d -BLOCK ELEMENTS
The elements of the group 3rd to 12th of the periodic table are called d -block elements. Their general outer electronic
configuration is (n-1)d1-10 ns0, 1 or 2
(n represent valence shell).
The d block elements are also called transition elements because they have partly or incompletely filled (n-1) d orbital
in their elementary state or in any of their common oxidation states.
Zinc, cadmium and mercury are d block elements, but not considered as transition elements because they have fully
filled d sub shell in their ground or excited state while transition elements have partially filled d subshell
Atomic radii:
The atomic radii of transition elements in a given series decrease with increase in atomic number but this decrease
becomes small after midway.
At the end of the series, there is slight increase in the atomic radii. This is due to electron-electron repulsions among fully
filled (n -l)d-electrons.
In a vertical row, i.e., in each group, the atomic radii are expected to increase from top to bottom due to the addition of a
newer shell. Therefore, the atomic radii of transition metals of second series have higher values than those of first
transition series. However, the transition metals of third series except the first member, lanthanum, have nearly the same
radii as metals of second transition series above them.
This is due to Lanthanoid contraction. Due to inclusion of fourteen 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.
Melting and boiling points:
The transition metals have very high melting and boiling points due to the involvement of ns electrons in addition to
(n-1)d electrons which gives extra strength to their metallic bonding.
The high melting and boiling points of transition metals are attributed to stronger forces that bind their atoms together.
The presence of one or more unpaired d-electrons contributes to higher interatomic forces and frequent metal-metal
bonding. This is clear from their high enthalpies of atomization.
In each series, the melting points of these metals rise to a maximum value upto middle with maximum number of
unpaired electrons and then decrease with increase in atomic number due to pairing of electrons.
When unpaired electrons are absent, the melting points or enthalpy of atomisation are low as in the case of Zn, Cd and
Hg
Standard reduction potential:
In a solution, the stability of the compounds depends upon electrode potentials. Electrode potential value depends upon
enthalpy of sublimation of the metal, the ionization enthalpy and hydration enthalpy,
M(s) → M+(aq) + e– HT (Total energy change)
This process involves three steps:
First Step: M(s) → M(g) HSub (Energy of sublimation)
Second Step: M(g) → M+(g) + e– IE (Ionisation Energy)
Third Step: M+(g)+aq → M+(aq) Hhyd. (Hydration Energy)
Thus, HT = HSub.+ I.E. + Hhyd.
HT is the total energy change when a solid metal, M, is brought in the aqueous medium in the form of monovalent ion, M+
(aq).
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.
Element Ti V Cr Mn Fe Co Ni Cu Zn
E0( M2+ / M)V -1.63 -1.18 -0.91 -1.18 -0.44 -0.28 -0.25 +0.34 -0.76
E0( M3+ / M2+)V -0.37 -0.26 -0.41 +1.57 +0.77 +1.97 - - -
It is evident that there is no regular trend in the E0(M2+/ M) values. This is due to irregular variation of ionisation energies
and sublimation energies of the atoms of the members of the transition series.
E0 values for Mn, Ni and Zn are more negative than expected
Mn and Zn readily lose two electrons to attain half-filled and fully filled stable configurations respectively, thus they readily
get oxidized while Ni2+has high hydration enthalpy due to which it is quite stable. That’s why Ni has a tendency of getting
oxidized to Ni2+, hence these three shows more negative E0 value than expected.
Copper shows positive electrode potential due to its high value of atomization enthalpy which is not compensated by its
hydration enthalpy. Thus, as a result, the overall effect E⊖(M2+/M) for copper is positive while all other elements have
negative reduction potential values, i.e., these elements except copper should have the capacity to liberate hydrogen from the
dilute acids
Though the Cu+ ion has a fully filled d orbital still it is not stable in an aqueous solution.
In the aqueous solution, the Cu2+ion is more stable than Cu+ ion because of the high hydration energy of the Cu2+
compensates for it.
So, the Cu+ ion is unstable in an aqueous medium and undergoes the disproportionation reaction, and gives Cu2+ and Cu as
the product.
E0 value for Sc3+/Sc2+ is very low. Hence, Sc3+ is stable. This is due to its noble gas configuration.
E0 value for Mn3+/ Mn2+ is high. This reflects that Mn2+ state is stable due to d5 configuration. On the other hand,
comparatively lower value of Fe shows the extra stability in +3 oxidation state (d5 configuration).
The comparatively low value of vanadium for V3+/ V2+ is related to the stability of its +2 oxidation state due to its half-
filled t2g stability.
Cr+2 is stronger reducing agent than Fe2+ as Cr3+ ion with d3 configuration has favorable crystal field stabilization
energy.
Cr2+ is reducing as its configuration changes from d4 to d3 , half-filled t2g level.
On the other hand, the change from Mn3+ to Mn2+ results in the half-filled (d5) configuration which has extra
stability. That is why Cr2+ is reducing and Mn3+ is oxidising when both have d4 configuration.
Oxidation states:
The variable oxidation state of transition metal is due to involvement of ns and (n-1)d-electrons in bonding
In general, the minimum oxidation state shown by a transition metal is equal to the number of ns-electrons. For the
elements of first transition series, +2 oxidation state is the most common. This state arises due to loss of 4s-electrons.
However, for chromium and copper, the lowest oxidation state is +1. This is due to their electronic configurations, 4s1
Scandium, shows fixed + 3 Oxidation state due to its noble gas configuration and thus scandium is the only transition
element which does not show variable oxidation state while the last element zinc also shows a fixed oxidation state of +2
due to its d10 configuration which is not a transition element.
In any group of d block, the higher oxidation states are more stable for heavier elements. It means on moving down the
group, the stability of higher oxidation state increases. Example in group 6, chromium is least stable in +6 oxidation state
and this is why chromium is behaving like a good oxidising agent at +6 while molybdenum and tungsten are quite stable in
+6 oxidation state and that is why they do not show any oxidising properties. Thus the stability order of their oxide is
WO3> MoO3 >CrO3.
Some of the transition metals form compounds in zero oxidation state they are found when a complex compound has
ligands which are capable of pi acceptor character with sigma bonding. The common examples are Ni(CO)4 and
Fe(CO)5 in which nickel and iron are in zerovalent state.
In +2 and +3 oxidation states, the bonds formed are mostly ionic. On the other hand, in higher oxidation states, the bonds
formed are essentially covalent. Higher oxidation states are usually attained with elements of high electronegativity such
as fluorine and oxygen:
Fluorine is the most electronegative, but still for highest oxidation state, Oxygen is favoured due to its multiple bond
formation tendency. Example the highest fluoride for Mn is MnF4 while its highest oxide is MnO4-
On comparing to p block elements d block elements shows difference in behavior of oxidation states as in d block on
moving down the group the stability of higher oxidation state increases while in p block the stability of higher oxidation
state decreases down the group due to inert pair effect.
Also, in d block, elements shows successive oxidation states while in p block elements shows alternative oxidation states
means successive oxidation states differ by 2.
In a lower oxidation state, the central atom has more electrons available to donate, making it behave like a base while
higher oxidation states compounds are electron deficient in nature which makes them behave as acids.
Example :MnO (Mn in +2 oxidation state) is basic, while Mn2O7 (Mn in +7 oxidation state) is acidic.
Formation of coloured ions : Most of the compounds of these metals are coloured in the solid or solution form due to
the presence of unpaired electrons in (n - 1)d sub shell. In these metal ions, the electrons can be easily promoted form
one energy level to another in the same d -orbital. It is called d - d transition.
Magnetic properties : The compounds of d -block elements may be both paramagnetic and diamagnetic. But most of
the compounds are paramagnetic. Paramagnetic character is directly proportional to the number of unpaired electrons.
Tendency to form complexes : These metal ions have great tendency to form complexes due to small size, high nuclear
charge and presence of vacant d -orbitals to accept a lone pair of electrons donated by ligands.
Formation of interstitial compounds : These metals form interstitial compounds (compounds in which small atoms like
H, C, N, etc. are trapped inside the crystal lattice) due to the presence of vacant d -orbitals.
Catalytic properties : These metals and their compounds act as good catalysts due to the following reasons:
(i) Tendency to form reaction intermediates with suitable reactants, which give a reaction path of lower Ea , so rate of
reaction increase.
(ii) Provide larger surface area on which the reactants may be adsorbed.
Alloy formation : These metals form alloys due to their similar size in a particular transition series and , therefore, the
atoms of one metal can substitute the atoms of other metal in its crystal lattice.
Alloys of transition metals with non-transition metals, such as brass (copper-zinc) and bronze (copper-tin)
COMPOUNDS OF d BLOCK
Potassium Dichromate, K2Cr2O7:
The potassium dichromate is mainly used in the production of potassium chrome alum, and in the leather tanning
industry. It is manufactured from chromite ore (FeO. Cr2O3) which is a mixed ore. The manufacture of potassium
dichromate involves the following steps:
Conversion of chromite into sodium chromate:
4FeO.Cr2 O3 + 8Na2CO3 + 7O2 → 8Na2CO4 + 2Fe2O3 + 8CO2
2. Conversion of sodium chromate into sodium dichromate:
2Na2CrO4 +H2SO4 → Na2Cr2O7 + Na2SO4 + H2O
3. Conversion of sodium dichromate into potassium dichromate:
Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
Na2Cr2O7 is deliquescent enough and changes its concentration and cannot be taken as primary standard solution
whereas K2Cr2O7 has no water of crystallisation and is not deliquescent.
Properties :
(i) It is an orange red crystalline compound. It is moderately soluble in cold water but freely soluble in hot water.
Both are tetrahedral and all the Cr-O bonds are equal in length due to resonance except the bridged oxygen in
dichromate.
(ii) On heating strongly, it decomposes liberating oxygen.
4K2Cr2O7 → 4K2CrO4 + 2Cr2O3 + 3O2
(iii) On heating with alkalies, it is converted to chromate, i.e., colour changes from orange to yellow. On acidifying the
yellow colour again changes to orange.
Both the ions are in equilibrium at pH = 4.
(iv) It acts as a powerful oxidising agent in acidic medium
2−
2Cr2O + 14H+ +6e– → 2Cr3+ + 2H2O
7
Potassium Permanganate, KMnO4
This is the most important and well-known compound of manganese. It is prepared from the pyrolusite dioxide mineral, a
simple ore (MnO2). The preparation involves two steps:
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
Oxidation of potassium manganate to potassium permanganate:
2K2MnO4 + Cl2 → 2KMnO4 + 2KCI
Properties:
(i) It is a purple coloured crystalline compound. It is fairly soluble in cold water and hot water. The solubility in hot water
is, however, more. It melts at 2500C.
(ii) The manganate and permanganate ions are tetrahedral; the green manganate is paramagnetic with one unpaired
electron but the permanganate is diamagnetic. The π-bonding takes place by overlap of p orbitals of oxygen with d
orbitals of manganese.
(iii) When heated strongly, it decomposes evolving oxygen.
2K2MnO4 → K2MnO4 + MnO4 + O2
(iv) Potassium permanaganate acts as an oxidizing agent in alkaline, neutral or acidic solutions.
MnO4– + 4H+ + 3e– → MnO2 + 2H2O (E = + 1.69 V)
MnO4– + 8H+ + 5e– → Mn2+ + 4H2O (E = + 1.52 V)
Uses of Potassium Permanganate
i) Oxidizing agent in laboratory & industry.
ii) in volumetric analysis − as intermediate solution generally.
iii) As Bayer’s reagent in organic chemistry for test of unsaturation the products being colourless, the decolourisation
of pink colour of the reagent takes place.
In Acidic Medium:
(i) Ferrous salts are oxidised to ferric salts.
(ii) Potassium iodide is converted to iodine.
(iii) H2S is oxidised to sulphur.
(iv) SO2 is oxidised to H2SO4.
(v) Nitrites are oxidised to nitrates.
(vi) Oxalic acid is oxidised to CO2.
(vii) Hydrogen halides (HCI, HBr or HI) are oxidized into X2(halogen).
In Neutral Medium:
(i) H2S is oxidised to sulphur.
(ii) Manganese sulphate is oxidised to MnO2
(iii) Sodium thiosuiphate is oxidised to sulphate and sulphur.
In Alkaline Medium
(i) Iodide is oxidized to iodate.
(ii) Ethylene is oxidized to ethylene glycol.
LANTHANIDES
Electronic Configuration [Xe] 4f1-14 5dO-1 6s2
Atomic and Ionic Sizes of Lanthanides
Atomic and ionic radii of lanthanides decrease with an increase in atomic number. This gradual decrease is known as
lanthanides contraction.
It is observed that in lanthanide series, there is a progressive decrease in the atomic and ionic radii with increasing atomic
number. This regular decrease with increase in atomic number is called lanthanide contraction.
Consequence of Lanthanide Contraction
• The almost identical radii of zirconium and haufmium is a consequence of the lanthanides contraction. It can be
account for their occur together in nature and for the difficulty faced in their separation
• Basic Strength of Hydroxide: Because of the lanthanide contraction, size of M3+ ions decreases and there is increase in
covalent character in M—OH and hence basic character decreases.
Uses of Lanthanides
Lanthanide are used in the production of alloy steels for plates and pipes. Mixed oxides of lanthanides are used as catalysts
in petroleum cracking industries.
Some lanthanum oxides are used as phosphors in television screens and other fluorescing surfaces.
Used in making alloy Mischmetal . It is also called cerium mischmetal, or rare-earth mischmetal. it contains
95% lanthanides and 5% iron. Its most common use is in the "flint" ignition device of many lighters and torches.
ACTINIDES
Actinides consist of elements that follow actinium and involve the filling of 5f subshell . All the actinides are
radioactive in nature. Due to their radioactivity and variability in oxidation states chemistry of actinides are more
complex than lanthanides.
Ionic sizes
There is a gradual decrease in the size of actinides across the series. It is referred as actinoid contraction which is just
like lanthanide contraction. This contraction is however greater from element to element in the series resulting from
the poor shielding of 5f electrons.
Oxidation States
The dominant oxidation state of these elements is +3 (similar to lanthanides). Besides +3 state, they also exhibit +4
oxidation state. Some actinides show still higher oxidation states. Actinides shows variable. Oxidation states due to
their comparable energies of 7s 6d and 5f
Magnetic behavior
All actinides are paramagnetic in nature. The paramagnetic nature which depends on the presence of unpaired
electrons.
Ionization enthalpies
The actinides have lower ionization enthalpies as comapre to lanthanides because 5f is more effectively shielded than 4f.
