Chapter:-8

The d-and f-Block Elements

1.The elements of periodic table belonging to group 3 to 12 are known as d Block elements.
The general electronic configuration of these elements is (n -1)d1-10ns1-2
2.d-Block elements are collectively known as Transition Elements because properties of these
elements vary in between s-Block and p-Block elements.
3.Group 12 elements i.e. Zn , Cd, Hg have completely filled (n-1) d-orbital in atomic & ionic state &
thus these elements are not considered as Transition Elements.
4.The atomic radii decreases from group 3 to 6 (i.e. Sc to Cr) because of increase in effective
nuclear charge gradually.
5.The atomic radii of group 7,8 9 &10 elements (i.e. Fe,Co,Ni) is almost same because pairing of
electrons take place in (n-1)d orbital causing repulsion i.e. shielding of (n-1)d orbital.
6.The transition elements show variable oxidation state due to small energy difference between
(n-1)d &ns orbital as a result both (n-1)d &ns electrons take part in bond formation.
7.Transition elements have high enthalpy of atomization/ sublimation Because of large number
of unpaired electrons in their atoms, they have stronger interatomic interaction and hence
strong metallic bonding is present between atoms.
8.Most of transition elements are paramagnetic due to presence of unpaired electrons in (n-1)
d orbital.
9.Most of transition elements are used as catalyst. It is due to (i) partially filled (n-1) d orbital (ii)
Variable oxidation state (iii) Ability to change oxidation state frequently.
10.Most of transition elements form coloured compounds due to presence of unpaired electrons
in (n-1) d orbital & thus they can undergo d-d transition.
11.Most of transition elements form complex compounds due to (i) small size (ii) high charge (iii)
presence of vacant d-orbital of suitable energy.
12.Transition elements have lower value of Reduction Potential due to high ionization potential,
high heat of sublimation & low enthalpy of hydration.
13.Transition elements form interstitial compounds because of
interstitial voids is similar to size of non- metals C, N, O, H.
14. Transition elements form alloys due to similar ionic radii.
POTASSIUM DICHROMATE: - Prepration

Effect of PH

Important chemical reaction:-

Prepration of KMnO4
Important chemical reaction:-
(a)Acidic Medium Structure of MnO4-MnO42-

(b)Alkaline medium

Inner Transition Elements

 The f-block elements are known as inner transition elements because they involve the filling for inner sub-shells (4f
or 5f)
 f-Block elements: The elements constituting the f -block are those in which the 4 f and 5 f orbitals are
progressively filled in the latter two long periods.
A. Lanthanides:
 It consists of elements that follows lanthanum and involve the filling of 4 subshell
Electronic Configuration : [Xe] 4f1-14 5d° 6s2 or [Xe] 4f1-14 5d1 6s2 Oxidation State: +3, +2 and +4.
Colouration:- Many of the lanthanides ions are coloured in solid state as well as in solutions. The
colour is due to the f-f transition since they have partly filled f-orbitals.
Lanthanide Contraction: The steady decrease in the size of lanthanide ions (M3+) with the increase in atomic no. is called
lanthanide contraction.
 Causes: As we move along the lanthanoid series, the atomic number gradually increases by one or we can say
number of electrons and protons increases.
 Addition of electrons to the same shell increases the effective nuclear charge. Increase in atomic number also
increases the number of electrons in the 4f orbital having poor shielding effect due to which the effective nucleus
the outer electrons also increases.
Consequence of Lanthanide Contraction:
(i) Covalent character of cations increase. hence basic character of Hydroxide decreases.
(ii) The electronegativity of trivalent ions increases slightly.
(iii) There is decrease in basic strength of oxides and hydroxides from La to Lu.
(iv) There is small increase in standard electrode potential values.
(v) Sizes of Zr and Hf; Nb and Ta are similar,
b. Actinides:
It consists of elements that follow Actinium and involve the filling of 5f subshell.

Actinoids contraction :-The ionic radii gradually decrease across the series due to the poor screening effect of
nuclear charge exerted by the f electrons. This is called Actinoids contraction
7s2 is stable configuration for actinides. Show +3,+4,+5,+6 & +7 oxidation state.
Mischmetall - It is a well known alloy which consists of a lanthanoid metal (~ 95%) and iron (~ 5%) and traces of S,
C, Ca and Al. A good deal of mischmetall is used in Mg-based alloy to produce bullets, shell
 Reasoning Based Questions (d & f – block elements)
1 d-block elements are called transition metals
Because the position of d-block is in between most electropositive metals in s-block and the electronegative
elements in p-block
2 Zn, Cd & Hg are not treated as true transition elements
Because they have completely filled d-orbitals in their atomic as well as stable ionic state
3 Cu & Ag are transition metals although they have completely filled d-orbitals
Cu2+ & Ag2+ have (n-1)d9 4s0 configuration.
4 Some d-block elements have irregular(exceptional) electronic configuration
Due to very small energy difference between (n-1)d & ns sub-shell
5 Atomic size does not change appreciably in a row of transition metals
Along the rows nuclear charge increases but the penultimate d-sub shell has poor shielding effect so atomic
and ionic size remain almost same .
6 In d-block horizontal similarities in properties are observed
Along the rows nuclear charge increases but the penultimate d-sub shell has poor shielding effect so atomic
and ionic size remain almost same hence similar properties.
7 Transition elements have variable oxidation states
Due to very small energy difference between (n-1)d & ns sub-shell electrons from both the sub-shell take
part in bonding
8 Transition metals have high melting and boiling points
A large number of unpaired electrons take part in bonding so they have very strong metallic bonds and hence
high m.pt & b.pt
9 Transition metals have high enthalpy of atomization
A large number of unpaired electrons take part in bonding so they have very strong metallic bonds and hence
high enthalpy of atomization
10 Transition metals show catalytic properties
Because they have variable oxidation states and hence can form different intermediates. They also provide
large surface area.
11 Transition metals and their salts are generally colored
Because they have partially filled d-sub shell and hence d-d electron transition takes place when they absorb
radiations from visible region and transmit complementary colors.
12 Transition metals form coordination compounds
Because they have large number of vacant orbitals in (n-1)d, ns, np & ns sub shells so they can accept electron
pairs from ligands
13 Transition metals form alloys
They have comparable atomic size and hence can be mixed uniformly
14 Transition metals form interstial compounds
Because small atoms like H, C, N etc can be entrapped in their metallic crystals
15 Zn, Cd & Hg have low boiling points and Hg is liquid.
They have full filled 3d-orbitals and no electorns from d-orbitals are taking part in metallic bonding so they
have weak metallic bonding. Due to larger atomic size Hg is liquid
16 Transition metals and many of their compounds show paramagnetic behaviour
Because they have unpaired electrons
17 d1 configuration is very unstable in ions
Because by loosing one electron they get extra stability
18 Cr 2+ is strongly reducing while Mn3+ is strongly oxidizing
E0 value for Cr3+/Cr2+ is negative but that of Mn3+/Mn2+ is positive so Cr2+ can loose electron to form Cr3+ while
Mn3+ accepts electron to form Mn2+. In case of Cr d4 to d3 occurs for Cr2+ to Cr3+. d3 is stable.
19 Cobalt(II) is stable in aqueous solution but in presence of complexing agents it gets oxidized
Oxidation state changes from +2 to +3 because in presence of ligands d-orbitals split up into t2g and eg having
0
the stable configuration t2g6 eg .
20 Mn2+ compounds are more stable than Fe2+
Mn2+ has half filled d-orbitals i.e 3d5 4s0 configuration
21 Fe3+ is stable
Due to half filled configuration i.e 3d5 4s0 configuration
22 The lowest oxides of transition metals is basic , the highest is amphoteric/acidic
 Because acidic characters ∞ oxidation state
23 Transition metals exhibit highest oxidation states in oxides and fluorides
Because of small size and high electronegativity oxygen or fluorine can oxidise the metal to its highest
oxidation state.
24 The highest oxidation state of transition metal is exhibited in oxoanions
Due to high EN of oxygen and high oxidizing property
25 For the first row transition metals the Eo values are:
Eo V Cr Mn Fe Co Ni Cu
(M2+/M) –1.18 – 0.91 –1.18 – 0.44 – 0.28 – 0.25 +0.34
Explain the irregularity in the above values.
The E0 (M2+/M) values are not regular which can be explained from the irregular variation of ionisation
enthalpies (Δ i H 1 + Δ i H 2) and also the sublimation enthalpies which are relatively much less for manganese
and vanadium.
26 Why is the E0 value for the Mn3+/Mn2+ couple much more positive than that for Cr3+/Cr2+ or Fe3+/Fe2+?
Explain.
Much larger third ionisation energy of Mn (where the required change is d5 to d4) is mainly responsible for this.
This also explains why the +3 state of Mn is of little importance.
27 Oxidising power increases in the series VO 2 + < Cr2O7 2– < MnO4 –
This is due to the increasing stability of the lower species to which they are reduced.
28 The ionization enthalpies (first and second) in the first series of the transition elements are irregular
Irregular variation of ionisation enthalpies is mainly attributed to varying degree of stability of different 3d-
configurations (e.g., d0, d5, d10 are exceptionally stable).
29 The E0(M2+/M) value for copper is positive (+0.34V).
Due to its its high enthalpy of atomization and low hydration energy
30 Mn exhibits largest number of oxidation states in 3d series.
Manganese (Z = 25), as its atom has the maximum number of unpaired electrons.
31 In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomization of zinc is the lowest.
In the formation of metallic bonds, no electrons from 3d-orbitals are involved in case of zinc, while in all other
metals of the 3d series, electrons from the d-orbitals are always involved in the formation of metallic bonds.
32 Silver atom has completely filled d orbitals (4d10) in its ground state but it is a transition element.
Silver can exhibit +2 oxidation state wherein it will have incompletely filled d-orbitals (4d9).
33 Zr has similar size to that of Hf
Due to lanthanoid contraction.
34 Actinoid contraction is greater from element to element than lanthanoid contraction.
The 5f electrons are more effectively shielded from nuclear charge. In other words the 5f electrons themselves
provide poor shielding from element to element in the series.
35 Explain why Cu+ ion is not stable in aqueous solutions?
Cu+ in aqueous solution underoes disproportionation, i.e.,
2Cu+(aq) → Cu2+(aq) + Cu(s) The E0 value for this is favourable.
36 2nd and corresponding third row transition elements have similar properties
Due to lanthanoid contraction they have similar size
37 Ce4+ is a strong oxidant
It can be converted into the most common oxidation state Ce3+
38 Eu2+ is a strong reducing agent.
It can be converted into the most common oxidation state Eu3+
39 Ce is the only lanthanoids exhibits +4 oxidation state
Ce4+ has noble gas configuration (Xe)