Chemistry -XIl L-1

MANAV STHALI SCHOOL

C.B.S.E. and International Primary Curriculum (U.K.)
R-Block, New Rajendra Nagar, New Delhi -110060

THE TRANSITION ELEMENTS (d- Block)

General electronic configuration:

(n-1)g1°ns2
1 series

IV VI VII VIl X XI XII

So Ti V Cr Mn Fe Co Cu Zn
21 22 23 24 25 26 27 28 29 30
3d' 3d 3d 3d 3d 3d' 3d 3d0
4s 45 4s 4s 4s 4$ 4s 4s 4s 4s

Group XII Atomic No. e.c.

1 series Zn 30 3dl°4s
2hd series Cd 48 4d05s
3 series Hg 80 Sd6s'

Q1. Why Zn,Cd and Hg are not regarded as transition elements ?

A1. The d- orbitals in these elements are completely filled in the ground state as well as in their common
oxidation states. Therefore, they are not regarded as transition elements.
PHYSICAL PROPERTIES
1. High Melting and Boiling Points:
The high melting points of these metals is due to the involvement of greater number of electrons
from
(n-1)d orbitals and ns orbitals.
The greater the number of unpaired d-electrons, greater is the interatomic metallic bonding,
greater is the number of bonds and therefore is the strength of these bonds. Thus transition metals
are very hard (except Zn, Cd and Hg)
Q2. Which transition element has the highest melting point ? Tungsten (W)
Q3. Which transition element has the highest melting point in the 3d-series ? Chromium (Cr)
Q4. Why transition metals have very high enthalpy of atomization (very high boiling point) ?

2. Variation in Atomic and ionic sizes:

The atomic radii of elements of a particular series decrease with increase in atomic number but this
decrease in atomic radii becomes small after midway.
Atomic radii of 3d series in pm
Chemistry-Xll L-1

Sc Ti Cr Mn Fe Co Ni Cu Zn
162 147 34 127 126 126 125 124 124 138

The atomic radii decreases across the series because the new electron enters a d- orbital, each time
the nuclear charge increases by unity. As the shielding effect of a d electron is less, the net
electrostatic attraction between the nuclear charge and the outermost electron increases and the
ionic(or atomic) radius decreases.
As the number of d-electrons increases, the screening effect increases. This neutralizes the effect of
increased nuclear charge due to increase in atomic number, and consequently, atomic radius
remains almost unchanged after chromium.
At the end of each period, there is a slight increase in the atomic radi.This 0s due to increased
electron-electron repulsions between the added electrons in the same orbitals which exceed the
ottractive forces due to increased nuclear charge.
Atomic radi increases from first (3d) to second (4d) series of the elements but the radiiof the third
(Sd) series are the same as those of the corresponding members of the second series. This is
because of filling of 4f orbitals before 5d series of elements begin.The filling of 4f before 5d orbital
results in a regular decrease in atomic radii caled Lanthanoid Contraction.This happens due to the
poor shielding effect of f electrons. The shielding effect of one 4f electron by another is less than
that of one d electron by another, and as the nuclear charge increases along the series, there is
regular decrease in the size of the entire 4fn orbitals.
3. Variable Oxidation States:
Transition elements show variable oxidation states due to the incomplete filling of d orbitals in sucn
a way that their oxidation states differ from each other by unity.
Element Electronic conf
Sc 3d'4s
Oxidation states
+3
T 3d4s +2,+3,+4
V 3d'4s
Cr 3d'4s +2,+3,+4,+5
+2,+3,+4,+5,+6
Mn
3d4s +2,+3,+4,+5, +6,+7
Fe 3d 4s +2,+3
Co 3d'4s
NE 3d'4s
+2,+3
Cu 3d°4s'
+2,+3,+4
+1,+2
Zn 3d°4s +2
1. The lowest oxidation state is shown is shown by Cr and Cu ie. +1 while for
+2.
other elemen
2 Highest oxidation state is shown by Mn(+7) in 3d series.
3. Highest oxidation state is shown by Ruthenium, Ru (+8)
in the 4d series and Osmium,
the 5d series.
4. In the +2 and +3
oxidation states, the bonds formed are mostly ionic.
5. The elements which give the greatest no. of oxidation states occur in or near the middle of the
series. e.g. Mn
6. The lesser no. of
oxidation states at the
lose or share (Sc or Ti) or too many d extreme ends arises from either too fewelectre
7. The oxidation state of Ni and Fe is
electrons (Cu,Zn)
zero in [Ni(CO)] and [Fe(COl.
CHEMISTRY - XII L-2 &3

MANAV STHALISCHOOL
C.B.S.E. and International Primary Curriculum (U.K)
R-Block, New Rajendra Nagar, New Delhi - 110060

PROPERTIES OF TRANSITION ELEMENTS

4. COMPLEX FORMATION
Transition Metals fom complexes due to their
small size
b high nuclear charge
C availability of vacant d- orbitals of appropriate energy ( which can accept lone pairs of
electrons donated by ligands)
e.g. [Cu(NH).. [Ni(CN)., [AgNH;)2]+. [Ni(CO).] etc.
5. COLOURED COMPOUNDs
Transition elements form coloured compounds because of the presence of unpaired electrons in d
orbitals.

Under the influence of the ligands attached, the d- orbitals split into two sets of orbitals having
slightly different energies.
(dz,dx'-y')

(5 d- orbitals)
(degenerate) (dxy,dyz,dzx)

The transition of electron can take place from one of the lower d-orbitals to higher d-orbital within
the same subshell. This is called d-d transition.
Thus, when white light falls on these complexes, they absorb a particular colour corresponding to a
particular frequency for the promotion of electron and the complementary colour is emitted. The
colour of complexes is due to the emitted radiation, e.g. Cu salts are bluish-green due to
absorption of red colour. Ti salts appear purple due to absorption of yellowcolour.
Q. Which of the following species are coloured ? Give reason.
Fe, Se, Ni, Cr, Zn, Fe
6. MAGNETIC PROPERTIES
Paramagnetic substances: are attracted by magnetic field.
Diamagnetic substances: are repelled by magnetic field.
The transition metal complexes are paramagnetic because of the presence of unpaired electrons in
d-orbitals,.
The paramagnetic character increases with increase in the number of unpaired electrons.
Magnetic moment = [n(n+2)] BM
7. CATALYTIC PROPERTIES
The catalytic activity of transition metals is due to their ability to adopt multiple oxidation states and
to form eomplexes.

a. Transition metals form intermediate componds because of their variable oxidation states and
provide a reaction path with lower activation energyfor the reaction.
CHEMISTRY - XII
L-283
b. Transition metals provide a suitable largesurface area for the reaction to take place.
The reactants are adsorbed on the surface of the catalyst where reaction occurs.
Cg. V;O, is used as catalyst for oxidation of SO: to SO; in the Contact process f
manufacture of H;SO; Ni in catalytic hydrogenation; finely divided iron in the synthe
ammonia by Haber's proceSs.
8 FORMATION OF INTERSTITLAL COMPOUNDS:
Interstitial compounds are those which are formed when small atoms like H,Cor Nare
trapped inside the erystal lattices of metals. They are non stoichiometric. They are neithr
ionic nor covalent.e.g. TiC, MnN, FesH
The physical and chemical characteristics of these compounds are as follows :
1. They have high melting points, higher than those of pure metals.
2. They are very hard.
3. They retain metallic conductivity
4. They are chemically inert.
9. ALLOY FORMATION
An alloy is a blend of metals prepared by mixing the components . Alloys are homogenco
solid solutions in which the atoms of one metal are distributed randomly among the atoms
the other.

Transition metals form alloys because of similar radi and, therefore, the ato
of one metal can substitute theatoms of other metal in its crystal lattice. Thus on cooling
mixture solution of 2or more transition metals , solid alloys are formed.e.g.
Brass(Cu+ Zn) and bronze(Cu +Sn)
CHEMISTRY-XI L4&5

MANAV STHALI SCHOOL

CB.S.E. and International Primary Curriculum (U.K)
R-Block, New Rajendra Nagar, New Delhi -110060

Preparation of Potassium permanganate

1 Conversion of pyrolusite ore to potassium manganate.

of
is fused with KOH or KzCO, in the presence of air to give a green mass due to the formation
Pyrolusite
potassium manganate.
2MnO, + 4KOH + O,’ 2K,MnO, + 2H,0

2MnO, + 2K,CO, + O; ’ 2K,MnO4 + 2C0,

potassium permanganate.
2. Oxidation of potassium manganate to
2K,Mn, + Clh ’ 2KCI + 2KMnO,

(purple)
+ 2 KOH + O2
2K,MnO, + O, t H,0 ’ 2KMnO,
2Mn0, + 2KMnO,
3K,MnO, + 2C0; ’ 2K,CO, +

Electrolytic Method oxidative fusion of MnO,

potassium permanganate is prepared by the alkaline
Commercially solution is taken in an
electrolytic oxidation of manganate. The potassium manganate
followed by manganate solution is
contains iron cathode and nickel anode. The potassium
electrolytic cell which solution is added in the cathode
compartment.
compartment while dilute alkali
taken in anodic to permanganate ion at anode
and hydrogen
manganate ion is oxidized
When current is passed, the
is liberated at cathode.
At anode: 2K,MnO, 2 +MnO
At cathode: 2H+ +2e’ 2H
2H>H2
volumetric analysis for the estimation
is used as an oxidizing agent in the laboratory in
Uses: It
iodides and hydrogen perOxide.
of ferrous salts, oxalates,
disinfectant and germicide. Used to purify well water.
Used as a
reagent.
organic chemistry under the name of Baeyer's
Used in decolourisation of
cotton, silk and other textile fabrics and for the
Used for bleaching of wool,
power.
oils because of its strong oxidizing
CHEMISTRY- XI L4 &5

Preparation of potassium dichromate:

Step 1

4 FeCr;04 + 8 Na,CO, + 70, ’8 NaCrO, + 2Fe,0, +8CO2

(yellow)
Step 2
2Na,CrO, + 2H+’ Na,Cr;O, + 2Na+ + H,0
Step 3
Na,Cr0, + 2KCI ’ K,Cr,0, + 2NaCl

Sodium dichromate is more soluble than potassium

dichromate.
Orange crystals of potassium dichromate crystallise out.

f-block elements
General electronic configuration:

(n-2) e (n-1) d ns?

LANTHANOIDS

ACTINOIDS

Lanthanoids

Oxidation States
All lanthanoids exhibit a common stable oxidation state of +3. In
addition, some lanthanoids show
+2 and +4 oxidation states also.

Cerium, Ce (58) [Xe] 4f 5d 6s'

Ce(4+) [Xe] 4f

Terbium, Tb(65) [Xe] 4f 5d° 6s

Tb(4+) [Xe] 4f
 L4 &5
CHEMISTRY XI

Europium, Eu(63) [Xe] 4f Sd° 6s?

Eu(2+) [Xe] 4f
Yterbium, Yb(70) (Xe] 4f"5d'6s?

Yb(2+) [Xe] 4f4

+3 oxidation states. This is because
Ianthanum(La), Gadolinium (Gd) and Lutetium(Lu) exhibit only half-filled and completely filled
acquire stable configurations of empty,
hy losing 3 electrons, they
4f-subshells.
cause of lanthanoid contraction ? What are its
o. What is lanthanoid contraction ? What is the
consequences ?
atomic
of lanthanide elements with increasfing
Ans. The steady decrease in atomic and ionic sizes
number is

called lanthanoid contraction.

Cause oflonthanoid contraction:

by
element to another, the nuclear charge increases
In the lanthanoid series, as we move from one
one electron is added. The 4f electrons shield each other from the nuclear charge
one unit and by
shapes of the f-orbitals.The nuclear charge increases
quite poorly because of the very diffused
and nuclear charge, the effective nuclear
one at each step.Hence, with increasing atomic no. of 4f electron shelI
charge experienced by each 4f electron increases. As a result, the whole
contracts at each successive element.

CONSEQUENCES OF LANTHANOID CONTRACTION:

TRANSITION SERIES.
1. RESEMBLENCE OF SECOND AND THIRD
possess almost the same size.
The pairs of elements: Zr-Hf, Nb-Ta, Mo-W etc.
2. SIMILARITY AMONG LANTHANOIDS

Ine chemical properties of lanthanoids are similar

because of very small change in radii of lanthanoids.
Tnus, it is very difficult to separate the elements in
pure state.
CHEMISTRY- XI L4 85

3. BASICITY DIFFERENCES
Due to lanthanoid contraction , the size of

Lanthanoid ions decreases regularly with increase

As the size decreases, the covalent character

Between lanthanide ion and OH- ions increases from La" to Lu, Therefore, the basic
strength of
Thus, La(OH), is most basic while Lu(OH), is the least

Q. What is a misch metal ?

Ans. Awell known alloy is misch metal which consists of a lanthanoid metal (about 95 %), iron
(about 5%) and traces of S, C, Ca and Al.
Q. What is the use of misch metal ?

Ans. Misch metal is used in Mg-based alloy to produce bullets, shell and lighter flint.
a. Differentiate between lanthanoids and actinoids.

|S.No. LANTHANOIDS ACTINOIDS

1
Mainly show Show +3 oxidation state. Also show
+3 Oxidation state except in a few higher oxidation states, +4 to +7.
cases where it is +2 and +4.
2 4f electrons have greater 5f electrons have poorer shielding
shielding effect. effect.
3. Lanthanoid contraction is lesser Actinoid contraction is greater from
from element to element. element to element.
4 Lanthanoid compounds are less Actinoid compounds are more basic.
basic.
|5. Lanthanoids do not form oxo Actinoids form oxo ions
ions. Like UO2+,Np02+
6 Except promethium, lanthanoids AIl the actinoids are
are
Radioactive.
non-radioactive.
7 Most of their ions are Most of the actinoid ions are
Colourless.
coloured.e.g. U3+(red), U4+{green)
0. Actinoid contrction is greater from element to element than
lanthanoid contraction. Why ?
Ans. This is due to poorer shielding effect by 5f
electrons in the actinoids than that by 4f
electrons in the lanthanoids.