Chemistry

Paper: CC-5
Inorganic Chemistry

Chapter -2
Chemistry of Elements of First Transition series

Lecture-2

by
Dr. Chandrani Sarkar
Department of Chemistry
Mahila College, Chaibasa
(A constituent college of Kolhan University)
ELECTRONIC CONFIGURATION: There are ten elements in the first
transition series.

Name Symbo Z Electronic configuartion Group

l
Scandium Sc 21 1s2 2s22p63s23p64s23d1 3 IIIB
Titanium Ti 22 1s2 2s22p63s23p64s23d2 4 IVB
Vanadium V 23 1s2 2s22p63s23p64s23d3 5 VB
Chromium Cr 24 1s2 2s22p63s23p64s13d5 6 VIB
Manganese Mn 25 1s2 2s22p63s23p64s23d5 7 VIIB
Iron Fe 26 1s2 2s22p63s23p64s23d6 8
Cobalt Co 27 1s2 2s22p63s23p64s23d7 9 VIII
Nickel Ni 28 1s2 2s22p63s23p64s23d8 10
Copper Cu 29 1s2 2s22p63s23p64s13d10 11 IB
Zinc Zn 30 1s2 2s22p63s23p64s23d10 12 IIB
Valence shell configuration = ns1-2(n-1)d1-10 = 4s1-23d1-10

Groups = 3 to 12 or IIIB to VIIB, VIII, IB, IIB

Properties of the elements of the first transition series

1. ATOMIC AND IONIC RADII
 The atomic radii of first transition elements lie in between those of s- and
p- block elements of the same period.

 The value of atomic radii initially deceases from Sc to V and become

almost constant from Cr to Cu. The last element Zn has comparatively
high atomic radius.

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
 s
r (Å) 1.44 1.32 1.22 1.17 1.17 1.17 1.16 1.15 1.17 1.25

Explanations: (a) The decrease in atomic radii from Sc to V is due to the increase
in the effective nuclear charge with the increase in atomic no.

(b) With the increase in no. of electrons in (n-1) d-subshell, the screening effect of
these d-electrons on the outermost ns-electrons also increases. This increased
screening effect neutralizes the effect of increased nuclear charge. As a result, the
atomic radii remain almost constant in the middle of the series.

(c) Increase in atomic radii towards the end is due to inter electron repulsions
between the pair electrons in the d-orbitals. This causes the expansions of electron
cloud. Ionic radii of divalent metal ion (M2+) also follow the same trend.

2. IONISATION ENERGY OR IONISATION ENTHALPY (I.E.)

In a transition series, the IE increases from left to right.

Elements Sc Ti V Cr Mn Fe Co Ni Cu Zn

1st IE 631 656 650 652 717 762 758 736 745 906
(kJ/mol)

Explanation: The increase in IE is primarily due to increase in nuclear charge

which would tend to attract the electron cloud with greater force.

The transition elements involve the gradual filling of electron in (n-1) d-subshell,
this also increase the screening effect. The outer ns- electrons are shielded more
and more. Thus, the effect of increasing nuclear charge is opposed by the increase
in screening effect. Consequently, the increase in IE of the transition metals is very
limited.

Very high value of IE of Zn is due to symmetrical and stable configuration

because of the presence of all filled orbitals. (4s23d10)
3. OXIDATION STATE:
 Most of these elements show variable oxidation states.

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

Explanation: The energy of ns and (n-1) d subshell (4s and 3d) are almost equal.
Hence transition elements show variable oxidation states due to the participation of
4s and 3d- electrons in the bonding.

Lower oxidation state is exhibited when 4s-electrons participate in bonding. Higher

OS are shown when 4s as well as 3d-electron take part in bonding.
  Most common OS of first transition elements is +2 which is due to the lose
of two 4s electrons.

 Highest oxidation state increases with increase in atomic number,

reaches a maximum in the middle and then starts decreasing.

 The stability of a OS depend upon the nature of the element with which the
transition metals forms the compound. The highest OS are found in
fluorides and oxides. Since fluorine and oxygen are the most electron
negative elements. Example: KMnO4, K2Cr2O7

 Stability of OS depends upon half-filled and full filled d-orbitals.

4. COLOUR OF TRANSITION METAL IONS:

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

Example: Aqueous solution of Ti (III) compound:

There is one d-electron in Ti (III) compound.

This compound absorbs light in 493nm (4930 Å) which corresponds to blue-

green in the white light. The transmitted light leaves the yellow, orange, red and
violet light and the aqueous solution of Ti(III) compound appears reddish
violet.
  The colour mainly depends on the transition metal ion and its OS and
the type of ligands present in compound.

Case I : d0 and d10 system (colourless)

Example Sc = 21= 3d14s2

Zn= 30= 3d104s2

Sc3+ = 3d0 (colourless or white)

Zn2+ = 3d10 (colourless or white)

 Complexes will be colourless if no light is absorbed or if the absorbed

wavelength is not in the visible region.
 Case II : d1 to d9 systems: Transition metal ions are coloured due to d-d
electron transition. Electrons from lower d-level absorb visible light and
moves to the higher d-level. This is called d-d transition.

Example: [NiCl4]2- Ni2+ = 3d8 (tetrahedral)

Co(NH3)6 Co3+ = 3d6 (octahedral)

Both are coloured due to d-d electron transition.

 The oxy anions in the highest oxidation state of metal are deep coloured.
This is because charge or electron transfer. Transfer of electron from oxygen
(reducing part) takes place towards metal (oxidizing part).

Example : KMnO4 K+1 + MnO4-1

Pottasium permanganate Oxyanion
(violet)
Mn= 25= 3d 4s2
5
Mn(VII)= 3d04s0

KMnO4 is coloured due to charge transfer.

Example: K2Cr2O7 2K+ + Cr2O72-

Pottasium dichromate Oxyanion
(orange)
 Cr= 24= 3d54s1 Cr(VI)= 3d04s0

K2Cr2O7 is coloured due to charge transfer.

5. Magnetic Property of transition metal ions:

 The magnetism of metals and other materials are determined by the orbital and
spin motions of the unpaired electrons and the way in which unpaired electrons
align with each other.

There are five types of magnetic properties shown by the substance:

1. Diamagnetism 2. Paramagnetism

3. Ferromagnetism 4. Anti-ferromagnetism

5. Ferrimagnetism

Diamagnetism: Substance having all paired electrons are called diamagnetic.

When it is placed in magnetic field, the lines of magnetic forces are repelled by it.
  d0 and d10 systems are diamagentic

Eg. ZnCl2 Zn2+ + 2 Cl-

Zn= 30= 3d104s2

Zn2+ = 3d104s0

It is diamagnetic

Sc3+, Cu+, Mn7+, Cr4+ are diamagnetic

Paramagnetism: Transition metals and their ions having unpaired electrons are
paramagnetic.

The magnetic moment is given by

μ¿ ¿L(L+1)+ 4S(S+1)]1/2 BM---------------(i)

Where, L= Resultant angular momentum quantum number (magnetic Q. No.)

S= n/2 = Resultant spin Q. No.

n= Number of unpaired electrons.

For most of the transition metal ion, the orbital contribution to magnetic moment is
zero (L=0).

μeff = μs = [4S(S+1)]1/2= [n(n+2)]1/2 BM --------------(ii)

Example: Ti2+ (μs= 2.83 BM), Fe3+ (μs= 5.91 BM)

Ferromagnetism: It is very strong paramagnetism. All the unpaired electrons

of metal ions at different lattice sites align in a particular direction (parallel)
giving very large number of unpaired electrons.
 Fe, Co and Ni are ferromagnetic. Higher the number of unpaired electron
greater will be ferromagnetism. The correct order is Fe> Co> Ni.

Example: Fe (26) = [Ar]3d64s2

Fe Fe3+ + 3e-
The crystal lattice of iron is shown as-

Anti-ferromagnetism:

 Antiferromagnetism is a type of magnetism in solids where unpaired electrons

align themselves into opposite or antiparallel arrangements throughout the
material. So that it exhibits almost no gross external magnetism (µ = 0 BM).

 In antiferromagnetic materials, the magnetism from magnetic atoms or ions

oriented in one direction is canceled out by the set of magnetic atoms or ions
that are aligned in the reverse direction.

Example: MnO

Ferrimagnetism:

 A ferrimagnetic material is one that has populations of atoms with opposing

magnetic moments, as in antiferromagnetism; however, in ferrimagnetic
materials, the opposing moments are unequal and a spontaneous magnetization
remains. This happens when the populations consist of different materials or
ions.(such as Fe2+ and Fe3+).

Example: Magnetite [iron(II,III)oxide, Fe3O4] is a ferrimagnet.

 Magn
etic behaviors of substances: (a) Diamagnetic (b) paramagnetic (c)
ferromagnetic (d) ferrimagnetic (e) Antiferromagnetic
6. Complex Formation:
Transition metals have very strong tendency to form co-ordination compounds
or complexes.

The complex formation ability of transition elements is due to –

(a) The small size of the transition metal cation.

(b) High effective nuclear charge

(c) High charge density or ionic potential.

(d) Presence of vacant d-orbitals of appropriate energy for bonding.

Metal ions behave as Lewis acid. Ligands behave as Lewis base. Hence, metal
in different oxidation state form complexes with different ligands in different co-
ordination number.

Example: K[Ag(CN)2], [Cu(NH3)4]SO4, [Co(NH3)6]Cl3 etc.

7. Catalytic property:
 Transition metals and their compounds are well known for their catalytic
activities.

Example: (i) Fe-Mo are catalyst in the synthesis of ammonia by Hebar process.

N2 (g) + 3H2 (g) 2NH3 ΔH= -95.3 kJ

(ii) V2O5 is used as catalyst in the manufacture of H2SO4 by contact process.

2SO2 + O2 2SO3 ΔH= -188 kJ