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d-Block
Part-01

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

4d Series

5d Series

6d Series

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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d-Block Part-01

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

1. 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.

2. 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.

(1) 3d–series
Sc → 18[Ar] 3d1 4s2
Ti → 18[Ar] 3d2 4s2
V → 18[Ar] 3d3 4s2
Cr → 18[Ar] 3d5 4s1
Mn → 18[Ar] 3d5 4s2
Fe → 18[Ar] 3d6 4s2
Co → 18[Ar] 3d7 4s2
Ni → 18[Ar] 3d8 4s2
Cu → 18[Ar] 3d10 4s1
Zn → 18[Ar] 3d10 4s2

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d-Block Part-01

(2) 4d–series
Y → 36[Kr] 4d1 5s2
Zr → 36[Kr] 4d 2
5s2
Nb → 36[Kr] 4d4 5s1
Mo → 36[Kr] 4d5 5s1
Tc → 36[Kr] 4d6 5s1
Ru → 36[Kr] 4d7 5s1
Rh → 36[Kr] 4d8 5s1
Pd → 36[Kr] 4d10 5s0
Ag → 36[Kr] 4d10 5s1
Cd → 36[Kr] 4d10 5s2

(3) 5d–series
La → 54[Xe] 5d1 6s2
Hf → 54[Xe] 5d2 6s2
Ta → 54[Xe] 5d3 6s2
W → 54[Xe] 5d4 6s2
Re → 54[Xe] 5d5 6s2
Os → 54[Xe] 5d6 6s2
Ir → 54[Xe] 5d7 6s2
Pt → 54[Xe] 5d9 6s1
Au → 54[Xe] 5d10 6s1
Hg → 54[Xe] 5d10 6s2

(4) 6d–Series
Ac → 86[Rn] 6d1 7s2
Rf → 86[Rn] 6d2 7s2
Db → 86[Rn] 6d3 7s2
Sg → 86[Rn] 6d4 7s2
Bh → 86[Rn] 6d5 7s2
Hs → 86[Rn] 6d6 7s2
Mt → 86[Rn] 6d7 7s2
Ds → 86[Rn] 6d8 7s2
Rg → 86[Rn] 6d10 7s1
Cn → 86[Rn] 6d10 7s2

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d-Block Part-01

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

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d-Block Part-01

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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d-Block
Part-02

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 Fe + Ni
(f) Invar Ni 36
(g) Alnico Al + Ni + Co
(h) Duralumin Cu + Al + Mn
(i) 22 Carrot gold Au + Ag
(j) 18 Carrot Au + Ag + Cu
(k) German Silver Ni + Cu + Zn
(l) White Metal Li + Pb
(m) Solder Sn + Pb
(n) Nichrome Ni + Cr + Fe
(o) Bell Metal Cu + Sn

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d-Block Part-02

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 :-

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

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d-Block Part-02

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

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.

Example:-

2Fe3+ +2I– → I2 +2Fe2+

2Fe2+ +S2O28– → 2Fe3+ +2SO24–
______________________
3+
2I– +S2O28– ⎯⎯→
Fe
2SO24– +I2

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d-Block Part-02

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 nueclear 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.

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d-Block Part-02

They show variable oxidation state.

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

(a) E0Cr+3 /Cr+2 = –ve

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

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d-Block Part-02

Trends in Stability of Higher Oxidation States

The highest oxidation states are shown generally among halides and oxides of transition elements.

(a) 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 TiX4 (tetrahalides, X = F, Cl, Br and I), VF5 and CrF6.
(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 (hydH1) of Cu2+ (aq) than Cu+, which is sufficiently high to
compensate second ionisation enthalpy of copper.

(b) 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, Sc2O3 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 MnF 4 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 MnO 4– 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 VO 43– and
VO2+ respectively.

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d-Block Part-02

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-Block
Part-03

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– ⎯⎯⎯⎯⎯ → Cr2O72– + H2O

Acidic medium
( 2H+ )

Cr2O72– ⎯⎯⎯⎯⎯ → 2CrO42– + H2O

Basic medium
( 2OH– )

 K2Cr2O7 is preferred over Na2Cr2O7 as a primary standard in volumetric analysis (titration) because Na2Cr2O7 is
hygroscopic in nature but K2Cr2O7 is not.

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d-Block Part-03

 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°.

Oxidising Property :-

Sodium and potassium dichromats are strong oxidising agents; the sodium salt has a greater solubility in water
and is extensively used as an oxidising agent in organic chemistry. Potassium dichromate is used as a primary
standard in volumetric analysis. In acidic solution, its oxidising action can be represented as follows :

Cr2O72– + 14H+ + 6e– ⎯→ 2Cr3+ + 7H2O

 Thus, acidified potassium dichromate will oxidise iodides to iodine, sulphides to sulphur, tin(II) to tin(IV) and iron(II)
salts to iron(III). The half-reactions are noted below :

6I– → 3I2 + 6 e–
3Sn2+ → 3Sn4+ + 6e–
3H2S → 6H+ + 3S + 6e–
6Fe2+ → 6Fe3+ + 6e–

 The full ionic equation may be obtained by adding the half-reaction for potassium dichromate to the half-reaction
for the reducing agent, for

Cr2O72– + 14H+ + 6Fe2+ → 2Cr3+ + 6Fe3+ + 7H2O

 Acidified K2Cr2O7 solution reacts with H2O2 in a etheral solution to give a deep blue solution due to the formation
of CrO5.
Cr2O72- +2H+ + 4H2O2 ⎯⎯
→2CrO5 +5H2O

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d-Block Part-03

K2Cr2O7 + H+

H2O2

CrO5

pyridine exposure

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 MnO 2 (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 MnO 2 followed by the electrolytic oxidation of
manganate (Vl).

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d-Block Part-03

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

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

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 :

 Acidified permanganate solution oxidises oxalates to carbon dioxide, iron(II) to iron(III), nitrites to nitrates and
iodides to free iodine. The half-reactions of reductants are:

5Fe2+ → 5Fe3+ + 5e–

5NO2– + 5H2O → 5NO3– + 10H+ + 10e–
10I– → 5I2 + 10e–

 A few important oxidising reactions of KMnO4 are given below :

In acidic solution :

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d-Block Part-03

(a) Iodine is liberated from potassium iodide :

10I– + 2MnO4– + 16H+ → 5I2 + 2Mn2+ + 8H2O

(b) Fe2+ ion (green) is converted to Fe3+ (yellow):

5Fe2+ + MnO4– + 8H+ → 5Fe3+ + Mn2+ + 4H2O

(c) Oxalate ion or oxalic acid is oxidised at 333 K:

5C2O42– + 2MnO4– + 16H+ → 2Mn2+ + 10CO2 + 8H2O

(d) Hydrogen sulphide is oxidised, sulphur being precipitated:

H2S → 2H+ + S2–

5S2– + 2MnO–4 + 16H+ → 2Mn2+ + 8H2O + 5S

(e) Sulphurous acid or sulphite is oxidised to a sulphate or sulphuric acid:

5SO32– + 2MnO4– + 6H+ → 2Mn2+ + 5SO42– + 3H2O

(e) Nitrite is oxidised to nitrate :

5NO2– + 2MnO4– + 6H+ → 2Mn2+ + 5NO3– + 3H2O

 In neutral or faintly alkaline solutions :

(a) A notable reaction is the oxidation of iodide to iodate:

2MnO4– + H2O + I– ⎯⎯→ 2MnO2 + 2OH– + IO3–

(b) Thiosulphate is oxidised almost quantitatively to sulphate:

8MnO4– + 3S2O32– + H2O ⎯⎯→ 8MnO2 + 6SO42– + 2OH–

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f-Block
Part-01

Introduction

01. The elements constituting the f – block are those in which the 4f and 5f orbitals are progressively filled.
02. 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.
03. The name inner transition metals are often used to refer to the elements of f–block.
04. 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

Ce ⎯→ Cerium
Pr ⎯→ Praseodymium
Nd ⎯→ Neodymium
Pm ⎯→ Promethium
Sm ⎯→ Samarium
Eu ⎯→ Europium
Gd ⎯→ Gadolinium
Tb ⎯→ Terbium
Dy ⎯→ Dysprosium
Ho ⎯→ Holmium
Er ⎯→ Erbium
Tm ⎯→ Thulium
Yb ⎯→ Ytterbium
Lu ⎯→ Lutetium

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f-Block Part-01

Electronic Configuration

58Ce ⎯→ 54[Xe] 4f1 5d1 6s2

59Pr ⎯→ 54[Xe] 4f3 5d° 6s2

60Nd ⎯→ 54[Xe] 4f4 5d° 6s2

61Pm ⎯→ 54[Xe] 4f5 5d° 6s2

62Sm ⎯→ 54[Xe] 4f6 5d° 6s2

63Eu ⎯→ 54[Xe] 4f7 5d° 6s2

64Gd ⎯→ 54[Xe] 4f7 5d1 6s2

65Tb ⎯→ 54[Xe] 4f9 5d° 6s2

66Dy ⎯→ 54[Xe] 4f10 5d° 6s2

67Ho ⎯→ 54[Xe] 4f11 5d° 6s2

68Er ⎯→ 54[Xe] 4f12 5d° 6s2

69Tm ⎯→ 54[Xe] 4f13 5d° 6s2

70Yb ⎯→ 54[Xe] 4f14 5d° 6s2

71Lu ⎯→ 54[Xe] 4f14 5d1 6s2

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 f 0 f7 f14
occupancies of the 4f orbitals.

Atomic and Ionic Radius

1. The overall decrease in ionic radii from lanthanum to lutetium is a unique feature in the chemistry of the

lanthanides.

2. This is due to poor shielding of nucleus by inner penultimate 4f orbital.

3. The cumulative effect of the contraction in size of the lanthanide series, known as lanthanide contraction.

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

5. The decrease in ionic radii of M3+ comparatively more regular.

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f-Block Part-01

Sm2+
110
Eu2+

La3+
Ce3+
Pr3+
100 Nd3+
Pm3+

Ionic radii/pm
Sm3+
Eu3+
Gd3+ Tm2+
Tb3+ Yb2+
Ce4+
Dy 3+

90 Pr4+ Ho3+
Er3+
Tm3+
Yb3+
Lu3+
Tb 4+

57 59 61 63 65 67 69 71
Atomic number

Trends in ionic radii of lanthanides

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.

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f-Block Part-01

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.

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%)

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f-Block Part-01

The Actinides :

Name

Th ⎯→ Thorium
Pa ⎯→ Protactinium

U ⎯→ Uranium
Np ⎯→ Neptunium
Pu ⎯→ Plutonium
Am ⎯→ Americium

Cm ⎯→ Curium
Bk ⎯→ Berkelium

Cf ⎯→ Californium

Es ⎯→ Einstenium

Fm ⎯→ Fermium

Md ⎯→ Mendelevium
No ⎯→ Nobelium
Lr ⎯→ Lawrencium

Electronic Configuration

90Th ⎯→ 86[Rn] 5f° 6d2 7s2

91Pa ⎯→ 86[Rn] 5f2 6d1 7s2

92U ⎯→ 86[Rn] 5f3 6d1 7s2

93Np ⎯→ 86[Rn] 5f4 6d1 7s2

94Pu ⎯→ 86[Rn] 5f6 6d0 7s2

95Am ⎯→ 86[Rn] 5f7 6d0 7s2

96Cm ⎯→ 86[Rn] 5f7 6d1 7s2

97Bk ⎯→ 86[Rn] 5f9 6d0 7s2

98Cf ⎯→ 86[Rn] 5f10 6d0 7s2

99Es ⎯→ 86[Rn] 5f11 6d0 7s2

100Fm ⎯→ 86[Rn] 5f12 6d0 7s2

101Md ⎯→ 86[Rn] 5f13 6d0 7s2

102No ⎯→ 86[Rn] 5f14 6d0 7s2

103Lr ⎯→ 86[Rn] 5f14 6d1 7s2

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.

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f-Block Part-01

The irregularities in the electronic configuration of actinides are related to the stabilities of the f 0, f7, f14
occupancies of the 5f orbitals.

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.

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f-Block Part-01

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 oxdiation 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. eg. 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.
+1
2Cu( aq ) ⎯→ Cu(+aq2 ) + Cu( s )
This is because that hydration energy of Cu ( aq ) ions is sufficiently high to compensate IE2 of Cu.
+2

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– + S2O82– ⎯⎯⎯

Fe(III)
→  + 2 SO42–

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