The d & f-Block Elements

Scandium (Z = 21) is a transition element Incompletely filled 3d orbitals in case of scandium

but Zinc (Z = 30) is not? Zn & Zn2+ have completely filled d orbitals (3d10)
Ag (4d10) but it is a transition element? Ag has +2 oxidation state having incompletely filled d-orbital
Transition elements exhibit higher Because of large number of unpaired electrons in their atoms they
enthalpies of atomisation? have stronger interatomic interaction
Enthalpy of atomization of zinc is low In the formation of metallic bonds, no electrons from 3d-orbitals
are involved in case of zinc(3d10)
Having no variable oxidation states. Scandium (Z = 21)
Largest number of oxidation states. Mn(+2 to +7) Because it has largest number of unpaired electrons
Why is Cr2+ reducing and Mn3+ oxidising Cr2+ changes from d4 to d3(stable).On the other hand, the change
when both have d4 configuration. from Mn2+ to Mn3+ results in the half-filled (d5)
0 2+
The E (M /M) value for copper is +ve Due to its high ΔaH0 and low ΔhydH0)
Oxidising power:VO2+ < Cr2O72– < MnO4– This is due to the increasing stability of the lower species
Account for the irregular variation of IE Due to varying degree of stability of different 3d-configurations
The E0 (M2+/M) values are not regular Due to the irregular variation of IE , sublimation enthalpies
0 3+ 2+
E of Mn /Mn is more positive than that Much larger third IE of Mn (where the required change
for Cr3+/Cr2+ or Fe3+/Fe2+? Explain. is d5 to d4) is mainly responsible for this.
Highest oxidation state of a metal exhibited Small size and high electronegativity O or F can oxidise the metal
in its oxide or fluoride to its highest oxidation state.
2+
Which is a stronger reducing agent Cr or Cr2+ is stronger reducing agent than Fe2+
2+
Fe and why ? Reason: d4 → d3 occurs in case of Cr2+ to Cr3+, d3 is stable
But d6 → d5 occurs in case of Fe2+ to Fe3+
Magnetic moment of a divalent ion in d5 Configuration (five unpaired electrons). The magnetic moment,
aqueous solution if its atomic number is 25. μ is μ = √5(5+2) = 5.92BM
Calculate the ‘spin only’ magnetic moment M2+ (aq) ion (Z = 27)  d7  3 unpaired electrons
of M2+ (aq) ion (Z = 27). μ = √3(3+2) = 3.87BM
What is meant by ‘disproportionation’ of When a particular oxidation state becomes less stable relative to
an oxidation state? Give an example. 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
Explain why Cu+ ion is not stable in Cu+ in aqueous solution undergoes disproportionation,
aqueous solutions? 2Cu+(aq) → Cu2+(aq) + Cu(s) The E0 is favourable for this
Lanthanoids to exhibit +4 oxidation state. Cerium (Z = 58)
Actinoid contraction is greater than 5f electrons themselves provide poor shielding from element to
lanthanoid contraction. Why? element in the actinoid series.
Mn2+ more stable than Fe2+ It is because Mn2+ has 3d5 configuration which is stability.
Stable oxidation state for : 3d3, 3d5, 3d8 and 3d3 (V): (+2), +3, +4, and +5 ; 3d5 (Cr): +3, +4, +6
3d4? 3d5 (Mn): +2, +4, +6, +7 ; 3d8 (Co): +2, +3 (in complexes)
3d4 There is no d4 configuration in the ground state.
Oxometal anions in which the metal Vanadate VO3−, Chromate Cr2O4− , Permanganate MnO4−
exhibits the oxidation state equal to its
group number.
What is lanthanoid contraction? What are Gradual decrease of atomic radii form La to Lu
the consequences of lanthanoid Consequences : similar properties of 2nd and 3rd rows transition
contraction? 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