3d- Transition Elements and Their Application

Class – BE Chemistry
Lecture-1
By Rajesh Paudel(RP)
3d- Transition Elements and Their Application

 In the periodic classification of elements, the elements have

been broadly divided into four blocks namely s, p, d and f blocks.
The divisions based on the type of the atomic sub-shell which
receives the last electron in the atom.
 The d-block elements are called transition metals. In these
elements the outermost shell consists one or two electrons in
their s-orbital but the last electron enter the one d-sub shell i.e.
(n-1)d.
3d- Transition Elements and Their Application

 The periodic table of elements has four main categories: main-

group metals, transition metals, lanthanides and actinides. The
transition metals bridge elements that fall on either side of them.
These elements conduct electricity and heat; they form ions with
positive charges. Their malleability and ductility make them ideal
materials for the manufacture any type of metal-based item.
Heavy metals(d-block) in periodic table
Transition elements [d-block elements]
 In chemistry "transition metal" is considered as any element in
the d-block of the periodic table, which includes groups 3 to
12 on the periodic table. In actual practice, the f-block
lanthanide and actinide series are also considered transition
metals and are called "inner transition metals".
 The name transition is due to the fact that they occupy the
position in between s-block and p-block elements.
 They represent the change in properties from most
electropositive s-block elements to least electropositive p-
block elements
 The transition metals are those elements which have partially
filled d-subshell in their ground state or in anyone of their
oxidation states.
 The general electronic configuration is (n-1)d1-10 nS1-2.
 First (3d) d-block Series (Sc–Zn)

Group 3 4 5 6 7 8 9 10 11 12

Atomic
21 22 23 24 25 26 27 28 29 30
Number

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn

Electron
Configur 3d14s2 3d24s2 3d34s2 3d54s1 3d54s2 3d64s2 3d74s2 3d84s2 3d104s1 3d104s2
ation
 The elements of this block have general characteristic properties
intermediate between the elements of s-block and p-block. In other
words d-block elements represent change (or transition) in properties
from most electropositive s-block elements to least electropositive p-
block elements. Therefore these are called transition elements.

 The elements of group IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII (with three
vertical columns) together with 10 vertical columns (from group 3 to
group 12) of the periodic table are called transition elements. These
are four transition series starting from 4th period. There are 4
transition series 3d, 4d, 5d and 6d series and are knows and 1st, 2nd, 3rd
and 4th transition series respectively.
General characteristics of transition metals:

• Metallic Character
• Melting and Boiling Point
• Atomic (Covalent) and Ionic Radii
• The ionization energy (IE)
• Color
• Formation of Alloys
• Interstitial Compounds
• Variable Oxidation State
• Catalytic Property
• Complex Formation
• Magnetic Property
• Density
Metallic Character
 All the transition elements are metals; this is because the
number of electrons in outermost shell is only 2.
 Transition metals are hard, malleable and ductile due to
presence of strong metallic bonds.
 Transition metals crystallize in all the three face centred
cubic (fcc), hexagonal close packed (hcp) and body
centred cubic (bcc) crystals.
 Transition metals of VIII and IB Groups are softer and more
ductile as compare to the other transition metals.
 Along with metallic bonding, transition metals also show
covalent bonding due to presence of unfilled d-orbitals.
 As transition elements are metals so they good conductors
of heat and electricity.
 Melting and Boiling Point
 Transition metals usually have very high value of melting
and boiling points due to presence of strong metallic
bonds.
 Zn, Cd and Hg metals have lower metaling and boiling
points as they have completely filled d orbitals because of
which no unpaired electron is available. Because of
unavailability of unpaired electrons, these metals do not
undergo covalent bonding. Rest of the transition metals
does have metallic as well as covalent bonding.
Atomic (Covalent) and Ionic Radii
 The covalent radii of the elements decrease from left to right
across a row in the transition series. This is because of the poor
screening by the d electrons due to which, the nuclear charge
attracts all of the electrons more strongly, hence a contraction
in size occurs.
 The atomic radii for the elements from Cr to Cu are very close
to one another. This closeness in atomic radii is due to the
shielding of outer 4s electrons by 3d electrons from the inward
pulls of nucleus. As a result of these two opposing effects, the
atomic radii do not alter much on moving from Cr to Cu.
 The elements in the first group in the d-block show the
excepted increase (due to the addition of extra shell) in size
Sc → Y → La. However in the subsequent groups there is an
increase between first and second members, but hardly any
increase between second and third elements. This is due to
lanthanide contraction (in f-block elements).
The ionization energy (IE)
 The first ionization energy of transition elements are higher than those of s-
block elements but lower than p-block elements.
 In a particular transition series, ionization energy although increases
gradually as we move from left to right but this increase is not appreciable.
 The increase in ionization energy is due to increase in nuclear charge, the
effect of increase in nuclear charge is partly balanced by the increase
in screening effect. Consequently, the increase in ionization energy along the
period of d-block elements is very small.
 In transition elements, on moving along the period, the addition of the extra
electron in the (n-1) d level takes place. This electron provides a screening
effect and shields the outer ns electrons from the nucleus pull.
 Because of this shielding effect of d electrons, the effect of nuclear charge
(effective nuclear charge) on outer ns electrons is somewhat less than the
actual nuclear charge.
 Thus the effects of the increasing nuclear charge and the shielding effect
created due to the expansion of (n-1)d orbital oppose each other.
 On account of these counter effects, the ionization potentials increase rather
slowly on moving in a period of the first transition series

First Ionization Energy

 The first ionization energy for the first four 3d series

elements (Sc, Ti, V and Cr) are almost same i.e. differ
only slightly from one another.
 The values of first ionization energy for Fe, Co, Ni and Cu
are also very close to one another.
 The value of first ionization energy for Zn is considerably
high due to extra-stability of completely filled 3d10 level.
Second ionization energy
 The second ionization emerges increases more or less
regularly with the increase of atomic number.
 The value of second ionization energy for Cr and Cu are
higher than those of their neighbors. This is due to the
fact that the electronic configurations of Cr + and Cu+ ions
have extra stable 3d5 and 3d10 levels.
 There is a sudden fall in the values of ionization potentials
in going from II B (Zn-group elements) to IIIA sub-group.
This is because in case of IIIA group elements the electron
to be removed is from a 4p-orbital which is incompletely
filled, while in case of the II B group elements, the
electron to be removed is from completely filled 4s-
orbital which required extra energy
Color

 Many compounds of transition elements are colored in

contrasts to those of s and p block elements.
 The color is due to the promotion of unpaired electrons
from one energy level to another in d-shell.
 This corresponds to fairly small amount of energy
difference and so light is absorbed in visible region.
 The atoms , ions or molecules which have unpaired
electrons in d-orbitals are colored because of the
promotion of unpaired electrons from one energy level to
higher energy level within same sub-shell
 Some compounds of transition metals are white, for
example ZnSO4 and TiO2. In these compounds it is not
possible to promote the electrons within the d-level.
Cause for color in transition metal compounds:
 When transition metals start bonding with other ligands, due to different symmetries of
the d orbitals and the inductive effects of the ligands on the electrons, the d orbitals
split apart and become non-degenerate. When an electron jumps from lower energy d
orbital to higher energy d orbital, that is a d-d transition, the energy of excitation
corresponds to the frequency of light absorbed.

 Thus, the energy required by the electrons for a change is provided by the light waves.
The frequency of a light wave is observed to lie invisible range. The frequency of light
absorbed depends on the nature of ligands. For example, if the electrons in an
octahedral metal complex can absorb green light and get promoted from the lower
energy d orbital to higher energy d orbital, the compound will reflect all the colors
except green. Hence, the complementary color of green will be observed as the color of
the compound.

 Whenever light falls on the transition element compounds electrons excite and
electrons absorb energy and excite. When these electrons de-excite they release visible
light wavelength. That's why transition element compounds exhibit colour.
eg

t2g
Examples:

Fig: Various colored compounds of transition

metals
Formation of Alloys
 Alloys are homogenous solid solutions of two or more
metals obtained by melting the components and then
cooling the melt.
 These are formed by metals whose atomic radii differ by
not more than 15% so that the atoms of one metal can
easily take up the positions in the crystal lattice of the
other. Since transition metals have similar atomic radii,
they form alloys very readily by.
 The alloy formed are relatively hard and have higher
melting point.
Interstitial Compounds
 Sometimes transition metals form non
stoichiometry compounds. These are compounds
of indefinite structure and proportions. For
example Fe0.94O. It is mostly due to the variable
valency of transition elements. Sometimes, non
stoichiometry is caused by defects in the solid
structures.
 Transition metals form number of interstitial
compounds, in which they take up atoms of small
size e.g. H, C and N in the vacant spaces in their
lattices. The presence of these atoms result in
decrease in malleability and ductility of the
metals but increases their tensile strength.
Variable Oxidation State
 They show variable oxidation states unlike s and p block elements.
The oxidation states changes in units of one, e.g. Fe2+ and Fe+3,
Cu+1 and Cu+2.
 Scandium can have an oxidation number of (+II) if both s electrons are
used for bonding and (+III) when two s and one d electrons are
involved. Similarly all the elements show variable oxidation states
depending upon the number of electrons available for bonding in their
s and d sub-shells.
 Transition metals have unique property to show variable oxidation
state. This property arises from the fact that the energy levels of 3d,
4d and 5d orbitals are very close to those of 4s, 5s and 6s orbitals
respectively and, therefore, electrons from both ns and (n-1)d orbitals
can be used, infect they are used, for the formation and bonds by
transition metals.
 The first five elements of first transition series up to Mn in
which 3d subshell is no more than half filled , the minimum
oxidation state is equal to the number of electrons in the 4s-
shell and maximum oxidation state is equal to the sum of the
4s and 3d electrons.
 Minimum oxidation state: All the transition elements except
Cr, Cu, Ag, Au and Hg which have a minimum oxidation state of
+1 exhibit a minimum oxidation state of +2.
 Maximum oxidation state: Each of the elements in groups III B
to VII B can show the maximum oxidation state equal to its
group number. For example, Cr in group VIB shows a maximum
oxidation state of +6 in Cr2O72– ion.
 Most of the elements in VIII group show a maximum oxidation
state equal to + 6. However, Ru and Os have a maximum
oxidation state equal to +8 which is the highest oxidation state
shown by any element.
Catalytic Property
 Many transition metals and their compounds have
catalytic properties. For e.g. V2O5, Fe, FeCl3, Ni, Pd
etc. This is due to following reasons
 Variable oxidation state: Due to variable oxidation state
they form unstable intermediate compounds and provide a
new path with lower activation energy for the reaction
(Intermediate compound formation theory)
 Large Surface area: Finely divided transition metals or
their compounds provide a large surface area for
adsorption and the adsorbed reactants react faster due to
the closer contact.
Examples:
Used as Ziegler – Natta catalyst
TiCl3

Converts SO2 to SO3 in the contact

V2O5 process for making H2SO4

Used as a catalyst to decompose

MnO2 KClO3 to give O2

Used in Haber – Bosch process for

Fe making NH3
Complex Formation
 The transition elements have a marked ability to form
coordination compounds with the Lewis bases, which are called
as ligands.
 Co3+ + 6NH3 → [Co(NH3)6]3+
 Fe2+ + 6CN– → [Fe(CN)6]4–
 s and p block elements form very few complexes. The reason
transition elements are so good at forming complex is as
follows:
 small size
 high nuclear charge
 have vacant low energy orbitals to accept lone pairs of electrons
donated by ligands.
 Note: Ligands are the species with lone pair of electrons which
they can readily donate.
Magnetic Property

 On the basis of behaviour in a magnetic field, substance are classified as

paramagnetic, diamagnetic and ferromagnetic. Those substance which are
attracted by the applied magnetic field are called paramagnetic where as
those which are repelled by the magnetic field are called diamagnetic.
Substances which are very strongly attracted by the applied field are
called ferromagnetic.
 Paramagnetism is a property due to the presence of unpaired electrons.
Thus most of the transition metals are paramagnetic. As the number of
unpaired electrons increases, the paramagnetic character also increases.
 The magnetic moment is calculated from the following formula μ =
√n(n+2) BM where n is the number of unpaired electrons and B. M stands
for Bohr magneton.
Atomic volumes and density

 Due to the filling of inner orbitals the increased nuclear

charge pulls the electronic cloud inward. This causes
atomic volume to decrease and thus density of transition
metals are very high.
 Mercury is an exception, which is a liquid at room
temperature all other elements are solid metals exhibiting
all the characteristics of a metal.
Summary
References:

 Engineering Chemistry by Jain and Jain

 Conceptual Chemistry, Divya Deurali Prakashan pvt. Ltd.
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 https://en.wikipedia.org/wiki/Transition_metal
 https://www.askiitians.com/iit-jee-d-and-f-block-elements/general-
characteristics-of-transition-elements/
 https://people.wou.edu/~courtna/ch462/tmcolors.htm
 https://byjus.com/chemistry/colour-transition-elements/