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(ii) Second transitions series or 4d series: This series consists of 10 elements of the 5th
period for which the filling of 4d sublevel takes place.
Atomic number Element Electronic configuration
39 Y [Kr] 4d15s2
40 Zr 4d25s2
41 Nb 4d45s1
42 Mo 4d55s1
43 Tc 4d55s2
44 Ru 4d75s1
45 Rh 4d85s1
46 Pd 4d105s0
47 Ag 4d105s1
48 Cd 4d105s2
Second (4d) Transition Series (Y–Cd)
(iii) Third transition series or 5d series: This series consist of 10 elements of 6 th period
for which the filling of 5d sublevel takes place
Atomic number Element Electronic configuration
57 La [Xe] 5d16s2
72 Hf 5d26s2
Dr. Brijesh Dabhi
73 Ta 5d36s2
74 W 5d46s2
75 Re 5d56s2
76 Os 5d66s2
77 Ir 5d76s2
78 Pt 5d96s1
79 Au 5d106s1
80 Hg 5d106s2
Third (5d) Transition Series (La–Hg)
(iv) Fourth transition series of 6d series: This series is incomplete and corresponds to
the filling of 6d sublevel.
Atomic number Element Electronic configuration
89 Ac [Rn] 6d17s2
104 Rf 6d27s2
105 Ha 6d37s2
106 Sg 6d47s2
107 Ns 6d57s2
108 Hs 6d67s2
109 Mt 6d77s2
110 Ds 6d87s2
111 Rg 6d107s2
112 Wb 6d107s2
Fourth (6d) Transition Series
The electronic configuration of transition elements, as shown above, has the following
characteristics
(i) An inner core of electrons with noble gas configuration
(ii) Most of the elements in the four series have two electrons in the outermost s orbital.
Some of the members like Cr, Cu, Nb, Mo, Ag, Pt, Ru etc., have only one electron in
ns orbital whereas Pd has no electron in the ns orbital.
(iii) (n–1) d orbitals are progressively filled-up with electrons.
Thus, it can be easily seen that the classification of d-block elements is primarily
based on the electronic configuration of their atoms.
(ii) At the end of the series, there is slight increase in the atomic radii.
Ionic radii
The trend followed by ionic radii is the same as that of atomic radii. The ionic radii of
transition metals are different in different oxidation states. As the oxidation state
increases, the effective positive charge on the nucleus increases. This increase in the
effective nuclear charge decreases the ionic radius. Thus, the ionic size of M 3+ cations
is smaller than those of M2+ cations. If oxidation state is same, ionic radii for metal
cations decrease with increase in atomic number.
The ionic radii of the transition metals are smaller than those of the representative
elements, belonging to the same period. This is because of the poor shielding (or
screening) effect of the d-orbitals. The d-orbitals are more diffused as compared to s
and p-orbitals and hence cannot shield the outermost electrons as effectively as s or p-
orbitals. This results in a greater attraction for the outermost electrons towards the
nucleus and thus decreasing the ionic radii.
Metallic Character
Transition elements exhibit all the characteristic properties of metals. They are hard,
lustrous, malleable and ductile. Transition elements have high melting and boiling
points, high thermal and electrical conductivity, and high tensile strength as metals.
The metallic character of transition elements is due to their relatively low ionization
energies and large number of vacant d-orbitals in the outermost shell. The availability
of vacant d-orbitals in the outermost shell gives rise to the possibility of excitation of
electrons to these orbitals thus explaining the high thermal and electrical conductivity.
The unpaired electrons present in d-orbitals of the transition elements interact to form
metallic bonds. Thus, the strength of the metallic bond and consequently metallic
character depend upon the number of unpaired d-electrons. If the number of unpaired
d-electrons is more, the overlapping of such electrons will be more, leading to
stronger bonding. Cr, Mn and W have maximum number of unpaired d-electrons and
thus behave as hard metals while elements like Zn, Cd and Hg are not very hard
metals due to absence of unpaired d-electrons.
The elements like Zn, Cd and Hg are soft and have low melting points because of the
absence of unpaired d-electrons.
Ionization Energies
(i) The first ionization energies of d-block elements lie between s-block and p-block
elements. The ionization energy gradually increases with increase in atomic number
across a series. The increase in ionization energy is due to the increase in nuclear
charge with increasing atomic number. As the nuclear charge progressively increases
it becomes more and more difficult to remove the outermost electron from the element
and hence ionization energy increase
In a given series, the difference in the ionization energy between any two successive
d-block elements is very less as compared to the difference between successive s-
block and p-block elements. This is because in transition elements, the electrons are
being filled in (n–1) d-subshell (penultimate) which screens the outermost ns
electrons from the nucleus. This screening effect opposes the effect of increased
nuclear charge and thus little difference in ionization energy is seen for successive
elements.
(ii) The first ionization energies of 5d elements are higher as compared to those of 3d and
4d elements. It should be noted that in 5d elements, 4f subshell is filled completely.
The electrons in 4f subshell have a very weak shielding effect owing to the highly
diffused nature of f-orbitals. This shielding result in greater effective nuclear charge
(iii) The magnitude of ionization energies of transition metals reflects the thermodynamic
stability of their compounds. A small value of ionization energy means that the
formation of ion from the metal atom is easy and consequently compound formation
is favoured. Thus, smaller the ionization energy of the metal, more stable is its
compound. The significance of the value of ionization energies can be seen from the
following table.
Element (IE1 + IE2) MJ mol–1 (IE3 + IE4) MJ mol–1 Total IE MJ mol–1
Ni 2.49 8.80 11.29
Pt 2.66 6.70 9.36
The sum of the first and second ionization energies (IE 1 + IE2) is less for Ni.
This means that Ni (II) compounds are easily formed as compared to Pt (II)
compounds. Thus, Ni (II) compounds are more stable than Pt (II) compounds
D H
M(S) ��� sub �
� M(g)
Now, the sum of the third and fourth ionization energies (IE 3 + IE4) is less for
Pt. Thus, Pt (IV) is more easily attained while more energy would be required for
obtaining Ni (IV) ion. Hence, Pt (IV) compounds are more stable than Ni (IV)
compounds. For example, K2PtCl6 (Pt in IV oxidation state) is a well-known
compound while corresponding nickel salt is not known.
Electrode potential
The stability of compounds in solution does not depend upon ionization energy solely.
It also depends upon factors such as energy of sublimation of the metal and the
hydration energy. All these factors can be chemically depicted as follows:
DH
M(s) ���
sub�
� M(g)
Where, DH sub is the enthalpy of sublimation
IE
M(g) �� � M + (g) + e -
Where, IE is the ionization energy
DH
hyd
M + (g) ���� � M + (aq)
Catalytic properties
Many transition metals and their compounds can be used as effective catalysts in
various processes. These metals or their compounds provide catalytic effect simply
because they can attain variable oxidation states. This fact is made clearer in the
following points.
(i) Transition elements have unpaired d-electrons and can have variable oxidation states.
This property of showing multiple oxidation state helps them to absorb an electron or
lose an electron to attain low and high oxidation states respectively. Thus, transition
Coloured Ions
Most of the transition metal compounds are coloured both in the solid state and in
aqueous solution. They differ from s and p-block elements in this respect. Colour is
always associated with adsorption of light of a particular wavelength in visible region.
Electrons absorb energy and get promoted to higher energy level. This transition of
electrons is responsible for coloured ions. The transition elements have incomplete d-
orbitals. Though these d-orbitals are degenerate, i.e. have the same energy, for an
isolated ion, but in compounds these orbitals are affected by the combining atoms or
molecules and lose their degeneracy. This loss of degeneracy makes transition of
electron from one d-orbital to another d-orbital which is otherwise forbidden. Such an
effect on the central metal by incoming ligands is called crystal field effect.
The difference in energy for these d-orbitals is very less and the radiation of light
corresponding to such small amount of energy comes within visible region of light.
Colours of some of the hydrated metal ions are given in the table below:
Oxidation state of the hydrated ions Colour
Sc(III), Ti (IV) Colorless
Ti (III) Purple
V(III) Green
V(II), Cr (III) Violet
Mn (III) Violet
Fe (III) Yellow
Mn (II) Pink
Fe (II) Green
CO (II) Pink
Ni (II) Green
Cu (II) Blue
Zn (II), Cu (I) Colourless
Sc (III) and Ti (IV) are colourless because they have empty d-orbitals and hence no
electron for promotion to higher level. Cu (I) and Zn (II) are also colourless since they
have completely filled d-orbitals leaving no empty orbital for promotion of electrons.
Magnetic Properties
Transition metal ions and their compounds show magnetic behaviour due to the
presence of unpaired electrons in (n–1) d-orbitals. A spinning electron has spin as well
as orbital motion. Thus a spinning electron revolving around the nucleus creates a
magnetic field around itself. In other words, an electron behaves as a micro-magnet
having a definite value of magnetic moment. When a substance is placed in an
external magnetic field, the magnetic moment of the electron either aligns or opposes
the external magnetic field. If the magnetic moment aligns itself than the substance
experiences attractive influence in a magnetic field and are said to show paramagnetic
character. The greater the number of unpaired electrons, greater will be the resulting
Halides:
(i) Transition elements react slowly with halogens at high temperature to form halides.
(ii) The order of reactivity of the halogen in the formation of halides of transition metal is
F > Cl > Br > I.
(iii) Transition metals attain their highest oxidation state in their fluorides owing to the
electronegativity of fluorine.
(iv) Halides of transition metals in higher oxidation state are not stable to hydrolysis and
are readily hydrolyzed to oxides. For example, TiCl4 reacts with water to give TiO2.
TiCl4 + 2H 2 O ��� TiO 2 + 4HCl
(v) Fluorides of transition metals are ionic in nature. The ionic character of halides
decrease with increase in the mass of the halogen. For example, CuF 2 is ionic whereas
CuCl2 and CuBr2 are covalent.
Sulphides:
(i) Sulphides of the transition metals can either be obtained by direct combination of
metals with sulphur or by the action of H2S or Na2S on the salts of these metals.
(ii) Transition metals are generally found in lower oxidation states in their Sulphides
since sulphur is not a good oxidizing agent.
(iii) The sulphides of transition metals are usually dark coloured or black and are insoluble
in water.
Group 5 elements:
(i) Group 5 consists of vanadium, niobium and tantalum.
(ii) The most stable oxidation state of this group is +5. Vanadium also shows oxidation
states of +3 and +4 in its compounds.
(iii) Niobium and tantalum have similar chemical properties.
(iv) Niobium alloys are used in jet engines.
(v) Tantalum is resistant to corrosion and hence it is used in analytical weights and in
instruments used in surgery of veins.
Groups 7 elements:
(i) Group 7 consists of manganese, technetium and rhenium.
(ii) The common oxidation states of manganese, the most important element of this group
are +2, +4 and +7.
(iii) Technetium occurs in traces in nature and is radioactive. Rhenium is also rare.
(iv) Manganese along with chromium is used in the manufacture of steel.
(v) Manganese dioxide is used as a catalyst while potassium permanganate is a very
common laboratory reagent.
(vi) Rhenium is used in electronic filaments, flash bulbs and high temperature
thermocouples.
Group 11 elements:
(i) Group 11 consists of copper, silver and gold. These metals are known as coinage
metals.
(ii) The most stable oxidation state for copper is +2 whereas for silver and gold +1 is the
most stable oxidation state.
(iii) These elements form alloys with many metals.
(iv) Silver and gold are used in jewellery.
Potassium Dichromate
Preparation of Potassium Dichromate:
Potassium dichromate is prepared from chromates which in turn are prepared from
iron chromate, FeCr2O4. The various steps involved are as follows:
It liberates I2 from KI
K 2 Cr2 O7 + 4H 2SO 4 ��� K 2SO 4 + Cr2 (SO 4 )3 + 4H 2O + 3[O]
6KI + 3H 2SO 4 + 3[O] �� � 3K 2SO 4 + 3I 2 + 3H 2O
_______________________________________________________
K 2 Cr2 O7 + 7H 2SO 4 + 6KI ��
� 4K 2SO 4 + Cr2 (SO 4 )3 + 3I 2 + 7H 2O
or Cr2 O72- + 14H + + 6I - ��
� 2Cr 3+ + 3I 2 + 7H 2 O
CH 2CH 2 OH + [O] ��
� CH 3CHO + H 2O
Etheyl alcohol Acetaldehyde
CH3CHO + [O] �� � CH 3COOH
Acetaldehyde Acetic acid
It oxidizes sulphides to sulphates
K 2 Cr2 O7 + 4H 2SO 4 ��� K 2SO 4 + Cr2 (SO 4 )3 + 4H 2 O + 3[O]
{Na 2SO3 + [O] �� � Na 2SO 4 } �3
_________________________________________________
K 2 Cr2 O7 + 4H 2SO 4 + 3Na 2SO3 ��
� K 2SO + Cr2 (SO 4 )3 + 4H 2O + 3Na 2SO 4
or Cr2 O 72- + 8H + + 2SO32- ��
� 2Cr +3 + 3SO24- + 7H 2 O
NOTE
NOTE
This test is used in detection of chloride ions in qualitative analysis.
At cathode: 2H + + 2e- �� � H2 �
Oxidation by potassium permanganate in neutral solution:
(i) It oxidizes hot manganese sulphate to manganese dioxide
2KMnO 4 + H 2 O �� � 2KOH + 2MnO 2 + 3[O]
3MnSO 4 + 3H 2 O + 3[O] �� � 3MnO 2 + 3H 2SO 4
2KOH + H 2SO 4 �� � K 2SO 4 + 2H 2 O
__________________________________________________
3MnSO 4 + 2KMnO 4 + 2H 2 O �� � 5MnO 2 + K 2SO4 + 2H 2SO 4
Uses:
(i) Potassium permanganate is used in volumetric analysis for estimation of ferrous salts,
oxalates, iodide and hydrogen peroxide.
(ii) It is used as a strong oxidizing agent in the laboratory.
(iii) It is also used as a disinfectant and germicide.
Difference:
Lanthanides and actinides differ in some of their characteristics as follows:
(i) Besides +3, lanthanides also show oxidation states of +2 and +4 while actinides
show higher oxidation states of +4, +5, +6 and +7 as well.
(ii) Lanthanide ions are colourless while most of the actinide ions are coloured.
(iii) Actinides have a greater tendency towards complex formation as compared to
lanthanides.
(iv) Lanthanide compounds are less basic while actinide compounds have appreciable
basicity.
2+ 2+
(v) Actinides form few important oxocations such as UO 2 , PuO 2 , etc, while such
oxocations are not known for lanthanides.
(vi) Almost all actinides are radioactive while lanthanides, except promethium, are
non-radioactive.
(vii) The magnetic properties of actinides can be easily explained while it is difficult to