Transition Element

 A transition element is a d block element which forms one or more stable ions
with an incomplete d electron sub-shell.
 When d block elements form ions, it is the 4s electron which are lost first. The
3d electrons repel the 4s electrons further from the nucleus so the 4s electrons
are pushed to an energy level higher than 3d therefore the 4s electrons are lost
first.
 Scandium and zinc are excluded as transition elements as they do not form ions
with an incomplete d electron sub-shell. Sc forms Sc3+ ions with no electrons in
the d orbitals and Zn only forms Zn2+, which has a completely filled d orbitals.

Range of Oxidation States

 Transition elements may have several different oxidation states due to the close
similarity in energy of 4s and 3d electrons
o The most common is +2
o The max up to Mn involves all the 4s and 3d electrons
o From Fe onwards, the +2 oxidation state dominates because the 3d
electrons become increasingly harder to remove as the nuclear charge
increases
o Higher oxidation states of transition elements are found in complex ions
or compound ions such as MnO4- and CrO42-
Characteristics of Transition Elements
 They show variable oxidation states in their compounds
 Their ions form coloured compounds
 Their ions form complex compounds
 They and their compounds are often good catalysts
 They have relatively high densities
 They have relatively high melting points and boiling points
 They have typical magnetic properties

Most compounds and ions of the transition elements are paramagnetic: when
placed in a magnetic field, they align themselves with the field. But they do not
retain their magnetism when the magnetic field is removed
Properties of Transition Elements

Atomic Radius and Density

The decrease in atomic radii is small and irregular, much less than that seen
moving across period 3. As you move across the elements, each additional electron
enters the penultimate 3d orbital which increases the shielding experienced by the
4s electrons. The increasing nuclear charge is nullified to a large extent by the
increase in shielding, causing an irregular decrease. The decreasing atomic radii
causes the increase in density.
Ionization Energy
The first ionization energy increases across the period. This increase is relatively
small compared to that of period 3. As you go across the row of transition
elements, electrons are added to the d orbital. This increases the screening effect on
the 4s electrons as the d orbital is closer to the nucleus, opposing the work of the
increasing nuclear charge, resulting in small increases. This can be contrasted with
going across period 3 where elements added do not add to the screening. (transition
elements are special in that they fill the 4s then 3d then 4p orbitals whereas in
period 3, electrons are added to the same orbital which ionization occurs, not
increasing the shielding effect).
Melting and Boiling Points
The d-block elements form metallic structures. Electrons are available from both
4s and 3d orbitals for delocalization to form metallic bonds. This results in
relatively high melting points and boiling points. The melting and boiling points
drop at Mn and Zn. This is because the extra stability of the half-filled Mn (3d5)
and filled Zn (3d10) d orbitals make electrons less available to the cloud of
electrons for metallic bonding. As a result the bonds are weaker and the melting
and boiling points are lowered.
Comparing Transition Elements with Calcium (Typical s block element)
Calcium is an s block element in group II placed just before the d block elements.
Although both are metals, they have significant differences.

The transition elements are harder and have higher melting points than calcium.
This is due to stronger metallic bonds. Calcium can only release its two outer s
electrons to form the delocalized sea of electrons but transition elements can
release electrons from both the 4s and the 3d sub-levels. There is a greater force of
attraction between the small (and often highly charged) transition element ions and
the sea of delocalized electrons in comparison with calcium
The atomic and ionic radii of calcium are much larger than the corresponding radii
for typical transition elements. Electrons in the d subshell are less effective at
shielding outer electrons than s or p electrons. So there is a relatively greater force
of attraction between the nucleus and the outer electrons which tends to pull the
electrons closer to the nucleus. The smaller radii causes transition elements to be
denser than calcium
The first ionization energies of transition elements are higher than that of calcium
because of this relatively greater force of attraction between the nucleus and outer
electrons
The electronegativity of all the transition elements is significantly higher compared
with calcium. The electronegativity increases across the series from Ti to Cu as the
elements get slightly metallic in character
Complex Ions and Ligand Exchange

A complex ion consists of a central transition metal ion surrounded by other

molecules or ions called ligands. A ligand is a neutral molecule or an anion with a
lone pair of electrons which can be donated into the empty d orbitals of the central
transition metal ion. Thus ligands form co-ordinate (dative) bonds with the central
ion. Some common ligands are H2O, NH3, Cl- and CN-.

The co-ordination
number of a complex ion
is the number of co-
ordinate bonds a ligand forms with the central transition metal ion.
o Monodentate ligands form one bond per ligand, e.g. water, ammonia
o Bidentate ligands form two bonds per ligand e.g. diaminoethane. These
ligands have two lone pairs available to form co-ordinate bonds
o Hexdentate ligands form 6 bonds per ligand e.g. EDTA
When dissolved in water, transition metal ions form hydrated complexes with
water molecules The high charge density of the central ion polarizes the O-H bond
of the water molecules causing the water molecules to become proton donors. Thus

[Fe(H2O)6]3+(aq) ⇌ [Fe(H2O)5(OH)]2+ (aq) + H+(aq)

most aqueous solutions of transition metal compounds are acidic.

In compounds where the transition metal ion has an oxidation state higher than 3+,
the polarizing effect of the central ion is even greater in aqueous solution. This
causes a loss of protons and water molecules resulting in the formation of the oxy-
anions. For example, MnO4- and CrO42- exist in aqueous solution instead of
[Mn(H2O)6]7+ and [Cr(H2O)6]6+ respectively.
Shapes of Complex Ions
The shape of a complex ion depends on:
o Its co-ordination number
o The type of ligand which bonds to the transition element ion
The shape of the complex cannot be predicted using the VSEPR theory because the
electrons in the d orbtials differ from those in s and p orbitals in their influence on
structure.
The most common co-ordination numbers are 2, 4 and 6ixx.
 Co-ordination number 2 – have a linear structure
 Co-ordination number 4 – may be either square planar or tetrahedral. Square
planar is found in Ni, Cu and Pt complexes. The tetrahedral is found in the
[COCl4]2- ion and the Ni(CO)4 molecule
 Co-ordination number 6 – octahedral structure

EDTA stands for ethylenediaminetetraacetic acid. It's a polydentate (multidentate)

ligand widely used in coordination chemistry and analytical chemistry. EDTA has
the ability to form stable complexes with metal ions through multiple coordination
sites.
Coloured Ions
Compounds appear coloured when they absorb energy that corresponds to certain
wavelengths of light in the visible spectrum. Aqueous Ti3+ ions appear purple
because they absorb light mostly in the green region of the spectrum. Most of the
light which passes through is from the violet, blue and red regions. So the solution
appears purple.

Transition metal ions form coloured complexes when surrounded by co-ordinating

ligands due to the interaction between the ligands and the d orbitals
 The 3d orbitals in an isolated transition element ion are described as degenerate
orbitals. They all have the same average energy
 The presence of the ligands in a complex affects the electrons in the d orbitals
of the transition element ion. Orbitals close to the ligands are pushed to slightly
higher energy levels than those further away. The orbitals split into two groups
 When an electron moves from a d orbital of lower energy to a d orbital of
higher energy, light is absorbed in the visible region of the spectrum
 The frequency of the light absorbed depends on the energy difference between
the split d levels. Different ligands split the d energy levels by different
amounts. So different ligands may cause different colours to be absorbed
Ions with d0 and d10 electronic arrangement have no possible d-d transitions and
hence appears colourless. So ions like Ti4+ and Sc3+ (both 3d0) and Cu+ and Zn2+
(both 3d10) generally do not give rise to coloured compounds

In the case of Zn2+Zn2+ ions, they are generally colorless because of the full
3d10 electronic configuration. This filled d-orbital does not have any available
energy levels to undergo electronic transitions that would lead to the
absorption of visible light. As a result, Zn2+Zn2+ compounds appear colorless
to the human eye.

On the other hand, Cu2+Cu2+ ions have an incomplete 3d9 electronic

configuration. This incomplete d-orbital allows for electronic transitions
within the d-orbitals, absorbing specific wavelengths of visible light and
giving rise to color in compounds containing Cu2+Cu2+ ions. The absorbed
wavelengths correspond to the complementary color of the observed color,
resulting in the compound appearing colored.
Ligand Exchange Reactions
Some ligands form stronger bonds with a particular metal ion than other ligands. If
there is more than one ligand in a solution, they can compete for a transition metal
cation. As a result, stronger ligands may displace weaker ligands from a complex.
For example, when cyanide ions are added to an aqueous solution of Fe3+, the
water ligands are replaced by the cyanide ligands
[Fe(H2O)6]3+(aq) + 6CN-(aq) ⇌ [Fe(CN)6]3-(aq) + 6H2O
Violet blue
This reaction is referred to as a ligand exchange reaction. The individual ligands
are displaced stepwise, and an equilibrium expression could be written for each
step, however it is more convenient to write an equilibrium expression for the
overall ligand displacement reaction. This equilibrium constant is called the
stability constant. Like all equilibrium constants, the stability constant varies with
temperature.
Kstab = ¿ ¿
Water molecules are typically excluded because they are present in large excess in
the solution and their concentration remains approximately constant throughout the
reaction.
The stability constant measures the stability of the complex formed with respect to
the aqua species. The values usually have a wide range and are often expressed as
its logarithm, log Kstab. The higher the value of the stability constant, the more
stable the complex formed and the more likely the complex will form. Colour
changes usually occur when the incoming ligands replace the existing ligands in a
complex.
Ligand Exchange in Hemoglobin
Haemogoblin is found in red blood cells. It consists of four globular proteins. At
the center of each protein is a Fe2+ ion complex known as haem. The Fe2+ ion has a
co-ordination number 6. Five of the co-ordination sites are occupied by nitrogen,
four from a planar ring structure called a porphyrin and the fifth one form one of
the protein. Water or a molecular oxygen ligand can reversible attach itself to the
sixth site.
In the lungs, oxygen attaches to the Fe2+ ion forming oxyhaemoglobin. In other
parts of the body, the oxygen is replaced by a water ligand forming
deoxyhaemoglobin. This allows haemoglobin to transport oxygen in the blood
from the lungs to the other parts of the body. Haemoglobin is capable of
transporting 4 molecules of oxygen at a time. Stronger ligands such as cyanide and
carbon monoxide can also bond to this site. However, they bond irreversibly to the
site and prevent haemoglobin form transporting oxygen in the body. This accounts
for the poisonous nature of these substances.