D BLOCK ELEMENTS

 The d-block elements, known for their distinct chemical and physical properties, are found in
groups 3 to 12 of the periodic table.
 They are characterized by having partially filled d-orbitals either in their elemental form or in
common oxidation states.
 Also known as transition metals due to its position as they show the transition of the journey
between S-block and P-block

Transition metals
defined as the one which has incompletely filled d orbitals at its ground state or in any one of
its oxidation states

exceptions- zinc, cadmium, mercury

 There are 4d series

 3d- Sc to Zn
 4d- Y to Cd
 5d- La to Hg
 6d- radioactive

Electronic configuration

The general electronic configuration of d-block elements is (n-1)d^{1-10}ns^{0-2}.

This means:The d-orbitals of the penultimate shell (the second-last shell) are being filled as
we move across the period.
For example:Scandium (Sc): 1s² 2s² 2p⁶ 3s² 3p⁶ 3d¹ 4s²Iron (Fe): 1s² 2s² 2p⁶ 3s² 3p⁶ 3d⁶ 4s²
Transition metals often lose their s-orbital electrons first when they ionize, resulting in
multiple possible oxidation states.

Properties

 ATOMIC RADIUS
The atomic radius of d-block elements (also called transition elements)
varies in a specific manner across the periods and down the groups in the
periodic table.

### General Trend Across the Periods:

The atomic radius of transition elements across a period (left to right)
decreases initially and then remains relatively constant. Here’s why:

1. Increased Nuclear Charge: As we move across the period, the number of

protons in the nucleus increases, causing a higher positive charge. This pulls
the electrons closer to the nucleus.

2. Poor Shielding of d-electrons: The d-electrons do not shield each other

very effectively, meaning the effective nuclear charge (the net positive
charge felt by the outer electrons) increases as more protons are added. This
causes the electrons to be pulled closer to the nucleus, decreasing the
atomic radius.

3. Electron-electron repulsion: As more electrons are added to the same d-

subshell, the repulsion among them increases, counteracting the effect of
increased nuclear charge to some extent, which is why the decrease in
atomic radius is not as pronounced as it is in s- and p-block elements.

4. Almost Constant Size in Later Elements: In the middle of the d-block (like
from Fe to Cu in the 3d series), the atomic radius becomes nearly constant.
This happens because the inward pull of electrons (due to increased nuclear
charge) is balanced by the increased electron-electron repulsion within the
d-subshell.

### Trend Down the Group:

As you move down a group (from 3d to 4d and 5d series), atomic radii
increase. However, the trend between the 4d and 5d series is special.

1. From 3d to 4d Series: The atomic radius increases normally due to the

addition of an extra shell, which increases the size of the atom.

2. From 4d to 5d Series: The increase is very small or almost negligible

because of the lanthanide contraction. This phenomenon occurs due to the
poor shielding of the 4f electrons in the lanthanides (which precede the 5d
series). This poor shielding results in a higher effective nuclear charge,
pulling the outer electrons closer and compensating for the increased
number of electron shells, hence causing the 5d elements to have similar
radii to the 4d elements.

### Example of Atomic Radii in 3d Series:

- Sc: 162 pm
- Ti: 147 pm
- V: 134 pm
 - Cr: 128 pm
- Mn: 127 pm
- Fe: 126 pm
- Co: 125 pm
- Ni: 124 pm
- Cu: 128 pm
- Zn: 137 pm

 Oxidation states
3d Series (First Transition Series)Early 3d elements like Sc, Ti, V, and Cr
exhibit stable higher oxidation states. Vanadium can exhibit +5 (e.g.,
V₂O₅).Chromium shows +6 in compounds like CrO₄²⁻ and CrO₃.As we move
across the series, the higher oxidation states become less stable:Manganese
exhibits a +7 state in MnO₄⁻, but Fe and Co stabilize at +2 and +3 states, with
Fe occasionally reaching +6 in rare ferrate compounds .Copper is stable in
the +1 and +2 states, and zinc exhibits only the +2 oxidation state.

In the 4d and 5d series (like Zr, Mo, W, and Os), higher oxidation states are
more common and stable than in the 3d series .Molybdenum and tungsten can exhibit oxidation
states as high as

+6 (e.g., MoO₃ and WO₃).Ruthenium (Ru) and osmium (Os) exhibit stable +8
states (e.g., OsO₄).The higher stability of oxidation states in the 4d and 5d series is due to the larger
atomic size,

lower effective nuclear charge, and the participation of 4d and 5d orbitals

in bonding.

 FORMATION OF ALLOY
(a) Transition elements have maximum tendency to form alloys.

(b) The reactivity of transition elements is very less and their sizes are almost
similar. Due to this a transition metal atom in the lattice can be easily replaced by
other transition metal atom and hence they have maximum tendency to form
alloys.

(c) In the alloys, ratio of component metals is fixed.

(d) These are extremly hard and have high melting point

. SOME IMPORTANT ALLOY

(a) Bronze Cu (75 - 90 %) +Sn ( 10 - 25 %) (b) Brass Cu ( 60 - 80 %) +Zn (20 - 40

%) (c) Gun metal (Cu + Zn + Sn) (87 : 3 : 10) (d) German Silver Cu + Zn + Ni ( 2
: 1 : 1) (e) Bell metal Cu (80 %) + Sn (20 %)
  FORMATION OF INTERSTITIAL COMPOUNDS
(a) Transition elements form interstitial compounds with smaller sized non metal
elements like hydrogen, carbon, boron, nitrogen etc.

(b) The smaller sized atoms get entrapped in between the interstitial spaces of the
metal lattices. These interstitial compounds are nonstoichiometric in nature and
hence cannot be given any definite formula.

(c) The smaller sized elements are held in interstitial spaces of transition elements
by weak Vander Waals forces of attractions.

(d) The interstitial compounds have essentially the same chemical properties as the
parent metals but they differ in physical properties such as density and hardness.
The process of adsorption of excess of H atom by the transition metals like Pd, Pt etc
is called occlusion

o Their chemical properties are the same as that of the parent metal

o These interstitial compounds are hard and show electrical and thermal conductivity
and luster.

o They have high melting points, higher than those of pure metals as the metal -
nonmetal bonds are stronger than metal-metal bonds in pure metals.

o Their densities are less than the parent metal.

o Hydrides of transition metals are used as powerful reducing agents.

o The metallic carbides are chemically inert and extremely hard as diamond.

o Steel and cast iron are examples of interstitial compounds of iron and carbon. In
these compounds, the malleability and ductility of iron are lost to a lesser or greater
extent, whereas the tenacity of metal increases.

 CATALYTIC PROPERTY

(a) Transition elements and their compounds exhibit catalytic properties.

This is due to their variable valency as well as due to the free valencies on
their surface
. (b) When transition elements and their compounds are in powdered state,
their catalytic properties exhibited will be to a greater extent. This is due to
greater surface area available in the powdered state
 (c) Transition metals and their compounds exhibiting catalytic properties in
various processes are

Examples

o MnO_2 acts as a catalyst for the decomposition of KClO_3 to O_2.

o The nickel acts as a catalyst in the hydrogenation of oils to fats.
o Vanadium pentoxide is used as a catalyst in the manufacture of H_2SO_4 by
contact process.
o Fe(III) catalyzes the reaction between iodide and persulphate ions.
o Titanium chloride (Ziegler-Natta catalyst) is used in the manufacture of high-
density polythene.
o In the manufacture of ammonia, Fe with Mo is used as a catalyst.
o Co-Th alloy is used in the Fischer Tropschin process in the synthesis of
gasoline.

 Ionization Enthalpy

o The ionization enthalpies of transition elements lie between those of s block and p block
elements. They are higher than those of s block elements and lower than those of p block
elements.
o The ionization enthalpies of transition metals are quite high and lie between those of block
and p block elements. The atomic radii and nuclear charge of the transition metals lie
between those of block and p block elements. They possess smaller atomic radii and higher
nuclear charge as compared to those of s-block elements. But the reverse is the trend when
compared with p-block elements.
o The first ionization enthalpy increases with an increase in atomic number across a given
transition series, although the increase is not very regular. The added electron enters into (n-
1) d-subshell and shields the valence electrons from the nucleus. Thus, the effect of the
increased nuclear charge is opposed by the screening effect of (n-1) d-electrons. Therefore,
the increase in ionization enthalpy with an increase in atomic number is rather slow and not
very regular
o The first ionization enthalpies of elements of the third transition series are higher than those
of the elements of the first and second transition series.
o The atoms of elements of the third transition series possess filled 4f-orbitals. 4f orbitals
exhibit a poor shielding effect on account of their peculiar diffused shape. As a result, the
valence electrons experience greater nuclear attraction. Consequently, it requires a greater
amount of energy to ionize elements of the third transition series. Therefore,
the ionization enthalpies of the elements of the third transition series are much higher than
those of the first and second series.
  Formation of colored ions

The colour of a substance depends upon the absorption of light of a particular wavelength,
of visible lights (400 to 800 nm). Most of the compounds of transition metals are coloured in
their solid or solution form. The colour of the compounds of the transition metals may be
attributed to the presence of incomplete (n-1) d orbital and the number of unpaired
electrons. In these compounds, the energies of the five orbitals in the same subshell do not
remain the same or equal.
The transition metal ions with no unpaired electrons are colourless. Eg. Se^{3+}(3d), Ti^{4+}
(3d^{10}), Cut (30) and Zn^{2+} (3d^{10}).
Ions with unpaired electrons are coloured. Ions with electronic configuration 3d to 3d are
coloured

In general, the colour of a transition ion can be related to

o The presence of unpaired d electrons
o d-d transition
o nature of groups i.e. ligands linked to the metal ions.
o the geometry of the complex formed by the metal ion.

 Density and hardness

D-block elements have high density and hardness, and other properties that make them
unique:

Density: D-block elements have high density because of their short atomic size and strong
metallic bonds. The density of d-block elements increases initially, then stabilizes, and finally
decreases along the period. Osmium and iridium are the densest d-block elements.

Hardness: D-block elements are harder than the metals of groups 1 and 2.

 MP & BP

Melting point
D-block elements typically have high melting points, usually above 9000 °C. The melting
point of d-block elements increases from d1 configuration to d5 configuration, and then
decreases. The highest melting points in their respective periods are possessed by group 6
elements chromium (Cr), molybdenum (Mo), and Tungsten (W).

Boiling point
Re has the highest boiling point among the d-block metals, followed by W and Ta. Mercury
has the lowest boiling point of all the metals.

Trend
The trend of melting and boiling points varies from group to group.

Reason for high melting and boiling points

The high melting and boiling points of d-block elements are generally based on how strong
the metallic bond is between their atoms.

Exceptions
Some exceptions to the high melting point rule include zinc, cadmium, and mercury.

 Complex formation

-block elements form complexes easily because of their small size, high nuclear charge, and
vacant d-orbitals:

Small size and high nuclear charge

D-block elements have a high charge density and can accept lone pairs of ligands.

Vacant d-orbitals
D-block elements have vacant d-orbitals that can accept electrons from ligands to form
bonds.

Polarizing power
D-block elements have a large polarizing power, which allows them to attract lone pairs from
other atoms.

Variable oxidation state

Some D-block elements, like Fe + 2 and Fe + 3, Cu + and Cu + 2, have variable oxidation states
and can form many complexes.

D-block elements are found in Groups 3-12 of the periodic table, which occupies most of the
middle section.

Chemical reactivity
The transition metals vary very widely in their chemical reactivity. Some of them are highly
electropositive and dissolve in mineral acids whereas a few of them are ‘noble’, i.e., they do
not react with simple acids. Some results of chemical reactivity of transition metals as
related to their E0 values are given below:

The metals of the first transition series (except copper) are relatively more reactive than the
other series. Thus, they are oxidized by H+ ions though the actual rate is slow, e.g., Ti and V
are passive to dilute non-oxidizing acids at room temperature.
As already explained, less negative E0 values for M2+/M along the series indicate a
decreasing tendency to form divalent cations.
More negative E0 values than expected for Mn, Ni and Zn show greater stability for Mn2+,
Ni2+ and Zn2+.
E0 values for the redox couple M3+/M2+ indicate that Mn3+ and Co3+ ions are the strongest
oxidizing agents in aqueous solution whereas Ti2+, V2+ and Cr2+ are strongest reducing
agents and can liberate hydrogen from a dilute acid, e.g.,
2cr2+ + 2h+ to 2 cr3+ = h2