The d & f-Block Elements
Scandium (Z = 21) is a transition element
but Zinc (Z = 30) is not?
Ag (4d10) but it is a transition element?
Transition elements exhibit higher
enthalpies of atomisation?
Enthalpy of atomization of zinc is low
Having no variable oxidation states.
Largest number of oxidation states.
Why is Cr2+ reducing and Mn3+ oxidising
when both have d4 configuration.
The E0(M2+/M) value for copper is +ve
Oxidising power:VO2+ < Cr2O72– < MnO4–
Account for the irregular variation of IE
The E0 (M2+/M) values are not regular
E0 of Mn3+/Mn2+ is more positive than
that for Cr3+/Cr2+ or Fe3+/Fe2+? Explain.
Highest oxidation state of a metal
exhibited in its oxide or fluoride
Which is a stronger reducing agent Cr2+ or
Fe2+ and why ?
Magnetic moment of a divalent ion in
aqueous solution if its atomic number is
25.
Calculate the ‘spin only’ magnetic
moment of M2+ (aq) ion (Z = 27).
What is meant by ‘disproportionation’ of
an oxidation state? Give an example.
Explain why Cu+ ion is not stable in
aqueous solutions?
Lanthanoids to exhibit +4 oxidation state.
Actinoid contraction is greater than
lanthanoid contraction. Why?
Mn2+ more stable than Fe2+
Stable oxidation state for : 3d3, 3d5, 3d8
and 3d4?
Oxometal anions in which the metal
exhibits the oxidation state equal to its
group number.
What is lanthanoid contraction? What are
the consequences of lanthanoid
contraction?
Incompletely filled 3d orbitals in case of scandium
Zn & Zn2+ have completely filled d orbitals (3d10)
Ag has +2 oxidation state having incompletely filled d-orbital
Because of large number of unpaired electrons in their atoms
they have stronger interatomic interaction
In the formation of metallic bonds, no electrons from 3d-orbitals
are involved in case of zinc(3d10)
Scandium (Z = 21)
Mn(+2 to +7) Because it has largest number of unpaired
electrons
Cr2+ changes from d4 to d3(stable).On the other hand, the change
from Mn2+ to Mn3+ results in the half-filled (d5)
Due to its high ΔaH0 and low ΔhydH0)
This is due to the increasing stability of the lower species
Due to varying degree of stability of different 3d-configurations
Due to the irregular variation of IE , sublimation enthalpies
Much larger third IE of Mn (where the required change
is d5 to d4) is mainly responsible for this.
Small size and high electronegativity O or F can oxidise the
metal to its highest oxidation state.
Cr2+ is stronger reducing agent than Fe2+
Reason: d4 → d3 occurs in case of Cr2+ to Cr3+, d3 is stable
But d6 → d5 occurs in case of Fe2+ to Fe3+
d5 Configuration (five unpaired electrons). The magnetic
moment, μ is μ = √5(5+2) = 5.92BM
M2+ (aq) ion (Z = 27)  d7  3 unpaired electrons
μ = √3(3+2) = 3.87BM
When a particular oxidation state becomes less stable relative to
other oxidation states, one lower, one higher, it is said to
undergo disproportionation. For example, Mn (VI) becomes
unstable relative to Mn(VII) and Mn (IV) in acidic solution.
3 MnO4 2– + 4 H+ → 2 MnO4- + MnO2 + 2H2O
Cu+ in aqueous solution undergoes disproportionation,
2Cu+(aq) → Cu2+(aq) + Cu(s) The E0 is favourable for this
Cerium (Z = 58)
5f electrons themselves provide poor shielding from element to
element in the actinoid series.
It is because Mn2+ has 3d5 configuration which is stability.
3d3 (V): (+2), +3, +4, and +5 ; 3d5 (Cr): +3, +4, +6
3d5 (Mn): +2, +4, +6, +7 ; 3d8 (Co): +2, +3 (in complexes)
3d4 There is no d4 configuration in the ground state.
Vanadate VO3−, Chromate Cr2O4− , Permanganate
−
MnO4
Gradual decrease of atomic radii form La to Lu
Consequences : similar properties of 2nd and 3rd rows transition
elements
In what way is the electronic configuration
of the transition elements different
from that of the non transition elements?
Oxidation states of the lanthanoids?
Transition metals are paramagnetic
Enthalpies of atomisation of the transition
metals are high.
Transition metal form coloured
compounds
Transition metals and their many
compounds act as good catalyst.
How is the variability in oxidation states
of transition metals different from
that of the non transition metals? Illustrate
with examples.
Which of the following will be coloured
Ti3+,V3+,Cu+,Sc3+,Mn2+, Fe3+ & Co2+.
Of the d4 species, Cr2+ is reducing while
Mn(III) is strongly oxidising.
Co(II) is stable in aq sol but in the
presence of complexing reagents it easily
oxidised.
The d1 configuration is unstable in ions.
Which transition metal has +1 oxidation
state most frequently and why?
Calculate the number of unpaired electrons
in the following gaseous ions: Mn3+,
Cr3+, V3+ and Ti3+. Which one of these is
the most stable in aqueous solution?
The lowest oxide of transition metal is
basic, the highest is
amphoteric/acidic.
A transition metal exhibits highest
oxidation state in oxides
and fluorides.
The highest oxidation state is exhibited in
oxoanions of a metal.
Which is the last element in the series of
the actinoids? Write the electronic
configuration of this element. Comment
on the possible oxidation state of
this element.
In transition elements the last electron goes into penultimate
shell
+3 is the common oxidation lso +3, oxidation states +2 and +4
For having unpaired electrons
Due to strong metallic bonding
Due to incompletely filled d-orbital there is d-d electron
transition
Because they can adopt variable oxidation states to form
different intermediate
In transition elements the oxidation states vary by one
For example, for Mn it may vary as +2, +3, +4, +5, +6, +7.
In the nontransition elements the variation is selective, always
differing by 2, e.g. +2, +4, or +3, +5 or +4, +6 etc.
Except Sc3+, all others will be coloured due to incompletely
filled 3d-orbitals, will give rise to d-d transitions.
Cr2+ is reducing as it change from d4 to d3, the latter is more
stable Mn(III) to Mn(II) is from 3d4 to 3d5 again 3d5 is stable
Due to CFSE, which more than compensates the 3rd IE.
The hydration or lattice energy more than compensates the
ionisation enthalpy involved in removing electron from d1.
Cu, because with +1 oxidation state an stable configuration, 3d10
Unpaired electrons Mn3+ = 4, Cr3+ = 3, V3+ = 2, Ti3+ = 1. Most
stable Cr3+
In lowest oxidation state ionic bond is formed but in highest
oxidation state covalent bond is formed
O and F are strong oxidizing agents and can excite electrons
Oxygen is strong oxidizing agent
Lawrencium(103)
5f 146d17s2
+3