d - and f - block elements

07 June 2025

Periodic table
Based upon the orbital in which the outermost or
valence electron enters

s- block elements p- block elements d- block elements f- block elements

(s -orbital) (p -orbital) (penultimate d- orbital) (antipenultimate d- orbital)
[Main group or representative elements]

(Group 3 - Group 12 elements lying in between s- and p-

block elements)

s- block d- block p-block

Metallic Non-metallic
Reducing property Oxidizing property
Electropositive Electronegative

Therefore, called as Transition elements.

Transition elements or d- block elements:

These are the elements in which the outermost electrons are progressively filled into penultimate (n - 1)d - orbitals.
The actual definition is: These are the elements having partially filled d - orbitals (d1 - d9) either in their elemental or the most
common oxidation state.
Example: Fe (Z = 26) : 3d6 4s2 (elemental state)
Fe2+ : 3d6 4s0 (common oxidation state)
Fe3+ : 3d5 4s0 (common oxidation state)

Zn, Cd and Hg are called Non-typical transition elements

Example: Zn (Z = 30) : 3d10 4s2 (elemental state)
Zn2+ : 3d10 4s0 (common oxidation state) - as there are no partially filled d - orbitals either in its elemental state or most
common oxidation state, it is called as non-typical transition element.

Cu, Ag and Au are called transition elements

Example: Cu (Z = 29) : 3d10 4s1 (elemental state)

Cu1+ : 3d10 4s0 (common oxidation state)
Cu2+ : 3d9 4s0 (common oxidation state) - as there are partially filled d - orbitals either in its most common oxidation
state, it is called as transition element. These are also called as coinage metals.

 All the transition elements are metals.

Classification of d - block elements

Series (n-1)d - orbital filled Period (n) No. of elements General electronic configuration
3d-series or first transition series 3d - orbital 4 10 [Ar] 3d1-10 4s1-2
4d-series or second transition series 4d - orbital 5 10 [Kr] 4d1-10 5s0-2
5d-series or third transition series 5d - orbital 6 10 [Xe] 5d1-10 6s1-2
6d-series or fourth transition series 6d - orbital 7 10 [Rn] 6d1-10 7s1-2

General electronic configuration for d - block elements: (n-1)d1-10 ns0-2

Electronic configurations
Group No. 3 4 5 6 7 8 9 10 11 12
IIIB IVB VB VIB VIIB VIIIB VIIIB VIIIB IB IIB
3d - series Sc Ti V Cr Mn Fe Co Ni Cu Zn
Exceptional
Z 21 22 23 24 25 26 27 28 29 30
configurations
4s 2 2 2 1 2 2 2 2 1 2
3d 1 2 3 5 5 6 7 8 10 10
4d - series Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Z 39 40 41 42 43 44 45 46 47 48

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 4s 2 2 2 1 2 2 2 2 1 2
3d 1 2 3 5 5 6 7 8 10 10
4d - series Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Z 39 40 41 42 43 44 45 46 47 48
5s 2 2 1 1 1 1 1 0 1 2
4d 1 2 4 5 6 7 8 10 10 10
5d - series La Hf Ta W Re Os Ir Pt Au Hg
Z 57 72 73 74 75 76 77 78 79 80
6s 2 2 2 2 2 2 2 1 1 2
5d 1 2 3 4 5 6 7 9 10 10
6d - series Ac Rf Db Sg Bh Hs Mt Ds Rg Cn
Z 89 104 105 106 107 108 109 110 111 112
7s 2 2 2 2 2 2 2 2 1 2
6d 1 2 3 4 5 6 7 8 10 10

(n - 1)d and ns orbitals have small energy gap between them and hence, both can take part in reactions or bond formations.

Comparison of electronic configurations of 3d - series elements

d0 - configuration:
 Only for Sc3+
 Both 3d- and 4s- electrons are involved
 Ti(IV), V(V), Cr(VI), Mn(VII) also possible
 Fe(VIII) is impossible or is unknown
d1 - configuration:
 Except V(IV), all others act as reducing agents or undergo disproportionation reactions.
 Examples:

Stable in aqueous solutions


d2 - configuration:
 Ranges from Ti(II) [Strong reducing agent] to Fe(VI) [Strong oxidizing agent].
 V(III) acts as a reducing agent.
d3 - configuration:
 Cr+3 is stable in aqueous solutions.
 Not so important for others.
d4 - configuration:
 Really no stable species
 Cr(II) is a strong reducing agent.
 Mn(III) undergoes disproportionation reaction.
d5 - configuration:
 Important for Mn(II) and Fe(III) ions.
reduction
Fe2+
d6 - configuration:
 Important for Fe(II) and Co(III)
 Fe(II) is a mild reducing agent as it can undergo oxidation to form Fe(III).
 Co(III) is stable in the presence of strong complexing agents.
d7 - configuration:
 Co(II) is stable in aqueous solutions.
Strong ligands
Co(III)
Oxidized
d8 - configuration:
 Ni(II) is important.
d9 - configuration:
 Cu(II) is important.
d10 - configuration:
 Cu(I) and Zn(II) are important.
Oxidation
Cu(II)
Disproportionation Cu(II) and Cu
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 Cu(I) and Zn(II) are important.
Oxidation
Cu(II)
Disproportionation Cu(II) and Cu

General characteristics of d - block elements

 The d - orbitals are at the periphery of an atom than s - and p - orbitals. Hence, are influenced easily by surrounding atoms
and also affect atoms surrounding them (d - electrons affect the properties).
Therefore, elements with similar dn configurations have similar magnetic and electronic properties.
 Greater horizontal similarities in properties than the main group elements.
 They have typical metallic properties - malleability, ductility, high tensile strength, high thermal and electrical conductivity,
metallic luster, etc.
 Except Zn, Cd, Hg and Mn, others have ≥ 1 crystal structures at normal temperatures.
 Atomic radii: s - block elements > d - block elements > p - block elements.
 They have high MP, BP, for their ions.

Depend upon the strength of metallic bonds in them.

Depend upon number of unpaired d - electrons
 IE1 : s - block elements < d - block elements < p - block elements.
 They exhibit variable oxidation states.
 The stability of oxidation states or tendency to act as reducing or oxidizing agent depend upon their SRP values.
 They are electropositive in nature.
 They form colored compounds.
 Most of the transition metals and their compounds are paramagnetic in nature.
 Transition metals and their compounds are used as catalysts.
 They form interstitial compounds.
 They form alloys.
 They form coordination compounds or complexes.

Metallic character
 Transition metals are hard, lustrous, malleable and ductile.
 They have high MP, BP, thermal and electrical conductivity and high tensile strength.
Reason: because of low IE and both ns and (n-1)d electrons take part in metallic bonding.

 No of unpaired d - electrons ↑, strength of metallic bond ↑and hardness ↑.

 Examples: Cr, Mo and W - Hard metals - because they have maximum number of unpaired electrons

and hence, maximum metallic bonding.

 Zn, Cd and Hg - not hard metals - because of no unpaired electrons [d10 configurations].

d - block elements have partially filled d - orbitals and hence, have metallic and covalent bonding.

Melting points and boiling points

 Have high MP and BP - because of presence of metallic bonding due to involvement of both ns and (n-1)d - electrons.

 MP - ↑ up to d5 - configuration, reaches maximum and then again ↓.

 3d - series: Sc < Ti < V < Cr > Mn < Fe > Co > Ni > Cu > Zn

Cr has the maximum MP while Zn has the least MP among 3d - series elements.

 4d - series: Zr < Nb < Mo > Tc < Ru > Rh > Pd > Ag

Mo has the maximum MP among 4d - series elements.

 5d - series: Hf < Ta < W > Re > Os > Ir > Pt > Au

W has the highest MP among d - block elements.

Mn and Tc have abnormally lower value of MP because they both have stable (n-1)d5 ns1 half-filled configurations and hence,
the electrons do not take part easily in the metallic bond formation.

Enthalpy of atomization ( )

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Enthalpy of atomization ( )
 Have high enthalpies of atomization and hence, high MP.
Because of more number of unpaired electrons.

Number of unpaired electrons ↑, Metallic bond strength ↑ and hence, enthalpy of atomization ↑

 3d - series: Zn < Mn < Sc < Cu < Cr < Fe < Co < Ni < Ti < V

Minimum Maximum


Because of more frequent metallic bonding in heavy metals (4d and 5d-series).

Density
 Along the period: Size ↓, mass ↑ and hence, density ↑

 There is a significant increase in density from Ti to Cu.

 Density of Sc, Ti and Y < 5 g/cm3 while for other elements, density > 5 g/cm3.

 Zn → lower density than expected because it has the configuration 3d10 4s2 which results in electron-electron repulsions
between paired electrons and ↑ in size > ↑ in mass.

 3d - series: Sc < Ti < V < Zn < Cr < Mn < Fe < Co < Ni ≈ Cu

 Density order: 3d< 4d < 5d

 Os (22.57 g/cm3) and Ir (22.61 g/cm3) have almost same densities.

Atomic properties
Atomic and ionic size or radii
 Along the period: ↑, size ↓

 Among the d-block elements: ↑, size ↓ but with irregularities.

 Sc Ti V Cr Mn Fe Co Ni Cu Zn

All d-electrons get paired

up resulting in greater
Z ↑, but, pairing of d-electrons start, electron-electron
Electron-electron repulsions ↑ repulsions than ↑ in
↑ in counterbalances repulsions Hence, size ↑
Hence, size remains almost constant
Z↑
Poor shielding effect of d-electrons
(More dominationg)
Hence, size ↓

 Down the group: 3d < 4d ≈ 5d

Because of lanthanoid contraction in 5d-series due to improper

shielding effect by 4f-electrons.

 Set of elements from 4d and 5d-series having similar size due to lanthanoid contraction are:

4d-series Zr Nb Mo
5d-series Hf Ta W

 Also, Size(M3+) < Size(M2+) due to greater Zeff in M+3 ions.

Ionization enthalpy or ionization potential (IE or IP)

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Ionization enthalpy or ionization potential (IE or IP)
 In transition series, IE increases from left to right with irregularities.
 IE1 : s - < d - < p - block elements

Because as atomic number ↑, Zeff ↑ and hence, size ↓

 Irregular trend in IE of d - block elements.

It is because the removal of electron alters the relative energies of the ns and (n-1)d orbitals, which results in reorganization
of energy which leads to exchange energy. Number of unpaired electrons ↑, Exchange energy ↑, stability ↑.
 IE1 of chromium (Z =24): [Ar]3d5 4s1 [Ar]3d5
→ exactly half filled EC, more exchange energy and high stability and hence, low IE1.
 IE1 of zinc (Z =30): [Ar]3d10 4s2
→ completely filled EC, more exchange energy and high stability and hence, high IE1.
 Similarly, the IE1 for Cd and Hg are high.
 Along the period, IE ↑.
 Successive IE: IE1 < IE2 < IE3
 IE1 of 5d-series > 3d- and 4d-series elements

Due to lanthanoid contraction, which is due to improper

shielding effect of 4f-electrons.

 Order of IE: IE1: Sc < V < Cr < Ti < Mn < Ni < Cu < Co < Fe < Zn
IE2: Sc < Ti < V < Mn < Fe < Cr < Co < Zn < Ni < Cu
IE3: Sc < Ti <V < Fe < Cr < Co < Mn < Ni < Cu < Zn

 Examples: (i) Abnormal high IE2 of copper.

Reason: Cu: [Ar]3d104s1 Cu+1: [Ar]3d104s0
Stable completely filled EC and hence, more exchange
energy and high stability and therefore, has high IE2

 (ii) Abnormal high IE3 of Mn.

Reason: Mn: [Ar]3d54s2 Mn+1: [Ar]3d54s1 Mn+2: [Ar]3d54s0

Stable half-filled EC and hence, more exchange energy

and high stability and therefore, has high IE3

(iii) Abnormal high IE4 of Fe.

Oxidation states
 Exhibit multiple or variable oxidation states.
Reason: Both ns and (n-1)d electrons take part in the reactions because of small energy gap
between ns and (n-1)d orbitals.
 Exceptions: Sc and Zn do not exhibit variable oxidation states in 3d series elements (group 3 and 12 elements).
 Number of oxidation states ↑ up to middle and then starts ↓

Because up to d5 configuration, number of unpaired d-electrons ↑ ad hence,

number of oxidation states ↑.
After d5, pairing of electrons start and number of unpaired electrons ↓ and
hence, number of oxidation states ↓

 Minimum oxidation state = Number of ns electrons

 Maximum oxidation state = Number of ns + (n-1)d electrons up to Mn

= Number of ns + unpaired (n-1)d electrons after Mn

Sc Ti V Cr Mn Fe Co Ni Cu Zn
+3 +2 +2 +1 +2 +2 +2 +2 +1 +2 Stable oxidation numbers
+3 +3 +2 +3 +3 +3 +3 +2
+4 +4 +3 +4 +4 +4 +4
+5 +4 +5 +5 +5
+5 +6 +6

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 +5 +6 +6
+6 +7
 Common oxidation state = +2 because of removal of ns electrons except Sc (+3).
 (n-1)d orbitals become more stable after Sc
 Maximum oxidation states: (i) 3d-series elements - Mn (+7) [KMnO4, Mn2O7]
(ii) d-block elements - +8 [Os and Ru]
 Maximum oxidation state possible only with oxygen or fluorine because of small size
and high electronegativity of O and F.
 Transition metals in lower oxidation states [+2 and +3] form ionic compounds.
 They form covalent compounds in higher oxidation states. [Fajan's rule]
 Example: KMnO4 (+7) and K2Cr2O7 (+6)
M - O bond is covalent bond because covalent character α Charge on the cation.
 V → VII, VIII, VIV, VV and Mn → MnII, MnIII, MnIV, MnV, MnVI, MnVII.
In transition metals, the oxidation states differ by one unit while in non-transition elements, the
oxidation states differ by 2 units [Pb2+ and Pb+4 / Sn2+ and Sn4+].
 Higher oxidation states are more stable in heavier elements.
Stability order: Cr(VI) < Mo(VI) < W(VI)

Unstable, strong OA

Oxidizing power order: Cr(VI) > Mo(VI) > W(VI)

 Relative stabilities of different oxidation states of an element can be explained using SRP values.
Example:

Because of higher SRP, Cu+1 has more tendency to get reduced and hence, Cu2+ is more stable than Cu+1.
 Trends in the stability of higher oxidation states in transition metal halides
ON Ti V Cr Mn Fe Co Ni Cu Zn
+6 CrF6
+5 VF5 CrF5
+4 TiX4 VX4' CrX4 MnF4
X = F → I; X' = F → Br; X'' = F, Cl; X''' = Cl → I
+3 TiX3 VX3 CrX3 MnF3 FeX3' CoF3 CuX2''
+2 TiX2''' VX2 CrX2 MnX2 FeX2 CoX2 NiX2 CuX''' ZnX2
+1
 Higher OS vary from +4 for Ti (TiX4) to +5 for V (VF5) to +6 for Cr (CrF6) to +4 for Mn (MnF4) or +7 for
Mn in oxyfluorides (MnO3F).
 Beyond Mn, no metal shows halides with OS greater than +3 except FeX3'and CoF3.
 The highest OS is more stable with fluorine because of high lattice energy in CoF3 or higher bond enthalpies
For higher covalent compounds like VF5 and CrF6.
 V shows +5 directly in VF5 but other halides of V (VX4, VX3 and VX2) undergo hydrolysis to give
Oxyhalides (VOX3) with V in +5 OS.
 In low OS, fluorides are not stable like in TiX2 and VX2.
 Cu(II) halides are known including CuF2 but not iodides i.e. CuX2 where X = F/Cl/Br ≠ I
 They oxidize iodide (I-) to iodine (I2).
2Cu+2 + 4 2Cu2I2 + I2
Hence, Cu2I2 exists but not CuI2 and Cu(I) compounds are unstable in aqueous solutions and therefore,
undergo disproportionation reactions.
2Cu+1 Cu2+ + Cu
Cu(II) ion is more stable in aqueous solution because of very high negative hydration enthalpy which compensates
IE2 of copper.
 Stability of higher oxidation states
 Oxygen stabilizes the higher oxidation states in their oxides because of their tendency to form pπ-dπ multiple bonds with
metal atoms or ions.
 The highest OS in oxides is equal to the group number and is attained inSc2O3 to Mn2O7.
 Beyond group 7, maximum OS is +2 in CuO, NiO and ZnO and +3 in Fe2O3.
 Ferrates [FeO4 has Fe in +6 OS but they readily decompose to form Fe2O3 and O2.
 The highest oxidation state are also present in oxo cations like VO2+ [V in +5], VO2+2 [V in +6] and TiO+2 [Ti in +4].
 MnF7 does not exist but Mn2O7 exists.
Reason: In Mn2O7, the oxygen stabilizes +7 OS by forming pπ-dπ multiple bonds. Hence, Mn2O7 exists. In MnF7, there is
crowding of fluoride ion resulting in more electron-electron repulsion and less stability. Hence, MnF7 does not exist.
 Metal oxides in highest OS are acidic and lowest oxidation sates are basic, while in intermediate oxidation states are
amphoteric.

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 amphoteric.
Example: CrO (basic), Cr2O3 (amphoteric) and CrO3 (acidic)

Magnetic properties
 Most of the transition metals and their compounds are paramagnetic in nature.
Reason: Due to the presence of unpaired electrons.
 A single electron behaves as a tiny magnet because of its orbital motion around the nucleus and spin motion about its
own axis. These motions produce and electric field and magnetic field mutually perpendicular to each other. The direction
Of magnetic field will be in the direction of spin motion of the electron. Depending upon the behavior towards a magnetic
filed, substances are classified as:
 Diamagnetic substances - which are weakly repelled by the magnetic field due to the absence of unpaired electrons or
presence of paired electrons. Examples: NaCl, KCl, wood, Cu2O, ZnO, etc.
 Paramagnetic substances - which are weakly attracted by the magnetic field due to the presence of one or more unpaired
electrons. Examples: Fe2+, Fe3+, Cr+3, O2, Cu2+, etc.
 Ferromagnetic substances - which are strongly attracted by the magnetic field due to the presence of large number of
unpaired electrons. Examples: Fe, Co, Ni, CrO2, etc.
CrO2 is used in magnetic tapes is cassette recorders.
 The magnetic field strength is expressed in terms of magnetic moment (μ) and is given by spin only formula as:

Where, n - number of unpaired electrons

BM - Bohr magneton (SI unit for magnetic moment)

Hence, n ↑, μ ↑, magnetic properties ↑. If n = 0, then μ = 0 and therefore, diamagnetic substance.

 Example: Calculate the magnetic moment of:

Sc3+, Mn2+, Cr3+, bivalent cation with Z = 28 and predict whether paramagnetic or diamagnetic.
 The magnetic moment of a bivalent cation is (35)1/2 BM. Calculate the number of unpaired electrons. Identify the element
and write its EC.
 Among Zn and Zn(II) salts, which one is diamagnetic and why?

Formation of colored compounds

 Most of the transition elements and their compounds are colored in their aqueous solutions due to the presence of unpaired
d-electrons, which show d - d transitions.
 In aqueous solutions, the degeneracy of the d-orbitals is lost and the d-orbitals split into a two sets i.e. t2g and eg. This is
known as crystal field splitting.
eg

t2g

When white light falls on the electron, it absorbs energy and gets excited from low energy d-orbitals (t2g) to high energy d-
orbitals (eg). This is called as d - d transition. The excited electron returns to the normal state emitting energy lying in visible
region. The color absorbed and the color observed are complementary to each other.

Color absorbed Color observed

Violet Yellowish green
Blue Yellow
Greenish blue Orange
Bluish green Red
Green Purple
Yellowish green Violet
Yellow Blue
Orange Greenish blue

 The frequency of light absorbed depends upon:

➢ Nature of the ligand
Size of the metal ion

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 ➢ Size of the metal ion
➢ Oxidation state
 The color depends upon:
➢ The number of electrons undergoing d - d transition
➢ Energy gap between t2g and eg set of orbitals.
 Examples:
➢ Sc(III) salts are colorless because Sc(III) = 3d04s0 - no unpaired d electrons and hence, no d-d transition.
➢ Zn and Zn(II) salts are colorless.
➢ Cu(I) salts are colorless while Cu(II) salts are colored.
 Metals ions have different colors in different oxidation states.
Example: Mn+7 (Pink/purple), Mn+6 (Dark green), Mn+3 (Blue), Mn+2 (Colorless).
 In KMnO4, Mn is present as Mn+7 → 3d0 4s0 → No unpaired d-electrons, no d-d transition and hence, should be colorless but
is pink or purple colored due to charge transfer spectra.
 Similarly, K2Cr2O7 (orange red), K2CrO4 (yellow), [Fe(H2O)5NO]2+ (brown), Fe4[Fe(CN)6]3 (Prussian blue) are colored due to
charge transfer spectra.
 Anhydrous CuSO4 is colorless because it does not involve crystal field splitting and hence, no d-d transition. CuSO4.5H2O is
blue colored because d-d transition due to crystal field splitting in the presence of water.

Formation of complexes or coordination compounds

 Transition metals form complexes due to:
➢ Small size of the metal ions
➢ High ionic charges
➢ Availability of vacant d-orbitals for bond formation
 Transition metals have partially filled d-orbitals and hence, can accept electron pairs from ligands and act as Lewis acids.
 Ligands are neutral or charged species containing at least one lone pair of electron that can be donated to the metal atom or
ion and hence, act as Lewis base.
 Complex representation:
 Examples: K4[Fe(CN)6], K3[Fe(CN)6], [Cu(NH3)4]SO4, K3[Hg(I)4], [Co(en)3]3+, [Cr(NH3)6]Cl3, etc.

Catalytic property
 Transition metals and their compounds act as very good catalysts due to:
➢ Tendency to adopt multiple oxidation states
➢ Tendency to form complexes
 A catalyst forms bonds with reactant molecules at its surface and thereby, increases the concentration of the reactants on
the surface and weakens the bonds between the reactant molecules and decreases the activation energy.
 Example: Fe(III) catalyzes reaction between iodide and persulphate ions.

Mechanism:
Step - 1:
Step - 2:
 Some of the catalyst used in industrial processes are:
➢

➢ Fe as catalyst and Mo as promoter in Haber's process.

➢ Pt-Rh gauze catalyst in Ostwald's process for the manufacture of nitric acid.

➢
➢ Adam's catalyst [Pt/
➢ Wilkinsons' catalyst [RhCl

Formation of interstitial compounds

 These are formed when small atoms like H, C, B or N are trapped inside the interstitial spaces in the crystal lattice of
metals. These are non-stoichiometric solids and are neither ionic nor covalent.
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 metals. These are non-stoichiometric solids and are neither ionic nor covalent.
Characteristics of interstitial compounds
 They are very hard.
 They have very high melting points higher than those of pure metals.
 They are chemically inert.
 They retain their metallic conductivity.

Formation of alloys
 These are homogeneous solid solutions in which atom of one metal are distributed randomly among the atoms of other
metal.
 These are formed by atoms having atomic radii within the range of 15% to each other.
 Examples:
➢ Brass (Cu + Zn)
➢ Bronze (Cu + Sn)
➢ German silver (50-60% Cu + 10-30% Ni + 20-30% Zn)
➢ Bell metal (80% Cu + 20% Sn)
➢ Gun metal (80% Cu + 10% Sn + 2+ Zn)
➢ Monel metal (?)

Some industrially important compounds

Potassium dichromate (
Manufacture
 Manufactured from chromite ore [FeO.Cr2O3 or FeCr2O4]

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 4d-series Zr Nb Mo
5d-series Hf Ta W

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 5d-series Hf Ta W

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