3d-Transition Elements and Their Application

Class: BE Chemistry
Lecture: 2
By: Rajesh Paudel
1. Electronic Configuration:
3d–series consists of elements from Sc (at no.21) to Zn (at no.30). These elements lie in the
4th period of the periodic table. In the atoms of these elements the last electron goes to 3d–
orbitals, i.e., in this series 3d orbitals are progressively filled up with electrons as we move
from Sc to Zn.

Atomic Electronic
Element Symbol
number configuration

Scandium 21 Sc [Ar] 3d14s2

Titanium 22 Ti [Ar] 3d2 4s2

Vanadium 23 V [Ar] 3d3 4s2

Chromium 24 Cr [Ar] 3d54s1

Manganese 25 Mn [Ar] 3d5 4s2

Iron 26 Fe [Ar] 3d6 4s2

Cobalt 27 Co [Ar] 3d7 4s2

Nickel 28 Ni [Ar] 3d8 4s2

Copper 29 Cu [Ar] 3d10 4s1

Zinc 30 Zn [Ar] 3d10 4s2

It may be noted that the configurations of Cr24 and Cu29 (two elements) are anomalous, since
Cr24 has 5 electrons (instead of 4) in 3d orbitals and Cu29 has 10 electrons (instead of 9 ) in these
orbitals. Thus the correct electronic configurations of Cr24 and Cu29 are [Ar]183d54s1 [instead of
[Ar]183d44s2 and [Ar]183d104s1 instead of [Ar]183d94s2 respectively due to extra-stability of half
fulfilled and fulfilled.

Note: Zn, Cd and Hg as transition metals but not true transition elements because transition
elements are those whose atoms have incomplete d-subshells.

Zinc (Zn) (30) : [Ar] 3d104s2

Cadmium (Cd) (48) : [Kr] 4d105s2

Mercury (Hg) (80) : [Xe] 5d106s2

Since these three elements have completely filled d-sub-shell. i.e. having (n-1)d10ns2
configuration. So they cannot be regarded as true transition elements. Group II B metals are
called volatile metal.

2. Variable Oxidation State:

Transition metal contain ns and (n–1)d orbitals. They show variable oxidation states as both
(n–1)d and ns electrons participate in bonding, due to nearly same energy levels.

Elements of first transition series show +1 and +2 as the lowest oxidation states due to presence
of two 4s electrons, with the exception of copper and chromium which have only one 4s electron
and the 3d electrons take part in the chemical bonding one after another, in addition to the +2
oxidation states, there are number of other oxidation states as illustrated below. The common
oxidation states are +2 and +3. The number of oxidation states increases with increase in the
number of unpaired 3d electrons.
E.g. scandium show only +2 and +3 oxidation states Due to the loss of two electrons from the 4s
orbital, Sc acquires +2 oxidation state & by the loss of one more electron from the 3d-orbital, it
acquires +3 oxidation state which has extra stable orbital.

Different or variable oxidation states of manganese are +2, +3, +4, +5, +6 and +7. Since
the electronic configuration of Mn is 1s2 2s2 2p6 3s2 3p6 3d5 4s2. Due to the presence of half filled
d–orbital, the +2 oxidation state of manganese is more stable.

Hence, among transition metals, manganese exhibits the largest number of oxidation
states ranging from +2 to +7. E.g. MnCl2, Mn2O3, MnO2, MnF5, K2MnO4, KMnO4 having
oxidation states are +2, +3, +4, +5, +6 & +7 respectively.

Mn2+ state is very stable due to extra stability of half filled 3d5subshell. The salts of manganese
in +2 oxidation state are known as manganese salts. Mn7+ is a good oxidizing agent, since it can
be easily reduced to Mn4+ and Mn2+.

Fe3+ more stable than Fe2+.Electronic configuration of Fe2+ is 1s2 2s2 2p6 3s2 3p6 3d6. While
electronic configuration of Fe3+ is 1s2 2s2 2p6 3s2 3p6 3d5. Due to the presence of half
filled‘d’ orbital, Fe3+ is more stable than Fe2+.

The salts of chromium in +2 oxidation state are called chromous salts e.g. chromous chloride
(CrCl2) and chromous sulphate (CrSO4). The salt of chromium in +3 oxidation state is known
as chromium or chromic salts. eg. chromic chloride (CrCl3).

Cuprous salts contain copper in +1 oxidation state e.g. cuprous iodide (Cu2I2). Cupric
salts contain copper in +2 oxidation state & also known as copper salts. E.g copper sulphate
(CuSO4), copper chloride (CuCl2).

The highest oxidation state of a metal exhibited in its oxide or fluoride only because oxygen and
fluorine have small size and high electronegativity, so they can easily oxidize the metal to
its highest oxidation state.
MnO4- (permanganate ion) has Mn+7 & CrO4-2 (chromate ion) has Cr+6. +8 oxidation states are
shown by both Os and Rh. Os in OsO4 has the most stable oxidation state. Atoms having high
electronegativity such as O or F stabilize higher oxidation states. Ligands which have the ability
to accept electrons from the metal (such as CO) through p-bonding stabilize lower oxidation
states (zero or +1).

Zn does not exist in variable oxidation states. The oxidation state of an element depends on its
electronic configuration is 1s2 2s2 2p6 3s2 3p6 3d10 4s2. When Zn loses two electrons from 4s-
orbital thus acquiring +2 oxidation state, it gets a very stable electronic configuration where in all
the electrons in d-orbital are paired. Zn2+: 1s2 2s2 2p6 3s2 3p6 3d10. Since d-orbitals are
completely filled with paired electrons, which is stable electronic configuration. Therefore, Zn
shows only one oxidation state of +2.

3. Complex Formation Tendency:

The cations of transition metals have strong tendency to form the complexes with molecules (such as,
H2O, NH3, CO, etc. ) and ions (such as CN-), e.g. [Ni (NH3)3]2+, [Ni(H2O)6]2+, [Fe(CN)6]4-,
[Fe(CN)6]3-, [Ni(CO)4], etc.

The transition metals have greater tendency to form complex compounds as they form large number
of compounds due to:

i. Small size of metal ion

ii. High ionic charge on them
iii. Availability of partially filled d-orbital for bond promotion

Transition elements form large number of complexes. Small sized transition metal cations have high
effective nuclear charge. Hence, they can accept lone pair of electrons from ligands to form coordinate
bonds. This is also facilitated by vacant inner d-orbital. For example, Ni forms complex Ni(CO)4.

4. Color Formation:

In contrast to 's' and 'p'-blocks elements, most of the compounds of transition elements are
colored both in solid state and in solution form.
Cu+2/Cu+ ----- Blue/Colorless
Ni+3/Ni+2 ----- Purple/Yellow
Ti+3/Ti+2 ----- Purple/Brown
Color in transition-series metal compounds is generally due to electronic transitions of two
principal types:
i. charge transfer transitions
ii. d-d transitions

More about charge transfer transitions:

An electron may jump from a predominantly ligand orbital to a predominantly metal
orbital , giving rise to a ligand-to-metal charge-transfer (LMCT) transition. These can most
easily occur when the metal is in a high oxidation state. For example, the colour of chromate,
dichromate and permanganate ions is due to LMCT transitions.

More about d-d transitions:

In an isolated atom or ion of a transition element, all the 5-d orbitals are of same energy
(degenerate). However, under the influence of combining ligands, these d- orbitals donot have
same energy. Now, they split into two sets of d-orbitals. One set consists of 3-d orbitals (t2g set:
dxy, dxz and dyz orbitals) and other consist of 2-d orbitals (eg set: d x2- y2 and dz2 orbitals).
One set consists of higher energy compared to the other. In octahedral complexes, t2g set has
lower energy than eg set whereas in tetrahedral complexes, eg set has lower energy than t2g set.

This process of splitting of 5-d orbitals into two sets of d-orbitals is known as Crystal Field
Splitting 'Δ' and the difference between the energies of two sets of d-orbitals is known as
Crystal Field Splitting Energy (ΔE).
A partial spectrochemical series listing of ligands from small Δ (weak field ligands) to large Δ
(strong field ligands) is given below:
I− < Br− < S2− < SCN− (S–bonded) < Cl− < N3− < F−< NCO− < OH− < C2O42− < O2−< H2O <
acac− (acetylacetonate) < NCS− (N–bonded) < CH3CN < gly (glycine) < py (pyridine) < NH3 <
en (ethylenediamine) < bipy (2,2'-bipyridine) < phen (1,10-phenanthroline) < NO2− (N–bonded)
< PPh3 < CN− < CO
Weak field ligands: H2O, F−, Cl−, OH−
Strong field ligands: CO, CN−, NH3, PPh3
Weak field ligands cause only a small degree of crystal field splitting. In transition metal ions, if
there are one or more unpaired electrons, in d-orbital, they can be excited from lower energy d-
orbital to higher energy d-orbital. For this excitation, a very small amount of energy is sufficient.
The wavelength of the light corresponding to this small amount of energy is present in the visible
light or sunlight or white light.
When transition metal compounds are exposed to white light, it absorbs certain color whose
wavelength is in the visible region (i.e 400 -750 nm) and the unpaired electron gets excited from
lower energy d-orbital to higher energy d-orbital. Now, the unabsorbed color or excess color is
reflected back which is no more white. This reflected color is the color of the substances.
i.e Color of substance = White light - Absorbed color
which is the reflected light and is the complementary color of absorbed color.
The excitation of electrons for d-orbital of lower energy to the d-orbital of higher energy is
known as d-d transition. For d-d transition to occur, color should be absorbed and for color
absorption, there must be the presence of unpaired electron in d-orbital.
For Eg.: Cu+2 ions absorb yellow color in the visible region and reflect back blue color
(complementary color). Thus the compound of Cu+2 are blue in color.

If there is no any unpaired electron in d-orbital, then d-d transition is not possible, no any color is
absorbed. When white light falls on the substances, total light is reflected back and the
substances appear white. Thus, compounds of Sc3+, Ti4+, V5+, etc. are white as these metal ions
have 3d0 configuration and the compounds of Zn2+, Cd2+ and Hg2+ are also white because they
have (n-1)d10 configuration.

Colour of transition metals is due to d-d transition of unpaired electrons. For example, in the
complex [Ti(H2O)6]3+, the Ti atom has oxidation state of +3. Its outer electronic configuration is 3d1. It
has one unpaired electron. This unpaired electron is excited from t2g level to eg level by absorbing
yellow light and hence appears violet coloured.

5. Magnetic Properties:

Transition metals shows magnetic behaviour. Those 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 behaviour. 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 behaviour.
An electron is a charged particle (negatively charged) which revolves around the nucleus and
spins on its own axis. A magnetic field is generated due to the orbital motion and spin of the
electron. The spinning of an electron in an orbit is very much similar to flow of electric current
in a closed circuit. Therefore, an unpaired electron is regarded as a micro magnet which has a
definite magnetic moment. A substance which contains an unpaired electron when placed in a
magnetic field interacts with the applied field. Consequently, an attractive force is exerted and
the paramagnetic property is shown. The number of unpaired electrons determines the magnitude
of magnetic moment. Higher the number of unpaired electrons more is the magnetic moment and
greater will be the paramagnetic behaviour of the substance.
In the case of paired electrons, the electrons in each pair will have opposite spin. The magnetic
field created by the electrons of same pair is equal and opposite in nature. Hence, the magnetic
field which is created by one electron is cancelled by the other. So the net effect of the magnetic
moment is zero. These kinds of substances show diamagnetic property and are repelled by the
applied magnetic field.
Magnetic moment (μ) = √n(n+2) B.M where n is the number of unpaired electrons and B.M
stands for Bohr Magneton.
Q. Why Mn(II) shows maximum paramagnetic character amongst the bivalent ions of the first
transition series?

6. Alloy Formation:

Alloys are homogeneous 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 (Fig.)

Now, as transition metals have similar atomic radii and other characteristics, hence they form
alloys very readily.

Alloys are generally harder, have higher melting points and more resistant to corrosion than the
individual metals.

The most commonly used are the ferrous alloys the metals chromium, vanadium, molybdenum,
tungsten and manganese are used in the formation of alloy steels and stainless steels.
Some alloys of transition metals with non-transition metals are also very common. e.g., brass (Cu
+ Zn) and bronze (Cu + Sn)

Transition metals form two different type of alloys. They are:

i. Interstitial alloy: In this alloy, small seized element like H, B, N, C, etc get trapped in
the interstitial position of transition lattice crystal. For Eg: Steel (Fe + C)
ii. Solid solution alloy: This alloy are formed by addition of one or more transition metal
like Ni, Cr, Mn, Zn, V, etc. to Iron (Fe). For Eg: Stainless steel (Fe + Ni + Cr + C),
Manganese Steel ( Fe + Mn + C), Nickel Steel (Fe + Ni)
Application of 3d-Transition Elements:

i. The two most useful properties of titanium include its resistance to corrosion and its high
strength-to-weight ratio.
ii. Chromium metal is highly valuable due to its high corrosion resistance and hardness.
iii. Manganese is a metal with important industrial metal alloy uses, particularly in stainless
steels.
iv. Copper is the most heavily used coinage metal due to its electrical properties, its
abundance (contrasted to silver and gold), and the attractiveness of its alloys — brass and
bronze.
v. Zinc is used in alloys with copper to create a harder metal known as brass.
vi. In galvanization, zinc coats iron by oxidizing to form a protective layer of zinc oxide
(ZnO) that protects the iron from rust.
vii. Cobalt and nickel are trace elements with properties similar to iron.
viii. Colors of transition metal compounds are due to two types of electronic transitions.
ix. Due to the presence of unpaired d electrons, transition metals can form paramagnetic
compounds.
x. Diamagnetic compounds have d-electrons that are all paired up.
xi. Transition metals are conductors of electricity, possess high density and high melting and
boiling points.
xii. Copper forms a rich variety of compounds with oxidation states +1 and +2, which are
often called cuprous and cupric, respectively.
xiii. The simplest compounds of copper are binary compounds (i.e., those containing only two
elements ). The principal compounds are the oxides, sulfides, and halides.
xiv. Amino acids form very stable chelate complexes with copper (II).
xv. Chromium is remarkable for its magnetic properties: it is the only elemental solid which
shows antiferromagnetic ordering at room temperature (and below).
xvi. Chromium(VI) compounds are powerful oxidants at low or neutral pH.
xvii. Manganese is an essential trace nutrient in all forms of life.