d- and f- block elements

1. Transition elements are those elements which have partially filled

penultimate d- subshell in their ground state or in any one of their commonly
occurring oxidation States.
Cu 3d10 4s1 Cu+2 3d9
Ag 4d10 5s1 Ag+2+ 4d9
Au 5d10 6s1 Au+3 5d8
2. Zn ,Cd and Hg are not considered as transition elements because these
elements do not have a partially filled (n-1)d- subshell either in the ground
state or in ions.
Zn 3d10 4s2 Zn+2 3d10
Cd 4d10 5s2 Cd+2 4d10
Hg 5d10 6s2 Hg+2 5d10
3. Electronic configuration: (n-1)d1-10 ns0,1 or 2
General trends in the chemistry of transition elements
1. Metallic character:
 All the transition elements are typical metals.
 They possess metallic lustre, high density, high melting and
boiling points, malleability and ductility, high tensile strength,
hardness ,brittleness .
 The properties of hardness and brittleness are associated with
covalent bonding.
 The presence of unpaired and unfilled d-orbitals favours
covalent bonding.
 Greater the number of unpaired d-electrons, greater the number
of covalent bonds and therefore, greater is the strength of these
bonds.
 Cr , Mo, and W are very hard metals as they have maximum
number of unpaired d- orbitals while Zn,Cd and Hg are soft in
nature as they do not have any unpaired d-orbitals.
2.Atomic radii
 The atomic radii of the transition metals lies between the s- and p-
block.
  The atomic radii of transition elements in a given series decrease with
increase in atomic number but this decrease becomes smaller after
midway.
 Atomic radii gradually decreases from Sc to Cr but from Cr to Cu it is
nearly the same
 Similar trend has been observed in the second and third transition
series
 The decrease in atomic radii in each series in the beginning is due to
an increase in nuclear charge from member to member.
 In the Midway onwards of the series both effective nuclear charge and
shielding effect become nearly equal and thus there is no change in
atomic radii in spite of the fact that atomic number increases
gradually.
 At the end of the series there is slight increase in the atomic radii due
to electron electron repulsions among (n -1)d- electrons. These
repulsions become predominant at the end of each series and thus size
increases.
 From top to bottom in each group the atomic radii increases as
expected but atomic radii of second and third transition series are
nearly the same due to lanthanoid contraction.
Due to inclusion of 14 elements between Lanthanum and Hafnium, there is
continuous decrease in size from Cerium to Lutetium (4f orbitals are
successively filled) and hence the size of Hafnium becomes nearly equal to
the size of Zirconium.
3. Melting and boiling points-
 Transition metals have very high melting and boiling points.
 In each series the melting points of these metals rise to a maximum value
and then decreases with increase in atomic number.
 Mn and Tc have abnormally low melting point
 Tungsten has the highest melting point 3683 K
 High melting point is due to the presence of unpaired electrons. Greater the
number of unpaired electrons more will be the inter atomic forces on
account of covalent bonding.
 Transition elements have high enthalpies of atomisation due to presence of
unpaired d electrons involving strong interatomic bonding.
  Zn ,Cd and Hg are soft metals i.e. their melting points are low due to
absence of unpaired d-electrons in them.
 Mn has abnormally low melting point probably due to stable electronic
configuration (3d5 -all orbitals are singly occupied, 4s2- fully filled).As the
3d- electrons are more tightly held by the nucleus the electrons are not
available for bonding resulting weaker metallic bonding in Mn in
comparison to Cr.
4. Ionization energies:
 The first ionization energies of majority of d- block elements lie in
between those of s- and p- block elements
 The ionization energies increase from left to right in each series however
the increase is not regular
 Ionization energies of Sc, Ti, V and Cr are fairly close to one another
similarly values of Fe, Ni and Cu are almost similar
 First ionization enthalpy of Zn is quite high due to its full filled 3d-
subshell.
 The second ionization energy values of Cr and Cu are exceptionally
higher than those of neighbouring elements
V<Cr<Mn and Ni < Cu<Zn
This is because of the electronic configuration of Cr+ which is 3d5 (half filled) and
Cu+ which is 3d10 (completely filled) that is an electron is to be removed from very
stable configuration.
 Third ionization energy of Mn is very high because the third electron is to be
removed from a stable configuration Mn+2 ,3d5 that is half filled 3d- subshell
 In vertical columns the first ionization energy decreases from first member
to second member as expected however third member has higher value than
second member.
This is due to lanthanide contraction that is the atomic radii of the elements of the
same group of the second and third transition series are nearly the same but atomic
numbers differ by 32. Thus the outer electrons are held very firmly and ionization
energy values are very high.
On account of this the members of 5d are Nobel under ordinary conditions that is
Pt,Au and Hg etc. are Noble metals.
 Significance of ionization energies:

 The thermodynamic stability of the compounds of the transition metals in

different oxidation states can be predicted on the values of of ionization
energies.
 Smaller the magnitude of ionisation energy of the metal, stable is the
compound in a particular oxidation State.
 Ni(II) compounds are more stable than Pt(II) compounds because the sum of
of first two I.E is less for nickel than Platinum.
 Pt(IV) compounds are more stable than Ni(IV) compounds as sum of first
four ionisation energies is less for platinum than nickel.
 K2[PtCl6] a well known stable compound of platinum where is the
corresponding compound of nickel does not exist
5.Coloured compounds:
 Most of the compounds of transition metals are coloured in the solid form or
in solution due to presence of incomplete (n-1)d subshell.
 Due to presence of unpaired electrons in d subshell and d- d transitions.
 The colour of [Ti(H2O)6]3+ ion is purple. It can be explained on d-d transition
in this complex ion. Ti has d1 configuration and this electron is present in
any one of the d orbitals of t 2g set. On absorption of yellow light this
electron is excited to eg set. When yellow portion of the white light is
absorbed the remaining part of the light purple is transmitted and the
solution having [Ti(H2O)6]3+ ions will appear purple.
 Salts of Zn+2, Cd+2 ,Hg+2 ,Cu+, Ag+2 ions are colourless as the excitation of of
electrons is not possible within d-orbitals.
 The transition metal ions which have completely empty d-orbitals such as
Sc+3 , Ti+4are also colourless.
6.Magnetic properties
 Larger the number of unpaired electrons in a substance, the greater is its
magnetic moment in Bohr magneton and larger shall be its paramagnetism.
 Most of the compounds of transition elements are paramagnetic in nature as
unpaired electrons in d-subshell are present.
 µ=√ n(n+2)
 n=number of unpaired electrons
 If n=0 substance will be diamagnetic.
 
7.Tendency to form complexes
 d -block elements have ability to form complex compounds because of three
reasons:
 Small size high nuclear charge and presence of vacant d- orbitals of
equivalent energy where the electrons donated by ligands can be
accommodated.
8.Catalytic properties
 Many of the d- block elements and their compounds act as catalyst in
various reactions because of their variable valencies, transition metals form
unstable intermediate compounds and provide a new path with lower
activation energy for the reaction.
9.Alloy formation
 Transition metals form a large number of alloys since d- block elements are
quite similar in atomic size, the atoms of one metal can substitute the atoms
of other metal in its crystal lattice.
10. Standard reduction potentials
 In a solution, stability of the compounds depends upon electrode potentials.
 Electrode potential value depends upon enthalpy of sublimation of the metal,
the ionization enthalpy and the hydration enthalpy.
 The smaller the value of total energy change for a particular oxidation state
in aq.solution, greater will be the stability of that oxidation State.
 The lower the electrode potential i.e. more negative the standard reduction
potential of the electrode more stable is the oxidation state of the transition
metal in an aqueous medium.
Trends in the(M2+/M) standard electrode potentials

Except copper, all other elements have negative reduction potential values i.e.
these elements except copper should have the capacity to liberate hydrogen
from dilute acids.
M + 2H+ M2+ + H2
 Chromium in spite of its high negative reduction potential value is an
unreactive metal as it does not liberate hydrogen due to a thin coating of
Cr2O3 on its surface
 Copper having positive E0 value does not liberate hydrogen from acids.
Copper has high enthalpy of atomization and low hydration energy.Hence
E0(Cu+2/Cu) is positive.
 Copper reacts only with oxidising acids such as HNO3 and concentrated
H2SO4
 The values of E0 for Mn, Zn and Ni are more negative than expected due to
extra stability of half filled d subshell(d5) in Mn+2 and completely filled (d10)
in Zn+2.

Trends in the(M3+/M2+) standard electrode potentials

 E0 value for Sc3+/Sc2+ is very low.Hence Sc3+ is stable due to noble gas
configuration.
 E0 value for Mn3+/Mn2+ is high hence Mn+2 is stable due to d5 configuration.
 11.Oxidation States
 The variable oxidation state of a transition metal is due to involvement of ns
and (n-1)d-electrons in bonding as the energy is of ns and (n-1)d- subshells
are nearly equal.
 Generally within the transition series the highest oxidation State increases
with increase of atomic number reaching to a maximum in the middle and
then starts decreasing
 In first transition series Mn shows the maximum oxidation state of +7
 The highest oxidation State shown by any transition metal is + 8 shown by
Ruthenium and Osmium
 Some of the transition metals form compounds in zero oxidation State for
exampleNi(CO)4.
 The relative stability of various oxidation states of a given element can be
explained on the basis of stability of d0 ,d5,d10 configuration.
Solve:
(i)Ti+4 is more stable than Ti+3
(ii)Mn+2 is more stable than Mn+3
(iii)Fe+3 is more stable than Fe+2
 The highest oxidation states are shown by transition metals when they
combine with most electronegative elements like oxygen and fluorine.
 Oxygen stabilizes the highest oxidation states more than F.
Due to its ability to form multiple bonds with the metal atoms.
For e.g. highest fluoride is MnF4 while highest oxide is Mn2O7.
 Oxidizing power in the series :VO2+ < Cr2O72- < MnO4- due to the
increasing stability of the species with lower oxidation state of metal to
which they are reduced.
 

12.Formation of interstitial compounds

 Small non metallic atoms such as as H,B,C,N are able to occupy interstitial
spaces of the lattices of the d- block elements to form combinations called as
interstitial compounds
Properties of interstitial compounds
These compounds differ in their physical properties such as density conductivity
etc. from their parent metals
These compounds possesses high melting points which are higher than those of
pure metals.
As a result of filling up of interstitial spaces the metals becomes rigid and hard
Steel is quite hard as it is an interstitial compound of iron and carbon.
LANTHANOIDS
 4f SERIES
 (n-2)f1-14 (n-1)d 0,1ns2
 4f1-145d0,16s2


 Oxidation states
common oxidation state =+3
+2,+4 also shown due to stable 4f0,4f7 or 4f14 cofigurations are achieved.
SOLVE
Ce and Tb shows +4 oxidation state.
Eu and Yb shows +2 oxidation state.
 Atomic and ionic radii(Lanthanide contraction)
In lanthanide series , there is regular decrease in the atomic as well as ionic
radii of trivalent ions as the atomic number increases from Ce to Lu.This
decrease in size of atoms and ions is called as Lanthanide contraction
Reason:
Due to poor shielding effect of 4f orbitals Zeff increases.
Consequences:
(I)The change in size is very small.Thus all the members of lanthanoid series
show similar chemical properties.Thus it is very difficult to separate these
elements in pure state.
(II)In vertical columns of transition elements,there is small change or no
change in size of atoms from second to third member.Thus,Zr-Hf,Nb-
Ta,Mo-W pairs possess similar properties.
(III)As the size of M+3 ions decrease from Ce+3 toLu+3 , the covalent nature
of M(OH)3 increases hence,basic strength decreases.