1

INTRODUCTION

The d-block elements are the elements in which the

last electron enters the d orbital of the penultimate
shell i.e. (n-1) d orbital where n is the outer most
shell.
The d block elements are also called transition
elements because their properties are intermediate
between the properties of highly electropositive s-
block elements and highly electronegative p-block
elements.
 Transition elements are defi ned as those elements
which have partly or incompletely fi led (n-1) d
orbital in their elementary state or in any of their
common oxidation states. 2
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 POSITION IN PERIODIC TABLE

These elements are placed in the middle part between s-

block and p-block elements in the long form of the periodic
table. The d-block elements belonging to the groups 3 to 12
and starting from the fourth period in the form of four
diff erent series of elements are called 3d,4d,5d and 6d
series.

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 ELECTRONIC CONFIGURATION

The 3d series includes all the elements from

Sc(Z=21) to Zn(Z=30) and belongs to 4 t h period.
The 4d series includes all the elements from
Y(Z=39) to Cd(Z=48) and belongs to 5 t h period.
The 5d series starts with element La(Z=57) and
then includes all the elements from Hf(Z=72) to
Hg(Z=80) which belong to 6 t h period.
The 6d series starts with elements Ac(Z=89) and
then includes all the elements from Rf(Z=104) to
Uub(Z=112) which belongs to 7 t h period.

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 ELECTRONIC CONFIGURATION OF
CHROMIUM & COPPER
The expected electronic confi guration of chromium should
be 1s2 2s2 2p6 3s2 3p6 3d4 4s2, in this the 4s subshell is
completely fi lled but 3d subshell is neither completely fi lled
or half fi lled. Due to inter electronic repulsion forces one
4s- electrons transfers to 3d subshell to acquire the observed
confi guration as 1s2 2s2 2p6 3s2 3p6 3d5 4s1.
Copper has expected electronic confi guration 1s2 2s2 2p6
3s2 3p6 3d9 4s2. The inter-electronic repulsion, forces one 4s
electron to enter 3d subshell. The observed electronic
confi guration of copper is 1s2 2s2 2p6 3s2 3p6 3d10 4s1.
There is a extra stability due to completely fi lled 3d
subshell and half fi lled 4s subshell.

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 THINK AND ANSWER
 Anomalous
   electronic configuration in the 3d series are of
(a) Cr and Fe (b) Cu and Zn (c) Fe and Cu (d) Cr and Cu
ANS: d)
 Zinc and mercury do not show variable valency like d-block
elements because
a)they are soft b)their d-shells are complete
c)they have only two electrons in the outermost subshell.
d)their d-shells are incomplete
ANS: b)
 Which block of elements are known as transition elements?
(a) p-block (b) s-block (c) d-block (d) f-block
ANS: c)
 Write the electronic configuration of chromium (Atomic
number;Cr=24)
ANS:[Ar]
 Which one is of the following is the lightest transition element?
a) Ti b)Sc c) Fe d) Hg
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ANS: b)
 GENRAL CHARACTERISTICS OF
TRANSITION ELEMENTS
i. Exhibit metallic properties such as
malleability, ductility, metallic luster etc.
ii. They involve strong metallic bonding and have
compact structure. Therefore they have high
density and high melting and boiling points.
iii. Good conductors of heat and electricity.
iv. In the transition metals (n-1) d and ns
electrons are of nearly same energy level.
Therefore most of these electrons take part in
chemical bonding. Hence they exhibit variable
oxidation states.
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vi. In the most of cations of the transition metals,
there are unpaired electrons.
vii. Form large number of complexes.
viii.Transition metals and their compounds have
catalytic property.
ix. Transition metals form organometallic
compounds.

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 GENERAL TRENDS IN PROPERTIES
OF FIRST ROW ELEMENTS

Metallic Character
Nearly all transition metals have the simple
hexagonal close packed (hcp), cubic close packed
(ccp) or body centered cubic(bcc) latt ices which are
characteristic of true metals.
The hardness of these metals indicates the presence
of covalent bonds in them.
The metals such as Cr, Mo and W have maximum number
of unpaired d-electrons. Therefore, these metals are very
hard. On the other hand, Zn, Cd, Hg are not very hard
because they do not have unpaired d-electrons.
The high melting and boiling points of transition
metals are due to their close-packed structures. 12
m.p. and b.p. of
transition metals
are very high as
compared to
representative
elements.

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 IONIZATION ENTHALPY

The fi rst ionization enthalpies of elements of third

transition series are higher than those of the elements of
fi rst and second transition series.
The atoms of elements of third transition series possess
fi lled 4f-orbitals. 4f orbitals exhibit poor shielding eff ect on
account of their peculiar diff used shapes.
 As a result, the valence electrons experience greater nuclear
att raction. Consequently, it requires greater amount of
energy to ionize elements of 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 .

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 OXIDATION STATE

 Transition element shows great variety of O.S.

 Loss of 4s and 3d electrons progressively leads to
formation of ions.
 Loss of 1 4s electron Form ion
Loss of 2 4s electron Form
Loss of 3 4s electron Form so on..

 No. of unpaired 3d electron increases O.S.

 Mn Shows highest O.S. located in or near middle of series.

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 OXIDATION
STATES K2FeO4

Energies of ns and (n-1) d levels are almost same.

Iron (3d6 4s2), Cobalt (3d7 4s2) and Nickel (3d 4s2) show+2
and+3 oxidation state.
 iron form salts in +2 as well as +3 oxidation state are called
ferric and ferrous compounds respectively .
Compounds of iron in +6 oxidation state known as ferrates.

K3Fe(CN)6
K4Fe(CN)6

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Copper(3d 1 0 4s 1 ) and zinc (3d 1 0 4s 2 ) exhibit +2 oxidation state.
Copper salts in +1 oxidation state are called cuprous salts.

Copper(I)
iodide
Copper in +2 O.S. are known
as copper or cupric salts.

CuSO4

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 Highest oxidation state is +8 which shown by Os and Rn.

Osmium tetroxide
OsO4
 Manganese shows +7 oxidation state.

MnO4

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 ATOMIC AND IONIC RADII

D orbitals in an atom are

As a result effective hence atomic radii
less penetrating or more
nuclear charge increases decrease gradually
diffused and therefore d
as atomic no. increases across a transition series
electrons offer smaller
along a transition series. from left to right.
screening effect.

IMP Give
Reason

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Q. Write two characteristics of the transition
elements.
Q.  Which metal in the first transition series
(3d series) exhibits +1 oxidation state most
frequently and why? 21
 COLOUR
 The colour of a substance depends upon the absorption of light
of a perticular wavelength,of visible lights(400 to 800nm)

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 In general colour of a transition ion can be related to
 presence of unpaired d electrons
 d-d transition
 Nature of groups
 Geometry of the complex formed by metal ions

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 CATALYTIC PROPERTIES

 many transition metals and complexes are used as catalyst

which infl uence the rate of chemical reaction.
 A + B + C  [A- B - C]  A – B + C
(reactant) (catalyst) (intermediate) (product) (catalyst)

 The transition elements on account of their variable

oxidation states are able to form unstable intermediates.
 Many transition metals are used as catalysts for reactions.
The commonly used transition metals as catalysts are Fe,
Co, Pt, Cr, Mn, etc.

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 MAGNETIC PROPERTIES

  Due to the presence of unpaired electrons in the (n-1) d-

orbitals, most of the transition metal ions and their
compound are paramagnetic i.e. they are att racted by the
magnetic fi eld.
 Those transition elements which have paired electrons are
diamagnetic i.e. they are repelled by the magnetic fi eld.
 Metals like Fe, Co, and Ni posses very high (special type)
paramagnetism where they obtain permanent magnetic
moment and are referred to as ferromagnetic.
 The magnetic moment is expressed in Bohr Magneton(B.M)
1B.M=

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  A paramagnetic substance is characterized by its eff ective
magnetic moment() which is given by the expression
= B.M.

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 FORMULATION OF INTERSTITIAL
COMPOUNDS
  Transition metals have defect in their crystal latt ice.
 The transition metals form a number interstitial compounds
with elements such as hydrogen, carbon, nitrogen, boron.
 The small atoms of these elements (C, N, H, B, etc.) occupy
the vacant spaces (interstices) in the latt ice of transition
metals resulting in the formation of interstitial compounds.
For example, TiC, ,N, etc.

Mn4N

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 ALLOY FORMATION

 Due to almost similar atomic sizes one metal easily replace

other metal from its latt ice to form solid solution called
alloy.
 Thus the transition metal are miscible with one another in
the molten state.
 alloys of transition metals with non-metals such as
brass(Cu-Zn) and bronze(Cu-Sn)

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 ALLOY

Ferrous alloy Non-Ferrous alloy

• Atoms of elements • Mixing atoms of
distributed randomly in transition metals other
atoms of iron in the atom iron with a non
mixture. transition elements.
• % of Fe is more • Eg. Brass( Cu+Zn)
• eg. Nickel steel,
chromium steel,
stainless steel etc.

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 FUN FACTS

‘Sterling silver’ actually ‘White Gold’ alloy of Au+

alloy not silver. Ag+ Cu+ other metals

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 USES OF ALLOY

 Bronze, an alloy of Cu and Tin is tough, strong and

corrosion resistant. It is used for making statues, medal and
trophies.
 Cupra-nickel, an alloy of Cu & Ni is used for making
machinery parts of marine ships, boats. For example, marine
condenser tubes.
 Stainless steel are used in the construction of the outer
fuselage of ultra-high speed air craft.
 Nichrome (Ni+Cr:: 80:20 ratio) has been developed
specially for gas turbine engins.
 titanium alloy used for fi re proof bulkheads.

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 CO MM ON Physical Chemical
properties properties
P R OP ER TI ES All d block
element are Electropositive
Lustrous and in nature
shining

Exhibit variable
Hard and have
valencies and
high density
form color salts.

Good reducing
Good electrical
agents and form
and thermal
insoluble
conductor
oxides.

Fe,Mo,Cu Zn
High tensile
are biological
strength and
important
mallleability
metals.

Many
Catalyse
compound are
biological
paramagnetic
reaction.
act as catalyst 33
 F-BLOCK ELEMENTS -
LANTHANOIDS
 The elements in which the diff erentiating electron (last
electron) enters into (n-2) f orbital are known as f-block
elements.
 In all 28 elements from atomic number 58 to 71 and from 90
to 103 are collectively called f-block elements.
 All these elements show intermediate behavior as compared
to electropositive and electronegative elements. Because of
periodic position and properties, these elements are also
known as inner transition elements.
 There are two series of inner transition elements.
Lanthanoid series (4f block elements) and actinoid series (5f
block elements).

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 A rare-earth element (REE) or rare-earth metal (REM ), as
defi ned by IUPAC, is one of a set of seventeen chemical
elements in the periodic table, specifi cally the fi fteen
lanthanides, as well as scandium and ytt rium.
 Scandium and ytt rium are considered rare-earth elements
because they tend to occur in the same ore deposits as the
lanthanides and exhibit similar chemical properties.
 Rare-earth elements are cerium (Ce), dysprosium (Dy), erbium
 (Er), europium (Eu), gadolinium (Gd), holmium (Ho), lanthanum
 (La), lutetium (Lu), neodymium (Nd), praseodymium (Pr), 
promethium (Pm), samarium (Sm), scandium (Sc), terbium (Tb), 
thulium (Tm), ytterbium (Yb) and yttrium (Y).
 They are not especially rare, but they tend to occur together in
nature and are diffi cult to separate from one another.

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 POSITION OF LANTHANOIDS

 Lanthanoids belong to group 3 of the periodic table and are

placed in the sixth period.
 Actual position is in between Lanthanum (Z=57) and Hafnium
(Z=72) all elements together at one place.
i. All these elements have same number of valency electrons,
one in 5d and two in 6s.
ii. Group valency of all lanthanoids is 3.
iii. All these elements from cerium to lutetium have similar
physical and chemical properties.
iv. These elements have atomic numbers between Lanthanum
(57) and Hafnium (72).
v. By placing lanthanoids as per increasing order of atomic
number the symmetry of periodic table would by disrupted.

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ELECTRONIC CONFIGURATION OF
LANTHANOIDS

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CHEMICAL REACTIVITY OF
LANTHANOIDS

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LANTHANOID CONTRACTION AND
ITS CONSEQUENCES

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 EFFECTS OF LANTHANOID
CONTRACTION

DECREASE IN BASICITY
 Due to the lanthanoid contraction the size of the tripositive
lanthanoid ion (M³⁺) regularly decreases with increase in
atomic number i.e. from La³⁺ to Lu³⁺.
 The ionic character of M-OH bond decrease and covalent
character of M-OH bond gradually increases.
 Basicity and ionic character of hydroxides decrease in the
order of La(OH)₃ >Ce(OH)₃>………….Lu(OH)₃. This is in
accordance with Fajan’s principle. (According to this rule,
larger size of cation, greater is the tendency of such
hydroxides to dissociate and stronger will be the base).

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IONIC RADII OF POST LANTHANOIDS
 The elements which follow the lanthanoids in the third
transition series are known as post lanthanoids.
 This trend disappears after the lanthanoids and pairs of
elements. Zr-Hf, (group 4) Nb-Ta, (group 5) Mo-W (group
6) and Tc-Re (group 7) etc. have almost identical sizes. This
atoms possess similar number of valence electrons and
similar properties. These pairs of elements are called
`Chemical twins’.
 A well known alloy of lanthanoid is misch metal.
(lanthanum metal, iron and traces of S, C, Ca, and Al). It is
used to manufacture bullets and shells. Mixed oxides are
used as catalysts.

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 ACTINOIDS

  The actinoid elements belong to the second inner transition

series in which electrons enter in 5f orbitals (Z=90 to 103).
 Actinium (Z=89) has electronic confi guration [Rn] 5f 6 7s².
There is no electron in 5f orbitals. The series of elements
from thorium (Z=90) to Lawrencium (Z=103) in which 5f
orbitals are progressively fi lled are called actinoids.
 Thorium and uranium metals are obtained from natural
sources. But elements Neptunium and successive heavier
elements are produced synthetically by the transformation
of naturally occurring elements by nuclear reactions.
 These man made elements having atomic number higher
than Uranium-92 are collectively called as trans-uranic
elements.

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 TRANSURANIC ELEMENT

Actinides Transactinide Elements Not Yet Discover

93 neptunium Np 104 rutherfordium Rf 119 ununennium Uue*

94 plutonium Pu 105 dubnium Db 120 unbinilium Ubn*
95 americium Am 106 seaborgium Sg 121 unbiunium Ubu*
96 curium Cm 107 bohrium Bh
97 berkelium Bk 108 hassium Hs
98 californium Cf 109 meitnerium Mt
99 einsteinium Es 110 darmstadtium Ds
100 fermium Fm 111 roentgenium Rg
101 mendelevium Md 112 copernicium Cn
102 nobelium No 113 nihonium Nh
103 lawrencium Lr 114 flerovium Fl
115 moscovium Mc
116 livermorium Lv
117 tennessine Ts
118 oganesson Og

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 POSITION IN PERIODIC TABLE

 Belongs to 3 r d group and 7 t h period.

 Interrupt 4 t h transition series

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ELECTRONIC CONFIGURATION

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OXIDATION STATE

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49
 QUESTIONS

Why do actinoid
show wide range
of O.S?

Write any two

difference Transition
between metals forms
Lanthanoid alloys. Why?
and acinoid.

Why is actinoid What are the

contraction different O.S.
grater than shown by
Lanthanoid? Lanthanoids?

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