THE d AND f BLOCK ELEMENTS

 The elements in which the differentiating electron enters into the d subshell of the
penultimate shell, (n-1) d subshell is usually referred to as transition elements.
 The elements in which the differentiating electron enters into the f subshell of the
antepenultimate shell, (n-2) f subshell is usually referred to as inner- transition
elements.
 Inner transition elements have been grouped into two series called Lanthanoid series
and Actinoid series.
 The presence of partially filled d or f orbitals in their atoms makes transition metals
different from that of non-transition elements.

THE TRANSITION ELEMENTS (D BLOCK ELEMENTS)

Transition elements are those elements which possess incompletely filled d-orbitals
in their ground state or in their ions existing in chemically significant oxidation
states.

 Except Zn, Cu, Hg all other elements have partially filled d-orbitals in their elementary
form (ground state) and are true transition elements. Therefore, these elements are not
considered as transition elements.

Q Zn, Cu, Hg are not regarded as transition elements.Why?

CLASSIFICATION OF TRANSITION ELEMENTS

Transition elements have been classified into four horizontal series called transition
series. Each series corresponds to the filling of a particular (n-1) d subshell.

1. First transition series or 3d series: - Filling of 3d subshell, Sc (21) to Zn (30), 4th

period, total 10 elements.
2. Second transition series or 4d series- Filling of 4d subshell, Y (39) to Cd (48), 5th
period, total 10 elements.
3. Third transition series or 5d series- Filling of 5d subshell, La (57) and those from
Hf (72) to Hg (80), total 10 elements.6th period.
4. Fourth transition series or 6d series- Filling of 6d subshell, Ac (89) and those from
Rf (104) and above .7th period. This series is incomplete.

GENERAL PROPERTIES

1. General the electronic configuration of these elements is (n-1) d 1–10 ns 1–2.

2. The d orbitals of the transition elements extend beyond the periphery of an atom
more than other orbitals. Hence, they are more influenced by the surroundings as
well as affect the atoms or molecules surrounding them.
3. Exhibit catalytic and magnetic properties and paramagnetic behaviour.
4. Melting and Boiling points -Melting and Boiling points of transition metals are
very high as compared to those of representative elements. The melting points first
increases, attain a maximum value and then steadily decreases as atomic number
increases.

Explanation:

 High mp and bp are due to their close packed structures. Transition metals are
held together by strong metallic bonds which have considerable amount of energy
to break the metallic bond.
 Strength of metallic bond depends on the number of unpaired electrons.
 Mn and Tc have abnormally low melting point: - They have 5 electrons in its d-
orbital. This is a half-filled stable configuration. Hence these electrons are not
free to participate in metallic bonding. Their lattice is loosely packed.
 Zn, Cd, Hg have no unpaired electrons. These metals are soft and have low
melting and boiling point.

Q: The melting point of Mn and Tc are abnormally low -Why?

5. Variation in the Atomic and Ionic sizes-

 In general, the atomic radii of transition elements belonging to a particular

series decreases with increase in atomic number. The decrease becomes
small after midway - The decrease in atomic radii with increase in the atomic
number is due to an increase in the nuclear charge. The screening effect
increases with increase in the number of d electrons. The effect of increased
nuclear charge with increase in atomic number is counter balanced by
increased shielding effect of the (n-1) d electrons.
 Near the end of each series, there is a slight increase in the atomic radii- The
electron repulsions between the added electrons in the similar orbitals
predominates over the attractive forces due to the increase in nuclear charge.
This results in the expansion of the electron cloud and consequently the
atomic radii increase.

Q: Why atomic radii remain almost constant from Mn to Ni?

 The atomic radii of transition elements increase on moving down the group.
However, the atomic radii of the elements of second and third transition
series are nearly the same-The increase in atomic radii on moving down the
group is due to an increase in the number of electronic shells. The almost
similar values of atomic radii of the second and third transition series are
due to Lanthanoid Contraction.

Q: Why the atomic radii of the elements of second transition series are larger
than those of the first transition series?
6. Enthalpy of Atomization- The enthalpy of atomization is the enthalpy change that
accompanies the total separation of all atoms in a chemical substance (either a
chemical element or a chemical compound). This is often represented by the symbol
ΔatH or ΔHat.

 Higher value of enthalpy of atomization of transition elements may be

attributed to the presence of a large number of unpaired electrons in their
atoms. Due to this, they possess stronger interatomic attractions and stronger
bonding.
 In case of zinc (3d104s2 configuration), no electrons from the 3d-orbitals are
involved in the formation of metallic bonds since all the orbitals are filled.
However, in all other elements belonging to 3d series one or more d-
electrons are involved in the metallic bonds. This means that the metallic
bonds are quite weak in zinc and it has therefore, lowest enthalpy of
atomisation in the 3d series.

Q: In the series Sc (Z = 21) to (Z = 30), the enthalpy of atomisation of zinc

is the lowest i.e., 126 kJ mol-1. Why?

7. Ionization enthalpy-

IE of transition elements lie between those of s block and p block elements.

 The ionization enthalpy of transition metals is quite high and lie between
those of s-block and p-block elements.
 The first IE increases with increase in atomic number across a given
transition series, although the increase is not very regular. - These
irregular trends in the first ionization enthalpy of transition metals can
be explained by considering the fact that the removal of one electron
alters the relative energies of 4s and 3d orbitals

The increase in IE with increase in atomic number across a given series

is due to an increase in the nuclear charge with increase in the atomic
number. The added electrons enter into (n-1) d subshell and shield the
valence electrons from the nucleus. Thus, the effect of increased nuclear
charge is opposed by the screening effect of (n-1) d electrons.

8. Oxidation State:

 Most of the transition metals exhibit several OS.

 The most common OS of the element belonging to the first transition
series except Sc is +2 .
 The bond formed by transition element in +2 and +3 are ionic.
 The bond formed by the higher OS are covalent and usually formed with F
or Oxygen.
 With in a group, maximum OS increases with atomic number.
  Highest OS of transition metals are found in their fluorides and oxides
because oxygen and F are the most electronegative elements.
 The highest OS shown by any transition element is 8.
 Transition elements also form compounds in low oxidation state. Os of Ni
in Ni (CO)4 is 0
Explanation: -
The energies of (n-1) d orbitals and ns orbitals are very close. Therefore, the electrons from
both can participate in the bond formation. The +1 and+2 OS involve the participation of ns
electrons but higher OS such as +3, +4, +5, +6 involve the use of (n-1) d electrons in addition
to ns electrons for bond formation.
TRENDS IN THE M2+/M STANDARD ELECTRODE POTENTIALS

 The standard electrode potentials of transition metals do not exhibit any regular trend.
This is due to the irregular variation in the ionization and sublimation energies across a
particular transition series.
 Generally, less negative E ⊝ values across the series due the general increase in the sum
of the first and second ionization enthalpies
 Except Cu all other elements possess negative value of SEP. That is why they act as
reducing agents.
 The unique behavior of Cu is due to its inability to liberate H2 from acids.
 The stability of the half-filled d sub-shell in Mn2+ and the completely filled d10
configuration in Zn2+ are related to their E ⊝ values, whereas E ⊝ for Ni is related to the
highest negative ∆hyd H ⊝
 E° value which measures the reducing power and which depends on

(Converting atoms from the electrode into the gas phase) -Sublimation enthalpy

M(s) M (g) ΔsubH= positive

Removing electrons from the gaseous atoms (ionization)

M(g) M+ (g) + e— ΔiH= positive

Solvating the resulting ions – Hydration enthalpy

M+ (g) M+ (aq) , ΔhydH= Negative

Due to the large negative value of hydration, the overall value become negative and
the redox couple can act as a strongest reducing agent.
 The oxidation state for which E° value is more negative will be more stable in aqueous
medium.
TRENDS IN THE M3+/M2+ STANDARD ELECTRODE POTENTIALS

 The low value for Sc reflects the stability of Sc3+ which has a noble gas configuration
 The highest value for Zn is due to the removal of an electron from the stable d10
configuration of Zn2+.
 The comparatively high value for Mn shows that Mn2+(d5) is particularly stable,
whereas comparatively low value for Fe shows the extra stability of Fe 3+ (d5).
 The comparatively higher value for V is related to the stability of V2+ (half-filled t2g
level).

TRENDS IN STABILITY OF HIGHER OXIDATION STATE

• Highest oxidation state of a metal exhibited in its oxide or fluoride only because F and
O are most electronegative elements
• For example, TiX4 (tetrahalides), VF5 and CrF6.
• The +7 state for Mn is not represented in simple halides but MnO 3F is known, and
beyond Mn no metal has a trihalide except FeX3 and CoF3.
• The ability of fluorine to stabilize the highest oxidation state is due to either higher
lattice energy as in the case of CoF3, or higher bond enthalpy for the higher covalent
compounds, e.g., VF5 and CrF6.
• All Cu (II) halides are known except the iodide. In this case, Cu2+ oxidises 𝐼 − 𝑡𝑜 𝐼2

• However, many copper (I) compounds are unstable in aqueous solution and undergo
disproportionation
• The stability of Cu2+ (aq) rather than Cu+(aq) is due to the much more negative
∆ℎ𝑦𝑑 𝐻 ⊝ of Cu2+ (aq) than Cu+, which compensates the second ionization enthalpy of
Cu.
• The highest oxidation number in the oxides coincides with the group number and is
attained in Sc2O3 to Mn2O7.
• Beyond Group 7, no higher oxides of Fe above Fe2O3, are known, although ferrates
(VI)(FeO4)2–, are formed in alkaline media but they readily decompose to Fe2O3 and
O2.
• The ability of oxygen to stabilize these high oxidation states exceeds that of fluorine.
Thus the highest Mn fluoride is MnF4 whereas the highest oxide is Mn2O7.
• A comparison of oxides and halides of these metals reveals that oxygen is more efficient
in stabilising higher oxidation states as compared to to F. Eg highest fluoride is MnF 4
and highest oxide is Mn2O7. This is due to the fact that oxygen can form multiple bonds
with metals, whereas F is unable to do so. In the covalent oxide Mn2O7, each Mn is
tetrahedrally surrounded by O’s including a Mn–O–Mn bridge

QUESTIONS

1. The sums of the first and second ionization enthalpies and those of the third and
fourth ionization enthalpies of nickel and platinum are given below:
IE1 + IE2 (kJ mol-1) IE3 + IE4 (kJ mol-1)
Ni 2.49 8.80
Pt 2.66 6.70

Taking these values into account write the following:

(i) The most common oxidation state for Ni and Pt and its reasons.
(ii) The name of the metal (Ni or Pt) which can form compounds in +4 oxidation
state more easily and why?

Solution

(i) Ni shows +2 oxidation state whereas Pt shows +4 .(IE 1+IE2) of Ni is less than that
for Pt whereas (IE3 + IE4) is less for Pt.
(ii)From the given data it is clear that Pt (IV) is more easily attained while more energy
would be required for obtaining Ni (IV) ion. Hence, Pt (IV) compounds are more stable
than Ni (IV) compounds

2. Out of Cr2+ and Cr3+, which one is stable in aqueous solution?

Solution: Cr3+ is more stable in aqueous solution due to higher hydration enthalpy
which is due to smaller size and higher charge
 3. How do the oxides of the transition elements in lower oxidation states differ from
those in higher oxidation states in the nature of metal-oxygen bonding and why?
Solution: Oxides of transition metal in lower oxidation state are ionic and basic in
nature whereas in higher oxidation state it forms covalent oxide which are acidic in
nature.
4. Name a transition element which does not exhibit variable oxidation states.
Solution: Scandium (Z = 21) does not exhibit variable oxidation states
5. Explain why Eo for Mn+3/Mn2+ couple is more positive than that for Fe3+/Fe2+.
Solution: Mn2+ has stable (3d5) configuration while Fe3+ is more stable (3d5)

MAGNETIC PROPERTIES

When a magnetic field is applied to substances, mainly two types of magnetic behaviour are
observed: diamagnetism and paramagnetism
• Diamagnetic substances are repelled by the applied field while the paramagnetic
substances are attracted.
• Substances which are attracted very strongly are said to be ferromagnetic. In fact,
ferromagnetism is an extreme form of paramagnetism.
• Many of the transition metal ions are paramagnetic due to the presence of unpaired
electrons.
• The magnetic moment is determined by the number of unpaired electrons and is
calculated by using the ‘spin-only’ formula, i.e., n is
the number of unpaired electrons
• Units of magnetic moment is Bohr magneton (BM). A single unpaired electron has a
magnetic moment of 1.73 Bohr magnetons (BM).

where n is the number of electrons and μ is the magnetic moment in units of Bohr
magneton (BM)

FORMATION OF COLOURED IONS BY TRANSITION ELEMENTS

 Most of the compounds of transition metals are coloured both in the solid state as well
as in the aqueous solutions.
 The colour of metal ion is due to d-d transition taking place between the splitted d
orbitals. When an electron from a lower energy d orbital is excited to a higher energy
d orbital, the energy of excitation corresponds to the frequency of light absorbed. This
frequency generally lies in the visible region.
  The transition metal ions having completely filled d orbitals or completely empty d-
orbitals are colourless. Cu+, Zn2+ (3d10), Cd 2+, Hg2+ etc having completely filled d
orbitals are colourless. Sc3+ (3d0), Ti 4+ (3d0) are colourless because they possess
completely empty d orbitals.

FORMATION OF COMPLEXES

Transition metal ion form a large number of complex compounds. In these

compounds, the transition metal ions coordinate to a number of negative ions or
neutral molecules having lone pair of electrons called Ligands. Ligand donate a pair
of electrons to the central metal ion forming a coordinate bond.

Explanation: Transition metal ion form complexes due to the following.

1. Small size
2. High nuclear charge
3. Availability of d orbitals of suitable energy to accommodate lone pair of electrons
donated by the ligands.

CATALYTIC PROPERTIES

Many of the transition metals and their compounds, particularly oxides acts as
catalysts for a number of chemical reactions. The catalytic property of transition
metals are due to

1. Presence of vacant d orbital.

2. Ability to exhibit variable oxidation state.
3. Tendency to form complexes.

 Finely divided Ni is used in several hydrogenation reaction.

 Finely divided Pt is used in the manufacture of Sulphuric acid.
 Finely divided Fe used in the synthesis of Ammonia.
 V2O5 is used in the manufacture of H2SO4 by contact process.
 TiCl4 is used in the manufacture of high density polythene.

FORMATION OF INTERSTITIAL COMPOUNDS

• Interstitial compounds are those which are formed when small atoms like H, C or N are
trapped inside the crystal lattices of metals.
• They are usually non stoichiometric and are neither typically ionic nor covalent, or
example, TiC, Mn4N, Fe3H, VH0.56 and TiH1.7, etc.
Properties:

• (i) They have high melting points, higher than those of pure metals.
• (ii) They are very hard, some borides approach diamond in hardness.
• (iii) They retain metallic conductivity.
• (iv) They are chemically inert.
The formation of an interstitial compound do not alter the chemical behavior of the
parent transition element, However many physical properties such as density, hardness,
rigidity , malleability ,ductility ,electrical conductivity etc get modified.considerably.

ALLOY FROMATION

Refer text book.