglyme, CH3O(CH2)2OCH3) and place in a 250 cm3 flask
equipped with magnetic stirrer, dropping funnel and reflux condenser.
• Warm the solution to reflux.
• Meanwhile, prepare a solution of I2 (3.2 g, 25 mmol) in the minimum
quantity of monoglyme (ca 10 cm3)
• Add this solution dropwise, via the dropping funnel, to the gently
refluxing NaBH4/PPh3 solution.
 • Reflux for a further 15 minutes.
• Remove the solvent using a rotary evaporator.
• Extract the product by from the residues using dichloromethane
• Filter by gravity to remove insoluble impurities.
• Carefully add an equal volume of diethyl ether to the filtrate to
precipitate the product. Note that crystallisation take a few minutes to
initiate – be patient!
• Filter by suction, wash with diethylether and air dry.
• Record the Yield (g, %)

2. Preparation of bis(triphenylphosphine)tetrahydroborato copper(I)

• Prepare a solution of triphenylphosphine (2.16 g) in chloroform (25

cm3).
• Add finely powdered anhydrous copper (I) chloride (0.4 g) with
stirring over about five minutes (if all the copper chloride has not
dissolved within this time, the reaction mixture should be filtered).
• To this solution, a suspension of powdered sodium borohydride (0.15
g) in ethanol (1 to 2 cm3) is added over ten minutes.
• After the addition is complete, the reaction mixture is stirred for
fifteen minutes.
• Pour the reaction mixture into water (5 cm3): a small amount of
decomposition may occur, with some gas evolution and a small
amount of elemental copper will be formed.
• Separate the organic phase (chloroform solution, lower layer) from
the aqueous phase in a separating funnel and wash with water (2 x 2.5
cm3).
• After separation, dry the chloroform layer (over anhydrous sodium
sulphate).
• Filter off the drying agent.
• Add diethyl ether (20 cm3) to the resulting solution to obtain
colourless crystals of your product, bis(triphenylphosphine) copper
tetrahydroborate.
• Filter off the product, wash with diethyl ether and dry in air.
• Record the yield (g, %).

Further Investigation
• Record the melting point of both compounds.
• Record the Infra-red spectrum of both compounds.

Summary As a conclusion, the technique used for the preparation of boron based
complexes could be learned. The specific characterizations, e.g. FT-IR and
NMR, are also applied to determine functional groups in the recorded
spectra of the prepared samples.
Assignment 1. Write a balanced equation for the formation of
triphenylphosphineborane.

2. Identify the bands in the infra-red spectrum arising from BH3 and PPh3.

3. Interpret the NMR spectra of Ph3PBH3 as fully as possible.

4. From the infra-red spectrum of Cu(PPh3)2BH4 (using Table I) deduce the

bonding mode of the BH4- ion.

5. Describe the reaction sequence that leads to the preparation of

(Ph3P)2CuBH4 and draw a diagram of its likely structure.

assessment* Not relevant