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02 d and f Block Elements

General Characteristics
Position in periodic Table
1. The d-block of the periodic table contains the elements of the groups 3-12 in which the d-orbitals are
progressively filled in each of the four long periods.
2. There are four series of the d-block elements.
3d series
21 22 23 24 25 26 27 28 29 30

Sc Ti V Cr Mn Fe Co Ni Cu Zn
Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc

4d Series
39 40 41 42 43 44 45 46 47 48

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium

5d Series
57 72 73 74 75 76 77 78 79 80

La Hf Ta W Re Os Ir Pt Au Hg
Lanthanum Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury

6d Series
89 104 105 106 107 108 109 110 111 112

Ac Rf Db Sg Bh Hs Mt Ds Rg Cn
Actinium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium

Q. Why d-block elements are called transition elements ?

(i) Their ultimate & Penultimate shell is incomplete as well as they show variable oxidation state.
(ii) A transition element is defined as the one which has incompletely filled d-orbitals in its ground state
or in any one of its oxidation state.
(iii) Zinc, Cadmium and Mercury of group 12 have full d10 configuration in their ground state as well as
in their common oxidation states and hence, are not regarded as transition metals.
(iv) All transition elements are ‘d’ block elements, but all ‘d’ block elements are not transition-elements.
All d-block elements are metals, they show all metallic properties

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Electronic configuration of the d-block Elements
(A) General Electronic Configurations
(n – 1)d1–10 ns1–2
The (n–1) stands for the inner d orbitals which may have one to ten electrons.
The (n) stands for the outer most s orbital which may have one or two electrons.
(B) Exceptions
(a) Above generalization has several exceptions because
(i) The energy difference between (n – 1)d and ns orbitals is very less.
(ii) Half and completely filled sets of orbitals are relatively more stable.
(b) A consequence of this factor is reflected in the electronic configuration of following elements.
(i) In 3d series — Cr and Cu
(ii) In 4d series — Nb, Mo, Tc, Ru, Rh, Pd, and Ag
(iii) In 5d series — Pt and Au
(iv) In 6d series — Rg
(C) Electronic configuration of all d-block elements.
(a) 3d–series (b) 4d–series
Sc → 18[Ar] 3d1 4s2 Y → 36[Kr] 4d1 5s2
Ti → 18[Ar] 3d2 4s2 Zr → 36[Kr] 4d2 5s2
V → 18[Ar] 3d3 4s2 Nb → 36[Kr] 4d4 5s1
Cr → 18[Ar] 3d5 4s1 Mo → 36[Kr] 4d5 5s1
Mn → 18[Ar] 3d5 4s2 Tc → 36[Kr] 4d6 5s1
Fe → 18[Ar] 3d6 4s2 Ru → 36[Kr] 4d7 5s1
Co → 18[Ar] 3d7 4s2 Rh → 36[Kr] 4d8 5s1
Ni → 18[Ar] 3d8 4s2 Pd → 36[Kr] 4d10 5s0
Cu → 18[Ar] 3d10 4s1 Ag → 36[Kr] 4d10 5s1
Zn → 18[Ar] 3d10 4s2 Cd → 36[Kr] 4d10 5s2

(c) 5d–series (d) 6d–Series

La → 54[Xe] 5d1 6s2 Ac → 86[Rn] 6d1 7s2
Hf → 54[Xe] 5d2 6s2 Rf → 86[Rn] 6d2 7s2
Ta → 54[Xe] 5d3 6s2 Db → 86[Rn] 6d3 7s2
W → 54[Xe] 5d4 6s2 Sg → 86[Rn] 6d4 7s2
Re → 54[Xe] 5d5 6s2 Bh → 86[Rn] 6d5 7s2
Os → 54[Xe] 5d6 6s2 Hs → 86[Rn] 6d6 7s2
Ir → 54[Xe] 5d7 6s2 Mt → 86[Rn] 6d7 7s2
Pt → 54[Xe] 5d9 6s1 Ds → 86[Rn] 6d8 7s2
Au → 54[Xe] 5d10 6s1 Rg → 86[Rn] 6d10 7s1
Hg → 54[Xe] 5d10 6s2 Cn → 86[Rn] 6d10 7s2

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d and f Block Elements
Atomic Radius
In period
In initial five elements attraction between nucleus
and valence shell remains more as compared to
repulsion between valence shell and penultimate
shell that’s why atomic radius decreases from Sc to
Mn.
In next three elements attraction between nucleus
and valence shell becomes equal to repulsion
between valence shell and penultimate shell that’s
why atomic radius of Fe, Co and Ni remains almost
equal.
In last two elements attraction between nucleus and
valence shell remains less as compared to repulsion
between valence shell and penultimate shell that’s
why atomic radius from Cu to Zn increases.
In group
Atomic radii of 4d series elements are more than 3d series elements.
4d and 5d series elements nearly same atomic radii due to lanthanide contraction.
Magnetic Properties
(i) Paramagnetic substances. The substances which are attracted by magnetic field are called
paramagnetic substances and this character arises due to the presence of unpaired electrons in the
atomic orbitals.
(ii) Diamagnetic substances. The substances which are repelled by magnetic field are called
diamagnetic substances and this character arises due to the presence of paired electrons in the
atomic orbitals.
Most of the transition metal ions or their compounds have unpaired electrons in d-sub-shell (from
configuration d1 to d9) and therefore, they give rise to paramagnetic character.
(iii) Metals, which have unpaired electrons show para-magnetism.
Spin only magnetic moment  = √𝐧(𝐧 + 𝟐)
here n = no. of unpaired electron
Unit : Bohr Magneton (B.M.)
Ferromagnetism
Substances attracted very strongly are said to be ferromagnetic, extreme form of paramagnetic.
Ferromagnetic materials  Fe, Co, Ni
Formation of interstitial compounds
• H, C, N trapped inside Crystal lattice of metals
• Non-stoichiometric
• TiC, Mn4N, Fe3H, VH0.56, TiH1.7
• Retain metallic conductivity
• High melting point than pure metal
• They are very hard
• They are chemically inert
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Formation of alloys

(i) Transition elements have maximum tendency to form alloys.

(ii) The reactivity of transition elements is very less and their sizes are almost similar. Due to this a
transition metal atom in the lattice can be easily replaced by other transition metal atom and hence
they have maximum tendency to form alloys.
(iii) In the alloys, ratio of component metals is fixed.
(iv) These are extremely hard and have high melting point.
Some important alloys
(a) Bronze Cu + Sn
(b) Brass Cu + Zn
(c) Gun metal Cu + Zn + Sn
(d) German Silver Cu + Zn + Ni
(e) Stainless Steel Cr + Ni
(f) Invar Ni 36
(g) Alnico Al + Ni + Co
(h) Duralumin Cu + Al + Mn
(i) 22 Carrot gold Au + Ag
(j) 18 Carrot gold Au + Ag + Cu
(k) Silver UK coins Cu + Ni
(l) White Metal Li + Pb
(m) Solder Sn + Pb
(n) Nichrome Ni + Cr + Fe
(o) Bell Metal Cu + Sn
Amalgam is a semisolid alloy which is formed by mixing a metal with Hg. Fe, Co, Ni do not form amalgam
due to large difference in size.
Formation of complex compounds
• Small size
• High charge density
• Availability of vacant orbital

Example :

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d and f Block Elements
Melting Point
(i) Melting and boiling point of d-block elements is more than that of s block elements.
Reason : Stronger metallic bond formed by present unpaired d-electrons.
(ii) In Zn, Cd, and Hg there is no unpaired electron present in d-orbital, hence due to absence of covalent
bond melting and boiling point are very low in series. (Volatile metals Zn, Cd, Hg)
(iii) In 3d series Sc to Cr melting and boiling point increases then Mn to Zn melting and boiling point
decreases
(iv) As the number of unpaired d-electron increases, the number of covalent bond and bond energy
between the atoms is expected to increase up to Cr-Mo-W family where each of the d-orbital has only
unpaired electron and the opportunity for covalent sharing is greatest.
(v) Mn and Tc have comparatively low melting point, due to weak metallic bond because of stable Half
filled (d5) configuration and high IP.
(vi) Lowest melting point Hg (– 38°C); Highest melting point W (3400°C)
Trends in melting points of transition elements

Heat of atomisation
• Enthalpy of atomization means the energy required to break the metallic bond.
• Stronger is the metallic bond more will be the heat of atomisation.
• More number of unpaired electrons will favour the formation of metallic bond.
• In case of Mn due to stable (n–1)d & ns configuration metallic bond is weak.
• Mn and Zn has low heat of atomisation due to stable configuration electron are not available for
metallic bonding.
Heat of Atomisation

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Catalytic Properties
• The transition metals and their compounds are known for their catalytic activity.
• This is due to -
Multiple oxidation states & presence of vacant orbital.
Catalyst Used
Fe Haber’s process for manufacture of NH3
V2O5 Contact process for H2SO4 manufacture
Pt Ostwald’s process of nitric acid
Ni Hydrogenation of oils.

Density
(i) The atomic volumes of the transition elements are low compared with the elements of group 1 and
2. This is because the increased effective nuclear charge. Consequently the densities of the transition
metals are high.
(ii) Across a period from left to right atomic volumes decrease and atomic masses increase. Hence the
densities increases across a period.
Sc < Ti < V < Cr < Mn < Fe < Co < Ni = Cu > Zn (Zn has lower density because of its large atomic
volume)
Minimum density in 3d series → Sc
Maximum density in 3d series → Ni and Cu
In Group : 3d < 4d < 5d
Elements with highest densities are
Osmium (Os) = 22.51 g/cm3, Iridium (Ir) = 22.61 g/cm3

Oxidation States
1. d-block element shows variable oxidation state due to partially filled configuration.
2. It has two types of oxidation states -
(a) Minimum oxidation state = ns electron
(b) Maximum oxidation state = ns electron + (n-1)d unpaired electron
3. The variability of oxidation states, a characteristic of transition elements arises out of incomplete
filling of d–orbitals in such a way that their oxidation states differ from each other by unity.
Example :-
V+2 V+3 V+4 V+5
4. In d-block elements the higher oxidation states are favoured by the heavier members.
Example :-
In group – 6 Mo (VI) and W(VI) are found to be more stable than Cr (VI).
Thus Cr (VI) in form of dichromate (Cr2 O2− 7 ) in acidic medium is a strong oxidizing agent, whereas
MoO3 and WO3 are not.
5. Low oxidation states are found when a complex compound has ligand capable of -acceptor
character in addition to the -bonding. (synergic ligand like CO)
Example :-
In Ni(CO)4 and Fe(CO)5, the oxidation state of nickel and iron is zero.
They show variable oxidation state.
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d and f Block Elements
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+1
+2 +2 +2 +2 +2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7
• Underlined states are the most stable ones.

Electrode Potential
In addition to ionisation enthalpy, the other factors such as enthalpy of sublimation, hydration enthalpy
etc. determine the stability of a particular oxidation state in solution. This can be explained in terms of their
electrode potential values. The oxidation potential of a metal involves the following process:
M(s) ⎯→ M+(aq) + e–
This process actually takes place in the following three steps as given in following flowchart :
The oxidation potential which gives the tendency of the overall change to occur, depends upon the net
effect of these three steps. The overall energy change is

H = subH + H + hydH
If SOP is +ve that means oxidation will be easy
If SRP is +ve that means reduction will be easy.
Some important examples :
1. E0M+2 /M  +ve only for Cu among 3d elements because hydration energy of Cu+2 is not enough to

compensate for sublimation energy, IE1 and IE2 for Cu.

2. E0M+3 /M+2
(i) E0Cr+3 /Cr+2 = –ve
that means Cr+2 acts as a reducing agent because Cr+3 has t2g half filled stable configuration.
(ii) E0Mn+3 /Mn+2 = +ve
that means Mn+3 acts as an oxidising agent due to stability of half filled (d5) configuration.

Trends in stability of higher oxidation states

The highest oxidation states are shown generally among halides and oxides of transition elements.
(I) In halides of transition elements
(i) The transition elements react with halogens at high temperatures to form transition metal
halides.
(ii) Since fluorine is the most electronegative element, the transition metals show highest
oxidation states with fluorine. The highest oxidation states are found in TiX 4 (tetrahalides,
X = F, Cl, Br and I), VF5 and CrF6.

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(iii) The +7 oxidation state for Mn is not shown by simple halides. However, MnO3F is known in
which the oxidation state of Mn is +7.
(iv) The tendency of fluorine to stabilise the highest oxidation state is due to either higher lattice
enthalpy as in case of CoF3 or higher bond enthalpy terms for the higher covalent compounds.
eg. VF5 and CrF6.
(v) Fluorides are relatively unstable in their low oxidation states. For example, vanadium form
only VX2 (X = Cl, Br or I) and copper can form CuX (X = Cl, Br, I). On the other hand all copper
(II) halides are known except the iodide. This is because, Cu2+ oxidises I– to I2.
2Cu2+ + 4I– ⎯→ Cu2I2(s) + I2
(vi) It has been observed that many copper (I) compounds are unstable in aqueous solution and
they undergo disproportionation
2Cu+ ⎯→ Cu2+ + Cu
Copper in +2 oxidation state is more stable than in +1 oxidation state. This can be explained
on the basis of much larger negative hydration enthalpy (hydH) of Cu2+ (aq) than Cu+, which is
sufficiently high to compensate second ionisation enthalpy of copper.
(II) In metal oxides and oxocations.
(i) The ability of oxygen to stabilize the highest oxidation state is demonstrated in their oxides.
The highest oxidation states in their oxides concides with the group number. For example, the
highest oxidation state of scandium of group 3 is +3 in its oxides, Sc 2O3 whereas the highest
oxidation state of manganese of group 7 is +7, in Mn2O7.
(ii) Besides the oxides, oxocation of the metals also stabilise higher oxidation states. For example,
VV as VO2+, VIV as VO2+ and TiIV as TiO2+.
(iii) It may be noted that the ability of oxygen to stabilise these high oxidation states exceeds that
of fluorine. For example, manganese forms highest fluoride as MnF4 whereas the highest oxide
is Mn2O7. This is due to the fact that oxygen has ability to form multiple bonds to metals.
(iv) The transition elements in the +2 and +3 oxidation states mostly form ionic bonds whereas
with higher oxidation states, the bonds are essentially covalent e.g. in MnO4– all bonds are
covalent. In these higher oxides the acidic character is predominant. Thus CrO3 gives H2CrO4
and H2Cr2O7 and Mn2O7 gives HMnO4. V2O5 is, however amphoteric though mainly acidic and
with alkalies as well as acids gives VO43– and VO2+ respectively.
Element (M) EoM3+ /M2+ EoM2+ /M Comments
Ti –0.37 –1.63 +3 Oxidation state is more stable
V –0.26 –1.18 +3 Oxidation state is more stable
Cr –0.41 –0.9 +3 Oxidation state is more stable
Mn 1.57 –1.18 +2 Oxidation state is more stable
Fe 0.77 –0.44 +2 Oxidation state is more stable
Co 1.97 –0.28 +2 Oxidation state is more stable
Ni - –0.25 +3 Oxidation state does not exist for Ni
Cu - 0.34 +3 Oxidation state does not exist for Cu. 0
Oxidation state is more stable
Zn - –0.76 +3 Oxidation state does not exist for Zn
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d and f Block Elements

BEGINNER’S BOX-1
1. Transition elements exhibit variable oxidation states in their compounds due to
(1) Strong shielding of (n–1) d-electrons
(2) Very small energy difference between (n–1)d and ns orbitals
(3) Presence of unpaired electrons
(4) High energy difference between (n–1)d and ns orbitals
2. Which element do not show more than one oxidation state
(1) Mn (2) Cr (3) Fe (4) Sc
3. Consider the ions Fe2+, Fe3+, Cr2+, Cr3+, Mn2+, Mn3+
(i) Strongest oxidising ion is
(1) Fe2+ (2) Cr3+ (3) Mn3+ (4) Mn2+
(ii) Strongest reducing ion is
(1) Fe+3 (2) Mn2+ (3) Cr2+ (4) Mn3+
4. Which compound does exist
(1) MnO3F (2) K2[CuI4] (3) MnF7 (4) CrF7
5. In the form of dichromate, Cr(VI) is a strong oxidising agent in acidic medium but Mo(VI) in MoO 3
and W(VI) in WO3 are not because
(1) Cr(VI) is more stable than Mo(VI) & W(VI)
(2) Mo(VI) and W(VI) are less stable than Cr(VI)
(3) H.O.S. of heavier members of group 6 of transition metals are more stable
(4) L.O.S. of heavier members of group 6 of transition metals are more stable
6. Which of the following show +8 oxidation state.
(1) Fe, Ru (2) Fe, Os (3) Ru, Os (4) Mo, W
7. Which catalyst is used in contact process ?
(1) Ni (2) V2O5 (3) Fe (4) AlCl3 + TiCl4
8. The element with maximum and minimum melting points in second transition series respectively.
(1) Cr and Zn (2) Cr and Hg (3) Cr and Cd (4) Mo and Cd
9. Which of the following metal ions is expected to be paramagnetic?
(1) Zn2+ (2) Ti3+ (3) Sc3+ (4) Ti4+
10. Which of the element have highest density –
(1) W (2) Os (3) Tc (4) Mo

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Potassium Dichromate K2Cr2O7
Preparation :
• Dichromates are generally prepared from chromate, which in turn are obtained by the fusion of
chromite ore (FeCr2O4) with sodium or potassium carbonate in free access of air.
• The reaction with sodium carbonate occurs as follows:
4FeCr2O4 + 8Na2CO3 + 7 O2 ⎯→ 8Na2CrO4 + 2Fe2O3 + 8CO2
The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to give a solution
from which orange sodium dichromate, Na2Cr2O7. 2H2O can be crystallised.
2Na2CrO4 + 2H+ ⎯→ Na2Cr2O7 + 2Na+ + H2O
• Sodium dichromate is more soluble than potassium dichromate. The latter is therefore, prepared by
treating the solution of sodium dichromate with potassium chloride.
Na2Cr2O7 + 2KCl ⎯→ K2Cr2O7 + 2NaCl
Orange crystals of potassium dichromate crystallise out. The chromates and dichromates are
interconvertible in aqueous solution depending upon pH of the solution. The oxidation state of
chromium in chromate and dichromate is the same.
2CrO42– ⎯⎯⎯⎯⎯
Acidic medium
( 2H+ )
→ Cr2O72– + H2O Cr2O72– ⎯⎯⎯⎯⎯
Basic medium
( 2OH– )
→ 2CrO42– + H2O

• K2Cr2O7 is preferred over Na2Cr2O7 as a primary standard in volumetric analysis (titration) because
Na2Cr2O7 is hygroscopic in nature but K2Cr2O7 is not.
• The structures of chromate ion, CrO42– and the dichromate ion, Cr2O72– are shown below. The
chromate ion is tetrahedral whereas the dichromate ion consists of two tetrahedra, sharing one
corner with Cr–O–Cr bond angle of 126°.

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d and f Block Elements
Oxidising Property :-

Acidified K2Cr2O7 (Orange)

H2S S
SO2 SO4–2
NO2– NO3–
SO3–2 SO4–2
Sn+2 Sn+4
Fe+2 Fe+3
Br– Br2
I– I2
C2H5OH CH3COOH

Cr+3
(Green)

Chromyl chloride test (used to identify ionic chlorides)

Generally Ionic or water soluble chloride gives chromyl chloride test.
4NaCl + K2Cr2O7 + 6H2SO4 ⎯→ 2CrO2Cl2 (Red orange vapour) + 2KHSO4 + 4NaHSO4 + 3H2O
NaOH solution
Na2CrO4 (Yellow)
AgCl, HgCl2 & PbCl2 are covalent or water insoluble chloride so they can’t give chromyl chloride test.

Potassium Permanganate (KMnO4)

Preparation :
• Potassium permanganate is prepared by fusion of MnO2 (Pyrolusite) with an alkali metal hydroxide
and an oxidising agent like KNO3.
This produces the dark green K2MnO4 which disproportionate in a neutral or acidic solution to give
permanganate.
2MnO2 + 4KOH + O2 ⎯→ 2K2MnO4 + 2H2O
3MnO42– + 4H+ ⎯→ 2MnO4– + MnO2 + 2H2O
• Commercially it is prepared by the alkaline oxidative fusion of MnO2 followed by the electrolytic
oxidation of manganate (Vl).

𝐅𝐮𝐬𝐞𝐝 𝐰𝐢𝐭𝐡 𝐊𝐎𝐇, 𝐨𝐱𝐢𝐝𝐢𝐬𝐞𝐝 𝐄𝐥𝐞𝐜𝐭𝐫𝐨𝐥𝐲𝐭𝐢𝐜 𝐨𝐱𝐢𝐝𝐚𝐭𝐢𝐨𝐧 𝐢𝐧

𝐰𝐢𝐭𝐡 𝐚𝐢𝐫 𝐨𝐫 𝐊𝐍𝐎𝟑 𝐚𝐥𝐤𝐚𝐥𝐢𝐧𝐞 𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧
𝐌𝐧𝐎𝟐 ሱۛۛۛۛۛۛۛۛۛۛۛۛۛۛۛۛۛሮ 𝐌𝐧𝐎𝟐–
𝟒 ; 𝐌𝐧𝐎𝟒 ሱۛۛۛۛۛۛۛۛۛۛۛۛۛۛۛۛۛሮ 𝐌𝐧𝐎–𝟒
𝟐–

𝐦𝐚𝐧𝐠𝐚𝐧𝐚𝐭𝐞 𝐢𝐨𝐧 𝐦𝐚𝐧𝐠𝐚𝐧𝐚𝐭𝐞 𝐩𝐞𝐫𝐦𝐚𝐧𝐠𝐚𝐧𝐚𝐭𝐞 𝐢𝐨𝐧

• In the laboratory, a manganese (II) ion salt is oxidised by peroxodisulphate to permanganate.

2Mn2+ + 5S2O82– + 8H2O ⎯→ 2MnO4– + 10SO42– + 16H+

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Physical Property :

• Potassium permanganate forms dark purple (almost black) crystals which are isostructural with
those of KClO4. The salt is not very soluble in water (6.4 g/100 g of water at 293 K), but when heated
it decomposes at 513 K.

2KMnO4 ⎯⎯
→ K2MnO4 + MnO2 + O2
The manganate and permanganate ions are tetrahedral; the π bonding takes place by overlap of p
orbitals of oxygen with d orbitals of manganese.
The green manganate is paramagnetic because of one unpaired electron but the permanganate is
diamagnetic due to the absence of unpaired electron.

Oxidising Property :

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d and f Block Elements

f-BLOCK ELEMENTS
Introduction
(a) The elements constituting the f – block are those in which the 4f and 5f orbitals are progressively
filled.
(b) These elements are formal members of group 3 from which they have been taken out to form a
separate f–block of the periodic table.
(c) The name inner transition metals are often used to refer to the elements of f–block.
(d) The f-block consists of the two series
(i) Lanthanides
The fourteen elements following lanthanum.
Because lanthanum closely resembles the lanthanides, it is usually included in any discussion of the
lanthanides.
(ii) Actinides
The fourteen elements following actinium.
Because actinium closely resembles the actinides, it is usually included in any discussion of the
actinides.
The lanthanides :
Name Electronic Configuration
59Ce ⎯→ 54[Xe] 4f3 5d0 6s2 (Cerium)

59Pr ⎯→ 54[Xe] 4f3 5d0 6s2 (Praseodymium)

60Nd ⎯→ 54[Xe] 4f4 5d0 6s2 (Neodymium)
61Pm ⎯→ 54[Xe] 4f5 5d0 6s2 (Promethium)
62Sm ⎯→ 54[Xe] 4f6 5d0 6s2 (Samarium)
63Eu ⎯→ 54[Xe] 4f7 5d0 6s2 (Europium)
64Gd ⎯→ 54[Xe] 4f7 5d1 6s2 (Gadolinium)
65Tb ⎯→ 54[Xe] 4f9 5d0 6s2 (Terbium)
66Dy ⎯→ 54[Xe] 4f10 5d0 6s2 (Dysprosium)
67Ho ⎯→ 54[Xe] 4f11 5d0 6s2 (Holmium)
68Er ⎯→ 54[Xe] 4f12 5d0 6s2 (Erbium)
69Tm ⎯→ 54[Xe] 4f13 5d0 6s2 (Thulium)
70Yb ⎯→ 54[Xe] 4f14 5d0 6s2 (Ytterbium)
71Lu ⎯→ 54[Xe] 4f14 5d1 6s2 (Lutetium)
• It may be noted that atoms of these elements have electronic configuration with 6s 2 common but
variable occupancy of 4f level.
• The irregularities in the electronic configuration of lanthanides are related to the stabilities of the f0,
f7, f14 occupancies of the 4f orbitals.
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Atomic and Ionic Radius Sm2+
110
Eu2+
1. The overall decrease in ionic radii from lanthanum to La3+

lutetium is a unique feature in the chemistry of the Ce3+

Pr3+
lanthanides. 100 Nd3+
Pm3+

Ionic radii/pm
Sm3+
2. This is due to poor shielding of nucleus by inner penultimate Eu3+
Tm2+
Gd3+
Yb2+
4f orbital. Ce4+ Tb3+
Dy3+

90 Pr 4+
Ho3+
3. The cumulative effect of the contraction in size of the Er3+
Tm3+
Yb3+
lanthanide series, known as lanthanide contraction. Tb4+
Lu3+

4. The decrease in atomic radii is not quite regular.

57 59 61 63 65 67 69 71
5. The decrease in ionic radii of M3+ comparatively more Atomic number

Trends in ionic radii of lanthanides

regular.

Consequences of lanthanide contraction

• Small size difference between size of 4d and 5d series of transition element.
• Effect of basic strength, Basic strength decreases on moving left to right.
• Steady decrease in size.

Oxidation States
1. The common oxidation state for lanthanides is +3 but it also shows +2 and +4 state.
2. (i) Ce → +4 and +3. Ce+4 act as a oxidant & used in volumetric Analysis.
(ii) Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides, MO2.
(iii) Eu2+ is a strong reducing agent changing to the common +3 state.
(iv) Yb2+ has f14 configuration is a reductant.
(v) Tb+4 has f7 configuration is a oxidant.
(vi) The behaviour of samarium is very much like europium, exhibiting both +2 and +3 oxidation
states.

General characteristics
1 Silvery white
2. Soft metals
3. Tarnish rapidly in air
4. Typical metallic structure
5. Good conductors of heat
6. Good conductors of electricity
7. (i) Many trivalent lanthanide ions are coloured both in the solid state and in aqueous solutions.
(ii) Colour of these ions may be attributed to the presence of unpaired f electrons However,
absorption bands are narrow, probably because of the excitation within f orbitals, called f-f
transition.
(iii) La3+ and Lu3+ ions does not show any colour but the rest do so.
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d and f Block Elements
8. (i) The lanthanide ions other than the f0 type (La3+ and Ce4+) and the f14 type (Yb2+ and Lu3+) are all
paramagnetic.
(ii) The paramagnetism rises to maximum in Nd.

Other Properties
Alloy Formation
Alloy of lanthanide with iron called misch metal (composition) → Ce – 50%, La – 25%, Nd – 15% & 10%
other rare – earth metal & iron or Lanthanoid metal (95%) + Iron (5%)
The Actinides :
Name Electronic configuration
90Th ⎯→ 86[Rn] 5f° 6d2 7s2 (Thorium)

91Pa ⎯→ 86[Rn] 5f2 6d1 7s2 (Protactinium)

92U ⎯→ 86[Rn] 5f3 6d1 7s2 (Uranium)

93Np ⎯→ 86[Rn] 5f4 6d1 7s2 (Neptunium)

94Pu ⎯→ 86[Rn] 5f6 6d0 7s2 (Plutonium)

95Am ⎯→ 86[Rn] 5f7 6d0 7s2 (Americium)

96Cm ⎯→ 86[Rn] 5f7 6d1 7s2 (Curium)

97Bk ⎯→ 86[Rn] 5f9 6d0 7s2 (Berkelium)

98Cf ⎯→ 86[Rn] 5f10 6d0 7s2 (Californium)

99Es ⎯→ 86[Rn] 5f11 6d0 7s2 (Einstenium)

100Fm ⎯→ 86[Rn] 5f12 6d0 7s2 (Fermium)

101Md ⎯→ 86[Rn] 5f13 6d0 7s2 (Mendelevium)

102No ⎯→ 86[Rn] 5f14 6d0 7s2 (Nobelium)

103Lr ⎯→ 86[Rn] 5f14 6d1 7s2 (Lawrencium)

• It may be noted that atoms of these elements have electronic configuration with 7s 2 common but
variable occupancy of 5f and 6d sub shell.
• The irregularities in the electronic configuration of actinides are related to the stabilities of the f0, f7,
f14 occupancies of the 5f orbitals.

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Ionic Sizes
• The general trend in lanthanides is observable in the actinides as well. There is a gradual decrease in
the size of atoms or M3+ ions across the series. This may be referred to as the actinide contraction
(like lanthanide contraction). The contraction is, however, greater from element to element in this
series resulting from poor shielding by 5f electrons.
Actinide Contraction
• Due to poor shielding of 5f orbitals. Actinide contraction is more effective than lanthanide
contraction.
Colour
• Actinides are generally coloured.
• The colour of actinides depends upon the number of 5f electrons.
• If there is no unpaired electrons it will be colourless.
Oxidation State
 Most common oxidation state is +3 beside that they show +4, +5, +6 oxidation state in certain
elements.
Complex Formation
• Actinides have stronger tendency towards complex formation.
Radioactivity
• All actinides are radioactive while lanthanides are non-radioactive [except promethium (pm)].
• Oxides and hydroxides of actinides are more basic than lanthanide.

BEGINNER’S BOX-2
1. conc.H2SO4
X ⎯⎯⎯⎯
K2Cr2O7
→ red brown vapours. X can be

(1) NaI (2) NaBr (3) Both (1) & (2) (4) None of these
H+
2. X ⎯⎯→
KOH
air
Y ⎯⎯
→ Z +X
black coloured dark green an oxidising agent
ore

True statement is
(1) X can't be MnO2 (2) Y can be KMnO4
(3) Z can be K2MnO4 (4) X is MnO2 and Y is K2MnO4
+
H
3. X −
Y ; Y ⎯⎯
SO
→ Z + SO4−2
2

OH

X and Y are oxy anion of Cr than oxidation state of Cr in X, Y, Z will be respectively

(1) +3, +6, +6 (2) +6, +3, +6 (3) +6, +6, +6 (4) +6, +6, +3
4. When KMnO4 solution is added to oxalic acid solution, the decolourisation is slow in beginning but
become instantaneous after some time because
(1) CO2 is a by product (2) Mn2+ acts as a catalyst
(3) Reaction in exothermic (4) MnO4– catalyzes the reaction
5. The elements from cerium (At.No. 58) to lutetium (At.No. 71) in which 4f energy levels are filled up
are known as :
(1) Lanthanides (2) Rare earth metals (3) Lanthanones (4) All the above
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d and f Block Elements
6. Which of the following is radioactive element :
(1) Ce (2) Lu (3) Eu (4) Pm
7. Which of the following ion is paramagnetic ?
(1) Ce+4 (2) Lu+3 (3) Yb+2 (4) Eu+2
8. Which of the following ion do not show colour?
(1) Lu3+ (2) Pm3+ (3) Eu3+ (4) Dy3+
9. Which type of hydroxide generally formed by Lanthanoids ?
(1) Ln(OH)3 (2) Ln(OH)2 (3) Ln(OH)4 (4) Ln(OH)6
10. Highest oxidation state +7 shown by which actinoids ?
(1) Np, Pu (2) Pa, U (3) Am, Cm (4) Cf, Es

NCERT QUESTIONS

Q.1 Why do the transition elements have higher boiling & melting points ?
Ans. Because of having larger number of unpaired electrons in their atoms, they have stronger
interatomic interaction. Hence strong metallic bonds between the atoms of these elements attribute
to their high melting and boiling points.
Q.2 Give the main difference in oxidation states of transition elements & p-block elements.
Ans. (i) The variation of oxidation state in transition elements is in such a way that their oxidation
state differ from each other by unity e.g. V+2, V+3, V+4, V+5. While in p block elements oxidation
states normally differ by two due to inert pair effect.
(ii) Stability of higher oxidation state in transition elements increase down the group
e.g. Pt+4 is more stable than Pt+2
While in p block elements lower oxidation state become increasingly stable down the group as result
of inert pair effect. e.g. Pb+2 is more stable than Pb+4.
Q.3 Explain why Cu+ ion is not stable in aqueous solutions.
Ans. Cu+ ions in aqueous solution undergoes disproportionation.
2Cu( aq ) ⎯→ Cu( aq ) + Cu( s )
+1 +2

+2
This is because that hydration energy of Cu ( aq ) ions is sufficiently high to compensate IE2 of Cu.
Q.4 Which is a stronger reducing agent Cr+2 or Fe+2 and why ?
Ans. Cr+2 is stronger reducing agent than Fe+2
Reason : d4 ⎯→ d3 occurs in case of Cr+2 ⎯→ Cr+3 but d6 ⎯→ d5 occurs in case of Fe+2 ⎯→ Fe+3 in a
medium like water d3 is more stable as compared to d5 (on the basis of CFSE value)
Q.5 In first transition series (3d series) the enthalpy of atomisation of zinc is lowest, why ?
Ans. In the formation of metallic bonds no e– from 3d subshell is involved in case of Zn because all 3d
orbitals are fulfilled. Which decrease strength of metallic bond as well as enthalpy of atomisation of
Zn.
Q.6 How iron (III) catalyses the reaction between iodide & persulphate?
Ans. 2Fe3+ + 2– ⎯→ 2Fe2+ + 
2Fe2+ + S2O82– ⎯→ 2Fe3+ + 2SO42–
_________________________________________________________________________

2 – + S O
2 8
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2– ⎯⎯⎯
Fe(III)
→  + 2 SO42–

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NEET : Chemistry

BEGINNER’S BOX ANSWERS KEY

Que. 1 2 3 4 5 6 7 8 9 10
BEGINNER'S BOX-1
Ans. 2 4 3, 3 1 3 3 2 4 2 2

Que. 1 2 3 4 5 6 7 8 9 10
BEGINNER'S BOX-2
Ans. 2 4 4 2 4 4 4 1 1 1

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