d- AND f- BLOCK ELEMENTS

• The d block elements are the elements in which the last electron enters the d-sub shell
of penultimate shell.
• The general electronic configuration is (n-1) d1-10ns1-2.
• d-block elements occupies the large middle section of periodic table between s- and p-
block elements.
• Elements of group 3 to 12 are belonging to d- block elements as they possess
properties that are transitions between s- and p- block elements.
• A transition element defined as the element which has incompletely filled d orbital in
its ground state or any one of its oxidation state.
• There are 4 series of transition elements

I. 1st Transition (3d) series: 21Sc to 30Zn

II. 2nd Transition (4d) series:39Y to 48Cd
III. 3rd Transition (5d) series:57La and 72Hf to 80Hg
IV. 4th Transition (6d) series: Incomplete and begins with 89Ac.

3d TRANSITION SERIES:
ELEMENTS (Z ELECTRONIC CONFIGURATION
)
Sc 21 4s23d1 Sc2+3d1
Ti 22 4s23d2 Ti2+3d2
V 23 4s23d3 V2+3d3
Cr 24 4s23d4 Cr2+3d4
Mn 25 4s23d5 Mn2+3d5
Fe 26 4s23d6 Fe2+3d6
Co 27 4s23d7 Co2+3d7
Ni 28 4s23d8 Ni2+3d8
Cu 29 4s13d10 Cu2+3d9
Zn 30 4s23d10 Zn2+3d10

Zn, Cd and Hg of group 12 has completely filled d-orbital (n-1)d¹⁰ in their ground state as
well as in their common oxidation state. Thus,they are not considered as transition metals.
PHYSICAL PROPERTIES:
MELTING AND BOILING POINTS:
Transition elements have high melting point and high enthalpy of atomization.
REASON: Greater the number of valance electrons stronger is the M-M bond (Metallic bond)

OXIDATION STATES:
• Transition metals exhibit various oxidation states because for the comparable energies of
(n-1)d and ns orbitals.
• The transition element which exhibits only one oxidation state is Scandium.
• Transition element which exhibit more than one O.S is Manganese.
• O.S of transition elements differ by unity. Highest O.S is found in compounds of Fluorides and
Oxides because of their small size and most electronegative nature.
• The ability of oxygen to stabilize high oxidation state exceeds that of Fluorine.
Eg: Highest fluoride of Mn is MnF4, the highest oxide if Mn2O7.
REASON: Because oxygen has the ability to form multiple bonds with metals.

ACIDIC AND BASIC NATURE OF OXIDES:

LEWIS THEORY:
Acids are electron acceptor and bases are electron donor. In general, metal in lower O.S
form basic oxide. Metal in higher O.S form acidic oxide. Metal in intermediate oxidation state
form amphoteric oxides.

QUESTION 1

MnO is basic whereas Mn2O7 is acidic why?

ANS- In MnO, Mn exhibit +2 O.S whereas in Mn2O7, Mn exhibit +7 O.S.

COMPARISON OF TRANSITION ELEMENTS AND NON-TRANSITION ELEMENTS

TRANSITION ELEMENTS (d- BLOCK) NON- TRANSITION ELEMENTS(p- BLOCK)
In d-block elements O.S differ from each In p-block elements O.S differ by units of 2
 other by unity. Eg:Sn2+and Sn4+, Pb2+ and Pb4+
Eg: Fe2+and Fe3+, Cu+ and Cu2+
The highest O.S of transition metals are The lower O.S of p-block elements are more
more stable for heavier elements in a stable for heavier elements due to inert pair
group. effect
Eg: Mo6+ and W6+ are more stable. Eg: In 15th group, Sb3+ is more stable than Sb5+
Bi3+ is more stable than Bi5+

MAGNETIC PROPERTIES:
• Many transition metals are paramagnetic which have unpaired electrons in d-orbitals.
• Sc3+ and Ti4+ (d0) and Cu+ and Zn2+ (d10) ions are diamagnetic due to the empty and
completely filled d-orbital.
• Magnetic moment (µ) can be calculated spin only formula:
µ (Bohr Magneton) when n is the number of unpaired electrons.
n=1 µ = 1.87 B.M
n=2 µ = 2.84 B.M
n=3 µ = 3.87 B.M
n=4 µ = 4.9 B.M
n=5 µ = 5.92 B.M

FORMATION OF COMPLEXES:
Transition metals form a large number of complex compounds.

REASONS:

• Smaller size of metal ions

• High ionic charges
• Availability of d-orbitals for bond formation
 • OXIDATION: Loss of electron ( Increase in Oxidation number )
• REDUCTION: Gain of electron ( Decrease in Oxidation number )
• OXIDISING AGENT ( OXIDANT ) : Easily reduced – More positive E⁰ value
• REDUCING AGENT ( REDUCTANT ): Easily oxidized – More negative E0 value
• HALF FILLED ORBITALS: s1, p3, d5, f7
• COMPLETELY FILLED ORBITALS: s2, p6, d10, f14
• STABILITY: Completely filled > Half filled > Incompletely filled

IONISATION ENTHALPY:
• Due to an increase in nuclear charge there is an increase in ionization enthalpy along
each series of the transition elements from left to right
• Although the 1st ionization enthalpy increases, the magnitude of the increase in the 2 nd
and 3rd ionization enthalpy for the successive elements, in general, is much higher.
• IE1 < IE2 < IE3 in each group.

NOTE:
▪︎When transition elements are in lower oxidation states it exhibits covalent characters.
▪︎When they are in higher oxidation states they exhibit ionic character.
▪︎Higher oxidation states are more stable for heavier members.
▪︎Low oxidation states are found when a complex compound has ligands, capable of π-
acceptor character in addition to σ- bonding.

Eg- In Ni(CO)4 and Fe(CO)5, the oxidation state of nickel and iron is zero.

STABILITY OF HIGHER OXIDATION STATES:

1.The ability of F to stabilize the highest oxidation state is due to high lattice energy or high
bond enthalpy in VF5 or CrF6.
2.The ability of oxygen to stabilize the highest oxidation state due to its ability to form multiple
bonds with metals.
3. All Cu(II) halides are known except the iodide. Cu2+ oxidizes I- to I2

4.Many copper (I) compounds are unstable in aqueous solution and undergo
disproportionation.
Cu+(aq) ---------🡪 Cu2+(aq) + Cu(s)
 The stability of Cu2+(aq) rather than Cu+(aq) is due to the much more negative Hydration
enthalpy of Cu2+(aq) than Cu+ which more than compensates for the 2nd ionization enthalpy
of Cu.
FORMATION OF COLOURED IONS:
Transition metals form coloured ions due to d-d transition of the electron in the d-
orbital by the absorption of light.

SPLITTING OF 5 DEGENERATE d-ORBITALS

In Zn2+ and Cd2+ all d- orbitals are fully filled, Ti4+ all d-orbitals are vacant. There is no d-d
transition due to the absence of unpaired electrons.They do not absorb radiations. So they are
colourless.

FORMATION OF INTERSTITIAL COMPOUNDS:

They are formed when small atoms like H,C or N are trapped inside the crystal lattice of
metals. They are non-stiochiometric. They are neither ionic nor covalent.
Examples :- TiC, Mn4N, Fe3H, VH0.56 and TiH1.7
Interstitial compounds have the following characteristics:
• High melting point than pure metals.
• Very hard
• Certain metallic Characters
• Chemically inert
ALLOY FORMATION:
• Transition metals form alloy because of similar radii and other characteristic property of
transition metals.
• These alloys are hard and have high melting point. Eg: Ferrous alloy
• Alloys of transition metals with non-transition metals such as brass (Cu-Zn) and
Bronze (Cu-Sn)

STANDARD ELECTRODE POTENTIAL [E0]:

• Electrode potentials are the measure of the value of total enthalpy change of the
reaction.
• It depends on enthalpy of atomization and hydration enthalpy.
• Lower the E0 value, the most stable is the oxidation state of the metal in aqueous state.
• For 1st row transition metals E0 values are not regular which can be explained from
irregular variation of ionization and sublimation enthalpies which are much less for Mn
and V.
• E0 value for copper is positive (0.34V) it has high enthalpy of atomisation and low
hydration enthalpy.
Greater amount of energy is required to transform Cu (3d10 4s1) into Cu2+ (3d9) due
to positive E0, Cu does not liberate H from acid.
• In general trend towards less negative E0 values across the series is related to general
increase in the sum of 1st and 2nd ionization enthalpies.
• It is interesting to note that the value of E0 for Mn, Ni and Zn are more negative than
expected.
• The stability of the half filled d- sub shell in Mn2+ and the completely filled d10
configuration of Zn2+ are related to their highest value of negative hydration enthalpy.
• Low E0 value for scandium is due to the stability of Sc3+ which has noble gas
configuration.
• High value of E0 for Mn shows that Mn2+ (d5) is stable whereas low E0 value for Fe shows
extra stability of Fe3+ (d5).
CHEMICAL REACTIVITY:
• The metals of 3d series except Cu are more reactive and are oxidized by acids
• E0 values of M2+/M indicate a decreasing tendency to form divalent cations (M2+) across
the series.
• E0 values for redox couple M3+/M2+ shows that Mn3+ and Co3+ ions are the strongest
oxidizing agents in aqueous solution.
• Ti2+, V2+, Cr2+ are strong reducing agents and will liberate hydrogen form a dilute acid.
Eg:

CATALYTIC PROPERTY:
• Most of the transition metals and their compounds are known for their catalytic activity. This
is due to their ability to adopt multiple oxidation state and to form complexes.

Eg:
V2O5 in contact
process
Finely divided Fe in
Haber process
Fe3+ catalysed
reaction between
iodide and
persulphate ion:

-------------------------------------------------------
INNER TRANSITION ELEMENTS:
The elements in which the additional electron enters (n-2) f-orbitals are called inner transition elements.
The valance shell electronic configuration of these elements can be represented as (n-2)f 0-14 (n-1)d0-1 ns2

LANTHANOIDS [4f- BLOCK ELEMENTS]:

• The series involving the filling of 4f- orbitals following lanthanum La (Z=57) is called the lanthanoid
series.
• It starts with 58 Ce to 71 Lu
• They are highly dense metals
• They have high melting points
• They form alloys easily with other metals
• They are soft, malleable and ductile with low tensile strength
• Many La3+ are coloured in solid state and aqueous solutions. This is because of the excitation within f-
subshell
• All La3+ ions are paramagnetic because of the presence of the unpaired electrons in 4f- orbital
• La3+ and Ce4+ (f0) and Yb2+ and Lu3+ (f14) are diamagnetic.
• Most common oxidation states of lanthanoids are 3+. Some elements exhibit 2+ and 4+ oxidation
state.
• All lanthanoids are highly electro positive metal and have almost similar chemical reactivity.
• In lanthanoids, only promethium is radioactive element.
• They have low ionization enthalpy.
• In their chemical behavior, the earlier members of the series are reactively similar to calcium but
with increasing atomic number, they behave more like aluminium.

LANTHANOID CONTRACTION:
• Decrease in atomic and ionic radii from lanthanum and lutetium in 4f-block elements is called
lanthanoid contraction.
• This is due to the imperfect shielding of one 4f electron by another 4f electron in same subshell.

CONSEQUENCES:
• The properties of second (4d) and third (5d) transition series are similar because of their similar radii.
• Difficulty in separation of lanthanoids in pure state.
• Basic strength of their hydroxides decreases from La(OH)3 to Lu(OH)3.

• They have similar physical and chemical properties

USES:

• They are used for the production of alloy steels for plates and pipes
• Mischmetal is an alloy of Lanthanoid metal (≈ 95%) and iron (≈ 5%) and traces of S, C, Ca and Al. It is
used in Mg based alloy to produce bullets, Shell and lighter flint.
• Mixed oxides of lanthanoids are used as a catalyst in petroleum cracking.
• Some Lu oxides are used as phosphorous in television screens and fluorescing surfaces.