General Properties of D-Blocks Elements

Atomic size:

A great degree of variation is seen in the atomic radii across each transition series. The atomic
radii of the d-block elements within a given series decreases with increase in the atomic number.
This is due to the increase in the nuclear charge that attracts the electron cloud inwards resulting
in decrease in size. However, the decrease a uniform decrease in atomic radius is not observed
across a period. The decrease in atomic radii is small compared to the S and P block elements.
This is due to the screening effect caused by the electrons of the (n-1)d subshell on the outermost
shell. As a result the nucleus cannot pull the outermost electrons. Thus, the size of the atom does
not alter much in moving from Cr to Cu.
The atomic radius increases on descending the group. In a given series, the atomic radius
decreases to a minimum for the group VIII elements and then it increases towards the end of the
series. This increase in radius towards the end of the series is due to the force of repulsion among
the added electrons. A close similarity is observed in the radii of the elements of the second and
third transition series due to the filling of 4f subshells.

Ionic size:

The ionic radius is similar to the pattern of atomic radii. Thus, for ions of a given charge the
radius decreases slowly with increase in atomic number.

Ionization enthalpy:

Ionization enthalpy is the energy required to remove the most loosely bound electron from the
isolated gaseous atoms to produce a cation. Those of transition elements tend to increase from
left to right in the periodic table as there is an increase in nuclear charge which accompanies the
filling of the inner d orbitals. However, there are some exceptions, for example, Titanium (22)
has first ionization enthalpy of 656kJ/mole whereas vanadium (23) has first ionization enthalpy
of 650kJ/mole.
These irregular trends in the first ionization enthalpy of transition metals can be explained by
considering the fact that the removal of one electron alters the relative energies of 4s and 3d
orbitals. Hence, in general, we can conclude that the unipositive ions furnish d n configuration
with no 4s electrons. Thus, there is a reorganization energy accompanying ionization with some
gains in exchange energy as the number of electrons increases from the transference of s
electrons into d orbitals. Let us analyze the general trend  in the first row:
First ionization enthalpies of transition elements show general trend of increase from left to right.
However, in case of chromium (24), the change in the value of first ionization enthalpy is lower
as there is no change in d orbital configuration whereas, zinc (30) shows a higher value as it
represents an ionization from 4s level.
The second ionization enthalpy for Cr and Cu are quite higher as the d 5 and d10 configuration of
M+ ions gets disrupted whereas, the value for Zn is correspondingly low as the ionization
consists of the removal of an electron which allows the production of the stable d10 configuration.
The trend in third ionization enthalpy doesn’t involve 4s orbitals and thus there is a greater
difficulty for the removal of an electron from Mn 2+ (d5) and Zn2+ (d10) ions. Thus, we see a
marked difference between third ionization enthalpies of iron (26) and manganese (25).

Oxidation state:
All the transition elements, apart from the first and the last, display various oxidation states. There is
an increase in the number of common oxidation states at first to a maximum toward the middle of
the table, and then there is a when we move from left to right across the first transition series. The
elements scandium through manganese (the first half of the first transition series), show the highest
oxidation state as their valence shell shows loss of all of the electrons in both the s and d orbitals.
Iron forms oxidation states from 2+ to 6+. Elements in first transition series form ions with a charge
of 2+ or 3+. The elements belonging to the second and third transition series generally are more
stable in higher oxidation states than the elements of the first series. In general, as the atomic radius
increases down a group, ions of the second and third series become larger than the ions in the first
series.

Formation of Coloured Ions:

When an electron from a lower energy d orbital is excited to a higher energy d orbital, the energy
of excitation corresponds to the frequency of light absorbed. This frequency generally lies in the
visible region. The colour observed corresponds to the complementary colour of the light
absorbed.
Catalytic Properties of d-block elements:
Most of transition metals are used as catalysts. This is due to the:

 presence of incomplete or empty d-orbitals,

 large surface area and
 variable oxidation state. For example, Fe, Ni, V 2O3, Pt, Mo, Co, etc., are used as
catalyst.

Such complex compounds are not formed by s – and p – block elements.

Explanation:
The transition elements form complexes because of the following reasons:

 Comparatively smaller size of their metal ions.

 Their high ionic charges. (Because of (i) and (ii), they have large charge/size ratio)
 Availability of vacant d-orbitals so that these orbitals can accept lone pairs of electrons
donated by the ligands.

Magnetic properties:

There are various substances which show magnetic behavior. We have substances that are
attracted by the magnetic field and are called paramagnetic. This phenomenon is called
paramagnetism. Paramagnetic property is only shown when the substance contains one or more
unpaired electrons. When a substance acquires a permanent magnetic moment, it is known as
ferromagnetic and the phenomenon is called ferromagnetism. On the other hand, we also have
substances which are repelled by magnetic field and are called as diamagnetic substances. A
substance shows diamagnetism when it contains only paired electrons.
Most of the transition elements show paramagnetic behavior. The unpaired electrons in (n-1) d
orbitals are responsible for the magnetic properties. The paramagnetic character of the transition
metals increases on moving from left to right as the number of unpaired electron increases from
one to five. The middle elements are found to possess the maximum paramagnetic property. The
magnetic properties decrease with the decrease in the number of unpaired electrons. The
transition metals which contain paired electrons depict diamagnetic behavior.

Formation of complex compounds:

All the elements of the d block are transition metals. Transition elements are those elements that
have partly or moderately filled d orbital in their ground state or the most constant oxidation
state. The cations of d-block elements have a strong tendency to form complexes with certain
molecules (e.g. CO, NO, NH3….etc) or ions (e.g. F-, Cl-, CN- ….etc) called ligands. Their
tendency to form complexes is due to two reasons.

1. Small size and high positive charge density. Transition metals have a little size and high
charge density constitutes a strong electrostatic force of magnetism with the ligands and
does constancy of the complex increases.
2. Presence of vacant (n-1)d orbitals which are of appropriate energy to accept lone pair and
unshared pair of electrons from the ligands for bonding with them. Transition elements
having a huge number of empty orbitals in which it can contain the lone pair of electrons
provided by the ligands, therefore, can play the role of Central metal ion or central metal
atom.

Examples of some complex compounds are, Cu(NH3)4]2+, [Ag(NH3)2]+, [Fe(CN)6]4-,….etc.

They are of proper energy to believe lone pair and unshared pair of electrons from the ligands.
Hence conversion elements form complexes simply. Most subsist in numerous oxidation states
and form many multifaceted ions and colored compounds. The partly filled subshells of d-block
elements incorporate (n-1) d subshell. The leftmost members in a phase in the d block are active
metals, but those to the right in the stage are fewer active. All the d-block elements hold a
comparable number of electrons in their outmost shell. Therefore, they acquire comparable
chemical properties.

Interstitial Compounds:

The transition metals form a large number of interstitial compounds in which small atoms such
as hydrogen, carbon, boron and nitrogen occupy the empty spaces (interstitial sites) in their
lattices (Fig.).
They are represented by formulae like TiC, TiH2, Mn4N, Fe3H, Fe3C etc. However, actually they
are non-stoichiometric materials, e.g., TiH1.7, VH0.56 etc. and the bonds present in them are
neither typically ionic nor covalent. Some of their important characteristics are as follows:

 They are very hard and rigid, e.g., steel which is an interstitial compound of Fe and Cis
quite hard. Similarly, some borides are as hard as diamond.
 They have high melting points which are higher than those of the pure metals.
 They show conductivity like that of the pure metal.
 They acquire chemical inertness.