TRANSITION METALS

• Elements from group 3 to 12 in the periodic table are called d- block elements
because their last electron enter into (n-1)d orbitals.
• d- block elements are also called transition elements because they are placed in
between s and p block elements and exhibit the average or transition properties of
s and p block elements. Example. They are more electronegative than s block
elements and less electronegative than p block elements.
• Transition elements are the elements in which their d-orbitals are partially filled
either in their neutral atomic state or in their most stable oxidation state. Most of
the d block elements are called transition elements, except Zinc(Zn), Cadmium(Cd)
and Mercury(Hg). i.e. these three elements do not have partially filled d- orbitals in
their atomic state or in their most stable oxidation state.
Electronic configuration of Zn(30): 1s2 2s2 2p6 3s2 3p6 3d10 4s2
Electronic configuration of Zn++(28): 1s2 2s2 2p6 3s2 3p6 3d10 4s0
Zinc has completely filled d orbitals both in normal atomic stat and in stable ionic
state. So it is not called transition metal.
• Zinc, Cadmium and mercury are called non-typical Transition Metals.
Classification of transition metals:
All d- block elements/transition metals are classified into four different blocks.
They are:
a. First transition series: Elements of 4th period from Scandium to Zinc are
called first transition series. They are also known as 3d- series.
b. Second transition series: Elements of 5th period from Yattrium to Cadmium
are called second transition series. They are also known as 4d- series.
c. Third transition series: Elements of 6th period, lanthanide and elements
from Hafnium to Mercury are called third transition series. They are also
known as 5d- series.
d. Fourth transition series: Elements of 7th period, Actinide and elements from
Rutherfordium are called fourth transition series. They are also known as 6d-
series.
General characteristics of transition metals
1. Electronic configuration: Their valence shell electronic configuration is ns1-2,
(n-1)d1-10. where n represent the valence shell and (n-1) represent the
penultimate shell.
2. Metallic character: All transition elements are metals. They are hard,
malleable and ductile due to strong metallic bond. They are good conductor
of heat and electricity.
3. Melting and boiling point: They have high melting and boiling points due to
strong metallic bond. Greater the number of unpaired electrons in d- orbital,
greater will be the strength of metallic bond and greater will be the melting
and boiling points. So, they have high enthalpies of atomization.
4. Variable valency and oxidation state: ns orbital and (n-1)d orbital of valence
shell and penultimate shell of transition metals have similar energy. So, due
to the involvement of electrons of these two orbitals in bonding, transition
metals show variable valency.
5. Size of atoms or ions: Elements of d block in each series or period has similar
atomic or ionic size. This is because on moving from left to right in d- block
element, the additional electron enter into the penultimate shell i.e. (n-1)d
orbital which shield the nuclear force of attraction towards valence electron. So
atomic size will not decrease but remain almost same.
6. Coloured compounds: Transition metals and their ions have high tendency
to form coloured compounds. This is due to partially filled d- orbital which
results in d-d transition of electron.
7. Magnetic properties: Most of the compounds of transition metals are
paramagnetic in nature. i.e. they are attracted in magnetic field.
8. Formation of complex: Transition metals or their ions have great tendency
to form complex compound or complex ions. Eg. [Fe(CN) 6]3-, [Cu(NH3)4]2+ etc.
9. Catalytic properties: Transition metals and their compounds act as catalyst in
different chemical reactions. This is due to presence of vacant d- orbitals and
variable oxidation state.
Non typical transition metals:
Those transition metals whose d- orbitals are completely filled (d10) and do
not exhibit the characteristic properties of typical transition metals are called
non typical transition metals. example, zinc, cadmium and mercury.
General properties of non typical transition metals are:
1. They have completely filled d- orbital. Their general valence shell
electronic configuration is (n-1)d10, ns2.
2. They do not show variable oxidation state.
3. They do not form coloured compounds.
4. They do not show catalytic properties.
5. They have relatively low melting and boiling points.
 Oxidation state of transition metals
 One of the most common feature of transition metals is that they show
variable oxidation state.
 s and p block elements most commonly have single valency and do not
show two or more than two valency or oxidation state. However, transition
metals show variable oxidation state in their combined state, this is because,
both ns and (n-1)d orbitals of transition metals have similar energy due to
which electrons of both orbitals can take part in bonding during the
formation of molecules or compounds.
 Oxidation state of transition metals depends on the number of unpaired
electrons present in (n-1)d orbitals. Greater the number of unpaired
electrons in (n-1)d orbitals, greater will be the oxidation state of the
transition metals.
 In 1st transition series Mn has highest, +7 oxidation state.
• In 2nd and 3rd transition series, Ruthenium and Osmium show maximum +8 oxidation
state respectively.
Conclusion:
1. All transition metals, except the last members of each series exhibit variable
oxidation state.
2. All electrons of d- orbitals do not take part in bonding but only the unpaired
electrons of d- orbitals take part in bonding. For example: according to the
configuration of iron (3d6 4s2), highest oxidation state of iron should be +8 but
paired electron on iron do not take part in bonding. So iron will have maximum +6
oxidation state.
3. Most common oxidation state of transition metal is +2.
4. Variable oxidation state of transition metal is due to involvement of electrons of
both valence shell (ns) and penultimate shell (n-1)d during chemical bonding.
5. Transition metals in low oxidation state like +2, +3 most commonly form ionic
compound but in higher oxidation state form covalent compound. Example: VCl2 is
ionic, VCl3 is less ionic and VCl4 is covalent.
 Complex formation
• Transition metals or their ions have a great tendency to form complex compound
with several molecules or ions called ligands. The tendency of formation of
complexes is due to following two factors:
a. Transition metals or their ions (cations) are small in size and have high
positive charge density due to which they can easily accept or attract the lone
pair of electrons from ligand and form complex compound.
b. Transition metal ions have vacant d- orbitals to which ligand can easily donate
its lone pair of electrons and form ligand- metal coordinate covalent bond (LM)
and form complex.
Complex ion: Complex ion is an electrically charged species (cation or anion)
consisting of metal atom or ion at its center surrounded two or more than two
ligands. The ligand and metal is bonded with coordinate covalent bond. Complex
ion is closed by square bracket []. Example: [Fe(CN)6]3-, [Cu(NH3)4]2+, [Ni(CN)4]4- etc.
Ligand: Molecule or ion which get bonded to the central metal atom or ion
through coordinate covalent bond during the formation of complex
compound is called ligand. Ligands are also called coordinating groups.
Ligands can be negative ions (such as Cl-, Br-, CN-, C2O4-- etc.) or neutral
molecules (such as NH3, H2O, CO, NO etc.) containing lone pair of electron.
The ligand which can share only one lone pair of electron to the central
metal atom is called monodentate ligand. Example: Cl-, Br-, CN-, NH3, H2O,
CO, NO etc.
The ligand which can share two lone pair of electron to the central metal
atom is called bidentate ligand. Example: CO3--, C2O4--, SO4-- etc.
EDTA (ethylenediamine tetraacetate) is a hexadentate (polydentate) ligand.
A polydentate ligand which can form closed cyclic ring with the central metal
atom or ion is called chelating ligand and the cyclic complex thus formed is
known as chelate.
Ligands can be classified into two types. They are:
a. Weak field ligand: The ligand that cause less splitting of the two set of d- orbitals
during the formation of complex compound is known as weak field ligand.
Example: I-, Cl-, F-, H2O, OH- etc. These ligands form high spin complex.
b. Strong field ligand: The ligand that cause high splitting of two set of d- orbitals
during the formation of complex is known as strong field ligand. Example: CN-,
NO2-, CO, NH3 etc. These ligands form low spin complex.
Coordination number: The total number of coordinate covalent bond formed by
central metal atom or ions with ligands in a complex compound is known as
coordination number.
Addition or molecular compounds: When solutions of two or more simple stable
salts are mixed together in certain proportion and is allowed to crystallize, crystals of
new compound are formed. This new compound is called addition or molecular
compound. Example: Carnallite: KCl.MgCl2.6H2O, Mohr’s salt: FeSO4.(NH4)2SO4.6H2O,
Potash alum: K2SO4.Al2(SO4)3.24H2O, tetramine copper(II) sulphate: [Cu(NH3)4]SO4
Addition compounds are of two types:
a. Double salt: Double salts are the addition compounds which are stable in
solid state but dissociate completely into constituent ions and loss their
identity when dissolved in water. Thus double salt retain their identity in
solid state but loss their identity when dissolved in water. Example:
Carnallite (KCl.MgCl2.6H2O), Mohr’s salt (FeSO4.(NH4)2SO4.6H2O), potash
alum (K2SO4.Al2(SO4)3.24H2O)) etc.
b. Complex compound or coordination compound or coordination complex
or complex salt: The addition or molecular compound which do not
dissociate completely into their constituent ions when dissolved in water
but retain their identity in solid as well as in solution is known as complex
compound. Example: tetramine copper sulphate: Cu(NH3)4.SO4, potassium
ferrocyanide: K4[Fe(CN)6], etc.
when tetramine copper sulphate is dissolved in water, then it dissociate
into two ions SO4-- and [Cu(NH3)4]++.
 Shape of complex ions: Werner’s coordination theory
Werner proposed a theory to explain the formation, shape and properties of complex
compound. According to Werner theory;
The central metal ion in a complex compound possess two types of valency; primary and
secondary.
Primary valency refers to the oxidation state of the central metal ion in a complex ion.
Secondary valency refers to the coordination number of metal which is satisfied by ligand.
It is the no. of coordinate covalent bond formed by ligand with metal.
Example: In complex [Cu(NH3)4]SO4, the oxidation state of copper is +2. so, its primary
valency is 2 which is satisfied or neutralized by SO4-- while copper ion is bonded coordinate
covalently with four ammonia molecule, so its secondary valency is 4.
Shape of complex ion:
The shape of complex ion depends on the secondary valency of the central metal ions i.e.
coordination number of the central metal ion. The coordinate covalent bond formed by
ligand is directed in a fixed position in the space around the central metal ion.
Therefore, the secondary valency or the coordination number determine the
shape or geometry of the complex or complex ion.
Example:
a. If the central metal ion has coordination number 2 then such complex ion
will have linear geometry. Example: [Ag(NH3)2]Cl,
b. If the central metal ions has coordination number 4 then the complex ion
will have either square planar geometry or tetrahedral geometry.
If the central metal atom undergo dsp2 hybridization then the complex ion will
have square planar geometry. Example: [Cu(NH3)4]SO4, [Ni(CN)4]2-,
However if the central metal atom undergo sp3 hybridization then the complex
ion will have tetrahedral geometry. Example: Na2[Zn(CN)4], Ni(CO)4, [CoCl4]2- etc.

c. If the central metal ion has coordination number 6 then such metal complex
ion will have octahedral geometry. Example: hexamine cobalt(III) chloride
[Co(NH3)6]Cl3, Hexaaqua copper(II) ion [Cu(H2O)6]2+etc.
 Crystal field theory
Crystal field theory (CFT) is a theory that is used to explain the interaction
between metal ion and ligand and the splitting of d- orbitals. Some important
postulates of crystal field theory are:
1. The CFT assumes that bonding between the metal cation and ligand is of
electrostatic in nature.
2. In absence of ligands, the d- orbitals of the metal ions are in degenerate
state. i.e. they have same energy. But during the formation of complex,
ligand approaches the central metal ion. During which the electrons of central
metal ion and ligand get repelled due to which the degenerate d- orbitals are
splitted into two set; t2g and eg. The three d- orbitals dxy, dxz and dyz belongs to
t2g set while the two d- orbitals dx2-y2 and dz2 belongs to eg set.
3. The crystal field splitting and the energy gap between the two set of d-
orbitals depend on the nature of metal ion, coordination no. of metal and
types of ligand.
Splitting of d- orbital in octahedral complex
 Colour of transition metal compound
When transition metal atom or ion is in free isolated state, their d- orbitals are in
degenerate state but when the metal atom or ion is surrounded by ligand (in
solution or compound state), the energy of five d –orbitals become different that
cause splitting of d- orbitals into two set t2g and eg. So when the compound is
exposed to light, electrons from low energy d- orbital can jump to high energy d-
orbital and vice- versa. This occurs with absorption and emission of energy in the
form of radiation. Since the energy difference of e g and t2g orbitals is equal to the
energy of visible radiation. Thus during the transition of electron form one d-
orbital to another visible radiations are absorbed or emitted due to which
transition metal compound appears coloured.
The transition of d -electron of central metal ion from one d- orbital to
another (i.e. from eg to t2g and vice versa) is known as d-d transition.
If d- orbitals of central metal atom or ion is partially filled then d-d
transition occurs. d-d transition of electron can only lead to absorption and
emission of radiation. Due to absorption and emission of visible radiation,
transition metal compound appears coloured.
If d- orbitals of transition metal atom or ion is either empty or full filled
then d-d transition is not possible due to which absorption and emission of
visible radiation will not occur and the complex compound will not appear
coloured.
Complex compound of metal ion like Zn++, Cu+, Cd++, Hg++ are colourless due
to completely filled d- orbital (i.e. d10 configuration) similarly complex
compound of metal ion like Sc3+, Ti4+ and V5+ etc. are also colourless due to
empty d- orbital (i.e. d0 configuration).
Relation between absorbed colour and transmitted light or
colour
Magnetic property of transition metal or their complex
Most of the transition metals and their compounds are paramagnetic in nature. The
substance which are attracted in magnetic field are called paramagnetic substance and the
phenomenon is known as paramagnetism. The substance will be paramagnetic in nature if
the compound contain unpaired electron in it.
Magnetic property of a substance is measured by quantity called magnetic moment (μ).
Mathematically,
Magnetic moment (μ) = BM …………………………(i)
Where, n is no. of unpaired electron and BM is a unit of magnetic moment called Bohr
magneton.
So, greater the number of unpaired electron in a compound greater will be the
magnetic moment of the compound. Equation (i) can be used to determine the no. unpaired
electron present in the given molecule or compound.
The substances which are repelled in magnetic field are called diamagnetic substances and
the phenomenon is known as diamagnetism. The substance which do not contain unpaired
electron will be diamagnetic in nature.
The substances that are highly attracted in magnetic field are called ferromagnetic
substances and the phenomenon is known as ferromagnetism. Ferromagnetic
substance can be permanently magnetized i.e. they can be used to make
permanent magnet. Example iron, nickel, cobalt etc.
Catalytic properties: Transition metals, their alloys and their compounds are used
as good catalyst in many chemical reactions. Catalytic activity of transition metals
or their compound is due to following reasons:
a. Due to the presence of vacant orbitals in transition metals or their compounds
and also due to their occurrence in variable oxidation state. The vacant
orbitals in transition metals can form temporary bonding with the reactant
molecules.
b. The finely divided transition metals or their compounds have large surface
area on which the reactant molecules can be adsorbed and react to form
product. So the large surface area of transition metal act as reaction/active site
for the reactant molecules to react and form product.
Some commonly used transition metals and their compounds as catalyst
are:
1. Ni, Pt or Pd is used as catalyst in hydrogenation reaction.
2. Finely divided iron(Fe) mixed with Molybdenum (Mo) as promoter is
used as catalyst in Haber’s process.
3. MnO2 is used as catalyst in in decomposition reaction of H2O2.
4. V2O5 is used as catalyst during oxidation of SO2 into SO3 in contact
process during manufacture of sulphuric acid.
5. Ziegler-Natta catalyst (TiCl4 + AlEt3) is used in manufacture of
polyethene.
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