MINI-PROJECT REPORT ON :- CRYSTAL FIELD

THEORY: ISOMERS,MAGNETIC PROPERTIES AND

COLOR

Submitted by

STUDENT’S NAME UNIVERSITY ROLL NUMBER

Shresth Sanskar 00719123
Shoumick Bardhan 00719122
Shivam Raut 00719121
Zimmy Kumar 00719157

Under the supervision of

Dr. Sibaprasad Maity
REPORT SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF BACHELOR OF TECHNOLOGY IN MECHANICAL ENGINEERING OF WEST
BENGAL UNIVERSITY OF TECHNOLOGY

MECHANICAL ENGINEERING DEPARTMENT

HALDIA INSTITUTE OF TECHNOLOGY, HIT
COLLEGE ROAD, KSHUDIRAM NAGAR , HALDIA,
WEST BENGAL 721657

CERTIFICATE OF RECOMMENDATION

We hereby recommend that the thesis prepared under our supervision

by Shresth Sanskar, Shoumick Bardhan, Shivam Raut and Zimmy
Kumar entitled Mini Project Report On Crystal Field Theory: Isomer,
Magnetic Properties and Color
be accepted in partial fulfillment of the requirements for the degree of
BACHELOR OF TECHNOLOGY IN “MECHANICAL
ENGINEERING”.

_____________________________________ ______________________
Head, Mechanical Engineering Department, Project Guide
Haldia Institute of Technology, Haldia

HALDIA INSTITUTE OF TECHNOLOGY, HIT

COLLEGE ROAD, KSHUDIRAM NAGAR, HALDIA,
WEST BENGAL 721657
ACKNOWLEDGEMENT

We would like to express our deep sense of gratefulness to our supervisor Dr. Sibaprasad
Maity, Associate Professor, in chemistry, Haldia Institute of Technology, for his valuable
advice and guidance, constant help and support throughout the period of carrying out the
project work and successful completion of the same in its present form. We are thankful to our
Head, Mechanical Engineering department, Deepak Jana and all other faculty members for
their help and support.

Many thanks are also extended to all our friends and colleagues at MCKV Institute of
Engineering for the valuable discussions we had with them.
Content

1. ABSTRACT

2. INTRODUCTION

3. LITERATURE REVIEW

4. CONCLUSION

5. REFERENCES
ABTRACT

The name crystal field is assigned to this theory because the electrons of the central metal ion in the environment of other
ligands are affected by their non-spherical electric field. Such an electric field is called crystal field and hence the name crystal
field theory.

 The metal ion in coordination entity is surrounded by ligands having lone pair of electrons through they coordinate to
the central metal ion.

 All types of ligands are regarded as point charges.

 The interaction between central metal ions and ligands are purely electrostatic. If the ligands are negatively charged,
ion-ion interactions occur. If ligands are neutral, ion-dipole interaction take place.

 The ligands surrounding the metal ions produce electric field and this electric field influences the energy of orbitals of
central metal ion, particularly d-orbitals.

 In case of free metal ion, all the five d-orbitals have same energy. Such orbitals having same energies are called
degenerate orbitals.

 The five degenerated d-orbitals of metal ion split into different sets of orbitals having different energies in presence of
electric field of ligands. This is called crystal field splitting.

 The number of ligands and their arrangement around the central metal ion will have different effect on the relative
energies of the five d-orbitals. Example the crystal field splitting will be different in different structures having
different coordination numbers.

 The magnetic properties, spectra, color and preference for particular geometry can be explain in the term of splitting
of d-orbitals in different crystal fields.
INTRODUCTION

The Crystal Field Theory (CFT) is a model for the bonding interaction between transition metals and ligands. It describes the
effect of the attraction between the positive charge of the metal cation and negative charge on the non-bonding electrons of the
ligand. When the ligands approach the central metal ion, the degeneracy of electronic orbital states, usually d or f orbitals, are
broken due to the static electric field produced by a surrounding charge distribution. CFT successfully accounts for some
magnetic properties, colors, and hydration energies of transition metal complexes, but it does not attempt to describe bonding.

Orientation of d-orbitals and there shapes

Crystal field splitting (Isomers)

If a spherically symmetric field of negative charges is placed around the metal, these orbital remains degenerated, but all of
them are raised in energy as a result of repulsion between the negative charges on the ligands and in the d-orbitals.
If , rather than spherical field, discrete charges (ligands) are allowed to interact with the metal, the electrons in the d-orbitals of
central metal ion will be repelled by the lone pair of the ligands. As a result of these interactions the degeneracy of d-orbitals
of metal ions is lost and these split into two set of orbitals having different energies. This is known as Crystal Field splitting
(∆).

The energy gap between t2g and eg sets is denoted by ∆0 (Octahedral Complexes) or ∆t (Tetrahedral Complexes) or 10Dq.
The energy difference arises due to difference in electrostatic field exerted by ligands on t 2g and eg sets of orbital sod central
metal ions. 10Dq or ∆ is called Crystal Field Splitting Energy (CFSE).

Crystal Field Splitting in OCTAHEDRAL Coordination entities:

Crystal Field Splitting in TETRAHEDRAL Coordination entities:

Colour in Coordination Compounds:

The colour in coordination compounds can be explained in term or crystal field theory. According to CFT the colour of
coordination compound arises due to intra d-d transition of the electron.

For example: [Ti(H2O6]3+ which is violet in color and an octahedral complex with single electron (Ti 3+ is a 3d1 system) in the
metal d-orbital is in t 2g level in the ground state of the complex. The next higher state available for the electron is the empty e g
level. If light corresponding to the energy of yellow-green region is absorbed, it would excite the electron from t 2g to eg level.
The color of a particular compound depends upon the magnitude of ∆, the crystal field splitting, which is further found to be
dependent on nature of ligand.
It is important to note that in the absence of ligand, crystal field splitting does not occur and hence the substance is colorless.
Example: the removal of water from [Ti(H2O6]Cl3 on heating renders it colorless.

Magnetic Properties of Coordination Compounds:

The transition metal complexes are known to be paramagnetic in nature. CFT help us to understand the magnetic properties in
term of magnetic susceptibility measurements. The magnetic properties of a substance depend on the oxidation state,
electronic configuration, coordination number of central metal and the nature of ligands.
A substance containing one or more unpaired electrons has definite vale of magnetic moment and is attracted in external
magnetic field, called paramagnetic substance. On the other hand substances having paired electron will have zero magnetic
moment and hence do not posses magnetic properties, called diamagnetic substances.
The magnetic moment depends on the number of unpaired electrons, greater the number of unpaired electrons more is the
magnetic moment.
µ=√n (n+2) where n is the number of unpaired electrons
Literature Review

CFT was developed by:

 Hons Bethe
 John Hasbrouck
In the year 1930s

According to this theory, the interaction between a transition metal and ligands arises from the attractions between positively
charged metal cation and the negatively charge on the non-bonding electrons of the ligands.

Bethe described a transition metal ion located centrally in an electrostatic field that is created by surrounding ionic or dipolar
atom and molecules. The electrostatic field due to the ligands has symmetry lower than the full rotation symmetry of the free
central ion.

The CFT model does not attempt to describe why the configuration of an ion with surrounding ligands is stable.
John Van Vleck, an American physicist then proposed an extended model known as the ligand field model. The field model
aims at predicting correct binding energy in addition to explaining of magnetic and spectral properties.

Simple Model for Crystal Field Theory:

An investigation for the prediction of the splitting of the 3d orbitals of a metal ion in the environment of ligands is being carried
out in year 2016. The electrons are considered to independent and their interaction between the ligands is representated by
Dirac Delta function in three dimensions. Discussion of several cases was done for the success this model.

The model developed in this paper for the splitting of the 3d orbitals of a metal ion in the ligand environment is extremely
simple and easy to apply because it only requires the calculation of the value of the d orbitals at the ligand position in space. It
provides the well known order of energy level in most of the cases and even yields the relative magnitudes of the splitting.
Although it fails to predict the splitting of d orbitals in distorted octahedral complexes.
CONCLUSIONS

Crystal Field Theory is a model that describes the breaking of degeneracy of electronic orbital states, usually d and f orbitals,
due to a static electric field produced by surrounding charge distribution.

This theory has been used to describe various spectroscopes of transition metal, coordination complexes in particular spectra.

CFT successfully accounts for some magnetic properties, colors, hydration, enthalpies and spinal structures of transition
metal complexes, but it does not attempt to describe bonding. CFT was developed by physicists Hans Bathe and John
Hasbrouck Van Vleck in 1930s.

CFT was subsequently combined with molecular orbital theory to form the more realistic and complex ligand field theory,
which delivers insight into the process of chemical bonding in transition metal complexes.

According to CFT, the interaction between the transition metal and ligands arises from the attraction between the positively
charged metal cation and negative charge on the non-bonding electrons of the ligand. The theory is developed by considering
energy changes of the five degenerated d-orbitals upon being surrounding by array of point charges consisting of ligands. As a
ligand approaches the metal ion, the electron from the ligand will be closer to some of the d-orbital and further away from
others, causing a loss of degeneracy. The electron in d-orbital and those in the ligands repel each other due to repulsion due to
like charges. Thus the electron closer to the ligand will have higher energy than those further away which result in the d-rbita;l
splitting in energy. This splitting is affected by the following factors:

 The nature of metal ions.

 The oxidation state of metal. Higher the oxidation state of metal larger it’s splitting.
 The arrangement of ligand around the metal ion.
 The nature of ligand surrounding the metal ion. The stronger the effect of ligands then the greater the difference
between the high and low energy od d group.
REFERENCES
 Dr. Sibaprasad Maity, Associate professor in chemistry.
 C. J. Ballhausen, Ligand Field Theory, McGraw-Hill Book Company, New York, 1962.
 R. G. Burns, Mineralogical Applications of Crystal Field Theory, (Cambridge University Press, Cambridge, 1993).
 F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, Interscience Publishers, New York, 1972.
 www.quora.com

 Comprehensive Chemistry by Dr. N. K. Verma and S. K. Khanna.