3-d Transition Elements and their applications

Marks: 10, Question: 1

 Introduction
 Electronic configuration
 Variable oxidation states
 Complex formation tendency
 Color formation
 Magnetic properties
 Alloy formation
1  Applications of 3-d transition elements
 Transition Elements
 The group of elements in the middle of the periodic table, which inner d and
f orbitals are not completely filled are called transition elements.
 They are also called d-block elements and f- block elements.
 Transition elements are placed between the highly reactive s- block metallic
element and p-block non metallic elements, they served as a bridge between two
sides of periodic table.

Characteristics of transition elements

i. Atomic radii
ii. Ionic radii
iii. Densities
iv. Metallic character
v. Melting and boiling points
vi. Ionization energies
vii. Oxidation state
viii. Formation of color
ix. Formation of complex
x. Catalyst formation
xi. Magnetic behavior 2
xii. Alloy formation
 Types of Transition series
1. First transition series
 10 elements (Sc-Zn) (21-30)
 3d transition elements
2. Second transition series
 10 Elements (Y-Cd) (39-48)
 4d transition elements
3. Third transition series
 5d transition elements
 10 Elements (Lanthanum (57) and from Hafnium(72) – Mercury (80)

4. Fourth transition series

 Called F group elements
 This consists of lanthanides and actinides.

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 3d transition element
 Transition elements which are as atoms or ions have partially filled i.e
(n-1)d orbital are d-block elements. From atomic number 21-30 i.e.
from scandium to zinc are 3-d transition elements.
Electronic configuration

Elements Atomic no. Electronic configuration

Scandium (Sc) 21 [Ar]3d14s2
Titanium(Ti) 22 [Ar]3d24s2
Vanadium(V) 23 [Ar]3d34s2
Chromium(Cr) 24 [Ar]3d54s1
Manganese(Mn) 25 [Ar]3d54s2
Iron (Fe) 26 [Ar]3d64s2
Cobalt (Co) 27 [Ar]3d74s2
Nickel (Ni) 28 [Ar]3d84s2
Copper(Cu) 29 [Ar]3d104s1
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Zinc (Zn) 30 [Ar]3d104s2
 According to the definition of transition element, the elements
such as Cu and its monovalent cation (Cu+)and Zn and its divalent
cation (Zn++) aren't supposed to be transition element because their
d orbitals are fulfilled.

 Characteristics of 3-d transition elements

 Variable oxidation states
 A no. assigned to an element in chemical combination which represents the
no. of electrons lost by an atom of that element in the compound is
oxidation number.
 The tendency of showing variable oxidation state depends on the no. of
unpaired electrons in (n-1)d orbitals. It is increased with increasing
unpaired electrons.
 They exhibit various oxidation states from +1 to +7.

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Table:- Oxidation state of 3-d series elements

Electroni Sc Ti V Cr Mn Fe Co Ni Cu Zn
c Conf.

3d1 3d2 3d3 3d5 3d5 3d6 3d74 3d8 3d10 3d10
4s2 4s2 4s2 4s1 4s2 4s2 s2 4s2 4s1 4s2

+1 +1

+2 +2 +2 +2 +2 +2 +2 +2 +2 +2

Oxid. +3 +3 +3 +3 +3 +3 +3 +3 (+3)

state +4 +4 +4 +4 +4 +4 +4

+5 +5 +5 +5 +5

+6 +6 +6

+7
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 Reasons
1. (n-1)d and ns orbitals in the atoms of d-block elements
have almost the identical energy and hence electron
can be removed from (n-1)d orbitals as easily as they
can be removed from ns orbital.
2. After removing ns electrons the remainder is called
core or kernel, in most of d-orbital elements, the core is
unstable and hence can loss one or more electron.
That’s why the removal of one or more electron from
unstable core gives variable oxidation state to the
transition element.

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 Complex formation
• Transition elements have a great tendency to form complex
compounds with certain molecules (eg:- CO, NO, NH3, H2O etc) or
ions (eg:- F-, Cl-, CN- etc).
• These molecules or ions attaching the metal atom or metal ion are
called ligands.
• These ligands contain one or more lone pairs of electrons which
they can easily donate to the transition metal atom or cation and
thus complete the vacant orbitals of those metal atoms or cations
through the formation of LM co-ordinate bonds.
• The complex is said to be stable if they exist at room temperature,
don’t oxidised by air, don’t hydrolysed by moisture.
• The elements of the first series element usually form following
types of complex tetrahedral(sp3), square planner(dsp2), trigonal
bipyramidal(dsp3), Octahedral(d2sp3 or sp3d2).
• Example: [Ni(NH3)6]2+, [Ni(H2O)6]2+, [Cu(NH3)4]2+ etc.
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 Reason
1. Due to small size of the transition metal atom or their cations and
high effective nuclear charge, they have high positive charge
density on them. The high positive charge density makes the
transition metal atoms or cations to accept the lone pairs of
electron from the ligands.
2. The transition metal atoms or cations have low energy vacant (n-
1)d orbitals in which they can accommodate the lone pair of
electrons donated by the ligands and thus can form L M.

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 Color formation
• Transition elements usually form colored compounds. By the influence of the
surrounding ligands, the splitting of d-orbitals of metal ion takes place.
• The d-orbitals are split by the surrounding ligands into two sets of orbitals of
low and high energy i.e. eg and t2g.

eg
d x2- y2 d z2

E
d-orbital
t 2g
d xy d yz d zx

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• The energy gap between these two levels is
comparatively small, consequently the excitation of an
electron from lower to higher d-level can be achieved by
absorption of visible light.
• The excited electron come back to its own position of
lower energy level d-orbital by transmitting light, this
causes the transition metal compound to appear colored.
• Color formation is only due to incomplete filling of d-
orbitals, where absorption of light could lead to d-d
electronic transition.
• During this d-d transition process they absorb certain
radiation from visible light and emit the reminder as
colored light, so the color of an ion is complimentary of
the color absorbed by it.
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• when visible light falls on the complex on off the
following conditions may occur-
 If Complex may absorb whole visible light, in this case it reflects black
color.
 If it reflects whole visible light, it appears white
 If it absorbs some portion of visible light and it reflects remaining portion
of visible light. In this case, it appears in different color.
 For e.g
++
 Hydrated copper Cu ion in [Cu(NH3)6]
2+ absorbs red portion of the

visible light or white light so, it appears blue green in the sunlight.

 The color exhibited by a transition metal ion depends upon the

excitation state of transition metal. For eg. Cr2+ (blue), Cr3+ (dark green),
Fe2+ (green), Fe3+ (yellow)

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 It may be pointed that the non metallic part associated with the
transition metal also modify the color. for e.g. CuO (black), Cu(OH)2
(pale blue), CuCl2 (yellow), CuBr2 (black) etc.
 In case of Zn++ and Cu+ don’t usually exhibit color compound due to
complete filling of d- orbital and hence d-d transition is not feasible.
 In the series Sc3+ , Ti4+ , V 5+, Mn7+, these ions may be considered
to have an empty d-orbital, hence d-d spectrum are impossible and
they should be colorless.
 Thus transition metal compounds having central metal ion with
empty d-orbitals or completely filled d-orbitals are colorless.
Reason:
The color of transition metal ion is associated with incompletely
filled (n-1)d orbitals. The transition metal ions containing the
unpaired d-electrons undergo electronic transition from lower
energy level to higher energy level of d orbitals.

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 Alloy Formation
 The solid solution of metals or metal and non-metal is called alloy.
 While metals are heated together or metal is heated with non-metal one of
the following condition may occur.
i. An ionic compound may be formed
ii. A simple mixture may result
iii. An interstitial alloy may be formed.
iv. A substitution alloy may be formed.
 Types of alloys formed by transition metals.
I. Interstitial alloys
 The alloys which are formed by small sized elements like (H, B, C and N)

get entrapped in between interstitial spaces of the transition metal lattice.

Eg:- steel (Iron + Carbon)
 By entrapping such small sized elements in transition metal, considerably

effect on the physical property such as hardness, malleability, ductility etc.

II. Solid solution alloys
 When one or more transition elements are mixed in its molten state ,
such type of mixture of alloys are called solid solution alloys. For eg:-
Brone (Cu+Sn), Brass (Cu+Zn), nickel steel (Ni+Fe) etc.
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 The mixing metal’s atomic radii shouldn’t differ by more than 15%.

 Reason
1. Due to their large atomic size, they pose voids (lattice sites) in the crytal
lattice and so small size atom (H, C, B, N) should occupy position in the sites
in the crystal lattice.
2. The size of the transition metals are quite similar and they can mutually
substitute for one another in crystal lattices.
3. Consequently, molten transition metals are mutually substitute for one
another and when a mixture of their solution is cooled, it gives an alloy.

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 Magnetic Properties
There are two types of magnetic properties shown by transition elements. –
Paramagnetic and Dimagnetic
#when a substance is placed in magnetic field of strenth H, the intensity of
magnetic field induced by the substance H0 may be greater than or less than
H. If the field in the substance is greater than H, the substance is paramagnetic,
which attracted into magnetic field. If the field in the substance is less than H,
the substance is diamagnetic which repelled by a magnetic field.
 The paramagnetism due to the presence of unpaired electron in any
transition metal ion or its compound can be explain on the basis of
magnetic moment (µ).

i.e. µ = 𝑛(𝑛 + 2) BM

n = no. of unpaired electron

BM stands for Bohr magneton.

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• The transition metal or ion which has a greater the no. of unpaired
electrons, it stands that have more strongly paramagnetic behavior.
• For eg:- Fe3+ has a strong paramagnetic properties that’s why it can form
permanent magnet when it is magnetised.
• In case of transition metal complex, the metal atom is surrounded by the
no. of ligand. Since the surrounding ligand obstruct the orbital motion of
the electron, the magnetic moment due to orbital motion of the electron
become quenched.
• QUESTION : The paramagnetism in 3-d transition series first increases and
reach some maximum value in the middle of the series then decreses,
explain.

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Metal ions dn confn unpaired e (n) µ= 𝑛(𝑛 + 2)BM
Sc2+& Sc3+
Ti2+& Ti3+
V2+& V3+
Cr3+ & Cr2+ d3 3 3.872
Mn2+ & Mn3+
Fe2+ & Fe3+
Co2+ & Co3+
Ni2+ & Ni3+
Cu2+
Zn2+

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Catalytic behavior
Many transition metals and their compounds are found to act as catalysis. Eg:- finely
divided Ni, Fe in Haber’s process, Pt, V2O5, MnO2, Zinc chromite etc.
Reasons
1. Since the transition metal have vacant orbitals an show variable oxidation states,
these metals can form unstable intermediate compounds with various reactants.
These intermediate compounds give reaction path for lower energy activation and
therefore increase the rate of reaction. These intermediate compounds readily
decompose to give final product and regenerating catalyst.
2. In some cases, the finely divided transition metal and their compounds provide a
large surface area on which reactants may be adsorbed. The adsorbed reactants
react faster due to their closer contact on the surface of catalyst to give product.

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 Application
 Analytical field
 Construction field
 Different types of complexes
 Color compounds

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1. What are transition elements? Which of the 3-d series elements is not a transition
elements and why?
2. Explain the cause of origin of paramagnetic and alloy formation in transition
elements.
3. Give the important characteristics of transition series. Explain the electronic
configuration of first transition elements.
4. List the industrial applications of transition elements. Explain the feature of transition
elements about complex formation.
5. Explain the origin of the adsorption spectra of transition elements with d to d
transition.
6. Explain why
a. FeCl3 is light brown in color and FeCl2 is greenish white in color.
b. Compounds of V5+ are colorless but those of V3+ are colorful.
c. Zinc (II) compounds are white and diamagnetic while copper (II) compounds are
colored and paramagnetic.
d. Paramagnetic properties increase from Sc to Mn and then decreases to Zn.
e. Transition elements show catalytical behavior.
f. Completely filled 3-d transition series are unable to form colored compounds.
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