CHINMAYA VIDYALAYA, KANNUR

d-and f-BLOCK ELEMENTS

1 The general electronic configuration of d block elements

( transition elements): (n-1)d1-10ns1or2
The elements Zn,Cd and Hg are not considered as d-
block elements( they are called as pseudo- transition
elements) because they do not have partially filled d-orbital
either in their ground state or their excited state. These
elements are also soft among the d-block elements.
Physical properties of d-block elements:
2 a) Transition metals are very hard and have low
volatility. They have high m.p and b.p .
REASON: STRONG INTER ATOMIC METALLIC
BONDING DUE INVOLVEMENT OF LARGER NO. OF
ELECTRONS FROM (n-1) d ORBITALS IN ADDITION
TO ns electrons.
b) Transition elements have high entahalpy of
atomization
REASON: strong interatomic interaction due to the
presence of large no. of unpaired electrons in their atoms.
Cr,Mo and W are very hard metals due to the large no of
unpaired electrons in them. So they have larger interatomic
interactions.
c) Ionisation enthalpy of each series increases from left
to right.
REASON : Due to an increase in nuclear charge which
accompanies the filling of the inner d orbitals.
d) These elements show variable oxidation states. The d
block elements show a wide variety of oxidation
states and each oxidation state differ from the other by
a value of +1 unlike the main group elements which
differ from each other by a value of +2.
REASON:due to the active participation of (n-1)d electrons
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d-and f-BLOCK ELEMENTS

along with the outer ns orbitals in bonding due to their

comparable energies.
Eg: Mn show a variety of oxidation state:+2 to +7.
Sc show only one oxidation state :+3. This is the only
element in the 3d series which cannot show variable
oxidation state.
Cu show two oxidation states:+1 and +2
Zn show only one oxidation state:+2
THE HIGHEST OXIDATION STATE OF AN METAL
IS EXHIBITED IN ITS FLOURIDE OR OXIDE ONLY.
REASON:Due to small size and high electronegativity of
oxygen and fluorine , Oxygen also has the ability to form
multiple bonds.Hence, they can oxidize the metal to the
highest oxidation state.

LOWEST OXIDATION STATES ARE FOUND IN THE

COMPLEX COMPOUND HAVING LIGANDS WHICH
SHOW Π CHARACTER IN ADDITION TO σ
BONDING.Eg: Ni(CO)4
e) Most of the transition elements are paramagnetic in
nature.
REASON: They have unpaired electrons in d-orbitals and
the magnetic moment is calculated using the formula
µ=[n(n+2) ]½ where n is the no of unpaired electrons.This
value is calculated in BOHR MAGNETON(BM)
f) The transition elements form coloured ions .
REASON: due to d-d transitions.
Nb: KMnO4 SHOW A VARIETY OF COLOURS DUE TO
CHARGE TRANSFER SPECTRA.
g) Transition elements form complexes.
REASON:Due to comparatively small sizes of metal ions,
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d-and f-BLOCK ELEMENTS

high charge aand the availability of vacant d-orbitals for

bond formation.
h) Catalytic property: transition elements show catalytic
property
REASON: Due to variable oxidation states, availability of
vacant d- orbital and provides large surface area on which
adsorption occurs faster.
i) Transition elements form interstitial compounds
REASON: Transition elements have vacant site in their
metal lattices in which small elements like H,C or N gets
trapped.
j) Transition elements form alloys.
REASON: They have similar atomic radii . so the metals
can substitute their positions.
LANTHANIDE CONTRACTION:
The steady decrease in the atomic and ionic radii of
lanthanides with increase in atomic no. arising due to the
poor shielding effect of the f-electrons . The f-electrons
cannot shield the valence electrons from the growing
nucleus . this effect is known as lanthanide contraction.
Consequences of lanthanide contraction:
a) The members in the second and third series are very
similar in their atomic and ionic sizes due to
lanthanide contraction.eg: Zr(160pm) and Hf(159pm)
have the same atomic radii.
b) Separating the lanthanides become difficult due to
lanthanide contraction.
c) Basic strength of the hydroxides decrease with
increase in atomic no.La(OH)3 is the most basic and
Lu(OH)3 is the least basic.
ACTINOIDS:
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d-and f-BLOCK ELEMENTS

The series involving the filling of incomplete filling of the

f-orbitals following the actinium are called actinides.
These are radioactive elements starting from thorium to
lawrencium.
Outer electronic configuration : (n-2) f1-14 (n-1)d0or 1ns2.
Actinoids are bigger than those of lanthanoids. They use
the 5f electrons also for bonding.and show a wide variety
of oxidation state than lanthanoids.
CHEMICAL REACTIVITY OF LANTHANIDES:
a) The common oxidation state of lanthanides is +3.
Some elements show +2 and +4 due to extra stability
of empty, half filled and fully filled 4f-orbitals.
b) They are heavy metals .
c) They react with water forming metal hydroxides and
oxygen.
d) They react quickly with air and get tarnished due to
oxide formation.
e) They also react with nitrogen , halogen , carbon, hot
water to form nitrides, halides ,carbides and
hydroxides respectively.
f) Most of the lanthanoids show colour and
paramagnetism due to the presence of unpaired
electrons and exhibit f-f transitions.
DIFFERENCES BETWEEN LANTHANOIDS AND
ACTINOIDS
LANTHANOIDS ACTINOIDS
It show +3 oxidation except Shows a wide range of
in a few cases where it has oxidation states due to a
the oxidation +2 &+4(Ce small energy gap between
exhibit +4) 5f,6d &7s orbitals. In
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d-and f-BLOCK ELEMENTS

addition to+3 , +4+5+6 &

+7 are also shown.
4f orbitals have greater 5f electrons have a poor
shielding effect.therefore screening effect. Therefore
the contraction in their ionic the contraction in their sizes
radii is less. is more.
The tendency to form They have a greater
complexes is less. tendency to form
complexes.
Lanthanoid compounds are Actinoid compounds are
less basic. more basic.
They do not form oxo ions . They form oxo anions such
as UO2+, NpO2+, UO22-.
Except Pm, these are non- All actinoids are
reactive. radioactive.
Most of their ions are Most of the actinoids are
colourless. coloured.
They are paramagnetic . They are also paramagnetic
Shows a decrease in the Shows a decrease in the
size of their atoms or ions size of their atoms or ions
in+3 state(lanthanide in +3 state(actinoid
contraction) contraction)Actinoid
contraction is more
prominent from element to
element due to poorer
sheiding effect by 5f
electrons.
Less reactive than actinoids. More reactive than
Earlier members in the lanthanoids. They become
series are quite reactive like very reactive when it is
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d-and f-BLOCK ELEMENTS

Ca, but the latter members finely divided.

behave more like Al.
CHEMICAL REACTIVITY AND E0 VALUES
Transition elements are highly electropositive that they can
dissolce in mineral acids although a few are noble ( they
are not affected by dil acids)In the 3d series all elements
except Cu are relatively more reactive and reacts with
1Macid. The E0 values for 3d series are as follows:
E V Cr Mn Fe Co Ni Cu Zn
E0M+2/M -1.18 -0.91 -1.18 -0.44 -028 -0.25 +0.34 -0.76
The stability of the transition metal ions in different
oxidation staes can be determined form the E0 values. The
electrode potential values depends on the following
factors:enthalpy of sublimation, ionization enthalpy and
hydration enthalpy. the more negative the electrode
potential of the electrode , more stable is the oxidation state
of the transition metal in the aqueous medium.
a) The E0M+2/M of 3d series is not regular .Give reason.
This arises due the irregular variation in ionization
enthalpies(ΔHi1+ ΔHi2) and also the sublimation enthalpies
which are relatively much less for Mn(240kJ/mol) and
V(470kJ/mol)
b) The E0 value for Cu is positive. Why?
This occur due to the fact that the enthalpy of atomization
is not compensated by the ΔHhydration.SoCu doesnot react
with dil acids liberating hydrogen .Only oxidising acids
like nitric acid and hot Conc.H2SO4Mreact with Cu and
gets reduced.
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d-and f-BLOCK ELEMENTS

c) The value of E0 FOR Mn, Ni and Zn are more negative

than expected. Give reason.
This occurs due to the peculiar configuration.(1) Mn2+ is
having a half filled stability (d5) (2)Ni2+ has the highest
hydration enthalpy and (3)Zn+2 has a completely filled
electronic configuration(d10)
d) How do you relate the general trend towards less negative
E0 values across the series?
It is related to the general increase in the ΔHi1+ ΔHi2
e) TRENDS IN THE E0M3+/M2+ :
E V Cr Mn Fe Co Ni Cu Zn
M3+/M2+ -0.26 -0.41 +1.57 +0.77 +1.97 - - -

f) a) Sc has the lowest value Sc3+ has [Ar] configuration.

b) Zn has the highest value due to the removal of an
electron from the stable d10 configuration.
c) The comparatively high value for Mn is due to the
stability of Mn2+(d5).
d) The comparatively low value for Fe is due to the extra
stability of Fe3+(d5).
e) Mn3+ and Co3+ are the strongest oxidizing agents in
aqueous solutions due to
1) Mn2+ is more stable than Mn3+
2) Co2+ is more stable in aueous solutions than Co3+
3) The ions Ti2+,V2+ and Cr2+ are strong reducing
agents and will liberate H2 from the dil acids.
f) Trends in the stability of higher oxidation states:
Mostly ionic bonds are formed in +2and +3 oxidation
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d-and f-BLOCK ELEMENTS

states. In compounds of higher oxidation states, the bonds

formed are mostly covalent since they are formed by
sharing of electronseg: In MnO4- , the bonds between Mn
and O are covalent.
Halides:
The highest oxidation no are achieved in TiF4, VF5 & Cr F5.
THE ABILITY OF FLOURINE TO STABILIZE THE
HIGHEST OXIDATION STATE IS DUE TO EITHER
THE HIGHER LATTICE ENTHALPY(CoF3) OR
HIGHER BOND ENTHALPY FOR HIGHER
COVALENT COMPOUNDS.(VF5 OR CrF6) AND
PARTLY DUE TO HIGH ELECTONEGATIVITY OF
FLUORINE.
Vshows an oxidation state of +5 inVF5,other halides
undergo hydrolysis to give oxohalides VOX3 in which
oxidation no of V IS +5
In low oxidation states Flourides are unstable.. eg:TiX2,
VX2, CuX whiere X cannot be F.
2Cu+4I- Cu2I2+I2
Many Cu(I) compounds are unstable in aqueous solution
and undergo disproportionation .
2Cu+ Cu2++Cu .
The greater stability of Cu2+ (aq) than Cu+(aq) is due to
much more negative enthalpy of hydration for Cu2+ than
Cu+. This compensates for the high second ionization
enthalpy of Cu.
OXIDES:
a) The highest oxidation state in oxide is same as that of
group 7 ,(Sc2O3 TO Mn2O7)
b) BEYOND group 7, the max. oxidation state is +3
(Fe2O3) although in ferrates, FeO4- 2,the highest
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d-and f-BLOCK ELEMENTS

oxidation state +6. These readily get decomposed to

form Fe2O3 & O2
c) Beside the oxides the higher oxidation state even more
than flourineeg: highest fluoride iof Mn is MnF4
when the highest oxidation states are also found in the
oxocations eg;V(V) in VO2+,V(VI) in VO+2 and
Ti(IV) in TiO2+
d) Oxygen stabilizes tge highest oxidation state even
more than fluorine. Eg,highest fluoride of Mn is
MnF4 whereas highest oxide is Mn2O7.REASON:
The ability of oxygen to form multiple bonds with
metal atoms eg:Mn2O7 Mn is tetrahedrally
surrounded by four oxygen atoms including one Mn-
O-Mn bridge. MnO4n- ions have tetrahedral structure.
As the oxidation number of a metal increases, ionic
character decreases(Fajan’s rule ) .In the higher oxides
have covalent properties and hence acidic character are
predominant.
Eg: V2O3>V2O4> V2O5(BASIC NATURE)
Mn2O7 is a covalent green oil. In aqueous it gives the
permanganic acid (HMnO4)
CrO3 Is acidic .it has a low bp. In aqueous state it gives
chromic acid (HMn O4)its potassium salt is given by the
formula KMnO4