DEPARTMENT OF CHEMISTRY

FACULTY OF SCIENCE

SOLID STRUCTURE &

COORDINATION CHEMISTRY
CHY3304

PRACTICAL MODULE
SECOND SEMESTER 2022/2023
Department of Chemistry
Faculty of Science
Universiti Putra Malaysia

Module 1 Title Symmetry

Course Code CHY3304
Module UPM/FS/CHY3304
Code/No
Duration 6 hours
Learning 1. M. T. Weller, T. L. Overton, J. P. Rourke and F. A. Armstrong, Inorganic
Resources Chemistry, 7th Edition, 2018, Oxford University Press.
2. G. L. Miessler, P. J. Fischer and D. A. Tarr, Inorganic Chemistry, 5th
Edition, 2014, Pearson.
3. http://www.jce.divched.org/JCEDLib/QBank/collection/ConcepTests/i
norsym.html
4. http://chemistry.rutgers.edu/undergrad/chem207/SymmetryGroupTheor
y.html

Prior Introduction
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 behaviour
of materials.

Several generalisations underlying 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 and so forced 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 which 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

infrared and Raman spectroscopy.

❖ Molecular orbital theories of chemical bonding.

❖ The analysis of the electronic spectra of transition metal compounds.

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 OPERATION are the motions applied to the
objects which carry it into equivalent configurations; SYMMETRY
ELEMENTS are the loci in space about which these 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 360°/n followed by
reflection through a mirror plane perpendicular to the axis of rotation (a
rotation–reflection operation).

Table 1: Important symmetry operations and symmetry elements

 Symmetry element Symmetry operation Symbol
‘whole of space’ Identity* E
n-fold symmetry axis Rotation by 2π/n Cn
Mirror plane Reflection 
Centre of inversion Inversion I
n-fold axis of Rotation by 2π/n Sn
improper rotationa followed by reflection
perpendicular to
rotation axis

*This symmetry element can be thought of as for the whole molecule

b
Note the equivalences S1 = , 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.

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 (h horizontal plane)
perpendicular to the Cn axis?

5. Does the molecule have the mirror planes that contain the Cn axis (v axis
or d)?

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

 Group of Low symmetry

Group of high symmetry

Terms To Symmetry element, symmetry operation, point group, rotation, identity,

Know mirror plane, centre of inversion

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

Outcomes 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 Practical Exercise
Contents &
Learning • Identify and list all the symmetry elements in the molecules in the
Activities 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 by the geometry of water (C2v) and NHF2 (Cs) molecules.

Assessment* Lab Report

Figure 1:1: Identification of point group
Department of Chemistry
Faculty of Science
Universiti Putra Malaysia

Module 2 Title The Structure of Solids

Course Code CHY3304
Module UPM/FS/CHY3304
Code/No
Duration 6 hours
Learning 1. M. T. Weller, T. L. Overton, J. P. Rourke and F. A. Armstrong,
Resources Inorganic Chemistry, 7th Edition, 2018, Oxford University Press.
2. G. L. Miessler, P. J. Fischer and D. A. Tarr, Inorganic Chemistry, 5th
Edition, 2014, Pearson.
3. http://www.kings.edu/chem.purdue.edu/genchem/topicreview/bp/ch13/s
tructure.html

Prior The Structures of Metals

Knowledge
The structures of pure metals can be thought of as identical perfects spheres.
The same can be said about the structure of the rare gases at very low
temperatures. These substances crystallise in one of four basic structures:
simple cubic (sc), bcc, hcp, ccp. Metallic compounds are found to be good
heat and electrical conductors and these properties could be correlated to
their crystal structures.

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 usually needs to expand in
order to accommodate the counters ions; but this is often a minor
perturbation of the anion arrangement. One important distinctive
characteristic that differentiate ionic solids from covalent compounds is
their high melting point. This could be attributed to their high lattice
enthalpy arising from the strong ionic bond.

Covalent Compounds

Many compounds are found to be in form of liquid or gas phase instead of

solid structure due to their weak intermolecular attraction. Generally, they
have low melting point and are poor thermal and electrical conductors. Most
organic compounds are predominantly covalent in nature; their chemical
and physical properties are fixed especially compositional variable and
crystal defect are not allowed.

The Packing of Spheres in Crystalline Solids

When crystals form, the particles that form the solid pack as tightly as
possible in order to maximise 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 (Figure 2.1).

Figure 2.1: Simple cubic packing

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 neighbours
– 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
by the spheres, making inefficient use of space and minimising attractive
farces.

2. Body-centred 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
 Figure 2.2: Body-centred packing

This structure of repeating pattern is called body-centred 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 middle layer of closest-packed structures consists of spheres in which

each sphere touches six nearest neighbours in the plane (Figure 2.3a). Two
layers formed by packing spheres are placed above and below in the same
direction (Figure 2.3b). In other words, the sphere of the third plane lies
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). Each sphere touches three spheres in the
plane above, three spheres in the plane below and six spheres in the same
plane. Thus, the coordination number is 12. About 74% of the space in
hexagonal closest packed structure (hcp) is filled. This is the most efficient
way of packing spheres.
 Figure 2.3: Hexagonal closest packed structure (a) Layer arrangement
(b) Hexagonal unit cell

4. Cubic Closest-packed Structure

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

sphere of the third layer is 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-
centred 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: Octahedral and tetrahedral sites

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 (Figure 2.6).

Figure 2.6: The six-coordinated octahedron

2. A Tetrahedral Hole
This hole is formed by a planar triangle of touching spheres that is cap by a
single sphere 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 (Figure 2.7).
 Figure 2.7: The four-coordinated tetrahedron

Terms to Know Simple cubic packing, Body-centred packing, Cubic-closed packing,

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

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

Outcomes 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 Practical Exercise

Contents &
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-
centred 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 neighbour 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 crystallise in sc, bcc, hcp
and ccp structures.

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

chemical and electrical properties depend strongly on how the atoms are
arranged. This also allows other modifying jobs, e.g., chemical doping, in
order to improve further their properties so that these materials could meet
the requirements 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 brief 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* Lab Report

Department of Chemistry
Faculty of Science
Universiti Putra Malaysia

Module 3 Title Crystal Systems and Structures

Course Code CHY3304
Module UPM/FS/CHY3304
Code/No
Duration 6 hours
Learning 1. M. T. Weller, T. L. Overton, J. P. Rourke and F. A. Armstrong,
Resources Inorganic Chemistry, 7th Edition, 2018, Oxford University Press.
2. G. L. Miessler, P. J. Fischer and D. A. Tarr, Inorganic Chemistry, 5th
Edition, 2014, Pearson.
3. http://dave.ucsc.edu/myrtreia/crystal.html

Prior Introduction
Knowledge
Crystals are built up of regular arrangement of atoms in three dimensions;
this arrangement can be represented by a repeat unit called the unit cell.
The unit cell is defined as the smallest repeating unit, which shows the full
symmetry of the crystal structure. There are seven independent unit cells
that are possible in three-dimensional crystal structures: the seven crystal
systems including cubic, tetragonal, orthorhombic, hexagonal, trigonal,
monoclinic, and triclinic. Each crystal system is governed by the presence
or absence of certain 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
are 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 systems and lattice types, resulting in the

Bravais lattices. There are fourteen possible Bravais lattices.
 Figure 3 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 3: 7 crystal systems and 14 Bravais lattices

Terms To Crystal systems, Bravais Lattices, Rock-salt, Wurtzite, Perovskite, Spinel

Know
Learning At the end of this module, students should be able to:
Outcomes 1. List down the seven crystal systems
2. Draw the fourteen Bravais lattices.
3. Understand the identities, similarities, and differences of the common
structures of metals and ionic compounds.

Course The students are required to observe the given structural models including
Contents & 7 crystal systems, different metal models, layered-structure models,
Learning perovskite and spinel.
Activities
 Based on the observation, draw and answer the following questions in the
assignment section.

Summary Several structures are studied herewith as they possess some common
characteristics 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 Bravais Lattices

Study the 14 models of Bravais lattices carefully.

(a) What is the essential symmetry for each Bravais lattice?
(b) What are the values of α, β and  for each type of unit cell?
(c) Comment on the variations of a, b, and c for each type of unit cell.
(d) What is Z, the number of atoms in each of the 14 Bravais 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 structures possess?
(b) Determine Z.
(c) Draw the structures.
(d) List down the similarities and differences among these structures.

Assessment* Lab Report

Department of Chemistry
Faculty of Science
Universiti Putra Malaysia

Module 4 Title Synthesis and UV-Vis Spectra of Vanadium Complexes

Course Code CHY3304
Module UPM/FS/CHY3304
Code/No
Duration 6 hours
Learning 5. Ophardt, C. E. & Stupgla, S. (1984) Synthesis and Spectra of Vanadium
Resources Complexes, Journal of Chemical Education, 61(12), 1102-1103
6. Fedorova, E. V., Rybakov, V. B., Senyavin, V. M., Anisimov, A. V. &
Asinov, L. A. (2005) Synthesis and Structure of Oxovanadium(IV)
Complexes [VO(acac)2] and [VO(Sal:L-alanine)(H2O)],
Crystallography Reports, 50(2), 224-229
7. M. T. Weller, T. L. Overton, J. P. Rourke and F. A. Armstrong, Inorganic
Chemistry, 7th Edition, 2018, Oxford University Press.
8. G. L. Miessler, P. J. Fischer and D. A. Tarr, Inorganic Chemistry, 5th
Edition, 2014, Pearson.

Prior In this experiment, you will learn about the complexes of vanadium and the
Knowledge interpretation of the electronic spectra of transition metals using Tanabe-
Sugano diagrams. The three oxidation states of vanadium, which can be
easily obtained, will be used in the observation of the electronic spectra
resulting from the d1, d2 and d3 electronic configurations. During this
experiment, you will be exposed to the fundamental aspects, such as simple
synthesis techniques, the principle of redox in the reaction synthesis and the
interpretation of visible spectra using Tanabe-Sugano diagrams.

Terms To Russell-Saunders term symbols, Hund’s rule, Orgel diagram, Tanabe-

Know Sugano diagram, Beer-Lambert law,

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

Outcomes 5. Synthesise vanadium complexes in three oxidation states which are +2,
+3 and +4.
6. Use UV-Vis spectrophotometer to obtain spectra of the complexes.
7. Interpret the UV-Vis spectra using a Tanabe-Sugano diagram.

Course Procedures
Contents &
Learning 1. Synthesis of (NH4)2[VO(tart)].H2O
Activities In a 200 ml beaker, add 18 ml glacial acetic acid with 32 ml water and 1 ml
85% N2H4.H2O. Boil the mixture in boiling water at 65oC. Separately,
dissolve 5.8 g NH4VO3 with 50 ml H2O and then add into the mixture. Stir
and heat it continuously until all the NH4VO3 dissolves and all the gas is
released completely. The colour of the solution will change to dark blue.

Cool down the mixture to room temperature. Next add and stir 7 g tartaric
acid and 23 ml concentrated NH4OH, in this order, into the mixture. Cool
down the purple solution in an ice bath. Drop wise, add in 150 ml acetone
SLOWLY (5-15 ml each time) into the solution to make sure
(NH4)2[VO(tart)].H2O precipitate out. This is an important step to get good
crystalline product. Filter and wash the crystals using acetone and then dry
the crystals at room temperature. Weigh the dried product.

2. Synthesis of VO(acac)2

In a 50 ml round-bottomed flask fitted with a reflux condenser, add 1.5 g

V2O5, 4 ml H2O, 3 ml 18 M H2SO4, 8 ml absolute ethanol and a magnetic
stirrer. Reflux the mixture on a hot plate for about an hour. The alcohol in
the mixture will cause the reduction of V(V) to V(IV) which is dark blue.
Write down the chemical equation for the reduction reaction.

Filter the dark blue solution with a Gooch No. 3 filter to extract any V2O5
left over. Add and stir 4 ml of acetylacetone (acac) to the filtrate. Neutralise
the acidic solution using Na2CO3 solution (6.5 g of Na2CO3 in 40 ml H2O)
by slowly adding it to the acidic solution. VO(acac)2 will appear greenish
blue in colour at a pH of 3.5. Filter and wash the crystals with distilled water.
Dry the crystals at room temperature. Weigh the dried product.

3. Characterisations by UV-Vis spectroscopy:

You will be using the UV-Vis spectrophotometer Shimadzu at Block A1

G51 to get the UV-Vis spectra of the complexes in aqueous solution (3.3
until 3.8). You are required to get the max for the peak of each spectrum, so
the concentration is not important, but you must make sure the solution is
concentrated enough to get the required peak in the visible region of the
spectra.

3.1 Preparation of ammonium vanadate, NH4VO3, stock solution

Dissolve 4 g of NH4VO3 in 250 ml H2O and 2 ml 6 M NaOH. Heating is

required to make sure all the NH4VO3 has dissolved.

3.2 Preparation of Zn/Hg amalgam

Swirl 40 g of single pieces of zinc with 50 ml 1 M HCl to get pure zinc.

Discard the acidic solution and swirl the zinc pieces with fresh 150 ml 0.1
 M HgCl2 for 1-2 mins. Filter and wash the amalgam about three times using
50 ml boiling water. The amalgam is then kept in a reagent bottle.

3.3 Preparation of [VO(OH2)5]2+ solution

In a 100 ml beaker, mix 10 ml stock solution of NH4VO3, 2 ml 3 M H2SO4,

0.4 g Na2SO4 and 0.8 g Na2SO3 in the fume hood. Shake the mixture for a
few minutes until the solution turns blue.

3.4 Preparation of [V(OH2)6]2+ solution

First, prepare the VO2+ ion in a 250 ml beaker with 50 ml stock solution of
NH4VO3 and 10 ml 3 M H2SO4. Discard the water from the amalgam and
add the VO2+ ion to the amalgam. Shake the mixture while passing a flow
of nitrogen gas to dispel oxygen in the solution continuously, until the
colour of the solution changes to purple blue. Close the bottle once it has
reached the final colour. CAUTION: Do the UV/Vis immediately.

3.5 Preparation of [V(OH2)6]3+ solution

In a 100 ml beaker, add 2 ml [VO(OH2)5]2+ and 2 ml [V(OH2)6]2+ to get a

brown solution. The colour of the solution will then change from brown to
green within 3 mins.

3.6 Preparation of [VO(tart)]2− solution

Dissolve 0.1 g (NH4)2[VO(tart)].H2O in 30 ml H2O and 0.8 ml 6 M NH4OH.

3.7 Preparation of [VO(acac)2] solution

Dissolve 0.1 g [VO(acac)2] in 20 ml methanol.

3.8 Preparation of [VO(tart)]2− solution

Dissolve 0.1 g (NH4)2[VO(tart)].H2O in 30 ml H2O and 0.8 ml 3 M H2SO4.

Summary Two vanadium complexes are prepared in this experiment which are
(NH4)2[VO(tart)].H2O and VO(acac)2. Solution of these complexes and
other solutions of vanadium with different oxidation states underwent UV-
Vis analysis. Each spectrum of the solution will have different maxima as it
has different vanadium oxidation state hence, has different electronic
transition. The experiment allows students to apply theory learn in class to
assign and interpret the electronic transition observed in the UV-Vis
spectrum using Tanabe-Sugano diagram. They will also learn to apply other
theory/rule (e.g. Hund’s rule, Beer-Lamberts law) in the process to interpret
the spectra.

Assignment Answer the following questions.

 1. Find the balance chemical equation for all the reaction synthesis and
prepared spectra solutions. What gas is released in Procedure 1?
2. Determine the name, oxidation state, d-electron configuration,
structure, and colour for VO3− (basic solution), VO2+ (acidic
solution), [VO(OH2)5]2+, [V(OH2)6]2+, [V(OH2)6]3+, [VO(tart)]2- and
[VO(acac)2].
3. Change the value of the wavelength of all absorption peaks to wave
numbers.
4. Based on the information from Q1 to Q3 and the Tanabe-Sugano
diagram, give the electron transition assignments for all the
absorption spectra observed.
5. Arrange the spectrochemical series of VO2+.
6. There might be differences between the absorption peak taken from
any spectra of the VO2+ complexes and its theoretical values. Why
does this happen?
7. Give an explanation on the difference between the spectra of the
basic and acidic solution of [VO(tart)]2− complexes.

Assessment* Lab Report

Department of Chemistry
Faculty of Science
Universiti Putra Malaysia

Module 5 Title Synthesis and Characterisation of Cobalt Complexes

Course Code CHY3304
Module UPM/FS/CHY3304
Code/No
Duration 6 hours
Learning 1. M. T. Weller, T. L. Overton, J. P. Rourke & F. A. Armstrong, Inorganic
Resources Chemistry, 7th Edition, 2018, Oxford University Press.
2. G. L. Miessler, P. J. Fischer & D. A. Tarr, Inorganic Chemistry, 5th
Edition, 2014, Pearson.
3. C. E. Housecroft, & A. G. Sharpe, Inorganic Chemistry, 5th Edition,
2018, Pearson.

Prior Coordination complexes are formed from the transition metals ions and
Knowledge various compounds that act as Lewis bases by donating electron density to
the d orbital on the transition metal ions. The compounds that act as Lewis
bases in the formation of these complexes are referred to as ligands. In the
formation of these complexes, the metal ions act as Lewis acids. Ligands
can be ions such as chloride ion or neutral compounds such as ammonia.
Metal complexes play a variety of roles in our physical environment.
Chlorophyll is a coordination complex of magnesium and haemoglobin is a
coordination complex of iron. In addition, many other pigments and dyes
owe their deep colour to the formation of complexes with metals.

Crystal Field Theory (CFT) most easily explains the bonding found in
transition metals coordination complexes. CFT is based on electrostatic
repulsion in the presence of a non-homogeneous field. The effect of this
field is to split the set of five d orbitals into two or more sites of orbitals of
different energy. In the case of six-coordinate complexes (octahedral
complexes) such as the ones to be studied in this experiment, the d orbitals
are split into two sets of orbitals with different energies. The set of orbitals
with the higher energy is called the eg set and the one with the lower energy
is called the t2g set. The energy difference between the two sets of orbitals
in an octahedral field is called the Crystal Field Splitting Energy and is
symbolised by o.

For many coordination complexes, this energy difference results in the

absorption of light in the visible region. Therefore, these complexes appear
coloured to our eyes. The magnitude of the energy difference o depends
upon both the metal ion and its valence and the nature of the ligands itself.
The more easily a ligand can donate electron density to a metal ion, the
 greater the magnitude of the energy difference. In this experiment, we will
attempt to determine the relative strength of chloride ion, bromide ion and
water as a ligand. In addition, we will look at the spectrum of a tetrahedral
complex in which four ligands surround the metal ion instead of six found
in octahedral complexes.

While CFT is a simple model that allows us to explain the spectral and
magnetic properties of these complexes, it still does not explain why some
complexes form and the quantitative aspects of the energetic of transition
metal complexes. A more sophisticated model that encompasses both ionic
and covalent characteristics is called Ligand Field Theory (LFT), which is
a form of molecular orbital (MO) theory.

Terms To Crystal field theory, Crystal field splitting energy, Ligand field theory,
Know Tanabe-Sugano diagrams, magnetic moment

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

Outcomes 1. Synthesise different Co(III) complexes.
2. Use a UV spectrophotometer to list the ligands according to their
spectrochemical strength.
3. Use a conductivity meter to determine the level of ionisation of the
Co(III) complexes.
4. Use a Gouy balance to determine the magnetic susceptibility of the
Co(III) complexes.
5. Interpret the IR spectra of the synthesised compound.

Course Procedures
Contents &
Learning 1. Synthesis of [CoCl(NH3)5]Cl2 (A)
Activities Into a 250 ml beaker add 20 ml of 15 M ammonia and 3.0 g NH4Cl. Mix
these until the ammonia chloride dissolves in the aqueous ammonia
solution. Place a quantity of CoCl2.6H2O in a mortar and pestle and grind
to a fine powder. Weigh 6.0 g of CoCl2.6H2O powder to the nearest
milligram and transfer it to the solution in the 250 ml beaker slowly while
stirring the mixture. At this point, a brown solid/liquid mixture should be
present. Now slowly add to the mixture drop wise while stirring, 18.9 ml of
10% H2O2 (CAUTION: This material can cause burns, please wear your
safety gloves).

When the bubbling ceases, carefully add 20 ml of concentrated HCl (12 M)

drop wise (CAUTION: HCl requires the use of safety gloves). Heat the
mixture until the solution is just boiling. Continue this heating for 20 mins
with occasional stirring. Cool the mixture to room temperature and then
cool in an ice bath until purplish crystals form. Filter the crystals using a
Bucher funnel and an aspirator. Rinse the crystals three times with 10 ml
portions of ice-cold methanol. Allow the crystals to dry on an evaporating
dish. When the crystals are dry, obtain the mass and percentage yield of
your product. Place the product in a vial labelled with your name, the
chemical formula, the mass, and percentage yield. The simplified overall
reaction that takes place in this synthesis is:

Co3+ + 5NH3 + 3Cl− → [Co(NH3)5Cl]Cl2

2. Synthesis of [Co(NH3)5(OH2)]Cl3 (B)

Into a 250 ml beaker, add 20 ml of 15 M ammonia and 3.0 g of NH4Cl. Mix

until the ammonium chloride dissolves in the aqueous ammonia solution.
Place a sufficient quantity of CoCl2.6H2O in a mortar and pestle and grind
to a fine powder. Weigh 6.0 g of CoCl2.6H2O powder to the nearest
milligram and transfer it to the solution in the 250 ml beaker slowly while
stirring the mixture. At this point, a brown solid/liquid mixture should be
present. Now slowly add drop wise while stirring the mixture, 18.0 ml of
10% H2O2 (CAUTION: This material can cause burns, please wear your
safety gloves).

When bubbling ceases, carefully add concentrated HCl (12 M) drop wise
with stirring until the solution is just acidic. (CAUTION: HCl requires the
use of safety gloves). Now add 2 or 3 drops of the acid in excess. You will
need to check the pH often using litmus paper. You must avoid adding a
large excess of the acid. Add 50 ml of cold methanol and cool the mixture
in an ice bath until pink crystals form. Filter the crystals using a Buchner
funnel and an aspirator. Rinse the crystal to dry on an evaporating dish.
When the crystals are dry, obtain the mass. Place the product in a vial
labelled with your name, the chemical formula and percentage yield of your
product. The simplified overall reaction that takes place in this synthesis is:

Co3+ + 5NH3 + H2O + 3Cl− → [Co(NH3)5(OH2)]Cl3

3. Synthesis of [Co(NH3)6]Cl3 (C)

Into a 250 ml beaker, add 10 ml of distilled water and 4.0 g of NH4Cl. Mix
these until the ammonium chloride dissolves in the water. Place enough
CoCl2.6H2O in a mortar and pestle and grind to a fine powder. Weigh 6.0 g
of CoCl2.6H2O to the nearest milligram and transfer it to the solution in the
250 ml beaker slowly while stirring the mixture. Now add 15 ml of 15 M
ammonia. Cool the mixture in an ice bath. After cooling for several minutes
in the ice bath, add 1 g of activated charcoal. To this add 15 ml of 10% H2O2
while the mixture is still in the ice bath (CAUTION: This material can
cause burns, please wear your safety gloves).
Remove the beaker and its content from the ice bath and heat to almost
boiling for 30 mins. Now cool the solution to a little below room
temperature (~20oC) and then filter the solid that has formed using a
Buchner funnel and an aspirator. Place the solid in a 250 ml beaker and add
39 ml of water and 1 ml of concentrated HCl. Stir the mixture. Heat the
mixture for a few minutes to dissolve the entire yellow product (The carbon
is black and will not dissolve). Now suction filter the mixture while it is still
hot to remove the charcoal (CAUTION: Here you should use beaker
tongs).

Transfer the filtrate to a 250 ml beaker and cool in an ice bath. Now add 10
ml of 12 M HCl (CAUTION: Here you should wear gloves). Continue to
cool in the ice bath until yellow crystals form. Filter the crystals using
Buchner funnel and an aspirator. Rinse the crystals three times with 10 ml
portions of ice-cold methanol. Allow the crystals to dry on an evaporating
dish. When the crystals are dry, obtain the mass and percentage yield of
your product. Place the product in a vial labelled with your name, the
chemical formula, the mass, and percentage yield. The simplified overall
reaction that takes place in this synthesis is:

Co3+ + 6NH3 + 3Cl− → [Co(NH3)6]Cl3

4. Synthesis of [Co(CO3)(NH3)4]NO3 (D)

Dissolve 20.0 g (0.21 mol) (NH4)2CO3 in 60 ml of concentrated aqueous

NH3. While stirring, pour this solution into a solution containing 15.0 g
(0.052 mol) [Co(OH2)6](NO3)2 in 30 ml H2O. Then slowly add 8 ml of a
30% H2O2 solution (CAUTION: This material can cause burns, please
wear your safety gloves). Pour the solution into an evaporating dish and
concentrate over a hot bench in a fume hood to (90 to 100 ml). Do not allow
the solution to boil. During the evaporating time, add, in small portions, 5.0
g (0.05 mol) (NH4)2CO3. Suction filter (with water aspirator) the hot
solution and cool the filtrate in an ice water bath. Under suction using a
Bucher funnel, filter off the red product crystals. Wash the
[Co(CO3)(NH3)4]NO3 in the filtration apparatus first with a few millilitres
of cold water (the compounds are somewhat soluble) and then with a similar
amount of cold ethanol. Allow the crystals to dry on an evaporating dish.
When the crystals are dry, obtain the mass and percent yield of your product.
Place the product in a vial labelled with your name, the chemical formula,
the mass, and percentage yield.

5. UV-Visible spectroscopy

Qualitative information concerning electronic structure and therefore

chemical bonding in transition metal complexes can be obtained from the
absorption band parameters. This can be obtained by examining the most
important characteristics of the absorption bands which are their energies,
intensities, and bandwidths.

Accurately prepare 10.00 ml of a ~0.01 M solution of product A, B, C and

D, in water and obtain the electronic spectra of the compounds by measuring
the absorbance from 400 to 680 nm.

6. Molar conductivity measurements

Molar conductivity measurements are useful for establishing whether

substances are ionic or covalent in solution. In addition, these measurements
provide us information regarding the number of ions formed when the
compound dissolves.

Using the dry salts; A, B, C and D, and a 10 ml volumetric flask, accurately

prepare 10.00 ml of 0.1 M solution. The easiest way to do this is to
accurately weigh your salt and dissolve it in a small beaker with a small
amount of distilled water. Once the salt has dissolved, you can very
carefully transfer this solution to the volumetric flask. Then you will need
to rinse the beaker at least three times with small (5 ml or less) quantities of
distilled water, pouring the rinsing into the 10 ml volumetric flask and then
diluting to the mark with distilled water. From this stock solution, prepare
solutions of 0.008 M, 0.004 M, 0.002 M, and 0.001 M by accurate dilution.
These solutions will be used to determine the number of ions your salt
breaks into when dissolved. To measure the conductivity of these solutions,
follow the instructions given by the demonstrator.

7. Magnetic susceptibility measurements

Magnetic susceptibility is a measure of the number of unpaired electrons

that a molecule has. Substances with one or more unpaired electrons exhibit
paramagnetism, a weak form of magnetism. Substances that have no
unpaired electrons are called diamagnetic.

Follow the instruction given by the demonstrator to get the magnetic

susceptibility of your complexes.

8. Infrared spectroscopy

There are several ways of obtaining an infrared spectrum of a sample:

i) as the neat (undiluted) substance when the compound is a

liquid
ii) as a gas, for volatile compounds
iii) as in solution using suitable solvents
iv) as a mull
v) as a compressed solid pellet.
 One or more of these techniques may be used depending on the nature of
the compound under examination. Your samples will be collected on an
Attenuated Total Reflectance (ATR) FT-IR spectrophotometer. Follow the
instructions given by the demonstrator to get the infrared spectra of your
complexes.

Summary Cobalt complexes with different composition of ancillary ligands are

synthesised and analysed. The complexes are formulated in a way that
different ancillary ligand would cause d orbitals to split into different energy
levels. This is done by substituting the ancillary ligand with different ligand
strength and the effect of this is observed in the UV-Vis spectrum and colour
of the complexes. The magnetism of each complex is also studied by using
Gouy balance. The effect of different ligand surrounding the metal centre to
its level of ionisation can be measured using the conductivity meter and the
trend can be observed. Infrared spectroscopy help to elucidate the functional
groups present in the complexes.

Assignment Answer the following questions.

1. Calculate the crystal field splitting energy by determining the energy

at the peak maximum of your spectrum using the Planck equation.
Repeat for each of the complexes and arrange the ligands in order of
their strength.
2. Compare the UV-Vis spectra for the octahedral complexes to the
spectrum of the tetrahedral complex given as a handout in the lab.
Are you able to draw any conclusion? If so, write your conclusions
in your written report.
3. Determine the number of ions in your salts from the molar
conductivity results.
4. Determine if your product is paramagnetic and how many unpaired
electrons are present in a molecule of the compounds based on the
magnetic susceptibility measurements.
5. Compare and discuss the infrared spectra for all the compounds.

Assessment* Lab Report

Department of Chemistry
Faculty of Science
Universiti Putra Malaysia

Module 6 Title Synthesis and Temperature Dependence of the Rate of Aquation

Study of trans-Dichloridobis(ethylenediamine)cobalt(III) Chloride
Course Code CHY3304
Module UPM/FS/CHY3304
Code/No
Duration 6 hours
Learning 1. M. T. Weller, T. L. Overton, J. P. Rourke & F. A. Armstrong, Inorganic
Resources Chemistry, 7th Edition, 2018, Oxford University Press.
2. G. L. Miessler, P. J. Fischer & D. A. Tarr, Inorganic Chemistry, 5th
Edition, 2014, Pearson.
3. C. E. Housecroft, & A. G. Sharpe, Inorganic Chemistry, 5th Edition,
2018, Pearson.

Prior In this experiment we will carry out the synthesis of a cobalt complex, trans-
Knowledge dichloridobis(ethylenediamine)cobalt(III) chloride, the structural formula
of which appears as (I):

+
Cl

H H H H
H 2C N N CH2
Co -
H2 C Cl
N N CH2
(green)
H H H H

Cl
(I)

In this ion, which is called an "octahedral complex" because the Co atom is

surrounded by atoms situated at the corners of an octahedron, the nitrogen
atoms are in the same plane as, and equidistant from, the cobalt atom. The
groups attached to the cobalt ion, i.e., Cl− and ethylenediamine, are called
ligands.

In aqueous solution one of the chloride ions is easily replaced by a water

molecule, forming the pink ion shown as (II):

trans-[CoCl2(en)2]+ + H2O → trans-[CoCl(en)2(OH2)]2+ + Cl−

 H H
+
O

H H H H
H 2C N N CH2
Co -
H2 C Cl
N N CH2
(pink)
H H H H

Cl
(II)

The synthesis of the trans-[CoCl2(en)2]+ complex will proceed by (i)

oxidising the Co(II) complex [Co(en)2(OH2)2]2+; (ii) addition of an excess
of HCl; (iii) removal of most of the water from the reaction mixture, forming
the green dichlorido complex ion II; and (iv) the purification of the green
crystals of trans-[CoCl2(en)2]Cl by recrystallisation.

A number of comments need to be made concerning this synthesis. The

Co(II) ion does not bind ligands (i.e., the Cl− or ethylenediamine groups) as
strongly as the Co(III) ion. The oxidation is carried out on the ion
[Co(en)2(OH2)2]2+ rather than aqueous Co(II) (which is actually
[Co(OH2)6]2+ in solution), because the ethylenediamine ligands stabilise the
Co(III) ion, which otherwise would react with water to produce O2
according to;

4Co3+ + 2H2O → 4Co2+ + O2 (g) + 4H+

The recrystallisation purification step, (iv), is a standard procedure in

chemical synthesis, and is based on the principle that a pure crystal is more
stable than one containing impurities. Thus, when an impure solid is
dissolved in a suitable solvent and crystals are allowed to re-form, the
impurities tend to remain in solution (assuming that the solubility of the
impurity is of the same of magnitude as the substance sought in a purified
state).

The reaction of (I) with water occurs in the two steps shown in Eq. 1 and 2;

trans-[CoCl2(en)2]+ → [CoCl(en)2]2+ + Cl− (slow step) (1)

[CoCl(en)2]2+ + H2O → [CoCl(en)2(OH2)]2+ (fast step) (2)

the first step (Eq. 1) corresponds to the ionisation of a chloride ion from the
complex I, whereas the second step (Eq. 2) involves the addition of a water
molecule to the product formed in the first step.
The overall rate of the overall reaction (aquation reaction) is determined by
step (1), which is a slow unimolecular process (i.e., a spontaneous process
involving a single molecule rather than the simultaneous interaction of two
or more molecules). Radioactive decay processes are also unimolecular
processes. For unimolecular processes it is known that the concentration of
the reactant, trans-[CoCl2(en)2]+ in this case, decreases with time as
described by the formula shown in Eq. 3.

CR(t) = Coe-kt = Co10-kt/2.3 (3)

where the symbols have the following meaning:

CR(t) = concentration of reactant at time t (measured in seconds)

after the reaction has begun.

Co = initial concentration of reactant before reaction started.

k = rate constant for reaction (expressed in units of s−)

t = time in seconds since initiation of reaction

Quantitatively we can see from Eq. 3 that the larger the value of k (which
must be positive), the more rapidly the complex ion trans-[CoCl2(en)2]+,
will be aquated. In practice we find that k for this reaction increases rapidly
with temperature. The temperature dependence of k, and hence the rate of
reaction, is predicted from absolute reaction rate theory to be of the form
shown in Eq. 4.

k = koe-Ef*/KT = ko 10-Ef*/2.3RT (4)

where the symbols have the following meaning:

ko = reaction rate as the approaches ∞ (t → ∞)

Ef* = activation energy for forward reaction (see below)

T = temperature, Kelvin (K)

R = a fundamental constant (called the ideal gas constant) with the value of
1,9878 x 10-3 kcal/mol deg

The activation energy (-Ef*) corresponds to an unspecified energy barrier

that must be surmounted before the reaction can occur. The diagram in Fig.
1 illustrates this idea:
Fig. 1: The energy of activation (Ef*) represents the energy barrier to the
removal of Cl from reactant species to form an unstable (5 ordinate)
intermediate.

In other words Ef* represents the energy required to remove one Cl− ion of
the complex ion which must occur before an H2O molecule can be added to
the complex. Note that Ef* has no relation to reaction, which is the
thermodynamic energy of reaction (note, however, that the activation
energy for the backward reaction will be Eb* = Ef* + reaction. The
"reaction coordinate" referred to the Fig. 1 is a parameter that is meant to
describe the position of some object in space, while E is analogous to the
potential energy of that object. The primary purpose of the present
experiment is the study of the aquation rate k as function of temperature.

The rate at which the aquation reaction, shown as Eq. 5, occurs will be
determined at

trans-[CoCl2(en)2]+ + H2O → [CoCl(en)2(OH2)]2+ + Cl− (5)

(green) (pink)

several temperatures in the range 50-70°C. Rather than measuring the rate
directly, we shall measure the time required for the reaction to reach the
point where half of the original reactant molecules have reacted (or half of
the maximum number of product molecules which can be formed, have been
formed). In other words, we shall measure the time required for the reaction
to be half completed. The reaction will be "followed" by observing the
colour of the solution. At the halfway point, half of the cobalt atoms are in
the form of the green complex and half in the form of the pink complex.
Now, since our eyes cannot passes until the green reaction mixture turns
grey. In practice the solution contains equal amounts of reactant and
product, viz., half of the starting material (green [CoCl2(en)2]+) has been
replaced by an equivalent amount of product (pink [CoCl(en)2(OH2)]2+), is
measured by (tgy), the time for the solution to become grey. Unfortunately,
the colour change from green to grey to pink is not easily observed. But the
time at which the solution is maximum grey colour (tgy) may be reasonably
accurately estimated to be tgy = (tg + tp)/2.

When the mixture of the two complexes is grey the concentration of the
reactant (CR) and concentration of the product (CP) stand in a constant ratio
as given by Eq. 6.

CR (t gy )
= CG (6)
CP (t gy )

where CG ~0.46. However, as is shown in the following equations, we do

not need to know the value of CG. In Eq. 6 we write CR(tgy) and CP(tgy) to
emphasise that these represent the concentrations of the reactant and product
at time tgy.

Since there is no loss of cobalt-containing material during reaction, the sum

of reactant and product concentrations must equal the concentration of the
product at time t=0 (the time when the reaction was initiated). In other
words, all of the cobalt we put into the reaction is still there at time tgy. We
may write

CR (t gy )+CP (t gy )=Co (7)

Where Co = initial concentration of reactant.

From Eq. 6 we may replace CP(tgy) by CR(tgy)/CG so Eq. 7 becomes

CR (t gy ) + CP (t gy )/CG = Co (8)

Eq. 8 is solved for CR(tgy) giving the result

C CG
CR (t gy ) = 1+1⁄o C = Co C (9)
3 G G +1

Substituting Eq. 9 into Eq. 3 we obtain

CG
CR (t gy ) = Co C = Co e−ktgy + Co 10−ktgy /2.3 (10)
G +1

We may take the log to the base 10 of Eq. 10, after cancelling the factor of
Co, to give the relationship shown in Eq. 11.
CG
log (C ) = −kt gy /2.3 (11)
G +1
or
CG +1
log ( ) = kt gy /2.3 (12)
CG

Solving Eq. 12 for k we find

1 CG +1
k = t 2.3 log ( ) (13)
gy CG

or
A
k=t (14)
gy

where we have defined A as

CG +1
A = 2.3 log ( ) (15)
CG

We observe that A is temperature independent.

According to Eq. 2, log k will depend on T (expressed in K) as follows:

f ΔE∗
log K = log k o − 2.3 RT (16)

If we take the log of Eq. 14 we obtain

1
log K = log A + log t (17)
gy

Combining Eq. 16 and 17, and rearranging, we find that

1 f ΔE∗
log t = log k o − log A − 2.3 RT (18)
gy

or
1 ΔE∗ 1
log t = (constant) − (2.3 fR) T (19)
gy

Eq. 19 is the basis of the analysis of the present experiment. Eq. 19 states
that a plot of log (1/tgy) (where tgy is observed at various temperatures by
you) vs. 1/T (T = temperature in K) should give a straight line, with a slope
of ∆Ef*/2.3K. We note that the temperature dependence of a simple
unimolecular reaction, like the one studied here, is related to ∆Ef*: if ∆Ef* is
large, the rate decreases very rapidly with a decrease in T; if ∆E f* is small,
the rate is not affected so adversely by a decrease in T. In the present
experiment you will tabulate the value of tgy for a range of temperature
between 50-70°C. Then these data will be plotted according to Eq. 19 and
 the best straight line determined for the data points. The values of log(tgy-1)
are plotted along the y axis and the values of 1/T along the x axis.

Terms To Ligand substitution, lability, inertness, activation energy, rate of reaction

Know
Learning At the end of this module, students should be able to:
Outcomes 1. Synthesise trans-dichloridobis(ethylenediamine)cobalt(III) chloride.
2. Calculate the actual and theoretical yield of the synthesised compound.
3. Calculate the time required for a reaction, which cannot be directly
observed.
4. Determine the value of a quantity from the slope of a linear plot of
experimentally obtained data.

Course Synthesis of trans-[CoCl2(en)2]Cl

Contents &
Learning 1. Weigh out ~12 g of CoCl2.6H2O, place in a 250 ml beaker, and dissolve
Activities in about 25 ml of H2O with stirring. Use a triple beam balance.
2. Add ~40 ml of 10% ethylenediamine solution. The solution will be
observed to darken considerably as the [Co(en)2(OH2)2]2+ complex is
formed. After about 10 minutes, cool the solution in an ice-bath for 15-
20 minutes before proceeding to step (3).
3. Add 10 ml of 30% H2O2, a few ml at a time, to the cold cobaltous
solution from step (2) while stirring the reaction mixture gently. Leave
the cobaltous solution in the ice bath during the addition of H2O2.
Bubbles of O2 will be observed as H2O2 disproportionates according to
the equation below:
2H2O2 → 2H2O + O2

Hydrogen peroxide, H2O2, reacts with the Co(II) ion according to the
equation below:

2Co2+ + H2O2 + 2H+ → 2Co3+ + 2H2O

it is assumed that the metal ions are suitably complexes although this
fact is not explicitly shown. After all the H2O2 has been added, remove
the reaction beaker from the ice bath and allow the solution to stand for
about 10 minutes. At this stage the solution is a disagreeable brownish
colour.

CAUTION: 30% H2O2 should not be allowed to come into contact

with skin or clothes. If it does, flush the area of contact immediately
with copious amounts of water.
4. Slowly add 40 ml of concentrated HCl (12 M) to the reaction mixture,
which will probably cause further bubbling as more H2O2 reacts to form
O2. Allow the mixture to stand 20-30 minutes; the reaction mixture can
be stored at this point.
5. It is the object of this step to evaporate the reaction mixture to the point
that solid product separates. The evaporation should be continued until
the mixture forms a slush. This step essentially forces the reaction as
shown below to form product:
[Co(en)2(OH2)2]3+ + 2Cl− → trans-[CoCl2(en)2]1+ + 2H2O

However, it is relatively slow step and requires some care. Transfer the
reaction mixture to a 4" evaporation dish and set up the arrangement
sketched in Fig. 2. The mixture can be evaporated on a hot plate in a
hood, if available. For a successful evaporation the following
precautions should be observed:

a. Maintain a low flame and never allow the solution to boil violently
(avoid splattering).
b. Maintain a gentle flow rate or air and always turn the air on with
the flow directed away from the liquid until the air flow rate has
been adjusted satisfactorily.

Fig. 2: The apparatus which can be used to evaporate the reaction mixture
to form the final product.

At the end of the evaporation step the solution will be a dark purple
colour, which will be replaced by a dark green colour as the chloride
ions replace the water molecules in the complex according to the
equation above. The reaction mixture may be stored at any stage of
this step.

6. The hot solution may be transferred to a 250 ml beaker (use tongs) and
chilled in an ice bath. After the solution is cool (below room
 temperature), filter the reaction mixture with the aid of vacuum* and
wash the solid with ~20 ml of conc. HCl. Save the solid material. The
solid should be predominantly green but may be contaminated with
areas of blue or purple, which arise from the Buchner funnel and scrape
the solid onto a watch glass. Weigh the moist material and record in your
notebook. The solid may be stored at this point. Use a triple beam
balance.
CAUTION: Do not carry out vacuum filtration unless this
procedure has been demonstrated in the laboratory.
7. The object of this step is the purification of the product by
recrystallisation. Make up a solution of 30 ml of conc. HCl and 10 ml
H2O. Transfer about 3-4 ml of this solution per gram of solid obtained
from step 6 to a 150 ml beaker and bring the mixture to a boil; the solid
product may require considerable stirring to help it dissolve in this hot
solution. After stirring for 3-4 minutes decant the hot solution into a
clean 250 ml beaker and chill the decanate in an ice bath. Save any solid
material left in the beaker after decantation. Allow the decanted solution
to remain in the ice bath for 1/2 hour before carrying out step 8.
8. There should be a crop for bright green crystals in the chilled solution
from step 7. Filter this solution with the aid of vacuum and save the
filtrate. If undissolved material is available from step 7, combine the
filtrate and this solid in a clean beaker. The recrystallised product should
be washed in the Buchner funnel as follows:
CAUTION: Remove the filtrate from the vacuum flask before
carrying out these steps.
a. With the vacuum off, pour ~10 ml of concentrated HCl over the
crystals while they are still in the Buchner funnel and allow the
mixture to stand for about ~30 seconds before the vacuum is
restarted and the HCl solution is pulled through the Buchner funnel.
b. Break the vacuum and carry out two successive washes with 9.5%
ethanol, following the same procedure as described for the previous
wash (a). After the second washing with ethanol leave the vacuum
on for 5-10 minutes to dry the crystals.
Note: Your demonstrator will give detailed directions on the technique
of vacuum filtration.
9. Scrape the green crystals onto a watch glass, allow them to air dry for
about 1/2 hour, and weigh them on the triple beam balance. Record the
weight in your notebook. At least 0.5 g of product should be obtained.
10. A second crop of crystals can be obtained from remaining filtrate by
reducing its volume and / or dissolving any undissolved product from
step 7, and repeating the recrystallisation process. If you do obtain a
second crop of crystals, keep the first and second crop separate because
the first crop will be much purer then the second. The first crop should
 be used to carry out the kinetics investigation described in the time-
dependence study section.

Notes

Take a clean, dry, large test tube to the storeroom to obtain a sample of the
starting material, CoCl26H2O.

1. Normally evaporation and work-up of the product will take two

laboratory periods. If evaporation proceeds slowly you may need to
work into a third period to finish this experiment.
2. By working carefully and rapidly you should be able to get to the
point where the reaction mixture is evaporated (step 5) in one
laboratory period; you should be able to get in about 45 minutes of
evaporation time before the period ends.
3. Evaporation may be done at your desk using the setup shown in Fig.
2 or by using the hot plate in the hood. If you use the hot plate, be
certain only the two leftmost switches are turned on.
4. Do all weightings on the laboratory balance-not the Mettler
balance. This includes weighing the final product.
5. Turn in the final product to your laboratory instructor.

Time-dependence study

1. Put 5 ml of distilled H2O in a 12 x 100 mm test tube and place this tube
in a 250 ml beaker filled with ice. Dissolve approximately 0.5 g of the
trans-[CoCl2(en)2]Cl in the thoroughly chilled water. Keep this solution
in an ice-bath throughout the experiment. Use a triple beam balance to
weigh the sample.
2. While the 5 ml of H2O in step 1 is being chilled, set up a bath as shown
in Fig. 3 and begin heating the water (do not allow the temperature to
raise above 70°C).
Fig. 3: A schematic representation of the apparatus used to estimate the
rate of a chemical reaction under controlled temperature
conditions.

The bath should be arranged so that the thermometer and test tube do not
touch the beaker sides or bottom, and a clear view of the test tube against a
white background is afforded. The thermometer should be turned so that the
temperature can be read while simultaneously observing colour changes in
the test tube. The contents of the test tube should be stirred with a very thin
stirring rod (the thinness reduces heat conduction temperature losses). The
main heating bath requires a stirring rod to maintain good water circulation
around the test tube. You should learn to control the temperature within 1°C
over a 3-5 minute period by gentle heating. During the experiment it will be
necessary to maintain the bath temperature while watching for colour
changes.

3. Determine the height in your medicine dropper that corresponds to a

volume of 0.25-0.5 ml. In the experiments to follow approximately 0.25-
0.5 ml of the chilled stock trans-[CoCl2(en)2]Cl solution will be used for
each aquation rate determination.
4. For each determination the following procedure will be found:
a. The temperature of the heated bath will be stabilized at the desired
temperature. The 12 x 100 mm test tube is filled up with distilled
water to the water bath line and allowed to come to temperature
equilibrium with the bath for at least 5 minutes before the aquation
reaction is initiated. The contents of the 12 x 100 mm test tube
should be below the water line of the bath.
b. 0.25-0.5 ml of the green stock solution is added to the test tube (with
rapid mixing) and the temperature of the bath constant, the solution
colour will be observed. The temperature of the bath and two times
for each solution colour will be noted and entered in the notebook:
 (1) the total elapsed time for the solution to turn green-grey (i.e.,
essentially grey with a greenish tinge) and (2) the total elapsed time
for the solution to turn pink-grey. These two times are referred to as
tg and tp respectively. These two times may be different by 10-30
sec, depending on the temperature of the reaction and the
characteristics of the observer.
c. After tp has been recorded, the test tube is emptied, and filled up to
the water line with distilled water. Always leave the thin stirring rod
in the test tube so that all parts of the system can thermally
equilibrate. After a new temperature is established carry out steps
(a) to (c).
The first few attempts to observe the aquation may inaccurate until you
become familiar with the nature of the colour changes. The rate of aquation
will vary between 10-500 s, depending on the temperature. It is
recommended that the first few runs be in the temperature range of 55-50°C.
It is required that at least 6 data points from each of the following
temperature ranges: 52-56°C, 57-61°C, 62-66°C. You should carry out 8-
10 aquation rate determinations and choose the 6-8 most reliable
experiments for the plot of the data. If these experiments take more than one
laboratory period the laboratory assistant will issue more of the trans-
[CoCl2(en)2]Cl for preparation of a new stock solution.

Summary Trans-dichloridobis(ethylenediamine)cobalt(III) chloride is synthesised

and recrystallised to give bright green crystals. This was then followed by
an experiment to determine the rate of aquation of trans-[CoCl2(en)2]Cl
where in the reaction, the two chlorido ligands is replaced by H2O. The time
for the reaction to happen was recorded at different temperature to study the
effect of temperature to the rate of aquation.

Assignment Calculation of yield

The yield (or percent-yield) is usually estimated for any experiment in

synthesis. The theoretical yield is that which might be expected if all of the
starting material (in this case CoCl2.6H2O) is converted to the desired
product [CoCl2(en)2]Cl. If the overall process is 100% successful one mole
of the starting Co-containing compound would yield one mole of the trans
complex as shown below.

CoCl26H2O→ [CoCl2(en)2]Cl

Starting the synthesis with 12 g of CoCl26H2O, with corresponds to 12/(mw

of CoCl26H2O), you should expect to obtain the same number of moles of
[CoCl2(en)2]Cl if the process, viz., the oxidation of the complex from
solution, were to go to completion. However, we would expect that some of
these intermediate steps (such as the isolation of the complex from solution)
 would not occur completely. Therefore the actual yield will be less than
expected if all steps were perfectly accomplished. A measure of the
efficiency of the synthesis is the percent yield, which is given by

actual yield
%yield = × 100
theoretical yield

Calculate the % yield for your preparation of trans-[CoCl2(en)2]Cl

Analysis of data

Prepare a table in your notebook of the following form:

T* T T−1 tg * tp * tgy tgy−1 log

tgy−1
(°C) (K) (K−1) (s) (s) (s) (s−1)

The quantities marked by an asterisk (*) are directly observed. The quantity
tgy is calculated from the expression tgy=½(tg + tp). The data will be graphed
log (tgy−1) plotted y-axis and T−1 plotted on the x-axis. Determine the
equation of the best straight line through the data points using the least-
squares method and draw in the line. Alternatively, plot the data on semi log
paper and draw the best straight line through the points; calculate the slope
from this plot.

From the discussion in section 1 you can determine ∆Ef* from your data.
Using the equation for the best straight line fit to your data, you can
determine the slope. According to Eq. 19, the slope is identified with the
quantity ∆Ef*/2.3R or
ΔE∗
least square slope = − (2.3 fR) (20)

Since the value of R is known (1.987 x 10−3 kcal/mol deg), the value of
∆Ef* may be found. If you have suitable thermodynamic tables available,
compare ∆Ef* with typical ∆Ereaction or ∆Hreaction values.

Assessment* Lab Report

Department of Chemistry
Faculty of Science
Universiti Putra Malaysia

Module 7 Title Identification of Vibrational Spectra and Bonding in Metal Carbonyl

Course Code CHY3304
Module UPM/FS/CHY3304
Code/No
Duration 6 hours
Learning 1. R. H. Crabtree, The Organometallic Chemistry of Transition Metals, 7th
Resources Edition, 2019, John Wiley & Sons.
2. M. T. Weller, T. L. Overton, J. P. Rourke & F. A. Armstrong, Inorganic
Chemistry, 7th Edition, 2018, Oxford University Press.
3. G. L. Miessler, P. J. Fischer & D. A. Tarr, Inorganic Chemistry, 5th
Edition, 2014, Pearson.

Prior The transition metal carbonyls are nonpolar volatile compounds. The
Knowledge carbonyl ligands are easily substituted by a vast range of ligands with a wide
variety of donor atoms (C, N, O, P, S etc.). The degree of substitution
depends on the ligand (both electronic and steric factors).

Apart from X-ray crystallography, important analytical technique for the

characterisation of metal carbonyls are infrared (IR) spectroscopy. The
carbonyl ligands give rise to intense CO stretching bands (CO) in the
infrared spectrum (2200−1600 cm−1). The spectrum is usually recorded as
a dilute solution. The number of carbonyl bands depends on both the
number of carbonyls and the structure of the complex. Hence, the IR
spectrum can be used as a structural tool.

The exact frequency of the CO bands depends on the donor/acceptor

properties of the other ligands in the complex. Thus, the IR spectrum is
sensitive to other factors such as the electronic properties of the ligands and
the oxidation state.

The changes in CO can be easily rationalised from the bonding model of
the M−CO bond, i.e., an OC→M σ-bond and a M→CO -bond. The
energies of the νCO band for the metal carbonyls correlates with the strength
of the carbon-oxygen bond, and inversely correlated with the strength of the
π-back bonding between the metal and the carbon.

Safety

All metal carbonyl complexes are toxic. These chemicals are rapidly
absorbed through the skin. Do not touch the materials with your fingers and
you must be careful not to spill solutions onto your skin. If you do so, wash
your hands thoroughly.

Handle organic solvents and bromine in the fume hoods. Petroleum ether is
very flammable.

Solid metal carbonyls are usually air stable; however, they tend to be more
air sensitive in solution. Consequently, reactions, especially those involving
heating, are carried out in an inert atmosphere such as nitrogen. The suitable
experimental setup is shown in Figure 1. Before commencing the heating,
flush the system with nitrogen, during the reflux maintain a slow flow of
gas and afterwards while allowing the apparatus to cool increase the flow
rate again to prevent suck-back.

Nitrogen out
to a gas bubbler

In

Nitrogen
from cylinder

Simple gas
bubbler

water

Heating mantle
plus stirrer

Figure 1. Experimental setup for a reflux in an inert atmosphere

Gentle flow of gas (~ 1 bubble per second)
Terms To 18-electron rule -back bonding, bond order, point group, IR-active bands
Know
Learning At the end of this module, students should be able to:
Outcomes 1. Synthesise a series of molybdenum metal carbonyl complexes.
2. Characterise the complexes with emphasis on the M−CO bonding mode
in the structure.

Course Procedures
Contents & NOTE: All reactions are to be carried out in an atmosphere of N2(g).
Learning
Activities For all the syntheses determine the percentage yield of the products and
record its melting points.

1. Synthesis of bis(pyridine)tetracarbonylmolybdenum,
[Mo(CO)4(py)2]
Hexacarbonylmolybdenum (0.125 g) in pyridine (2 ml) is heated under
reflux for about 50 mins. Allow the solution to cool and add petroleum
ether (~15 ml). After crystallisation has finished, filter the orange-red
solid and wash with petroleum ether and dry in vacuo. If necessary,
recrystallise from acetone/water.

2. Synthesis of 2,2'-bipyridinetetracarbonylmolybdenum,
[Mo(CO)4(bpy)]
Hexacarbonylmolybdenum (0.125 g) and 2,2'-bipyridine (0.08 g) are
heated under reflux in toluene (6 ml) for ~2 hr. After cooling collect the
brick-red crystals, wash with toluene and petroleum ether and dry in
vacuo.

3. Synthesis of bis(triphenylphosphine) tetracarbonylmolybdenum,

[Mo(CO)4(PPh3)2]
Hexacarbonylmolybdenum (0.10 g) and triphenylphosphine (0.225 g)
are heated under reflux in toluene (5 ml) for ~2 hr. After cooling collect
the yellow crystals, wash with toluene and petroleum ether and dry in
vacuo.

4. Synthesis of dibromo(2,2’-bipyridine) tricarbonylmolybdenum(II),

[Mo(CO)3(bpy)Br2]
[Mo(bpy)(CO)4] (0.05 g) in CH2Cl2 (3 ml) is treated with bromine
(0.026 g) in CCl4 (4 ml) drop wise with stirring. Leave for several
minutes, filter the orange solid, wash with petroleum ether and dry in
vacuo. CAUTION: Handle bromine in the fume hood.

Characterisation
 Infrared Spectroscopy

Solution spectra are recorded using a solution cell (CaF2 windows separated
by a thin Teflon spacer). The cell is filled using a syringe or a Pasteur
pipette. After use rinse the cell twice with solvent and return it to the
desiccator.

Before recording the spectrum of a compound in either the X, Y or Z

channel, you need to record the spectrum of the solvent in the background
channel of the Perkin Elmer spectrophotometer.

Prepare a dilute solution of the complex (a few crystals in about 10−15

drops) in dichloromethane (DCM). Fill the solution cell and record the
spectrum in the range 2200−1600 cm-1. NOTE: the baseline should be a
smooth straight line with no solvent bands.

UV-Visible Spectroscopy

Prepare a dilute solution of the complex (~ 5 x 10−4 M). Using quartz

cuvettes, record the spectrum in the range 700−300 nm. Use solvent such as
dimethyl formamide (DMF) or acetone.

Summary Three molybdenum carbonyls complexes which are [Mo(CO)4(py)2],

[Mo(CO)4(bpy)] and [Mo(CO)4(PPh3)2] were synthesised via reflux
method. The [Mo(CO)4(bpy)] underwent substitution reaction whereby a
CO ligand is substituted with a Br ligand to obtain [Mo(CO)3(bpy)Br]Br.
The complexes underwent FT infrared analysis where CO stretching in the
spectra obtained are compared to deduce the structure of the complex. The
CO stretching bands are intense and affected by the surrounding ligand in
structure. The effect of the donor/acceptor properties of other ligand exist
in the structure can be studied as the effect can be observed in the trends of
the CO stretching in the FTIR analysis of the complexes. Factor such as 
back-bonding, bonding strength (Hook’s law) can be applied to interpret
and rationalised the results obtain in the experiment.

Assignment Answer the following questions.

1. Outline any trends in the CO stretching frequencies.

2. Assuming octahedral geometry, determine the point groups of the
complexes and predict the number of IR active C−O bands for each
structure. Note: certain complex might have more than one
possible isomer.
3. Is the IR spectrum observed for each compound consistent with its
structure?
4. Which complexes can exist as geometric isomers? Which isomer
was produced in your synthesis?
 5. Tabulate the electronic spectra of all the compounds. Are there any
trends?
Assessment* Lab Report