d - block elements

Transition elements:
 Belong to d-block, groups 3-12
 Elements in which the differentiating electron enters into the d-subshell
of the penultimate shell i.e. (n-1)d subshell
 All metals
 They are called ‘transition’ because they are present between the s and
p block elements. The d-block elements show a transitional behavior
between the highly electropositive s block and weakly electropositive p
block.
 Definition: those elements which possess incompletely filled d-orbitals in
their ground state or in their ions existing in chemically significant
oxidation states

Classification:

a) First transition or 3d series

Sc (21) – Zn (30)
4th period
b) Second transition or 4d series
Y (39) – Cd (48)
5th period
c) Third transition or 5d series
La (57), Hf (72) – Hg (80)
6th period
d) Fourth transition or 6d series
Ac (89), at.no 104 and above
7th period

Electronic configuration: (n-1)d1-10 ns1-2

Cr and Cu have exceptional electronic configuration. Their 3d subshell acquires
one electron from the 4s subshell to become half filled and completely filled
respectively. Thus these elements are of lower energy and hence more stable.

According to the definition…

Zn, Cd, Hg cannot be regarded as transition elements. Hence the end members
of all three transition series aren’t transition elements in the true sense as they
possess completely filled d-orbitals in their elementary form as well as
commonly existing ions. Infact, they do not exhibit general characteristic
properties of transition elements and behave differently than the elements of
d-block.

However, Cu which also has completely filled d-orbital is considered a

transitional element in it +2 oxidation state i.e. Cu2+.
General Properties:

1. Atomic radii

 Decrease with increase in atomic number, but decrease becomes

small midway and remains almost constant after middle.
This is due to increase in nuclear charge as atomic number
increases in the beginning, then shielding effect increases. Hence,
nuclear charge and shielding effect gets counterbalanced
towards the end.
(exception. Mn – 137)

 Near the end of each series, there is a slight increase.

This is due to expansion of electron cloud because of the
increase in nuclear charge by the repulsions between the added
electrons which predominate over the existing attractive forces.
eg. Zn – 137 (3d) , Cd -151 (4d), Hg -151 (5d)

 Increase on moving down the group for 3d series but remain

almost same for 4d and 5d series.
This is due to increase in no.of electronic shells. But in 4d and 5d
series there is no increase due to lanthanoid contraction.

2. Ionic radii

 Decrease with increase in oxidation state

 If same oxidation state, decrease with increase in nuclear charge

3. Metallic properties and lattice structures

 All except Zn, Cd, Hg, Mn exhibit all typical properties of metals
(lustre, malleability, conductivity, ductility, high tensile strength,
hardness etc)
 This is due to their low ionization enthalpies and presence of
vacant orbitals in outermost shells which favours formation of
metallic bonds between them.
Hardness is due to covalent bonds in them. Higher the no.of
unpaired electrons, more covalent bonds and harder the element.
Eg, Cr, Mo, W
Since they exhibit metallic properties and are hard, both metallic
as well as covalent bonding exist together in them.

4. Melting and Boiling points:

 First increases to a maximum n then decreases steadily

They very high points are due to the closely packed structures
and strong metallic bonds which also exhibit covalent character.
Hence it requires considerable amount of energy to break it.
The strength of the bonds depend on the no.of unpaired
electrons, therefore as atomic number increases the electrons
get paired and bond strength decreases. Thus the MP and BPs
reduce gradually.
However, elements with fully filled e.c have low MP and BP (Zn,
Cd, Hg).
Mn and Tc also have very low points due to their complicated
lattice structures.

5. Enthalpies of atomization:
  Generally exhibit high enthalpies. (4d, 5d > 3d)
This is due to presence of large no.of unpaired electrons in their
atoms which causes stronger interatomic attraction because of
which they have stronger bonding between atoms.

6. Ionization enthalpy:

 Higher than s-block and lower than p-block

This is because their atomic radii and nuclear charge lie between
the s and p block elements i.e. smaller atomic radii and higher
nuclear charge than s-block and reverse for p-block.

 1st I.E increases with increase in atomic number slowly and

irregularly
This is due to opposition of the effect of increased nuclear
charge by the screening effect.

 5d series I.E > 3d and 4d series I.E

This is due to lanthanoid contraction i.e. deshielding of electrons
in 4f orbitals.
7. Oxidation states:

 Most of them exhibit variable ox.states

This is because the energies of (n-1)d – orbitals and ns – orbitals
are very close and thus both are available for bond formation.
(lower ox.states – ns orbital
Higher ox.states – (n-1)d orbitals)

 Most common ox.state of 3d series: +2

(except Sc - +3)

 Bonds formed by +2 & +3 states are ionic whereas higher states

are covalent

 Relative stability of ox.state depends on standard electrode

potential i.e. more negative, greater stability in +n ox.state

 Low oxidation states such as 0 and +1 also exist.

Eg. Ni(CO)4 has zero ox.state.

 Maximum ox.state: 3d – Mn (+7)

4d – Ru (+8)
5d – Os (+8)

This is because maximum ox.state increases with atomic number.

Also the highest ox.states are found in Oxygen or Fluorine as they
are most electronegative.

8. Formation of coloured ions:

  Most transition elements form coloured ions
This is due to the d-d transitions taking place between the
splitted d-orbitals (refer co-ord. compounds chapter notes for
explanation)
Hence, the metal ions with empty or fully filled d-orbitals are
colourless.
Eg. Sc3+, Ti4+, Zn2+, Cu+

9. Magnetic properties:

 Paramagnetic: attracted by magnetic field since it contains one or

more paired electrons
 Ferromagnetism: special case of paramagnetism in which a
substance acquires permanent magnetic moment
 Diamagnetic: repelled by magnetic field since it contains all
electrons paired

 Most of them show paramagnetic behavior

This is due to the presence of unpaired (n-1) d- orbitals. As the
no.of unpaired electrons increase from 1-5 on moving from left to
right, the paramagnetism increases. Thus maximum
paramagnetism is in the middle. On moving further, paramagnetic
nature decreases.

 Magnetic moment is expressed in Bohr magnetons.

Formula: √n(n+2)

10.Catalytic properties:
  Finely divided Ni – hydrogenation reactions (of oils for
manufacture of vegetable ghee)

 Finely divided Pt – contact process, ostwald’s process

 Finely divided Fe – haber’s process

 V2O5 – contact process

 TiCl4 – manufacture of high density polythene

Their catalytic activity is due to presence of vacant d-orbitals, variable

valencies and ox.states, tendency to form complexes. Because of these
properties, they form unstable reaction intermediates in certain reactions
which provide an alternate path involving lower activation energy. This
causes an increase in rate of reaction and catalyses the process.

Or in other cases, they provide a large surface area with free valencies
through which reactant molecules get adsorbed on their surface.

11.Formation of complexes:

 They form a large number of complex compunds

This is due to their small size, high nuclear charge and vacant d-
orbitals.

12.Formation of interstitial compounds:

Interstitial compounds are those which are formed when small atoms
like H, C or N get trapped inside the crystal lattices of metals.

These compounds are:

 Hard and rigid
  MP is high
 Exhibit conductivity
 Chemically inert

13.Alloy formation:

 They form a number of alloys which are hard with high MPs.
This is due to their small, very similar atomic sizes which enables
them to easily replace one metal by another from its lattice to
form a solid solution.

14.Formation & Nature of oxides:

 General formulae of 3d series:

MO, M2O3, M3O4, MO2, M2O5, MO3
  Oxides formed in Lower ox.states – basic, Intermediate ox.states
are amphoteric and Higher ox.states – acidic
 Basic and amphoteric oxides dissolve in non-oxidising acids to
form hexaaqua ions
 Some oxides dissolve in acids or bases to give oxometallic salts.

15.Halides

 Order of reactivity: F>Cl>Br>I

 Reaction requires high temperature for initiation since it involves
high temperature

 Halides of higher ox.states exhibit greater tendency for hydrolysis

 Fluorides are ionic whereas ionic nature decreases with increase
in atomic mass of halogen for chlorides, bromides and iodides.

16.Sulphides

 Reaction by direct combination of sulphur with metal or action of

H2S and Na2S.

 Generally formed in lower ox.states since sulphur is a good

oxidizing agent.
 Usualy coloured or black
 Insoluble in water

LEARN POTASSIUM DICHROMATE AND POTASSIUM

PERMANGANATE FROM BOOK,

PAGES 478-483 (PREP, MARKED PROPERTIES, USES,

STRUCTURE ONLY)