D AND F BLOCK ELEMENT

Inroduction  Elements in which the last electron enters in the d–subshell of penultimate shell.
 The general electronic configuration (n – 1) d 1–10 ns1–2, where n is outermost shell.
 The d-block consisting of groups 3–12 occupies the large middle section of the periodic table
Transition  Element which has incompletely filled d-orbitals in its ground state or any one of its oxidation
Elements states.
 Zinc, cadmium and mercury of group 12 have full d 10 configuration in their ground state as well as
in their common oxidation states and hence, are not regarded as transition metals
Electronic Configuration of Element
3 Sc (21) Ti(22) V(23) Cr(24) Mn(25) Fe(26) Co(27) Ni(28) Cu(29) Zn(30)
d [Ar]3d1, [Ar]3d2, [Ar]3d3, [Ar]3d5, [Ar]3d5, [Ar]3d6, [Ar]3d7, [Ar]3d8, [Ar]3d10,4 [Ar]3d10,4
4s2 4s2 4s2 4s1 4s2 4s2 4s2 4s2 s1 s2
4 Y(39) Zr(40) Nb(41) Mo(42) Tc(43) Ru(44) Rh(45) Pd(46) Ag(47) Cd(48)
d [Kr]4d1, [Kr]4d2, [Kr]4d4, [Kr]4d5, [Kr]4d6, [Kr]4d7, [Kr]4d8, [Kr]4d10 [Kr]4d10,5 [Kr]4d10,5
5s2 5s2 5s1 5s1 5s1 5s1 5s1 ,5s0 s1 s2
5 La(57) Hf(72) Ta(73) W(74) Re(75) Os(76) Ir(77) Pt(78) Au(79) Hg(80)
d [Xe]5d1, [Xe]5d2, [Xe]5d3, [Xe]5d4, [Xe]5d5, [Xe]5d6, [Xe]5d7, [Xe]5d9, [Xe]5d10, [Xe]5d10,
6s2 6s2 6s2 6s2 6s2 6s2 6s2 6s1 6s1 6s2
6 Ac(89) Rf(104) Db(105) Sg(106) Bh(107) Hs(108) Mt(109) Ds(110) Rg(111) Cn(112)
d [Rn]6d1, [Rn]6d2, [Rn]6d3, [Rn]6d4, [Rn]6d5, [Rn]6d6, [Rn]6d7, [Rn]6d8, [Rn]6d10, [Rn]6d10,
7s2 7s2 7s2 7s2 7s2 7s2 7s2 7s2 7s1 7s2
(a)Atomicrad  The atomic radii of transition elements are smaller than
ii those of s-block elements and larger than those of p-
block elements in a period.
 In a transition series, as the atomic number increases, the
atomic radii first decreases till the middle, becomes
almost constant and then increases towards the end of the
period.
 The decrease in atomic radii in the beginning is due to
the increase in the effective nuclear charge with the
increase in atomic number.
 The atomic radii remain almost constant in the middle of
the series because, the increase in the number of
electrons in (n – 1) d–subshell, the screening effect of
these d-electrons on the outermost ns-electrons also
increases. This increased screening effect
counterbalances the effect of increased nuclear charge,
 Increase in atomic radii towards the end may be
attributed to the electron–electron repulsion. The pairing
of electrons in the d-orbitals of the penultimate shell
occurs only after the d–subshell is half filled. The
repulsive interactions between the paired electrons in d-
orbitals (of the penultimate shell) causes the expansion of
the electron cloud and thus, resulting in increased atomic
size.

Lattice
Structure

Ionic radii  The ionic radii of the transitional elements follow the same order as their atomic radii. In general,
the ionic radii decrease with increase in oxidation state.
Ionisation  The first ionisation enthalpies of transition elements are higher than those of s-block elements but
enthalpies lower than p-block elements
 Reason: The increase in ionisation enthalpy is due to increase in nuclear charge with increase in
 D AND F BLOCK ELEMENT

atomic number which tends to attract the electron cloud with greater force
 The irregular variations of first and second ionisation enthalpies in the first transition series is
mainly due to varying degree of stability of different 3d-configuration.
 For example, Cr has low first ionisation enthalpy because loss of one electron gives stable
3d5 configuration and Zn has very high first ionisation enthalpy because the electron has to be
removed from 4s-orbital of the stable 3d104s2 configuration.
 The first ionisation enthalpies of 5d-transition elements are higher than those of 3d and
4d elements. This is due to greater effective nuclear charge acting on the outer valence electrons
in these elements because of the ineffective shielding of the nucleus by 4f-electrons.
Melting and  Except zinc, cadmium and mercury all the other transition elements generally have high melting
boiling points and boiling points. This is due to higher no. of unpaired electron which lead to strong metallic
bond.
 In first transition series after chromium, the number of unpaired electrons decreases, hence the
melting point also decreases. Manganese possesses anomalous melting and boiling points because
it has stable 3d 54s2 configuration, i.e., electrons are held tightly by nucleus so that the
delocalisation is less and the metallic bond is much weaker than that of preceding element.
Oxidation
states

Standred It depends on three factor (Ionisation enthalpy,Enthalpy of atomisation and Hydration enthalpy)
Electrode
Potential

 The E0(M2+/M)value for copper is positive (+0.34) because

of high
 enthalpy of atomisation and Low hydration enthalpy
 It is interesting to note that the value of E0 for Mn,Ni and Zn
are more negative than expected from the trend.The stability
of half filled d subshell in Mn+2 and the completely filled d10
configuration in Zn+2 are releated to their E0 value.Whereas
E0 for Ni is related to the highest negative hydration enthalpy
 Cr+2 reducing and Mn+3 oxidising while both have d4
configuration because Cr+2 changes from d4 to d3and the
latter have half filled t2g stable electronic configuration
whereas Mn+3 changes to Mn+2 in which later have stable
half filled electronic configuration.

 The low value for Sc reflects the stability of Sc3+ which has
a noble gas configuration. The highest value for Zn is due to
the removal of an electron from the stable d10 configuration
of Zn. The comparatively high value for Mn shows that
Mn2+(d5) is particularly stable, whereas comparatively low
value for Fe shows the extra stability of Fe3+ (d5). The
comparatively low value for V is related to the stabilityof V2+
(half-filled t2glevel,
Magnetic
Properties

Formation Transtion metal are coloured due to d-d transtion.Zn+2 salt are white due to absence of unpaire
of Coloured electron.
Ions
 D AND F BLOCK ELEMENT

Formation This is due to the comparatively smaller sizes of the metal ions, their high ionic charges and the
of Complex availability of d orbitals for bond formation.
Compounds
Catalytic It is due to exhibit multiple oxidation states and to form complexes.they also provide large surface area
Properties for catalytic activity
Enthalpy of Transtion metal have very high enthalpy of atomisation due to having higher no of unpaired
atomisation electron which lead to strong metallic bond and higher enthalpy of atomisation.Zn,Cd,Hg have
lowest enthalpy of atomistion in their respective period due to completely filled d sub shell
Prepration of
K2Cr2O7

Chemical
Recation and
structure

Structure

Prepration of It is prepared by fusion of pyrolusite, MnO2, with KOH in the presence of an oxidising agent like
KMnO4 KNO3
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
3MnO42– + 4H+ →2MnO4– + MnO2 + 2H2O
Thermal 2KMnO4 → K2MnO4 + MnO2(s) + O2
Decompositio
n
Oxidation Basic Reaction:- KMnO4 + H2SO4 → K2SO4 + 2MnSO4 + 3H2O + 5[O]
Reaction in MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
acidic
Medium 10I– + 2MnO4– + 16H+ → 2Mn2+ + 5I2 + 8H2O
2MnO4−+10Fe2++16H+→2Mn2++10Fe3++8H2O
2MnO4−+5C2O42−+16H+→2Mn2++8H2O+10CO2

Oxidation 2KMnO4 + H2O → 2KOH + 2MnO2 + 3[O]

Reaction in MnO4– + 2H2O + 3e– → MnO2 + 4OH–
Basic
Medium 2MnO4– + I– + H2O → IO3– + 2MnO2 + 2OH–

F block  There are two series of f block element Lanthanide and Actinide
element  Inner Transition element because last electron enter in f sub shell which is inner to d sub shell
 general electronic configuration [Inert gas](n-2)f1-14 (n-1)d0-2 ns1-2
Electronic configuration of f block element
 D AND F BLOCK ELEMENT

Atomic and Atomic and Ionic size decrease from lanthanum to lutetium it is called lanthanoid contraction
Ionic Sizes Reason :-Poor Shielding of f subshell
 Consequance:- The almost identical radii of Zr (160 pm) and Hf (159 pm)
 They found together in nature and difficult to seperate
Oxidation  Most common oxidation state is +3
States  Ce+4 (Due to full filled stable electronic configuration) but in solution +3 oxidation state
is more stable so it tend to convrt in +3 oxidation state in solution so act as good oxidising
agent and can oxidise water but the reaction rate is very slow and hence Ce(IV) is a good
analytical reagent.
 Eu2+ is stable due to Due to half filled stable electronic configuration.it is a good reducing
agent because +3 oxidation state is more stable in solution so tends to convert in +3
oxidation state.
 Yb2+ is stable due to Due to full filled stable electronic configuration.act as reducing
agent.
 Tb+4 stable Due to full filled stable electronic configuration.Act as oxidising agent.

Chemical
Properties

Uses A well known alloy is mischmetall 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 and lighter flint. Mixed oxides of lanthanoids are employed as catalysts in
petroleum cracking.
Actinoid Gradual decrease in the size of atoms or M3+ ions across the series. This is called actinoid
Ionic Sizes contraction.Actinoid contraction is greater than Lanthanoid contraction due to poor shildinf of
5f subshell than 4f subshell
Oxidation The actinoids show in general +3 oxidation state.The exhibit oxidation state form +3 to +7
States because of less energy diffrance between 5f,4d and 6s subshell
 D AND F BLOCK ELEMENT

Comparasion
of properties
of
Lanthanoid
and actinoid

Use of d  Iron and steels are the most important construction materials
block element  TiO for the pigment industry and MnO2 for use in dry battery cells. battery industry also
requires Zn and Ni/Cd
 The ‘silver’ UK coins are a Cu/Ni alloy
 Essential catalysts in the chemical industry. V2O5 catalyses the oxidation of SO2 in the
manufacture of sulphuric acid. TiCl4 with A1(CH3)3 forms the basis of the Ziegler
catalysts used to manufacture polyethylene (polythene)
 Iron catalysts are used in the Haber process for the production of ammonia from N2/H2
mixtures.
 Nickel catalysts enable the hydrogenation of fats to proceed
 the Wacker process the oxidation of ethyne to ethanal is catalysed by PdCl2
 Nickel
 complexes are useful in the polymerisation of alkynes and other organic compounds such
as benzene
 The photographic industry relies on the special light-sensitive properties of AgBr