UG Sem-III

Chemistry
Paper: CC-5
Inorganic Chemistry

Chapter -2
Chemistry of Elements of First Transition Series

Lecture-1

by

Dr. Chandrani Sarkar

Department of Chemistry
Mahila College, Chaibasa
(A constituent college of Kolhan University)
 CONTENTS

 Characteristic properties of d-block elements

 Properties of the elements of the first transition

series

 Their binary compounds and complexes illustrating

relative stability of their oxidation states

 Coordination number and Geometry

 d-Block element:
 The elements which last electron enters in (n-1) d-subshell are called d-
block elements or Transition elements.

 Transition elements have partly filled (n-1) d- subshell in free state or any
one of their oxidation state

Sc= 21= 1s2 2s22p63s23p64s23d1

Fe= 26= 1s2 2s22p63s23p64s23d6
Ag= 47= 1s2 2s22p63s23p64s23d104p6 5s14d10= [Kr] 5s14d10

 d-block elements are in the middle of the periodic table. Highly

electropositive metals of s-block are on the left and less electropositive non-
metals of p-block are on the right of d-block.
 The electropositive character and ionisation enthalpy of d-block are
between s-block and p-block.
 Other properties of d-block elements are in between elements of s-block
and p-block, hence d-block elements are called transition elements.
 POSITION IN PERIODIC TABLE
 Transition elements or d-block elements occupies the central position in PT in
between s-block and p-block.

Valence shell configuration = ns1-2(n-1)d1-10 (n=4 or 5 or 6 or 7)

Groups = 3 to 12
= IB to VIIB and VIII
Periods = 4 to 7

 Transition elements are spread over four periods (rows). These rows are called
1st , 2nd , 3rd and 4th transition series depending upon the filling 3d, 4d, 5d and
6d orbitals, respectively.

 Each period has ten elements

s-block d-block or transition p-block
elements
More Electropositive character, less Less
electropositive than s-block but more than p- electropositive
block
Period Group No. of
elements
3 4 5 6 7 8 9 10 11 12

III IV VB VIB VII VIII IB IIB

B B B
4 Sc Ti V Cr Mn Fe Co Ni Cu Zn 10
21 22 23 24 25 26 27 28 29 30
3d1 3d- series or 1st transition series 3d10
5 Y Zr Nb Mo Tc Rn Rh Pd Ag Cd 10
39 40 41 42 43 44 45 46 47 48

4d1 4d- series or 2nd transition series 4d10

6 La *Hf Ta W Re Os Ir Pt Au Hg 10
57 72 73 74 75 76 77 78 79 80

5d1 5d- series or 3rd transition series 5d10

7 Ac *Rf Db Sg Bh Hs Mt Uun Uuu Uub 10

89 104 105 106 107 108 109 110 111 112

6d1 6d- series or 4th transition series 6d10

GENERAL PROPERTIES OF d-BLOCK ELEMENTS
d-block elements are also called transition elements because their properties marks
a transition between the highly reactive metallic elements of s-block ( which
form distinctly ionic compound) and the element of the p-block (which form
covalent compound).
General characteristic of d-block elements are summarized below:

1. All the d-block elements are metals. They are hard and have very high melting
and boiling point.
2. Transition elements have high densities.
3. Most of the transition metals are malleable and ductile.
4. Most of the transition metals are good electrical conductors.
5. These elements form coloured compound.
6. These elements form alloy with other metals.
7. These elements are well known to form co-ordination complexes.
8. Most of the elements are used as catalyst.
9. Transition metals exhibit several oxidation states.
10.Most of the transition metals form paramagnetic compounds.
IMPORTANT PHYSICAL CONSTANTS OF THE ELEMENTS
OF FIRST TRANSITION SERIES
IMPORTANT PHYSICAL CONSTANTS OF THE ELEMENTS
OF SECOND TRANSITION SERIES
IMPORTANT PHYSICAL CONSTANTS OF THE ELEMENTS
OF THIRD TRANSITION SERIES
 IMPORTANT PERIODIC PROPERTIES
1. ATOMIC RADII: The atomic radii of the elements decrease from left to
right across a row in the transition series. This results in the increase of effective
nuclear charge only marginally and hence there occurs only a small change in the
atomic radii.

 There is an increase in the atomic radii in going from the 4th period to 5th
period elements within any column.

 All the elements in 6th period beyond lanthanum have nearly the same atomic
radii as that of the corresponding elements in the 5th period. This similarity in
the radii in the 5th and 6th period transition elements can be explained in terms of
lanthanide contraction.

Atomic radii of transition elements

2. DENSITY:
 The densities of transition elements are very high compared to the alkali and
alkaline earth metals.

 The densities increases ongoing down the group from period 4 elements to
period 6 elements, with the highest values being those of Osmuim and
Iridium.

 The densities of the elements of the 3rd series are nearly twice those of the
corresponding elements of the 2nd transition series.

Densities of the transition elements

3. METLING AND BOILING POINT:
 In each transition metal series, the melting point rises to a maximum around
the middle and then decreases.

 The melting and boiling point increase on moving down the group.
4. IONISATION ENERGY:

“The amount of energy absorbed to detach the most loosely bound electron
from an isolated atom in gaseous state is called Ionization energy (I.E.)”.
M (g) + IE1 M+1(g) + e-1

M+1(g) + IE2 M+2(g) +e-1 IE1<IE2 (IE- Ionisation energy)

 IE of the transition metals are higher than those of s-block elements and less
than the elements of p-block.
 The 1st IE increases along the transition series.
 The 1st IE of 3rd transition series are higher than those of the 1st and 2nd
transition series.
5. STRUCTURE OF SOLIDS: With the exception of Hg, all the transition
metals are solid.
6. OXIDATION STATES:
 Transition elements exhibit a large number of oxidation states in their
compounds.
 The commonly found OS is +2 or +3

Sc Ti V Cr Mn Fe Co Ni Cu Zn
+2 +2 +2 +2 +2 +2 +2 +2 +1 +2
+3 +3 +3 +3 (+3) +3 +3 +3 +2
+4 +4 (+4) +4 +4 (+4)
+5
+6 (+6) (+6)
+7
Various oxidation states of 1st transition series
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
+3 (+3) (+2) +2 +2 +2 +2 +2 +1 +2
+4 (+3) +3 (+4) +3 +3 (+3) (+2)
(+4) +4 (+5) +4 +4 +4 (+3)
+5 +5 (+5) (+6)
+6 (+6)
(+7)
(+8)

Various oxidation states of 2nd transition series

 La Hf Ta W Re Os Ir Pt Au Hg
+3 (+3) (+2) +2 (-1) +2 +2 +2 +1 +1
+4 (+3) (+3) (+1) +3 +3 (+3) +3 +2
(+4) +4 (+2) +4 +4 +4
+5 +5 +3 +6 (+6) (+5)
+6 +4 +8 (+6)
+5
(+6)
+7

Various oxidation states of 3rd transition series

The wide variety of oxidation states (i.e. variable OS) exhibited by transition metals
can be attributed to

• The availability of both ns and (n-1) d electrons for bond formation

• The energies of ns and (n-1) d electrons are very similar.

7. MAGNETIC PROPERTIES:
 Most of the compounds of transition metals are paramagnetic in nature.

 The observed and calculated magnetic moment value of the first half of the
transition metal ions are very close whereas the later half of the transition
metal ions are higher than the spin-only values. This difference arises due
to some contributions from the orbital magnetic moment.

8. FORMATION OF ALLOY:

 The d-block metals form a wide range of alloys.

9. COLOUR:
 When a substance absorbs a part of the visible light, it appears colour. The colour
of the compound is that of unabsorb or reflected light (complementary colour).

 Many transition metal compounds are highly coloured and these impart
fascinating colours when dissolved in water.

 Colour of transition metal compounds arise due to the presence of incomplete

(n-1) d subshell and is attributed to the electronic transition (d-d transition) from
one energy level to another in the d-subshell.

 The colour mainly depends on the transition metal ion and its OS and the
type of ligands present in compound.
10. COMPLEX FORMATION:

Transition elements are well known for their ability to form complexes. This
ability of transition elements to form complexes is due to-

• The small size of the transition metal cation.

• High effective nuclear charge
• Availability of vacant d-orbitals of appropriate energy for bonding.
11. CATALYIC ACTIVITY:
Transition metals and their compounds are well known for their catalytic
activities.

Nickel is used as catalyst for the hydrogenation of unsaturated compounds

Iron-Molybdenum is used as a catalyst in the synthesis of ammonia by Haber’s

process.

Platinum is used in the contact process for the combination of SO2 with O2 to
generate SO3

Vanadium petaoxide is used for the oxidation of SO2 with O2 to prepare SO3

Manganese dioxide is used to catalyze the decomposition of H2O2.

The catalytic activity of the transition elements is due to the availability of d-

orbitals. The d-orbitals which are exposed to the surface, participate in the
formation of activated complex which serves as a reactive intermediate in the
overall reactions. These reactive intermediates provide low energy reaction