d & f Block Elements

 The elements that can be found from the third group to the twelfth group of the modern periodic
table are called d-block elements.

 The valence electrons of these elements fall under the d orbital.

 d-block elements are also called transition elements or transition metals because they exhibit
transitional behaviour between s block and p block elements.

 Elements that have at least one unpaired electron in their d orbital in atomic or any oxidation state
are called transition elements.

 All transition elements are d-block elements, but all d-block elements are not transition elements.
e.g. Zn, Cd and Hg

 Their outer most shell e- ( ns electrons) as well as second last valence shell e- (n-1) d can
participate in bond formation.

 First series: These are called the 3d series of elements. They are classified in the 4 th period.
Atomic numbers are from 21 to 30. (Sc to Zn)

 Second series: These are called the 4d series of elements. They are classified in the 5th period.
Atomic numbers are from 39 to 48. (Y to Cd).

 Third series: These are called the 5d series of elements. They are classified in the 6th period.
Atomic numbers are 57 and 72 to 80. (La, Hf to Hg).

 Fourth series: These are called the 6d series of elements. They are classified in the 7th period.
Atomic numbers are 89 and 104 to 112. (Ac, Rf to Cn). This is an incomplete series.

 General electronic configuration

 The general configuration for d block elements is (n-1)d1-10 ns1-2.

 Metallic character

 All the transition elements are metallic in nature.

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 A metallic bond is quite strong due to its greater effective nuclear charge and a large number of
valence electrons.

 These are hard and possess high densities and high enthalpies of atomisation. Due to the presence
of free electrons.

 These are good conductors of heat and electricity. The order of conductivity is Ag > Cu > Au > Al.

 Density

 The atomic volume of the transition elements is low compared to the s block. Their density is
comparatively high. Os and Ir have the highest density. All the d-block elements, except Sc, Y and
Ti have densities greater than 5 gm cm-3.

 In all the groups, there is a normal increase in density from 3d to 4d series and from 4d to 5d; it
increases just double due to the lanthanide contraction. That means, due to a double increase in
atomic mass, the density of 5d elements is nearly twice that of 4d elements. Ti<Zr<<Hf.

 In 3d series Sc→ Cr density increases, Mn, Fe, Co Ni → almost constant, Cu → Zn decreases. In the
3d series, Cu has the highest density, and Sc has the lowest density.

 Melting point and boiling point

 Due to a stronger metallic bond and the presence of a covalent bond formed by unpaired d
electrons, the melting point and boiling point of d-block are greater than s block elements.

 There is no unpaired electron present in the d orbital of Zn, Cd and Hg. So, due to the absence of a
covalent bond, their melting point and boiling point are very low.

 In 3d series Sc → Cr melting point and boiling point increase, Mn → Zn melting point and boiling
point decrease.

 Manganese(Mn) and technetium(Tc) show abnormal values in the trend.

 Tungsten(W) has the highest m.p. (3410oC).

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 Mercury(Hg) is liquid at room temperature (m.p. – 38.9°C) due to absence of unpaired electrons,
and weak metallic bonding.

 Enthalpy of Atomisation

 The energy required to convert metal lattice into atoms is called enthalpy of atomisation.

 They have high enthalpy of atomisation due to strong metallic bond because of their small
size and d-d overlapping.

 Greater the number of unpaired valence electron stronger is the metallic bonding hence higher is
the enthalpy of atomisation.

 Those transition metals which have higher enthalpy of atomisation have low electrode potential
thus they are less reactive & hence act as noble metals.

 Atomic size

 Atomic radii depend on effective nuclear charge Zeff and screening effect.

 Ionic radii and atomic radii of d-block elements are smaller than s-block elements.

 In 3d series, Sc → Cr radius decreases, Mn → Ni radius remains constant, Cu → Zn radius increases.

 Atomic and ionic size Ions of the same charge in a given series exhibit regular decrease in radius
with increasing atomic number, because the new electron enters in a d – orbital and nuclear
charge increases by unity.

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 In last of the series, a small increase in size is observed due to electron-electron repulsion.

 (Atomic and ionic radii increase from 3d-series to 4d-series but the radii of the third (Sd) series
elements are virtually the same as those of the corresponding member of the second series. It can
be explained on the basis of lanthanoid contraction [poor shielding of 4f ].

 Due to lanthanide contraction Zr and Hf Have almost similar radii.

 Formation of Alloy

 Alloy is a homogeneous mixture of two or more metals.

 The reactivity of transition elements is very less and their sizes are almost similar. Because of this,
a transition metal atom in the lattice can be easily replaced by other transition metal atoms, and
hence they have a maximum tendency to form alloys.

 They are hard and have very high melting point.

 The metals Mo, W, Cr, Ni, and V are used for the production of stainless steel.

 Amalgam is an alloy formed by mercury with other metals, Iron and platinum do not form any
alloy with mercury.

Important Alloys

 Bronze: Cu (75-90%) + Sn(10 – 25%)

 Brass: Cu (60-80%) + Zn(20 – 40%)

 Gunmetal: (Cu + Zn + Sn) 87:3:10

 Bell metal: Cu (80%) + Sn (20%)

 Nichrome: Ni + Cr + Fe

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 Colour Property

 Most of the compounds of transition metals are coloured.

 Cause: (a) d-d transition

(b) charge transfer

(c) structural defect

 Due to the presence of unpaired electrons in their d orbitals, most of the transition metal ions
show colour properties.

 They need only a less amount of energy to excite electrons. Hence, they absorb visible regions of
light exhibiting colour.

 Ti+2=[Ar]d2, V+2 =[Ar]3d3 etc., have unpaired electrons in their d orbitals. Therefore, they are
coloured.

 Transition metals which do not have any unpaired electrons in their d orbitals (3d 0 and
3d10 configuration) do not show any colour property.

For example, Sc+3 =[Ar]3d0, Cu+1 =[Ar]3d10 are colourless ions.

 Potassium permanganate KMnO4 (dark pink) and K2Cr2O7 (orange) have a d0 configuration
because of the charge transfer spectrum. The below table shows coloured metal ions.

Ni+2Green; Cu+2Blue; Co+2Blue; Fe+2Pale green; Ti+3Purple

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 Magnetic properties

 Most of the transition metals have unpaired electrons in their d orbitals, they are paramagnetic in
nature. Those metal ions that have (n-1)d0 and (n-1)d10 configurations show diamagnetic nature.

 The magnetic moment due to the spinning of unpaired electrons can be found by using the
equation μ =

 Here, n =number of unpaired electrons in the metal ion

μ = magnetic moment in Bohr magnetons

 For diamagnetic substances, the magnetic moment will be zero.

 When the number of unpaired electrons increases, the magnetic moment also increases, and thus
the paramagnetic nature increases.

 Transition metal ions with d5 configuration have a maximum number of unpaired electrons, and
hence they have maximum paramagnetic nature.

 Ferromagnetic: Some substances are attracted very strongly by the applied magnetic field. These
are called ferromagnetic materials. (Permanent Magnetism) Example: Fe, Co, Ni, etc.

 Catalytic property

 Many transition elements show catalytic property because:

a. Large surface area

b. Vacant d- orbitals
c. They have variable oxidation state
d. They have ability to form complexes
 Catalyst adsorbs reactant molecules on its surface and forms bonds using electrons of d & s
orbitals. This results in increase in concentration of reactant at the catalyst surface and also
weakens the bond in the reactant molecule and lowers the activation energy.

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 Transition metals and their compounds exhibiting catalytic properties in various processes are
given below.
(a) V2O5 is used in the contact process for the manufacture of H2SO4.
(b) Fe is used in Haber’s process for the manufacture of NH3.
(c) Ni is used in the hydrogenation of oils.
(d) Cu is used in the dehydrogenation of alcohols.
(e) TiCl4 is used as a catalyst in Vinyl polymerisation.
(f) Pt is used in Ostwald’s process of nitric acid.

 Formation of Interstitial Compounds

 Transition elements react with elements like nitrogen, hydrogen, boron, etc., to form interstitial
compounds.

 The smaller-sized atoms get trapped in between the interstitial spaces of the metal lattices.

 These interstitial compounds are non-stoichiometric in nature. So, they cannot be given any
definite formula.

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 Weak Vander Waals forces of attraction are responsible for holding smaller-sized elements in
interstitial spaces of transition elements.

 The interstitial compounds have the same chemical properties as the parent metals but they differ
in physical properties, such as hardness and density.

The physical and chemical properties of the interstitial compounds are as follows:

 These compounds are chemically inert in nature.

 These compounds have very high melting points (Greater than that of the parent transition
metals).

 These compounds are very hard.

 The conductivity exhibited by them is similar to their parent metal.

 Complex Formation

These elements form complex coordinate compounds because they have

a. Small ionic size

b. Vacant d orbitals
c. High nuclear charge
d. High charge density on the ion

Cu2+ (aq) + 4 NH3 (aq)  [Cu(NH3)4]2+ (aq)

(blue) (deep blue)

AgCl (s) + 2 NH3 (aq) → [Ag (NH3)2]Cl (aq)

(white ppt) (Colourless )

 Ionisation Enthalpy

 Generally increases due to increases in nuclear charge from left to right in series .

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 IE1<IE2< IE3 in each group due to positive charge on them.

 IE1 of 5d series is much higher than those of 4d and 3d due to weak shielding by 4f electrons.

3d > 4d < 5d

 Oxidation State

 Transition elements have variable oxidation state , due to very small energy difference between
(n-1)d and ns sub-shell. Electrons from both the sub-shell take part in bonding.

 No. of Oxidation states α no. of unpaired electrons.

 Mn shows all oxidation states from +2 to +7.

 Low oxidation state are found when a complex compound has ligands capable of π-acceptor
character in addition to the sigma bonding, e.g. Ni(CO)4, Fe(CO)5.

 Standard electrode potential

 Value of electrode potential depends on enthalpy of atomisation , sum of ionisation enthalpies and
hydration enthalpy.

 Due to positive electrode potential, Cu does not liberate hydrogen from acids .

 It must be noted that the value of E0 for Mn , Ni and Zn are more negative than expected from the
trend.

Reduction potential α ΔaH α I.E α 1/ΔhydH

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 Reactivity

 Though the transition elements are moderately electropositive, yet they are not very reactive
because of their:

(i) High heat of sublimation

(ii) High ionisation enthalpy

 Potassium dichromate (K2Cr2O7)

 Preparation:

From Chromite ore (FeCr2O4)

4 FeCr2O4 + 8Na2CO3+ 7O2 → 8Na2CrO4+ 2Fe2O3+ CO2

(chromite ore)

2 Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O

Na2Cr2O7 + 2 KCI → K2Cr2O7 + 2 NaCl

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 Physical Properties:

 Orange-red coloured crystalline compound.

 Moderately soluble in cold water but freely soluble in hot water.

 It melts at 398°C.

 K2Cr2O7 is preferred over Na2Cr2O7 as a primary standard in volumetric estimation because

Na2Cr2O7 is hygroscopic in nature but K2Cr2O7 is not.

 Effect of pH on Potassium dichromate

Cr2O72- + 2 OH- → 2 CrO42- + H2O

(Orange) (Yellow)

2 CrO42- + 2 H+ → Cr2O72- + H2O

(Yellow) (orange)

 Oxidising nature of Potassium dichromate

Powerful oxidising agent in acidic medium (dil. H2SO4)

Cr2O7 2- + 14H+ + 6e- → 2Cr3+ + 7H2O

6Fe2+ + Cr2O7 2- + 14 H+ → 6Fe3+ + 2Cr3+ + 7H2O

6I- + Cr2O7 2- + 14 H+ → 3I2 + 2Cr3+ + 7H2O

3Sn2+ + Cr2O7 2- + 14 H+ → 3Sn4+ + 2Cr3+ + 7H2O

3H2S + Cr2O7 2- + 14 H+ → 3S + 2Cr3+ + 7H2O

Note: Oxidation state of Cr changes from +6 to +3

 Uses Of Potassium Dichromate

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 Used as a primary standard in volumetric analysis for the estimation of reducing agents such as
oxalic acid, ferrous ions, iodide ions, etc.

 For tanning of leather, photography etc.

 As a cleansing agent for glass ware in the form of chromic acid.

 Structure of ions

POTASSIUM PERMANGANATE (KMnO4)

 Preparation:

From pyrolusite ore(MnO2)

2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O

(K2MnO4 → 2K+ + MnO42-)

3MnO42- + 4H+ → 2MnO4- + 2H2O + MnO2

 Physical Properties :

 It is purple coloured crystalline compound.

 Sparingly soluble in water at room temperature.

 Chemical Properties:

 Effect of heating

2KMnO4 → K2MnO4 + MnO2 + O2

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 Oxidising nature of KMnO4

 KMnO4 shows strong oxidising nature.

 It shows different oxidising nature in different medium.

 Acidic medium:

MnO4-+ 8H+ + 5e- → Mn2+ + 4H2O

 Neutral or faintly alkaline medium:

MnO4- + 2H2O + 3e- → MnO2 + 4OH-

 Strongly alkaline medium:

MnO4- + e-→ MnO42-

 In acidic medium (presence of dil. H2SO4) :

MnO4-+ 8H+ + 5e- → Mn2+ + 4H2O

5Fe2+ + MnO4- + 8H+ → 5Fe3+ + Mn2+ + 7H2O

 Iodide is oxidised to Iodine

 H2S is oxidised to Sulphur

 SO2 is oxidised to H2SO4

 Nitrite(NO2-) is oxidised to Nitrate(NO3-)

 Oxallic acid is oxidised to CO2

This reaction is slow at room temperature, but is rapid at 60°C.

Mn(II) ions produced catalyse the reaction; thus the reaction is autocatalytic.

 In slightly alkaline & neutral medium :

 In slightly alkaline medium KMn04 is reduced to MnO2

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(MnO4- to MnO2)

 2 MnO4- + I- + H2O → 2 MnO2 + IO3- + 2 OH-

 8 MnO4- + 3 S2O32- + H2O → 8 MnO2 + 6 SO42- + 2 OH-

Permanganometric titrations in the presence of HCl are unsatisfactory as HCl is oxidised to chlorine
by KMn04 .

 Uses of KMnO4

 Used as an oxidising agent in laboratory and industry.

 Alkaline potassium permanganate is called Bayer's reagent. This reagent is used in organic
chemistry for testing unsaturation.

 KMnO4 is used in the manufacture of saccharin, benzoic acid, acetaldehyde,etc.

 KMnO4 is used as a reagent in qualitative analysis and as primary standard in quantitative

analysis.

 KMnO4 is used as an antiseptic

 Structure of ions

 f -Block Elements

 f -block elements are also called inner transition elements.

 The elements in which the electrons enter (n-2)f orbitals are called the f block elements.

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 The electronic configuration of f block elements is (n-2)f(1−14)(n-1)d(0−1)ns2.

 Position of f - block elements

 f -block elements are placed separately at the bottom of the periodic table. They are a subset of the
6th and 7th periods.

 4f-series (first inner-transition series) The last electron enters in 4f-orbital. The elements
belonging to this series are also known as lanthanoids.
 5f-series (second inner-transition series) The last electron enters in 5f-orbital. The elements
belonging to this series are also known as actinoides.

 Lanthanides

 The fifteen elements from lanthanum (at. no. 57) to lutetium (at. no. 71) are known as lanthanides
or rare earths.

 They are called lanthanides because the elements in the series are chemically similar to
lanthanum.

 These are reactive elements. So, they are not found in nature in the free state.

 Lanthanides are non-radioactive (except for promethium(Pm), which is radioactive).

 Properties of Lanthanides

 Lanthanides are good conductors of electricity and heat.

 They have melting points ranging from 1000 K to 1200 K (Samarium is an exception, 1623 K).

 These are soft metals with a silvery-white colour.

 When exposed to air, their brightness reduces rapidly, and their colour dulls.

 A decrease in atomic and ionic radii from lanthanum to lutetium is observed. This is called the
lanthanoid contraction.

 They are non-radioactive in nature except for promethium

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1. Electronic configuration

 The general electronic configuration of these elements is

[Xe]4f0 – 14 5d0-1 6s2.

2. Oxidation state

 The most common and most stable oxidation state of lanthanides is +3 but some elements also
exhibit +2 and +4 oxidation states in which they leave behind stable ions,

e.g., Ce4+ , Eu2+ and Yb2+

3. Magnetic properties

 All lanthanide ions with the exception of La3+, Lu3+ and Ce4+, are paramagnetic in nature.

4. Lanthanoid contraction

 Steady decrease in the atomic and ionic radii as the atomic number of the lanthanide elements
increases is called lanthanide contraction.
 This is because the additional electron goes to 4f-subshell and 4f-orbitals being large and diffuse,
have poor shielding effect. The effective nuclear charge increases which causes the contraction in
the size of electron charge cloud. This contraction in size is quite regular and is known as
lanthanoid contraction.

Consequences of lanthanoid contraction

(i) Covalent character of cations increase.

(ii) The electronegativity of trivalent ions increases slightly.

(iii) There is decrease in basic strength of oxides and hydroxides from La to Lu.

(iv) There is small increase in standard electrode potential values.

5. Colour

 The species containing unpaired electrons are coloured and so on in the case of lanthanide ions.

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6. Melting and boiling pOints

 Lanthanides have high melting and boiling points but there is no regular trend.

7. Density

 Lanthanides have densities varying from 6.67 to 9.7 g cm -3, but there is no regular trend for these
values.

8. Electronegativity

 For lanthanides the electronegativity values are almost same as that of s-block elements.
Lanthanides form ionic compounds.

9. Ionisation energies

 The ionisation energy values of lanthanoids are not very high due to their large size and
comparable with those of alkaline earth metals.

10. Complex compound

 Due to their large ionic SIze, they have little tendency to form complexes.

11. Reactivity

 Due to their low values of ionisation energies, the lanthanides are very reactive.

12. Alloys

 They form alloy especially with iron e.g., misch metal rare earths 94 - 95%, iron ~ 5% and S, C, Ca
and Al in traces. Mg mixed with 3% misch metal is used for making jet engine parts.

 Actinides

The second series of f- block elements are called actinides. These are elements with atomic numbers
starting from 89 and ending at 103. These elements are radioactive in nature. From neptunium (after
Uranium 92) to onwards the elements are man-made (artificially prepared) and also known as trans-
uranic elements.

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 Properties of Actinides
 Actinides have a radioactive nature.
 These elements appear to be silvery.

 A decrease in atomic and ionic radii from actinium to lawrencium is seen. This is known as actinoid
contraction.

 These metals usually exhibit an oxidation state of +3. Elements belonging to the first half of the
series are known to exhibit higher oxidation states.

 These metals are highly reactive. The reactivity increases when they are finely divided.

1. Electronic configuration

 The last electron in such elements enters in the 5f atomic orbital. Their general electronic
configuration is [Rn]5 f0 – 14 6d0 – 1 7s2

2. Oxidation state

 The common oxidation state is +3 but other oxidation states are also exhibited by actinides upto
the maximum being +7.

3. Actinide contraction

 It is similar to lanthanide contraction due to poor shielding or 5f – electrons

4. Melting and boiling points

 They have high values for melting and boiling points but there is no regular trend.

5. Density

 The value of density vary from 7.0 gcm-3 to 20 gcm-3. Again there is no regular trend in density.

6. Reducing character

 They are strong reducing agents as they have high E° values approximately 2.0 V.

7. Reactivity
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 Actinide are very reactive in nature and combine with oxygen and halogens like lanthanoids.

8. Coloured ions

 Actinide ions are coloured due to the presence of unpaired electrons and f-f transitions.

9. Complex formation

 They have higher tendency to form complex compounds.

 Difference Between Lanthanides-Actinides

 Lanthanides are non-radioactive in nature except promethium. All actinides are radioactive.

 The paramagnetic properties of lanthanides can be easily explained. This is difficult in the case of
actinides.

 Lanthanides are involved in the filling of 4f- orbitals. Actinides are involved in the filling of 5f-
orbitals.

 The compounds formed by lanthanides are less basic. The compounds of actinides are highly
basic.

 Lanthanides do not have a tendency to form oxo-cations. Oxo-cations of actinide series

 Similarities between Lanthanides and Actinides

 They are involved in the filling of (n-2) f orbitals.

 Lanthanides and actinides have oxidation state of +3.

 Lanthanides and actinides are highly electropositive and very reactive in nature.

 They show magnetic properties.

 As the atomic number increases, there is a decrease in atomic and ionic size.

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 Uses of f - Block Elements

Some applications of the f block elements are:

 Lanthanide alloys (mischmetal) utilized for the creation of instrumental steels and heat resistance.

 Carbides, Borides, and nitrides of lanthanides come in use as refractories.

 Lanthanide oxides come in use in cleaning glass as abrasives.

 Thorium is a part of cancer treatment and glowing gas mantles.

 We utilize Uranium as an atomic fuel.

 Plutonium is a part of nuclear reactors and nuclear bombs.

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