CHEMISTRY PROJECT 20-04-2021

NAME: ODE SAMSON TOJU

CONTENTS
• Introduction and meaning of transition elements.
• Completely filled, half filled and partially filled orbitals
• Electronic configuration
• Variable oxidation states
• General properties
• Formation of metal complexes
• Meaning of Ligand and types of ligands
• Coordination chemistry and nomenclature of
coordination compounds
 INTRODUCTION AND MEANING OF TRANSITION
ELEMENTS
By definition, transition elements are those elements containing an
incomplete d-subshell in at least one of their compounds (i.e having
a partially filled ‘d’ or ‘f’ subshell in any of their commonly
occurring oxidation states as well as the atomic states).
There are four horizontal rows or series d-block elements.
It is found that not all the d-block elements are transition metals and
not all the ions of a transition metal show transitional properties.
By strict definition scandium (3d1 4s ), zinc (3d10 4s2 )
cadmium(4d10 5s2 )and mercury (5d10 6s2 ) are not d-block transition
elements though they belong to d-block. This is because scandium
forms only scandium (III) compounds with in which Sc3+ ions has an
empty d-subshell, and zinc forms Zn2+ ion exclusively with its d-
subshell filled completely.
The element copper shows some intermediate behavior/properties
between transition and non-transition because of its formation of
compounds in two oxidation states (copper (I) cu+ and copper (II)
cu2+). Cu2+ ion is a transition metal ion due to the presence of an
empty d-subshell while Cu+ ion is not a transition metal ion as it has
no transitional characteristics.
3d0
Sc3+ [Ar]

3d10 4s
2+
Zn [Ar]
COMPLETELY FILLED, HALF FILLED AND
PARTIALLY FILLED ORBITALS
 ELECTRONIC CONFIGURATION OF
TRANSITION METALS

The region of the periodic table in which the transition metals are
found is known as d-block because proceeding across each row each
successive element has an additional d-electron.
The lowest energy electron configuration for the first row transition
metals is shown below

Group (column) number 3 4 5 6

atomic number 21 22 23 24
element symbol Sc Ti V Cr
electron configuration 3d14s2 3d24s2 3d34s2 3d54s1

The valence configuration for first series transition metals (Groups

3-12) is usually 3dn4s2.
Exceptions: The electron configurations for chromium (3d54s1).
This is because 3d and 4s orbitals are very close in energy and the
energy of 3d orbitals drops going across the row.
For both chromium and copper, the configuration having more
electrons in 3d orbitals is of lower energy.
For chromium this is because the difference in 3d and 4s orbital
energies is similar to the pairing energy(Electron pairs are of higher
energy).
The 3d54s1 configuration is of lower energy because this
configuration has the maximum number of unpaired electrons for a
d-subshell.
 VARIABLE OXIDATION STATES
All transition elements except the first and the last member in each
series show variable oxidation states. This is because of difference
in energy in the(n-1)d and ns orbitals is very little. Hence electrons
from both the energy levels can be used for bond formation.
These are achieved by loss of ‘s’ orbital electrons from the
neutral atom before exposing the ‘d’ electrons. The maximum
possible oxidation states equals the total number of electrons in the
‘s’ and ‘d’ orbitals and in the valence shell of the transition metal.
E.g for Mn with a total number of seven electrons in both ‘s’ and ‘d’
orbital exist as aqueous ions in all oxidation states from +2 to +7.
-The highest oxidation states of transition metals are found in
fluorides and oxides since fluorine and oxygen are the most
electronegative elements. The highest oxidation states shown by any
transition element is +8. Both O and Ru show +8 oxidation states
but the most stable oxidation state of O in OsO4. Manganese shows
+7 highest oxidation state in Mno4 - .
-Higher oxidation states are stabilized by atoms of high
electronegativity like O or F whereas lower oxidation states (zero or
+1) are stabilized by ligands which can accept electrons from the
metal through pi bonding (such as CO).
-In going down the group the stability of higher oxidation states
increases while that of lower oxidation states decreases.
-The relative stability of different oxidation states of transition
metal atoms with respect to oxidation can be determined by with the
help of standard electrode potential data. eg Eo value for Cr 3+ /Cr 2+
=0.41volts and Cr2+/Cr3+=0.41volts suggest that Cr2+ is unstable
(due to partially filled d-orbital) and it is oxidized to Cr 3+ (which is
more stable) and acts as a reducing agent whereas Mn3+ is unstable
and is reduced to Mn2+ (which is more stable since it has half filled
3d-orbital) and acts as an oxidation agent, it may be noted that both
Cr2+ and Mn3+ are d4 species. Thus Cr2+ is more readily oxidized
than Mn2+.
An empty or half filled or completely filled subshell are stable
hence, Sc3+,Ti4+,Mn2+,Fe3+,Zn2+ and Cd3+ are stable. The higher the
oxidation state of the ions in solution, the lower its ionic property
and the less metallic property thus, the higher its covalent
property.eg TiCl2 is a high melting point solid while TiCl4 is a low
melting point liquid, therefore, compounds of Mn2+ are more ionic
than either Mn4+ or Mn7+ compounds. The lower oxidation state
metals are oxidizing agents.

GENERAL PROPERTIES OF TRANSITION ELEMENTS

• High melting and boiling points
• Formation of complex ions
• They form coloured ions
• Possession of catalytic action i.e they are used as a catalyst
• They are paramagnetic and diamagnetic
• Formation of interstitial
Formation of crystal structure with the same
shape(isomorphism)
• Variable oxidation state

High Boiling point, Density and melting point

Melting points of the d-block metals are generally very high (even
higher than that of the s-block metals) due to the presence of strong
metallic bonds.
The densities of the d-block metals are much higher than that of the
s-block metals due to small atomic size of the s-block metals.

Formation of complex ions

A complex ion is an ion in which a central metal cation is bonded
(by a dative bond) to a number of anions or neutral molecules
(called Ligands) in excess of its oxidation number of valency. If
the ligands are easily removed, the complex is said to be stable.
In general, stable complexes are formed with ligands like O2- or
CN-e.g MnO4-, CrO42-,[Cu(CN)4]3-, while unstable complexes are
formed with ligands like H2O, NH3, Cl- etc.

Formation of coloured ions

Most of the d-block metals form coloured substance or compounds
and most of their complexes are coloured due to their incompletely
filled d-orbitals. The colour of a particular transition metal ion
depends on the nature of the ligands (either neutral molecule such
as water, which contains one pair of electrons or negative ion such
as the chloride ion).
The colour of transition elements result when an electron in the
‘d’ orbital of lower energy absorb visible light of a certain
wavelength (photon of light) and then move into the orbital of
higher energy.

Catalytic Property or Activity

This is associated with their variable oxidation states. Transition
metal ions function as catalysts by changing their oxidation between
iodide and peroxide sulphate ion.
2I-(aq)+S2O82-(aq) I2(aq) + 2SO42-(aq)
The above reaction occur in steps as follows:
2Fe3+(aq) + 2I-(aq) 2Fe2+(aq) + I2(aq)
2Fe2+(aq) + S2O82-(aq) 2Fe3+(aq) + 2S042-(aq)
2I(aq) + S2O82-(aq) I2(aq) + 2SO42-(aq)

Paramagnetism and Diamagnetism

Paramagnetism is the weak repulsion of substance from a strong
magnetic field while diamagnetism is the weak attraction of
substance to a strong magnetic field. Paramagnetism is due to
magnetic field produced by an unpaired electron in an orbital.
This is one of the major characteristic of the transition element (at
their d orbital) i.e they have an unpaired d electrons.
Diamagnetism is due to magnetic field produced by paired electrons
in an orbital (‘d’ orbital for the transition element)

Formation of Interstitial Compound

Interstitial compounds are compounds with no true bond(i.e no
definite chemical formula).Thus they are non-stiochiometry.
Transition metals form interstatial hydrides, nitrites and carbides
when hydrogen, nitrogen and carbon combine with transition
elements respectively.

Isomorphism
This refers to the crystal structure with the same shape. Transition
elements can replace each other in some compounds without
altering the crystal structure due to the similarity in size of the ion
of the transition metals. The best known example of isomorphous
salts are alums of formular
K+M3+(SO42-).12H2O
Where M3+ can be Al3+,Ti3+,V3+,Cr3+,Mn3+,Fe3+ or Co3+, Where K+
is an ion of group IA elements.
 MEANING OF LIGANDS
A Ligand is an ion or molecule, which donates a pair of electrons to
the central metal atom or ion to form a coordination complex. The
word ligand is from latin, which means ‘tie or bind’. Ligands can be
anions, cations and neutral molecules. Ligands act as lewis
bases(donate electron pairs) and central metal atoms viewed as
lewis acid(electron pair acceptor). Examples of ligands include
anions like Cl-,CN-,OH- and molecules like CO, H2O, NH3.

TYPES OF LIGANDS
• Monodentate Ligand
Monodentate ligand is the one where a single donor atom shares an
electron pair to form a coordinate bond with the central metal ion.
e.g Cl-,OH-,CN-,etc.
• Polydentate ligands

A polydentate ligand has two or more donor atoms linked to the

central metal ion. Based on the number of donor atoms, polydentate
ligands are further classified as:
a.Bidentate ligands:The ligands which bind to central metal
through two donor atoms are called bidentate ligands.
e.g
1. Ethylenediammine binds to the central metal atom through two
nitrogen atoms.
2. Similarly, oxalate ligand (C2O42-) utilizes electron pair on each
of its negatively charged oxygen atoms on linking with central
metal.
b. Hexadentate ligands: The ligands which binds to central
metal through six donor atoms are called hexadentate ligands. E.g
Ethylenediaminetetraacetate ion (EDTA)4- binds to metal by
electron pairs of four oxygen and two nitrogen atoms.
• Ambidentate ligands: The ligands which have two
donor atoms and use the electron pair of either donor
atoms to form a coordinate bond with the metal ion are
called ambidentate ligands. E.g
a. The ligand NO-2 links to the metal ion through nitrogen
or oxygen
b. SCN- has two donor atoms nitrogen and sulphur either of
which links to metal M SCN- or M NCS-.
Coordination chemistry and nomenclature of coordination
compounds